Substituted benzene compounds, process for their preparation, and herbicidal and defoliant compositions containing them

BACKGROUND OF THE INVENTION

[0001] Use of uracils as herbicides ha previously been reported. For example, U.S. Pat. Nos. 4,859,229 and 4,746,352 describe 3-phenyl uracil derivatives as herbicides. However the phenyl ring in the described compounds carry only four substituents. U.S. Pat. No. 4,927,451 describes herbicidal compounds carrying five substituents on the phenyl ring with a dihydrouracil ring. EP patent 0705829 describes uracil herbicides carrying pentasubstituted phenyl ring with a carbon linked substiutent at position 2 of the phenyl ring. U.S. Pat. Nos. 5,346,881, 5,441,925, 5,169,431, 5,476,834, 5,602,077, and WO patents 97/08170, 08171, 12886 and 42188 describe uracil herbicides carrying a fused pentasubstituted phenyl ring where the 2 position of the phenyl ring is substituted either with a carbon, oxygen or nitrogen. U.S. Pat. No. 5,116,404 and JP patent 05025144 describe uracil compounds with a 3-phenyl group which may be pentasubstituted but none of these patents appears to make obvious the compounds of the present invention which carry a nitrogen linked substituent at position 2 of the phenyl ring along with substituents at positions 3, 4,and 6 and there appears to be no indication as to the criticality of the substitution pattern of the phenyl moiety in order to introduce the high herbicidal activity in combination with selectivity towards crops. Similarly use of pyrazole, tetrahydrophthalimide, triazolinone, tetrazolinone, and triazolidine derivatives as herbicides has been described before such as U.S. Pat. Nos. 5,281,571, 4,881,967, 5,084,085, WO patent 85/01939, and Japanese patent 1-121290 respectively. Pyridazinones, pyridyls, bicyclic hydantoins, phthalimides, pyrimidinones, pyrazinones, and pyridinones have also been described as herbicides such as WO patents 97/07104, 95/02580, 95/23509, EP patent 0786453, WO patents 97/06150, 97/11060, and 97/28127. However, despite the broad coverage of these patents, the general structure of the present invention has not been described.

SUMMARY OF THE INVENTION

[0002] This invention delineates a method for the control of undesired vegetation in a plantation crop by the application to the locus of the crop an effective amount of a compound described herein. The herbicidal and defoliant compounds of the present invention are described by the following general formula I or its salts:

[0003] wherein X is hydrogen, halogen, nitro, amino, NHR, N(R)2, amide, thioamide, cyano, alkylcarbonyl, alkoxycarbonyl, alkylsulfonamide, unsubstituted or substituted alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonylalkoxy, benzyloxy, aryloxy, or heteroaryloxy;

[0004] Y is hydrogen, halogen, or nitro;

[0005] W is hydrogen, OR, SR, NHR, N(R)2, CH2R, CH(R)2, or C(R)3, halogen, nitro, or cyano, where multiple R groups represent any possible combination of substituents described by R; R is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heteroaryl, alkoxy, cycloalkyloxy, aryloxy, heteroaryloxy, alkylsulfonyl, benzyl, alkylcarbonyl, alkenylcarbonyl, alkynylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, or heteroaryloxycarbonyl, where any of these groups may be unsubstituted or substituted with any of the functional groups represented by one or more of the following: halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkylsilyl, alkylcarbonyl, haloalkylcarbonyl, alkoxy, alkoxycarbonyl, haloalkoxy, haloalkoxycarbonyl, alkylsulfonyl, haloalkylsulfonyl, aryl, heteroaryl, or cycloalkyl;

[0006] Q is a heterocycle, examples of which are as follows:

[0007] wherein R1 is hydrogen, alkyl, haloalkyl, alkenyl, alkynyl, amino, alkoxyalkyl, acetyl, alkoxycarbonylamino, alkylcarbonylamino, or alkoxycarbonyl;

[0008] R2 is alkyl or haloalkyl;

[0009] R1 and R2 could combine to form a five- or six-membered heterocyclic ring;

[0010] R3 is hydrogen, halogen, nitro, amino, alkylamino, haloalkylamino, cyano, or amide;

[0011] R8 and R9 are independently oxygen, sulfur, or imino group;

[0012] Q6, Q7, and Q10 may optionally be unsaturated containing one or two double bonds in the 6-membered ring;

[0013] Z is amino, hydroxyl, thiol, formyl, carboxyl, cyano, alkylcarbonyl, arylcarbonyl, azido, or one of the following:

[0014] wherein R4 is alkyl, alkenyl, alkynyl, amino, cycloalkyl, heterocycloalkyl, alkylsulfonyl, arylsulfonyl, benzyl, aryl, heteroaryl, alkylcarbonyl, alkenylcarbonyl, alkynylcarbonyl, cycloalkylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkoxycarbonyl, alkylthiocarbonyl, cycloalkyloxycarbonyl, aryloxycarbonyl, arylthio-carbonyl, aryl-thiocarbonyl, heteroaryloxycarbonyl, aminocarbonyl, alkylaminocarbonyl, arylaminocarbonyl, heteroarylaminocarbonyl, alkoxycarbonylcarbonyl or arylcarbonylcarbonyl, where any of these groups may be unsubstituted or substituted with any of the functional groups represented by one or more of the following: halogen, cyano, nitro, amino, dialkylamino, hydroxyl, carboxyl, alkyl, alkenyl, alkynyl, cycloalkyl, alkylcarbonyl, alkylcarbonyloxy, alkoxy, alkoxycarbonyl, alkylthio, alkylthiocarbonyl, alkoxythiocarbonyl alkylaminocarbonyl, arylaminocarbonyl, alkylsulfonyl, alkenyloxycarbonyl, alkynyloxycarbonyl, aryl, arylcarbonyl, aryloxy, aryloxycarbonyl, arylthio, heteroaryl, heteroaryloxycarbonyl or methylenedioxy, wherein the alkyl moiety or aryl moiety may be substituted with halogen, cyano, nitro, alkyl, alkoxy, haloalkyl, haloalkoxy, alkoxycarbonyl, cycloalkyl, aryl, or heterocycloalkyl; and R5 is hydrogen or any one of the groups represented by R4; or R4 and R5 could combine to form a 4-8 membered heterocyclic ring;

[0015] wherein R6 represents alkyl, haloalkyl, dialkylamino, unsubstituted or substituted aryl and heteroaryl; and R7 represents hydrogen, halogen or any of the groups represented by R6;

[0016] —OR4,

[0017] —SR4,

[0018] —CH2R10,

[0019] —CH(R10)2,

[0020] —C(R10)3, or

[0021] —CH═CHR10

[0022] wherein R10 is carboxyl, alkyl, alkenyl, alkynyl, amino, cycloalkyl, heterocycloalkyl, alkylsulfonyl, arylsulfonyl, benzyl, aryl, heteroaryl, alkylcarbonyl, alkenylcarbonyl, alkynylcarbonyl, cycloalkylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkoxyc arbonyl, alkylthiocarbonyl, cycloalkyloxy carbonyl, aryloxy carbonyl, arylthio-carbonyl, aryl-thiocarbonyl, heteroaryloxycarbonyl, aminocarbonyl, alkylaminocarbonyl, arylaminocarbonyl, heteroarylaminocarbonyl, alkoxycarbonylcarbonyl or arylcarbonylcarbonyl, where any of these groups may be unsubstituted or substituted with any of the functional groups represented by one or more of the following: halogen, cyano, nitro, amino, dialkylamino, hydroxyl, carboxyl, alkyl, alkenyl, alkynyl, cycloalkyl, alkylcarbonyl, alkylcarbonyloxy, alkoxy, alkoxycarbonyl, alkylthio, alkylthiocarbonyl, alkoxythiocarbonyl alkylaminocarbonyl, arylaminocarbonyl, alkylsulfonyl, alkenyloxycarbonyl, alkynyloxycarbonyl, aryl, arylcarbonyl, aryloxy, aryloxycarbonyl, arylthio, heteroaryl, heteroaryloxycarbonyl or methylenedioxy, wherein the alkyl moiety or aryl moiety may be substituted with halogen, cyano, nitro, alkyl, alkoxy, haloalkyl, haloalkoxy, alkoxycarbonyl, cycloalkyl, aryl, or heterocycloalkyl;

[0023] provided that (1) Z is not alkyl, alkoxy, haloalkyl, haloalkoxy, alkylthio, haloalkylthio, alkenyl, haloalkenyl, amino, monoalkylamino, dialkylamino, alkoxyalkoxy or cyano, when Q is Q1 and R2 is haloalkyl,

[0024] (2) Z is not amino when Q is Q3, and

[0025] (3) Z is not hydroxyl, alkoxy, alkenyloxy, alkynyloxy, haloalkoxy, haloalkenyloxy, or —NR4R5, wherein R4 is alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, alkylsulfonyl, alkylcarbonyl, alkoxycarbonyl, or cycloalkylalkyl, and R5 is alkyl, alkenyl, alkynyl, cycloalkyl, haloalkyl, haloalkenyl, alkylcarbonyl, alkoxycarbonyl, or cycloalkylalkyl, when Q is Q14 or Q15.

DETAILED DESCRIPTION OF THE INVENTION

[0026] In the above definitions, the term alkyl used either alone or in compound words such as haloalkyl indicates either straight chain or branched alkyls containing 1-8 carbon atoms. Alkenyl and alkynyl include straight chain or branched alkenes and alkynes respectively containing 2-8 carbon atoms. The term halogen either alone or in the compound words such as haloalkyl indicates fluorine, chlorine, bromine, or iodine. Further a haloalkyl is represented by an alkyl partially or fully substituted with halogen atoms which may be same or different. A cycloalkyl group implies a saturated or unsaturated carbocycle containing 3-8 carbon atoms. A heterocycloalkyl group is a cycloalkyl group carrying 1-4 heteroatoms which are representd by oxygen, nitrogen, or sulfur atoms. An aryl group signifies an aromatic carbocycle containing 4-10 carbon atoms, and may be phenyl or naphthyl. A heteroaryl group is an aromatic ring containing 1-4 heteroatoms which are represented by oxygen, nitrogen, or sulfur atoms, and may for example be furanyl, pyridyl, thienyl, pyrimidinyl, benzofuranyl, quinolyl, benzothienyl or quinoxalyl.

[0027] The compound of the formula I may form a salt with an acidic substance or a basic substance. The salt with an acidic substance may be an inorganic acid salt such as a hydrochloride, a hydrobromide, a phosphate, a sulfate or a nitrate. The salt with a basic substance may be a salt of an inorganic or organic base such as a sodium salt, a potassium salt, a calcium salt, a quaternary ammonium salt such as ammonium salt or a dimethylamine salt.

[0028] The compound of the formula I may exist as geometrical or optical isomers and the present invention includes all of these isomeric forms.

[0029] Preferred compounds for the reasons of ease of synthesis or greater herbicidal efficacy are represented by the formula I wherein

[0030] (1) Z is —NR4R, or —CH2R10,

[0031] (2) X is halogen or cyano; Y is halogen; W is —OR; and R is alkyl, alkenyl, or alkynyl, where any of these groups may be unsubstituted or substituted with any of the functional groups represented by one or more of the following: halogen, cyano, nitro, amino, or carboxyl, or

[0032] (3) Q is Q1 or Q6; R1 is alkyl, amino or haloalkyl; R2 is haloalkyl; R3 is hydrogen; and R8 and R9 are independently oxygen, sulfur, or imino group,

[0033] Still more preferred compounds for the reasons of greater herbicidal efficacy are represented by formula I wherein

[0034] X is halogen; Y is fluorine; W is OR; R is alkyl, alkenyl, or alkynyl, where any of these groups may be unsubstituted or substituted with halogen or cyano; Q is Q1 or Q6; R1 is alkyl, amino, or haloalkyl; R2 is haloalkyl; R3 is hydrogen; and R8 and R9 are independently oxygen, sulfur, or imino group; Z is —NR4R5; R4 is alkylcarbonyl, alkenylcarbonyl, alkynylcarbonyl, cycloalkylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkoxycarbonyl, alkylthiocarbonyl, cycloalkyloxycarbonyl, aryloxycarbonyl, arylthio-carbonyl, aryl-thiocarbonyl, heteroaryloxycarbonyl, aminocarbonyl, alkylaminocarbonyl, arylaminocarbonyl, heteroarylaminocarbonyl, alkoxycarbonylcarbonyl, arylcarbonylcarbonyl, where any of these groups may be unsubstituted or substituted with any of the functional groups represented by one or more of the following: halogen, cyano, nitro, amino, dialkylamino, hydroxyl, carboxyl, alkyl, alkenyl, alkynyl, cycloalkyl, alkylcarbonyl, alkylcarbonyloxy, alkoxy, alkoxycarbonyl, alkylthio, alkylthiocarbonyl, alkoxythiocarbonyl alkylaminocarbonyl, arylaminocarbonyl, alkylsulfonyl, alkenyloxycarbonyl, alkynyloxycarbonyl, aryl, arylcarbonyl, aryloxy, aryloxycarbonyl, arylthio, heteroaryl, heteroaryloxycarbonyl, or methylenedioxy, wherein the alkyl moiety or aryl moiety may be substituted with halogen, cyano, nitro, alkyl, alkoxy, haloalkyl, haloalkoxy, alkoxycarbonyl, cycloalkyl, aryl, or heterocycloalkyl; and R5 is hydrogen; or Z is —CH2R10; R10 is carboxyl, alkyl, alkenyl, or alkynyl, where any of these groups may be unsubstituted or substituted with any of the functional groups represented by one or more of the following: halogen, cyano, nitro, amino, dialkylamino, hydroxyl, carboxyl, alkyl, alkenyl, alkynyl, cycloalkyl, alkylcarbonyl, alkylcarbonyloxy, alkoxy, alkoxycarbonyl, alkylthio, alkylthiocarbonyl, alkoxythiocarbonyl alkylaminocarbonyl, arylaminocarbonyl, alkylsulfonyl, alkenyloxycarbonyl, alkynyloxycarbonyl, aryl, arylcarbonyl, aryloxy, aryloxycarbonyl, arylthio, heteroaryl, heteroaryloxycarbonyl, or methylenedioxy, wherein the alkyl moiety or aryl moiety may be substituted with halogen, cyano, nitro, alkyl, alkoxy, haloalkyl, haloalkoxy, alkoxycarbonyl, cycloalkyl, aryl, or heterocycloalkyl.

[0035] Certain intermediates of the present invention are novel. These are 3-(2-amino-4-chloro-6-fluoro-3-methoxyphenyl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione, 3-(2-amino-4-chloro-6-fluoro-3-methoxyphenyl)-1-amino-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione and represented by the following formulae (III-V):

[0036] wherein X, Y, W and Q are the same as defined above; and M is nitro.

[0037] wherein X′ and Y′ are halogens; and R is the same as defined above.

[0038] The compounds described by the formula I can be prepared by the procedures as described herein. In general, the compounds described in this invention can be prepared by one of the two routes depending on whether the heterocyclic ring (e.g. uracil ring) is formed prior to or after the nitration at the 2 position of the phenyl ring in the final product.

[0039] As depicted in Scheme 1, the starting materials for these preparations are the compounds represented by the formula VIc. These compounds can be prepared starting from the nitro compound VIa via the amine VIb by the procedures described in literature, for example U.S. Pat. No. 4,859,229 (1989). Nitration of Vic is typically carried out by its slow addition to a mixture of sulfuric acid and nitric acid in a ratio of 9:1. Typically 3-4 ml of the nitration mixture is used for 2-3 mmol of VI and the addition is carried out between 0 to −30° C. followed by stirring at ambient temperature for 0.5-2 hr. Product (VII) is separated by addition of the solution to ice water and filtration of the precipitate. The product can also be extracted from aqueous layer into organic solvents such as ether or ethyl acetate and purified by crystallization or column chromatography. Alkylation of VII to VIII can be accomplished by treatment of VII with alkyl halide, haloalkyl halide, especially the respective chloride, bromide, or sulfate in the presence of a base such as potassium carbonate or sodium hydride in an inert solvent such as acetone, dimethylformamide, dimethylsulfoxide, tetrahydrofuran, methyl ethyl ketone, or acetonitrile at a temperature range of 0 to 130° C. VIII can be reduced to the amine (IX) under typical reduction conditions such as treatment with iron in acetic acid or ethanolic hydrochloric acid; or by hydrogenation using palladium on carbon or platinum oxide as catalyst. The product IX is purified by typical purification procedures of recrystallization or column chromatography.

[0040] The amine (IX) can be derivatized to yield a variety of products generally represented by the formula X. For example amides can be prepared by treatment of IX with alkyl or aryl acid halides, typically chlorides, or anhydrides in the presence of base in an inert solvent. Typically organic bases such as triethylamine, diisopropylethylamine, or pyridine can be used in inert solvents such as tetrahydrofuran, acetonitrile, or dioxane at a temperature range of ambient to reflux temperature for 2-24 hr. Pyridine can be used alone as solvent and base. Acylation catalysts such as dimethylaminopyridine (DMAP) can be added to facilitate the reaction. Typical work-up procedure includes removal of solvent followed by partitioning of the product between aqueous and organic solvents such as ether, ethyl, acetate or methylene chloride. Depending upon the reactivity of the acid halide, the product typically consists of a monoamide, diamide, or a mixture of the two. These can be purified/resolved typically by column chromatography. Mono or dialkyl (amino) derivatives of IX can be prepared by its treatment with alkyl or haloalkyl halides in the presence of base such as potassium or sodium carbonate, or sodium hydride in an inert solvent such as tertahydrofaran or dimethylformamide at a temperature of ambient to 120° C. for 2-24 hr. Mono or dicarbamoyl derivatives of IX can be prepared by its treatment with alkylhaloformates such as methyl or ethylchloroformate in the presence of base such as potassium or sodium carbonate in an inert solvent such as tertahydrofaran or dimethylformamide at a temperature of ambient to 120° C. for 2-24 hr. Mono or diurea derivatives of IX can be prepared by its treatment with an alkyl or aryl isocyanate, for example methyl or ethyl isocayante, in the presence of a base such as triethylamine in an inert solvent such as toluene or tetrahydrofuran. Alternatively, IX is first converted into its isocyanate derivative by treatment with phosgene or triphosgene in toluene or tetrahydrofuran at reflux temperature for 2-6 hr. This isocyanate can, in turn, be treated with an alkyl or aryl amine such as methyl or ethyl amine in the presence of a base such as triethylamine in an inert solvent such as toluene or tetrahydrofuran at a temperature range of ambient to 130° C. for 2-12 hr to furnish the corresponding urea. IX can be treated with an alkyl dihalide such as 1,4-diiodobutane in an inert solvent such as toluene or acetonitrile at reflux temperature in the presence of a base such as potassium or sodium carbonate to furnish the corresponding cyclized product such as a pyrrolidine derivative. IX can be treated with an aromatic or aliphatic aldehyde or ketone or its diethyl or dimethyl acetal derivative in an inert solvent such as toluene or methylene chloride to furnish the corresponding imino derivative. Alternatively, a monoacetyl derivative of IX can be treated with a dehydrochlorinating agent such as phosphorus pentachloride to furnish the corresponding iminochloride.

[0041] The starting uracil derivative represented by formula XI in Scheme 2 can be prepared according to the procedure as described before. The compound XI is nitrated with concentrated nitric acid at 0° C. to ambient temperature for 15˜30 minutes. Product (XII) is obtained by addition of the product mixture to ice-water followed by filtration.

[0042] The starting uracil derivative represented by formula XIII in Scheme 3 can be prepared according to the procedure as previously described. Compound XIII can be nitrated with nitric acid at 0° C. for 15˜30 minutes. Product (XIV) is obtained by addition of ice followed by filtration.

[0043] The desired starting tetrazole derivatives represented by formula XV in Scheme 4 can be prepared according to the literature procedure of WO 85/01939. These compounds can be nitrated with nitric acid at ambient temperature or at 0° C. for 15˜30 minutes. Product (XVI) is isolated by addition of ice followed by extraction into an organic solvent such as ether or ethyl acetate and purified. XVII can be prepared by the reduction of XVI typically by catalytic hydrogenation in presence of catalysts such as palladium on carbon or by treatment with iron in acetic acid or in ethanolic hydrochloric acid. XVIII can be prepared by reacting XVII with a halide in presence of a base at 50 to 120° C. for 1˜5 hours. Further modification of XVIII to XIX is carried out according to the general procedures described for the preparation of X from IX (Scheme I).

[0044] The starting triazolinone derivative represented by formula XX in Scheme 5 can be prepared according to the literature procedure of U.S. Pat. No. 4,980,480 (1990). The compound XX is nitrated with concentrated nitric acid at −15 to 0° C. for 0.5-2 hr. Product (XXI) is obtained by addition of the product mixture to ice-water followed by filtration.

[0045] The desired starting pyrazole derivatives represented by formula XXII in Scheme 6 can be prepared according to the literature procedure of U.S. Pat. No. 5,281,571 (1994). These compounds can be nitrated in sulfuric acid-nitric acid mixture (9:1) with a ratio of 3-4 ml of the nitrating solution to 3-4 mmol of XXII. The addition is carried out between -15 to −30° C. followed by stirring at ambient temperature for 1-2 hr. Product (XXIII) is isolated by addition of water followed by extraction into an organic solvent such as ether or ethyl acetate and purified. XXIV can be prepared by the reduction of XXIII typically by catalytic hydrogenation in presence of catalysts such as palladium on carbon or by treatment with iron in acetic acid or in ethanolic hydrochloric acid. Further modification of XXIV to XXV is carried out according to the general procedures described for the preparation of X from IX (Scheme I).

[0046] The desired starting tetrahydrophthalimide derivative represented by formula XXVI in Scheme 7 can be prepared according to the literature procedure of U.S. Pat. No. 4,484,941 (1984). The compound can be nitrated with nitric acid at 0° C. to ambient temperature for half hour. The product (XXVII) is isolated by addition of ice followed by extraction into an organic solvent such as ether, ethyl acetate, or methylene chloride and purified. XXVIII can be prepared by the reduction of XXVII typically by catalytic hydrogenation in presence of catalysts such as palladium on carbon or by treatment with iron in acetic acid or in ethanolic hydrochloric acid. XXIX can be prepared by reacting XXVIII with (substituted)alkyl halide in the presence of a base such as potassium carbonate. Further modification of XXIX to XXX is carried out according to the general procedures described for the preparation of X from IX (Scheme I).

[0047] Scheme 8 describes the preparation of intermediates represented by the formulae XXXIII and IV. The starting materials (amino phenols and alkyl derivatives represented by the formula VIb) are prepared according to the procedure as described in literature such as U.S. Pat. No. 4,670,046 (1987) which upon treatment with phthalic anhydride in acetic acid can afford phthalimide derivative (XXXI). Nitration of XXXI can be carried out by its addition to a mixture of sulfuric acid and nitric acid (9:1) at −15 to −30° C. followed by addition of water and extraction of the product (XXXII) in organic solvents such as ethyl acetate or ether. XXXII can be reduced to the corresponding amine (XXXIII) by conventional methods such as treatment with iron in acetic acid or ethanolic hydrochloric acid or by catalytic hydrogenation in the presence of palladium on carbon. Amino group of XXXIII can be derivatized as described before in Scheme 1 to furnish XXXIV which in turn can be deprotected to furnish XXXV. Removal of the protecting phthalimido group can be accomplished by several methods such as treatment with hydrazine in a polar solvent such as dimethylsulfoxide or by treatment with on organic amine such as methyl amine in ethanol. XXV can then be derivatized to the desired compound (X) according to the known procedures as described before in Schemel. Alternatively, XXXII can first be subjected to deprotection to afford the amine IV which can be modified to introduce the heterocyclic ring such as the uracil ring (U in XXXVI) according to the known procedures. Nitro group in XXXVI can then be reduced to afford the amine which can then be derivatized as described previously to afford X.

[0048] Scheme 9 delineates a process for the preparation of the intermediates represented by the formula V. Starting materials represented by the formula XXXIX are prepared by the nitration of XXXVII which gives XXXVIII which can be reduced to XXXIX according to the literature procedure of Japanese patent 01186849 (1989). The amino group in XXXIX is protected by forming amide or carbamate XL and the latter is nitrated to give XLI. Deprotection of XLI leads to the ortho-nitro aniline V. V can be converted into the desired compounds represented by XLV according to the procedures as shown in the scheme.

[0049] Scheme 10 describes the preparation of intermediate represented by the formulae XLVIII. The starting material (XLVI) can be prepared according to the method described in patents, such as U.S. Pat. No. 5,154,755 (1992). XLVI reacts with ethyl chloroformate at basic condition to give the carbamate XLVII. The latter is nitrated with a mixture of nitric acid and sulfuric acid to give the intermediate XLVIII which can be N-alkylated with an alkylhalide in the presence of base to furnish XLIX.

[0050] Scheme 11 describes an alternative procedure for the preparation of compounds represented by the formula LVII with varying R groups. Reduction of L to LI is carried out using conventional procedures such as catalytic reduction or iron-acetic acid mixture. The aniline LI is reacted with phenyl chloroformate to afford a carbamte represnted by the formula LII which is nitrated with an inorganic salt such as ammonium or potassium nitrate in an acid anhydride such as acetic anhydride according to published perocedure such as described in WO 97/42188. Resultant nitro derivative LIII is cyclized to furnish the uracil derivative LIV upon reaction with an appropriately substituted amino crotonate in the presence of an inorganic or organic base exemplified by 1,8-diazabicylo[5.4.0]undec-7-ene (DBU). LIV is N-derivatized to afford LV followed by reduction to aniline LVI according to conventional procedures as described before. LVII is then derivatized to afford the final compounds represented by the formula LVII according to the procedures as described before.

[0051] Scheme 12 desribes a process for the preparation of compounds represented by the formula LXII which are trisubstituted phenyl derivatives. Ortho-nitroaniline derivatives represented by the formula LVIII are the starting materials which are converted to a ortho-nitro uracil derivatives (LX) according to previously described procedures, e.g. via the NH uracil derivative (LIX). Nitro groups is then converted to an amino group (LXI) via conventional reduction procedures such as cataytic or iron-acetic acid reduction followed by derivatization to furnish LXII.

[0052] Scheme 13 describes a procedure for the preparation of trisubstituted phenyl derivatives represented by the formula LXVI. Direct nitration of LXIII, where X and Q (a heterocylce) are as previously defined, using nitration reagents such as nitric acid or a mixture of sulfuric acid-nitric acid leads to ortho-nitro compounds represented by the formula LXIV which are reduced to the corresponding aniline derivatives (LXV) by reduction procedures such as catatlytic reduction or iron-acetic acid. Aniline (LXV) is then derivatized to furnish LXVI.

[0053] Scheme 14 delineates a procedure for the preparation of tetrasubstituted phenyl derivatives represented by the formula LXXIV. The process is akin to one described in scheme 11 for the prepration of pentasubstituted phenyl derivatives (LVII). The nitro intermediates (LXVII) are reduced to the anilines (LXVIII) via conventional procedures followed by derivatization to the phenyl carbamate (LXIX) by reaction with a phenylhaloformate. Nitration to LXX (inorganic nitrate-acid anhydirde) is followed by the uracil ring formation (appropriately substituted crotonate-DBU) (LXXI) and N-derivatization to furnish LXXII. Reduciton to the aniline (LXXIII) is carried out by procedures such as catalytic reduction or iron-acetic acid followed by derivatization to furnish LXXIV.

[0054] Scheme 15 describes vaious procedures for the derivatization of the amino group in LXXV via diazonium salts represented by LXXVI. The diazonium salts are prepared by treatment of the aniline with an inorganic nitrite solution such as sodium or potassium nitrite in an acid such as sulfuric or hydrochloric acid or by treatment of the aniline with an organic nitrite such as t-butyl nitrite in an organic solvent such as acetonitrile. Reaction is carried out between 10-−15° C. which results in a stable solution of the diazonium salt which is reduced to the corresponding hydrazine derivative represented by the formula LXXVII by reducing agents exemplified by stannic chloride. Hydrazine derivatives are then derivatized to a variety of compounds represented by the formula (LXXXVI) via Conventional reacions such as acylation, alkylation, Schiff base formation, etc. The diazonium group in LXXVI is replaced by a hydroxyl to furnish the corresponding phenol (LXXVIII) by its treatment with an aqueous solution of cuprous oxide in presence of cupric nitrate or cupric sulfate at ambient temperature. LXXVIII is then derivatized to furnish LXXXVI via conventional reactions such as acylation, alkylation, etc. Treatment of the diazonium salts (LXXVI) with disulfides (RSSR) leads to the formation of corresponding thioethers represented by the formula LXXIX which can be further modified according to conventional procedures leading to sulfur analogs represented by the formula LXXXVI. LXXVI can be treated with inorganic cyanides leading to the formation of cyano derivatives (LXXXI) which can be oxidized via conventional routes to furnish carboxylic acids (LXXXV) which can then be derivatized leading to LXXXVI. The diazonium group can also be replaced with an azido group furnishing LXXX. LXXVI can be treated with inorganic iodides to afford the iodo compounds (LXXXII) which can be converted to the corresponding aldehydes (LXXXIII) (which are also directly obtainable from LXXVI via conventional procedures). LXXXIII can be reduced to furnish corresponding benzyl alcohols (LXXXIV) which can be derivatized to LXXXVI.

[0055] Scheme 16 describes an alternatived procedure for the formation of amides (XC). Reaction of the ortho-amino phenol LXXXVII with an aliphatic or aromatic acyl halide in an organic solvent such as 1,4-dioxane or tetrahydrofuran in the absence or presence of an inorganic or organic base such as potassium carbonate, sodium carbonate, or triethylamine, regioselectively leads to the formation of corresponding amide represented by the formula LXXXIX. LXXXIX can also be produced by the hydrolysis of a corresponding alkyl ether such as methyl ether (LXXXVIII) by treatment with strong Lewis acids such as boron tribromide or boron tribromide-dimethyl sulfide complex. Phenol group in LXXXIX is then derivatized by treatment with a halide in the presence of base such as sodium carbonate or potassium carbonate in an organic solvent such as as acetone, methyt-ethyl ketone, dimethylsulfoxide, or tetrahydrofuran at ambient to reflux temperatures.

[0056] Scheme 17 describes a procedure for the preparation of pyridazinone derivatives represented by the formula XCVII and XCVIII. Desired starting pyridazinone derivatives represented by formula XCI and XCIV can be prepared according to the literature procedure of WO 97/07104. These compounds can be nitrated with nitric acid or a mixture of nitric acid and sulfuric acid at ambient temperature or at 0° C. for 15˜30 minutes. The products XCII and XCV are isolated by addition of ice followed by filtration. XCIII and XCVI can be prepared by the reduction with iron in acetic acid or in ethanolic hydrochloric acid. Methylation of XCIII can be carried out by reacting XCIII with methyl iodide in presence of a base at 50 to 120° C. for 1˜5 hours. Further modification of XCVI to XCVIII is carried out by treatment of the aniline with an organic nitrite (such as t-butyl nitrite) in an organic solvent (such as acetonitrile) and alkyl acrylate in the presence of copper(II) chloride. Modification of XCVI to XCVII is carried out by treatment of the aniline with an alkyl or aryl acid halide at 50 to 120° C. for 1˜5 hours.

EXAMPLE 1

Preparation of 3-(4-chloro-6-fluoro-3-methoxy-2-nitrophenyl)-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (Compound no. I1-1)

[0057] 3-(4-Chloro-6-fluoro-3-methoxyphenyl)-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (10.0 g, 29.5 mmol) was slowly added to a stirred mixture of con. sulfuric acid (36 ml) and con. nitric acid (4 ml) with stirring at −15° C. The solution was then slowly warmed to room temperature and allowed to stir for 2 hr. Addition of the solution to ice-water resulted in a light yellow precipitate which was separated by filtration to afford the title compound (9.1 g). NMR data for the compound are listed in Table XVIII.

EXAMPLE 2

Preparation of 3-(4-chloro-6-fluoro-3-methoxy-2-nitrophenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (Compound no. 1-5)

[0058] 3-(4-Chloro-6-fluoro-3-methoxy-2-nitrophenyl)-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (9 g, 23.5 mmol) was dissolved in dimethylformamide (90 ml) and to this were added potassium carbonate (3.9 g, 28.2 mmol) and dimethylsulfate (10.2 g, 47 mmol) with stirring. The solution was stirred at ambient temperature for 12 hr and water was added. Product was extracted in ethyl acetate and the organic layer was washed with water and dried over anhydrous sodium sulfate. Removal of the solvent afforded a crude product which was purified by column chromatography on silica gel. Elution of the column with methylene chloride afforded the title compound (7.8 g).

EXAMPLE 3

Preparation of 3-(2-amino-4-chloro-6-fluoro-3-methoxyphenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (Compound no. 1-4)

[0059] 3-(4-Chloro-6-fluoro-3-methoxy-2-nitrophenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (7.5 g, 18.9 mmol) was dissolved in acetic acid (75 ml) and 4.2 g (75.6 mmol) of iron powder was added. The solution was stirred at ambient temperature under nitrogen atmosphere for 6 hr and water was added. Extraction was carried out with ethyl acetate. Organic layer was washed with water, brine, and dried with anhydrous sodium sulfate followed by evaporation to afford the title compound (6.8 g).

EXAMPLE 4

Preparation of 3-[4-chloro-2-(2,4-difluorobenzoyl)amino-6-fluoro-3-methoxyphenyl]-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (Compound no. 2-42)

[0060] 3-(2-Amino-4-chloro-6-fluoro-3-methoxyphenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (2.0 g, 5.4 mmol) and triethylamine (0.66 g, 6.5 mmol) were dissolved in anhydrous tetrahydrofuran (30 ml) and stirred under ice cooling. To this solution was slowly added 2,4-difluorobenzoyl chloride (0.96 g, 5.4 mmol) and solution refluxed for 2 hr. Another batch of 2,4-difluorobenzoyl chloride (0.19 g, 1.1 mmol) was added and solution refluxed for 2 hr. Solvent was removed in vacuo and the product purified by column chromatography on silica gel using hexane-ethyl acetate (3:1) as the eluent to afford the title compound (2.2 g).

EXAMPLE 5

Preparation of 3-(4-chloro-2-diacetylamino-6-fluoro-3-methoxyphenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (Compound no. 2-2)

[0061] A mixture of 3-(2-amino-4-chloro-6-fluoro-3-methoxyphenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (0.5 g, 1.4 mmol), triethylamine (0.53 g, 5.6 mmol), acetic anhydride (0.57 g, 5.6 mmol), and anhydrous toluene (10 ml) was refluxed for 12 hr. Solvent was removed in vacuo and the product purified by chromatography on silica gel. Column was eluted with hexane-ethyl acetate (7:3) to furnish the title compound (0.34 g).

EXAMPLE 6

Preparation of 3-(4-chloro-2-dimehtylamino-6-fluoro-3-methoxyphenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (Compound no. 1-11)

[0062] To a solution of 3-(2-amino-4-chloro-6-fluoro-3-methoxyphenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (0.6 g, 1.6 mmol) in toluene (10 ml) was added potassium carbonate (0.27 g, 1.92 mmol) followed by dimethylsulfate (0.69 g, 3.2 mmol). The solution was refluxed for 2 hr and solvent was removed in vacuo. Residue was chromatographed on silica gel and product eluted with methylene chloride to afford the title compound (0.12 g).

EXAMPLE 7

Preparation of 3-(4-chloro-6-fluoro-3-methoxy-2-methoxycarbonylaminophenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (Compound no. 4-1)

[0063] A solution of 3-(2-amino-4-chloro-6-fluoro-3-methoxyphenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (1.25 g) and triethylamine (1 ml) in ethyl acetate (20 ml) was added to a solution of triphosgene (1.0 g) in ethyl acetate (15 ml) stirred under nitrogen. The mixture was heated at reflux for 2 hr, cooled, filtered and the filtrate evaporated under reduced pressure to give a buff colored solid (1.4 g). 1H NMR (CDCl3, 300 MHz) 3.58 (3H, s), 4.00 (3H, s), 6.38 (1H, s), 7.12 (1H, d, J=8.8 Hz) ppm.

[0064] The above isocyanate (0.5 g) dissolved in N,N-dimethylformamide (10 ml) was treated with dry methanol (2 ml) and stirred at room temperature for two days. Water and ethyl acetate were added and the solution separated. The organic phase was dried over sodium sulfate, evaporated, and chromatographed on silica gel eluting with ethyl acetate-hexane (1:3) to give the title compound as a white solid (0.17 g).

EXAMPLE 8

Preparation of 3-[2-bis(methylaminocarbonyl)amino-4-chloro-6-fluoro-3-methoxyphenyl]-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (Compound no. 3-1)

[0065] To a solution of 3-(2-amino-4-chloro-6-fluoro-3-methoxyphenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (0.5 g, 1.4 mmol) and triethylamine (0.17 g, 1.7 mmol) in anhydrous toluene (10 ml) was added methyl isocyanate (0.1 g, 1.7 mmol) with stirring. The solution was refluxed for 2 hr and solvent removed. Residue was chromatographed on silica gel in methylene chloride-methanol (99:1) to furnish the title compound (0.56 g).

EXAMPLE 9

Preparation of 3-[4-chloro-2-(dimethylaminomethynyl)imino-6-fluoro-3-methoxyphenyl]-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (Compound no. 1-31)

[0066] A mixture of 3-(2-amino-4-chloro-6-fluoro-3-methoxyphenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (0.5 g, 1.4 mmol) and dimethylformamide dimethylacetal (0.8 g, 7 mmol) was refluxed for 4 hr under a blanket of nitrogen. Excess reagent was removed in vacuo and product extracted with ether. Solvent was removed to afford a residue which was chromatographed on silica gel. Elution of the column with hexane-ethyl acetate (6:4) afforded the title compound (0.22 g).

EXAMPLE 10

Preparation of 3-(2-amino-4-chloro-6-fluoro-3-hydroxyphenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (Compound no. 1-16)

[0067] 3-(2-Amino-4-chloro-6-fluoro-3-methoxyphenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (1.1 g, 2.7 mmol) was dissolved in 50 ml of anhydrous 1,2-dichloroethane and 3.4 g (10.8 mmol) of borontribromide-dimethylsulfide complex was added to the solution. The solution was refluxed for 16 hr and methylene chloride (100 ml) was added. Washing with water followed by drying (anhydrous sodium sulfate) and removal of the solvent afforded a residue which was triturated with ether to afford the title compound (0.6 g).

EXAMPLE 11

Preparation of 3-(4-chloro-6-fluoro-3-hydroxy-2-nitrophenyl)-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (Compound no. 1-2)

[0068] 3-(4-chloro-2-fluoro-5-hydroxyphenyl)-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione (2.5 g) was added to an ice cooled con. nitric acid (50 ml). After stirring for 1 hr, the reaction mixture was poured into ice-cold water. The yellow crystals were collected by filtration to afford the title compound (0.9 g). The filtrate was extracted by ethyl acetate (200 ml) and washed with brine. The organic phase was dried over anhydrous sodium sulfate. After removal of the solvent, 0.6 g of title compound was obtained as yellow crystal.

EXAMPLE 12

Preparation of 3-(4-chloro-6-fluoro-3-hydroxy-2-nitrophenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (Compound no. 1-17)

[0069] 3-(4-Chloro-2-fluoro-5-hydroxyphenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (1.06 g) was added to ice-cold con. nitric acid (10 ml). After stirring for 30 min, crushed ice was added. The yellow crystals were collected by filtration to afford the title compound (1.2 g).

EXAMPLE 13

Preparation of 1-(4-chloro-6-fluoro-3-hydroxy-2-nitrophenyl)-4-(3-fluoropropyl)-1,4-dihydro-5-oxo-5H-tetrazole (Compound no. 5-4)

[0070] 1-(4-Chloro-2-fluoro-5-hydroxyphenyl)-4-(3-fluoropropyl)-tetrazolinone (2.91 g) was gradually added into an ice-cooled nitric acid (20 ml) and stirred for 30 minutes. Crushed ice was added followed by extraction with ethyl acetate. The ethyl acetate extract was washed with water, dried over sodium sulfate, concentrated, and filtered through a silica gel SPE column (2 g) to give the title compound as a yellow solid (3.4 g).

EXAMPLE 14

Preparation of 1-(2-amino-4-chloro-6-fluoro-3-hydroxyphenyl)-4-(3-fluoroproyl)-1,4-dihydro-5-oxo-5H-tetrazole (Compound no. 5-5)

[0071] Iron powder (2.3 g) was added to a solution of 1-(4-chloro-6-fluoro-3-hydroxy-2-nitrophenyl)-4-(3-fluoropropyl)-1,4-dihydro-5-oxo-5H-tetrazole (3.4 g) in acetic acid (50 ml) and stirred at room temperature over night. The reaction mixture was filtered through a celite bed. The filtrate was concentrated under reduced pressure and purified by a silica gel column, eluted with hexane-ethyl acetate (2:1) to give yellow crystals (2.75 g).

EXAMPLE 15

Preparation of 1-(2-amino-4-chloro-6-fluoro-3-propargyloxyphenyl)-4-(3-fluoroproyl)-1,4-dihydro-5-oxo-5H-tetrazole (Compound no. 5-17)

[0072] The mixture of 1-(2-amino-4-chloro-6-fluoro-3-hydroxyphenyl)-4-(3-fluoropropyl)-tetrazolinone (0.28 g), propargyl bromide (0.13 g), and potassium carbonate (0.14 g) in acetonitrile (5 ml) was heated under reflux for 0.5 hour. The solvent and excess reagent were removed under reduced pressure. The residue was purified by a silica gel column, eluted with ethyl acetate to give the desired product (0.33 g).

EXAMPLE 16

Preparation of 1-(2-amino-4-chloro-6-fluoro-3-isopropyloxyphenyl)-4-(3-fluoropropyl)-1,4-dihydro-5-oxo-5H-tetrazole (Compound no. 5-18)

[0073] The mixture of 1-(2-amino-4-chloro-6-fluoro-3-hydroxyphenyl)-4-(3-fluoropropyl)-1,4-dihydro-5-oxo-5H-tetrazole (0.30 g), isopropyl iodide (1.2 ml), and potassium carbonate (0.14 g) in acetonitrile (5 ml) was heated under reflux for 2 hours. The reaction mixture was evaporated and purified by a silica gel column, eluted with hexane-ethyl acetate (2:1) to give the desired product (0.29 g).

EXAMPLE 17

Preparation of 1-(4-chloro-6-fluoro-3-hydroxy-2-nitrophenyl)-4-difluoromethyl-3-methyl-1,2,4-triazolinone (Compound no. 6-1)

[0074] 1-(4-Chloro-2-fluoro-5-hydroxyphenyl)-4-difluoromethyl-3-methyl-1,2,4-triazolinone (0.21 g) was added to con. nitric acid (1.5 ml) at ambient temperature. The solution was vigorously stirred at ambient temperature for 15 min. Reaction mixture was poured into ice-cold water and yellow precipitate was collected by filtration to afford the title compound (0.17 g) as a 1:1 mixture with oxidative compound.

EXAMPLE 18

Preparation of 1-(2-amino-4-chloro-6-fluoro-3-hydroxyphenyl)-4-difluoromethyl-3-methyl-1,2,4-triazolinone (Compound no. 6-2)

[0075] To a stirred solution of 1-(4-chloro-6-fluoro-3-hydroxy-2-nitrophenol)-4-difluoromethyl-3-methyl-1,2,4-triazolinone (0.15 g) in a mixed solvent of con. hydrochloric acid (5 ml) and methanol (5 ml) was added 0.3 g of iron powder at ambient temperature. The resulting mixture was refluxed for 1 hr and the solution was concentrated under reduced pressure. The residue was extracted with ethyl acetate (200 ml) and the organic phase was washed with brine and dried over anhydrous sodium sulfate. Solvent was removed under reduced pressure to give title compound as a brown oil.

EXAMPLE 19

Preparation of 4-chloro-3-(4-chloro-6-fluoro-3-methoxy-2-nitrophenyl)-1-methyl-5-trifluoromethyl-1H-pyrazole (Compound no. 7-1)

[0076] 4-Chloro-3-(4-chloro-2-fluoro-5-methoxyphenyl)-1-methyl-5-trifluoromethyl-1H-pyrazole (1.2 g, 3.5 mmol) was slurried with 4 ml of con. sulfuric acid and was slowly added to a stirred 4 ml mixture of con. sulfuric acid-con. nitric acid (9:1) at −15° C. Solution was allowed to stir at ambient temperature for 2 hr and then added to ice water. Extraction with ethyl acetate and removal of the solvent afforded a crude product which was chromatographed on silica gel. Elution of the column with hexane-methylene chloride (4:6) furnished the title compound (0.72 g).

EXAMPLE 20

Preparation of 4-chloro-3-(2-amino-4-chloro-6-fluoro-3-methoxyphenyl)-1-methyl-5-trifluoromethyl-1H-pyrazole (Compound no. 7-2)

[0077] 4-Chloro-3-(4-chloro-6-fluoro-3-methoxy-2-nitrophenyl)-1-methyl-5-trifluoromethyl-1H-pyrazole (0.48 g, 1.24 mmol) was dissolved in toluene (8 ml) and 0.05 g of 10% palladium on carbon was added. The solution was vigorously stirred under hydrogen atmosphere for 4 hr at ambient temperature and the catalyst was removed by filtration. Removal of the solvent afforded a residue which was chromatographed on silica gel. Elution of the column with hexane-methylene chloride (3:7) furnished the title compound (0.38 g).

EXAMPLE 21

Preparation of 6-chloro-4-fluoro-2-nitro-3-(tetrahydrophthalimido)phenol (Compound no. 8-1)

[0078] 2-Chloro-4-fluoro-5-(tetrahydrophthalimido)phenol (5.0 g) was added into nitric acid (50 ml) at 0° C., warmed up to room temperature in 30 minutes. Crushed ice was added and the solution extracted with methylene chloride. The organic phase was washed with water, dried over anhydrous sodium sulfate, and purified by a silica gel column, eluted with methylene chloride-ethyl acetate (19:1) to give 3.67 g of the desired product.

EXAMPLE 22

Preparation of 2-amino-6-chloro-4-fluoro-3-(tetrahydrophthalimido)phenol (Compound no. 8-2)

[0079] Iron powder (2.48 g) was added into a solution of 6-chloro-4-fluoro-2-nitro-3-(tetrahydrophthalimido)phenol (3.67 g) in acetic acid (60 ml) and stirred at room temperature for two hours. The reaction mixture was diluted with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, evaporated to give 3.6 g of the title compound.

