Benzaldehyde oxime derivatives, production and use thereof

FIELD OF THE INVENTION
The present invention relates to novel benzaldehyde oxime derivatives, specifically .alpha.-azolyl-2-substituted benzaldehyde oxime derivatives, their production, and fungicidal, herbicidal and growth regulating compositions containing them.
BACKGROUND OF THE INVENTION
U.S. Pat. No. 4,599,348 (JP-A 60-87269), JP-A 1-308260, JP-A 3-68559, JP-A 5-1046 and W092/09581 disclose .alpha.-azolylbenzaldehyde oxime derivatives and their insecticidal and fungicidal activities. There is still a need for compounds having superior activity, utility, etc., as well as low toxicity.
OBJECTS OF THE INVENTION
The main object of the present invention is to provide novel compounds having excellent fungicidal, herbicidal and growth regulating activities.
Another object of the present invention is to provide processes for producing the above novel compounds.
Another object of the present invention is to provide novel fungicidal, herbicidal and growth regulating compositions.
These objects as well as other objects and advantages of the present invention will become apparent to those skilled in the art from the following description.
SUMMARY OF THE INVENTION
The present inventors have intensively studied to achieve the above objects. As a result, it has been found that novel benzaldehyde oxime derivatives having various groups attached to their 2-position via an oxygen atom or sulfur atom, specifically .alpha.-azolyl-2-substituted benzaldehyde oxime derivatives, have excellent herbicidal activity, growth regulating activity, particularly growth inhibiting activity, as well as excellent fungicidal activity.
That is, the present invention provides a compound of the formula (I): ##STR1## wherein R.sup.1 is alkoxycarbonylalkyl, optionally substituted acylalkyl, optionally substituted phenyl, optionally substituted phenylalkyl, optionally substituted phenoxyalkyl, an optionally substituted heterocyclic group or optionally substituted heterocyclic alkyl; R.sup.2 is hydrogen, alkyl, alkenyl, alkynyl, halogenated alkyl, halogenated alkenyl, halogenated alkynyl, cycloalkyl, optionally substituted phenyl, optionally substituted benzyl, an optionally substituted heterocyclic group or optionally substituted heterocyclic alkyl; R.sup.3 is hydrogen, alkyl, alkoxy or halogen; X is 0 or S; Y is CH or N; and .about. represents any configuration of the E-isomer, Z-isomer or a mixture of E- and Z-isomers; provided that, when X is 0, R.sup.1 is not optionally substituted phenyl, and that when X is 0, R.sup.1 is not unsubstituted benzyl; or a salt thereof.
The present invention also provides a fungicidal composition comprising as an active ingredient a compound of the formula (I) and an inert carrier or diluent.
The present invention also provides a herbicidal composition comprising as an active ingredient a compound of the formula (I) and an inert carrier or diluent.
The present invention also provides a growth regulating composition comprising as an active ingredient a compound of the formula (I) and an inert carrier or diluent.
The present invention also provides a process for producing a compound of the formula (I): ##STR2## wherein each symbol is as defined above, which comprises reacting a compound of the formula (XIII): ##STR3## wherein each symbol is as defined for the formula (I), with a compound of the formula (III):
R.sup.1 --L (III)
wherein L is halogen, alkylsulfonyl, alkylsulfonyloxy or arylsulfonyloxy and R.sup.l is as defined for the formula (I), in the presence of a base.
The present invention also provides a process for producing a compound of the formula (I): ##STR4## wherein each symbol is as defined above, which comprises reacting a compound of the formula (XI): ##STR5## wherein A is halogen and the other symbol is as defined for the formula (I), with a compound of the formula (XII): ##STR6## wherein Y is as defined for the formula (I), and then, if necessary, reacting the resulting compound with a compound of the formula (XXII):
R.sup.2 --L (XXII)
wherein L is halogen, alkylsulfonyl, alkylsulfonyloxy or arylsulfonyloxy and R.sup.2 is as defined for the formula (I) except that R.sup.2 is not hydrogen, in the presence of a base.
The present invention also provides a process for producing a compound of the formula (I): ##STR7## wherein each symbol is as defined above, which comprises reacting a compound of the formula (X): ##STR8## wherein each symbol is as defined for the formula (I), with a compound of the formula (XIV): ##STR9## wherein W is carbonyl or sulfinyl, Z is chlorine bromine or ##STR10## and Y is as defined for the formula (I).
The present invention also provides a process for producing a compound of the formula (I): ##STR11## wherein each symbol is as defined above, which comprises reacting a compound of the formula (XIII): ##STR12## wherein each symbol is as defined for the formula (I), with a compound of the formula (XXIII):
R.sup.1 --OH (XXIII)
wherein R.sup.1 is as defined for the formula (I).
DETAILED DESCRIPTION OF THE INVENTION
Examples of the alkoxycarbonylalkyl represented by R.sup.1 include alkoxycarbonylalkyl composed of alkoxycarbonyl having 2 to 6 carbon atoms and alkyl having 1 to 3 carbon atoms, such as methoxycarbonylmethyl, methoxycarbonylethyl, ethoxycarbonylmethyl, ethoxycarbonylethyl, etc. In particular, methoxycarbonylmethyl is preferred.
Examples of the optionally substituted acylalkyl represented by R.sup.1 include acylalkyl composed of acyl having 1 to 8 carbon atoms (e.g., formyl, acetyl, propionyl, benzoyl, nicotinoyl, etc.) and alkyl having 1 to 3 carbon atoms, such as acetylmethyl, acetylethyl, benzoylmethyl, benzoylethyl, etc. When the acylalkyl is substituted, the substituent is selected from the same substituents as those of the optionally substituted phenyl represented by R.sup.1 described below. The optionally substituted acylalkyl is preferably benzoylmethyl.
The optionally substituted phenyl represented by R.sup.1 includes unsubstituted phenyl and substituted phenyl. The substituted phenyl has 1 to 5 substituents selected from C.sub.1-5 alkyl (e.g., methyl, ethyl, isopropyl, tert-butyl, etc.), C.sub.1-4 alkoxy (e.g., methoxy, ethoxy, propoxy, etc.), phenyl, phenoxy, benzyloxy, C.sub.1-4 alkylthio (e.g., methylthio, ethylthio, propylthio, etc.), C.sub.1-3 alkylsulfonyl (e.g., methylsulfonyl, ethylsulfonyl, propylsulfonyl, etc.), cyano, nitro, halogen (e.g., fluorine, chlorine, bromine, iodine), halogenated C.sub.1-3 alkyl (e.g., trifluoromethyl, trichloromethyl, etc.) and halogenated C.sub.1-3 alkoxy (e.g., trifluoromethyloxy, trichloromethyloxy, etc.). These substituents may be at any possible position in the phenyl. When X is 0, R.sup.1 is not optionally substituted phenyl.
Examples of the optionally substituted phenylalkyl represented by R.sup.1 include that composed of the above optionally substituted phenyl and alkyl having 1 to 6 carbon atoms, such as phenylmethyl, phenylethyl, phenylpropyl, phenylbutyl, etc., each of which may optionally be substituted. Preferred examples of the optionally substituted phenylalkyl include optionally substituted 1-phenylalkyl (e.g., benzyl, 1-phenylethyl, 1-phenylpropyl, etc.), optionally substituted phenethyl, optionally substituted 3-phenylpropyl, etc. When X is 0, the optionally substituted phenylaklyl is not unsubstituted benzyl.
Examples of the optionally substituted phenoxyalkyl represented by R.sup.1 include that composed of optionally substituted phenoxy and alkyl having 1 to 6 carbon atoms, such as phenoxymethyl, phenoxyethyl, phenoxypropyl, phenoxybutyl, etc., each of which may optionally be substituted. Preferred examples of the optionally substituted phenoxyalkyl include 2-phenoxyethyl, 3-phenoxypropyl and 4-phenoxybutyl each of which may optionally be substituted.