EXAMPLE 23

Preparation of N-(2-amino-4-chloro-6-fluoro-3-propargyloxyphenyl)tetrahydrophthalimide (Compound no. 8-3)

[0080] A mixture of 2-amino-6-chloro-4-fluoro-3-(tetrahydrophthalimido)phenol (0.31 g), propargyl bromide (0.2 ml), potassium carbonate (0.14 g), and acetonitrile (5 ml) was heated under reflux for 0.5 hr. The solvent and excess reagent were removed under reduced pressure. The residue was purified by a silica gel column, eluted with ethyl acetate to give the title product (0.2 g).

EXAMPLE 24

Preparation of N-(2-amino-4-chloro-6-fluoro-3-isopropyloxyphenyl)tetrahydrophthalimide (Compound no. 8-4)

[0081] A mixture of 2-amino-6-chloro-4-fluoro-3-(tetrahydrophthalimido)phenol (0.31 g), isopropyl iodide (1.2 ml), potassium carbonate (0.14 g), and acetonitrile (5 ml) was heated under reflux for 2 hr. The solvent and excess reagent were removed under reduced pressure. The residue was purified by a silica gel column, eluted with ethyl acetate to give the title product (0.21 g).

EXAMPLE 25

Preparation of N-(2-amino-4-chloro-3-cyclopentyloxy-6-fluorophenyl)tetrahydrophthalimide (Compound no. 8-5)

[0082] A mixture of 2-amino-6-chloro-4-fluoro-3-(tetrahydrophthalimido)phenol (0.31 g), cyclopentyl bromide (1.3 ml), potassium carbonate (0.14 g), and acetonitrile (5 ml) was heated under reflux for 2 hr. The solvent and excess reagent were removed under reduced pressure. The residue was purified by a silica gel column, eluted with ethyl acetate to give the title product (0.17 g).

EXAMPLE 26

Preparation of 2-chloro-4-fluoro-5-(phthalimido)methoxybenzene

[0083] 4-Chloro-2-fluoro-5-methoxyaniline (10.0 g, 57 mmol) and phthalic anhydride (8.5 g, 57 mmol mmol) were dissolved in glacial acetic acid (200 ml) and the solution refluxed for 2 hr. Water was added and the resultant precipitate was separated by filtration. The residue was washed with water and dried to afford the title compound (16.7 g); 1H NMR (CDCl3, 300 MHz) 3.89 (3H, s), 6.9 (1H, d, J=6.3 Hz), 7.33 (1H, d, J=9.0 Hz), 7.82 (2H, m), 7.97 (2H, m) ppm.

EXAMPLE 27

Preparation of 6-chloro-4-fluoro-2-nitro-3-(phthalimido)methoxybenzene

[0084] 2-Chloro-4-fluoro-5-(phthalimido)methoxybenzene (5.0 g, 16.4 mmol) was slowly added to a stirred mixture of con. sulfuric acid-con. nitric acid (10:1, 20 ml) at −20° C. Solution was then warmed to ambient temperature and allowed to stir for 1 hr. Addition to ice-water resulted in a light yellow precipitate which was separated by filtration. Column chromatography on silica gel in hexane-methylene chloride (3:7) furnished the title compound (3.2 g); 1H NMR (CDCl3, 300 MHz) 4.06 (3H, s), 7.54 (1H, d, J=8.5 Hz), 7.84 (2H, m), 7.97 (2H, m) ppm.

EXAMPLE 28

Preparation of 3-chloro-5-fluoro-2-methoxy-6-(phthalimido)aniline

[0085] 6-Chloro-4-fluoro-2-nitro-3-(phthalimido)methoxybenzene (0.5 g, 1.4 mmol) was dissolved in glacial acetic acid (5 ml) and reduced iron (0.32 g, 5.6 mmol) was added. The solution was stirred at ambient temperature under a stream of nitrogen for 12 hr. Water was added and the product extracted with ethyl acetate followed by washings with water, brine, and drying (anhydrous sodium sulfate). Removal of the solvent afforded the title compound (0.4 g); 1H NMR (CDCl3, 300 MHz) 3.87 (3H,s), 4.21 (2H, br s), 6.65 (1H, d, J=9.4 Hz), 7.81 (2H, m), 7.95 (2H, m) ppm.

EXAMPLE 29

Preparation of 4-chloro-6-fluoro-3-methoxy-2-nitroaniline

[0086] 3-Chloro-5-fluoro-2-methoxy-6-phthalimido)aniline (0.6 g, 1.7 mmol) was dissolved in dimethylsulfoxide (3 ml) and anhydrous hydrazine (0.22 g, 6.8 mmol) was added. The solution was stirred at ambient temperature for 12 hr under a stream of nitrogen. Water was added and the product extracted with ether. The organic layer was washed with water, dried (anhydrous sodium sulfate), and evaporated to furnish the title compound (0.22 g). 1H NMR (CDCl3, 300 MHz) 3.98 (3H, s), 5.09 (2H, br s), 7.2 (1H, d, J=10.5 Hz) ppm.

EXAMPLE 30

Preparation of 4-chloro-6-fluoro-3-methoxy-2-nitrophenyl isocyanate

[0087] 4-Chloro-6-fluoro-3-methoxy-2-nitroaniline (0.5 g, 2.27 mmol) was dissolved in anhydrous toluene (30 ml) and triethylamine (0.46 g, 4.54 mmol) was added. This solution was slowly added to a stirred solution of triphosgene (0.67 g, 2.27 mmol) in toluene (30 ml) and the solution refluxed for 2 hr. The solution was cooled and filtered. Clear filtrate was evaporated in vacuo to afford the title compound. 1H NMR (CDCl3, 3.00 MHz) 3.96 (3H, s), 7.38 (1H, d, J=8.8 Hz) ppm.

EXAMPLE 31

Preparation of 3-[4-chloro-6-fluoro-3-methoxy-2-nitrophenyl]-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (Compound no. 1-5) from 4-chloro-6-fluoro-3-methoxy-2-nitrophenyl isocyanate

[0088] Sodium hydride (0.06 g, 2.27 mmol) was suspended in 10 ml anhydrous dimethylformamide and to this was slowly added a solution of ethyl-3-amino-4,4,4-trifluorocrotonate (0.42 g, 2.27 mmol) in anhydrous toluene (10 ml). The solution was stirred for 15 min. until the evolution of hydrogen gas ceased. The solution was cooled to −30° C. and a solution of 4-chloro-6-fluoro-3-methoxy-2-nitrophenyl isocyanate (2.27 mmol) in anhydrous toluene (10 ml) was slowly added with stirring. The solution was then allowed to warm to room temperature and methyl iodide (1.31 g, 9.1 mmol) was added. After stirring for 4 hr at ambient temperature, water was added and product extracted with ethyl acetate. Column chromatography on silica gel in hexane:methylene chloride (4:6) afforded the title compound (0.13 g).

EXAMPLE 32

Preparation of 2-chloro-4-fluoro-5-(phthalimido)phenol

[0089] 5-Amino-2-chloro-4-fluorophenol (3.0 g, 18.6 mmol) and phthalic anhydride (3.3 g, 22.3 mmol) were dissolved in glacial acetic acid (60 ml) and the solution refluxed for 2 hr. Water was added and the resultant precipitate was separated by filtration. The residue was washed with water and dried to afford the title compound (5.04 g); 1H NMR (CDCl3+CD3OD, 300 MHz) 3.68 (1H, s), 6.93 (1H, d, J=6.6 Hz), 7.27 (1H, d, J=9.1 Hz), 7.84 (2H, dd, J=3.0, 5.5 Hz), 7.97 (2H, dd, J=3.0, 5.5 Hz) ppm.

EXAMPLE 33

Preparation of 6-chloro-4-fluoro-2-nitro-3-(phthalimido)phenol

[0090] 2-Chloro-4-fluoro-5-(phthalimido)phenol (5.0 g, 17.1 mmol) was slowly added with stirring to con. nitric acid (50 ml) at −10° C. Solution was then warmed to ambient temperature and allowed to stir for 0.5 hr. Addition to ice-water resulted in a light yellow precipitate which was separated by filtration to afford the title compound (5.5 g); 1H NMR (CDCl3+CD3OD, 300 MHz) 4.36 (1H, br s), 7.61 (1H, d, J=8.6 Hz), 7.88 (2H, dd, J=3.0, 5.5 Hz), 7.99 (2H, dd, J=3.0, 5.5 Hz) ppm.

EXAMPLE 34

Preparation of 4-chloro-2,5-difluoronitrobenzene (XXXVIII)

[0091] 1-Chloro-2,5-difluorobenzene (31.7 g, 0.21 mol);was dissolved in sulfuric acid (110 ml) at −40° C., then a solution of sulfuric acid (20 ml) and nitric acid (30 ml) was added dropwise. The mixture was stirred for 1 hr while temperature slowly raised to 20° C. The product was forced to crystallize by mixing the reaction mixture with ice-water (500 ml), the yellow crystals were filtered, washed with cold water and dried in fume hood overnight. (38.0 g). 1H NMR (CDCl3, 300 MHz) 7.46 (1H, dd, J=9.8, 9.9 Hz), 7.96 (1H, dd, J=7.9, 7.9 Hz) ppm.

EXAMPLE 35

Preparation of 4-chloro-2,5-difluoroaniline (XXXIX)

[0092] 1-Chloro-2,5-difluoro-4-nitrobenzene (XXXVIII) (17.5 g) was dissolved in acetic acid (150 ml) in a 1 L 3-neck round bottom flask equipped with cooling condenser. To it iron powder (35.0 g) was added slowly while the solution was stirred by an overhead stirrer. The reaction was exothermic which occurred in less than 30 min and generated much heat that was absorbed by a cooling bath. After that, ethyl acetate (300 ml) was added and the mixture filtered. The solution was washed with water and dried over sodium sulfate. The product was purified by column chromatography (silica gel, hexane:ethyl acetate, 4:1) (14.3 g). 1H NMR (CDCl3, 300 MHz) 3.89 (2H, br), 6.56 (1H, m), 7.02 (1H, m) ppm.

EXAMPLE 36

Preparation of ethyl 4-chloro-2,5-difluorophenylcarbamate (XL)

[0093] 4-Chloro-2,5-difluoroaniline (XXXIX) (2.1 g, 12.8 mmol) was mixed with pyridine (20 ml) at 0° C., to it was dropwise added ethyl chloroformate (1.5 g, 13.8 mmol). After stirring for 2.5 hr while temperature slowly raised to room temperature, pyridine was evaporated and the residue crystallized in ice-water (100 ml). The crystals were filtered, washed with water and dried in fume hood overnight (2.7 g). 1H NMR (CDCl3, 300 MHz) 1.33 (3H, t, J=7.1 Hz), 4.23 (2H, q, J=7.1 Hz), 6.89 (1H, br), 7.12 (1H, dd, J=6.5, 6.5 Hz), 8.05 (1H, dd, J=7.8, 9.6 Hz) ppm.

EXAMPLE 37

Preparation of ethyl 4-chloro-3,6-difluoro-2-nitrophenylcarbamate (XLI)

[0094] Ethyl 4-chloro-2,5-difluorophenylcarbamate (XL) (2.4 g, 10.2 mmol) was added to a mixture of sulfuric acid (12.5 ml) and nitric acid (0.8 ml) at −30° C. After stirring for 1.5 hr (−30° C. to r.t.), it was poured into ice water (50 ml) and yellow crystals formed immediately which were filtered, washed with water and dried in fume hood overnight (2.8 g). 1H NMR (CDCl3, 300 MHz) 1.30 (3H, t, J=7.1 Hz), 4.22 (2H, q, J=7.1 Hz), 6.97 (1H, br), 7.45 (1H, dd, J=6.3, 6.3 Hz) ppm.

EXAMPLE 38

Preparation of 4-chloro-3,6-difluoro-2-nitroaniline (V)

[0095] Ethyl 4-chloro-3,6-difluoro-2-nitrophenylcarbamate (XLI) (0.9 g, 3.2 mmol) was mixed with acetic acid (30 ml) and hydrobromic acid (48%, 25 ml), the mixture was stirred at 150° C. for 4 hr and then the volume reduced to half by evaporation. Ethyl acetate (50 ml) was added and the solution was washed with water (15 ml×3) and dried over sodium sulfate. The product was purified by column chromatography (silica gel, hexane) (0.56 g). 1H NMR (CDCl3, 300 MHz) 5.73 (2H, br), 7.24 (1H, dd, J=6.1, 6.1 Hz) ppm.

EXAMPLE 39

Preparation of 3-(4-chloro-5-ethoxycarbonylamino-2-fluorophenyl)-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (XLVII)

[0096] Ethyl chloroformate (2.58 g) was dropwise added into a solution of 3-(5-amino-4-chloro-2-fluorophenyl)-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (XLVI) in pyridine (25 ml) at 0° C., and stirred at room temperature for one hr. The reaction mixture was diluted with ethyl acetate, washed with 1N hydrochloric acid followed by water, and dried over sodium sulfate. After concentration, the crystals (5.46 g) were collected by filtration. 1H NMR (CDCl3, 300 MHz) 1.31 (3H, t, J=7.1 Hz), 4.22 (2H, q, J=7.1 Hz), 6.20 (1H, s), 7.14 (1H, br), 7.29 (1H, d, J=8.8 Hz), 7.36 (1H, d, J=6.0 Hz), 8.26 (1H, bd, J=6.4 Hz) ppm.

EXAMPLE 40

Preparation of 3-(4-chloro-3-ethoxycarbonylamino-6-fluoro-2-nitrophenyl)-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (Compound no. 1-33)

[0097] 3-(4-Chloro-5-ethoxycarbonylamino-2-fluorophenyl)-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (XLVII) (1.0 g) was stirred with sulfuric acid (2 ml) at 0° C., then a mixture of nitric acid (1 ml) and sulfuric acid (1 ml) was dropwise added. After stirring at room temperature for 3 hr, it was poured into ice water (50 ml) and yellow crystals formed immediately which was filtered, washed with water and dried in fume hood overnight (0.5 g).

EXAMPLE 41

Preparation of 3-(4-chloro-3-ethoxycarbonylamino-6-fluoro-2-nitrophenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (Compound no. 1-34)

[0098] 3-(4-chloro-3-ethoxycarbonylamino-6-fluoro-2-nitrophenyl)-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (0.96 g) was stirred with dimethyl sulfate (0.72 ml) and potassium carbonate (0.33 g) in N,N-dimethylformamide (10 ml) at room temperature overnight. The reaction mixture was diluted with ethyl acetate, washed with water, dried over sodium sulfate, evaporated to give the title compound (1.1 g, oil).

EXAMPLE 42

Preparation of 3-[4-chloro-6-fluoro3-methyl-2-(2-naphthoyl)aminophenyl]-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (Compound no. 2-122)

[0099] Preparation of 4-chloro-2-fluoro-5-methyl-N-phenoxycarbonylaniline

[0100] 4-Chloro-2-fluoro-5-methylaniline (5 g, 31.4 mmol) was dissolved in tetrahydrofuran (100 ml) and potassium carbonate (6.0 g, 37.7 mmol) and phenyl chloroformate (5.9 g, 37.7 mmol) were added. Solution was refluxed for 3 hr and the solvent was removed under reduced pressure. Product was purified by column chromatography on silica gel (eluent, methylene chloride:hexane, 6:4; 7.15 g).

[0101] Preparation of 4-chloro-2-fluoro-5-methyl-6-nitro-N-phenoxycarbonylaniline

[0102] 4-Chloro-2-fluoro-5-methyl-N-phenoxycarbonylaniline (7.1 g, 25.4 mmol) was dissolved in chloroform (68 ml) and trifluoroaceticanhydride (13.5 ml) and ammoniun nitrate (2.4 g, 30.5 mmol) were slowly added with stirring at ambient temperature. The stirring was continued for 18 hr when a second batch of ammonium nitrate (0.4 g, 5 mmol) was added and stirring continued for 8 hr. Water was added and solution was neutralized by slow addition of sodium bicarbonate solution followed by extraction with chloroform. Organic layer was dried and evaporated under reduced pressure to afford an oily product (8.5 g) which was used for the next step without purification.

[0103] Preparation of 3-(4-chloro-6-fluoro-3-methyl-2-nitrophenyl)-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione

[0104] Ethyl 3-amino-4,4,4-trifluorocrotonate (6.1 g, 33.1 mmol) was dissolved in dimethylformamide (47 ml) and stirred at −10° C. To this solution was slowly added 1,8-diazabicyclo[5.4.0]undec-7-ene (6.3 g, 41.4 mmol) and solution stirred for 0.5 hr. To this solution was slowly added a solution of 4-chloro-2-fluoro-5-methyl-6-nitro-N-phenoxycarbonylaniline (8.5 g) in dimethylformamide (25 ml) followed by stirring at ambient temperature for 14 hr. Solution was then heated to 80° C. and stirred at this temperature for 4 hr. Water was added and pH adjusted to 4 by addition of dilute hydrochloric acid. Product was extracted with ethyl acetate followed by evaporation of the solvent to afford the crude product (10.1 g) which was subjected to N-methylation as follows.

[0105] Preparation of 3-(4-chloro-6-fluoro-3-methyl-2-nitrophenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione

[0106] 3-(4-Chloro-6-fluoro-3-methyl-2-nitrophenyl)-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (10.1 g) was dissolved in dimethylformamide (100 ml) and potassium carbonate (5.7 g, 41.3 mmol) and dimethylsulfate (11.9 g, 55.1 mmol) were added. Solution was stirred at ambient temperature for 14 hr, water was added and product extracted with ethyl acetate. The title compound was separated by column chromatography on silica gel (eluent, hexane-ethyl aceatate, 9:1; 8.5 g).

[0107] Preparation of 3-(2-amino-4-chloro-6-fluoro-3-methylphenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione

[0108] 3-(4-Chloro-6-fluoro-3-methyl-2-nitrophenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (2.0 g, 5.2 mmol) was dissolved in acetic acid (20 ml) and iron powder (1.2 g, 21.5 mmol) was added. Solution was stirred at ambient temperature for 14 hr. Water was added and product extracted with ethyl acetate followed by evaporation under reduced pressure. Title compound was separated by column chromatography on silica gel (eluent, hexane-ethyl acetate, 7:3; 1.5 g).

[0109] Preparation of 3-[4-chloro-6-fluoro3-methyl-2-(2-naphthoyl)aminophenyl]-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione

[0110] 3-(2-Amino-4-chloro-6-fluoro-3-methylphenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (0.5 g, 1.4 mmol) was dissolved in 1,4-dioxane (20 ml) and triethyl amine (0.29 g, 2.9 mmol) and 2-naphthoyl chloride (0.41 g, 2.2 mmol) were added. Solution was heated under reflux for 4 hr and solvent removed under reduced pressure. Product was subjected to column chromatography on silica gel and the title compound was eluted with hexane-ethyl acetate (8:2; 0.3 g).

EXAMPLE 43

Preparation of N-[4-chloro-6-fluoro3-methoxy-2-(2-naphthoyl)aminophenyl]phthalimide (Compound no. 13-3)

[0111] 3-Chloro-5-fluoro-2-methoxy-6-(phthalimido)aniline (0.32 g, 1 mmol), 2-naphthoyl chloride (0.23 g, 1.2 mmol), and triethyl amine (0.12 g, 1.2 mmol) were dissolved in tetrahydrofuran (20 ml) and solution refluxed for 3 hr. Solvent was then removed under reduced pressure and the residue subjected to column chromatography on silica gel. Title compound was eluted with hexane-ethyl acetate (7:3; 0.12 g).

EXAMPLE 44

Preparation of 3-(2-amino-4-chloro-3-difluoromethoxy-6-fluorophenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione ( Compound no. 1-38)

[0112] 3-(2-Amino-4-chloro-6-fluoro-3-hydroxyphenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (1.41 g, 4.0 mmol) and potassium carbonate (0.69 g, 5.0 mmol) were suspended in dimethylformamide (50 ml) and stirred at 90° C. Chlorodifluoromethane was bubbled through the solution for 4 hr and water was added. Product was extracted with ethyl acetate and subjected to column chromatography (silica gel; eluent, methylene chloride-methanol, 99.5:0.5) to furnish the title compound (0.78 g).

EXAMPLE 45

Preparation of 3-[4-chloro-6-fluoro-3-methyl-2-(phenoxycarbonylamino)phenyl]-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (Compound no. 4-52)

[0113] 3-(4-Chloro-6-fluoro-2-isocyanato-3-methylphenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione

[0114] 3-(2-Amino-4-chloro-6-fluoro-3-methylphenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (1.0 g, 2.9 mmol) and triethylamine (0.58 g, 5.7 mmol) were dissolved in ethyl acetate (15 ml) and the solution was slowly added to a solution of triphosgene (0.85 g, 2.9 mmol) in ethyl acetate (15 ml). Solution was heated under reflux for 2 hr and filtered. Solvent was evaporated to afford the title compound as a residue which was used for the next step.

[0115] 3-(4-Chloro-6-fluoro-3-methyl-2-phenoxycarbonylaminophenyl)-1-methyl-6-trifluoromethyl-2,4(1 H, 3H)-pyrimidinedione

[0116] 3-(4-Chloro-6-fluoro-2-isocyanato-3-methylphenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (1.4 mmol) and triethylamine (0.14 g, 1.4 mmol) were dissolved in toluene (15 ml) and the solution was treated with phenol (0.13 g, 1.4 mmol). Solution was stirred for 0.3 hr at ambient temperature and water was added. Product was extracted with ethyl acetate. Removal of the solvent followed by column chromatography on silica gel (eluent, methylene chloride) afforded the title compound (0.3 g).

EXAMPLE 46

Preparation of 3-[4-chloro-6-fluoro-3-hydroxy-2-(2-naphthoylamnino)phenyl]-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (Compound no. 2-114)

[0117] 3-(2-Amino-4-chloro-6-fluoro-3-hydroxyphenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (0.50 g, 1.4 mmol) and 2-naphthoyl chloride (0.27 g, 1.4 mmol) were dissolved in 1,4-dioxane (10 ml) and the solution heated under reflux for 4 hr. Solvent was evaporated under reduced pressure and the product purified by column chromatography on silica gel (eluent, hexane-ethyl acetate, 8:2) to furnish the title compound (0.60 g).

EXAMPLE 47

Preparation of 3-[4-chloro-3-difluoromethoxy-6-fluoro-2-(2-naphthoylamino)phenyl]-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (Compound no. 2-115)

[0118] 3-[4-Chloro-6-fluoro-3-hydroxy-2-(2-naphthoylamino)phenyl]-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (0.51 g, 1.0 mmol) dissolved in dimethylformamide (5 ml) was slowly added to a stirred suspension of sodium hydride (0.03 g, 1.3 mmol) in dimethylformamide (5 ml) at −10° C. Chlorodifluoromethane was bubbled through the solution for 0.5 hr with stirring at −10° C. followed by addition of water. Product was extracted with ethyl acetate and solvent evaporated under reduced pressure. Residue was subjected ot column chromatography on silica gel (eluent, hexane-ether, 25:75) to furnish the title compound (0.03 g).

EXAMPLE 48

Preparation of 3-[4-chloro-2-(2-naphthoylamino)phenyl]-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (Compound no. 2-131)

[0119] To a solution of triphosgene in anhydrous ethyl acetate (150 ml) was added dropwise a solution of 4-chloro-2-nitroaniline (10 g) and triethylamine (12 g) in anhydrous ethyl acetate (50 ml) at 0° C. under nitrogen atmosphere. After addition, the resulting mixture was heated at reflux temperature for 1 hr, then allowed to cool to ambient temperature. The precipitate was removed by filtration through Celite and the filtrate was concentrated to give title compound as an brown solid.

[0120] To a suspension of sodium hydride (60% dispersion in oil, 2.5 g) in anhydrous N,N-dimethylformamide (100 ml) was added dropwise a solution of ethyl-3-amino-4,4,4-trifluorocrotonate in toluene (50 ml) at 0° C. under nitrogen atmosphere. After addition, the mixture was stirred for 20 min at same temperature, then cooled to −30° C. A solution of (4-chloro-2-nitrophenyl)isocyanate in toluene (50 ml) was added dropwise. After stirring for 20 min, the cold bath was removed and the resulting mixture was stirred overnight at ambient temperature. The reaction mixture was partitioned between ethyl acetate and 1 N-hydrochloric acid. The organic phase was washed with brine (×2) and dried over anhydrous sodium sulfate. The solvent was removed in vacuo and the residue was purified by column chromatography on silica gel eluted with ethyl acetate and hexane (1:1) to afford 3-(4-chloro-2-nitrophenyl)-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (10.2 g).as a yellow solid.

[0121] Preparation of 3-(4-chloro-2-nitrophenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione

[0122] A mixture of 3-(4-chloro-2-nitrophenyl)-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (3 g), dimethyl sulfate (1.7 g) and potassium carbonate (1.85 g) in N,N-dimethylformamide (100 ml) was stirred at 55° C. overnight. The resulting mixture was allowed to cool to ambient temperature and filtered through Celite to remove unsoluble precipitate. The filtrate was diluted with a mixed solvent of ethyl acetate and hexane (1:1, 200 ml), washed with brine (×2) and dried over anhydrous sodium sulfate. After removal of the solvent, the residue was solidified. The yellow solid was recrystallized from ethyl acetate and hexane to give desired compound ( 2.3 g).

[0123] Preparation of 3-(2-amino-4-chlorophenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione

[0124] To a stirred suspension of 3-(4-chloro-2-nitrophenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (1 g) in methanol (20 ml), and conc. hydrochloric acid (10 ml) was added iron (powdered, 0.48 g) unded vigorous stirring. After addition, the mixture was heated at reflux temperature for 1 hr. The oil bath was removed and the solution was allowed to cool to ambient temperature. Ethyl acetate (200 ml) was added, washed with brine (×2) and dried over anhydrous sodium sulfate. After removal of the solvent, the residue was purified by column chromatography on silica gel using ethyl acetate-hexane (1:3) as the eluent to give the title compound.

[0125] Preparation of 3-[4-chloro-2-(2-naphthoylamino)phenyl]-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (Compound no. 2-131)

[0126] A solution of 3-(2-amino-4-chlorophenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (0.4 g), 2-naphthoyl chloride (0.29 g) and triethyl amine (0.19 g) in anhydrous tetrahydro furan (30 ml) was heated at reflux temperature overnight under nitrogen atmosphere. The reaction mixture was diluted with ethyl acetate (200 ml), washed with brine (×2) and dried over anhydrous sodium sulfate. The solvent was removed unded reduced pressure and the residue was purified by column chromatography on silica gel using ethyl acetate and hexane (1:3) as the eluent give a pale yellow solid. The solid was recrystallized from ethyl acetate-hexane to give the title compound as a white crystal (0.42 g).

EXAMPLE 49

Preparation of 3-[4-chloro-6-fluoro-2-(2-naphthoylamino)phenyl]-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (Compound no. 2-145)

[0127] A mixture of (2-amino-4-chloro-6-fluorophenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (0.25 g), triethylamine (0.15 g) and 2-naphthoyl chloride (0.21 g) in anhydrous tetrahydrofuran (30 ml) was heated at reflux temperature overnight under nitrogen atmosphere. The mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with brine and dried over anhydrous sodium acetate. The solvent was removed in vacuo and the residue was purified by column chromatography on silica gel using ethyl acetate-hexane (1:4) as the eluent to give the title compound as an white solid (0.26 g).

EXAMPLE 50

Preparation of N-[4-chloro-2-(2-naphthoylamino)phenyl]phthalimide (Compound no. 13-5)

[0128] A reaction solution of N-(2-amino-4-chlorophenyl) phthalimide (0.5 g), triethylamine (0.28 g) and 2-naphthoyl chloride (0.35 g) in anhydrous tetrahydrofuran (50 ml) was heated at reflux temperature for 6 hr under nitrogen atmosphere. The resulting mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with brine (×2) and dried over anhydrous sodium sulfate. The solvent was removed and the residue was purified by column chromatography on silica gel using ethyl acetate-hexane(1 :5) to give the title compound (0.35 g) as a yellow solid.

EXAMPLE 51

Preparation of 3-(2-benzylthioacetylamino-4-chloro-6-fluoro-3-methoxyphenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (Compoun no. 2-165)

[0129] A solution of benzylmercaptan (51.0 mg) in tetrahydrofuran (1.0 ml) was slowly added to a suspension of sodium hydride (16.4 mg) in tetrahydrofuran stirred under nitrogen at 0° C. The solution warmed to room temperature over 20 minutes and tetrabutylammonium bromide (11 mg) was added. The suspension was cooled to −78° C. and a solution of 3-(2-chloroacetylamino-4-chloro-6-fluoro-3-methoxyphenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione(150 mg) added. After stirring for a further 30 minutes the mixture was allowed to warm to room temperature overnight. Water and ethyl acetate were added and the solution separated and the organic phase was washed with water, brine and dried over sodium sulfate. The solution was concentrated and chromatographed on silica gel eluting with methylene chloride: ethyl acetate, 10:1, to give a white solid (137 mg).

EXAMPLE 52

Preparation of 3-(2-aminocarbonylamino-4-chloro-6-fluoro-3-methoxyphenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (Compound no. 3-26)

[0130] A solution of the isocyanate (1 mM) in dioxane (20 ml), stirred at 0° C., was treated with a solution of 0.5 M ammonia in dioxane (3 mM) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) (3 drops). The solution was allowed to warm to room temperature and stirred overnight. Chromatography on silica gel eluting with ethyl acetate gave the product as a yellow solid (271 mg).

EXAMPLE 53

[0131] Preparation of 3-(4-chloro-6-fluoro-3-methoxy-2-thiomethylphenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (Compound no. 17-1)

[0132] A solution of t-butylnitrile (73 mg) in methylene chloride (1 ml) was added to a stirred, ice cold solution of 3-(2-amino-4-chloro-6-fluoro-3-methoxyphenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (200 mg) and methyl disulfide (102 mg) in dry methylene chloride (4 ml). It was stirred at 0° C. for 1.5 h and allowed to warm to room temperature overnight. 1 N Hydrochloric acid was added and the mixture extracted with ethyl acetate, washed with water, brine and dried over sodium sulfate. The solution was concentrated under reduced pressure and the residue chromatographed on silica gel eluting with ethyl acetate : hexane, 5:1 gave the product as a yellow powder (189 mg).

EXAMPLE 54

Preparation of 2-(4-chloro-6-fluoro-3-hydroxy-27nitrophenyl)-5-trifluoromethylpyridazin-3-one (Compound no. 11-2)

[0133] Nitric acid (70%, 12 ml) was added to the ice-cooled 2-(4-chloro-2-fluoro-5-hydroxyphenyl)-5-trifluoromethylpyridazin-3-one (1.25 g) and stirred at room temperature for 30 minutes. Crushed ice was added. The precipitate was collected by filtration and washed with water to give 1.20 g of the desired product, m.p. 146-8° C.

EXAMPLE 55

Preparation of 2-(2-amino-4-chloro-6-fluoro-3-hydroxyphenyl)-5-trifluoromethylpyridazin-3-one (Compound no. 11-3)

[0134] To a stirred solution of 2-(4-chloro-6-fluoro-3-hydroxy-2-nitrophenyl)-5-trifluoromethylpyridazin-3-one (0.601 g) in acetic acid (6 ml) was added 0.38 g of iron powder at ambient temperature and stirred for 4 hours. The reaction mixture was partitioned between ethyl acetate and water. The organic phase was dried over anhydrous sodium sulfate. After removing the solvent under reduced pressure, the residue was purified by silica gel column chromatography, eluted with hexane-ethyl acetate (2: 1) to give 0.515 g of the title compound.

EXAMPLE 56

Preparation of 2-(2-amino-4-chloro-6-fluoro-3-methoxyphenyl)-5-trifluoromethylpyridazin-3-one (Compound no. 11-4) (BY715) and 2-(4-chloro-6-fluoro-3-methoxy-2-methylaminophenyl)-5-trifluoromethylpyridazin-3-one (Compound no. 11-5)

[0135] 2-(2-Amino-4-chloro-6-fluoro-3-methoxyphenyl)-5-trifluoromethylpyridazin-3-one (0.515 g), methyl iodide (0.248 g), and potassium carbonate (0.219 g) were mixed in acetonitrile (10 ml) and heated at reflux for 2 hours. The reaction mixture was partitioned between ethyl acetate and water. The organic phase was dried over anhydrous sodium sulfate. After removing the solvent under reduced pressure, the residue was purified by silica gel column chromatography, eluted with hexane-ethyl acetate (4: 1) to give 0.40 g of 2-(2-amino-4-chloro-6-fluoro-3-methoxyphenyl)-5-trifluoromethylpyridazin-3-one (Compound no. 11-4), m.p. 156-7° C. and 2-(4-chloro-6-fluoro-3-methoxy-2-methylaminophenyl)-5-trifluoromethylpyridazin-3-one (Compound no.1 1-5)(7 mg).

EXAMPLE 57

Preparation of 2-(4-chloro-6-fluoro-3-methoxy-2-naphthoylamidophenyl)-5-trifluoromethylpyridazin-3-one (Compound no. 11-6)

[0136] 2-(2-Amino-4-chloro-6-fluoro-3-methoxyphenyl)-5-trifluoromethylpyridazin-3-one (0.153 g) and 2-naphthoyl chloride (0.097 g) were mixed in dioxane (10 ml) and heated at reflux for 5 hours. The reaction mixture was partitioned between ethyl acetate and water. The organic phase was dried over anhydrous sodium sulfate. After removing the solvent under reduced pressure, the residue was purified by silica gel column chromatography, eluted with hexane-ethyl acetate (4: 1) to give 0.198 g of the title compound, m.p. 190-2° C.

EXAMPLE 58

Preparation of 2-(2,4-dichloro-6-fluoro-3-methoxyphenyl)-5-trifluoromethylpyridazin-3-one (Compound no. 11-7) and 2-[4-chloro-2-(2-chloro-2-ethoxycarbonylethyl)-6-fluoro-3-methoxyphenyl]-5-trifluoromethylpyridazin-3-one (Compound no. 11-8)

[0137] Copper(II) chloride (0.119 g), t-butyl nitrite (0.115 g), and ethyl acrylate (3 ml) were placed in a flask, and cooled with a dry ice-acetone bath at −65° C. To this mixture 2-(2-amino-4-chloro-6-fluoro-3-methoxyphenyl)-5-trifluoromethylpyridazin-3-one (0.25 g) in acetonitrile (4 ml) was added and stirred. The reaction mixture was gradually warmed up to room temperature over night. The reaction mixture was partitioned between ethyl acetate and water. The organic phase was dried over anhydrous sodium sulfate. After removing the solvent under reduced pressure, the residue was purified by silica gel column chromatography, eluted with hexane-ethyl acetate (9:1) to give 0.077 g of 2-(2,4-dichloro-6-fluoro-3-methoxyphenyl)-5-trifluoromethylpyridazin-3-one and 0.033 g of 2-[4-chloro-2-(2-chloro-2-ethoxycarbonylethyl)-6-fluoro-3-methoxyphenyl]-5-trifluoromethylpyridazin-3-one.

EXAMPLE 59

Preparation of 2-(4-chloro-6-fluoro-3-hydroxy-2-naphthoylamidophenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (Compound no. 2-194)

[0138] Boron tribromide-emthyl sulfide complex (5.15 g) was added to a solution of 2-(4-chloro-6-fluoro-3-methoxy-2-naphthoylamidophenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione in 1,2-dichloroethane (150 ml) and heated at reflux for 1 hour. The reaction mixture was partitioned between methylene chloride and water. The organic phase was dried over anhydrous sodium sulfate. After removing the solvent under reduced pressure, the residue was purified by silica gel column chromatography, eluted with hexane-ethyl acetate (4:1 and 2:1) to give the title compound (4.127 g), m.p. 150-2° C.

EXAMPLE 60

Preparation of 2-(4-chloro-3-ethoxy-6-fluoro-2-naphthoylamidophenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (Compound no. 2-196)

[0139] 2-(4-Chloro-6-fluoro-3-hydroxy-2-naphthoylamidophenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (0.203 g), ethyl iodide (75 mg) and potassium carbonate (55 mg) were stirred in methylethyl ketone (9 ml) and dimethyl sulfoxide (1 ml) at room temperature over night. The reaction mixture was filtered and evaporated under reduced pressure. The residue was purified by silica gel column chromatography, eluted with hexane-ethyl acetate (4:1) to give the title compound (0.16 g).

EXAMPLE 61

Preparation of 3-[4-chloro-2-diazanyl-6-fluoro-3-methoxyphenyl]-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (Compound no. 15-1)

[0140] 3-(2-Amino-4-chloro-6-fluoro-3-methoxyphenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (0.9 g, 2.4 mmol) was dissolved in conc. hydrochloric acid (5 ml) and the mixture cooled to −15° C., a solution of NaNO2 (0.2 g in 2 ml of H2O) was added slowly. After stirred for 20 min, a solution of SnCl2•2H2O (1.5 g in 4 ml of conc. hydrochloric acid) was added and the reaction continued at −15° C. for 30 min, then at room temperature for 30 min. The aqueous mixture was extracted with ethyl acetate (5 ml×3) and the organic phase washed with brine and dried over Na2SO4. Column chromatography was used to purify the product (silica gel, hexane/ethyl acetate=6/4). Yield: 0.5 g, 1.3 mmol.

EXAMPLE 62

Preparation of 3-[4-chloro-2-(2-cyclopropanecarbonyldiazanyl)-6-fluoro-3-methoxyphenyl]-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (Compound no. 15-2)

[0141] 3-[4-chloro-2-diazanyl-6-fluoro-3-methoxyphenyl]-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (0.15 g, 0.4 mmol) was dissolved in dioxane (10 ml) and added with cyclopropanecarbonyl chloride (0.04 g, 0.4 mmol) and triethylamine (0.04 g, 0.4 mmol). After stirred for 1 hr, the mixture was poured into water (15 ml) and extracted with ethyl acetate (10 ml×3). Organic phase was washed with brine and dried over Na2SO4. Final purification involved column chromatography (silica gel, ether). Yield: 0.15 g, 0.34 mmol.

EXAMPLE 63

Preparation of 3-{4-chloro-2-[2, 2-(cyclopropylmethylene)diazanyl]-6-fluoro-3-methoxyphenyl}-1-methyl-6-trifluoromethyl-2,4(1 H, 3H)-pyrimidinedione (Compound no. 15-11)

[0142] 3-[4-chloro-2-diazanyl-6-fluoro-3-methoxyphenyl]-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (0.12 g, 0.31 mmol) was added to a methanol (10 ml) solution of cyclopropanecarboxaldehyde (0.024 g, 0.34 mmol) and the mixture was stirred for 3 hr. After evaporation of solvent, the residue was purified by column chromatography (silica gel, hexane/ether=3/2). Yield: 0.13 g, 0.31 mmol.

EXAMPLE 64

Preparation of 3-(4-chloro-6-fluoro-2-hydroxy-3-methoxyphenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (Compound no. 16-6)

[0143] An acetonitrile (10 ml) solution of copper (II) sulfate (0.52 g, 3.26 mmol), copper (I) oxide (0.47 g, 3.26 mmol) and copper (II) nitrate hemipentahydrate (0.76 g, 3.26 mmol) was stirred at −30° C., and added with tert-butyl nitrite (0.41 g, 3.97 mmol) and then an acetonitrile (3 ml) solution of 3-(2-amino-4-chloro-6-fluoro-3-methoxyphenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (0.94 g, 2.56 mmol). After stirred for 16 hr (−30° C. to room temperature), the mixture was poured into cold 5% hydrochloric acid (30 ml) and then extracted with ethyl acetate (20 ml×3). The organic phase was washed with brine and dried over Na2SO4. Preparative TLC was used for purification (silica gel plates, 2000 microns, ether). Yield: 0.16 g, 0.44 mmol.

EXAMPLE 65

Preparation of 3-[4-chloro-6-fluoro-3-methoxy-2-(2-naphthoyloxy)phenyl]-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (Compound no. 16-7)

[0144] 3-(4-chloro-6-fluoro-2-hydroxy-3-methoxyphenyl)-1-methyl-6-trifluoromethyl-2,4(1 H, 3H)-pyrimidinedione (0.10 g, 0.27 mmol) was dissolved in dioxane (10 ml) and the solution added with 2-naphthoyl chloride (0.062 g, 0.33 mmol), triethylamine (0.033 g, 0.33 mmol). After stirred for 2 hr, solvent was evaporated and the residue purified by column chromatography (silica gel, hexane/ether=4/1). Yield: 0.12 g, 0.23 mmol.

EXAMPLE 66

Preparation of 3-{4-chloro-2-[2-chloro-2-(ethoxycarbonyl)ethyl]-6-fluoro-3-methoxyphenyl}-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (Compounds no. 14-4 and 14-5)

[0145] A solution of 3-(2-amino-4-chloro-6-fluoro-3-methoxyphenyl)-1-methyl-6-trifluoromethyl-2,4(1H, 3H)-pyrimidinedione (0.94 g, 2.56 mmol) in acetonitrile (3 ml) was slowly added to an acetonitrile (9 ml) solution of ethyl acrylate (6 ml), tert-butyl nitrite (0.41 g, 3.97 mmol), and copper (II) chloride (0.42 g, 3.12 mmol) at −20° C. After stirred for 16 hr (−20° C. to room temperature), the mixture was poured into cold 5% hydrochloric acid (30 ml) and extracted with ethyl acetate (20 ml×3), the organic phase was washed with cold 5% NaHCO3 and brine, dried over Na2SO4. Column chromatography was used for purification (silica gel, hexane/ether=9/1) which also isolated two isomers. Yield: isomer-I (eluted earlier), 0.23 g, 0.47 mmol; isomer-2 (eluted later), 0.14 g, 0.29 mmol.

[0146] Using the procedures as described in Schemes 1-17 and Examples 1-66, the compounds of this invention can be readily prepared. Tables I-XVII list structures for few representative compounds of this invention.

1TABLE I

No.XYWR1R2R3R4R5R8R91-1ClFOCH3HCF3HOOOO1-2ClFOHHCF3HOOOO1-3ClFOCH3HCF3HHHOO1-4ClFOCH3CH3CF3HHHOO1-5ClFOCH3CH3CF3HOOOO1-6BrFOHCH3CF3HOOOO1-7BrFOCH3CH3CF3HHHOO1-8BrFOHCH3CF3HHHOO1-9ClFOCH3CH3CF3NO2OOOO1-10ClFOCH3CH3CF3NH2HHOO1-11ClFOCH3CH3CF3HCH3CH3OO1-12ClFOCH3NH2CF3HOOOO1-13ClFOCH3NH2CF3HHHOO1-14ClFOCH3C2H5CF3HOOOO1-15ClFOCH3C2H5CF3HHHOO1-16ClFOHCH3CF3HHHOO1-17ClFOHCH3CF3HOOOO1-18ClFOCH2CNCH3CF3HHHOO1-19ClFpropargyloxyCH3CF3HHHOO1-20ClFOCH2CH═CHCOOCH3CH3CF3HHHOO1-21ClFcyclopentyloxyCH3CF3HHHOO1-22ClFbenzyloxyCH3CF3HHHOO1-23ClF3-nitro-2-pyridyloxyCH3CF3HHHOO1-24ClFOCH3CH3CHF2HHHOO1-25ClFOCH3CH3CF3ClHHOO1-26ClFOCH3CH3CF3HHHSO1-27ClFOCH3CH3CF3HHHOS1-28CNFOCH3CH3CF3HHHOO1-29ClHOCH3CH3CF3HHHOO1-30ClFOCH3CH3CF3H═C(CCl3)ClOO1-31ClFOCH3CH3CF3H═C(H)N(CH3)2OO1-32ClFOCH3CH3CF3H—(CH2)4—OO1-33ClFNHCOOCH2CH3HCF3HOOOO1-34ClFNHCOOCH2CH3CH3CF3HOOOO1-35ClFCH3HCF3HOOOO1-36ClFCH3CH3CF3HOOOO1-37ClFCH3CH3CF3HHHOO1-38ClFOCHF2CH3CF3HHHOO1-39ClFOCH2-2-naphthylCH3CF3HHHOO1-40ClFOCH3CH3CF3H—N—N—OO1-41HHHCH3CF3HHHOO1-42HHHCH3CF3HOOOO1-43CNHHCH3CF3HOOOO1-44CNHHCH3CF3HHHOO1-45ClClOHCH3CF3HOOOO1-46OCH3FHCH3CF3HOOOO1-47ClClOCH3CH3CF3HHHOO1-48OCH(CH3)COOCH2CH3HHCH3CF3HHHOO1-49OCH(CH3)COOCH2CH3HHCH3CF3HOOOO1-50OCHF2FHCH3CF3HOOOO1-51OCHF2FHCH3CF3HHHOO1-52CF3HHCH3CF3HOOOO1-53OCHF2FHCH3CF3HCH(Me)CO2EtHOO1-54ClFHCH3CF3HCH(Me)CO2EtHOO1-55ClFOCH3CH3CF3HCH(Me)CO2EtHOO1-56ClFOHNH2CF3HHHOO1-57ClFOCH2CNNH2CF3HHHOO1-58ClFOCH2COOCH3NH2CF3HHHOO1-59ClFOCH2COOCH2CH3CH3CF3HHHOO1-60ClFOCH(CH3)COOCH2CH3CH3CF3HHHOO1-61ClFOCH2CH3CH3CF3HHHOO1-62ClFOCH2CH3CH3CF3HCH2CH3HOO1-63ClFOCH(CH3)2CH3CF3HHHOO1-64ClFOCH(CH3)2CH3CF3HCH(CH3)2HOO1-65ClHHHCF3NO2OOOO1-66ClHOHCH3CF3HOOOO1-67ClNO2OHCH3CF3HOOOO1-68OCF3HHCH3CF3HOOOO1-69ClNO2OCH3HCF3HOOOO1-70ClFFHCF3HOOOO1-71ClHOHCH3CF3HHHOO1-72ClHOCH3CH3CF3HHHOO1-73OCF3HHCH3CF3HHHOO

[0147]

2

TABLE II

No.
X
Y
W
R1
R2
R3
R4
R5
R8
R9

2-1
Cl
F
OCH3
CH3
CF3
H
COCH3
H
O
O

2-2
Cl
F
OCH3
CH3
CF3
H
COCH3
COCH3
O
O

2-3
Cl
F
OCH3
CH3
CF3
H
CO-t-C4H9
H
O
O

2-4
Cl
F
OCH3
CH3
CF3
H
acryloyl
acryloyl
O
O

2-5
Cl
F
OCH3
CH3
CF3
H
methacryloyl
H
O
O

2-6
Cl
F
OCH3
CH3
CF3
H
methacryloyl
methacryloyl
O
O

2-7
Cl
F
OCH3
CH3
CF3
H
3,3-dimethylacryloyl
H O
O

2-8
Cl
F
0CH3
CH3
CF3
H
3,3-dimethylacryloyl
3,3-
O
O

dimethylacryloyl

2-9
Cl
F
OCH3
H
CF3
H
COCF3
H
O
O

2-10
Cl
F
OCH3
CH3
CF3
H
COCF3
H
O
O

2-11
Cl
F
OCH2CN
CH3
CF3
H
COCF3
H
O
O

2-12
Cl
F
OCH3
CH3
CF3
NHCOCF3
COCF3
H
O
O

2-13
Cl
F
OCH3
CH3
CF3
H
COCH2Cl
H
O
O

2-14
Cl
F
OCH3
CH3
CF3
H
COCH2CN
H
O
O

2-15
Cl
F
OCH3
CH3
CF3
H
COCOOCH3
H
O
O

2-16
Cl
F
OCOCH2COOCH2CH3
CH3
CF3
H
COCH2COOCH2CH3
H
O
O

2-17
Cl
F
OCH3
CH3
CF3
H

c
-C3H5-carbonyl
H
O
O

2-18
Cl
F
OCH3
CH3
CF3
H

c
-C3H3-carbonyl

c
-C3H3-
O
O

carbonyl

2-19
Cl
F
OCH3
CH3
CF3
H
cyclohexanoyl
H
O
O

2-20
Cl
F
OCH3
CH3
CF3
H
cyclohexanoyl
cyclohexanoyl
O
O

2-21
Cl
F
OCH3
CH3
CF3
H
SO2CH3
SO2CH3
O
O

Cl
F
OCH3
CH3
CF3
H
SO2CH3
H
O
O

2-22
Cl
F
OCH3
CH3
CF3
H
benzoyl
H
O
O

2-23
Cl
F
OCH3
CH3
CF3
H
3-CH3-benzoyl
H
O
O

2-24
Cl
F
OCH3
CH3
CF3
H
4-CH3-benzoyl
H
O
O

2-25
Cl
F
OCH3
CH3
CF3
H
4-CH3-benzoyl
4-CH3-benzoyl
O
O

2-26
Cl
F
OCH3
CH3
CF3
H
4-CH3-benzenesulfonyl
H
O
O

2-27
Cl
F
OCH3
CH3
CF3
H
4-C2H5-benzoyl
H
O
O

2-28
Cl
F
OCH2CN
CH3
CF3
H
4-C2H5-benzoyl
H
O
O

2-29
Cl
F
OCH3
CH3
CF3
H
4-n-C3H7-benzoyl
4-n-C3H7-
O
O

benzoyl

2-30
Cl
F
OCH3
CH3
CF3
H
4-t-C4H9-benzoyl
H
O
O

2-31
Cl
F
OCH3
CH3
CF3
H
4-vinylbenzoyl
H
O
O

2-32
Cl
F
OCH3
CH3
CF3
H
3,4-(CH3)2-benzoyl
H
O
O

2-33
Cl
F
OCH3
CH3
CF3
H
4-CF3-benzoyl
H
O
O

2-34
Cl
F
OCH3
CH3
CF3
H
4-CF3-benzoyl
4-CF3-benzoyl
O
O

2-35
Cl
F
OCH3
CH3
CF3
H
3,5-(CF3)2-benzoyl
3,5-(CF3)2-
O
O

benzoyl

2-36
Cl
F
OCH3
CH3
CF3
H
4-CH2Cl-benzoyl
H
O
O

2-37
Cl
F
OCH3
CH3
CF3
H
4-C6H5-benzoyl
H
O
O

2-38
Cl
F
OCH3
CH3
CF3
H
4-C6H3-benzoyl
4-C6H5-benzoyl
O
O

2-39
Cl
F
OCH3
CH3
CF3
H
2-F-benzoyl
H
O
O

2-40
Cl
F
OCH3
CH3
CF3
H
4-F-beNzoyl
H
O
O

2-41
Cl
F
OCH3
CH3
CF3
H
2,3-F2-benzoyl
H
O
O

2-42
Cl
F
OCH3
CH3
CF3
H
2,4-F2-benzoyl
H
O
O

2-43
Cl
F
OCH3
CH3
CF3
H
2,4-F2-benzoyl
2,4-F2-benzoyl
O
O

2-44
Cl
F
OCH3
NH2
CF3
H
2,4-F2-benzoyl
H
O
O

2-45
Cl
F
OCH2CN
CH3
CF3
H
2,4-F2-benzoyl
2,4-F2-benzoyl
O
O

2-46
Cl
F
OCH3
CH3
CF3
H
2,4-F2-thiobenzoyl
H
O
S

2-47
Cl
F
OCH3
CH3
CF3
H
2,6-F2-benzoyl
H
O
O

2-48
Cl
F
OCH3
CH3
CF3
H
3,4-F2-benzoyl
H
O
O

2-49
Cl
F
OCH3
CH3
CF3
H
3,4-F2-benzoyl
3,4-F2-benzoyl
O
O

2-50
Cl
F
OCH3
CH3
CF3
H
3,5-F2-benzoyl
H
O
O

2-51
Cl
F
OCH3
CH3
CF3
H
3,5-F2-benzoyl
3,5-F2-benzoyl
O
O

2-52
Cl
F
OCH3
CH3
CF3
H
2,3,4,5,6-F5-benzoyl
H
O
O

2-53
Cl
F
OCH3
CH3
CF3
H
2-Cl-benzoyl
H
O
O

2-54
Cl
F
OCH3
CH3
CF3
H
3-C1-benzoyl
H
O
O

2-55
Cl
F
OCH3
CH3
CF3
H
3-Cl-benzoyl
3-Cl-benzoyl
O
O

2-56
Cl
F
OCH3
CH3
CF3
H
4-Cl-benzoyl
H
O
O

2-57
Cl
F
OCH3
CH3
CF3
H
4-Cl-benzoyl
4-Cl-benzoyl
O
O

2-58
Cl
F
OCH3
CH3
CF3
H
2,4-Cl2-benzoyl
H
O
O

2-59
Cl
F
OCH3
CH3
CF3
H
3,4-Cl2-benzoyl
H
O
O

2-60
Cl
F
OCH3
CH3
CF3
H
3-Br-benzoyl
3-Br-benzoyl
O
O

2-61
Cl
F
OCH3
CH3
CF3
H
4-Br-benzoyl
H
O
O

2-62
Cl
F
OCH3
CH3
CF3
H
4-Br-benzoyl
4-Br-benzoyl
O
O

2-63
Cl
F
OCH3
CH3
CF3
H
4- OCH3-benzoyl
H
O
O

2-64
Cl
F
OCH3
CH3
CF3
H
4-(OC2H5)-benzoyl
H
O
O

2-65
Cl
F
OCH3
CH3
CF3
H
4-(OC2H5)-benzoyl
4-(OC2H5)-
O
O

benzoyl

2-66
Cl
F
OCH3
CH3
CF3
H
4-I-benzoyl
H
O
O

2-67
Cl
F
OCH3
CH3
CF3
H
4-CN-benzoyl
H
O
O

2-68
Cl
F
OCH3
CH3
CF3
H
4-N(CH3)2-benzoyl
H
O
O

2-69
Cl
F
OCH3
CH3
CF3
H
4-NO2-benzoyl
4-NO2-benzoyl
O
O

2-70
Cl
F
OCH3
CH3
CF3
H
3,5-(NO2)2-benzoyl
H
O
O

2-71
Cl
F
OCH3
CH3
CF3
H
4-OCF3benzoyl
4-OCF3-
O
O

benzoyl

2-72
Cl
F
OCH3
CH3
CF3
H
4-OCF3-benzoyl
H
O
O

2-73
Cl
F
OCH3
CH3
CF3
H
piperonyloyl
H
O
O

2-74
Cl
F
OCH3
CH3
CF3
H
1-naphthoyl
H
O
O

2-75
Cl
F
OCH3
CH3
CF3
H
2-naphthoyl
H
O
O

2-76
Cl
F
OCH3
H
CF3
H
2-naphthoyl
H
O
O

2-77
Cl
F
OCH3
NH2
CF3
H
2-naphthoyl
H
O
O

2-78
Cl
F
OCH3
CH3
CF3
H
cinnamoyl
H
O
O

2-79
Cl
F
OCH3
CH3
CF3
H
2,4-F2-cinnamoyl
H
O
O

2-80
Cl
F
OCH3
CH3
CF3
H
2-methylcinnamoyl
H
O
O

2-81
Cl
F
OCH3
CH3
CF3
H
α-methylcinnamoyl
H
O
O

2-82
Cl
F
OCH3
CH3
CF3
H
2-chlorocinnamoyl
H
O
O

2-83
Cl
F
OCH3
CH3
CF3
H
2-chlorocinnamoyl
2-
O
O

chlorocinnamoyl

2-84
Cl
F
OCH3
CH3
CF3
H
4-chlorocinnamoyl
H
O
O

2-85
Cl
F
OCH3
CH3
CF3
H
4-methoxycinna-moyl
H
O
O

2-86
Cl
F
OCH3
CH3
CF3
H
3-phenylpropionyl
H
O
O

2-87
Cl
F
OCH2CN
CH3
CF3
H
3-phenylpropionyl
H
O
O

2-88
Cl
F
OCH3
CH3
CF3
H
4-phenylbutyryl
H
O
O

2-89
Cl
F
OCH3
CH3
CF3
H
COCH2OCH2C6H5
H
O
O

2-90
Cl
F
OCH3
CH3
CF3
H
2-furoyl
H
O
O

2-91
Cl
F
OCH3
CH3
CF3
H
3-CH3-2-furoyl
H
O
O

2-92
Cl
F
OCH3
CH3
CF3
H
furylacryloyl
H
O
O

2-93
Cl
F
OCH3
CH3
CF3
H
COCH2-(2-thiophene)
H
O
O

2-94
Cl
F
OH
CH3
CF3
H
3-CH3-2-thiophenoyl
H
O
O

2-95
Cl
F
OCH3
CH3
CF3
H
5-CH3-2-thiophenoyl
H
O
O

2-96
Cl
F
OCH3
CH3
CF3
H
5-CH3-2-thiophenoyl
5-CH3-2-
O
O

thiophenoyl

2-97
Cl
F
OCH3
CH3
CF3
H
thiophene-2-carbonyl
thiophene-2-
O
O

carbonyl

2-98
Cl
F
OCH3
CH3
CF3
H
3-pyridoyl
H
O
O

2-99
Cl
F
OCH3
CH3
CF3
H
4-pyridoyl
H
O
O

2-100
Cl
F
OCH3
CH3
CF3
H
2-Cl-5-pyridoyl
2-Cl-5-
O
O

pyridoyl

2-101
Cl
F
OH
CH3
CF3
H
3-NO2-2-pyridoyl
H
O
O

2-102
Cl
F
OH
CH3
CF3
H
2-pyrimidoyl
H
O
O

2-103
Cl
F
OCH3
CH3
CF3
H
benzothiophene-2-
H
O
O

carbonyl

2-104
Cl
F
OCH3
CH3
CF3
H
2-quinoyl
H
O
O

2-105
Cl
F
OCH3
CH3
CF3
H
2-quinoxaloyl
H
O
O

2-106
Br
F
OCH3
CH3
CF3
H
2,4-F2-benzoyl
H
O
O

2-107
Cl
F
OCH3
CH3
CHF2
H
2,4-F2-benzoyl
H
O
O

2-108
Cl
F
OCH3
CH3
CF3
Cl
2,4-F2-benzoyl
H
O
O

2-109
Cl
F
OCH3
CH3
CF3
H
2,4-F2-benzoyl
H
S
O

2-110
Cl
F
OCH3
CH3
CF3
H
2,4-F2-benzoyl
H
O
S

2-111
CN
F
OCH3
CH3
CF3
H
2,4-F2-benzoyl
H
O
O

2-112
Cl
H
OCH3
CH3
CF3
H
2,4-F2-benzoyl
H
O
O

2-113
Cl
F
OCH3
CH3
CF3
H
3-(2-thienyl)acryloyl
H
O
O

2-114
Cl
F
OH
CH3
CF3
H
2-naphthoyl
H
O
O

2-115
Cl
F
OCHF2
CH3
CF3
H
2-naphthoyl
H
O
O

2-116
Cl
F
OCH3
CH3
CF3
H
COCH2OCOCH3
COCH2OCOCH3
O
O

2-117
Cl
F
OCH3
CH3
CF3
H
COCH2OCOCH3
H
O
O

2-118
Cl
F
OCH3
CH3
CF3
H
COCOOCH2CH3
H
O
O

2-119
Cl
F
OCH3
CH3
CF3
H
COCH2OC6H5
H
O
O

2-120
Cl
F
OCH3
CH3
CF3
H
COCH2OC6H5
COCH2OC6H5
O
O

2-121
Cl
F
OCH3
CH3
CF3
H
COCOC6H5
H
O
O

2-122
Cl
F
CH3
CH3
CF3
H
2-naphthoyl
H
O
O

2-123
Cl
F
CH3
CH3
CF3
H
cinnamoyl
H
O
O

2-124
Cl
F
OCH3
CH3
CF3
H
CO-2,6-dimethylphenyl
H
O
O

2-125
Cl
F
OCH3
CH3
CF3
H
2-F-cinnamoyl
H
O
O

2-126
Cl
F
OCH3
CH3
CF3
H
2-nitro-cinnamoyl
H
O
O

2-127
Cl
F
OCH3
CH3
CF3
H
2-methoxy-cinnamoyl
H
O
O

2-128
Cl
F
OCH3
CH3
CF3
H
2,6-dichloro-cinnamoyl
H
O
O

2-129
Cl
F
OCH3
CH3
CF3
H
COCH2CH2-2-
H
O
O

methylphenyl

2-130
Cl
F
OCH3
CH3
CF3
H
COCH2CH2-2,5-
H
O
O

dimethylphenyl

2-131
Cl
H
H
CH3
CF3
H
2-naphthoyl
H
O
O

2-132
Cl
F
OCH3
CH3
CF3
H
COCH2CH2-2,5-
H
O
O

dimethylphenyl

2-133
Cl
F
OCH3
CH3
CF3
H
COCH2O-4-F-phenyl
H
O
O

2-134
Cl
F
OCH3
CH3
CF3
H
3-chlorocinnamoyl
H
O
O

2-135
Cl
F
OCH3
CH3
CF3
H
COCH2O-4-Cl-phenyl
H
O
O

2-136
Cl
F
OCH3
CH3
CF3
H
α-cyano-cinnamoyl
H
O
O

2-137
Cl
H
H
CH3
CF3
H
cinnamoyl
H
O
O

2-138
CN
H
H
CH3
CF3
H
O
O
O
O

2-139
H
H
H
CH3
CF3
H
2-naphthoyl
2-naphthoyl
O
O

2-140
CN
H
H
CH3
CF3
H
2-naphthoyl
H
O
O

2-141
CN
H
H
CH3
CF3
H
cinnamoyl
H
O
O

2-142
H
H
H
CH3
CF3
H
2-naphthoyl
H
O
O

2-143
OCH3
H
H
CH3
CF3
H
2-naphthoyl
H
O
O

2-144
Cl
Cl
OCH3
CH3
CF3
H
2-naphthoyl
H
O
O

2-145
Cl
F
H
CH3
CF3
H
2-naphthoyl
H
O
O

2-146
OCH(CH3)COOCH2CH3
H
H
CH3
CF3
H
2-naphthoyl
H
O
O

2-147
Cl
F
H
CH3
CF3
H
cyclopropyl
H
O
O

2-148
OCHF2
F
H
CH3
CF3
H
2-naphthoyl
H
O
O

2-149
CF3
H
H
CH3
CF3
H
2-naphthoyl
H
O
O

2-150
Cl
F
OH
CH3
CF3
H
phenylacetyl
H
O
O

2-151
Cl
F
OCH3
CH3
CF3
H
phenylacetyl
H
O
O

2-152
Cl
F
OCH3
CH3
CF3
H
3-methoxy-
H
O
O

2-naphthoyl

2-153
Cl
F
OCH3
CH3
CF3
H
1-methoxy-
H
O
O

2-naphthoyl

2-154
Cl
F
OCH3
CH3
CF3
H
2,4-dichloro-
H
O
O

phenoxyacetyl

2-155
Cl
F
OCH3
CH3
CF3
H
3-methyl-2-naphthoyl
H
O
O

2-156
Cl
F
OCH3
CH3
CF3
H
6-methyl-2-naphthoyl
H
O
O

2-157
Cl
F
OCH3
CH3
CF3
H
3-chloro-2-naphthoyl
H
O
O

2-158
Cl
F
OCH3
CH3
CF3
H
5-bromo-2-naphthoyl
H
O
O

2-159
Cl
F
OCH3
CH3
CF3
H
4-bromo-2-naphthoyl
H
O
O

2-160
Cl
F
OCH3
CH3
CF3
H
4-bromo-2-naphthoyl
4-bromo-2-
O
O

naphthoyl

2-161
Cl
F
OCH3
CH3
CF3
H
8-fluoro-2-naphthoyl
H
O
O

2-162
Cl
F
OCH3
CH3
CF3
H
5-chloro-2-naphthoyl
H
O
O

2-163
Cl
F
OCH3
CH3
CF3
H
5-cyano-2-naphthoyl
H
O
O

2-164
Cl
F
OCH3
CH3
CF3
H
chloroacetyl
H
O
O

2-165
Cl
F
OCH3
CH3
CF3
H
benzylthioacetyl
H
O
O

2-166
Cl
F
OCH3
CH3
CF3
H
bromoacetyl
H
O
O

2-167
Cl
F
OCH3
CH3
CF3
H
phenylthioacetyl
H
O
O

2-168
Cl
F
OCH3
CH3
CF3
H
methylthioacetyl
H
O
O

2-169
Cl
F
OCH3
CH3
CF3
H
2-naphthylthio-acetyl
H
O
O

2-170
Cl
F
OCH3
CH3
CF3
H
ethoxycarbonyl-
H
O
O

methylthioacetyl

2-171
Cl
F
OCH3
CH3
CF3
H
ethoxycarbonyl-ethyl-2-
H
O
O

thioacetyl

2-172
Cl
F
OCH3
CH3
CF3
H
ethylthioacetyl
H
O
O

2-173
Cl
F
OCH3
CH3
CF3
H
i-propylthioacetyl
H
O
O

2-174
Cl
F
OCH3
CH3
CF3
H
propylthioacetyl
H
O
O

2-175
Br
F
OCH3
CH3
CF3
H
2-cinnamoyl
H
O
O

2-176
Br
F
OCH3
CH3
CF3
H
2-cinnamoyl
2-cinnamoyl O
O

2-177
Br
F
OCH3
CH3
CF3
H
2-cinnamoyl
H
O
O

2-178
Br
F
OCH3
CH3
CF3
H
2-cinnamoyl
2-cinnamoyl O
O

2-179
CN
F
OCH3
CH3
CF3
H
2-cinnamoyl
H
O
O

2-180
CN
F
OCH3
CH3
CF3
H
2-naphthoyl
H
O
O

2-181
CN
F
OCH3
CH3
CF3
H
2-naphthoyl
H
O
O

2-182
Br
F
OCH3
CH3
CF3
H
4-vinylbenzoyl
H
O
O

2-183
Br
F
OCH3
CH3
CF3
H
4-vinylbenzoyl
4-vinylbenzoyl
O
O

2-184
Cl
F
OCH3
NH2
CF3
H
2-naphthoyl
H
O
O

2-185
Cl
F
OCH3
NH2
CF3
H
2-cinnamoyl
H
O
O

2-186
Cl
F
OCH3
NH2
CF3
H
2-cinnamoyl
2-cinnamoyl
O
O

2-187
Cl
F
OCH3
NH2
CF3
H
benzyloxyacetyl
H
O
O

2-188
Cl
F
OCH2CN
NH2
CF3
H
2-naphthoyl
H
O
O

2-189
Cl
F
OCH2COOCH2CH3
CH3
CF3
H
2-naphthoyl
H
O
O

2-190
Cl
F
OCH2COOCH2CH3
CH3
CF3
H
2-cinnamoyl
H
O
O

2-191
Cl
F
OCH(CH3)COOCH2CH3
CH3
CF3
H
2-naphthoyl
H
O
O

2-192
Cl
F
OH
NH2
CF3
H
2-naphthoyl
H
O
O

2-193
4-CF3-
H
H
CH3
CF3
H
2-naphthoyl
H
O
O

pyridyloxy

2-194
Cl
F
OH
CH3
CF3
H
2-naphthoyl
H
O
O

2-195
Cl
F
OCH2C≡CH
CH3
CF3
H
2-naphthoyl
H
O
O

2-196
Cl
F
OCH2CH3
CH3
CF3
H
2-naphthoyl
H
O
O

2-197
Cl
F
OCH(CH3)2
CH3
CF3
H
2-naphthoyl
H
O
O

2-198
Cl
F
OCH3
CH3
CF3
H
Hexanoyl
H
O
O

2-199
Cl
F
3-NO2-
CH3
CF3
H
2-naphthoyl
H
O
O

pyridyloxy

2-200
Cl
F
OCH2CN
CH3
CF3
H
2-naphthoyl
H
O
O

2-201
CH3
H
H
CH3
CF3
H
2-naphthoyl
H
O
O

2-202
Cl
H
OCH3
CH3
CF3
H
2-naphthoyl
H
O
O

2-203
OCF3
H
H
CH3
CF3
H
2-naphthoyl
H
O
O

2-204
Cl
H
H
CH3
CF3
H

c
-C3H5-carbonyl
H
O
O

2-205
H2NC(S)
H
H
CH3
CF3
H
2-naphthoyl
H
O
O

2-206
Cl
F
OCH3
CH3
CF3
H

c
-C3H5-carbonyl
H
O
O

2-207
COOCH3
H
H
CH3
CF3
H
2-naphthoyl
H
O
O

[0148]

3

TABLE III

No.
X
Y
R
R1
R2
R3
R4
R5
R8
R9

3-1
Cl
F
CH3
CH3
CF3
H
CONHCH3
CONHCH3
O
O

3-2
Cl
F
CH3
CH3
CF3
H
CONHCH2CH2CH3
H
O
O

3-3
Cl
F
CH3
CH3
CF3
H
CON[CH(CH3)2]2
H
O
O

3-4
Cl
F
CH3
CH3
CF3
H
CONHC6H5
H
O
O

3-5
Cl
F
CH3
CH3
CF3
H
CON(CH3)C6H5
H
O
O

3-6
Cl
F
CH3
CH3
CF3
H
CONHCH2C6H5
H
O
O

3-7
Cl
F
CH3
CH3
CF3
H
CONHCH(CH3)-C6H5
H
O
O

3-8
Cl
F
CH3
CH3
CF3
H
CON(CH3)CH2C6H5
H
O
O

3-9
Cl
F
CH3
CH3
CF3
H
CONHCH2-(4-CH3)phenyl
H
O
O

3-10
Cl
F
CH3
CH3
CF3
H
CONH CH2-2,4-F2-phenyl
H
O
O

3-11
Cl
F
CH3
CH3
CF3
H
CONH CH2CH2C6H5
H
O
O

3-12
Cl
F
CH3
CH3
CF3
H
CONH CH2CH2CH2C6H5
H
O
O

3-13
Cl
F
CH3
CH3
CF3
H
CONH-2-naphthoyl
H
O
O

3-14
Cl
F
CH2CN
CH3
CF3
H
CONHCH2C6H5
H
O
O

3-15
Cl
F
CH3
H
CF3
H
CONHCH2C6H5
H
O
O

3-16
Cl
F
CH3
NH2
CF3
H
CONHCH2C6H5
H
O
O

3-17
Cl
F
CH3
CH3
CHF2
H
CONHCH2C6H5
H
O
O

3-18
Cl
F
CH3
CH3
CF3
Cl
CONHCH2C6H5
H
O
O

3-19
Cl
F
CH3
CH3
CF3
H
CONHCH2C6H5
H
S
O

3-20
Cl
F
CH3
CH3
CF3
H
CONHCH2C6H5
H
O
S

3-21
CN
F
CH3
CH3
CF3
H
CONHCH2C6H5
H
O
O

3-22
Cl
H
CH3
CH3
CF3
H
CONHCH2C6H5
H
O
O

3-23
Cl
F
CH3
CH3
CF3
H
CON(C6H5)CH2C6H5
H
O
O

3-24
Cl
F
CH3
CH3
CF3
H
CONHCH(C6H5)C6H5
H
O
O

3-26
Cl
F
CH3
CH3
CF3
H
CONH2
H
O
O

[0149]

4

TABLE IV

No.
X
Y
W
R1
R2
R3
R4
R5
R8
R9

4-1
Cl
F
OCH3
CH3
CF3
H
COOCH3
H
O
O

4-2
Cl
F
OCH3
CH3
CF3
H
COOCH3
COOCH3
O
O

4-3
Cl
F
OCH3
CH3
CF3
H
COO-phenyl
H
O
O

4-4
Cl
F
OCH3
CH3
CF3
H
COO-[2,4-(CH3)2]-phenyl
H
O
O

4-5
Cl
F
OCH3
CH3
CF3
H
COOCH2-phenyl
H
O
O

4-6
Cl
F
OCH3
CH3
CF3
H
COOCH2-(2-F)-phenyl
H
O
O

4-7
Cl
F
OCH3
CH3
CF3
H
COOCH2-(4-F)-phenyl
H
O
O

4-8
Cl
F
OCH3
CH3
CF3
H
COOCH2-(2-CF3)-phenyl
H
O
O

4-9
Cl
F
OCH3
CH3
CF3
H
COOCH2-(4-CF3)-phenyl
H
O
O

4-10
Cl
F
OCH3
CH3
CF3
H
COO-2-naphthyl
H
O
O

4-11
Cl
F
OCH3
CH3
CF3
H
COO-cyclohexyl
H
O
O

4-12
Cl
F
OCH3
CH3
CF3
H
COOCH2-cyclohexyl
H
O
O

4-13
Cl
F
OCH3
CH3
CF3
H
C(O)-S-phenyl
H
O
O

4-14
Cl
F
OCH2CN
CH3
CF3
H
COO-phenyl
H
O
O

4-15
Cl
F
OCH3
H
CF3
H
COO-phenyl
H
O
O

4-16
Cl
F
OCH3
NH2
CF3
H
COO-phenyl
H
O
O

4-17
Cl
F
OCH3
CH3
CHF2
H
COO-phenyl
H
O
O

4-18
Cl
F
OCH3
CH3
CF3
Cl
COO-phenyl
H
O
O

4-19
Cl
F
OCH3
CH3
CF3
H
COO-phenyl
H
S
O

4-20
Cl
F
OCH3
CH3
CF3
H
COO-phenyl
H
O
S

4-21
CN
F
OCH3
CH3
CF3
H
COO-phenyl
H
O
O

4-22
Cl
H
OCH3
CH3
CF3
H
COO-phenyl
H
O
O

4-23
Cl
F
OCH2CN
CH3
CF3
H
COOCH2-phenyl
H
O
O

4-24
Cl
F
OCH3
CH3
CF3
H
COOCH2-(2,6-di-Cl)-phenyl
H
O
O

4-25
Cl
F
OCH3
CH3
CF3
H
COO-[2,4,6-(CH3)3]-phenyl
H
O
O

4-26
Cl
F
OCH3
CH3
CF3
H
COOCH2-[3,4-(CH3)2-
H
O
O

phenyl

4-27
Cl
F
OCH3
CH3
CF3
H
COO-(2-t-butyl)-phenyl
H
O
O

4-28
Cl
F
OCH3
CH3
CF3
H
COOCH2-2-naphthyl
H
O
O

4-29
Cl
F
OCH3
CH3
CF3
H
COOCH2-(2,6-di-F)-phenyl
H
O
O

4-30
Cl
F
OCH3
CH3
CF3
H
COOCH2-(3,4-di-F)-phenyl
H
O
O

4-31
Cl
F
OCH3
CH3
CF3
H
COOCH2-(4-ethyl)-phenyl
H
O
O

4-32
Cl
F
OCH3
CH3
CF3
H
COOCH2-(3,4-di-Cl)-phenyl
H
O
O

4-33
Cl
F
OCH3
CH3
CF3
H
COOCH2-(2-CF3)-phenyl
H
O
O

4-34
Cl
F
OCH3
CH3
CF3
H
COOCH2-(2-NO2)-phenyl
H
O
O

4-35
Cl
F
OCH3
CH3
CF3
H
COOCH2-(2-OCH3)-phenyl
H
O
O

4-36
Cl
F
OCH3
CH3
CF3
H
COOCH2-2-pyridyl
H
O
O

4-37
Cl
F
OCH3
CH3
CF3
H
COOCH2-[3,5-(CH3)2]-
H
O
O

phenyl

4-38
Cl
F
OCH3
CH3
CF3
H
COOCH2-[2,5-(CH3)2]-
H
O
O

phenyl

4-39
Cl
F
OCH3
CH3
CF3
H
COOCH2-(2,5-di-F)-phenyl
H
O
O

4-40
Cl
F
OCH3
CH3
CF3
H
COOCH2-(4-OCH3)-phenyl
H
O
O

4-41
Cl
F
OCH3
CH3
CF3
H
COOCH2-(3,4-OCH2O)-
H
O
O

phenyl

4-42
Cl
F
OCH3
CH3
CF3
H
COOCH2-(4-i-C3H7)-phenyl
H
O
O

4-43
Cl
F
OCH3
CH3
CF3
H
COOCH2-(4-CF3)-phenyl
H
O
O

4-44
Cl
F
OCH3
CH3
CF3
H
COOCH2-(3-F)-phenyl
H
O
O

4-45
Cl
F
OCH3
CH3
CF3
H
COOCH2-(4-OCF3)-phenyl
H
O
O

4-46
Cl
F
OCH3
CH3
CF3
H
COOCH-(c-C3H5)-phenyl
H
O
O

4-47
Cl
F
OCH3
CH3
CF3
H
COOCH(CH3)-phenyl
H
O
O

4-48
Cl
F
OCH3
CH3
CF3
H
COOCH2-(2,3,4,5,6-penta-
H
O
O

F)-phenyl

4-49
Cl
H
H
CH3
CF3
H
COOCH2-(2-F)-phenyl
H
O
O

4-50
Cl
H
H
CH3
CF3
H
COO-phenyl
H
O
O

4-51
Cl
F
CH3
CH3
CF3
H
COOCH2-(2-F)-phenyl
H
O
O

4-52
Cl
F
CH3
CH3
CF3
H
COO-phenyl
H
O
O

4-53
Cl
F
CH3
CH3
CF3
H
COO-3,4-dimethylphenyl
H
O
O

4-54
Cl
F
CH3
CH3
CF3
H
COOCH2-2-Cl-phenyl
H
O
O

4-55
Cl
F
CH3
CH3
CF3
H
COO-2,6-dimethylpheny
H
O
O

4-56
Cl
F
CH3
CH3
CF3
H
COOCH2-2-methylphenyl
H
O
O

4-57
Cl
F
CH3
CH3
CF3
H
COOCH2CH2-phenyl
H
O
O

4-58
Cl
F
CH3
CH3
CF3
H
COOCH2-2-methoxyphenyl
H
O
O

4-59
Cl
F
CH3
CH3
CF3
H
COO-2,6-dimethoxyphenyl
H
O
O

4-60
Cl
F
CH3
CH3
CF3
H
COOCH2-4-methylphenyl
H
O
O

4-61
Cl
F
CH3
CH3
CF3
H
COOCH2-4-Cl-phenyl
H
O
O

4-62
Cl
F
CH3
CH3
CF3
H
COOCH2-2,4-
H
O
O

dichlorophenyl

4-63
Cl
F
CH3
CH3
CF3
H
COOCH2-3,4-
H
O
O

dimethoxyphenyl

4-64
Cl
F
CH3
CH3
CF3
H
COOCH2-4-nitrophenyl
H
O
O

4-65
Cl
F
CH3
CH3
CF3
H
COOCH2-3-methoxyphenyl
H
O
O

4-66
Cl
F
CH3
CH3
CF3
H
COSCH2-phenyl
H
O
O

4-67
Cl
F
CH3
CH3
CF3
H
COOCH2-3-nitrophenyl
H
O
O

4-68
Cl
F
CH3
CH3
CF3
H
COOCH2-3-methylphenyl
H
O
O

4-69
Cl
F
CH3
CH3
CF3
H
COOCH2-2,4,6-
H
O
O

trimethylphenyl

4-70
Cl
F
CH3
CH3
CF3
H
COOCH2-2-furanyl
H
O
O

[0150]

5

TABLE V

No.
X
Y
R
R1
R4
R5

5-1
Cl
F
CH3
H
O
O

5-2
Cl
F
H
H
O
O

5-3
Cl
F
CH3
(CH2)3F
H
H

5-4
Cl
F
H
(CH2)3F
O
O

5-5
Cl
F
H
(CH2)3F
H
H

5-6
Cl
Cl
CH3
H
O
O

5-7
Cl
Cl
CH3
(CH2)3F
O
O

5-8
Cl
Cl
H
(CH2)3F
O
O

5-9
Cl
Cl
H
(CH2)3F
H
H

5-10
Cl
F
CH3
(CH2)3F
COCH3
H

5-11
Cl
F
CH3
(CH2)3F
benzoyl
H

5-12
Cl
F
CH3
(CH2)3F
CH3
CH3

5-13
Cl
F
CH3
(CH2)3F
COOCH3
H

5-14
Cl
F
CH3
(CH2)3F
CONHCH3
H

5-15
Cl
Cl
CH2C≡CH
(CH2)3F
H
H

5-16
Cl
Cl
CH(CH3)2
(CH2)3F
H
H

5-17
Cl
F
CH2C≡CH
(CH2)3F
H
H

5-18
Cl
F
CH(CH3)2
(CH2)3F
H
H

5-19
CN
F
CH3
(CH2)3F
benzoyl
H

5-20
Cl
H
CH3
(CH2)3F
benzoyl
H

5-21
Cl
F
CH3
(CH2)3F
2,4-F2-benzoyl
H

5-22
Cl
F
CH3
(CH2)3F
4-C2H5-benzoyl
H

5-23
Cl
F
CH3
(CH2)3F
3-phenyl-
H

propionyl

5-24
Cl
F
CH2CN
(CH2)3F
2,4-F2-benzoyl
H

5-25
Cl
F
CH2CN
(CH2)3F
2-naphthoyl
H

5-26
Cl
F
CH3
(CH2)3F
2-naphthoyl
H

5-27
Cl
F
CH3
(CH2)3F
2-naphthoyl
2-naphthoyl

5-28
Cl
F
CH3
(CH2)3F
benzyloxyacetyl
H

[0151]

6

TABLE VI

No.
X
Y
W
R1
R2
R4
R5

6-1
Cl
F
OH
CHF2
CH3
O
O

6-2
Cl
F
OH
CHF2
CH3
H
H

6-3
Cl
F
OCH3
CHF2
CH3
H
H

6-4
Cl
F
OCH3
CHF2
CH3
COCH3
H

6-5
Cl
F
OCH3
CHF2
CH3
benzoyl
H

6-6
Cl
Cl
OCH3
CHF2
CH3
CH3
CH3

6-7
Cl
Cl
OCH3
CHF2
CH3
COOCH3
H

6-8
Cl
F
OCH3
CH3
CH3
benzoyl
H

6-9
Cl
F
OCH3
CHF2
CH2CH3
benzoyl
H

6-10
Cl
Cl
OCH3
CHF2
CH3
CONHCH3
H

6-11
CN
F
OCH3
CHF2
CH3
benzoyl
H

6-12
Cl
H
OCH3
CHF2
CH3
benzoyl
H

6-13
Cl
Cl
H
CHF2
CH3
2,4-difluoro-
H

benzoyl

6-14
Cl
F
OCH3
CHF2
CH3
2,4-difluoro-
H

benzoyl

6-15
Cl
F
OCH3
CHF2
CH3
2-naphthoyl
H

6-16
Cl
Cl
H
CHF2
CH3
2-naphthoyl
H

6-17
Cl
Cl
OCH3
CHF2
CH3
2-naphthoyl
H

6-18
Cl
Cl
HNC(O)C2H5
CHF2
CH3
O
O

6-19
Cl
Cl
HNC(O)C2H5
CHF2
CH3
H
H

6-20
Cl
Cl
NH2
CHF2
CH3
H
H

6-21
Cl
F
H
CHF2
CH3
O
O

6-22
Cl
F
H
CHF2
CH3
H
H

6-23
Cl
F
H
CHF2
CH3
2,4-F2-
H

benzoyl

6-24
Cl
F
H
CHF2
CH3
2-naphthoyl
H

[0152]

7

TABLE VII

No.
X
Y
R
R1
R2
R3
R4
R5

7-1
Cl
F
CH3
CH3
CF3
Cl
O
O

7-2
Cl
F
CH3
CH3
CF3
Cl
H
H

7-3
Cl
F
H
CH3
CF3
Cl
H
H

7-4
Cl
F
CH3
CH3
CF3
Cl
COCH3
H

7-5
Cl
F
CH3
CH3
CF3
Cl
benzoyl
H

7-6
Cl
Cl
CH3
CH3
CF3
Cl
CH3
CH3

7-7
Cl
Cl
CH3
CH3
CF3
Cl
COOCH3
H

7-8
Cl
Cl
CH3
CH3
CF3
Cl
CONHCH3
H

7-9
CN
F
CH3
CH3
CF3
Cl
benzoyl
H

7-10
Cl
H
CH3
CH3
CF3
Cl
benzoyl
H

7-11
Cl
F
CH3
CH2CH3
CF3
Cl
benzoyl
H

7-12
Cl
F
CH3
CH3
OCHF2
Cl
benzoyl
H

7-13
Cl
F
CH3
CH3
CF3
Br
benzoyl
H

7-14
Cl
F
CH3
CH3
CF3
Cl
2-naphthoyl
H

7-15
Cl
F
CH3
CH3
CF3
Cl
cinnamoyl
H

[0153]

8

TABLE VIII

No.
X
Y
W
R4
R5

8-1
Cl
F
OH
O
O

8-2
Cl
F
OH
H
H

8-3
Cl
F
OCH2C≡CH
H
H

8-4
Cl
F
OCH(CH3)2
H
H

8-5
Cl
F
O-c-pentyl
H
H

8-6
Cl
F
OCH3
O
O

8-7
Cl
F
OCH3
H
H

8-8
Cl
F
OCH3
2,4-F2-benzoyl
H

8-9
Cl
F
OCH3
2-naphthoyl
H

8-10
Cl
F
OCH3
4-C2H5-benzoyl
H

8-11
Cl
F
OCH3
3-phenyl-propionyl
H

8-12
CN
F
OCH3
2,4-F2-benzoyl
H

8-13
Cl
F
OCH2C≡CH
2,4-F2-benzoyl
H

8-14
Cl
F
OCH2C≡CH
2-naphthoyl
H

8-15
Cl
F
OCH2C≡CH
4-C2H5-benzoyl
H

8-16
Cl
F
OCH2C≡CH
3-phenyl-propionyl
H

8-17
CN
F
OCH2C≡CH
2,4-F2-benzoyl
H

8-18
Cl
F
OCH(CH3)2
2,4-F2-benzoyl
H

8-19
Cl
F
OCH(CH3)2
2-naphthoyl
H

8-20
Cl
F
OCH(CH3)2
4-C2H5-benzoyl
H

8-21
Cl
F
OCH(CH3)2
3-phenyl-propionyl H

8-22
CN
F
OCH(CH3)2
2,4-F2-benzoyl
H

8-23
Cl
F
OCH3
COCH3
H

8-24
Cl
F
OCH3
benzoyl
H

8-25
Cl
F
OCH3
CH3
CH3

8-26
Cl
F
OCH3
COOCH3
H

8-27
Cl
F
OCH3
CONHCH3
H

8-28
CN
F
OCH3
benzoyl
H

8-29
Cl
H
OCH3
benzoyl
H

8-30
Cl
F
OCH3
4-vinyl-benzoyl
H

8-31
Cl
F
OCH3
cinnamoyl
H

8-32
Cl
NO2
H
O
O

8-33
Cl
H
H
O
O

8-34
NO2
H
H
O
O

8-35
Cl
H
H
H
H

8-36
Cl
H
H
2-naphthoyl
H

[0154]

9

TABLE IX

No.
X
Y
W
R4
R5
R8
R9

9-1
Cl
F
OH
O
O
O
O

9-2
Cl
F
OH
H
H
O
O

9-3
Cl
F
OCH3
O
O
O
O

9-4
Cl
F
OCH3
H
H
O
O

9-5
Cl
F
OCH3
COCH3
H
O
O

9-6
Cl
F
OCH3
benzoyl
H
O
O

9-7
Cl
F
OCH3
CH3
CH3
O
O

9-8
Cl
F
OCH3
COOCH3
H
O
O

9-9
Cl
F
OCH3
CONHCH3
H
O
O

9-10
CN
F
OCH3
benzoyl
H
O
O

9-11
Cl
H
OCH3
benzoyl
H
O
O

9-12
Cl
H
H
O
O
O
S

9-13
Cl
H
H
H
H
O
S

9-14
Cl
H
H
2-naphthoyl
H
O
S

9-15
Cl
F
OCH3
2-naphthoyl
H
O
O

9-16
Cl
F
OCH3
2,4-F2-benzoyl
H
O
O

9-17
Cl
H
H
O
O
O
O

9-18
Cl
H
H
H
H
O
O

9-19
Cl
H
H
2-naphthoyl
H
O
O

[0155]

10

TABLE X

No.
X
Y
R
R5
R4

10-1
Cl
F
H
O
O

10-2
Cl
F
H
H
H

10-3
Cl
F
CH3
O
O

10-4
Cl
F
CH3
H
H

10-5
Cl
F
CH3
COCH3
H

10-6
Cl
F
CH3
benzoyl
H

10-7
Cl
F
CH3
CH3
CH3

10-8
Cl
F
CH3
COOCH3
H

10-9
Cl
F
CH3
CONHCH3
H

10-10
CN
F
CH3
benzoyl
H

10-11
Cl
H
CH3
benzoyl
H

[0156]

11

TABLE XI

No.
X
Y
W
R1
R2
Z

11-1
Cl
F
OCH3
H
CF3
NO2

11-2
Cl
F
OH
H
CF3
NO2

11-3
Cl
F
OH
H
CF3
NH2

11-4
Cl
F
OCH3
H
CF3
NH2

11-5
Cl
F
OCH3
H
CF3
NHCH3

11-6
Cl
F
OCH3
H
CF3
NH-2-naphthoyl

11-7
Cl
F
OCH3
H
CF3
Cl

11-8
Cl
F
OCH3
H
CF3
CH2CHClCOOCH2CH3

11-9
Cl
F
OH
CH3
CF3
NO2

11-10
Cl
F
OH
CH3
CF3
NH2

11-11
Cl
F
OCH3
CH3
CF3
NH2

11-12
Cl
F
OCH3
CH3
CF3
NHCH3

11-13
Cl
F
OCH3
CH3
CF3
NH-2-naphthoyl

11-14
Cl
F
OCH3
CH3
CF3
NO2

11-15
Cl
F
OCH3
CH3
CF3
NHCOCH3

11-16
Cl
F
OCH3
CH3
CF3
NH-benzoyl

11-17
Cl
F
OCH3
CH3
CF3
N-(CH3)2

11-18
Cl
F
OCH3
CH3
CF3
NHCOO-phenyl

11-19
Cl
F
OCH3
CH3
CF3
NHCONHCH3

11-20
CN
F
OCH3
CH3
CF3
2-naphthoyl-NH

11-21
Cl
F
OCH3
CH3
CH3
2-naphthoyl-NH

11-22
Cl
H
OCH3
CH3
CF3
2-naphthoyl-NH

11-23
Cl
F
OCH3
CH3
CF3
Cl

11-24
Cl
F
OCH3
CH3
CF3
CH2CHClCOOCH2CH3

[0157]

12

TABLE XII

No.
X
Y
W
R4
R5
R8
R9

12-1
Cl
F
OH
O
O
S
O

12-2
Cl
F
OH
H
H
S
O

12-3
Cl
F
OH
H
H
S
O

12-4
Cl
F
OCH3
H
H
S
O

12-5
Cl
F
OCH3
2-naphthoyl
H
S
O

12-6
Cl
H
H
O
O
O
O

12-7
Cl
H
H
H
H
O
O

12-8
Cl
H
H
2-naphthoyl
H
O
O

12-9
Cl
F
OCH3
COCH3
H
S
O

12-10
Cl
F
OCH3
benzoyl
H
S
O

12-11
Cl
F
OCH3
CH3
CH3
S
O

12-12
Cl
F
OCH3
COO-phenyl
H
S
O

12-13
Cl
F
OCH3
CONHCH3
H
S
O

12-14
CN
F
OCH3
2-naphthoyl
H
S
O

12-15
Cl
H
OCH3
2-naphthoyl
H
S
O

[0158]

13

TABLE XIII

No.
X
Y
W
R4
R5

13-1
Cl
F
OH
O
0

13-2
Cl
F
OH
H
H

13-3
Cl
F
OCH3
2-naphthoyl
H

13-4
Cl
F
OCH3
2,4-difluorobenzoyl
H

13-5
Cl
H
H
2-naphthoyl
H

13-6
Cl
F
OCH3
COCH3
H

13-7
Cl
F
OCH3
benzoyl
H

13-8
Cl
F
OCH3
CH3
CH3

13-9
Cl
F
OCH3
COO-phenyl
H

13-10
Cl
F
OCH3
CONHCH3
H

13-11
CN
F
OCH3
2-naphthoyl
H

13-12
Cl
H
OCH3
2-naphthoyl
H

[0159]

14

TABLE XIV

No.
X
Y
W
Q
R1
R2
R3
Z
R8
R9

14-1
Cl
F
OCH3
Q1
CH3
CF3
H
CH2CH2CO2CH2CH3
O
O

14-2
Cl
F
OCH3
Q1
CH3
CF3
H
CH═CHCO2CH2CH3
O
O

14-3
Cl
F
OCH3
Q1
CH3
CF3
H
CH2CHClCO2CH3
O
O

14-4
Cl
F
OCH3
Q1
CH3
CF3
H
CH2CHClCO2C2H5
O
O

(isomer-1)

14-5
Cl
F
OCH3
Q1
CH3
CF3
H
CH2CHClCO2C2H5
O
O

(isomer-2)

14-6
Cl
F
OCH3
Q1
CH3
CF3
H
CH2CHClCO2-n-C3H7
O
O

(isomer-1)