The above optionally substituted phenyl or optionally substituted phenoxy may be attached to any possible position of the alkyl. When the phenylalkyl or phenoxyalkyl is substituted, the substituent is selected from the same substituents as those of the optionally substituted phenyl represented by R.sup.1, and the substituent may be at any possible position in the phenyl ring. Preferably, the substituent is selected from C.sub.1-5 alkyl (e.g., methyl, ethyl, isopropyl, tert-butyl, etc.), C.sub.1-4 alkoxy (e.g., methoxy, ethoxy, propoxy, etc.), halogen (e.g., fluorine, chlorine, bromine, iodine), halogenated C.sub.1-3 alkyl (e.g., trifluoromethyl, trichloromethyl, etc.) and halogenated C.sub.1-3 alkoxy (e.g., trifluoromethyloxy, trichloromethyloxy, etc.).
Examples of the heterocyclic group of the optionally substituted heterocyclic group represented by R.sup.1 include thienyl (e.g., 2-thienyl, etc.), pyridyl (e.g., 2-pyridyl, etc.), isoxazolyl (e.g., isoxazol-3-yl, isoxazol-5-yl, etc.), benzoxazolyl (e.g., benzoxazol-2-yl, etc.), thiazolyl (e.g., thiazol-2-yl, etc.), benzothiazolyl (e.g., benzothiazol-2-yl, etc.), pyrimidinyl (e.g., pyrimidin-2-yl, pyrimidin-4-yl, etc.), thiadiazolyl (e.g., 1,3,4-thiadiazol-2-yl, etc.), 1,3-dioxolanyl (e.g., 1,3-dioxolan-2-yl, etc.), quinolyl (e.g., 2-quinolyl, etc.), quinoxalinyl (e.g., quinoxalin-2-yl, etc.), etc. In particular, 2-pyridyl is preferred. When the heterocyclic group is substituted, the substituent is selected from the same substituents as those of the optionally substituted phenyl represented by R.sup.1 described above. These substituents may be at any possible position in the heterocyclic group.
Examples of the optionally substituted heterocyclic alkyl represented by R.sup.1 include that composed of the above optionally substituted heterocyclic group represented by R.sup.1 and alkyl having 1 to 4 carbon atoms, such as heterocyclic methyl, heterocyclic ethyl, heterocyclic propyl, etc., each of which may optionally be substituted. In particular, optionally substituted heterocyclic methyl is preferred. The optionally substituted heterocyclic group may be at any possible position in the alkyl. When the heterocyclic group is substituted, the substituent is selected from the same substituents as those of the above optionally substituted phenyl represented by R.sup.1. These substituents may be at any possible position in the heterocyclic group.
R.sup.1 is preferably optionally substituted phenylalkyl, optionally substituted phenoxyalkyl, optionally substituted heterocyclic group or optionally substituted heterocyclic alkyl.
Examples of the alkyl represented by R.sup.2 include alkyl having 1 to 6 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, isobutyl, etc.
Examples of the alkenyl represented by R.sup.2 include alkenyl having 2 to 6 carbon atoms such as vinyl, allyl, crotyl, etc. In particular, allyl is preferred.
Examples of the alkynyl represented by R.sup.2 include alkynyl having 2 to 6 carbon atoms such as ethynyl, propynyl, butynyl, etc.
Examples of the halogenated alkyl, halogenated alkenyl and halogenated alkynyl represented by R.sup.2 include alkyl, alkenyl and alkynyl represented by R.sup.2 each of which is substituted with at least one halogen (e.g., fluorine, chlorine, bromine, iodine).
Examples of the cycloalkyl represented by R.sup.2 include cycloalkyl having 3 to 8 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.
Examples of the optionally substituted phenyl, optionally substituted benzyl, optionally substituted heterocyclic group and optionally substituted heterocyclic alkyl represented by R.sup.2 include the same groups as those represented by R.sup.1.
R.sup.2 is preferably alkyl or alkenyl, more preferably methyl, ethyl or allyl.
Examples of the alkyl represented by R.sup.3 include alkyl having 1 to 4 carbon atoms such as methyl, ethyl, propyl, butyl, etc.
Examples of the alkoxy represented by R.sup.3 include alkoxy having 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy, butoxy, etc.
Examples of the halogen represented by R.sup.3 include fluorine, chlorine, bromine and iodine.
R.sup.3 is preferably hydrogen, alkyl, alkoxy or halogen, more preferably hydrogen, methyl, methoxy, fluorine or chlorine. R.sup.3 may be at any possible position in the phenyl, preferably at 5-position in the phenyl.