14-7
Cl
F
OCH3
Q1
CH3
CF3
H
CH2CHClCO2-n-C3H7
O
O

(isomer-2)

14-8
Cl
F
OCH3
Q1
CH3
CF3
H
CH2CHClCO2-n-C4H9
O
O

(isomer-1)

14-9
Cl
F
OCH3
Q1
CH3
CF3
H
CH2CHClCO2-n-C4H9
O
O

(isomer-2)

14-10
Cl
F
OCH3
Q1
CH3
CF3
H
CH2CHClCO2-n-C5H11
O
O

(isomer-1)

14-11
Cl
F
OCH3
Q1
CH3
CF3
H
CH2CHClCO2-n-C5H11
O
O

(isomer-2)

14-12
Cl
F
OCH3
Q1
CH3
CF3
H
CH2CHClCO2-n-C6H13
O
O

(isomer-1)

14-13
Cl
F
OCH3
Q1
CH3
CF3
H
CH2CHClCO2-n-C6H13
O
O

(isomer-2)

14-14
Cl
F
OCH3
Q1
CH3
CF3
H
CH2CHClCO2-i-C4H9
O
O

(isomer-1)

14-15
Cl
F
OCH3
Q1
CH3
CF3
H
CH2CHClCO2-i-C4H9
O
O

(isomer-2)

14-16
Cl
F
OCH3
Q1
CH3
CF3
H
CH2CHClCO2-i-C5H11
O
O

(isomer-1)

14-17
Cl
F
OCH3
Q1
CH3
CF3
H
CH2CHClCO2-i-C5H11
O
O

(isomer-2)

14-18
Cl
F
OCH3
Q1
CH3
CF3
H
CH2CHClCO2-t-C4H9
O
O

14-19
Cl
F
OCH3
Q1
CH3
CF3
H
CH2CHClCO2—CH2C≡CH
O
O

(isomer-1)

14-20
Cl
F
OCH3
Q1
CH3
CF3
H
CH2CHClCO2—CH2C≡CH
O
O

(isomer-2)

14-21
Cl
F
OCH3
Q1
CH3
CF3
H
CH2CHClCO2CH2CF3
O
O

14-22
Cl
F
OCH3
Q1
CH3
CF3
H
CH2CHClCO2—CH2CF2CHF2
O
O

14-23
Cl
F
OCH3
Q1
CH3
CF3
H
CH2CHClCO2CH2CF2CF2CF3
O
O

(isomer-1)

14-24
Cl
F
OCH3
Q1
CH3
CF3
H
CH2CHClCO2CH2CF2CF2CF3
O
O

(isomer-2)

14-25
Cl
F
OCH3
Q1
CH3
CF3
H
CH2CHClCO2CH2CH2OCH3
O
O

14-26
Cl
F
OCH3
Q1
CH3
CF3
H
CH2CHClCO2CH2CH2OC2H5
O
O

14-27
Cl
F
OCH3
Q1
CH3
CF3
H
CH2CHClCO2CH2CH2OPh
O
O

(isomer-1)

14-28
Cl
F
OCH3
Q1
CH3
CF3
H
CH2CHClCO2CH2CH2OPh
O
O

(isomer-2)

14-29
Cl
F
OCH3
Q1
CH3
CF3
H
CH2CHClCO2—CH2CH2CN
O
O

14-30
Cl
F
OCH3
Q1
CH3
CF3
H
CH2CHClCO2CH2CH2BrCH2Br
O
O

(isomer-1)

14-31
Cl
F
OCH3
Q1
CH3
CF3
H
CH2CHClCO2CH2CH2BrCH2Br
O
O

(isomer-2)

14-32
Cl
F
OCH3
Q1
CH3
CF3
H
CH2CHBrCO2C2H5 (isomer-1)
O
O

14-33
Cl
F
OCH3
Q1
CH3
CF3
H
CH2CHBrCO2C2H5 (isomer-2)
O
O

14-34
Cl
F
OCH3
Q1
CH3
CF3
H
CH2C(CH3)ClCO2C2H5
O
O

14-35
Cl
F
OCH3
Q1
CH3
CF3
H
CH2C(CH3)ClCO2-n-C3H7
O
O

14-36
Cl
F
OCH3
Q1
CH3
CF3
H
CH2C(CH3)ClCO2-n-C4H9
O
O

14-37
Cl
F
OCH3
Q1
CH3
CF3
H
CH2C(CH3)ClCO2-n-C5H11
O
O

14-38
Cl
F
OCH3
Q1
CH3
CF3
H
CH2C(CH3)ClCO2-n-C6H13
O
O

14-39
Cl
F
OCH3
Q1
CH3
CF3
H
CH2C(CH3)ClCO2-i-C3H7
O
O

14-40
Cl
F
OCH3
Q1
CH3
CF3
H
CH2C(CH3)ClCO2-i-C4H9
O
O

14-41
Cl
F
OCH3
Q1
CH3
CF3
H
CH2C(CH3)ClCO2—CH2Ph
O
O

14-42
Cl
F
OCH3
Q1
CH3
CF3
H
CH2C(CH3)ClCO2—CH═CH2
O
O

14-43
Cl
F
OCH3
Q1
CH3
CF3
H
CH2C(CH3)ClCO2—CH2CH═CH2
O
O

14-44
Cl
F
OCH3
Q1
CH3
CF3
H
CH2C(CH3)ClCO2—CH2C≡CH
O
O

14-45
Cl
F
OCH3
Q1
CH3
CF3
H
CH2C(CH3)ClCO2—CH2CF2CHF2
O
O

14-46
Cl
F
OCH3
Q1
CH3
CF3
H
CH2C(CH3)ClCO2—CH(CF3)2
O
O

14-47
Cl
F
OCH3
Q1
CH3
CF3
H
CH2C(CH3)ClCO2—CH2CH2OCH3
O
O

14-48
Cl
F
OCH3
Q1
CH3
CF3
H
CH2C(CH3)ClCO2—CH2CH2SCH3
O
O

14-49
Cl
F
OCH3
Q1
CH3
CF3
H
CH2C(CH3)ClCO2-tetrahydrofurfuryl
O
O

14-50
Cl
F
OCH3
Q1
CH3
CF3
H
CH2C(CH2CO2CH3)ClCO2C2H5
O
O

14-51
Cl
F
OCH3
Q1
CH3
CF3
H
CH2C(CN)ClCO2C2H5
O
O

14-52
Cl
F
H
Q5
CHF2
CH3
—
CH2CHClCO2C2H5
—
—

14-53
Cl
F
OCH3
Q6
—
—
—
CH2CHClCO2C2H5
O
O

14-54
Cl
F
CH3
Q1
CH3
CF3
H
CH2CClCOOCH2CH3
O
O

14-55
Cl
F
CH3
Q1
CH3
CF3
H
CH2CClCOOCH2CH3
O
O

14-56
Cl
F
OCH3
Q3
CH3
CF3
Cl
CH2CClCOOCH2CH3
—
—

14-57
Cl
H
H
Q1
CH3
CF3
H
CO-phenyl
O
O

14-58
Cl
H
H
Q1
CH3
CF3
H
(cis)CHCH-2-naphthyl
O
O

14-59
Cl
H
H
Q1
CH3
CF3
H
(trans)CHCH-2-naphthyl
O
O

14-60
Cl
F
H
Q1
CH3
CF3
H
CH2(Cl)CHCOOCH2CH3
O
O

14-61
Cl
F
OCH3
Q5
CH3
CF3
H
CH2(Cl)CHCOOCH2CH3
O
O

14-62
Cl
F
OCH2CH3
Q1
CH3
CF3
H
Cl
O
O

14-63
Cl
F
OCH2CH3
Q1
CH3
CF3
H
CH2CHClCOOCH2CH3
O
O

14-64
Cl
F
OCH2CH3
Q1
CH3
CF3
H
CH2CHClCOOCH2CH3
O
O

14-65
Cl
F
OCH2CH3
Q1
CH3
CF3
H
CH2CHClCOOCH2CH2CH3
O
O

14-66
Cl
F
OCH2CH3
Q1
CH3
CF3
H
CH2CHClCOOCH2CH2CH3
O
O

14-67
Cl
F
OCH(CH3)2
Q1
CH3
CF3
H
Cl
O
O

14-68
Cl
F
OCH(CH3)2
Q1
CH3
CF3
H
CH2CHClCOOCH2CH3
O
O

14-69
Cl
F
OCH(CH3)2
Q1
CH3
CF3
H
CH2CHClCOOCH2CH3
O
O

14-70
CH3
H
H
Q1
CH3
CF3
H
CH2CHClCOOCH2CH3
O
O

14-71
COOCH3
H
H
Q1
CH3
CF3
H
CH2CHClCOOCH2CH2CH3
O
O

14-72
Cl
F
OCH3
Q8
CH3
CF3
H
CH2CHClCOOCH2CH2CH3
O
O

14-73
Cl
F
OCH3
Q1
CH3
CF3
H
CH2CHClCOOH
O
O

14-74
Cl
F
OCH3
Q9
H
CF3
Cl
NO2
—
—

14-75
Cl
F
OCH3
Q9
H
CF3
Cl
NH2
—
—

14-76
Cl
F
OCH3
Q9
H
CF3
Cl
NH-2-naphthoyl
—
—

14-77
Cl
F
OCH3
Q9
H
CF3
Cl
CH2CHClCOOCH2CH3
—
—

[0160]

15

TABLE XV

No.
X
Y
W
R1
R2
R4
R5
R8
R9

15-1
Cl
F
OCH3
CH3
CF3
NH2
H
O
O

15-2
Cl
F
OCH3
CH3
CF3
c-C3H5-carbonyl-NH—
H
O
O

15-3
Cl
F
OCH3
CH3
CF3
benzoyl-NH—
H
O
O

15-4
Cl
F
OCH3
CH3
CF3
2,4-F2-benzoyl-NH—
H
O
O

15-5
Cl
F
OCH3
CH3
CF3
2-naphthoyl-NH—
H
O
O

15-6
Cl
F
OCH3
CH3
CF3
ethoxycarbonyl-NH—
H
O
O

15-7
Cl
F
OCH3
CH3
CF3
phenoxycarbonyl-NH—
H
O
O

15-8
Cl
F
OCH3
CH3
CF3
2,4-F2-PhNHC(O)—NH—
H
O
O

15-9
Cl
F
OCH3
CH3
CF3
H5C2OC(O)N(CH3)C(O)—NH—
H
O
O

15-10
Cl
F
OCH3
CH3
CF3
H2C═CHCH═N—
H
O
O

15-11
Cl
F
OCH3
CH3
CF3
c-C3H5—CH═N—
H
O
O

15-12
Cl
F
OCH3
CH3
CF3
H3CC(CH3)═N—
H
O
O

15-13
Cl
F
OCH3
CH3
CF3
H3COCH2C(CH3)═N—
H
O
O

15-14
Cl
F
OCH3
CH3
CF3
H3CS CH2CH2CH═N—
H
O
O

15-15
Cl
F
OCH3
CH3
CF3
PhCH2CH═N—
H
O
O

15-16
Cl
F
OCH3
CH3
CF3
H5C2OC(O)CH2C(CH3)═N—
H
O
O

15-17
Cl
F
OCH3
CH3
CF3
PhCH(CH3)CH═N—
H
O
O

15-18
Cl
F
OCH3
CH3
CF3

H
O
O

15-19
Cl
F
OCH3
CH3
CF3

H
O
O

15-20
Cl
F
OCH3
CH3
CF3
2,4-F2—PhCH═N—
H
O
O

15-21
Cl
F
OCH3
CH3
CF3
F3CC(CF3)═N—
H
O
O

15-22
Cl
F
OCH3
CH3
CF3
2-naphthyl-CH═N—
H
O
O

[0161]

16

TABLE XVI

No.
X
Y
W
R1
R2
R4
R8
R9

16-1
Cl
Cl
H
CH3
CF3
H
O
O

16-2
Cl
Cl
H
CH3
CF3
CH3
O
O

16-3
Cl
Cl
H
CH3
CF3
2,4-F2-benzyl
O
O

16-4
Cl
Cl
H
CH3
CF3
2,4-F2-benzoyl
O
O

16-5
Cl
Cl
H
CH3
CF3
2-naphthoyl
O
O

16-6
Cl
F
OCH3
CH3
CF3
H
O
O

16-7
Cl
F
OCH3
CH3
CF3
2-naphthoyl
O
O

16-8
Cl
F
OCH3
CH3
CF3
CH2-2-naphthyl
O
O

16-9
Cl
F
OCH3
CH3
CF3
2-naphthoyl
O
S

16-10
Cl
F
OCH3
CH3
CF3
2-naphthoyl
S
O

16-11
CN
F
OCH3
CH3
CF3
2-naphthoyl
O
O

16-12
Cl
H
OCH3
CH3
CF3
2-naphthoyl
O
O

16-13
Cl
F
OCH3
CH3
CF3
CONH-phenyl
O
O

16-14
Cl
F
OCH3
CH3
CF3
CONHCH3
O
O

[0162]

17

TABLE XVII

No.
X
Y
W
R1
R2
R4
R8
R9

17-1
Cl
F
OCH3
CH3
CF3
methyl
O
O

17-2
Cl
F
OCH3
CH3
CF3
isopropyl
O
O

17-3
Cl
F
OCH3
CH3
CF3
benzyl
O
O

17-4
Cl
F
OCH3
CH3
CF3
2-naphthyl
O
O

17-5
Cl
F
OCH3
CH3
CF3
2-hydroxyethyl
O
O

17-6
Cl
F
OCH3
CH3
CF3
benzyl
O
S

17-7
Cl
F
OCH3
CH3
CF3
benzyl
S
O

17-8
CN
F
OCH3
CH3
CF3
benzyl
O
O

17-9
Cl
H
OCH3
CH3
CF3
benzyl
O
O

17-10
Cl
F
OCH2CH3
CH3
CF3
benzyl
O
O

[0163]

18

TABLE XVIII

1
H NMR data

No.
NMR (CDCl3, 300 Mhz) ppm

1-1
(CDCl3+CD3OD) 4.04 (3H, s), 6.19 (1H, s), 7.57 (1H, d, J=8.6 Hz)

1-2
(DMSO-d6), 3.30 (2H, br s), 6.54 (1H, s), 8.12 (1H, d, J=9.2 Hz)

1-3
(CDCl3+CD3OD) 3.85 (3H, s), 6.2 (1H, s), 6.58 (1H, d, J=9.4 Hz)

1-4
3.57 (3H, br q, J=1.2 Hz), 3.86 (3H, s), 4.04 (2H, br s), 6.37 (1H, s), 6.66 (1H, d, J=9.4

Hz)

1-5
3.55 (3H, hr g, J=1.1 Hz), 4.04 (3H, s), 6.33 (1H, s), 7.51 (1H, d, J=8.6 Hz)

1-6
3.57 (3H, g, J=1.1 Hz), 6.38 (1H, s), 7.85 (1H, d, J=8.0 Hz), 10.57 (1H, br)

1-7
3.52 (3H, g, fr=0.7 Hz), 3.82 (3H, s), 4.13 (2H, br), 6.32 (1H, s), 6.79 (1H, d, ~k9.1 Hz)

1-8
3.48 (3H, s), 4.90 (3H, br), 6.30 (1H, s), 6.69 (1H, d, J=9.0 Hz)

1-9
(Acetone-d6) 3.68 (3H, br g, J=1.4 Hz), 4.05 (3H, s), 8.03 (1H, d, J=9.1 Hz)

1-10
3.52 (3H, br s), 3.86 (3H, s), 4.05 (2H, br s), 4.63 (2H, br s), 6.66 (1H, d, J=9.7 Hz)

1-11
2.74 (6H, s), 3.57 (3H, br s), 3.84 (3H, s), 6.35 (1H, s), 7.01 (1H, d, J=8.8 Hz)

1-12
4.05 (3H, s), 4.61 (2H, s), 6.24 (1H, s), 7.52 (1H, d, J=8.6 Hz)

1-13
3.78 (3H, s), 5.24 (2H, s), 5.41 (2H, br s), 6.21 (1H, s), 6.56 (1H, d, J=9.5 Hz)

1-14
1.43 (3H, m), 4.06 (3H, s), 4.31 (2H, m), 6.32 (1H, s), 7.56 (1H, m)

1-15
1.15 (3H, m), 3.85 (3H, s), 3.35 (2H, m), 6.48 (1H, s), 6.55 (1H, m)

1-16
(CDCl3+CD3OD) 3.55 (3H, br g, J=1.1 Hz), 6.36 (1H, s), 6.61 (1H, d, J=9.2)

1-17
3.57 (3H, d, J=1.2 Hz), 6.38 (1H, s), 7.67 (1H, d, J=8.3 Hz), 10.47 (1H, br s)

1-18
3.51 (3H, hr q, J=0.9 Hz), 4.94 (2H, s), 5.66 (2H, br s), 6.39 (1H, s), 6.65 (111 d, J=9.4

Hz)

1-19
2.58 (1H, m), 3.55 (3H, hr q, J=4.3 Hz), 4.17 (2H, br s), 4.7 (2H, d, J=2.4 Hz), 6.35

(1H, s), 6.65 (1H, d, J=9.3 Hz)

1-20
3.57 (3H, d, J=0.8 Hz), 3.78 (3H, s), 4.02 (2H, br s), 4.65 (2H, dd, J=4.4, 1.9 Hz), 6.28

(1H, dt, J=15.7, 1.9 Hz), 6.65 (1H, d, J=9.3 Hz), 7.01 (1H, dt, J=15.7, 4.4 Hz)

1-21
1.63-1.94 (8H, m), 3.55 (3H, s), 3.97 (2H, s), 4.8 (1H, m), 6.34 (1H, s), 6.65 (1H, d,

J=9.6 Hz)

1-22
3.54 (3H, br q, J=~1.1 Hz), 3.94 (2H, br s), 5.0 (2H, s), 6.34 (1H, s), 6.69 (1H, d, Jr=9~4

Hz), 7.3-7.5 (5H, m)

1-23
3.58 (3H, br q, J=1.2 Hz), 4.15 (2H, br s), 6.38 (1H, s), 6.78 (1H, d, J=9.2 Hz), 7.22

(1H, m), 8.36 (2H, m)

1-30
3.52 (3H, hr g, J=1.1 Hz), 3.75 (3H, s), 6.31 (1H, s), 7.22 (1H, d, ~k8.8 Hz)

1-31
2.87 (3H, s), 2.96 (3H s), 3.53 (3H, s), 3.64 (3H, s), 6.30 (1H, s), 6.86 (1H, d, J=8.9

Hz), 7.68 (1H, s)

1-32
1.83 (4H, m), 3.21 (4H, m), 3.55 (3H, br s), 3.72 (3H, s), 6.34 (1H, s), 6.86 (1H, d,

J=8.9 Hz)

1-33
1.27 (3H, t, J=7.1 Hz), 4.20 (2H, g, J=7.1 Hz), 6.21 (1H, s), 7.62 (1H, d, J=8.8 Hz)

1-34
1.26 (3H, t, J=7.1 Hz), 4.16 (2H, q, J=7.1 Hz), 3.53 (3H, s), 6.35 (1H, s), 7.70 (1H, d,

J=8.5 Hz)

1-36
2.40 (3H, d, J=1.1 Hz), 3.54 (3H, d, J=1.3 Hz), 6.33 (1H, s), 7.51 (1H, d, J=8.5 Hz)

1-37
2.23 (3H, d, J=0.9 Hz), 3.57 (3H, d, J1.1 Hz), 6.38 (1H, s), 6.74 (1H, d, J=9.4 Hz)

1-38
3.57 (3H, d, J=1.1 Hz), 4.17 (2H, br s), 6.37 (1H, s), 6.50 (1H, t, 1k74.0 Hz), 6.72 (1H,

d, J=9.1 Hz)

1-40
3.56 (3H, d, J=1.1 Hz), 3.96 (3H, s), 6.36 (1H, s), 7.07 (1H, d, J=8.7 Hz)

1.8 Hz), 8.54 (1H, d, J=1.8FIz)

1-44
3.57 (3H, d, J=1.1 Hz), 6.39 (1H, s), 7.13 (3H, m)

1-45
3.58 (3H, d, J=1.2 Hz), 6.38 (1H, s), 7.87 (1H, s), 10.61 (1H, br s)

1-46
3.55 (3H, d, J=1.2 Hz), 3.93 (3H, s), 6.37 (1H, s), 7.27 (2H, m), 7.77 (1H, dd, J=2.1,

1.0 Hz)

1-47
3.50 (3H, d, J=0.9 Hz), 3.81 (3H, s), 3.96 (2H, s), 6.31 (1H, s), 6.88 (1H, s)

1-48
1.27 (3H, t, J=7.1 Hz), 1.58 (3H, d, J=6.8 Hz), 3.55 (3H, d, J=1.1 Hz), 3.64 (2H, br s),

4.22 (2H, m), 4.70 (1H, q, J=6.8 Hz), 6.36 (1H, s), 6.38 (2H, m), 6.88 (1H, d,

J=9.2 Hz)

1-49
1.29 (3H, t, J=7.1 Hz), 1.68 (3H, d, J=6.8 Hz), 3.54 (3H, d, J=1.0 Hz), 4.26 (2H, m), 4.82

(1H, g, J=6.8 Hz), 6.36 (1H, s), 7.25 (2H, m), 7.74 (1H, m)

1-50
3.57 (3H, q, J=1.2 Hz), 6.38 (1H, s), 6.65 (1H, t, J=71.1 Hz), 7.37 (1H, dd, J=9.3,

2.7 Hz , 7.85 1H, dd, J=2.7, 2.5 Hz

1-51
3.49 (3H, d, J=1.0 Hz), 6.30 (3H, m), 6.42 (1H, t, J=73.2 Hz), 7.8 (2H, br s)

1-52
3.57 (3H, d, J=1.2 Hz), 6.40 (1H, s), 7.57 (1H, d, J=8.2 Hz), 8.04 (1H, dd, J=8.2,

1.6 Hz), 8.53 (1H, m)

1-53
1.27 (1.5H, t, J=7.1 Hz), 1.28 (1.5H, t, J=7.1 Hz), 1.44 (1.5H, d, J=6.9 Hz), 1.45 (1.5H,

d, J=6.9 Hz), 3.58 (3H, s), 4.08 (1H, m), 4.20 (2H, q, J=7.1 Hz), 4.39 (0.5H, d,

J=7.2 Hz), 4.43 (0.5H, d, J=7.2 Hz), 6.26 (1H, m), 6.39 (2H, m), 6.50 (1H, t, J=73.3 Hz)

1-54
1.27 (1.5H, t, J=7.1 Hz), 1.28 (1.5H, t, J=7.1 Hz), 1.44 (1.5H, d, J=6.9 Hz), 1.46 (1.5H,

d, J=6.9 Hz), 3.57 (3H, m), 4.11 (1H, m), 4.22 (2H, m), 4.35 (0.5H, d, J=7.4 Hz), 4.43

(0.5H, d, J=7.1 Hz), 6.36 (0.5H, s), 6.38 (0.5H, s), 6.49 (1H, m), 6.62 (1H, dd, J=9.1,

2.0 Hz)

1-55
1.22 (1.5H, t, J=7.1 Hz), 1.23 (1.5H, t, J=7.1 Hz), 1.36 (1.5H, d, J=6.9 Hz), 1.38 (1.5H,

d, J=6.9 Hz), 3.55 (3H, m), 3.82 (1.5H, s), 3.86 (1.5H, s), 4.0-4.4 (4H, m), 6.36 (1H,

s), 6.76 (0.5H, d, J=9.1 Hz), 6.79 (0.5H, d, J=9.1 Hz)

1-56
4.73 (2H, br s), 5.50 (3H, br), 6.16 (1H, s), 6.53 (1H, d, J=9.3 Hz)

1-57
4.42 (2H, br s), 4.70 (2H, br s), 4.72 (2H, s), 6.16 (1H, s), 6.60 (1H, d, J=9.1 Hz)

1-58
3.77 (3H, s), 4.64 (2H, br s), 4.87 (2H, s), 5.28 (2H, br s), 6.17 (1H, s), 6.52 (1H, d,

J=9.2 Hz)

1-59
1.29 (3H, t, J=7.1 Hz), 3.55 (3H, q, J=1.0 Hz), 4.23 (2H, q, J=7.1 Hz), 4.64 (2H, s),

4.82 (2H, br s), 6.35 (1H, s), 6.60 (1H, d, J=9.2 Hz)

1-60
1.27 (3H, t, J=7.1 Hz), 1.659 (1.5H, d, J=7.0 Hz), 1.666 (1.5H, d, J=7.0 Hz), 3.55 (3H,

s), 4.20 (2H, q, J=7.1 Hz), 4.73 (1H, m), 6.346 (0.5H, s), 6.355 (0.5H, s), 6.61 (1H, d,

J=9.3 Hz)

1-61
1.41 (3H, t, J=7.0 Hz), 3.52 (3H, q, J=1.0 Hz), 4.04 (2H, q, J=7.0 Hz), 4.10 (2H, br s),

6.32 (1H, s), 6.62 (1H, d, J=9.5 Hz)

1-62
1.16 (3H, t, J=7.1 Hz), 1.42 (3H, t, J=7.1 Hz), 2.99 (2H, qJ=7.1 Hz), 3.57 (3H, q,

J=1.1 Hz), 4.03 (2H, q, J=7.1 Hz), 4.14 (1H, br s), 6.35 (1H, s), 6.63 (1H, d, J=9.4

Hz)

1-63
1.35 (6H, d, J=6.2 Hz), 3.55 (3H, q, J=1.2 Hz), 3.95 (2H, br s), 4.50 (1H, q, J=6.2 Hz),

6.34 (1H, s), 6.66 (1H, d, J=9.4 Hz)

1-64
1.06 (3H, t, J=6.3 Hz), 1.37 (6H, d, J=6.2 Hz), 3.57 (3H, q, J=1.2 Hz), 3.83 (2H, br s),

4.52 (1H, g, J=6.2 Hz), 6.35 (1H, s), 6.70 (1H, d, J=9.3 Hz)

1-65
7.62 (1H, d, J=8.5 Hz), 8.37 (1H, 2d, J=2.6 Hz, 8.4 Hz), 8.83 (1H, d, J=2.6 Hz)

1-66
3.56 (3H, s), 6.37 (1H, s), 6.86 (1H, d, J=~8.4 Hz), 7.77 (1H, d, J=8.4 Hz), 10.75 (1H,

broad)

1-67
3.56 (3H, s), 6.37 (1H, s), 8.55 (1H, s)

1-68
3.56 (3H, s), 6.39 (1H, s), 7.45 (111., d, J=8 .7 Hz), 7.64 ( 1H, 2d, J=1.7 Hz, 8.7 Hz), 8.13

(1H, d, J=1.7 Hz)

1-69
4.15 (3H, s), 6.14 (1H, s), 8.51 (1H, s), 12.8 (1H, broad)

1-70
6.26 (1H, s), 7.62 (1H, 2d, J=6.1 Hz, 8.3 Hz), 8.3 (1H, broad)

1-71
3.56 (3H, s), 4.8 (3H, broad), 6.38 (1H, s), 6.59 (1H, d, J=8.7 Hz), 6.85 (1H, d, J8.7 Hz)

1-72
3.56 (3H, s), 3.89 (3H, s), 6.37 (1H, s), 6.75 (1H, d, J=8.7 Hz), 6.87 (1H, d, J8.7 Hz)

1-73
3.55 (3H, s), 3.75 (2H, s), 6.36 (1H, s), 6.73 (2H, m), 7.01 (1H, 2d, J=2.4 Hz, 6.9 Hz)

2-1
2.04 (3H, s), 3.57 (3H, br q, J=1.1 Hz), 3.86 (3H, s), 6.30 (1H, s), 7.22 (1H, d, J=9.6

Hz)

2-2
2.29 (3H, s), 2.33 (3H, s), 3.53 (3H, br s), 3.78 (3H, s), 6.3 (1H, s), 7.42 (1H, d, J=8.8

Hz)

2-3
1.14 (9H, s), 3.56 (3H, s), 3.82 (3H, s), 6.29 (1H, s), 7.19 (1H, d, J=9.0 Hz), 7.61 (1H,

br s)

2-4
3.49 (3H, br q, J=1.0 Hz), 3.75 (3H, s), 5.70-5.79 (2H, m), 6.26 (1H, s), 6.40-6.55 (4H,

m), 7.42 (1H, d, J=8.7 Hz)

2-5
1.95 (3H, s), 3.55 (3H, br s), 3.84 (3H, s), 5.45 (1H, s), 5.70 (1H, s), 6.27 (1H, s), 7.20

(1H, d, J=9.0 Hz), 7.62 (1H, br s)

2-6
1.90 (3H, s), 1.91 (3H, s), 3.49 (3H, br s), 3.79 (3H, s), 5.46 (2H, s), 5.64 (1H, s), 5.66

(1H, s), 6.27 (1H, s), 7.30 (1H, d, J=8.8 Hz)

2-7
1.86 (3H, s), 2.05 (3H, s), 3.56 (3H, br s), 3.82 (3H, s), 5.66 (1H, br s), 6.27 (1H, s),

7.17 (1H, d, J=9.0 Hz), 7.23 (1H, br s)

2-8
1.85 (6H, m), 2.12 (6H, m), 3.47 (3H, br q, J=1.0 Hz), 3.77 (3H, s), 5.91 (1H, m), 5.98

(1H, m), 6.25 (1H, s), 7.34 (1H, d, J=8.7 Hz)

2-9
(CDCl3+CD3OD) 3.86 (3H, s), 6.16 (1H, s), 7.37 (1H, d, J=8.9 Hz)

2-10
3.54 (3H, br s), 3.86 (3H, s), 6.31 (1H, s), 7.32 (1H, d, J=9.0 Hz)

2-11
(CDCl3+CD3OD) 3.55 (3H, br s), 4.87 (2H, s), 6.35 (1H, s), 7.44 (1H, d, J=8.7 Hz)

2-12
(CDCL3+CD3OD) 3.59 (3H, br s), 3.87 (3H, s), 7.37 (1H, d, J=8.8 Hz)

2-13
3.56 (3H, br g, J=1.1 Hz), 3.89 (3H, s), 4.08 (2H, s), 6.3 (1H, s), 7.25 (1H, d, J=9 Hz)

2-14
3.52 (3H, brq, J=1.1 Hz), 3.74 (2H, m), 3.85 (3H, s), 6.39 (1H, s), 7.53 (1H, d, J=9.3

Hz), 9.03 (1H, m)

2-15
3.56 (3H, s), 3.91 (3H, s), 3.95 (3H, s), 6.29 (1H, s), 7.24 (1H, d, J=9.0 Hz), 9.00 (1H,

s)

2-16
1.27 (3H, t, J=7.1 Hz), 1.28 (3H, t, J=7.1 Hz), 3.42 (2H, s), 3.57 (3H, br s), 4.04 (2H,

s), 4.10-4.30 (4H, m), 6.40 (1H, s), 7.33 (1H, d, J=9.8 Hz), 8.07 (1H, s)

2-17
0.95 (2H, m), 1.10 (2H, m), 1.50 (1H, m), 3.55 (3H, s), 6.37 (1H, s), 7.22 (1H, d,

J=9.0 Hz), 7.92 (1H, br s), 8.41 (1H, br, s)

2-18
0.70-1.20 (8H, m), 1.96 (1H, m), 2.15 (1H, m), 3.54 (3H, br s), 3.75 (3H, s), 6.35 (111

s), 7.38 (1H, d, J=8.6 Hz)

2-19
1.40 (5H, m), 1.70 (5H, m), 2.25 (1H, m), 3.32 (3H, s), 3.82 (3H, s), 6.34 (1H, s), 7.17

(1H, d, J=9.0 Hz), 7.68 (3H, s)

2-20
1.20 (10H, m), 1.70 (10H, m), 2.50 (2H, m), 3.50 (3H, s), 3.68 (3H, s), 6.31 (1H, s),

7.36 (1H, m)

2-21
3.37 (3H, s), 3.44 (3H, s), 3.55 (3H, br s), 4.18 (3H, s), 6.33 (1H, s), 7.43 (1H, d, J=8.8

Hz)

3.2 (3H, s), 3.55 (3H, s), 3.96 (3H, s), 6.35 (1H, s), 6.48 (1H, br s), 7.29 (1H, d,

J=8.8 Hz)

2-22
3.52 (3H, br s), 3.64 (3H, s), 6.29 (1H, s), 6.85 (1H, d, J=9.1 Hz), 7.4 (5H, m), 7.68

(1H, s)

2-23
2.39 (3H, s), 3.52 (3H, s), 3.82 (3H, s) 6.23 (f H, s), 7.20 (1H, d, J=9.0 Hz), 7.32 (2H,

m), 7.53 (2H, m), 8.02 (lH, s)

2-24
2.42 (3H, s), 3.53 (3H, s), 3.82 (3H, s), 6.22 (1H, s), 7.20 (1H, d, J=9.0 Hz), 7.26 (2H,

d, J=7.8 Hz), 7.67 (2H, d, J=7.8 Hz), 7.91 (1H, s)

2-25
2.32 (3Hx2, s), 3.28 (3H, s), 3.82 (3H, s), 6.02 (1H, s), 7.10 (4H, d, J=7.9 Hz), 7.26

(1H, d, 19.0 Hz), 7.73 (4H, m)

2-26
2.40 (3H, s), 3.44 (3H, s), 3.54 (3H, d, J=1.l Hz), 6.29 (1H, s), 6.55 (1H, br s), 7.18

(1H, d, J=8.9 Hz), 7.25 (2H, d, J=8.3 Hz), 7.68 (2H, d, J=83 Hz)

2-27
1.26 (3H, t, J=7.7 Hz), 2.71 (2H, q, J=7.7 Hz), 3.54 (3H, s), 3.83 (3H, s), 6.23 (1H, s),

7.21 (1H, d, J=9.0 Hz), 7.29 (2H, d, J=8.2 Hz), 7.70 (2H, d, J=8.2 Hz), 7.86 (1H, br s)

2-28
1.26 (3H, t, J=7.6 Hz), 2.71 (2H, q, J=7.6 Hz), 3.51 (3H, br s), 4.78 (2H, s), 6.25 (1H,

s), 7.28 (3H, m), 7.73 (2H, m), 7.84 (1H, br s)

2-29
0.95 (6H, t, J=7.2 Hz), 1.66 (4H, m), 2.64 (4H, m), 3.53 (3H, br s), 3.83 (3H, s), 6.23

(1H, s), 7.21 (1H, d, J=9.3 Hz), 7.27 (4H, m), 7.70 (2H, m), 8.00 (2H, m)

2-30
1.35 (9H, s), 3.55 (3H, s), 3.83 (3H, s), 6.23 (1H, s), 7.20 (1H, m), 7.49 (2H, d, J==8.6

Hz), 7.73 (2H, d, J=8.6 Hz), 7.88 (1H, br s)

2-31
3.54 (3H, s), 3.83 (3H, s), 5.40 (1H, d, J=10.9 Hz), 5.87 (1H, d, J47.6 Hz), 6.78 (1H,

dd, J=17.6, 10.9 Hz), 7.22 (1H, d, J=9.0 Hz), 7.49 (2H, d, J=8.2 Hz), 7.75 (1H, d,

J=8.2 Hz), 8.01 (1H,brs)

2-32
2.31 (3H, s), 2.32 (3H, s), 3.54 (3H, d, J=1.0 Hz), 3.82 (3H, s), 6.23 (1H, s), 7.19 (1H, d,

J=9.1 Hz), 7.22 (1H, d, J=7.8 Hz), 7.50 (1H, dd, J=7.8, 1.7 Hz), 7.56 (1H, br s),

7.86 (1H, br s)

2-33
3.62 (3H, s), 3.84 (3H, s), 6.25 (1H, s), 7.25 (1H, d, J=8.9 Hz), 7.75 (2H, d, J8.3 Hz),

7.89 (2H, d, J=8.3 Hz), 7.92 (1H, br s)

2-34
3.54 (3H, br s), 3.84 (3H, s), 6.26 (1H, s), 7.30 (1H, d, J9.3 Hz), 7.72 (4H, m), 7.94

(2H, m), 8.17 (2H, m)

2-36
3.56 (3H, d, J=1.1 Hz), 3.85 (3H, s), 4.64 (2H, s), 6.25 (1H, s), 7.24 (1H, d, J9.0 Hz),

7.52 (2H, d, J=8.3 Hz), 7.79 (2H, d, J=8.3 Hz), 7.91 (1H, br s)

2-37
3.53 (3H, s), 3,83 (3H, s), 6.25 (1H, s), 7.20 (1H, d, J=9.0 Hz), 7.45 (3H, m), 7.63 (4H,

m), 7.84 (2H, d, J=8.2 Hz), 8.13 (1H, s)

2-38
3.32 (3H, s), 3.86 (3H, s), 6.08 (1H, s), 7.52 (iSH, m), 7.95 (4H, m)

2-39
3.56 (3H, br s), 3.89 (3H, s), 6.27 (1H, s), 7.15-7.3 (2H, m), 7.24 (1H, d, J=9.1 Hz),

7.54 (1H, m), 7.92 (1H, m), 8.43 (1H, hr d, J=13.8 Hz)

2-40
3.53 (3H, br s), 3.83 (3H, s), 6.23 (1H, s), 7.12 (2H, m), 7.22 (1H, d, J=9.1 Hz), 7.79

(2H, m), 7.97 (1H, br s)

2-41
3.57 (3H, hr q, J=1.1 Hz), 3.9 (3H, s), 6.29 (1H, s), 7.2 (1H, m), 7.26 (1H, d, J=9.1

Hz), 7.36 (1H, m), 7.63 (1H, m), 8.29 (1H, d, J=11.1 Hz)

2-42
3.56 (3H, br s), 3.89 (3H, s), 6.27 (1H, s), 6.97 (2H, m), 7.25 (1H, d, J=9 Hz), 7.97

(1H, m), 8.37 (1H, hr d, J=13.3 Hz)

2-43
3.44 (3H, br s), 3.96 (3H, s), 6.24 (1H, s), 6.64 (2H, m), 6.86 (2H, m), 7.35 (1H, d, J=8.8

Hz), 7.78 (2H, m)

2-44
3.88 (3H, s), 6.26 (1H, s), 6.98 (2H, m), 7.23 (1H, d, J=9 Hz), 7.96 (1H, m), 8.46 (1H,

m)

2-45
3.43 (3H, hr q, J=1.3 Hz), 5.1 (2H, s), 6.36 (1H, s), 6.9-7.15 (4H, m), 7.77 (1H, d, J=9.1

Hz), 7.7-7.9 (2H, m)

2-46
3.52 (3H, s), 3.91 (3H, s), 6.75-7.05 (2H, m), 6.95 (1H, s), 7.39 (1H, d, J=8.9 Hz), 8.03

(1H, m), 8.56 (1H, m)

2-47
3.55 (3H, br s), 3.91 (3H, s), 6.32 (1H, s), 6.93 (2H, m), 7.25 (1H, d, J=8.9 Hz), 7.39

(1H, m), 8.03 (1H,hrs)

2-48
3.55 (3H, br q, J=1.0 Hz), 3.83 (3H, s),45.26 (1H, s), 7.24 (1H, d, 19.1 Hz), 7.25

(1H, m), 7.54 (1H, m), 7.65 (1H, m), 8.05 (1H, br s)

2-49
3.39 (3H, br s), 3.77 (3H, s), 6.1 (1H, s), 7.10-7.40 (2H, m), 7.34 (1H, d, J=8.8 Hz),

7.60-8.00 (4H, m)

2-50
3.54 (3H, br s), 3.81 (3H, s), 6.26 (1H, s), 7.01 (1H, m), 7.25 (1H, d, J=9.3 Hz), 7.31

(2H, m), 8.28 (1H, s)

2-51
3.43 (3H, br s), 3.79 (3H, s), 6.15 (1H, s), 6.95-7.75 (7H, m)

2-53
3.56 (3H, d, J=1.2 Hz), 3.91 (3H, s), 6.32 (1H, s), 7.26 (1H, d, J=9.0 Hz), 7.35 (1H,

ddd, J=8.6, 6.1, 2.5 Hz), 7.42 (2H, m), 7.52 (1H, dd, J=7.4, 1.2 Hz), 7.83 (1H, br s)

2-54
3.53 (3H, s), 3.82 (3H, s), 6.26 (1H, s), 7.22 (1H, d, J=9.0 Hz), 7.39 (1H, dd, J=7.8, 7.9

Hz), 7.53 (1H, m), 7.62 (1H, m), 7.77 (1H, m), 8.06 (1H, br s)

2-55
3.36 (3H, s), 3.81 (3H, s), 6.11 (1H, s), 7.30 (3H, m), 7.43 (2H, m), 7.76 (4H, m)

2-56
3.53 (3H, s), 3.83 (3H, s), 6.23 (1H, s), 7.23 (1H, d, J=9.0 Hz), 7.44 (2H, d, J=8.7 Hz),

7.72 (2H, d, J=8.7 Hz), 7.92 (1H, s)

2-57
3.32 (3H, s), 3.78 (3H, s), 6.06 (1H, s), 7.34 (SH, m), 7.80 (4H, m)

2-58
3.56 (3H, d, J=1.0 Hz), 3.89 (3H, s), 6.32 (1H, s), 7.27 (1H, d, J9.0 Hz), 7.31 (1H, dd,

J=8.1, 1.9 Hz), 7.47 (2H, m), 7.92 (1H, br s)

2-59
3.55 (3H, d, J=1.1 Hz), 3.84 (3H, s), 6.25 (1H, s), 7.25 (1H, d, J=9.1 Hz), 7.54 (1H, d,

J=8.3 Hz), 7.60 (1H, dd, J=8.3, 2.0 Hz), 7.88 (1H, br s), 7.89 (1H, d, J=2.0 Hz)

2-60
3.54 (3H, br s), 3.83 (3H, s), 6.26 (1H, s), 7.24 (1H, d, J=9.0 Hz), 7.34 (2H, m), 7.65-

7.75 (2H, m), 7.92-8.25 (4H, m)

2-61
3.53 (3H, s), 3.82 (3H, s), 6.23 (1H, s), 7.22 (1H, d, J=9.0 Hz), 7.61 (4H, m), 7.95 (1H,

s)

2-62
3.33 (3H, s), 3.80 (3H, s), 6.06 (1H, s), 7.31 (1H, d, J=9.0 Hz), 7.51 (4H, m), 7.73 (4H,

m)

2-63
3.54 (3H, d, J=1.1 Hz), 3.83 (3H, s), 3.87 (3H, s), 6.22 (1H, s), 6.95 (2H,d, J=8.8 Hz),

7.21 (1H, d, J=9.1 Hz), 7.75 (2H, d, J=8.8 Hz), 7.78 (1H, hr. s)

2-64
1.44 (3H, t, J=7.0 Hz), 3.52 (3H, s), 3.82 (3H, s), 4.06 (2H, q, J=7.0 Hz), 6.22 (1H, s),

6.90 (2H, d, J=9.0 Hz), 7.20 (1H, d, J=9.0 Hz), 7.73 (2H, d, J9.0 Hz), 7.91 (1H, s)

2-66
3.55 (3H, d, J=1.0 Hz), 3.84 (3H, s), 6.25 (1H, s), 7.25 (1H, d, J=9.1 Hz), 7.51 (2H, d,

J=8.6 Hz), 7.85 (2H, d, J=8.6 Hz), 7.88 (1H, br s)

2-67
3.85 (3H, s), 6.22 (1H, s), 7.25 (1H, d, J=9.9 Hz), 7.76 (2H, d, J=8.4 Hz), 7.85 (2H, d,

J=8.4 Hz), 7.96 (1H, br s)

2-69
3.40 (3H, br s), 3.79 (3H, s), 6.12 (1H, s), 7.36 (1H, d, J=8.7 Hz), 8.06 (4H, m), 8.25

(4H, m)

2-70
3.50 (3H, br s), 3.87 (3H, s), 6.32 (1H, s), 7.51 (1H, d, J=8.8 Hz), 9.07 (2H, m), 9.12

(1H, m), 9.91 (1H, br s)

2-71
3.33 (3H, s), 3.77 (3H, s), 7.20 (4H, m), 7.31 (1H, d, J=8.8 Hz), 7.92 (4H, m)

2-72
3.54 (3H, s), 3.83 (3H, s), 6.24 (1H, s), 7.25 (3H, m), 7.82 (2H, m), 8.02 (1H, s)

2-73
3.54 (3H, br s), 3.83 (3H, s), 6.05 (2H, s), 6.23 (1H, s), 6.85 (1H, d, J=7.8 Hz), 7.21

(1H, d, J=8.8 Hz), 7.25-7.34 (2H, m), 7.80 (1H, br s)

2-74
3.52 (3H, s), 3.84 (3H, s), 6.25 (1H, s), 7.24 (1H, d, J=9.0 Hz), 7.50 (4H, m), 7.90 (3H,

m), 8.20 (1H, br s)

2-75
3.64 (3H, s), 3.85 (3H, s), 6.24 (1H, s), 7.24 (1H, d, J=9.0 Hz), 7.80 (7H, m), 8.32

(1H, s)

2-76
3.87 (3H, s), 6.1 (1H, s), 7.31 (1H, d, J=9.0 Hz), 7.60 (2H, m), 7.80-8.05 (SH, m), 8.38

(1H, s)

2-77
3.83 (3H, s), 4.69 (2H, s), 6.21 (1H, s), 7.35 (1H, d, J=8.9 Hz), 7.50-7.60 (3H, m),

7.80-7.85 (4H, m), 8.07 (1H, s)

2-78
3.56 (3H, s), 3.86 (3H, s), 6.28 (1H, s),1i49 (1H, d, J=15.6 Hz), 7.21 (1H, d, J=9.0

Hz), 7.39 (4H, m), 7.50 (2H, m), 7.63 (1H, d, J15.6 Hz)

2-79
3.57 (3H, s), 3.86 (3H, s), 6.28 (1H, s)~, 6.54 (1H, d, J=15.7 Hz), 6.84-6.94 (3H, m),

7.22 (1H, d, J=9.0 Hz), 7.36 (1H, br s), 7.48 (1H, q, J=7.7 Hz), 7.67 (1H, d, J15.7

Hz)

2-80
2.41 (3H, s), 3.57 (3H, s), 3.86 (3H, s), 6.29 (1H, s), 6.40 (1H, d, J=15.4 Hz), 7.19-7.32

(4H, m), 7.33 (1H, br s), 7.53 (1H, d, J=7.2 Hz), 7.93 (1H, d, J=15.4 Hz)

2-81
2.12 (3H, d, J=1.3 Hz), 3.57 (3H, d, J=0.9 Hz), 3.88 (3H, s), 6.29 (1H, s), 7.20 (1H, d,

J=9.1 Hz), 7.36 (5H, m), 7.66 (1H, br s)

2-82
3.57 (3H, br s), 3.85 (3H, s), 6.29 (1H, s), 6.48 (1H, d, J15.6 Hz), 7.16 (1H, d, J9.0

Hz), 7.28 (2H, m), 7.40 (1H, dd, J=7.9, 1.6 Hz), 7.53 (1H, dd, J=7.4, 1.6 Hz), 7.67

(1H, br s), 7.98 (1H, d, J=15.6 Hz)

2-83
3.46 (3H, br s), 3.83 (3H, s), 6.24 (1H, s), 6.80 (1H, d, J15.5 Hz), 6.91 (1H, d, J15.5

Hz), 7.30 (4H, m), 7.39 (2H, m), 7.45 (1H, d, J=8.8 Hz), 7.56 (1H, dd, J=7.6, 1.8 Hz),

7.59 (1H, dd, J=7.6, 1.8 Hz), 8.18 (1H, d, J=15.5 Hz), 8.20 (1H, d, J=15.5 Hz)

2-84
3.56 (3H, br s), 3.84 (3H, s), 6.29 (1H, s), 6.45 (1H, d, J=15.6 Hz), 7.18 (1H, d, J=9.0

Hz), 7.54 (2H, d, J=8.6 Hz), 7.40 (2H, d, J=8.6 Hz), 7.55 (1H, d, J=15.6 Hz), 7.59

(1H, brs)

2-85
3.56 (3H, br s), 3.84 (3H, s), 3.85 (3H, s), 6.28 (1H, s), 6.35 (1H, d, J=15.5 Hz), 6.89

(2H, d, J=~8.7 Hz), 7.19 (1H, d, J=9.0 Hz), 7.35 (1H, br s), 7.45 (2H, d, J=8.7 Hz),

7.58 (1H, d, J=15.5 Hz)

2-86
2.60 (2H, q, J=7.7 Hz), 2.91 (2H, t, J=7.7 Hz), 3.56 (3H, s), 3.69 (3H, s), 6.26 (1H, s),

7.1-7.3 (6H, m)

2-87
2.66 (2H, m), 2.92 (2H, m), 3.55 (3H, s), 4.52 (2H, s), 6.28 (1H, s), 7.1-7.4 (6H, m)

2-88
1.90 (2H, tt, J=7.5, 7.4 Hz), 2.29 (2H, d, J=7.4 Hz), 2.61 (2H, t, J=~7.5 Hz), 3.52 (3H, d,

J=0.7 Hz), 3.84 (3H, s), 6.28 (1H, s), 7.13-7.32 (7H, m)

2-89
3.54 (3H, s), 3.82 (3H, s), 4.02 (2H, s), 4.55 (2H, s), 6.15 (1H, s), 7.16 (1H, d, J9.0

Hz), 7.4 (5H, m), 8.5 5 (1H, s)

2-90
3.56 (3H, d, J=1.1 Hz), 3.87 (3H, s), 6.26 (1H, s), 6.55 (1H, dd, J=3.6, 1.8 Hz), 7.17

(1H, dd, J=3.6, 0.5 Hz), 7.22 (1H, d, J=9.1 Hz), 7.54 (1H, dd, J=1.8, 0.5 Hz), 8.18

(1H, brs)

2-91
2.25 (3H, s), 3.46 (3H, s), 3.81 (3H, s), 6.25 (1H, s), 6.39 (1H, s), 7.18 (1H, d, J=9.0

Hz), 7.39 (1H, s), 8.30 (1H, s)

2-92
3.56 (3H, d, J=0.8 Hz), 3.85 (3H, s), 6.28 (1H, s), 6.39 (1H, d, J=15.2 Hz), 6.48 (1H,

dd, J=3.4, 1.8 Hz), 6.60 (1H, d, J=3.4 Hz), 7.19 (1H, d, J=9.0 Hz), 7.34 (1H, br s),

7.40 (1H, d, J=15.2 Hz), 7.48 (1H, d, J=1.8 Hz)

2-93
3.45 (3H, s), 3.66 (3H, s), 3.80 (2H, s), 6.16 (1H, s), 7.00 (4H, m), 7.55 (1H, br s)

2-94
2.46 (3H, s), 3.56 (3H, s), 3.88 (3H, s), 6.26 (1H, s), 6.94 (1H, m), 7.20 (1H, d, J=9.0

Hz), 7.36 (1H, m), 7.65 (1H, s)

2-95
2.45 (3H, s), 3.47 (3H, s), 3.78 (3H, s), 6.17 (1H, s), 6.70 (1H, m), 7.13 (1H, d, J=9.0

Hz), 7.32 (1H, m), 7.63 (1H, s)

2-96
2.41 (6H, s), 3.26 (3H, s), 3.78 (3H, s), 5.97 (1H, s), 6.59 (2H, m), 7.24 (1H, d, J=9.0

Hz), 7.39 (2H, m)

2-97
3.31 (3H, s), 3.84 (3H, s), 6.03 (1H, s), 7.05 (2H, m), 7.40 (2H, m), 7.70 (3H, m)

2-98
3.54 (3H, s), 3.84 (3H, s), 6.25 (1H, s), 7.25 (1H, d, J=9.7 Hz), 7.41 (1H, dd, J=7.7, 4.8

Hz), 8.01 (1H, d, J=7.7 Hz), 8.32 (1H, br s), 8.78 (1H, br s), 9.01 (1H, br s)

2-100
3.42 (3H, q, J=1.0 Hz), 3.79 (3H, s), 6.12 (1H, s), 7.35 (1H, d, J=8.6 Hz), 7.56 (1H, d,

J=8.0 Hz), 7.39 (1H, d, J=8.0 Hz), 8.15 (1H, dd, J=8.0, 2.2 Hz), 8.16 (1H, dd, J=8.0,

2.2 Hz), 8.77 (1H, d, J=2.2 Hz), 8.91 (1H, d, J=2.2 Hz)

2-101
3.59 (3H, br q, J=1.2 Hz), 6.36 (1H, s), 6.99 (1H, dd, J=4.9, 8.3 Hz), 7.27 (1H, d, J8.7

Hz), 8.44 (1H, dd, J=1.7, 4.8 Hz), 8.6 (1H, dd, J=1.7, 8.3 Hz), 9.79 (1H, br s)

2-102
(CDCl3+CD3OD) 3.54 (3H, br s), 6.33 (1H, s), 6.82 (1H, t, J=5.0 Hz), 7.2 (1H, d, J=8.8

Hz), 8.38 (2H, d, J=5.0 Hz)

2-103
3.55 (3H, q, J=1.0 Hz), 3.~9 (3H, s), 6.26 (1H, s), 7.22 (1H, d, J=9.1 Hz), 7.45 (3H, m),

7.83 (3H, m), 7.99 (1H, br s)

2-104
3.58 (3H, s), 3.92 (3H, s), 6.26 (1H, s), 7.20 (1H, d, J=9.0 Hz), 7.65 (1H, m), 7.85 (2H,

m), 8.17 (2H, m), 8.33 (1H, m), 10.05 (1H, s)

2-105
3.60 (3H, br s), 3.92 (3H, s), 6.27 (1H, s), 7.27 (1H, d, J9.0 Hz), 7.93 (2H, m), 8.20

(2H, m), 9.60 (1H, s), 10.12 (1H, s)

2-106
3.56 (3H, q, J=0.7 Hz), 3.86 (3H, s), 6.27 (1H, s), 6.95 (2H, m), 7.41 (1H, d, J=8.7 Hz),

7.95 (1H, m)

2-113
3.56 (3H, q, J=1.0 Hz), 3.86 (3H, s), 6.26 (1H, d, J=15.2 Hz), 6.28 (1H, s), 7.05 (1H,

dd, J5.0, 3.6 Hz), 7.20 (1H, d, J=9.0 Hz), 7.25 (1H, d, J=3.6 Hz), 7.27 (1H, br s),

7.38 (1H, d, J5.0 Hz), 7.75 (1H, d, J=15.2 Hz)

2-114
3.56 (3H, d, J=0.9 Hz), 6.40 (1H, s), 7.28 (1H, d, J=9.21 Hz), 7.50-7.65 (2H, m), 7.70-

7.80 (1H, m), 7.80-8.0 (3H, m), 8.35 (1H, m), 8,63 (1H, br s)

2-115
3.54 (3H, d, J=0.9 Hz), 6.24 (1H, s), 6.51 (1H, t, J=73.1 Hz), 7.32 (1H, d, J=8.8 Hz),

7.50-7.65 (2H, m), 7.70-7.82 (1H, m), 7.85-7.95 (3H, m), 8.07 (1H, br s), 8.29 (1H, br

s)

2-116
2.09 (3H, s), 2.14 (3H, s), 3.50 (3H, d, J1.0 Hz), 3.79 (3H, s), 4.8-5.0 (4H, m), 6.29

(1H, s), 7.47 (1H, d, J=8.9 Hz)

2-117
2.18 (3H, s), 3.56 (3H, d, J=1.1 Hz), 3.86 (3H, s), 4,58 (2H, s), 6.30 (1H, s), 7.24 (1H,

d, J=9.0 Hz)

2-118
1.40 (3H, t, J=7.1 Hz), 3.56 (3H, d, J=1.0 Hz), 3.91 (3H, s), 4.39 (2H, q, J7.1 Hz),

6.29 (1H, s), 7.25 (1H, d, J=9.1 Hz), 9.01 (1H, br s)

2-119
3.54 3H, s , 3.72 3H, s , 4.56 2H, s , 6.24 1H, s , 6.85-7.40 6H, m , 8.50 1H, br s

2-120
3.45 (3H, s), 3.85 (3H, s), 4.8-5.15 (4H, m), 6.27 (1H, s), 6.8-7.0 (6H, m), 7.20-730

(4H, m), 7.48 (1H, d, J=8.7 Hz)

2-121
3.59 (3H, s), 3.93 (3H, s), 6.35 (1H, s), 7.26 (1H, d, J=9.0 Hz), 7.40-7.70 (3H, m), 8.20

(2H, m), 8.97 (1H, br s)

2-122
2.33 (3H, s), 3.49 (3H, d, J=0.9 Hz), 6.24 (1H, s), 7.34 (1H, d, J=9.1 Hz), 7.50-7.62

(2H, m), 7.75-7.95 (5H, m), 8.31 (1H, br s)

2-123
2.28 (3H, s), 3.54 (3H, s), 6.29 (1H, s), 6.59 (1H, d, J=15.5 Hz), 7.20-7.50 (6H, m),

7.63 (1H, d, J=15.5 Hz)

2-124
2.29 (6H, s), 3.56 (3H, s), 3.93 (3H, s), 6.32 (1H, s), 7.05 (2H, m), 7.20 (2H, m), 7.47 (1H,

br s)

2-125
3.57 (3H, s), 3.87 (3H, s), 6.29 (1H, s), 6.62 (1H, d, J=15.7 Hz), 7.1-7.5 (5H, m), 7.72

(1H, d, J=15.7 Hz)

2-126
3.52 (3H, s), 3.80 (3H, s), 6.24 (1H, s), 6.32 (1H, d, J=15.6 Hz), 7.11 (1H, br d,

J=8.8 Hz), 7.4-7.6 (4H, m), 7.95 (2H, m)

2-127
3.56 (3H, s), 3.86 (3H, s), 3.89 (3H, s), 6.28 (1H, s), 6.64 (1H, d, J15.7 Hz), 6.95

(2H, m), 7.19 (1H, d, J=9.0 Hz), 7.35 (2H, m), 7.46 (1H, dd, J7.6, 1.4 Hz), 7.88

(1H, d, J=15.7 Hz)

2-128
3.59 (3H, s), 3.88 (3H, s), 6.31 (1H, s), 6.65 (1H, d, J=15.9 Hz), 7.20 (2H, m), 7.35

(2H, d, J=8.l Hz), 7.37 (1H, br s), 7.72 (1H, d, J=45.9 Hz)

2-129
2.28 (3H, s), 2.53 (2H, t, J=7.3 Hz), 2.88 (2H, t, J=7.3 Hz), 3.56 (3H, s), 3.73 (3H, s),

6.26 (1H, s), 7.11 (SH, m), 7.35 (1H, br s)

2-130
2.33 (3H, s), 2.36 (3H, s), 3.57 (3H, s), 3.86 (3H, s), 6.29 (1H, s), 6.40 (1H, d,

J=15.4 Hz), 7.09 (2H, br s), 7.20 (1H, d, J=9.0 Hz), 7.33 (1H, br s), 7.35 (1H, s), 7.90

(1H, d, J=15.4 Hz)

2-131
3.54 (3H, d, J=1.0 Hz), 6.37 (1H, s), 7.21 (1H, d, J=8.6 Hz), 7.33 (1H, dd, J=8.6,

2.1 Hz), 7.60 (2H, m), 7.77 (1H, dd, J=8.6, 1.8 Hz), 7.88 (3H, m), 7.98 (1H, br s), 8.01

(1H, d, J=2.l Hz), 8.26 (1H, d, J=1.3 Hz)

2-132
2.21 (3H, s), 2.27 (3H, s), 2.48 (2H, t, J=7.8 Hz), 2.81 (2H, t, J=7.8 Hz), 3.57 (3H, s),

3.73 (3H, s), 6.27 (1H, s), 6.92 (2H, m), 7.02 (1H, d, J=7.6 Hz), 7.12 (1H, br d,

J=8.6 Hz), 7.51 (1H, br s)

2-133
3.55 (3H, d, J=1.0 Hz), 3.76 (3H, s), 4.52 (2H, s), 6.26 (1H, s), 6.88 (2H, dd, J=9.1,

2.4 Hz), 7.02 (2H, dd, J=9.1, 8.1 Hz), 7.20 (1H, d, J=9.0 Hz), 8.48 (1H, br s)

2-134
3.57 (3H, s), 3.86 (3H, s), 6.28 (1H, s), 6.50 (1H, d, J=15.5 Hz), 7.23 (1H, d, J=9.0 Hz),

7.35 (4H, m), 7.50 (1H, br s), 7.58 (1H, d, J=15.5 Hz)

2-135
3.55 (3H, d, J=1.0 Hz), 3.76 (3H, s), 4.52 (2H, s), 6.26 (1H, s), 6.87 (2H, d, J=9.0 Hz),

7.20 (1H, d, J=9.0 Hz), 7.29 (2H, d, J=9.0 Hz), 8.45 (1H, br s)

2-136
3.58 (3H, d, J=1.0 Hz), 3.93 (3H, s), 6.33 (1H, s), 7.26 (1H, d, J=9.1 Hz), 7.54 (3H, m),

7.95 (2H, d, J=8.3 Hz), 8.14 (1H, s), 8.28 (1H, s)

2-137
3.55 (3H, s), 6.37 (1H, s), 6.40 (1H, d, J=15.5 Hz), 7.16 (1H, d, J=8.6 Hz), 7.19 (1H, br

s), 7.29 (1H, dd, J=8.5, 1.9 Hz), 7.38 (3H, m), 7.48 (2H, m), 7.70 (1H, d, J=15.5 Hz),

7.99 (1H, br s)

2-139
3.19 (3H, s), 5.98 (1H, s), 7.17 (1H, dd, J=8.0, 1.2 Hz), 7.2-7.6 (7H, m), 7.7-7.9 (6H,

m), 7.93 (2H, dd, J=8.6, 1.7 Hz), 8.53 (2H, br s)

2-140
3.56 (3H, d, J=1.0 Hz), 6.40 (1H, s), 7.42 (1H, d, J=8.3 Hz), 7.60 (3H, m), 7.78 (1H, dd,

J=8.6, 1.8 Hz), 7.92 (3H, m), 8.01 (1H, br s), 8.29 (1H, br s), 8.38 (1H, d, J=1.6 Hz)

2-141
3.59 (3H, s), 6.41 (1H, s), 6.42 (1H, d, J=15.5 Hz), 7.16 (1H, br s), 7.38 (4H, m), 7.52

2H, m , 7.59 1H, dd, J=8.2, 1.7 Hz , 7.75 1H, d, J=15.5 Hz , 8.40 1H, br s

2-142
3.47 (3H, s), 6.29 (1H, s), 7.1-7.9 (11H, m), 8.21 (1H, s)

2-143
3.55 (3H, d, J=1.0 Hz), 3.87 (3H, s), 6.38 (1H, s), 6.89 (1H, dd, J=8.9, 2.9 Hz), 7.18

(1H, d, J=8.9 Hz), 7.58 (3H, m), 7.79 (1H, dd, J=8.6, 1.7 Hz), 7.90 (4H, m), 8.29 (1H,

br s)

2-144
3.54 (3H, d, J=1.0 Hz), 3.87 (3H, s), 6.25 (1H, s), 7.60 (3H, m), 7.8-8.0 (5H, m), 8.30

(1H,brs)

2-145
3.57 (3H, d, J=1.0 Hz), 6.38 (1H, s), 7.12 (1H, dd, J=9.3, 2.2 Hz), 7.59 (2H, m), 7.78

(1H, dd, J=8.6, 1.8 Hz), 7.8-8.0 (5H, m), 8.28 (1H, br s)

2-146
1.27 (1.5H, t, J=7.1 Hz), 1.27 (1.5H, t, J=7.1 Hz), 1.62 (3H, d, J=6.7 Hz), 3.53 (3H, s),

4.23 (2H, m), 4.79 (1H, m), 6.35 (1H, s), 6.85 (1H, m), 7.15 (1H, d, J=9.0 Hz), 7.5-7.6

(3H, m), 7.77 (1H, dd, J=8.6, 1.6 Hz), 7.89 (4H, m), 8.26 (1H, s)

2-147
0.84 (2H, m), 1.03 (2H, m), 1.50 (1H, m), 3.58 (3H, d, J=1.0 Hz), 6.36 (1H, s), 7.05

(1H, d, J=7.8 Hz), 7.35 (1H, br s), 7.88 (1H, br s)

2-148
3.57 (3H, d, J=1.0 Hz), 6.39 (1H, s), 6.61 (1H, t, J=72.7 Hz), 6.88 (1H, dd, J=10.2,

2.6 Hz), 7.59 (2H, m), 7.76 (2H, m), 7.90 (3H, m), 8.05 (lh, br s), 8.27 (1H, s)

2-149
3.56 (3H, d, J=1.0 Hz), 6.38 (1H, s), 7.43 (1H, d, J=8.4 Hz), 7.6 (3H, m), 7.78 (1H, dd,

J=8.6, 1.8 Hz), 7.90 (3H, m), 8.09 (1H, br s), 8.28 (2H, s)

2-150
3.41 (3H, d, J=1.1 Hz), 3.71 (1H, s), 3.80 (2H, s), 6.11 (1H, s), 7.1-7.4 (6H, m), 8.88

(1H, s)

2-151
3.50 (3H, d, J=1.0 Hz), 3.58 (3H, s), 3.62 (2H, s), 6.15 (1H, s), 7.14 (1H, d, J=9.1 Hz),

7.2-7.4 (6H, m)

2-152
3.58 (3H, s), 3.90 (3H, s), 4.14 (3H, s), 6.25 (1H, s), 7.21 (1H, d, J=9.0 Hz), 7.26 (1H,

s), 7.44 (1H, m), 7.55 (1H, m), 7.76 (1H, m), 7.85 (1H, m), 8.58 (1H, s), 10.10 (1H, s)

2-153
3.57 (3H, s), 3.91 (3H, s), 4.10 (3H, s), 6.22 (1H, s), 7.22 (1H, d, J=9.0 Hz), 7.23 (1H,

s), 7.64 (2H, m), 7.91 (1H, m), 7.99 (1H, d, J=8.7 Hz), 8.22 (1H, m), 10.20 (1H, s)

2-154
3.56 (3H, s), 3.87 (3H, s), 4.55 (2H, s), 6.27 (1U, s), 6.82 (1H, d, J 8.8 Hz), 7.21 (2H,

m), 7.44 (1H, s), 8.72 (1H, s)

2-155
2.52 (3H, s), 3.56 (3H, s), 3.90 (3H, s), 6.31 (1H, s), 7.20 (1H, d, J=9.0 Hz), 7.55 (2H,

m), 7.81 (4H, m), 10.15 (1H, s)

2-156
2.55 (3H, s), 3.52 (3H, s), 3.83 (3H, s), 6.22 (1H, s), 7.20 (1H, d, J=9.0 Hz), 7.41 (1H,

m), 7.66 (1H, s), 7.79 (3H, m), 8.15 (1H, s), 8.26 (1H, s)

2-157
3.58 (3H, s), 3.94 (3H, s), 6.35 (1H, s), 7.25 (1H, d, J=9.0 Hz), 7.61 (2H, m), 7.78

(2H, s), 7.92 (2H, m), 8.04 (1H, s)

2-158
3.55 (3H, s), 3.84 (3H, s), 6.24 (1H, s), 7.22 (1H, d, J=9.0 Hz), 7.42 (1H, m), 7.90

(3H, m), 8.14 (1H, s), 8.32 (2H, m)

2-159
3.56 (3H, s), 3.96 (3H, s), 6.35 (1H, s), 7.13 (1H, d, J=9.0 Hz), 7.70 (6H, m), 8.15

(1H, s)

2-160
3.55 (3H, s), 3.86 (3H, s), 6.24 (1H, s), 7.22 (1H, d, J=9.0 Hz), 7.74 (4H, m), 7.92

(4H, m), 8.10 (4H, m)

2-161
3.55 (3H, s), 3.86 (3H, s), 6.25 (1H, s), 7.23 (2H, m), 7.57 (1H, m), 7.72 (1H, m), 7.91

(2H, m), 8.18 (1H, s)

2-162
3.55 (3H, s), 3.85 (3H, s), 6.24 (1H, s), 7.23 (1H, d, J=9.0 Hz), 7.49 (1H, m), 7.69

1H, m , 7.90 3H, m , 8.13 1H, sm , 8.34 2H, m

2-163
3.56 (3H, s), 3.86 (3H, s), 6.25 (1H, s), 7.25 (1H, d, J=9.0 Hz), 7.66 (1H, m), 8.05

(3H, m), 8.19 (1H, m), 8.32 (1H, d, J=8.7 Hz), 8.39 (1H, s)

2-164
3.35 (3H, s), 3.89 (3H, s), 4.10 (2H, s), 6.37 (1H, s), 7.25 (1H, d, J=9.0 Hz), 8.33 (1H,

s)

2-165
3.10 (2H, s), 3.57 (3H, s), 3.90 (2H, s), 4.11 (3H, s), 6.30 (1H, s), 7.20 (1H, d, J=9.0

Hz), 7.27 (5H, s), 8.65 (1H, s)

2-166
3.57 (3H, s), 3.90 (SH, s), 4.10 (2H, s), 6.37 (1H, s), 7.25 (1H, d, J=9.0 Hz), 8.15 (1H,

s)

2-167
3.50 (3H, s), 3.55 (3H, s), 3.69 (2H, s), 6.16 (1H, s), 7.18 (1H, d, J=9.0 Hz), 7.28 (5H,

m), 8.33 (1H, s)

2-168
2.14 (3H, s), 3.20 (2H, s), 3.56 (3H, s), 3.88 (3H, s), 6.29 (1H, s), 7.20 (1H, d, J=9.0

Hz), 8.67 (1H, s)

2-169
3.36 (3H, s), 3.52 (3H, s), 3.79 (2H, m), 5.96 (1H, s), 7.17 (1H, d, J=9.0 Hz), 7.49

(3H, m), 7.75 (3H, m), 8.75 (1H, m)

2-170
1.28 (3H, t, J=7.1 Hz), 3.32 (2H, s), 3.36 (2H, s), 3.55 (3H, s), 3.88 (3H, s), 4.18 (2H,

g, J=7.1 Hz), 6.30 (1H, s), 7.21 (1H, d, J=9.0 Hz), 8.33 (1H, s)

2-171
1.26 (3H, t, J=7.1 Hz), 2.62 (2H, m), 2.85 (2H, m), 3.26 (2H, s), 3.56 (3H, s), 3.88

(3H, s), 4.15 (2H, g, J=7.1 Hz), 6.35 (1H, s), 7.21 (1H, d, J=9.0 Hz), 8.66 (1H, s)

2-172
1.27 (3H, t, J=7.4 Hz), 2.60 (2H, m), 3.27 (2H, s), 3.56 (3H, s), 3.88 (3H, s), 6.28

1H, s , 7.20 1H, d, J=9.0 Hz , 8.73 1H, s

2-173
1.28 (6H, m), 2.97 (1H, m), 3.29 (2H, s), 3.57 (3H, s), 3.87 (3H, s), 6.28 (1H, s), 7.20

(1H, d, J=9.0 Hz), 8.79 (1H, s)

2-174
0.99 (3H, m), 1.60 (2H, m), 2.53 (2H, m), 3.25 (2H, s), 3.57 (3H, s), 3.90 (3H, s), 6.28

(1H, s), 7.20 (1H, d, J=9.0 Hz), 8.80 (1H, s)

2-175
3.53 (3H, q, J=3.9 Hz), 3.79 (3H, s), 6.30 (1H, s), 6.90 (1H, d, J15.7 Hz), 7.36 (3H,

m), 7.53 (4H, m), 9.84 (1H, s)

2-176
3.41 (3H, s), 3.79 (3H, s), 6.23 (1H, s), 7.58 (1H, d, J=8.5 Hz), 6.84 (1H, d, J=15.6

Hz), 6.90 (1H, d, J=15.6 Hz), 7.35 (6H, m), 7.50 (4H, m), 7.79 (1H, d, J=15.6 Hz),

7.82 (1H, d, J=15.6 Hz)

2-177
3.50 (3H, s), 3.79 (3H, s), 6.23 (1H, s), 7.30 (1H, d, J=8.7 Hz), 7.56 (2H, m), 7.85 (4H,

m), 8.31 (1H, s), 8.40 (1H, s)

2-178
3.21 (3H, s), 3.88 (3H, s), 6.04 (1H, s), 7.59 (SH, m), 7.87 (8H, m), 8.50 (1H, s), 8.57

(1H, s)

2-179
3.57 (3H, s), 4.03 (3H, s), 6.29 (1H, s), 6.52 (1H, d, J=15.6 Hz), 7.28 (1H, d, J 8.4

Hz), 7.38 (3H, m), 7.47 (2H, m), 7.62 (1H, d, J=15.6 Hz), 7.80 (1H, s)

2-180
3.50 (3H, s), 4.00 (3H, s), 6.22 (1H, s) 7.27 (1H, d, J=8.5 Hz), 7.59 (2H, m), 7.87

(4H, m), 8.32 (1H, s), 8.38 (1H, s)

2-181
3.52 (3H, s), 3.80 (3H, s),6.23 (1H, s), 7.17 (1H, d, J=9.1 Hz), 7.58 (2H, m), 7.87

(4H, m), 8.26 (1H, d, J=55.6 Hz), 8.31 (1H, s)

2-182
3.53 (3H, q, J=0.8 Hz), 3.80 (3H, s), 5.41 (1H, d, J=10.9 Hz), 5.87 (1H, d, J=17.6 Hz),

6.23 (1H, s), 6.75 (1H, dd, J=17.6, 10.9 Hz), 7.37 (1H, d, J=8.8 Hz), 7.47 (2H, d,

J=8.3 Hz), 7.73 (2H, d, J=8.3 Hz), 8.00 (1H, s)

2-183
3.28 (3H, s), 3.80 (3H, s), 5.34 (1H, d, J=11.0 Hz), 5.35 (1H, d, J=11.0 Hz), 5.80 (1H,

d, J=17.6 Hz), 5.81 (1H, d, J=17.6 Hz), 6.03 (1H, s), 6.67 (1H, dd, J=17.6, 11.0 Hz),

Hz), 7.3-7.6 (10H, m), 7.77 (1H, d, J=15.5 Hz), 7.82 (1H, d, J=15.5 Hz)

2-187
3.78 (3H, s), 3.78 (2H, s), 4.58 (2H, s), 4.70 (2H, s), 6.07 (1H, s), 7.14 (1H, d, J=9.1

Hz), 7.35 (5H, m), 8.58 (1H, s)

2-188
4.67 (2H, s), 4.76 (2H, d J=5.3 Hz), 6.10 (1H, s), 7.26 (1H, d, J=8.8 Hz), 7.57 (2H, m),

7.77 (1H, m), 7.87 (3H, s), 8.19 (1H, m), 8.30 (1H, s)

2-189
1.28 (3H, t, J=7.1 Hz), 3.55 (3H, s), 4.26 (2H, q, J=7.1 Hz), 4.82 (2H, s), 6.22 (1H, s),

7.21 (1H, d, J=8.8 Hz), 7.57 (2H, m), 7.94 (4H, m), 8.52 (1H, s), 10.46 (1H, s)

2-190
1.30 (3H, t, J=7.1 Hz), 3.58 (3H, s), 4.31 (2H, q, J=7.1 Hz), 4.78 (2H, s), 6.27 (1H, s),

6.67 (1H, d, J=15.7 Hz), 7.15 (1H, d, J=8.9 Hz), 7.38 (3H, m), 7.95 (2H, m), 7.62

(1H, d, J=15.7 Hz)

2-191
1.27 (3H, t, J=7.1 Hz), 1.29 (3H, t, J=7.1 Hz), 1.69 (3H, d, J=7.0 Hz), 1.70 (3H, d,

J=7.0 Hz), 3.56 (3H, s), 3.63 (3H, s), 4.25 (4H, m), 4.95 (2H, m), 6.12 (1H, s), 6.41

(1H, s), 7.19 (2H, d, J=8.9 Hz), 7.56 (4H, m), 7.95 (8H, m), 8.54 (1H, s), 8.69 (1H, s),

10.41 (1H, s), 10.65 (1H, s)

2-192
4.95 (2H, s), 6.23 (1H, s), 7.25 (1H, d, J=10.0 Hz), 7.59 (2H, m), 7.87 (4H, s), 8.27

(1H, m), 9.28 (1H, s)

2-193
3.56 (3H, q, J=0.5 Hz), 6.40 (1H, s), 7.16 (1H, dd, J=8.7, 2.6 Hz), 7.34 (1H, d, J=8.7

Hz), 7.5-7.7 (3H, m), 7.7-8.0 (6H, m), 8.10 (1H, dd, J=8.6, 1.6 Hz), 8.18 (1H, br d),

8.27 (1H, brs)

2-194
3.53 (3H, q, J=0.8 Hz), 6.36 (1H, s), 7.25 (1H, d, J=9.1 Hz), 7.60 (2H, m), 7.76 (1H, dd,

J=8.7, 1.8 Hz), 7.90 (3H, m), 8.21 (1H, s), 8.33 (1H, d, J=1.5 Hz)

2-195
2.45 (1H, d, J=2.4 Hz), 3.55 (3H, q, J=0.8 Hz), 4.77 (2H, dd, J=6.1, 2.4 Hz), 6.23 (1H,

s), 7.23 (1H, d, J=9.0 Hz), 7.59 (2H, m), 7.90 (4H, m), 8.32 (1H, d, J=0.7 Hz), 8.36

(1H, s)

2-196
1.28 (3H, t, J=7.1 Hz), 3.51 (3H, q, J=0.5 Hz), 4.05 (2H, q, J=7.1 Hz), 6.25 (1H, s),

7.57 (2H, m), 7.88 (4H, m), 8.31 (1H, s), 8.38 (1H, s)

2-197
1.20 (3H, t, J=6.2 Hz), 1.29 (3H, t, J=6.2 Hz), 3.54 (3H, q, J=0.6 Hz), 4.43 (1H, q,

J=6.2 Hz), 6.23 (1H, s), 7.59 (2H, m), 7.80 (1H, m), 7.90 (3H, s), 8.20 (1H, s), 8.30

(1H, s)

2-198
0.89 (3H, t), 1.25 (4H, m), 1.53 (2H, m), 2.23 (2H, m), 3.56 (3H, q, J=0.9 Hz), 3.83

(3H, s), 6.30 (1H, s), 7.20 (1H, d, J=9.0 Hz), 7.58 (1H, br s)

2-199
3.54 (3H, q, J=0.7 Hz), 6.29 (1H, s), 6.73 (1H, dd, J=8.3, 4.5 Hz), 7.43 (1H, d, J=9.9

Hz), 7.57 (2H, m), 7.86 (5H, m), 8.21 (1H, dd, J=8.3, 1.7 Hz), 8.37 (1H, dd, 14.5,

1.7 Hz), 8.45 (1H, br s)

2-200
3.52 (3H, q, J=1.0 Hz), 4.82 (2H, d, J=‡Hz)~ 6.26 (1H, s), 7.31 (1H, d, J=8.8 Hz),

7.59 (2H, m), 7.93 (5H, m), 8.35 (1H, d, J=1.1 Hz)

2-201
2.43 (3H, s), 3.54 (3H, q, J=0.9 Hz), 6:36 (1H, s), 7.18 (2H, m), 7.59 (2H, m), 7.8 (6H,

m), 8.28 (1H, s)

2-202
3.51 (3H, s), 3.87 (3H, s), 6.24 (1H, s), 7.12 (1H, d, J=8.8 Hz), 7.42 (1H, d, J=8.8 Hz),

7.59 (2H, m), 7.81 (1H, m), 7.91 (3H, m), 8.06 (1H, s), 8.31 (1H, s)

2-203
3.53 (3H, s), 6.34 (1H, s), 7.17 (1H, m), 7.26 (1H, m), 7.57 (2H, m), 7.73 (1H, 2d,

J=1.6 Hz, 8.6 Hz), 7.88 (4H, m), 8.18 (1H, s), 8.23 (1H, s)

2-204
0.78 (2H, m), 0.97 (2H, m), 1.4 (1H, m), 3.55 (3H, s), 6.34 (1H, s), 7.12 (1H, m), 7.24 (1H,

m), 7.43 (1H, m), 7.85 (1H, broad)

2-205
3.36 (3H, s), 6.22 (1H, s), 7.24 (1H, d, J=8.4 Hz), 7.41 (2H, m), 7.65 (4H, m), 7.86 (1H, 2d,

J=2.0 Hz, 8.4 Hz), 8.0-8.2 (4H, m), 8.55 (1H, s)

2-206
0.76-0.93 (4H, m), 1.50 (1H, m), 3.55 (3H, s), 3.85 (3H, s)6.31 (1H, s), 7.19 (1H, d,

J=8.9 Hz), 7.6 (1H, broad)

2-207
3.44 (3H, s), 3.82 (3H, s), 6.24 (1H, s), 7.32 (1H, d, J=8.3 Hz), 7.48 (2H, m), 7.6-7.8

(5H, m), 8.10 (1H, s), 8.23 (1H, s), 8.78 (1H , s)

3-1
2.74 (3H, d, J=4.7 Hz), 2.76 (3H, d, J=4.7 Hz), 3.53 (3H, br q, J=1.3 Hz), 3.83 (3H, s),

6.3 (1H, s), 6.66 (1H, m), 7.35 (1H, m), 7.39 (1H, d, J=8.8 Hz)

3-2
0.76 (3H, t, J=7.4 Hz), 1.28 (2H, m), 2.96 (2H, m), 3.57 (3H, s), 3.84 (3H, s), 5.22 (1H,

m), 6.33 (1H, s), 6.70 (1H, s), 7.14 (1H, d, 19.0 Hz)

3-3
1.22 (12H, m), 3.54 (3H, br s), 3.83 (3H, s), 3.86 (2H, m), 6.25 (1H, s), 6.45 (1H, s),

7.04 1H,d,J=9.l Hz

3-4
3.52 (3H, s), 3.76 (3H, s), 6.30 (1H, s), 6.90-7.25 (6H, m), 7.37 (1H, s), 7.61 (1, s)

3-6
3.46 (3H, s), 3.77 (3H, s), 4.19 (2H, m), 5.75 (1H, m), 6.19 (1H, s), 6.90-7.30 (7H, m)

3-7
(rotameric mixture) 1.16 (3H, d, J=6.8 Hz), 1.23 (3H, d, J=6.8 Hz), 3.47 (3H, s), 3.53

(3H, s), 3.77 (6H, s), 4.72 (2H, m), 5.72 (2H, m), 6.11 (1H, s), 6.33 (1H, s), 6.95-7.35

(14H, m)

3-8
2.99 (3H, s), 3.55 (3H, s), 3.63 (3H, s), 4.38 (1H, d, J=16.2 Hz), 4.58 (1H, d, J=16.2

Hz),6.27 (1H, s), 6.58 (1H, s), 7.12 (1H, d, J=9.1 Hz), 7.19 (2H, m), 7.33 (3H, m)

3-9
2.31 (3H, s), 3.47 (3H, s), 3.79 (3H, s), 4.17 (2H, m), 5.58 (1H, m), 6.18 (1H, s), 6.74

(1H, s), 6.90-7.15 (5H, m)

3-10
(CDCl3+CD3OD) 3.52 (3H, br s), 3.82 (3H, s), 4.29 (2H, m), 6.23 (1H, s), 6.50 (1H,

m), 6.70-6.85 (2H, m), 7.14 (1H, d, J=9.0 Hz), 7.22 (1H, m)

3-11
2.57 (2H, m), 3.21 (2H, m), 3.54 (3H, s), 3.74 (3H, s), 5.51 (1H, m), 6.27 (1H, s), 7.00-

7.30 (7H, m)

3-12
(CDCl3+CD3OD) 1.72 (2H, m), 2.58 (2H, m), 3.11 (2H, m), 3.53 (3H, s), 3.85 (3H, s),

5.78 (1H, m), 6.28 (1H, s), 7.05-7.35 (7H, m)

3-13
3.55 (3H, s), 3.81 (3H, s), 6.35 (1H, s), 7.08 (1H, m), 7.1 (1H, d, J=9.0 Hz), 7.25-7.45

(3H, m), 7.55-7.80 (SH, m)

3-23
3.59 (3H, s), 3.64 (3H, s), 4.62 (1H, d, J=14.8 Hz), 4.98 (1H, d, J=14.8 Hz), 6.33 (1H,

s), 6.47 (1H, s), 6.95-7.50 (11H, m)

3-24
3.40 (3H, s), 3.78 (3H, s), 5.88 (1H, m), 5.98 (1H, m), 6.12 (1H, s), 7.00-7.30 (12H,

m)

3-26
3.56 (3H, s), 3.89 (3H, s), 4.86 (2H, s), 6.50 (1H, s), 6.33 (1H, s), 7.25 (1H, d, J=

9.0 Hz)

4-1
3.54 (3H, s), 3.64 (3H, s), 3.84 (3H, s), 6.24 (1H, s), 7.25 (1H, s)

4-2
2.87 (3H, s), 2.96 (3H, s), 3.53 (3H, s), 3.63 (3H, s), 6.3 (1H, s), 6.85 (1H, d, J=8.9 Hz)

4-3
3.51 (3H, d, J=1.0 Hz), 3.95 (3H, s), 6.35 (1H, s), 6.81 (1H, br s), 7.03 (2H, m), 7.22

(1H, d, J=9.0 Hz), 7.23 (1H, m), 7.34 (2H, m)

4-4
2.22 (6H, s), 3.50 (3H, d, J=0.5 Hz), 3.94 (3H, ~), 6.35 (1H, s), 6.72 (1H, dd, J=8.2, 2.5

Hz), 6.77 (1H, d, J=2.5 Hz), 6.84 (1H, br s), 7.07 (1H, d, J=8.2 Hz), 7.20 (1H, d,

19.0 Hz)

4-5
3.49 (3H, d, J=1.0 Hz), 3.83 (3H, s), 5.05 (1H, d, J=12.3 Hz), 5.12 (1H, d, J12.3 Hz),

6.20 (1H, s), 6.68 (br s), 7.15 (1H, d, J=9.0 Hz), 7.26-7.37 (5H, m)

4-7
3.50 (3H, br s), 3.82 (3H, s), 5.01 (1H, d, J=12.2 Hz), 5.07 (1H, d, J=12.2 Hz), 6.20

(1H, s), 6.69 (1H, br s), 7.02 (2H, m), 7.17 (1H, d, J=9.0 Hz), 7.28 (2H, m)

4-10
3.48 (3H, br s), 3.99 (3H, s), 6.37 (1H, s), 6.98 (1H, br s), 7.14 (1H, dd, J=8.9, 2.3 Hz),

7.24 (1H, d, J=9.0 Hz), 7.43-7.51 (3H, m), 7.37 (7.84 (3H, m)

4-11
1.20-1.85 (10H, m), 3.56 (3H, br s), 3.86 (3H, s), 4.57 (1H, m), 6.32 (1H, s), 6.53 (1H,

s), 7.17 (1H, d, J=9.0 Hz)

4-13
3.54 (3H, d, J=1.1 Hz), 3.78 (3H, s), 6.33 (1H, s), 7.15 (1H, br s), 7.17 (1H, d, J=9.0

Hz), 7.43-7.52 (5H, m)

4-23
3.50 (3H, s), 4.75 (2H, m), 5.13 (2H, m), 6.24 (1H, s), 6.54 (1H, s), 7.25 (1H, d, J=8.7

Hz), 7.35 (5H, m)

4-24
3.57 (3H, s), 3.86 (3H, s), 5.37 (2H, m), 6.30 (1H, s), 6.70 (1H, s), 7.16 (1H, d, J=9.0

Hz), 7.20-7.40 (3H, m)

4-25
2.06 (6H, s), 2.25 (3H, s), 3.52 (3H, s), 3.94 (3H, s), 6.32 (1H, s), 6.83 (2H, s), 7.09

(1H, br s), 7.20 (1H, d, J=9.0 Hz)

4-26
2.25 (6H, s), 3.51 (3H, s), 3.83 (3H, s), 5.01 (2H, m), 6.21 (1H, s), 6.65 (1H, br s),

7.00-7.20 (4H, m)

4-27
1.30 (9H, s), 3.50 (3H, s), 3.96 (3H, s), 6.32 (1H, s), 6.84 (1H, m), 7.10-7.40 (5H, m)

4-28
3.43 (3H, s), 3.82 (3H, s), 5.25 (2H, m), 6.12 (1H, s), 6.73 (1H, br s), 7.16 (1H, d,

J=9.0 Hz), 7.30-7.55 (3H., m), 7.70-7.85 (4H, m)

4-29
3.57 (3H, s), 3.85 (3H, s), 5.17 (1H, d, J=11.9 Hz), 5.27 (1H, d, J=11.9 Hz), 6.28 (1H,

s), 6.64 (1H, br s), 6.92 (2H, m), 7.17 (1H, d, J=9.0 Hz), 7.34 (1H, m)

4-30
3.49 (3H, s), 3.84 (3H, s), 4.99 (1H, d, J=12.6 Hz), 5.06 (1H, d, J=12.6 Hz), 6.23 (1H,

s), 6.64 (1H, br s), 7.00-7.25 (4H, m)

4-31
1.23 (3H, t, J=7.6 Hz), 2.64 (2H, q, J=7.6 Hz), 3.50 (3H, d, J0.9 Hz), 3.83 (3H, s), 5.02

(1H, d, J=12.1 Hz), 5.08 (1H, d, J=12.1 Hz), 6.22 (1H, s), 6.67 (1H, br s), 7.10-7.30

(5H, m)

4-32
3.52 (3H, s), 3.85 (3H, s), 5.03 (2H, m), 6.24 (1H, s), 6.64 (1H, br s), 7.10-7.21 (2H,

m), 7.3 8-7.44 (2H, m)

4-33
3.52 (3H, d, J=0.8 Hz), 3.86 (3H, s), 5.22 (1H, d, J=13.2 Hz), 5.31 (1H, d, J=13.2 Hz),

6.22 (1H, s), 6.71 (1H, br s), 7.18 (1H, d, J=9.0 Hz), 7.40-7.60 (3H, m), 7.68 (1H, m)

4-34
3.54 (3H, s), 3.88 (3H, s), 5.49 (2H, s), 6.28 (1H, s), 7.24 (1H, d, J=9.0 Hz), 7.45-7.70

(3H, m), 8.09 (1H, m)

4-35
3.53 (3H, s), 3.83 (3H, s), 3.84 (3H, s), 5.12 (1H, d, J=12.5 Hz), 5.18 (1H, d, J=12.5

Hz), 6.24 (1H, s), 6.72 (1H, br s), 6.80-6.95 (2H, m), 7.15 (1H, d, J=9.0 Hz), 7.20-

7.40 (2H, m)

4-36
3.51 (3H, d, J=1.0 Hz), 3.87 (3H, s), 5.17 (1H, d, J=13.5 Hz), 5.24 (1H, d, J=13.5 Hz),

6.24 (1H, s), 6.89 (1H, br s), 7.18 (1H, d, J=9.0 Hz), 7.20-7.29 (2H, m), 7.68 (1H, m),

8.58 (1H, m)

4-37
2.31 (6H, s), 3.52 (3H, s), 3.84 (3H, s), 5.01 (2H, m), 6.23 (1H, s), 6.65 (1H, br s), 6.92

(2H, br s), 6.96 (1H, br s), 7.16 (1H, d, J=9.0 Hz)

4-38
2.25 (3H, s), 2.31 (3H, s), 3.53 (3H, d, J=0.9 Hz), 3.84 (3H, s), 5.04 (1H, d, J=12.2

Hz), 5.09 (1H, d, J=12.2 Hz), 6.25 (1H, s), 6.65 (1H, br s), 7.08 (3H, m), 7.16 (1H, d,

J=9.0 Hz)

4-39
3.53 (3H, br s), 3.86 (3H, s), 5.14 (2H, m), 6.27 (1H, s), 6.70 (1H, br s), 6.90-7.10 (3H,

m), 7.19 (1H, d, J=9.0 Hz)

4-40
3.51 (3H, d, J=0.9 Hz), 3.81 (3H, s), 3,82 (3H, s), 4.98 (1H, d, J=12.0 Hz), 5.05 (1H, d,

J=12.0 Hz), 6.22 (1H, s), 6.63 (1H, br s), 6.87 (2H, m), 7.16 (1H, d, J=9.0 Hz), 7.25

(2H, m)

4-41
3.53 (3H, d, J=0.9 Hz), 3.83 (3H, s), 4.95 (1H, d, J=12.l Hz), 5.01 (1H, d, k12.1 Hz),

5.96 (2H, s), 6.25 (1H, s~, 6.63 (1H, br s), 6.78 (3H, m), 7.17 (1H, d, J=9.0 Hz)

4-42
1.24 (6H, d, J=6.9 Hz), 2.91 (1H, m), 3.50 (3H, d, J=0.9 Hz), 3.82 (3H, s), 5.02 (1H, d,