X is preferably 0.
Y is preferably CH.
Preferred examples of the compounds of the formula (I) include those wherein R.sup.1 is optionally substituted phenylalkyl, optionally substituted phenoxyalkyl or optionally substituted pyridyl; R.sup.2 is alkyl; R.sup.3 is hydrogen, alkyl, alkoxy or halogen; X is 0; and Y is CH.
More preferred examples of the compounds of the formula (I) include:
a compound of the formula (I) wherein R.sup.1 is 4-methylphenylmethyl, R.sup.2 is methyl, R.sup.3 is hydrogen, X is 0, and Y is CH (Compound No. 3);
a compound of the formula (I) wherein R.sup.1 is 2-chlorophenylmethyl, R.sup.2 is methyl, R.sup.3 is hydrogen, X is 0, and Y is CH (Compound No. 7);
a compound of the formula (I) wherein R.sup.1 is 4-methylphenylmethyl, R.sup.2 is ethyl, R.sup.3 is 5-methyl, X is 0, and Y is CH (Compound No. 995);
a compound of the formula (I) wherein R.sup.1 is 1-phenylethyl, R.sup.2 is methyl, R.sup.3 is hydrogen, X is 0, and Y is CH (Compound No. 491);
a compound of the formula (I) wherein R is 1-phenylethyl, R.sup.2 is methyl, R.sup.3 is 5-fluoro, X is 0, and Y is CH (Compound No. 1101);
a compound of the formula (I) wherein R.sup.1 is 5-trifluoromethyl -2-pyridyl, R.sup.2 is ethyl, R.sup.3 is hydrogen, X is 0, and Y is CH (Compound No. 183);
a compound of the formula (I) wherein R.sup.1 is 5-trifluoromethyl -2-pyridyl, R.sup.2 is methyl, R.sup.3 is hydrogen, X is 0, and Y is CH (Compound No. 83);
a compound of the formula (I) wherein R.sup.1 is 5-trifluoromethyl -2-pyridyl, R.sup.2 is methyl, R.sup.3 is 5-chloro, X is 0, and Y is CH (Compound No. 583);
a compound of the formula (I) wherein R.sup.1 is 5-trifluoromethyl -2-pyridyl, R.sup.2 is methyl, R.sup.3 is 5-fluoro, X is 0, and Y is CH (Compound No. 783);
a compound of the formula (I) wherein R.sup.1 is 3,5-dichloro -2-pyridyl, R.sup.2 is methyl, R.sup.3 is 5-chloro, X is 0, and Y is CH (Compound No. 581);
a compound of the formula (I) wherein R.sup.1 is 3-phenylpropyl, R.sup.2 is methyl, R.sup.3 is hydrogen, X is 0, and Y is CH (Compound No. 497);
a compound of the formula (I) wherein R.sup.1 is 2-phenoxylethyl, R.sup.2 is methyl, R.sup.3 is 5-chloro, X is 0, and Y is CH (Compound No. 552);
a compound of the formula (I) wherein R.sup.1 is 2-(4-chlorophenoxy)ethyl, R.sup.2 is methyl, R.sup.3 is hydrogen, X is 0, and Y is CH (Compound No. 863);
a compound of the formula (I) wherein R.sup.1 is 4-phenoxybutyl, R.sup.2 is methyl, R.sup.3 is hydrogen, X is 0, and Y is CH (Compound No. 495); and
a compound of the formula (I) wherein R.sup.1 is 4-phenoxybutyl, R.sup.2 is ethyl, R.sup.3 is hydrogen, X is 0, and Y is CH (Compound No. 876). These compound Nos. are those described in Examples hereinafter.
Each compound of the present invention exists as E-or Z-isomer and includes both of the isomers and mixtures thereof in any mixing ratios. This is indicated by the wave line .about. in this specification.
The compound of the present invention also includes its hydrochloric acid salt, sulfuric acid salt, nitric acid salt, oxalic acid salt and p-toluenesulfonic acid salt.
The compound of the formula (I) of the present invention can be prepared, for example, according to the following synthetic routes.