J=12.1 Hz), 5.08 (1H, d, J=12.1 Hz), 6.23 (1H, s), 6.70 (1H, br s), 7.15 (1H, d, J=9.0

Hz), 7.22 (4H, m)

4-43
3.48 (3H, d, J=1.0 Hz),3.85 (3H, s), 5.10 (1H, d, J=13.0 Hz), 5.18 (1H, d, J13.0 Hz),

6.18 (1H, s), 6.72 (1H, br s), 7.18 (1H, d, J=9.0 Hz), 7.41 (2H, m), 7.60 (2H, m)

4-44
3.50 (3H, d, J=1.0 Hz), 3.85 (3H, s), 5.05 (1H, d, J=12.8 Hz), 5.12 (1H, d, J=12.8 Hz),

6.22 (1H, s), 6.68 (1H, br s), 6.95-7.10 (3H, m), 7.18 (1H, d, J=9.0 Hz), 7.30 (1H, m)

4-45
3.49 (3H, d, J=0.9 Hz), 3.82 (3H, s), 5.05 (1H, d, J=12.6 Hz), 5.11 (1H, d, J=12.6 Hz),

6.21 (1H, s), 6.79 (1H, br s), 7.10-7.20 (3H, m), 7.31-7.36 (2H, m)

4-46
0.89 (4H, br s), 3.54 (3H, d, J=1.0 Hz), 3.75 (3H, s), 4.15 (2H, m), 6.28 (1H, s), 6.56

(1H, br s), 7.15 (1H, d, J=9.0 Hz), 7.26 (SH, m)

4-47
1.50 (3H, d, J=6.6 Hz), 3.48 (3H, s), 3.84 (3H, s), 5.69 (1H, q, J=6.6 Hz), 5.97 (1H, s),

6.73 (1H, br s), 7.14 (1H, d, J=9.0 Hz), 7.20-7.40 (5H, m)

4-48
3.57 (3H, d, J=0.9 Hz), 3.86 (3H, s), 5.19 (1H, d, J=12.3 Hz), 5.25 (1H, d, J=12.3 Hz),

6.31 (1H, s), 6.61 (1H, br s), 7.20 (1H, d, J=9.0 Hz)

4-49
3.52 (3H, d, J=0.9 Hz), 5.22 (2H, s), 6.33 (1H, s), 6.53 (1H, br s), 7.00-7.45 (7H, m)

4-50
3.54 (3H, s), 6.36 (1H, s), 6.84 (1H, br s), 7.05-7.45 (8H, m)

4-51
2.20 (3H, s), 3.45 (3H, d, J=0.8 Hz), 5.10 (2H, m), 6.22 (1H, s), 6.90-7.10 (2H, m),

7.15-7.27 (3H, m)

4-52
2.42 (3H, s), 3.52 (3H, s), 6.37 (1H, s), 7.00-7.40 (6H, m)

4-53
2.21 (6H, s), 3.50 (3H, hr d J=0.5 Hz), 3.94 (3H, s), 6.35 (1H, s), 6.73 (2H, m), 6.84 (1H,

br s), 7.07 (1H, d, J=8.1 Hz), 7.20 (1H, d, J=9.0 Hz)

4-54
3.53 (3H, hr d, J=1.1 Hz), 3.85 (3H, s), 5.16 (1H, d, J=12.9 Hz), 5.25 (1H, d,

J=12.9 Hz), 6.24 (1H, s), 6.71 (1H, br s), 7.18 (1H, d, J=9.0 Hz), 7.2-7.4 (4H, m)

4-55
2.11 (6H, s), 3.52 (3H, s), 3.95 (3H, s), 6.33 (1H, s), 7.03 (3H, br s), 7.08 (1H, br s),

7.22 (1H, d, J=9.0 Hz)

4-56
3.5 1 (3H, hr d, J=1.l Hz), 3.83 (3H, s), 5.07 (1H, d, J=12.3 Hz), 5.14 (1H, d, J=12.3 Hz),

6.23 (1H, s), 6.68 (1H, br s), 7.1-7.3 (4H, m)

4-57
2.88 (2H, t, J=6.5 Hz), 3.55 (3H, s), 3.77 (3H, s), 4.25 (2H, t, J=6.5 Hz), 6.29 (1H, s),

6.52 (1H, br s), 7.1-7.4 (6H, m)

4-58
3.52 (3H, hr d, J=1.0 Hz), 3.83 (3H, s), 3.84 (3H, s), 5.12 (1H, d, J=12.5 Hz), 5.17 (1H, d,

J=12.5 Hz), 6.24 (1H, s), 6.71 (1H, br s), 6.90 (2H, m), 7.15 (1H, d, J=9.0 Hz), 7.2-

7.3 (2H, m)

4-59
3.50 (3H, s), 3.74 (6H, s), 6.32 (1H, s), 6.56 (2H, d, 18.S Hz), 7.11 (1H, t, J8.S Hz),

7.14 (1H, br s), 7.18 (1H, d, J=9.0 Hz)

4-60
2.34 (3H, s), 3.50 (3H, br d, J=1.1 Hz), 3.83 (3H, s), 5.00 (1H, d, J=12.1 Hz), 5.07 (1H,

d, J=12.1 Hz), 6.20 (1H, s), 6.64 (1H, br s), 7.1-7.2 (5H, m)

4-61
3.50 (3H, hr d, J=1.0 Hz), 3.83 (3H, s), 5.01 (1H, d, J=12.5 Hz), 5.07 (1H, d, J=12.5 Hz),

6.20 (1H, s), 6.66 (1H, br s), 7.17 (1H, d, J=9.0 Hz), 7.2-7.3 (4H, m)

4-62
3.53 (3H, hr d, J=1.0 Hz), 3.85 (3H, s), 5.12 (1H, d, J=13.0 Hz), 5.20 (1H, d, J=13.0 Hz),

6.25 (1H, s), 6.67 (1H, br s), 7.19 (1H, d, J=9.0 Hz), 7.2-7.3 (2H, m), 7.41 (1H, d,

J=1.9 Hz)

4-63
3.51 (3H, hr d, J=1.0 Hz), 3.83 (3H, s), 3.88 (3H, s), 3.89 (3H, s), 4.99 (1H, d,

J=12.0 Hz), 5.04 (1H, d, J=12.0 Hz), 6.20 (1H, s), 6.59 (1H, br s), 6.8-6.9 (3H, m),

7.16 (1H, d, J=9.0 Hz)

4-64
3.51 (3H, br d, J=0.9 Hz), 3.86 (3H, s), 5.15 (1H, d, J=13.5 Hz), 5.21 (1H, d, J=13.5 Hz),

6.21 (114, s), 6.68 (1H, br s), 7.21 (1H, d, J=9,0 Hz), 7.46 (2H, d, J=8.7 Hz), 8.21 (2H,

d, J=8.7 Hz)

4-65
3.50 (3H, br d, J1.0 Hz), 3.81 (3H, s), 3.85 (3H, s), 5.02 (1H, d, J=12.511z), 5.10 (1H,

12.5 Hz), 6.21 (1H, s), 6.67 (1H, br s), 6.8-6.9 (3H, m), 7.17 (1H, d, J=9.0 Hz),

7.25 (1H, t, J=7.7 Hz)

4-66
3.53 (3H, br d, J=0.9 Hz), 3.82 (3H, s), 4.11 (2H, s), 6.29 (1H, s), 7.04 (1H, br s), 7.20

(1H, d, J=9.0 Hz), 7.25 (5H, m)

4-67
3.52 (3H, brd, J=1.0 Hz), 3.86 (3H, s), 5.17 (1H, d, J=13.2 Hz), 5.21 (1H, d, J=13.2 Hz),

6.24 (1H, s), 6.65 (1H, br s), 7.20 (1H, d, J=9.0 Hz), 7.53 (1H, t, J=8.0 Hz), 7.63 (1H,

d, J=8.0 Hz), 8.18 (2H, m)

4-68
2.35 (3H, s), 3.50 (3H, br d, J=1.0 Hz), 3.83 (3H, s), 5.02 (1H, d, J=12.2 Hz), 5.10 (1H,

d, J=12.2 Hz , 6.22 1H, s , 6.65 1H, br s , 7.1-7.3 5H, m

4-69
2.27 (3H, s), 2.30 (6H, s), 3.54 (3H, hr d, J=1.1 Hz), 3.83 (3H, s), 5.10 (1H, d,

J=11.811z), 5.16 (1H, d, J=11.8 Hz), 6.25 (1H, s), 6.63 (1H, br s), 6.87 (2H, s), 7.13

(1H, d, J=9.0 Hz)

4-70
3.55 (3H, hr d, 111.l Hz), 3.83 (3H, s), 4.99 (1H, d, J=13.l Hz), 5.08 (1H, d, J=13.1 Hz),

6.27 (1H, s), 6.35 (2H, m), 6.63 (1H, br s), 7.17 (1H, d, J=9.0 Hz), 7.41 (1H, m)

5-1
2.05 (1H, br s), 4.05 (3H, s), 7.66 (1H, d, J=8.8 Hz)

5-2
4.36 (2H, br s), 7.61 (1H, d, J=8.7 Hz)

5-3
2.30 (2H, dt, J=27.2, 5.6 Hz), 3.85 (3H, s), 4.22 (2H, t, J=6.8 Hz), 4.42 (2H, br s), 4.60

(2H, dt, J=46.9, 5.6 Hz), 6.65 (1H, d, J=9.5 Hz)

5-4
2.24 (2H, dt, J=26.7, 5.7 Hz), 4.19 (2H, t, J=6.9 Hz), 4.61 (2H, dt, J=47.0, 5.7 Hz),

7.86 (1H, d, J=9.0 Hz)

5-5
2.30 (2H, dt, J=26.4, 5.7 Hz), 4.17 (2H, t, J=6.8 Hz), 4.55 (2H, dt, J=47.0, 5.7 Hz),

4.88 (2H, br s), 6.55 (1H, d, J=9.6 Hz), 8.07 (1H, hr)

5-6
4.06 (3H, s), 7.87 (1H, s)

5-7
2.13 (2H, m), 3.06 (3H, s), 3.93 (2H, t, J=4.8 Hz), 4.60 (2H, hr d, J=47.0 Hz), 7.53

(1H, s)

5-8
2.30 (2H, dt, J=26.4, 5.6 Hz), 4.24 (2H, t, J=6.7 Hz), 4.58 (2H, dt, J=46.8, 5.6 Hz), 7.87

(1H, s), 9.62 (1H, s)

5-9
2.06 (1H, s), 2.30 (2H, dtt, J=27.7, 6.8, 5.4 Hz), 4.24 (2H, t, J=6.8 Hz), 4.60 (2H, dt,

J=46.9, 5.4 Hz), 5.90 (2H, s), 6.77 (1H, s)

5-15
2.30 (2H, dtt, J=26.0, 6.1, 5.5 Hz), 2.62 (1H, d, J=2.4 Hz), 4.2 1 (2H, t, J=6.8 Hz), 4.48

(2H, s), 4.60 (2H, dt, J=46.9, 5.5 Hz), 4.73 (2H, d, J=2.4 Hz), 6.92 (1H, s)

5-16
1.35 (6H, d, J=6.2 Hz), 2.29 (2H, dtt, J=27.7, 5.9, 5.5 Hz), 4.2 1 (2H, t, J=6.8 Hz), 4.29

(2H, br s), 4.53 (1H, g, J=6.2 Hz), 4.59 (2H, dt, J=46.9, 5.5 Hz), 6.92 (1H, s)

5-17
2.30 (2H, dt, J=26.4, 5.7 Hz), 2.75 (1H, t, J=2.5 Hz), 4.19 (2H, t, J=6.8 Hz), 4.61

(2H, dt, J=47.0, 5.7 Hz), 4.72 (2H, d, J=2.5 Hz), 5.02 (2H, br s), 6.61 (1H, d, J=9.4

Hz)

5-18
1.35 (6H, d, J=6.0 Hz), 2.30 (2H, dtt, J=26.9, 6.8, 5.4 Hz), 4.21 (2H, t, J=6.8 Hz), 4.37

(2H, br s), 4.52 (1H, penta, J=6.0 Hz), 4.59 (2H, dt, J=46.5, 5.4 Hz), 6.65 (1H, d,

J=9.6 Hz)

5-26
2.08 (2H, m), 3.84 (3H, s), 4.09 (2H, t, J=6.7 Hz), 4.31 (2H, dt, J=46.9, 5.6 Hz), 7.26

(1H, d, J=9.1 Hz), 7.55 (2H, m), 7.89 (4H, m), 8.40 (1H, s), 8.53 (1H, br s)

5-27
1.67 (2H, dt, 1126.5, 5.8 Hz), 3.86 (3H, s), 3.89 (2H, s), 3.97 (2H, dt, J=42.4, 5.6 Hz),

7.27 1H, d, J=8.7 Hz , 7.52 4H, m , 7.78 4H, m , 7.88 4H, m , 8.54 214, s

5-28
2.22 (2H, dt, J=26.2, 5.8 Hz), 3.81 (3H, s), 4.01 (2H, s), 4.13 (2H, d, J=6.8 Hz),

4.52 (2H, dt, J=46.9, 5.6 Hz), 4.64 (2H, s), 7.23 (1H, d, J=9.1 Hz), 7.36 (5H, m), 8.67

(1H, br s)

6-1
2.48 (3H, s), 7.03 (1H, t, J=57.9 Hz), 7.65 (1H,A, J=8.6 Hz), 9.88 (1H, s)

6-2
2.48 (3H, s), 4.25 (2H, br s), 5.70 (1H, br s), 6.59 (1H, d, J=9.4 Hz), 7.07 (1H, t, J=58.0

Hz)

6-13
2.53 (3H, s), 6.89 (1H, ddd, J=12.5, 8.3, 2.4 Hz), 7.05 (1H, m), 7.10 (1H, t, J=58.0 Hz),

7.33 (1H, d, J=2.2 Hz), 8:21 (1H, ddd, J=9.1, 9.1, 6.5 Hz), 8.57 (1H, d, J=2.2 Hz), 8.72

(1H, br d, J=16.5 Hz)

6-14
2.37 (3H, s), 3.88 (3H, s), 6.94 (1H, ddd, J=1 0.9, 8.3, 2.3 Hz), 6.99 (1H, m), 7.05 (1H,

t, J=58.0 Hz), 7.26 (1H, d, J=9.1 Hz), 8.04 (1H, ddd, J=8.8, 8.8, 6.5 Hz~, 8.48 (1H, br d,

J=13.4 Hz)

6-15
2.31 (3H, s), 3.88 (3H, s), 7.03 (1H, t, J=58.0 Hz), 7.25 (1H, d, J=9.4 Hz), 7.60 (2H, m),

7.8-8.0 (4H, m), 8.25 (1H, s), 8.40 (1H, s)

6-16
2.54 (3H, s), 7.12 (1H, d, J=58.0 Hz), 7.35 (1H, d, J=2.3 Hz), 7.61 (2H, m), 7.83 (1H,

dd, J=8.5, 1.8 Hz), 7.90 (3H, m), 8.29 (1H, s), 8.48 (1H, d, J=2.3 Hz), 8.64 (1H, br s)

6-17
2.29 (3H, s), 3.89 (3H, s), 7.03 (1H, t, J=58.0 Hz), 7.53 (1H, s), 7.60 (2H, m), 7.92 (4H,

m), 8.07 (1H,brs), 8.37 (1H, br s)

6-18
1.29 (3H, t, J=7.l Hz), 2.45 (3H, s), 4.3 (2H, q, J=7.l Hz), 6.7 (1H, broad), 7.03 (1H, t,

J=58.0 Hz), 7.83 (1H, s)

6-19
1.27 (3H, t, J=7.0 Hz), 2.48 (3H, s), 4.18 (2H, q, J=7.0 Hz), 4.51 (2H, s), 6.67 (1H, s),

6.91 (1H, s), 7.08 (1H, t, J=58.0 Hz)

6-20
2.38 (3H, s), 4.77 (4H, s), 7.16 (1H, t, J=57.7 Hz), 7.17 (1H, s)

6-21
2.47 (3H, s), 7.04 (1H, t, J=7.2 Hz), 7.59 (1H, 2d, J=2.3 Hz, 8.6 Hz), 7.91 (1H, t, J=2.1 Hz)

6-22
2.47 (3H, s), 3.65 (2H, s), 6.75 (1H, 2d, J=2.2 Hz, 9.4 Hz), 7.07 (1H, t, J=57.9 Hz),

7.20 (1H, t, J=1.8 Hz)

6-23
2.52 (3H, s), 6.9-7.1 (3H, m), 7.10 (1H, t, J=57.9 Hz), 7.14 (1H, 2d), 8.06 (1H, m),

9.76 (1H, s)

6-24
2.51 (3H, s), 6.93 (1H, 2d, J=2.2 Hz, 8.9 Hz), 7.12 (1H, t, J=58.0 Hz), 7.12 (1H, s),

7.61 (2H, m), 7.9-8.0 (3H, m), 8.07 (1H, 2d, J=1.7 Hz), 8.68 (1H, s), 9.74 (1H, s)

7-1
4.01 (3H, s), 4.03 (3H, br g, J=1.0 Hz), 7.43 (1H, d, J=8.4 Hz)

7-2
3.84 (3H, s), 4.06 (3H, s), 4.57 (2H, s), 6.57 (1H, d, J=9.3 Hz)

7-3
4.07 (3H, br d, J=0.9 Hz), 6.61 (1H, d, J=9.2 Hz)

7-14
3.87 (3H, s), 3.91 (3H, s), 7.23 (1H, d, J=8.9 Hz), 7.60 (2H, m), 7.80-7.96 (4H, m),

8.13 (1H, br s), 8.32 (1H, br s)

7-15
3.86 (3H, s), 3.97 (3H, s), 6.45 (1H, d, J=15.6 Hz), 7.20 (1H, d, J=8.9 Hz), 7.30-7.52

(6H, m), 7.60 (1H, d, J=15.6 Hz)

8-1
1.84 (4H, m), 2.44 (4H, m), 7.62 (1H, d, J=8.5 Hz), 9.88 (1H, br)

8-2
1.79 (4H, m), 2.41 (4H, m), 5.53 (3H, br), 6.53 (1H, d, J=9.1 Hz)

8-3
1.81 (4H, m), 2.43 (4H, m), 2.58 (1H, t, J=2.4 Hz), 4.24 (2H, br s), 4.69 (2H, t, J=2.4

Hz), 6.60 (1H, d, J=9.2 Hz)

8-4
1.35 (6H, d, J=6.2 Hz), 1.82 (4H, m), 2.43 (4H, m), 4.11 (2H, br s), 4.48 (1H, q, J=6.2

Hz), 6.60 (1H, d, J=9.4 Hz)

8-5
1.77 (4H, m), 1.82 (4H, m), 2.43 (4H, m), 2.34 (4H, m), 4.04 (2H, br s), 4.79 (1H, m),

6.61 (1H, d, J=9.4 Hz)

8-6
1.82 (4H, m), 2.42 (4H, m), 4.03 (3H, s), 7.48 (1H, d, J=8.6 Hz)

8-7
1.80 (4H, m), 2.08 (2H, br s), 2.41 (4H, m), 3.83 (3H, s), 6.60 (1H, d, J=9.4 Hz)

8-8
1.78 (4H, m), 2.38 (4H, m), 3.86 (3H, s), 6.96 (2H, m), 7.25 (1H, d, J=9.0 Hz), 8.01

(1H, m), 8.19 (1H, d, J=12.6 Hz)

8-9
1.68 (4H, m), 2.32 (4H, m), 3.82 (3H, s), 7.22 (1H, d, J=9.1 Hz), 7.59 (2H, m), 7.91

(5H, m), 8.34 (1H, s)

8-13
1.76 (4H, m), 2.34 (4H, m), 2.37 (1H, t, J=2.4 Hz), 4.77 (2H, t, J=2.4 Hz), 6.95 (2H,

m), 7.27 (1H, d, J=8.9 Hz), 8.04 (1H, m), 8.38 (1H, hr d, J=12.5 Hz)

8-18
1.28 (6H, d, J=6.2 Hz), 1.76 (4H, m), 2.32 (4H, m), 4.45 (1H, q, J=6.2 Hz), 6.95 (2H,

m), 7.24 (1H, d, J=9.0 Hz), 8.00 (1H, m), 8.31 (1H, br d, J=12.7 Hz)

8-30
1.71 (4H, m), 2.33 (4H, m), 3.80 (3H, s), 5.39 (1H, d, J=10.9 Hz), 5.86 (1H, d, J=17.6

Hz), 6.75 (1H, dd, J=17.6, 10.9 Hz), 7.21 (1H, d, J=9.0 Hz), 7.47 (2H, d, J8.2 Hz),

7.77 (2H, d, J=8.2 Hz), 7.85 (1H, s)

8-31
1.76 (4H, m), 2.38 (4H, m), 3.82 (3H, s), 6.52 (1H, d, J=15.6 Hz), 7.19 (1H, d, J=9.0

Hz), 7.37 (3H, m), 7.47 (3H, m), 7.65 (1H, d, J=15.6 Hz)

8-32
1.85 (4H, m), 2.45 (4H, m), 8.31 (2H, s)

8-33
1.81 (4H, m), 2.43 (4H, m), 7.37 (1H, d, J=8.5 Hz), 7.69 (1H, 2d, J=2.3 Hz, 8.5 Hz), 8.10

(1H, d, J=2.3 Hz)

8-34
1.86 (4H, m), 2.46 (4H, m), 7.72 (1H, d, J=8.8 Hz), 8.56 (1H, 2d, J=2.6 Hz, 8.8 Hz), 8.92

(1H, d, J=2.6 Hz)

8-35
1.80 (4H, m), 2.40 (4H, m), 3.83 (2H, s), 6.79 (2H, m), 6.91 (1H, d, J=8.3 Hz).

8-36
1.78 (4H, m), 2.40 (4H, m), 7.15-7.30 (2H, m), 7.6 (2H, m), 7.9 (4H, m), 8.14 (1H, d,

J=2.2 Hz), 8.34 (1H, s), 8.59 (1H, s)

9-1
1.91 (4H, m), 3.67 (4H, m), 7.65 (1H, d, J=8.3 Hz)

9-3
1.87 (4H, m), 3.62 (4H, m), 4.03 (3H, s), 7.53 (1H, d, J=8.5 Hz)

9-4
1.88 (4H, m), 3.65 (4H, m), 3.85 (3H, s), 4.28 (2H, s), 6.64 (1H, d, J=9.5 Hz)

9-12
2.01 (4H, m), 3.73 (2H, m), 3.92 (1H, m), 4.15 (1H, m), 7.53 (1H, d, J=8.5 Hz), 7.76

(1H, J=8.5, 2.4 Hz), 8.21 (1H, d, J=2.4 Hz)

9-13
1.90 (4H, m), 3.69 (2H, m), 3.95 (2H, m), 4.85 (2H, br s), 6.79 (2H, m), 7.00 (1H, d,

J=8.3 Hz)

9-14
1.94 (4H, m), 3.69 (2H, m), 4.03 (2H, m), 7.27 (2H, m), 7.59 (2H, m), 7.94 (4H, m),

8.19 (1H, d, J=2.0 Hz), 8.47 (1H, s), 9.11 (1H,brs)

9-15
1.70 (4H, m), 3.50 (4H, m), 3.83 (3H, s), 7.23 (1H, d, J=9.0 Hz), 7.59 (2H, m), 7.92

(4H, m), 8.34 (1H, s), 8.43 (1H, s)

9-16
1.82 (4H, m), 3.58 (4H, m), 3.87 (3H, s), 6.9-7.1 (2H, m), 7.27 (1H, d, J=9.0 Hz), 8.07

(1H, m), 8.49 (1H, d, J=13.1 Hz)

9-17
1.89 (4H, m), 3.65 (4H, m), 7.53 (1H, d, J=8.6 Hz), 7.72 (1H, 2d, J=2.3 Hz, 8.5 Hz), 8.13

(1H, d, J=2.3 Hz)

9-18
1.85 (4H, m), 3.63 (4H, m), 4.03 (2H, s), 6.82 (2H, m), 7.09 (1H, 2d, J=0.6 Hz, 8.0 Hz)

9-19
1.80 (4H, m), 3.60 (4H, m), 7.22 (1H, 2d, J=2.3 Hz, 8.7 Hz), 7.35 (1H, d, J=8.7 Hz), 7.56

(2H, m), 7.89 (4H, m), 8.08 (1H, d, J=2.3 Hz), 8.43 (1H, s), 9.41 (1H, s)

11-1
4.05 (3H, s), 7.30 (1H, m), 7.53 (1H, d, J=8.7 Hz), 8.01 (1H, d, J=2.1 Hz)

11-2
7.33 (1H, m), 7.70 (1H, d, J=8.4 Hz), 8.06 (1H, d, J=2.1 Hz), 10.29 (1H, s)

11-3
6.53 (1H, d, J=9.5 Hz), 6.53 (3H, br), 7.40 (1H, s), 8.17 (1H, s)

11-4
3.86 (3H, s), 4.33 (2H,brs), 6.65 (1H, d, J=9.5 Hz), 7.34 (1H, dq, J=2.2, 1.0 Hz), 8.10

(1H, d, J=2.2 Hz)

11-5
3.31 (3H, s), 3.79 (3H, s), 4.33 (2H, br s), 7.21 (1H, d, J=1.1 Hz), 7.49 (1H, d, J=8.8

Hz), 7.95 (1H, d, J=2.2 Hz)

11-6
3.86 (3H, s), 7.26 (1H, d, J=9.2 Hz), 7.27 (1H, dq, J=2.2, 1.1 Hz), 7.56 (2H, m),

7.88 (4H, m), 7.97 (1H, d, J=2.2 Hz), 8.38 (1H, s), 8.79 (1H, s)

11-7
3.93 (3H, s), 7.30 (1H, d, J=8.7 Hz), 7.35 (1H, dq, 12.2, 1.1 Hz), 8.08 (1H, d, J=2.2

Hz)

11-8
1.20, 1.23 (3H, t, J=7.1 Hz), 3.20 (2H, m), 3.94 (3H, s), 4.16 (2H, q, J=7.1 Hz), 4.52

(1H, m), 7.32 (2H, m), 8.08 (1H, m)

11-9
2.43 (3H, g, J=2.1 Hz), 7.67 (1H, d, J=8.5 Hz), 8.01 (1H, s), 10.2 (1H, br)

11-10
2.46 3H, ,J=1.8 Hz,2.63 3H,br,6.60 1H,d,J=9.4 Hz,8.08 1H, s

11-11
2.45 (3H, g, J=1.9 Hz), 3.87 (3H, s), 6.66 (1H, d, J=9.6 Hz), 8.06 (1H, s)

11-12
2.44 (3H, g, J=1.9 Hz), 2.58 (3H, s), 3.84 (3H, s), 6.60 (1H, d, J=9.4 Hz), 8.03 (1H, s)

11-13
2.38 (3H, q, J=1.8 Hz), 3.88 (3H, s), 7.26 (1H, d, J=9.3 Hz), 7.59 (2H, m), 7.80 (1H,

m), 7.91 (4H, m), 8.11 (1H, s), 8.30 (1H, s)

12-1
1.64 (3H, m), 1.91 (1H, m), 2.10 (1H, m), 2.35 (1H, m), 3.16 (1H, m), 4.17 (1H, m),

4.82 (1H, m), 7.66 (1H, d, J=8.2 Hz), 10.4 (1H, broad)

12-2
1.61 (3H, m), 1.91 (1H, m), 2.10 (1.H, m), 2.38 (1H, m), 3.13 (1H, m), 4.11 (1H, m),

4.14 (2H, s), 4.87 (1H, m), 5.49 (1H, s), 6.64 (1H, d, J=9.0 Hz)

12-3
1.61 (3H, m), 1.90 (1H, m), 2.08 (1H, m), 2.35 (1H, m), 3.10 (1H, m), 4.07 (1H, m),

4.2 (2H, broad), 4.88 (1H, m), 5.5 (1H, broad), 6.63 (1H, d, J9.0 Hz)

12-4
1.60 (3H, m), 1.89 (1H, m), 2.09 (1H, m), 2.34 (1H, m), 3.09 (1H, m), 3.85 (3H, s),

4.11 (1H, m), 4.3 (2H, broad), 4.87 (1H, m), 6.63 (1H, d, J=9.3 Hz)

12-5
1.4-1.7 (3H, m), 1.7-2.4 (3H, m), 2.95 (1H, m), 3.85 (3H, s), 3.97 (1H, m), 4.71 (1H,

m), 7.26 (1H, m), 7.60 (2H, m), 7.93 (4H, m), 8.15 (1H, s), 8.44 (1H, s)

12-6
1.54 (3H, m), 1.78 (1H, m), 2.07 (1H, m), 2.27 (1H, m), 2.95 (1H, m), 4.01 (1H, m),

4.22 (1H, m), 7.44 (1H, d, J=8.S Hz), 7.69 (1H, 2d, J=2.3 Hz, 8.5 Hz), 8.11 (1H, d,

J=2.3 Hz)

12-7
1.50 (3H, m), 1.78 (1H, m), 2.05 (1H, m), 2.28 (1H, m), 2.89 (1H, m), 3.90 (1H, m),

3.95 (2H, s), 4.15 (1H, m), 6.81 (2H, m), 6.99 (1H, d, J=7.9 Hz)

12-8
1.41 (3H, m), 1.68 (1H, m), 1.93 (1H, m), 2.24 (1H, m), 2.83 (1H, m), 3.88 (1H, m),

4.11 (1H, m), 7.23 (2H, m), 7.54 (2H, m), 7.87 (4H, m), 7.97 (1H, s), 8.38 (1H, s),

9.11 (1H, s)

13-1
4.36 (1H, br s), 7.61 (1H, d, J=8.6 Hz), 7.88 (2H, m), 7.99 (2H, m)

13-2
5.42 (1H, br s), 6.58 (1H, d, J=9.4 Hz), 7.95 (4H, m)

13-3
3.86 (3H, s), 7.28 (1H, d, J=9.0 Hz), 7.50-7.95 (IOH, m), 8.03 (1H, br s), 8.28 (1H, br

s)

13-4
3.89 (3H, s), 6.89 (2H, m), 7.30 (1H, d, J=9.0 Hz), 7.70-7.95 (5H, m), 8.34 (1H, m)

13-5
7.33 (2H, m), 7.56 (2H, m), 7.7-8.0 (8H, m), 8.19 (1H, d, J=1.4 Hz), 8.32 (1H, s), 8.56

(1H, brs)

14-1
1.23 (3H, t, J=7.1 Hz), 2.51 (2H, m), 2.75 (2H, m), 3.55 (3H, s), 3.90 (3H, s), 4.10 (2H,

g, J=7.1 Hz), 6.36 (1H, s), 7.20 (1H, d, J=8.9 Hz)

14-2
1.30 (3H, t, J=7.1 Hz), 3.56 (3H, s), 3.82 (3H, s), 4.23 (2H, q, J=7.1 Hz), 6.36 (1H, s),

6.60 (1H, d, J16.2 Hz), 7.31 (1H, d, J=8.6 Hz), 7.36 (1H, d, J=16.2 Hz)

14-3
3.01 (1H, m), 3.25 (1H, m), 3.57 (3H, s), 3.70, 3.73 (3H, 2s), 3.93, 3.94 (3H, 2s), 4.55

(1H, m), 6.36, 6.37 (1H, 2s), 7.26 (1H, d, J=8.8 Hz)

14-4
1.23 (3H, t, J=7.1 Hz), 3.03 (1H, m), 3.22 (1H, m), 3.55 (3H, s), 3.94 (3H, s), 4.14 (2H,

m), 4.51 (1H, m), 6.37 (1H, s), 7.26 (1H, d, J=8.8 Hz)

14-5
1.24 (3H, t, J=7.1 Hz), 2.95 (1H, m), 3.31 (1H, m), 3.56 (3H, s), 3.93 (3H, s), 4.16 (2H,

m), 4.54 (1H, m), 6.35 (1H, s), 7.26 (1H, d, J=8.8 Hz)

14-6
0.89 (3H, t, J=7.4 Hz), 1.61 (2H, m), 3.02 (1H, m), 3.23 (1H, m), 3.56 (3H, s), 3.94

(3H, s), 4.07 (2H, m), 4.53 (1H, m), 6.37 (1H, s), 7.25 (1H, d, J=8.8 Hz)

14-7
0.90 (3H, t, J=7.4 Hz), 1.62 (2H, m), 2.96 (1H, m), 3.31 (1H, m), 3.56 (1H, s), 3.94

(3H, s), 4.08 (2H, m), 4.56 (1H, m), 6.36 (1H, s), 7.25 (1H, d, ~h8.9 Hz)

14-8
0.90 (3H, t, J=7.3 Hz), 1.33 (2H, m), 1.58 (2H, m), 3.03 (1H, m), 3.22 (1H, m), 3.55

(3H, s), 3.94 (3H, s), 4.08 (2H, m), 4.52 (1H, m), 6.37 (1H, s), 7.26 (1H, d, J=8.8 Hz)

14-9
0.91 (3H, t, J=7.3 Hz), 1.33 (2H, m), 1.59 (2H, m), 2.98 (1H, m), 3.32 (1H, m), 3.56

(3H, s), 3.93 (3H, s), 4.11 (2H, m), 4.56 (1H, m), 6.35 (1H, s), 7.25 (1H, d, J=8.8 Hz)

14-10
0.88 (3H, t, J=6.7 Hz), 1.27 (4H, m), 1.60 (2H, m), 3.02 (1H, m), 3.22 (1H, m), 3.56

(3H, s), 3.94 (3H, s), 4.09 (2H, m), 4.52 (1H, m), 6.37 (1H, s), 7.25 (1H, d, J=8.9 Hz)

14-11
0.89 (3H, t, J=6.7 Hz), 1.31 (4H, m), 1.61 (2H, m), 2.96 (1H, m), 3.30 (1H, m), 3.56

(3H, s), 3.93 (3H, s), 4.10 (2H, m), 4.56 (1H, m), 6.35 (1H, s), 7.26 (1H, d, J=8.9 Hz)

14-12
0.87 (3H, t, J=6.4 Hz), 1.27 (6H, m), 1.59 (2H, m), 3.03 (1H, m), 3.22 (1H, m), 3.56

(3H, s), 3.94 (1H, s), 4.08 (2H, m), 4.52 (1H, m), 6.37 (1H, s), 7.25 (1H, d, J=8.8 Hz)

14-13
0.88 (3H, t, J=6.9 Hz~, 1.28 (6H, m), 1.59 (2H, m), 2.96 (1H, m), 3.32 (1H, m), 3.56

3H, s), 3.94 (3H, s), 4.10 (2H, m), 4.56 (1H, m), 6.35 (1H, s), 7.26 (1H, d, J=8.811z)

14-14
0.88 (6H, m), 1.90 (1H, m), 3.02 (1H, m), 3.23 (1H, m), 3.56 (3H, s), 3.87 (2H, m),

3.94 (3H, s), 4.54 (1H, m), 6.37 (1H, s), 7.25 (1H, d, J=8.9 Hz)

14-15
0.89 (6H, m), 1.91 (1H, m), 2.96 (1H, m), 3.32 (1H, m), 3.56 (3H, s), 3.89 (2H, m),

3.94 (3H, s), 4.58 (1H, m), 6.35 (1H, s), 7.26 (1H, d, J8.9 Hz)

14-16
0.89 (6H, m), 1.50 (2H, m), 1.60 (1H, m), 3.02 (1H, m), 3.21 (1H, m), 3.56 (3H, s),

3.94 (3H, s), 4.13 (2H, m), 4.52 (1H, m), 6.37 (1H, s), 7.25 (1H, d, J=8.911z)

14-17
0.88 (6H, m), 1.49 (2H, m), 1.62 (1H, m), 2.96 (1H, m), 3.30 (1H, m), 3.56 (3H, s),

3.93 (3H, s), 4.14 (2H, m), 4.56 (1H, m), 6.35 (1H, s), 7.25 (1H, d, J=8.9 Hz)

14-18
1.44, 1.46 (9H, 2s), 2.90 (1H, m), 3.31 (1H, m), 3.56 (3H, s), 3.92, 3.93 (3H, 2s), 4.42

(1H, m), 6.34, 6.37 (1H, 2s), 7.26 (1H, d, J=9.0 Hz).

14-19
2.51 (1H, m), 3.05 (1H, m), 3.20 (1H, m), 3.56 (3H, s), 3.94 (3H, s), 4.59 (1H, m), 4.68

(2H, m), 6.37 (1H, s), 7.26 (1H, d, J=8.9 Hz)

14-20
2.51 (1H, m), 2.99 (1H, m), 3.29 (1H, m), 3.56 (3H, s), 3.94 (3H, s), 4.61 (1H, m), 4.70

(2H, m), 6.36 (1H, s), 7.26 (1H, d, J=8.911z)

14-21
3.0-3.3 (2H, m), 3.56 (3H, s), 3.93, 3.94 (3H, 2s), 4.3-4.6 (2H, m), 4.69 (1H, m), 6.35,

6.37 (1H, 2s), 7.28 (1H, d, J8.8 Hz)

14-22
3.06 (1H, m), 3.24 (1H, m), 3.56 (3H, s), 3.93, 3.94 (3H, 2s), 4.4-4.6 (2H, m), 5.86

(1H, m), 6.36, 6.37 (1H, 2s), 7.28 (1H, d, J=8.8 Hz)

14-23
3.04-3.2 1 (2H, m), 3.56 (3H, s), 4.47, 4.65 (2H, 2m), 4.69 (1H, m), 6.37 (1H, s), 7.28

(1H, d, J=8.7 Hz)

14-24
3.02 (1H, m), 3.24 (1H, m), 3.56 (3H, s), 3.93 (3H, s), 4.61 (2H, m), 4.70 (1H, m), 6.35

(1H, s), 7.28 (1H, d, J=8.7 Hz)

14-25
2.98 (1H, m), 3.30 (1H, m), 3.34 (3H, s), 3.53 (2H, m), 3.56 (3H, s), 3.94 (3H, s), 4.25

(2H, m), 4.62 (1H, m), 6.35 (1H, s), 7.26 (1H, d, J=8.911z)

14-26
1.18 (3H, m), 3.05 (1H, m), 3.27 (1H, m), 3.4-3.6 (4H, m), 3.56 (3H, s), 3.93, 3.94

(3H, 2s), 4.29 (2H, m), 4.61 (1H, m), 6.35, 6.37 (1H, 2s), 7.26 (1H, d, J8.811z)

14-27
3.04 (1H, m), 3.21 (1H, m), 3.54 (3H, s), 3.91 (3H, s), 4.10 (2H, m), 4.45 (2H, m), 4.61

(1H, m), 6.35 (1H, s), 6.92 (3H, m), 7.27 (3H, m)

14-28
2.99 (1H, m), 3.30 (1H, m), 3.55 (3H, s), 3.90 (3H, s), 4.12 (2H, m), 4.46 (2H, m), 4.64

(1H, m), 6.34 (1H, s), 6.93 (3H, m), 7.26 (3H, m)

14-29
2.66 (2H, m), 3.07 (1H, m), 3.21 (1H, m), 3.56 (3H, s), 3.95 (3H, s), 4.30 (2H, m), 4.63

(1H, m), 6.35, 6.38 (1H, 2s), 7.28 (1H, d, J=8.9 Hz)

14-30
3.08 (1H, m), 3.22 (1H, m), 3.56 (3H, s), 3.70 (2H, m), 3.95 (3H, s), 4.30 (1H, m), 4.5l

(2H, m), 4.65 (1H, m), 6.38 (1H, s), 7.27 (1H, d, J=8.711z).

14-31
3.02 (1H, m), 3.42 (1H, m), 3.57 (3H, s), 3.72 (2H, m), 3.95 (3H, s), 4.29 (1H, m), 4.52

(2H, m), 4.66 (1H, m), 6.36 (1H, s), 7.27 (1H, d, J=8.811z)

14-32
1.22 (3H, t, J=7.l Hz), 3.13 (1H, m), 3.31 (1H, m), 3.55 (3H, s), 3.95 (3H, s), 4.13 (2H,

m), 4.46 (1H, m), 6.38 (1H, s), 7.25 (1H, d, J=8.911z).

14-33
1.23 (3H, t, J=7.111z), 3.08 (1H, m), 3.41 (1H, m), 3.57 (3H, s), 3.93 (3H, s), 4.12 (2H,

m), 4.49 (1H, m), 6.36 (1H, s), 7.25 (1H, d, J=8.911z)

14-34
1.27 (3H, m), 1.61, 1.64 (3H, 2s), 3.20 (1H, m), 3.54 (3H, s), 3.61 (1H, m), 3.84 (3H,

s), 4.18 (2H, m), 6.32, 6.37 (1H, 2s), 7.27 (1H, 2d)

14-35
0.94 (3H, m), 1.62, 1.65 (3H, 2s), 1.67 (2H, m), 3.21 (1H, m), 3.54 (3H, s), 3.62 (1H,

m), 3.84 (3H, s), 4.09 (2H, m), 6.33, 6.37 (1H, 2s), 7.27 (1H, 2d, J=8.811z, 8.8 Hz)

14-36
0.94 (3H, m), 1.41 (2H, m), 1.61, 1.65 (3H, 2s), 1.63 (2H, m), 3.21 (1H, m), 3.54 (3H,

s), 3.60 (1H, m), 3.84 (3H, s), 4.12 (2H, m), 6.32, 6.37 (1H, 2s), 7.27 (1H, 2d,

J=8.8 Hz, 8.9 Hz)

14-37
0.90 (3H, m), 1.33 (4H, m), 1.61, 1.64 (3H, 2s)., 1.65 (2H, m), 3.20 (1H, m), 3.54 (3H,

s), 3.59 (1H, m), 3.84 (3H, s), 4.12 (2H, m), 6.32, 6.37 (1H, 2s), 7.27 (1H, 2d,

J=8 .9 Hz, 8.7 Hz)

14-38
0.89 (3H, m), 1.30 (6H, m), 1.61~ 1.64 (3H, 2s), 1.65 (2H, m), 3.20 (1H, m), 3.54 (3H,

s), 3.59 (1H, m), 3.84 (3H, s), 4.11 (2H, m), 6.32, 6.36 (1H, 2s), 7.27 (1H, 2d,

J=8.8 Hz, 8.8 Hz)

14-39
1.26 (6H, m), 1.59, 1.62 (3H, 2s), 3.20 (1H, m), 3.54 (3H, s), 3.63 (1H, m), 3.85 (3H,

s), 4.98 (1H, m), 6.32, 6.37 (1H, 2s), 7.27 (1H, 2d, J=8.8 Hz, 8.8 Hz)

14-40
0.94 (6H, m), 1.62, 1.65 (3H, 2s), 1.96 (1H, m), 3.21 (1H, m), 3.54 (3H, s), 3.62 (1H,

m), 3.84 (3H, s), 3.92 (2H, m), 6.32, 6.37 (1H, 2s), 7.27 (1H, 2d, J8.8 Hz, 8.8 Hz)

14-41
1.63, 1.66 (3H, 2s), 3.22 (1H, m), 3.53 (3H, s), 3.63 (1H, m), 3.79 (3H, s), 5.16 (2H,

m), 6.29, 6.36 (1H, 2s), 7.25 (1H, 2d, J=8.8 Hz, 8.8 Hz), 7.35 (5H, m).

14-42
1.64, 1.67 (3H, 2s), 3.23 (1H, m), 3.52, 3.55 (3H, 2s), 3.66 (1H, m), 3.84 (3H, s),

4.71 (1H, m), 5.00 (1H, m), 6.33, 6.37 (1H, 2s), 7.18 (1H, m), 7.27 (1H, 2d, J=8.8 Hz,

8.8 Hz)

14-43
1.63, 1.66 (3H, 2s), 3.21 (1H, m), 3.54 (3H, s), 3.62 (1H, m), 3.84 (3H, s), 4.63 (2H,

m), 5.31 (2H, m), 5.89 (1H, m), 6.33, 6.37 (1H, 2s), 7.27 (1H, 2d, J=8.911z, 8.7 Hz)

14-44
1.63 (3H, m), 2.52 (1H, m), 3.18 (1H, m), 3.56 (3H, s), 3.60 (1H, m), 3.84 (3H, s), 4.74

(2H, m), 6.34, 6.37 (1H, 2s), 7.26, 7.27 (1H, 2d, J=8.7 Hz, 8.8 Hz)

14-45
1.65, 1.68 (3H, 2s), 3.19 (1H, m), 3.51 (1H, m), 3.55 (3H, s), 3.83 (3H, s), 4.49 (2H,

m), 5.86 (1H, m), 6.34, 6.37 (1H, 2s), 7.28 (1H, 2d, J=8.811z, 8.8 Hz)

14-46
1.67, 1.68 (3H, 2s), 3.18 (1H, m), 3.53, 3.55 (3H, 2s), 3.66 (1H, m), 3.82, 3.83 (3H,

2s), 5.73 (1H, m), 6.35, 6.37 (1H, 2s), 7.31 (1H, 2d, J=8.911z, 8.8 Hz)

14-47
1.63, 1.65 (3H, 2s), 3.20 (1H, m), 3.36, 3.37 (3H, 2s), 3.55 (3H, s), 3.63 (3H, m), 3.84

(3H, s), 4.29 (2H, m), 6.33, 6.36 (1H, 2s), 7.27 (1H, 2d, J=8.8 Hz, 8.8 Hz).

14-48
1.62, 1.64 (3H, 2s), 2.16 (3H, t, J=2.4 Hz), 2.73 (2H, m), 3.20 (1H, m), 3.55 (3H, s),

3.59 (1H, m), 3.84 (3H, s), 4.30 (2H, m), 6.33, 6.36 (1H, 2s), 7.27 (1H, 2d, J=8.8 Hz,

8.8 Hz)

14-49
1.63, 1.65 (3H, 2s), 1.8-2.1 (4H, m), 3.20 (1H, m), 3.54 (3H, s), 3.61 (1H, m), 3.81

(2H, m), 3.84 (3H, s), 4.13 (3H, m), 6.33, 6.36 (1H, s), 7.27 (1H, 2d, J=8.7 Hz, 8.9 Hz)

14-50
3.05 (2H, m), 3.29 (1H, m), 3.52, 3.57 (3H, 2s), 3.59 (1H, m), 3.68 (3H, s), 3.76 (3H,

s), 3.79, 3.80 (3H, 2s), 6.32, 6.35 (1H, 2s), 7.29 (1H, 2d, J=8.911z, 8.8 Hz)

14-51
1.31, 1.35 (3H, 2t, J=7.211z, 7.1 Hz), 3.50 (1H, m), 3.55, 3.57 (3H, 2s), 3.68 (1H, m),

3.92, 3.94 (3H, 2s), 4.31 (2H, m), 6.35, 6.38 (1H, 2s), 7.34 (1H, 2d, J=8.911z, 8.9 Hz)

14-52
1.26 (3H, t, J=7.l Hz), 2.48 (3H, s), 3.07 (1H, m), 3.38 (1H, m), 4.21 (2H, q, J=7.l Hz),

4.51 (1H, m), 7.07 (1H, t, J=58.0 Hz), 7.23 (2H, m)

14-53
1.24 (3H, t, J=7.l Hz), 1.90 (4H, m), 3.15 (1H, m), 3.43 (1H, m), 3.65 (4H, m), 3.92

(3H, s), 4.18 (2H, m), 4.48 (1H, m), 7.26 (1H, d, J10.511z)

14-54
1.16 (3H, t, J=7.2 Hz), 2.36 (3H, s), 3.04 (1H, m), 3.26 (1H, m), 3.48 (3H, s), 4.00-4.25

(3H, m.), 6.30 (1H, s), 7.20 (1H, d, J=8.8 Hz)

14-55
1.18 (3H, t, J=7.2 Hz), 2.37 (3H, s), 3.03 (1H, m), 3.31 (1H, m), 3.50 (3H, s), 4.00-4.25

(3H, m), 6.28 (1H, s), 7.20 (1H, d, J=8.7 Hz)

14-56
1.21 (3H, t, J=7.2 Hz), 3.10-3.45 (2H, m), 3.90 (3H, s), 4.07 (3H, br d, J=0.9 Hz), 4.16

(2H, g, J=7.2 Hz), 4.54 (1H, br t, J=7.3 Hz), 7.20 (1H, d, J=8.6 Hz)

14-57
3.45 (3H, d, J=1.l Hz), 6.21 (1H, s), 7.30 (1H, d, J=8.4 Hz), 7.46 (2H, t, J=7.S Hz), 7.5-

7.8 (5H, m)

14-58
3.31 (3H, d, J=0.911z), 6.29 (1H, s), 6.32 (1H, d, J=12.l Hz), 6.80 (1H, d, J=12.1 Hz),

7.15 (1H, d, J=8.5 Hz), 7.28 (2H, m), 7.35 (1H, dd, J=8.5, 2.3 Hz), 7.42 (2H, m), 7.6-

7.8 (4H, m)

14-59
3.48 (3H, s), 6.34 (1H, s), 6.72 (1H, d, J=16.0 Hz), 7.02 (1H, d, J=8.4 Hz), 7.18 (1H, d,

J=16.0 Hz), 7.30 (1H, dd, J=10.7, 2.3 Hz), 7.39 (2H, m), 7.48 (1H, dd, J=8.7, 1.2 Hz),

7.73 (5H, m)

14-60
1.25 (1.5H, t, J=7.l Hz), 1.26 (1,~H, t, J=~7.1 Hz), 2.92 (1H, m), 3.26 (1H, m), 3.57 (3H,

m), 4.22 (2H, m), 4.36 (1H, m),~6.37 (0.5H, s), 6.38 (0.5H, s), 7.2-7.3 (2H, m)

14-61
1.21 (3H, m), 2.49 (3H, s), 3.33 (2H, m), 3.90 (3H, s), 4.18 (2H, m), 4.52 (1H, t,

J=7.2 Hz), 7.05 (1H, t, J=58.0 Hz)7.25 (1H, d, J=8.9 Hz)

14-62
1.46 (3H, t, J=z7.0), 3.58 (3H, s), 4.12 (2H, q, J=7.0 Hz), 6.37 (1H, s), 7.26 (1H, d, J

8.7 Hz)

14-63
1.22 (3H, t, J=7.2 Hz), 1.47 (3H, t, J=7.0), 3.00 (1H, dd, 14.2, 5.2 Hz), 3.23 (1H, dd,

J=14.2, 8.4 Hz), 3.55 (3H, q, J=0.8 Hz), 4.12 (2H, q, J=7.0), 4.12 (2H, m), 4.57 (1H,

dd, J=8.4, 5.2 Hz), 6.37 (1H, s), 7.26 (1H, d, J=8.7 Hz)

14-64
1.23 (3H, t, J=7.1 Hz), 1.46 (3H, t, J=7.0 Hz), 2.94 (1H, dd, 14.4, 6.4 Hz), 3.32 (1H,

dd, J=14.4, 7.0 Hz), 3.55 (3H, q, J=0.8 Hz), 4.10 (2H, q, J=7.0 Hz), 4.17 (2H, q,

J=7.1 Hz), 4.61 (1H, dd, J=7.0, 6.4 Hz), 6.34 (1H, s), 7.25 (1H, d, J=8.9 Hz)

14-65
0.89 (3H, t, J=7.3 Hz), 1.46 (3H, t, J=7.0 Hz), 1.62 (2H, qt, J=7.3, 6.9 Hz), 3.03 (1H,

dd, J=14.2, 5.4 Hz), 3.21 (1H, dd, J=14.2, 8.3 Hz), 3.55 (3H, q, J=1.0 Hz), 4.04 (2H,

q, J=7.0 Hz), 4.10 (2H, m), 4.59 (1H, dd, J=8.3, 5.4 Hz), 6.37 (1H, s), 7.25 (1H, d, J=

8.8 Hz)

14-66
0.90 (3H, t, J=7.3 Hz), 1.46 (3H, t, J=7.0 Hz), 1.63 (2H, qt, J=7.3, 6.9 Hz), 2.94 (1H,

dd, J=14.4, 6.8 Hz), 3.32 (1H, dd, J14.4, 6.9 Hz), 3.55 (3H, q, J=1.0 Hz), 4.07 (2H,

q, J=7.0 Hz), 4.10 (2H, m), 4.64 (1H, dd, J=6.9, 6.8 Hz), 6.35 (1H, s), 7.25 (1H, d, 1k

8.9 Hz)

14-67
1.38 (6H, t, J=6.2), 3.57 (3H, q, J=1.2 Hz), 4.58 (1H, q, J=6.2 Hz), 6.37 (1H, s), 7.27

(1H, d, 8.7 Hz)

14-68
1.22 (3H, t, J=7.1 Hz), 1.34, 1.39 (6H, t, J=6.2 Hz), 3.03 (1H, dd, J=14.2, 5.3 Hz), 3.26

(1H, dd, J14.2, 8.3 Hz), 3.55 (3H, s), 4.14 (3H, q, J=7.1 Hz), 4.58 (1H, dd, J=8.3, 5.3

Hz), 4.68 (1H, q, J=6.2 Hz), 6.36 (1H, s), 7.25 (1H, d, J=8.9 Hz)

14-69
1.22 (3H, t, J7.1 Hz), 1.35, 1.37 (6H, t, 1k6.2 Hz), 2.94 (1H, dd, J=14.4, 6.5 Hz), 3.35

(1H, dd, J=14.4, 7.1 Hz), 3.56 (3H, s), 4.16 (3H, q, J=7.1 Hz), 4.64 (1H, q, J=6.2 Hz),

4.66 (1H, dd, J=7.1, 6.5 Hz), 6.34 (1H, s), 7.25 (1H, d, J=8.9 Hz)

14-70
1.25 (3H, t, J=7.1 Hz), 2.39 (3H, s), 2.89 (1H, dd, J=14.8, 7.8 Hz), 3.23 (1H, dd,

J=14.8, 6.1 Hz), 3.56 (3H, q, J=4.0 Hz), 4.17 (2H, q, J=7.1 Hz), 4.39 (1H, dd, 1k7.8,

6.1 Hz), 6.37, 6.38 (1H, s), 7.00 (1H, d, J=8.0 Hz), 7.22 (1H, d, 1k8.0 Hz), 7.27 (1H,

s)

14-71
0.89 (3H, m), 1.63 (2H, m), 3.00 (1H, m), 3.30 (1H, m), 3.54, 3.55 (3H, s), 3.93 (3H,

s), 4.09 (1H, m), 6.36, 6.38 (1H, s), 7.23 (1H, d, J=8.2 Hz), 8.07 (1H, dd, J=8.2, 1.9

Hz), 8.16 (1H, d, J=1.9 Hz)

14-72
0.86, 0.88 (3H, t, J=6.8 Hz), 1.57, 1.62 (2H, m), 2.43 (3H, s), 2.96 (1H, dd, J44.2, 6.9

Hz), 3.39 (1H, dd, J=14.2, 7.2 Hz), 3.93 (3H, s), 4.05 (2H, m), 4.54 (1H, dd, J=7.2,

6.9 Hz), 7.28, 7.29 (1H, d, J=8.8 Hz), 8.02, 8.04 (1H, s)

14-73
3.14 (2H, m), 3.54 (3H, 2s), 3.94 (3H, 2s), 4.63 (1H, m), 6.38 (1H, 2s), 7.25 (1H, d,

J=8.9 Hz), 9.5 (1H, broad)

14-74
4.06 (3H, s), 7.47 (1H, d, J=8.4 Hz), 8.10 (1H, m), 8.80 (1H, m)

14-75
3.87 (3H, s), 6.61 (1H, d, J=9.4 Hz), 8.12 (1H, m), 8.88 (1H, m)

15-1
3.53 3H, s,3.7 2H,broad,6.4 1H,broad,6.29 1H, s,6.68 1H,d,J=9.l Hz

15-2
0.7-0.9 (4H, m), 1.23 (1H, m), 3.51 (3H, s), 3.87 (3H, s), 6.24 (1H, s), 6.47 (1H, s), 6.83

(1H, d, 1k9.0 Hz), 8.02 (1H, s)

15-3
3.02 (3H, s), 3.92 (3H, s), 5.99 (1H, s), 6.74 (1H, s), 6.79 (1H, d, J=9.0 Hz), 7.38 (2H,

2d), 7.53 (1H, 2d), 7.72 (2H, d, J=7.2 Hz), 8.85 (1H, s)

15-4
3.31 (3H, s), 4.05 (3H, s), 6.20 (1H, s), &86 (2H,~m), 6.89 (1H, d, 1h9.l Hz), 7.03 (1H, m),

8.12 (1H, m), 8.23 (1H, m)

15-5
2.91 (3H, s), 3.91 (3H, s), 5.99 (1H, s), 6.76 (1H, d, J=9.0 Hz), 6.81 (1H, s), 7.59 (2H,

m), 7.82 (4H, m), 8.32 (1H, s), 8~.98 (1H, s)

15-6
1.21 (3H, t, J=7.1 Hz), 3.55 (3H, s), 3.95 (3H, s), 4.07 (2H, q, J=7.l Hz), 6.28 (1H, bs),

6.31 (1H, s), 6.43 (1H, bs), 6.87 (1H, d, J=9.1 Hz)

15-7
3.46 (3H, s), 3.93 (3H, s), 6.29 (1H, s), 6.52 (1H, bs), 6.90 (1H, d, J=9.0 Hz), 7.10 (3H,

m), 7.21 (1H, m), 7.34 (2H, m)

15-8
3.28 (3H, s), 3.90 (3H, s), 6.11 (1H, s), 6.66 (1H, s), 6.84 (3H, m), 6.93 (1H, d,

J=8.9 Hz), 7.87 (1H, s), 8.07 (1H, m)

15-9
1.33 (3H, t, J=7.1 Hz), 3.16 (3H, s), 3.50 (3H, s), 4.05 (3H, s), 4.18 (2H, m), 6.29 (1H,

s), 6.68 (1H, s), 6.85 (1H, d, J=9.l Hz), 9.73 (1H, s)

15-10
3.54 (3H, s), 3.85 (3H, s), 5.40 (2H, m), 5.96 (1H, m), 6.32 (1H, s), 6.72 (1H, d,

J=9.2 Hz), 7.32 (1H, d), 8.13 (1H, s)

15-11
0.51 (2H, m), 0.82 (2H, m), 1.27 (1H, m), 3.56 (3H, s), 3.83 (3H, s), 6.34 (1H, s), 6.67

(2H, m), 7.82 (1H, s)

15-12
1.76 (3H, s), 1.80 (3H, s), 3.54 (3H, s), 3.87 (3H, s), 6.31 (1H, s), 6.69 (1H, d,

J=9.1 Hz), 7.63 (1H, s)

15-13
1.69 (3H, s), 3.39 (3H, s), 3.54 (3H, s), 3.83 (3H, s), 4.13 (2H, s), 6.30 (1H, s), 6.66

(1H, d, J=9.3 Hz), 9.79 (1H, s)

15-14
2.07 (3H, s), 2.33 (2H, m), 2.52 (2H, m), 3.56 (3H, s), 3.86 (3H, s), 6.33 (1H, s), 6.72

(1H, d, J=9.2 Hz), 7.06 (1H, t, J=5.2 Hz), 7.92 (1H, s)

15-15
3.30 (2H, d, J=5.9 Hz), 3.52 (3H, s), 3.84 (3H, s), 6.33 (1H, s), 6.72 (1H, d, J=9.1 Hz),

7.07 (2H, d, J=7.5 Hz), 7.28 (4H, m), 7.95 (1H, s)

15-16
1.25 (3H, t, J=7.1 Hz), 1.91 (3H, s), 2.98 (2H, 2d), 3.54 (3H, s), 3.89 (3H, s), 4.11 (2H,

g, J=7.1 Hz), 6.30 (1H, s), 6.74 (1H, d, J=9.1 Hz), 7.76 (1H, s)

15-17
1.24 (3H, m), 3.46 (1H, m), 3.50, 3.55 (3H, 2s), 3.84 (3H, s), 6.33, 6.37 (1H, 2s), 6.71

(1H, d, J=9.2 Hz), 7.10 (3H, m), 7.28 (3H, m), 7.91 (1H, s)

15-18
2.32 (2H, m), 2.81 (2H, m), 3.55 (3H, s), 3.57 (2H, m), 3.94 (3H, s), 6.32 (1H, s), 6.74

(1H, d, J=9.l Hz), 7.18 (4H, m), 7.75 (1H, s)

15-19
2.46 (2H, m), 2.91 (2H, m), 3.25 (2H, m), 3.57 (3H, s), 3.87 (3H, s), 6.36 (1H, s), 6.69

(1H, d, J=9.1 Hz), 7.19 (4H, m), 7.64 (1H, s)

15-20
3.51 (3H, s), 3.90 (3H, s), 6.35 (1H, s), 6.77 (3H, m), 7.25 (1H, m), 7.83 (1H, s), 8.36

(1H, s)

15-21
3.54 (3H, s), 3.86 (3H, s), 6.31 (1H, s), 6.37 (1H, s), 6.79 (1H, d, J=9.3 Hz)

15-22
3.53 (3H, s), 3.90 (3H, s), 6.41 (1H, s), 6.74 (1H, d, J=9.2 Hz), 7.39 (1H, m), 7.48 (2H,

m), 7.66 (2H, m), 7.80 (3H, m), 8.34 (1H, s)

16-1
3.55 (3H, s), 6.36 (1H, s), 6.61 (1H, d, J=2.1 Hz), 7.04 (1H, d, J=2.1 Hz), 7.97 (1H, s)

16-2
3.56 (3H, s), 3.81 (3H, s), 6.35 (1H, s), 6.94 (1H, d, J=2.0 Hz), 7.16 (1H, d, J=2.0 Hz)

16-3
3.54 (3H, s), 5.11 (2H, s), 6.34 (1H, s), 6.8-6.9 (2H, m), 6.96 (1H, d, J=2.0 Hz), 7.19

(1H, d, J=2.1 Hz), 7.25 (1H, m)

16-4
3.53 (3H, s), 6.35 (1H, s), 6.86 (1H, m), 7.00 (1H, m), 7.49 (1H, d, J=2.2 Hz), 7.71 (1H,

d, J=2.2 Hz), 8.02 (1H, m)

16-5
3.42 (3H, s), 6.31 (1H, s), 7.49 (1H, d, J=2.2 Hz), 7.61 (3H, m), 7.93 (4H, m), 8.58 (1H,

m)

16-6
3.54 (3H, s), 3.86 (3H, s), 6.35 (1H, s), 6.82 (1H, d, J=9.2 Hz), 6.9 (1H, broad)

16-7
3.44 (3H, s), 3.88 (3H, s), 6.26 (1H, s), 7.29 (1H, d, J=8.9 Hz), 7.63 (2H, m), 7.95 (3H,

m), 8.09 (1H, 2d, J=1.7 Hz, 8.6 Hz), 8.71 (1H, s)

17-1
2.39 (3H, s), 3.56 (3H, s), 3.97 (3H, s), 6.37 (1H, s), 7.28 (1H, d, J=9.0 Hz)

17-2
1.15 (6H, m), 3.56 (3H, s), 3.73 (2H, m), 3.95 (3H, s), 6.36 (1H, s), 7.28 (1H, d, J=9.0

Hz)

17-3
3.51 (3H, s), 4.01 (3H, s), 4.10 (2H, m), 6.32 (1H, s), 7.24 (5H, m), 7.30 (1H, d, J=8.6

Hz)

17-4
3.14 (3H, s), 3.83 (3H, s), 6.19 (1H, s), 7.46 (8H, m)

17-5
3.14 (2H, m), 3.57 (5H, m), 3.96 ~ (3H, s), 6.40 (1H, s), 7.28 (1H, d, J=9.0 Hz)

[0164] The compounds of the present inventions exhibit excellent herbicidal effects when used as an active ingredient of a herbicide. The herbicide can be used for a wide range of applications, for example on crop lands such as paddy fields, upland farms, orchards and mulberry fields, and non-crop lands such as forests, farm roads, playgrounds, and factory sites. The application method may be suitably selected for soil treatment application and foliar application.

[0165] The compounds of the present invention are capable of controlling noxious weeds including grass (gramineae) such as bamyardgrass (Echinochloa crus-galli), large crabgrass (Digitaria sanguinalis), green foxtail (Setaria viridis), goosegrass (Eleusine indica L.), wild oat (Avena fatua L.), Johnsongrass (Sorghum halepense), quackgrass (Agropyron repens), alexandergrass (Brachiaria plantaginea), paragrass (Panicum purpurascen), sprangletop (Leptochloa chinensis) and red sprangletop (Leptochloa panacea); sedges (or Cyperaceae) such as rice flatsedge (Cyperus iria L.), purple nutsedge (Cyperus rotundus L.), Japanese bulrush (Scirpus Juncoides), flatsedge (Cyperus serotinus), small-flower umbrellaplant (Cyperus difformis), slender spikerush (Eleocharis acicularis), and water chestnut (Eleocharis kuroguwai); alismataceae such as Japanese ribbon wapato (Sagittaria pygmaea), arrow-head (Sagittaria trifolia) and narrowleaf waterplantain (Alisma canaliculatum); pontederiaceae such as monochoria (Monochoria vaginalis) and monochoria species (Monochoria korsakowii); scrophulariaceae such as false pimpernel (Linderniapyxidaria) and abunome (Dopatrium Junceum); lythraceae such as toothcup (Rotala indica) and red stem (Ammannia multiflora); and broadleaves such as redroot pigweed (Amaranthus retroflexus), velvetleaf (Abutilon theophrasti), morningglory (Ipomoea hederacea), lambsquarters (Chenopodium album), prickly sida (Sida spinosa L.), common purslane (Portulaca oleracea L.), slender amaranth (Amaranthus viridis L.), sicklepod (Cassia obtusifolia), black nightshade (Solanum nigrum L.), pale smartweed (Polygonum lapathifolium L.), common chickweed (Stellaria media L.), common cocklebur (Xanthium strumarium L.), flexuous bittercress (Cardamine flexuosa WITH.), henbit (Lamium amplexicaule L.) and threeseeded copperleaf (Acalypha australis L.). Accordingly, it is useful for controlling noxious weeds non-selectively or selectively in the cultivation of a crop plant such as corn (Zea mays L.), soybean (Glycine max Merr.), cotton (Gossypium spp.), wheat (Triticum spp.), rice (Oryza saliva L.), barley (Hordeum vulgare L.), oat (Avena saliva L.), sorgo (Sorghum bicolor Moench), rape (Brassica napus L.), sunflower (Helianthus annuus L.), sugar beet (Beta vulgaris L.), sugar cane (Saccharum officinarum L.), Japanese lawngrass (Zoysia Japonica stend), peanut (Arachis hypogaea L.) or flax (Linum usitatissimum L.).

[0166] For use as herbicides, the active ingredients of this invention are formulated into herbicidal compositions by mixing herbicidally active amounts with inert ingredients known to the art to facilitate either the suspension, dissolution or emulsification of the active ingredient for the desired use. The type of formulation prepared recognizes the facts that formulation, crop and use pattern all can influence the activity and utility of the active ingredient in a particular use. Thus for agricultural use the present herbicidal compounds may be formulated as water dispersible granules, granules for direct application to soils, water soluble concentrates, wettable powders, dusts, solutions, emulsifiable concentrates (EC), microemulsion, suspoemulsion, invert emulsion or other types of formulations, depending on the desired weed targets, crops and application methods.

[0167] These herbicidal formulations may be applied to the target area (where suppression of unwanted vegetation is the objective) as dusts, granules or water or solvent diluted sprays. These formulation may contain as little as 0.1% to as much as 97% active ingredient by weight.

[0168] Dusts are admixtures of the active ingredient with finely ground materials such as clays (some examples include kaolin and montmorillonite clays), talc, granite dust or other organic or inorganic solids which act as dispersants and carriers for the active ingredient; these finely ground materials have an average particle size of less than 50 microns. A typical dust formulation will contain 1% active ingredient and 99% carrier.

[0169] Wettable powders are composed of finely ground particles which disperse rapidly in water or other spray carriers. Typical carriers include kaolin clays, Fullers earth, silicas and other absorbent, wettable inorganic materials. Wettable powders can be prepared to contain from 1 to 90% active ingredient, depending on the desired use pattern and the absorbability of the carrier. Wettable powders typically contain wetting or dispersing agents to assist dispersion in water or other carriers.

[0170] Water dispersible granules are granulated solids that freely disperse when mixed in water. This formulation typically consists of the active ingredient (0.1% to 95% active ingredient), a wetting agent (1-15% by weight), a dispersing agent (1 to 15% by weight) and an inert carrier (1-95% by weight). Water dispersible granules can be formed by mixing the ingredients intimately then adding a small amount of water on a rotating disc (said mechanism is commercially available) and collecting the agglomerated granules. Alternatively, the mixture of ingredients may be mixed with an optimal amount of liquid (water or other liquid) and passed through an extruder (said mechanism is commercially available) equipped with passages which allow for the formation of small extruded granules. Alternatively, the mixture of ingredients can be granulated using a high speed mixer (said mechanism is commercially available) by adding a small amount of liquid and mixing at high speeds to affect agglomeration. Alternatively, the mixture of ingredients can be dispersed in water and dried by spraying the dispersion through a heated nozzle in a process known as spray drying (spray drying equipment is commercially available). After granulation the moisture content of granules is adjusted to an optimal level (generally less than 5%) and the product is sized to the desired mesh size.

[0171] Granules are granulated solids that do not disperse readily in water, but instead maintain their physical structure when applied to the soil using a dry granule applicator. These granulated solids may be made of clay, vegetable material such as corn cob grits, agglomerated silicas or other agglomerated organic or inorganic materials or compounds such as calcium sulfate. The formulation typically consists of the active ingredient (1 to 20%) dispersed on or absorbed into the granule. The granule may be produced by intimately mixing the active ingredient with the granules with or without a sticking agent to facilitate adhesion of the active ingredient to the granule surface, or by dissolving the active ingredient in a solvent, spraying the dissolved active ingredient and solvent onto the granule then drying to remove the solvent. Granular formulations are useful where in-furrow or banded application is desired.

[0172] Emulsifiable concentrates (EC) are homogeneous liquids composed of a solvent or mixture of solvents such as xylenes, heavy aromatic naphthas, isophorone or other proprietary commercial compositions derived from petroleum distillates, the active ingredient and an emulsifying agent or agents. For herbicidal use, the EC is added to water (or other spray carrier) and applied as a spray to the target area. The composition of an EC formulation can contain 0.1% to 95% active ingredient, 5 to 95% solvent or solvent mixture and 1 to 20% emulsifying agent or mixture of emulsifying agents.

[0173] Suspension concentrate (also known as flowable) formulations are liquid formulations consisting of a finely ground suspension of the active ingredient in a carrier, typically water or a non-aqueous carrier such as an oil. Suspension concentrates typically contain the active ingredient (5 to 50% by weight), carrier, wetting agent, dispersing agent, anti-freeze, viscosity modifiers and pH modifiers. For application, suspension concentrates are typically diluted with water and sprayed on the target area.

[0174] Solution concentrates are solutions of the active ingredient (1 to 70%) in solvents which have sufficient solvency to dissolve the desired amount of active ingredient. Because they are simple solutions without other inert ingredients such as wetting agents, additional additives are usually added to the spray tank mix before spraying to facilitate proper application.

[0175] Microemulsions are solutions consisting of the active ingredient (1 to 30%) dissolved in a surfactant or emulsifier, without any additional solvents. There are no additional solvents added to this formulation. Microemulsions are particularly useful when a low odor formulation is required such as in residential turfgrass applications.

[0176] Suspoemulsions are combinations of two active ingredients. One active ingredient is made as a suspension concentrate (1-50% active ingredient) and the second active is made as a emulsifiable concentrate (0.1 to 20%). A reason for making this kind of formulation is the inability to make an EC formulation of the first ingredient due to poor solubility in organic solvents. The suspoemulsion formulation allows for the combination of the two active ingredients to be packaged in one container, thereby minimizing packaging waste and giving greater convenience to the product user.

[0177] The herbicidal compounds of this invention may be formulated or applied with insecticides, fungicides, acaricides, nematicides, fertilizers, plant growth regulators or other agricultural chemicals. Certain tank mix additives, such as spreader stickers, penetration aids, wetting agents, surfactants, emulsifiers, humectants and UV protectants may be added in amounts of 0.01% to 5% to enhance the biological activity, stability, wetting, spreading on foliage or uptake of the active ingredients on the target area or to improve the suspensibility, dispersion, redispersion, emulsifiability, UV stability or other physical or physico-chemical property of the active ingredient in the spray tank, spray system or target area.

[0178] The compositions of the present invention may be used in admixture with or in combination with other agricultural chemicals, fertilizers, adjuvants, surfactants, emulsifiers, oils, polymers or phytotoxicity-reducing agents such as herbicide safeners. In such a case, they may exhibit even better effects or activities. As other agricultural chemicals, herbicides, fungicides, antibiotics, plant hormones, plant growth regulators, insecticides, or acaricides may, for example, be mentioned. Especially with herbicidal compositions having the compounds of the present invention used in admixture with or in combination with one or more active ingredients of other herbicides, it is possible to improve the herbicidal activities, the range of application time(s) and the range of applicable weed types. Further, the compounds of the present invention and an active ingredient of another herbicide may be separately formulated so they may be mixed for use at the time of application, or both may be formulated together. The present invention covers such herbicidal compositions.

[0179] The blend ratio of the compounds of the present invention with the active ingredient of other herbicides can not generally be defined, since it varies depending on the time and method of application, weather conditions, soil type and type of formulation. However one active ingredient of other herbicide may be incorporated usually in an amount of 0.01 to 100 parts by weight, per one part by weight of the compounds of the present invention. Further, the total dose of all of the active ingredients is usually from 1 to 10000 g/ha, preferably from 5 to 500 g/ha. The present invention covers such herbicidal compositions.

[0180] As the active ingredients of other herbicides, the following (common name) may be mentioned. Herbicidal compositions having the compounds of the present invention used in combination with other herbicides, may occasionally exhibit a synergistic effect.

[0181] 1. Those that are believed to exhibit herbicidal effects by disturbing auxin activities of plants, including a phenoxy acetic acid type such as 2,4-D, 2,4-DB, 2,4-DP, MCPA, MCPP, MCPB or naproanilide (including the free acids, esters or salts thereof), an aromatic carboxylic type such as 2,3,6 TBA, dicamba, dichlobenil, a pyridine type such as picloram (including free acids and salts thereof), triclopyr or clopyralid and others such as naptalam, benazolin, quinclorac, quinmerac or diflufenzopyr (BAS 654H).

[0182] 2. Those that are believed to exhibit herbicidal effects by inhibiting photosynthesis of plants including a urea type such as diuron, linuron, isoproturon, chlorotoluron, metobenzuron, tebuthiuron or fluometuron, a triazine type such as simazine, atrazine, cyanazine, terbuthylazine, atraton, hexazinone, metribuzin, simetryn, ametryn, prometryn, dimethametryn or triaziflam, a uracil type such as bromacil, terbacil or lenacil, an anilide type such as propanil or cypromid, a carbamate type such as desmedipham or phenmedipham, a hydroxybenzonitrile type such as bromoxynil or ioxynil, and others such as pyridate, bentazon and methazole.

[0183] 3. A quaternary ammonium salt type such as paraquat, diquat or difenzoquat, which is believed to be converted to free radicals by itself to form active oxygen in the plant and thus to exhibit quick herbicidal effects.

[0184] 4. Those which are believed to exhibit herbicidal effects by inhibiting chlorophyll biosynthesis in plants and abnormally accumulating a photsensitizing peroxide substance in the plant body, including a diphenyl ether type such as nitrofen, lactofen, acifluorfen-sodium, oxyfluorfen, fomesafen, bifenox, or chlomethoxyfen, a cyclic imide type such as chlorphthalim, flumioxazin, cinidon-ethyl, or flumiclorac-pentyl, and others such as oxadiazon, sulfentrazone, thidiazimin, azafenidin, carfentrazone, isopropazole, fluthiacet-methyl, pentoxazone, pyraflufen-ethyl and oxadiargyl.

[0185] 5. Those which are believed to exhibit herbicidal effects characterized by whitening activities by inhibiting chromogenesis of plants such as carotenoids including a pyridazinone type such as norflurazon, chloridazon or metflurazon, a pyrazol type such as pyrazolate, pyrazoxyfen or benzofenap, and others such as fluridone, fluramone, diflufencam, methoxyphenone, clomazone, amitrole, sulcotrione, mesotrione, isoxaflutole and isoxachlortole.

[0186] 6. Those which exhibit herbicidal effects specifically to gramineous plants including an aryloxyphenoxypropionic acid type (either as a mixture of isomers or as a resolved isomer) such as diclofop-methyl, pyrofenop-sodium, fluazifop butyl or fluazifop-p-butyl, haloxyfop-methyl, quizalofop p-ethyl, quizalafop p-tefuryl, fenoxaprop ethyl or fenoxaprop-p-ethyl, flamprop-M-methyl or flamprop-m-isopropyl or cyhalofop-butyl and a cyclohexanedione type such as alloxydim-sodium, sethoxydim, clethodim, tepraloxydim or tralkoxydim.

[0187] 7. Those which are believed to exhibit herbicidal effects by inhibiting amino acid biosynthesis of plants, including a sulfonylurea type such as chlorimuron-ethyl, nicosulfaron, metsulfuron-methyl, triasulfuron, primisulfuron, tribenuron-methyl, chlorosulfuron, bensulflron-methyl, sulfometuron-methyl, prosulfuron, halosulfuron or halosulfuron-methyl, thifensulfuron-methyl, rimsulfuron, azimsulfuron, flazasulfuron, imazosulfuron, cyclosulfamuron, flupyrsulfuron, iodosulfuron, ethoxysulfuron, flucarbazone, sulfosulfuron, oxasulfuron a triazolopyrimidinesulfonamide type such as flumetsulam, metosulam, chloransulam or chloransulam-methyl, an imidazolinone type such as imazapyr, imazethapyr, imazaquin, imazamox, imazameth, imazamethabenz methyl, a pyrimidinesalicylic acid type such as pyrthiobac-sodium, bispyribac-sodium, pyriminobac-methyl or pyribenzoxim (LGC-40863), and others such as glyphosate, glyphosate-ammonium, glyphosate-isopropylamine or sulfosate.

[0188] 8. Those which are believed to exhibit herbicidal effects by interfering with the normal metabolism of inorganic nitrogen assimilation such as glufosinate, glufosinate-ammonium, phosphinothricin or bialophos.

[0189] 9. Those which are believed to exhibit herbicidal effects by inhibiting cell division of plant cells, including a dinitroaniline type such as trifluralin, oryzalin, nitralin, pendamethalin, ethafluralin, benefin and prodiamine, an amide type such as bensulide, napronamide, and pronamide, a carbamate type such as propham, chlorpropham, barban, and asulam, an organophosphorous type such as amiprofos-methyl or butamifos and others such as DCPA and dithiopyr.

[0190] 10. Those which are believed to exhibit herbicidal effects by inhibiting protein synthesis of plant cells, including a chloroacetanilide type such as alachlor, metolachor (including combinations with safeners such as benoxacor, or resolved isomeric mixtures of metolachlor including safeners such as benoxacor) propachlor, acetochlor (including combinations with herbicide safeners such as dichlormid or MON 4660 or resolved isomeric mixtures of acetochlor containing safeners such as dichlormid or MON 4660), propisochlor or dimethenamid or an oxyacetamide type such as flufenacet.

[0191] 11. Those in which the mode of action causing the herbicidal effects are not well understood including the dithiocarbamates such as thiobencarb, EPTC, diallate, triallate, molinate, pebulate, cycloate, butylate, vemolate or prosulfocarb and miscellaneous herbicides such as MSMA, DSMA, endothall, ethofumesate, sodium chlorate, pelargonic acid and fosamine. A few formulation examples of the present invention are given as follows.

19IngredientChemical%Trade NameNameSupplierFunctionwt./wt.Formulation example 1. Emulsifiable ConcentrateCompoundActive5.02-75IngredientToximulCalcium sulfonate andStepan Co.Emulsifier2.5H-Anonionic surfactantblendToximulCalcium sulfonate andStepan Co.Emulsifier7.5D-Anonionic surfactantblendAromaticAromatic hydrocarbonExxonSolventQS200Chemicalto 100%Co.Formulation example 2. Suspension ConcentrateCompoundActive10.002-75IngredientProyleneAnti-5.00glycolfreezeAntifoamSilicone defoamerDowAnti-foam0.501530CorningRhodopol 23Xanthan gumRhone-Suspend-0.25Poulencing AidMorwetNapthaleneWitco Corp.Dispersant3.00D-425formaldehydecondensateIgepalOctylphenol ethoxylateRhone-Wetting3.00CA-720PoulencagentProxel GXL1,2 benziso-thia-ICIPreser-0.25zolin-3-oneAmericasvativeWaterDiluent68.00Formulation example 3. Wettable PowderCompoundActive50.002-75IngredientGeroponSodium-N-methyl-N-Rhone-Wetting3.00T-77oleoyl tauratePoulencagentLomar PWNapthalene SulfonateHenkelDispersant5.00Corp.Kaolin clayKaolin clayJ. M. HuberFiller42.00Formulation example 4. Water Dispersible GranuleCompoundActive50.002-75IngredientMorwetWitco Corp.Wetting2.00EFWagentMorwetNapthaleneWitco Corp.Dispersant10.00D-425formaldehydecondensateASP 400Kaolin ClayEngelhardFiller38.00Corp.

[0192] Test Example

[0193] A standard greenhouse herbicide activity screening system was used to evaluate the herbicidal efficacy and crop safety of these test compounds. Seven broadleaf weed species including redroot pigweed (Amaranthus retroflexus, AMARE), velvetleaf (Abutilon theophrasti, ABUTH), sicklepod (Cassia obtusifolia, CASOB), ivyleaf morningglory (Ipomoea hederacea, IPOHE), lambsquarters (Chenopodium album, CHEAL), common ragweed (Ambrosia artemisiifolia L., AMBEL), and cocklebur (Xanthium strumarium, XANST) were used as test species. Four grass weed species including green foxtail (Setaria viridis, SETVI), barnyardgrass (Echinochloa crus-galli, ECHCG), johnsongrass (Sorghum halepense, SORHA), and large crabgrass (Digitaria sanguinalis, DIGSA) were also used. In addition, three crop species, field corn (Zea mays L., var. Dekalb 535, CORN), soybean (Glycine max L., var. Pella 86, SOY), and upland rice (Oryza sp., var.Tebonnet, RICE) were included.

[0194] Pre-emerge test

[0195] All plants were grown in 10 cm square plastic pots which were filled with a sandy loam soil mix. For pre-emerge tests, seeds were planted one day prior to application of the test compounds. For post-emerge tests, seeds were planted 8-21 days prior to the test to allow emergence and good foliage development prior to application of the test substances. At the time of the post-emerge application, plants of all species were usually at the 2-3 leaf stage of development.

[0196] All test compounds were dissolved in acetone and applied to the test units in a volume of 187 l/ha. Test materials were applied at rates ranging from 15 g ai/ha to 1000 g ai/ha using a track sprayer equipped with a TJ8001E even flow flat fan spray nozzle. Plants were arranged on a shelf so that the top of the canopy (post-emerge) or top of the soil surface (pre-emerge) was 40-45 cm below the nozzle. Pressurized air was used to force the test solution through the nozzle as it was mechanically advanced (via electrically driven chain drive) over the top of all test plants/pots. This application simulates a typical commercial field herbicide application.

[0197] Post-emerge test

[0198] In the post-emerge test, a commercial non-ionic surfactant was also included (0.25% v/v) to enhance wetting of the leaf surfaces of target plants. Immediately after application, test units of the pre-emerge applications were watered at the soil surface to incorporate the test materials. Subsequently, these test units were bottom-watered. Post-emerge test units were always bottom-watered.

[0199] At 14 days after application of the test materials, phytotoxicity ratings were recorded. A rating scale of 0-100 was used as previously described in Research Methods in Weed Science, 2nd edition, B. Truelove, Ed., Southern Weed Science Society, Auburn University, Auburn, Alabama, 1977. Briefly, “0” corresponds to no damage and “100” corresponds to complete death of all plants in the test unit. This scale was used both to determine efficacy against weed species and damage to crop species. Herbicide activity data for various compounds of this invention, which are shown by compound No. in Tables 1-8, are shown in Tables 11 and 12. The data demonstrate significant differences between compounds for both efficacy against weeds and selectivity for crop species. For selected compounds, excellent activity against a majority of the weed species was observed with minimal damage to at least one of the crop species.

[0200] Following table XIX shows comparative data for the pre-emerge herbicidal activity of compound 1.4 of present invention and the compound 2 reported in the Japanese patent Toku Kai Hei 5-25144 (1993). The data clearly shows the high level of activity observed with compound 1.4.

20TABLE XIXComparative herbicidal activity of compounds 1.4 and 2Cmpd.Rateno.(gai/ha)AMAREABUTHCASOBIPOHECHEALXANSTSETVIECHCGSORHADIGSAMAIZESOYRICE1.43.930950030000000007.810010030060060003000015.690100100010020800030001031.310010005010010801030300152062.5100100809010050100304095040501251001009510010050100959510040906025010010010010010090100100100100951006523.900000000000007.8000000000000015.6000000000000031.3000000000000062.50000000000000125003003000000000250050500506000000015

[0201] Tables XX and XXI show pre-emerge and post-emerge herbicidal activity data respectively for a few representative examples of the compounds described herein.

21TABLE XXPre-emerge Herbicidal 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00100—10010010010010010010015-363100100100100100100100100100100100909525010010010010010010010010010010010010010015-463100100100100100—10080—100909080250100100100100100—100100—10010010010015-563100100100100100—10070—100908070250100100100100100—10099—10099999915-66310010090100100—9999100100959598250100100100100100—1001001001009510010015-76310010010095100—100809590958590250100100100100100—10010010010010010010015-863604020060—200—30100152501001008070100—040—10080909015-9631001009099100—10099100901008595250100100100100100—1001001001001009810015-10631001008010010010010099100100100758025010010010010010010010010010010010010010015-1163100100100100100—10010010010099100100250100100100100100—10010010010010010010015-1346100100100100100—1009999100603590185100100100100100—10010010010010010010015-146310010090100100—100100100100994099250100100100100100—1001001001001009910015-1563100100100100100—1001001001001009595250100100100100100—10010010010010010010015-16631001009090100—10080100100906590250100100100100100—10010010010010010010015-1763100100100100100—10010010010010080100250100100100100100—1001001001001009510015-186310010010090100—957575100758090250100100100100100—100100100100100959915-1963100100100100100—100100100100958090250100100100100100—10010010010010010010015-20631001006080100—10050—10080657025010010010080100—100100—100959510015-2163100100100100100—100991001001009599250100100100100100—10010010010010010010015-226310010010050100—9060—100402530250100100100100100—100100—10090959916-263407501080—100000002501001006050100—60103050150016-6637090505090—0000201002501001007090100—4050507060907016-76300000—0000000250500000—000000017-163309501090—50002010010250901008070100—8070608010103017-2633000060—000000025060200090—000000017-4633000020—000000025010060101070—200010001017-563806003090—00000002501001003035100—50020600010

[0202]

22

TABLE XXI

Post-emerge Herbicidal Activity

Rate

AB

Cmpd.
g
AM
UT
CAS
IPO
CHE
AM
SET
ECH
SOR
DIG

CO
RIC

no
ai/ha
ARE
H
OB
HE
AL
BEL
VI
CG
HA
SA
SOY
RN
E

1-4
63
30
100
60
100
60
50
—
0
0
0
80
0
0

250
95
100
100
100
95
90
—
40
70
50
100
20
35

1-5
63
0
10
0
0
0
0
0
0
0
0
10
0
0

250
40
60
30
70
50
30
0
0
0
0
50
5
0

1-9
63
100
100
90
100
100
90
90
70
90
90
100
30
40

1-10
63
10
30
0
20
10
0
0
0
0
0
0
0
0

250
30
90
10
70
50
30
0
0
0
0
40
0
0

1-11
63
40
70
0
40
50
10
0
0
0
0
10
0
0

250
60
100
0
70
95
10
50
0
0
0
30
0
0

1-13
63
100
100
30
100
100
70
30
30
10
0
80
20
30

250
100
100
70
100
100
85
90
70
90
75
100
80
80

1-15
63
0
30
0
0
0
0
0
0
0
0
0
0
0

250
30
50
0
40
20
0
0
0
0
0
15
0
0

1-16
63
30
30
0
20
30
0
0
0
0
0
0
0
0

250
70
50
0
50
60
0
0
0
0
0
10
0
0

1-18
63
70
100
30
80
70
—
70
0
50
50
50
0
0

250
100
100
95
100
100
—
70
0
50
50
100
0
0

1-19
63
30
100
10
30
30
—
20
0
0
0
40
5
25

250
70
100
30
95
90
—
95
80
70
10
95
45
80

1-20
63
90
100
0
100
90
—
0
30
10
10
100
10
20

250
100
100
50
100
100
—
60
80
70
20
100
40
50

1-21
63
95
85
10
70
75
10
10
0
0
0
40
5
10

250
100
100
30
90
95
30
30
0
0
0
40
5
10

1-22
63
60
100
0
40
40
—
0
0
0
0
30
5
10

250
80
100
0
90
80
—
80
0
10
0
60
15
40

1-30
63
10
30
0
20
0
0
0
0
0
0
0
0
0

250
30
100
30
100
60
70
0
0
0
0
20
10
20

1-31
63
10
20
0
10
0
0
0
0
0
0
0
0
0

250
30
50
0
50
40
0
0
0
0
0
20
0
10

1-32
63
10
30
0
0
0
0
0
0
0
0
0
0
0

250
30

0
70
60
30
0
0
0
0
10
0
0

1-37
63
90
100
65
100
95
—
20
30
10
10
60
10
25

250
100
100
90
100
100
—
80
90
70
70
100
60
60

1-38
63
80
100
50
80
—
—
10
0
0
10
80
25
35

250
100
100
90
100
—
—
80
80
80
80
100
70
70

1-51
63
70
60
40
40
30
70
0
0
—
10
10
10
10

250
70
80
60
95
95
90
30
10
—
20
50
20
30

1-53
63
80
100
60
95
50
—
0
0
0
0
95
0
10

250
100
100
95
100
100
—
80
50
40
50
100
30
60

1-54
63
100
100
90
100
100
100
40
20
—
40
99
50
40

250
100
100
100
100
100
100
60
75
—
70
100
70
45

1-55
63
10
80
10
30
0
70
0
0
0
0
0
0
0

250
10
90
20
95
20
50
40
0
0
30
20
10
0

1-59
63
95
100
40
100
100
—
10
30
10
0
90
45
30

250
100
100
100
100
100
—
70
80
50
40
100
80
60

1-60
63
90
100
50
90
99
—
0
0
0
0
90
0
10

250
100
100
90
100
100
—
10
20
20
50
100
50
40

1-61
63
50
70
60
100
30
70
10
0
—
10
20
10
10

250
70
100
70
100
70
85
30
10
—
30
80
30
35

1-63
63
10
70
0
95
20
0
0
0
0
0
0
0
10

250
10
100
0
90
50
50
20
30
0
0
80
0
40

2-1
63
50
100
50
100
95
30
0
0
0
0
90
10
30

250
100
100
100
100
100
85
30
10
0
0
100
15
70

2-2
63
90
95
—
95
60
0
0
0
0
0
50
0
20

250
100
100
—
100
100
70
30
40
50
30
95
0
60

2-3
63
10
80
0
60
30
—
0
0
0
0
70
0
0

250
40
100
0
100
30
—
0
0
0
0
90
10
40

2-4
63
0
0
0
0
50
—
0
0
10
0
30
0
0

250
70
50
0
20
50
—
0
0
10
0
30
0
0

2-5
63
20
90
10
50
40
—
0
0
0
0
60
5
30

250
40
100
50
90
70
—
0
0
30
0
60
10
40

2-6
63
0
0
0
0
0
—
0
0
0
0
0
0
0

250
10
70
0
30
30
—
0
0
0
0
5
5
0

2-7
63
10
70
0
50
40
—
0
0
0
0
70
0
40

250
50
95
30
90
50
—
30
0
0
0
90
10
40

2-8
63
0
0
0
0
0
—
0
0
0
0
10
0
0

250
20
40
0
50
60
—
0
0
0
0
10
0
0

2-10
63
0
95
0
60
50
0
0
0
0
0
20
5
0

250
30
100
10
100
90
50
70
60
20
40
65
0
5

2-11
63
0
80
—
50
40
—
0
0
0
0
5
5
0

250
30
100
—
60
65
—
20
0
0
0
15
5
0

2-12
63
0
20
0
0
0
0
0
0
0
0
0
0
0

250
10
65
0
50
40
10
0
0
0
0
0
0
0

2-14
63
40
90
10
40
30
—
0
0
0
0
15
0
10

250
70
95
10
80
40
—
0
0
0
0
20
10
30

2-15
63
0
70
10
40
40
10
0
0
0
0
10
0
0

250
20
90
10
90
60
40
0
0
0
0
30
0
0

2-16
63
50
100
10
99
80
—
50
90
40
20
70
70
40

250
100
100
80
100
100
100
100
100
95
60
100
90
45

2-18
63
0
0
0
0
0
—
0
0
0
0
0
0
0

250
95
40
10
30
50
—
0
0
0
0
20
0
0

2-19
63
40
90
0
70
50
—
0
0
0
0
80
0
0

250
75
100
10
100
50
30
30
0
0
0
100
0
20

2-23
63
70
100
95
100
70
90
—
0
50
0
100
40
50

250
100
100
100
100
90
100
—
30
90
70
100
90
95

2-24
63
100
100
100
100
99
100
20
70
60
10
100
70
70

250
100
100
100
100
100
100
70
95
90
50
100
95
90

2-26
63
0
0
0
0
0
0
0
0
0
0
0
0
0

250
20
40
0
30
20
0
0
0
0
0
0
0
0

2-27
63
100
100
50
90
90
60
—
0
20
10
100
50
60

250
100
100
90
100
100
90
—
80
85
70
100
95
95

2-28
63
100
100
30
60
60
—
30
0
0
0
60
15
90

250
100
100
20
50
60
—
30
0
0
0
90
25
90

2-29
63
90
100
20
75
80
50
20
0
0
0
60
10
40

250
100
100
40
100
90
60
50
20
10
20
90
25
60

2-30
63
0
30
0
0
0
0
—
0
0
0
0
0
0

250
20
70
0
20
50
10
—
0
0
0
10
0
0

2-31
63
100
100
—
90
80
—
10
10
100
90
40
50

250
90
100
—
100
95
—
20
40
30
20
95
60
70

2-32
63
100
100
80
100
95
—
0
0
50
0
100
30
30

250
100
100
100
100
100
—
90
90
95
70
100
95
80

2-33
63
90
100
70
100
80
70
50
10
0
0
60
10
20

250
95
100
80
100
95
95
40
60
20
40
90
40
60

2-34
63
95
100
100
75
85
70
—
0
40
10
90
60
65

250
95
100
100
95
90
85
—
30
80
30
95
90
85

2-36
63
100
100
60
100
95
80
50
10
10
20
75
10
25

250
100
100
60
100
100
95
60
0
10
20
100
20
40

2-37
63
0
0
0
0
0
0
—
0
0
0
0
0
0

250
10
30
0
0
20
0
—
0
0
0
10
0
0

2-39
63
70
100
60
99
90
50
20
0
10
0
95
20
30

250
95
100
90
100
95
95
80
60
60
50
99
70
70

2-40
63
90
100
50
100
80
80
10
0
30
10
100
40
50

250
100
100
90
100
95
100
90
100
100
90
100
90
95

2-41
63
95
100
60
100
95
50
20
0
0
0
90
15
10

250
100
100
95
100
100
95
30
30
70
20
100
80
70

2-42
63
95
100
65
100
90
70
50
30
10
0
100
10
60

250
100
100
100
100
100
95
80
80
95
30
100
60
90

2-44
63
50
100
20
50
60
60
0
0
0
0
90
0
0

250
90
100
70
100
90
90
50
10
30
10
100
20
10

2-45
63
10
30
0
20
30
—
0
0
0
0
10
0
0

250
20
40
20
30
30
—
40
0
0
0
20
5
10

2-46
63
30
50
0
0
10
—
0
0
0
0
10
0
10

250
70
100
0
20

—
30
10
0
0
80
20
30

2-47
63
90
100
70
70
80
50
20
0
0
0
100
10
20

250
100
100
100
100
100
90
30
10
0
0
100
15
45

2-48
63
95
100
50
100
95
85
20
0
30
0
100
50
80

250
100
100
100
100
100
100
70
80
60
20
100
70
80

2-49
63
20
90
30
70
60
50
—
0
0
0
70
0
0

250
40
100
50
70
60
40
—
0
0
0
60
10
10

2-50
63
90
100
80
100
70
40
40
0
0
10
90
10
60

250
100
100
90
100
90
65
60
30
40
30
90
70
65

2-52
63
30
30
0
10
10
20
0
0
0
0
0
0
0

2-53
63
90
100
70
90
95
70
20
0
0
0
100
10
30

250
100
100
100
100
100
90
40
70
50
20
100
70
70

2-54
63
100
100
90
100
100
90
10
20
50
10
100
80
90

250
100
100
100
100
100
100
50
90
80
20
100
80
95

2-56
63
100
100
100
100
100
70
80
0
0
0
100
30
45

250
100
100
100
100
100
100
60
50
60
30
100
80
90

2-58
63
100
100
100
95
100
100
50
20
20
10
100
40
50

250
100
100
100
100
100
100
60
90
90
40
100
90
85

2-59
63
100
100
90
100
100
70
20
0
30
0
75
70
70

250
100
100
100
100
100
100
20
30
65
30
90
80
80

2-61
63
100
100
100
100
100
100
60
40
20
20
100
35
60

250
100
100
100
100
100
95
90
70
70
50
100
90
90

2-63
63
100
100
100
100
99
80
50
10
20
0
100
50
70

250
100
100
100
100
100
100
95
100
100
70
100
95
95

2-64
63
85
100
40
70
80
60
20
30
20
10
50
50
60

250
100
100
70
90
100
90
50
40
20
20
60
60
90

2-66
63
100
100
160
100
100
100
90
70
10
10
95
15
50

250
100
100
70
90
100
75
80
50
50
20
90
70
90

2-67
63
100
100
100
99
100
100
20
0
0
0
100
20
70

250
100
100
100
100
100
100
30
40
80
40
100
95
80

2-69
63
40
100
10
50
50
40
0
0
0
0
20
0
0

250
50
100
30
40
60
30
0
0
0
0
30
0
0

2-70
63
70
100
10
60
50
30
20
0
0
0
10
0
0

250
70
100
20
60
70
30
0
0
0
0
20
0
0

2-72
63
70
100
70
50
70
70
—
0
0
0
15
0
0

250
90
100
95
60
80
60
—
0
0
0
30
10
20

2-73
63
100
100
60
100
70
100
50
30
10
30
95
25
20

250
100
100
100
100
95
100
90
60
50
30
100
50
70

2-74
63
95
100
30
60
70
70
0
0
0
0
60
0
25

250
100
100
70
60
70
95
20
0
0
0
100
15
50

2-75
63
100
100
100
100
100
—
30
10
20
0
100
10
70

250
100
100
100
100
100
—
80
50
40
20
100
15
80

2-77
63
10
100
40
60
100
—
0
0
0
0
40
0
20

250
100
100
100
95
80
—
0
0
0
0
90
10
40

2-78
63
100
100
70
80
100
—
30
10
0
0
80
25
50

250
100
100
100
100
100
—
30
10
10
0
100
30
65

2-81
63
100
100
70
100
90
—
40
50
20
20
90
30
60

250
100
100
100
100
100
—
60
90
80
80
100
90
90

2-82
63
100
100
100
60
90
—
40
20
0
0
60
10
50

250
100
100
100
90
90
—
50
30
30
30
50
25
40

2-83
63
40
50
0
10
20
—
0
0
0
0
10
0
100

250
90
70
0
20
50
—
0
0
0
0
10
0
0

2-84
63
80
30
20
30
30
—
30
0
0
0
10
10
0

250
100
100
100
70
80
—
0
0
0
0
70
10
20

2-86
63
100
100
100
100
100
—
90
90
70
30
100
90
80

250
100
100
100
100
100
—
100
100
100
95
100
100
100

2-87
63
100
100
40
100
80
—
30
10
10
10
95
30
40

250
100
100
100
100
90
—
40
50
50
50
100
80
75

2-89
63
70
100
50
90
60
—
20
0
0
0
80
0
60

250
100
100
60
100
90
—
20
10
10
0
99
0
70

2-92
63
20
100
0
20
20
—
0
0
0
0
10
0
10

250
50
100
30
100
80
—
0
0
0
0
80
30
60

2-98
63
75
100
100
100
70
80
—
0
0
0
100
20
40

250
100
100
100
100
90
100
—
20
90
50
100
90
90

2-100
63
80
100
70
100
80
70
60
0
0
0
100
15
45

250
100
100
60
100
80
90
70
30
60
20
100
80
70

2-102
63
0
0
0
0
0
—
0
0
0
0
0
0
0

250
40
30
0
0
0
—
0
0
0
0
40
0
0

2-105
63
100
100
80
100
80
100
70
10
0
0
100
0
0

250
100
100
80
100
90
100
100
30
30
10
100
10
30

2-115
63
100
100
90
90
100
—
0
10
0
20
50
5
20

250
100
100
95
95
100
—
0
20
0
50
50
5
50

2-117
63
10
80
40
90
—
—
0
0
0
0
30
5
10

250
70
100
95
100
—
—
0
0
0
0
90
20
40

2-118
63
30
60
0
50
—
—
0
0
0
0
40
10
10

250
30
80
30
90
—
—
0
0
0
0
90
20
10

2-119
63
90
100
30
100
80
—
40
40
60
30
100
70
60

250
100
100
60
100
100
—
90
90
90
80
95
90
90

2-120
63
90
100
30
100
80
—
20
40
40
10
70
50
50

250
100
100
30
100
80
—
60
30
50
60
90
70
90

2-121
63
90
70
10
100
60
—
0
0
0
25
0
10
15

250
100
100
60
100
80
—
20
0
10
10
60
20
25

2-122
63
100
100
100
100
100
—
90
30
30
40
90
40
35

250
100
100
100
80
100
—
95
50
60
60
100
40
60

2-123
63
100
100
100
100
100
—
20
10
10
10
70
35
60

250
100
100
100
100
100
—
30
20
30
30
95
40
70

2-124
63
30
40
0
20
30
—
0
0
0
0
15
0
0

250
90
95
20
30
50
—
0
0
0
0
15
5
0

2-125
63
100
100
90
100
100
—
40
20
30
20
90
10
40

250
100
100
100
100
100
—
40
20
30
20
90
10
40

2-126
63
80
90
60
80
80
—
30
0
0
20
30
10
10

250
100
100
60
100
95
—
40
10
10
30
60
10
50

2-127
63
100
100
100
100
70
—
30
30
20
20
35
10
30

250
100
100
60
95
100
—
40
20
20
30
70
15
35

2-128
63
100
100
60
100
100
—
50
10
—
10
60
5
10

250
100
100
80
100
100
—
60
20
—
35
60
15
—

2-129
63
100
100
80
100
100
—
80
30
—
30
100
70
35

250
100
100
100
100
100
—
90
50
—
70
100
100
75

2-130
63
100
100
80
100
100
—
60
50
—
30
80
10
20

250
100
100
70
100
100
—
70
60
—
50
90
30
25

2-131
63
100
100
80
100
100
—
70
30
—
30
90
15
10

250
100
100
100
100
100
—
90
60
—
70
100
70
75

2-132
63
100
100
100
100
100
—
40
20
—
10
80
60
50

250
100
100
99
100
100
—
60
40
—
25
100
75
80

2-133
63
100
100
80
90
100
—
70
50
—
30
100
70
75

250
100
100
100
100
100
—
75
85
—
70
95
95
95

2-134
63
100
100
90
100
100
—
20
10
10
0
70
10
50

250
100
100
100
100
100
—
60
30
30
30
90
20
80

2-135
63
100
100
70
100
100
—
15
0
—
0
50
10
20

250
100
100
100
95
100
—
40
20
—
10
90
25
40

2-136
3
100
100
60
80
95
—
20
0
—
0
70
15
5

250
100
100
100
100
100
100
—
30
10
—
20
90
10
10

2-137
63
100
100
100
100
100
—
10
0
—
0
70
10
10

250
100
100
90
90
100
—
30
30
—
10
90
60
70

2-140
63
100
100
100
100
100
—
40
30
—
20
100
10
50

250
100
100
100
100
100
—
60
85
—
65
100
70
80

2-141
63
95
100
50
100
95
—
20
10
—
10
70
5
15

250
95
100
95
95
100
—
40
30
—
30
70
5
15

2-142
63
0
0
0
0
20
—
0
0
—
0
15
10
10

250
40
40
10
50
60
—
0
0
—
0
30
15
0

2-143
63
100
100
70
60
—
—
0
0
—
0
100
10
40

250
100
100
100
100
—
—
40
30
—
40
95
35
70

2-143
63
100
100
70
60
—

250
100
100
100
100
—
—
40
30
—
40
95
35
70

2-144
63
75
85
60
60
—
—
0
0
—
0
40
40
15

250
90
100
85
70
—
—
30
10
—
0
40
20
35

2-145
63
95
100
100
100
—
—
0
0
0
0
80
10
35

250
100
100
100
100
—
—
40
20
10
10
95
20
60

2-146
63
30
70
20
40
30
—
0
0
0
0
10
10
10

250
30
75
50
50
40
—
0
0
0
0
10
5
10

2-147
63
100
100
80
100
100
95
20
10
—
20
90
15
50

250
100
100
95
100
100
100
40
50
—
50
100
90
75

2-148
63
100
100
95
80
100
—
50
50
0
40
80
25
0

250
90
100
100
90
100
—
40
20
10
40
90
30
10

2-149
63
80
100
95
70
90
—
10
20
0
0
80
0
0

250
80
100
95
95
95
—
20
50
0
20
90
15
10

2-151
63
10
0
10
30
10
20
0
0
0
0
0
0
0

250
20
50
50
100
10
30
0
0
0
0
0
0
10

2-152
63
100
100
100
100
98
—
30
30
20
20
60
15
40

250
100
100
100
100
100
—
50
50
40
30
70
30
65

2-153
63
60
95
0
100
80
—
20
10
0
0
70
5
0

250
90
100
30
95
95
—
30
20
20
10
50
5
10

2-154
63
100
100
50
100
100
—
40
80
—
10
90
10
65

250
100
100
100
100
100
—
95
95
—
85
100
85
90

2-155
63
100
100
100
100
100
—
50
30
30
40
80
70
25

125
100
100
100
100
100
—
70
60
50
50
99
90
80

2-158
63
100
95
90
20
90
50
10
0
0
0
40
0
20

250
100
100
100
80
95
100
70
50
0
30
50
0
60

2-161
63
100
100
100
100
100
30
0
20
0
0
80
0
20

250
100
100
100
100
100
100
20
60
30
50
80
20
70

2-163
63
100
99
90
98
100
—
50
55
0
30
80
35
20

250
100
100
90
95
100
—
60
70
10
45
85
40
55

2-168
63
20
60
0
60
30
—
0
0
0
0
30
5
10

250
50
100
80
100
50
—
10
0
0
0
80
10
30

2-169
63
10
70
10
50
30
—
0
0
0
0
70
10
10

250
0
80
10
40
40
—
0
0
0
0
50
10
10

2-170
63
20
35
10
50
60
—
10
0
0
0
30
5
5

250
30
90
60
95
50
—
20
20
10
30
90
15
10

2-171
63
30
60
30
60
40
—
0
0
0
0
20
0
0

250
50
100
40
100
90
—
10
0
10
10
80
10
10

2-172
63
60
60
50
90
35
30
0
0
0
0
20
5
0

250
60
100
90
100
60
80
10
0
0
0
80
10
10

2-173
63
50
60
50
100
40
30
0
0
0
0
20
0
0

250
50
100
70
80
65
50
0
0
0
0
40
5
10

2-174
63
60
60
60
70
55
—
10
0
0
0
30
10
20

250
60
80
75
80
85
—
10
0
0
10
80
25
20

2-175
63
100
100
100
100
100
—
0
0
0
0
80
10
50

250
100
100
100
100
100
—
20
20
10
10
90
10
80

2-176
63
100
50
10
70
80
—
0
0
0
0
15
0
10

250
100
90
30
95
90
—
0
0
0
0
35
5
30

2-177
63
100
100
100
100
100
—
45
20
30
30
95
15
50

250
100
100
100
100
100
—
60
40
40
50
100
20
60

2-178
63
50
40
0
30
30
—
0
0
0
0
10
0
0

250
70
50
0
20
40
—
0
0
0
0
15
0
0

2-179
63
100
100
80
80
80
—
30
70
10
0
90
15
30

250
100
100
100
100
100
—
55
50
50
—
100
15
60

2-180
63
100
100
100
100
100
—
60
40
—
40
100
5
20

250
100
100
100
100
100
—
70
60
—
40
100
20
65

2-181
63
100
100
160
100
100
—
70
40
—
30
90
10
15

250
100
100
100
100
100
—
80
60
—
70
95
20
60

2-182
63
90
100
60
100
95
—
10
0
—
0
70
5
0

250
95
100
95
100
100
—
80
30
—
20
100
70

2-183
63
0
0
0
0
0
—
0
0
—
0
10
0
0

250
10
50
0
40
80
—
0
0
—
0
30
0
0

2-184
63
100
100
100
100
100
—
60
40
—
20
95
10
40

250
100
100
100
100
100
—
80
50
—
90
100
75
65

2-185
63
80
100
40
60
70
—
0
0
—
0
50
0
20

250
100
100
60
80
100
—
20
0
—
10
75
5
35

2-187
63
99
100
70
100
100
—
40
20
—
10
100
15
50

250
100
100
100
100
100
—
60
40
—
40
100
75
90

2-188
63
85
100
55
100
80
—
10
30
—
0
70
25
20

250
90
100
90
100
100
—
20
40
—
10
95
45
40

2-189
40.5
100
85
40
60
100
—
0
0
0
0
15
0
0

162
100
100
60
100
100
—
0
10
0
0
60
5
5

2-190
63
95
90
20
50
90
—
0
0
0
0
20
5
0

250
99
90
80
90
100
—
0
10
50
0
95
10
5

2-191
63
40
70
30
80
—
—
0
0
0
0
20
10
10

250
90
90
80
100
—
—
10
0
0
0
35
20
20

2-192
63
70
85
40
50
60
—
0
0
0
0
40
5
0

250
70
85
60
70
50
—
0
0
0
0
70
15
20

2-194
63
99
95
50
95
90
95
20
0
0
0
50
5
30

250
99
100
70
99
100
90
20
10
10
20
95
5
40

2-196
63
100
100
100
90
100
100
30
10
10
10
100
10
30

250
100
100
100
100
100
90
20
10
10
20
—
15
—

2-197
63
100
100
80
100
100
—
10
0
0
10
70
10
20

250
100
100
80
90
100
—
20
20
50
10
100
10
30

2-198
63
80
80
50
80
80
—
10
5
0
10
90
10
10

250
95
100
30
100
90
—
10
5
50
10
95
40
30

2-199
63
95
100
100
100
100
—
50
60
40
30
90
30
80

250
100
100
100
100
100
—
90
100
95
95
100
90
90

2-200
63
100
100
100
100
100
—
30
0
0
0
80
10
10

250
100
100
100
100
100
—
50
0
0
0
95
20
20

2-201
63
99
95
60
95
95
—
20
50
0
35
75
30
60

250
100
99
85
95
98
—
30
60
0
45
85
35
65

2-202
63
100
100
100
100
100
—
30
10
—
0
90
15
20

250
100
100
100
100
100
—
40
40
—
30
100
30
60

2-203
63
100
100
100
60
100
—
20
10
10
10
30
10
25

250
100
100
100
95
100
—
30
30
20
30
60
10
30

2-204
63
50
40
10
30
20
10
0
0
0
0
30
5
0

250
70
80
500
60
95
70
20
0
0
10
80
10
30

2-205
63
90
100
90
100
70
70
10
0
0
10
40
10
30

250
40
100
100
70
70
100
10
0
0
10
30
20
30

2-206
63
20
50
50
70
50
—
0
0
0
30
30
0
0

250
50
90
80
90
70
—
0
30
0
20
70
0
70

3-1
63
0
0
0
0
0
0
0
0
0
0
0
0
0

250
60
0
0
30
60
0
0
0
0
0
0
10
0

3-4
63
0
40
0
0
0
—
0
0
0
0
10
0
0

250
0
50
0
0
0
—
0
0
0
0
20
0
10

3-6
63
100
100
40
90
50
—
0
0
0
0
95
20
30

250
100
100
90
100
90
—
40
20
20
10
100
70
70

3-26
63
50
60
20
60
50
—
0
0
0
0
15
3
10

250
65
60
60
90
60
—
0
0
0
0
30
10
30

4-1
63
50
100
30
100
60
40
0
0
0
0
50
10
30

250
95
100
50
100
98
90
10
0
20
0
100
20
50

4-2
63
50
70
0
70
40
0
0
0
0
0
40
0
0

250
85
100
40
100
95
30
20
0
0
0
75
10
30

4-23
63
100
100
80
100
80
—
40
20
10
10
95
35
60

250
100
100
100
100
100
—
70
60
50
40
100
80
80

4-24
63
100
100
70
100
100
—
50
—
40
40
80
35
20

250
100
100
100
100
100
—
80
—
60
50
95
70
45

4-26
63
100
100
30
100
90
—
20
10
10
20
40
5
15

250
100
100
60
100
100
—
60
50
50
50
80
20
45

4-27
63
60
70
20
70
60
—
0
0
0
0
30
5
0

250
80
100
40
80
100
—
10
0
0
0
50
10
10

4-28
63
80
100
50
60
70
—
10
0
0
0
40
0
10

250
100
100
50
80
90
—
30
20
10
20
50
5
15

4-29
63
100
100
90
100
90
—
80
70
60
50
100
90
80

250
100
100
100
100
100
—
99
90
100
90
100
100
85

4-30
63
100
100
100
100
100
—
80
50
50
50
100
90
80

250
100
100
100
100
100
—
100
90
100
85
100
99
85

4-31
63
100
100
10
100
100
—
20
10
0
0
40
10
20

250
100
100
30
100
100
—
40
10
10
10
80
25
40

4-32
63
100
90
80
100
100
—
30
0
10
10
50
20
20

250
100
100
80
100
100
—
50
20
30
20
80
30
40

4-33
63
100
100
30
100
90
—
30
10
0
10
70
15
30

250
100
100
70
100
100
—
40
20
30
30
80
25
40

4-34
63
100
100
90
100
100
—
50
20
30
35
90
25
40

250
100
100
100
100
90
—
75
50
30
60
95
50
80

4-36
63
100
100
100
100
100
—
90
20
10
30
100
50
60

250
100
100
100
100
100
—
90
60
90
70
100
100
100

4-37
63
100
100
90
100
100
—
90
20
40
50
80
20
10

250
100
100
100
100
100
—
90
60
60
70
100
60
60

4-38
63
100
100
90
100
100
—
60
50
—
40
80
40
35

250
100
100
100
100
100
—
80
50
—
40
100
85
50

4-39
63
100
100
100
100
100
—
80
60
—
50
100
70
60

250
100
100
100
100
100
—
90
90
—
80
100
100
60

4-40
63
100
100
100
100
100
—
80
50
—
40
90
30
40

250
100
100
100
100
100
—
90
90
—
90
100
75
50

4-41
63
100
100
100
100
100
—
95
80
—
90
100
75
50

250
100
100
100
100
100
—
95
90
—
100
100
90
85

4-42
63
75
100
0
40
80
—
0
0
—
0
20
0
0

250
100
100
0
30
90
—
0
10
—
0
40
0
0

4-43
63
70
60
50
40
80
—
0
0
—
0
30
0
0

250
100
100
60
40
90
—
40
10
—
0
40
10
0

4-44
63
100
100
100
100
100
—
95
70
—
70
100
90
70

250
95
100
100
100
100
—
90
90
—
95
100
100
80

4-45
63
90
100
80
95
100
—
30
20
—
10
30
10
10

250
95
100
80
100
100
—
60
20
—
20
80
20
20

4-46
63
100
95
80
100
90
—
10
20
—
0
50
10
10

250
100
90
95
80
100
—
10
30
—
20
100
80
70

4-47
63
75
100
100
85
100
—
40
30
—
40
90
30
30

250
95
10
100
100
100
—
60
50
—
30
95
65
60

4-48
63
100
100
95
100
100
—
30
20
—
20
95
90
80

250
100
100
100
100
100
—
40
80
—
40
100
90
80

4-49
63
100
100
80
80
100
—
30
10
0
10
40
20
10

250
100
100
100
100
100
—
30
10
10
10
90
80
70

4-50
63
30
60
0
30
40
—
0
0
0
0
15
0
0

250
70
95
20
90
95
—
0
0
0
0
20
10
0

4-53
63
70
100
30
100
60
—
10
0
0
0
60
5
30

250
100
100
90
100
90
—
70
60
40
40
90
70
65

4-54
63
100
100
90
100
100
—
80
70
40
30
70
40
90

250
100
100
100
100
100
—
90
80
40
30
70
75
100

4-55
63
50
100
20
40
50
—
10
0
0
0
30
10
0

250
80
100
40
85
90
—
40
20
10
10
60
5
30

4-56
63
100
100
100
100
100
—
90
50
40
20
100
80
65

250
100
100
100
100
100
—
100
90
90
70
100
100
85

4-57
63
100
100
60
100
95
—
50
30
30
10
95
40
50

250
100
100
100
100
100
—
90
40
50
60
100
90
80

4-58
63
100
100
90
100
100
—
50
30
30
20
100
30
60

250
100
100
100
100
100
—
90
40
50
60
100
70
75

4-59
63
90
100
30
100
90
—
0
0
0
0
60
5
50

250
100
100
60
100
100
—
30
20
30
20
90
25
60

4-60
63
100
100
60
100
100
—
65
60
50
40
90
25
50

250
100
100
100
100
100
—
90
50
50
60
100
55
70

4-61
63
100
100
100
100
100
—
70
40
50
60
100
50
40

250
100
100
100
100
100
—
80
60
70
70
95
70
80

4-62
63
100
100
90
100
100
—
60
20
30
10
100
30
30

250
100
100
100
100
100
—
80
40
30
50
90
45
30

4-63
63
100
100
100
100
100
—
0
0
0
0
90
10
10

250
100
100
100
100
100
—
30
20
10
10
100
30
60

4-64
63
100
100
60
100
100
—
50
20
10
10
100
30
15

250
100
100
100
100
100
—
80
30
30
30
90
40
50

4-65
63
100
100
100
100
100
—
100
60
70
60
100
80
70

250
100
100
100
100
100
—
100
70
80
80
100
90
80

4-66
63
80
100
20
100
80
—
10
0
0
10
40
15
30

250
100
100
90
100
100
—
60
40
50
50
80
60
70

4-67
63
100
100
100
100
100
—
90
40
—
70
100
55
50

250
100
100
100
100
100
—
90
70
—
80
100
70
70

4-68
63
100
100
100
100
100
—
100
90
—
75
100
95
60

250
100
100
100
100
100
—
100
98
—
90
100
100
80

4-69
63
100
100
40
70
90
—
40
20
—
20
40
5
0

250
100
100
70
100
100
—
80
40
—
50
80
35
40

4-70
63
90
100
60
100
90
—
60
40
—
30
100
40
70

250
100
100
90
100
100
—
95
80
—
70
100
90
10

5-17
63
0
90
0
30
20
—
0
0
0
0
15
0
10

250
30
100
30
40
60
—
80
20
10
0
70
10
50

5-18
63
0
70
0
0
10
—
0
0
0
0
10
0
20

250
10
70
0
0
10
—
0
0
0
0
20
10
20

5-26
63
100
100
90
90
100
—
40
20
—
20
70
10
50

250
90
100
100
70
100
—
70
60
—
30
80
15
60

5-28
63
100
100
90
100
100
—
10
0
—
10
60
25
60

250
100
100
100
100
100
—
30
50
—
30
90
70
70

6-13
63
70
100
0
50
85
—
60
0
0
20
30
15
10

250
90
90
30
60
90
—
90
30
10
30
45
20
30

6-14
63
80
100
60
100
100
—
90
20
30
60
100
60
60

250
100
100
90
100
100
—
100
90
90
90
100
100
90

6-15
63
100
100
100
100
100
—
50
40
—
30
90
15
60

250
100
100
100
100
100
—
85
70
—
60
90
25
90

6-16
63
100
100
80
100
100
—
30
20
—
20
40
20
20

250
90
100
60
75
100
—
60
40
—
30
70
35
70

6-17
63
90
60
50
50
90
—
0
0
—
0
20
5
0

250
70
100
70
70
90
—
30
30
—
20
20
15
10

6-19
63
0
0
0
0
0
—
0
0
0
0
0
0
0

250
30
50
0
30
60
—
0
0
0
0
10
0
0

6-20
63
0
0
0
0
0
—
0
0
0
0
0
0
0

250
60
50
0
40
60
—
0
0
0
0
10
0
0

6-22
63
70
60
0
20
50
—
0
0
0
0
30
0
0

250
100
80
0
70
70
—
0
0
0
0
30
0
30

6-23
63
20
40
0
10
20
—
0
0
0
10
0
0
0

250
85
55
10
30
70
—
30
0
0
10
30
15
15

6-24
63
0
20
0
0
30
—
0
0
0
0
10
0
0

250
88
95
10
60
90
—
40
0
0
0
20
0
0

7-2
63
100
100
—
80
95
0
20
30
20
20
40
10
30

250
100
100
—
100
100
10
50
90
40
70
80
10
20

7-14
63
—
—
—
—
—
—
—
—
—
—
—
—
—

250
70
95
60
100
90
—
20
10
—
10
40
25
15

8-2
63
95
100
50
50
40
30
40
20
10
30
40
10
20

250
100
100
30
90
80
90
60
30
0
30
80
20
15

8-3
63
90
90
0
40
70
—
0
0
0
0
20
0
20

250
100
100
50
60
90
—
70
0
20
0
30
0
80

8-4
63
70
60
0
0
70
—
0
0
0
0
30
0
50

250
90
80
10
20
90
—
30
0
0
0
50
0
50

8-5
63
40
70
0
0
70
—
0
0
0
0
20
0
40

250
100
90
10
40
70
—
20
0
0
0
50
0
50

8-7
63
95
95
0
10
95
—
0
0
0
0
50
10
0

250
100
100
90
70
99
—
90
20
0
10
90
10
90

8-13
63
100
100
30
50
90
—
30
20
10
20
30
10
30

125
100
100
50
60
90
—
30
40
20
10
60
40
70

8-18
63
100
100
30
50
70
—
30
10
10
10
30
5
50

250
100
100
40
60
80
—
30
30
3020
70
30
60

8-30
63
100
100
80
100
100
—
40
30
30
20
90
10
40

250
100
100
100
100
100
—
70
70
50
40
95
15
35

8-31
63
100
100
60
100
100
—
20
—
10
10
80
10
45

250
100
100
80
100
100
—
20
—
30
30
90
10
30

8-36
63
95
100
70
100
95
—
10
0
0
10
30
10
10

250
90
100
95
85
100
—
10
20
10
5
40
15
20

9 4
63
50
50
20
45
70
—
20
—
0
0
40
5
10

250
80
100
60
100
85
—
30
—
10
0
90
10
40

9-14
63
85
100
40
80
95
—
10
0
—
0
60
15
0

250
100
100
40
90
100
—
20
10
—
10
90
50
40

9-15
63
100
100
100
100
100
—
10
0
0
0
100
5
40

250
100
100
100
100
100
—
35
10
10
20
100
10
70

9-16
63
30
100
50
90
65
—
0
0
0
10
90
5
30

250
75
100
85
100
80
—
20
10
0
0
100
65
70

9-19
63
80
100
80
75
100
—
10
0
0
0
60
10
15

250
98
100
95
90
100
—
20
10
0
10
80
10
25

11-6
63
100
100
100
70
80
100
10
50
0
0
10
0
20

250
100
100
100
100
100
100
50
80
0
0
40
20
60

11-13
63
100
95
85
98
100
—
55
65
0
40
65
45
45

250
100
100
85
98
100
—
40
55
15
60
85
45
65

12-2
63
30
100
50
90
100
—
0
30
10
0
60
10
20

250
100
100
95
100
100
—
50
80
90
70
100
100
80

12-3
63
95
90
20
50
90
—
0
0
0
0
20
5
0

250
99
90
80
90
100
—
0
10
50
0
95
10
5

12-5
63
70
100
40
100
100
—
20
10
—
0
40
25
20

250
85
100
60
99
99
—
10
10
—
10
30
20
15

12-8
63
80
100
50
90
95
—
20
10
0
10
40
5
20

250
90
100
70
80
99
—
25
10
10
0
80
10
15

13-3
63
90
100
90
75
100
—
10
0
—
0
30
10
25

250
90
90
100
70
100
—
30
20
—
10
40
10
20

13-4
63
100
100
95
85
95
—
20
10
—
0
70
5
30

250
95
100
100
85
100
—
40
30
—
10
90
5
50

13-5
63
70
70
40
50
95
—
0
0
0
0
10
7
10

250
75
70
30
60
90
—
10
0
0
20
25
15
20

14-1
63
100
85
55
85
80
—
40
85
25
80
100
85
40

250
100
98
70
100
98
—
70
95
75
95
100
100
80

14-2
63
100
80
50
75
95
—
30
0
0
20
35
35
25

250
100
100
60
100
95
—
20
45
30
40
40
45
30

14-3
63
95
100
10
50
90
—
30
99
80
99
100
100
5

250
100
100
75
100
100
—
70
100
70
100
100
100
80

14-4
63
100
80
50
50
100
—
30
85
—
75
100
70
15

250
100
100
100
60
100
—
65
99
—
95
100
80
40

14-5
63
100
100
10
30
100
—
60
40
—
95
20
70
20

250
100
100
50
100
100
—
95
100
—
100
95
100
30

14-6
63
95
90
50
70
80
40
30
99
50
50
100
50
0

250
100
100
100
100
100
80
80
100
65
75
100
60
35

14-7
63
95
50
0
20
90
50
60
100
70
80
85
95
10

250
100
100
20
60
99
90
85
100
90
100
99
100
25

14-8
63
90
60
30
30
70
10
10
95
—
40
95
40
5

250
100
100
80
95
99
50
40
99
—
85
100
80
30

14-10
63
90
70
0
0
60
10
30
98
—
75
80
70
5

250
100
100
90
80
100
—
90
100
50
100
100
60
20

14-11
63
95
80
50
90
50
—
80
100
80
99
60
100
10

250
100
100
80
100
100
—
100
100
9
100
100
60
20

14-12
63
85
10
20
40
90
80
30
98
—
50
95
30
0

250
90
85
80
70
99
80
40
99
—
60
100
85
10

14-13
63
90
30
0
40
60
30
20
100
—
65
75
55
0

250
100
80
20
60
100
40
40
99
—
90
98
100
15

14-14
63
50
50
0
30
50
70
50
100
0
90
100
10
0

250
100
100
60
50
90
70
70
100
20
100
100
50
30

14-15
63
100
60
0
50
50
20
70
100
50
95
40
20
0

250
100
90
50
90
100
100
80
100
40
100
100
60
0

14-16
63
60
60
20
40
95
—
0
95
0
95
100
0
0

250
100
100
40
50
100
—
30
100
30
100
100
70
10

14-17
63
100
100
20
20
90
—
20
100
50
100
80
70
0

250
100
100
30
70
100
—
70
100
90
100
100
95
0

14-18
63
100
30
20
30
99
0
10
99
10
20
10
20
10

250
100
60
60
60
100
10
20
100
30
60
40
50
25

14-19
63
90
60
40
30
90
—
0
100
0
100
100
0
0

250
100
100
70
90
100
—
30
100
0
100
100
40
20

14-20
63
95
99
0
50
80
—
0
100
10
100
70
0
0

250
100
100
50
70
100
—
50
100
90
100
100
80
10

14-21
63
90
100
30
40
70
50
10
99
10
70
95
50
10

250
100
95
60
50
95
95
40
100
70
98
10
100
45

14-22
63
50
30
0
10
50
100
30
100
40
80
95
10
0

250
100
100
50
80
90
100
60
100
60
95
100
50
10

14-23
63
50
50
20
80
50
50
60
100
40
50
100
0
0

250
100
90
70
95
80
40
70
100
50
95
100
40
20

14-24
63
40
70
0
20
80
50
0
100
0
95
30
10
10

250
90
100
0
40
90
50
50
100
50
100
100
20
50

14-25
63
95
100
50
70
80
100
50
100
40
95
100
100
10

250
100
100
80
100
100
100
80
100
95
100
100
100
50

14-26
63
90
70
50
20
60
100
0
100
30
100
100
40
10

250
100
100
90
100
100
100
0
100
70
100
100
100
10

14-27
63
50
70
50
70
90
—
0
99
0
70
95
5
0

250
90
80
30
50
100
—
20
100
10
95
100
10
0

14-28
63
90
100
20
50
95
—
0
100
0
20
80
10
0

250
100
100
30
70
100
—
30
100
50
50
100
70
40

14-29
63
90
50
0
80
30
100
20
100
50
70
100
15
0

250
100
100
40
80
60
100
70
100
70
95
100
50
10

14-30
63
70
60
20
0
50
—
0
100
0
60
100
10
0

250
100
100
60
50
100
—
30
100
50
100
100
20
0

14-31
63
90
90
50
10
70
—
0
100
0
95
50
10
0

250
100
100
50
70
90
—
50
100
20
100
100
50
0

14-32
63
95
90
20
0
0
40
40
100
0
70
70
0
0

250
100
95
40
20
80
40
70
100
10
90
100
0
0

14-33
63
100
90
0
20
20
0
40
100
10
70
10
10
0

250
100
100
0
20
70
100
90
100
95
100
70
95
0

14-34
63
100
99
40
60
100
40
100
100
60
70
99
80
25

250
100
100
100
90
100
100
100
100
80
99
100
100
70

14-35
63
100
95
0
70
100
100
50
100
30
50
100
100
80

250
100
100
90
100
100
100
95
100
70
95
100
100
100

14-36
63
100
95
20
30
99
100
85
99
20
40
95
95
35

250
100
100
40
70
100
95
99
100
40
65
100
95
60

14-37
63
100
100
20
30
100
100
90
100
0
80
90
20
70

250
100
100
50
100
100
100
100
100
30
100
100
95
100

14-38
63
100
100
0
70
100
—
90
100
0
95
0
50
0

250
100
100
0
70
100
—
100
100
30
100
20
100
40

14-39
63
100
99
60
20
100
50
95
100
30
60
90
30
90

250
100
100
100
50
100
50
100
100
40
100
100
50
100

14-40
63
100
90
20
30
100
90
85
100
20
20
50
35
15

250
100
100
60
60
100
100
99
100
20
40
95
70
75

14-41
63
100
100
0
30
100
—
90
100
40
100
100
100
20

250
100
100
0
50
100
—
100
100
70
100
100
100
95

14-42
63
100
100
60
100
100
—
100
100
60
95
100
100
95

250
100
100
90
100
100
—
100
100
95
100
100
100
100

14-43
63
100
100
40
95
100
—
90
100
80
80
100
95
95

250
100
100
90
100
100
—
100
100
95
100
100
100
100

14-44
63
100
100
0
50
100
—
100
100
30
100
100
100
90

250
100
100
0
90
100
—
100
100
80
100
100
100
100

14-45
63
100
100
30
100
100
100
70
100
70
90
90
70
70

250
100
100
30
100
100
100
95
100
90
100
100
100
100

14-46
63
95
100
60
100
100
—
90
100
80
80
100
95
60

250
100
100
90
100
100
—
100
100
95
100
100
100
100

14-47
63
100
100
0
80
100
100
90
100
70
95
100
40
100

250
100
100
70
100
100
100
100
100
80
100
100
100
100

14-48
63
100
100
0
0
100
80
50
50
0
70
95
40
70

250
100
100
100
100
100
—
100
100
90
90
100
100
100

14-49
63
100
100
70
100
100
100
80
100
70
70
95
80
50

250
100
100
95
100
100
100
100
100
95
95
100
100
95

14-50
63
100
30
90
0
50
—
0
0
0
0
0
10
30

250
100
50
100
0
100
—
0
0
0
50
20
30
50

14-51
63
0
0
0
0
0
0
0
10
0
0
0
0
0

250
0
50
0
30
10
20
0
20
0
0
30
0
0

14-52
63
20
90
0
100
—
—
0
0
0
0
0
0
0

250
50
100
70
100
—
—
0
10
0
0
100
10
0

14-54
63
40
60
0
30
20
—
10
30
0
0
30
5
10

250
50
80
30
80
60
—
10
30
0
10
35
15
10

14-55
63
30
70
10
70
30
—
0
10
0
0
10
5
20

250
—
—
—
—
—
—
—
—
—
—
—
—
—

14-56
63
100
70
30
100
99
90
30
20
30
10
40
10
0

250
100
100
40
100
100
80
70
80
70
50
50
30
25

14-59
63
20
50
0
30
10
—
0
0
0
0
0
0
0

250
20
30
10
30
10
—
0
0
0
0
10
0
0

14-60
63
70
100
40
100
99
—
20
50
20
10
100
10
10

250
100
100
70
100
100
—
30
75
50
60
100
60
20

14-61
63
20
30
0
20
40
—
0
0
0
0
0
0
0

250
60
60
30
50
75
—
20
60
20
70
40
70
30

14-62
63
30
40
0
30
10
40
0
0
—
0
15
5
0

250
50
60
30
50
20
30
0
0
—
0
15
5
5

14-63
63
95
90
95
70
80
20
50
100
—
40
95
35
5

250
100
100
100
70
100
50
70
99
—
90
100
80
15

14-64
63
100
100
10
30
70
30
30
100
—
40
80
99
5

250
100
100
20
80
99
40
70
100
—
99
90
100
10

14-65
63
100
100
90
50
90
—
100
100
30
99
100
0
0

250
100
100
100
70
100
—
100
100
50
100
100
50
10

14-66
63
95
100
80
70
80
—
95
100
60
100
80
90
0

250
100
100
90
90
99
—
100
100
80
100
99
100
10

15-1
63
100
100
100
100
100
—
80
80
—
90
100
80
75

250
100
100
100
100
100
—
100
99
—
100
100
95
95

15-2
63
20
80
10
90
—
—
0
0
0
0
40
15
50

250
95
100
75
100
—
—
80
90
70
80
100
80
75

15-3
63
95
100
70
95
95
—
30
10
0
20
90
25
50

250
100
100
100
100
100
—
80
90
90
80
100
80
90

15-4
63
70
100
80
100
100
—
50
40
—
30
90
50
70

250
100
100
80
100
100
—
80
90
—
70
100
90
95

15-5
63
70
100
40
90
100
—
70
70
—
30
100
70
60

250
100
100
80
100
100
—
80
90
—
70
100
90
90

15-6
63
50
100
30
50
—
—
30
20
—
0
60
25
60

250
85
100
70
100
—
—
75
95
—
90
100
80
95

15-7
63
100
100
60
100
100
—
30
40
—
20
90
60
50

250
100
100
100
100
100
—
90
95
—
75
100
80
90

15-8
63
20
70
0
50
95
—
0
0
—
0
60
0
10

250
60
100
40
90
90
—
30
20
—
0
90
55
60

15-9
63
10
80
10
100
—
—
0
0
—
0
40
30
50

250
95
100
60
85
—
—
80
90
—
80
95
70
90

15-10
63
100
100
100
100
100
—
30
10
30
60
95
45
50

250
100
100
100
100
100
—
75
80
70
90
95
65
80

15-11
63
95
100
90
100
100
—
40
50
50
50
95
45
65

250
100
100
100
100
100
—
80
99
99
95
100
85
99

15-12
63
95
100
90
100
100
—
70
70
80
95
100
80
80

250
100
100
100
100
100
—
100
100
99
100
100
95
99

15-13
63
80
100
60
100
95
—
20
20
10
10
95
15
60

250
95
100
100
100
100
—
60
85
70
70
100
50
90

15-14
63
100
100
80
100
100
—
20
20
20
20
100
20
40

250
100
100
100
100
100
—
55
90
70
60
100
65
50

15-15
63
100
100
80
90
100
—
40
30
30
40
95
45
70

250
100
100
100
100
100
—
95
100
99
100
100
90
95

15-16
63
80
100
80
100
100
—
30
10
10
20
95
15
70

250
100
100
100
100
100
—
60
90
70
80
100
45
80

15-17
63
90
100
80
100
—
—
40
50
20
40
90
35
75

250
100
100
100
100
—
—
90
99
95
99
100
80
90

15-18
63
100
100
40
90
100
—
20
10
0
10
90
20
30

250
100
100
100
100
100
—
80
95
99
100
100
80
85

15-19
63
100
100
75
100
100
—
40
50
40
50
90
35
65

250
100
100
100
100
100
—
100
100
100
100
100
85
90

15-20
63
100
100
80
100
100
—
80
50
—
30
95
40
35

250
100
100
100
100
100
—
100
100
—
90
100
85
80

15-21
63
95
100
100
100
100
—
50
60
40
30
90
30
80

250
100
100
100
100
100
—
90
100
95
95
100
90
90

15-22
63
100
100
70
100
100
—
40
40
—
30
90
30
50

250
100
100
100
100
100
—
95
100
—
90
100
90
90

16-2
63
60
40
0
0
30
—
0
0
0
0
10
0
0

250
60
70
10
0
70
—
0
0
0
0
40
10
20

16-4
63
0
0
0
0
0
—
0
0
0
0
0
0
0

250
0
0
0
0
0
—
0
0
0
0
0
0
0

16-6
63
70
70
0
30
0
—
0
0
20
20
0
0
0

250
70
100
0
70
70
—
0
0
40
80
0
0
10

16-7
63
0
0
0
0
0
—
0
0
0
0
0
0
0

250
0
0
30
30
0
—
0
0
0
0
0
0
0

17-1
63
10
70
20
80
30
—
0
0
0
0
10
0
0

250
30
70
10
80
60
—
0
0
0
0
30
0
0

17-2
63
0
0
0
0
0
—
0
0
0
0
0
0
0

250
30
50
10
20
40
—
0
0
0
0
10
0
0

17-4
63
20
35
10
40
20
—
0
0
0
0
10
0
0

250
70
70
20
80
40
—
0
0
0
0
15
0
0

17-5
63
10
50
10
30
40
—
0
0
0
0
20
0
0

250
40
80
20
70
80
—
0
0
0
0
35
10
0

	Number	Date	Country
Parent	09530373	Apr 2000	US
Child	09930149	Aug 2001	US

	Number	Date	Country
Parent	08958313	Oct 1997	US
Child	PCT/US98/17197	Aug 1998	US

Substituted benzene compounds, process for their preparation, and herbicidal and defoliant compositions containing them

Information

Publication Number

Date Filed

Date Published

Inventors

Original Assignees

CPC

US Classifications

International Classifications

Abstract

Description

Claims

Divisions (1)

Continuation in Parts (1)