Route 1 ##STR13## wherein L is halogen, alkylsulfonyl, alkylsulfonyloxy or arylsulfonyloxy; R.sup.4 is hydrogen, alkyl or optionally substituted benzyl; and R.sup.1, R.sup.3 and X are as defined above.
Examples of the halogen represented by L include chlorine, bromine, iodine, etc. Examples of the alkylsulfonyl represented by L include C.sub.1-5 alkylsulfonyl such as methanesulfonyl, ethanesulfonyl, etc. Examples of the alkylsulfonyloxy represented by L include alkylsulfonyloxy having optionally halogenated C.sub.1-5 alkyl, such as methanesulfonyloxy, ethanesulfonyloxy, trichloromethanesulfonyloxy, etc. Examples of the arylsulfonyloxy represented by L include optionally substituted benzenesulfonyloxy such as p-toluenesulfonyloxy, benzenesulfonyloxy, etc. Examples of the alkyl represented by R.sup.4 include alkyl having 1 to 5 carbon atoms such as methyl, ethyl, isopropyl, etc. Examples of the optionally substituted benzyl represented by R.sup.4 include benzyl optionally substituted with the same substituent(s) as those of the above optionally substituted phenyl represented by R.sup.1, such as benzyl, 4-chlorobenzyl, 4-methylbenzyl, etc.
The compound (IV) can be prepared by reacting the compound (II) with the compound (III) in the presence of a base in the absence of a solvent or in an appropriate solvent.
The amount of the compound (III) to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (II).
Examples of the base include metal hydroxides (e.g., sodium hydroxide, potassium hydroxide, etc.), metal carbonates (e.g., sodium carbonate, potassium carbonate, etc.), metal alkoxides (e.g., sodium methoxide, sodium ethoxide, potassium tert-butoxide, etc.), metal hydrides (e.g., sodium hydride, etc.), amines (e.g., pyridine, triethylamine, etc.), etc. The amount of the base to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (II).
Examples of the solvent include N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), hexamethylphosphoric triamide (HMPA), aromatic hydrocarbons (e.g., toluene, benzene, xylene, etc.), saturated hydrocarbons (e.g., cyclohexane, hexane, etc.), alcohols (e.g., methanol, ethanol, isopropanol, butanol, etc.), ethers (e.g., tetrahydrofuran (THF), dioxane, etc.), halogenated hydrocarbons (e.g., dichloromethane, 1,2-dichloroethane, etc.), ketones (e.g, acetone, ethyl methyl ketone, etc.), nitriles (e.g., acetonitrile, etc.), water, etc. These solvents can be used alone or in combination thereof.
The reaction temperature is normally -10.degree. C. to 200.degree. C., preferably 0.degree. C. to 180.degree. C. The reaction time varies with the compounds but is generally 0.5 to 48 hours.
The compound (IV) thus obtained can be used in the next step as the reaction mixture or crude product, or after purification by conventional methods (e.g., chromatography, recrystallization, etc.).
Alternatively, the compound (IV) can also be prepared by the following reaction.
Route 1 (continued) ##STR14## wherein each symbol is as defined above.
That is, the compound (IV) can be prepared by reacting the compound (V) with the compound (VI) in the presence of a base in the absence of a solvent or in an appropriate solvent.
The amount of the compound (VI) to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (V).
Examples of the base include metal hydroxides (e.g., sodium hydroxide, potassium hydroxide, etc.), metal carbonates (e.g., sodium carbonate, potassium carbonate, etc.), metal alkoxides (e.g., sodium methoxide, sodium ethoxide, potassium tert-butoxide, etc.), metal hydrides (e.g., sodium hydride, etc.), amines (e.g., pyridine, triethylamine, etc.), etc. The amount of the base to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (II).
Examples of the solvent include N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), hexamethylphosphoric triamide (HMPA), aromatic hydrocarbons (e.g., toluene, benzene, xylene, etc.), saturated hydrocarbons (e.g., cyclohexane, hexane, etc.), alcohols (e.g., methanol, ethanol, isopropanol, butanol, etc.), ethers (e.g., tetrahydrofuran (THF), dioxane, etc.), halogenated hydrocarbons (e.g., dichloromethane, 1,2-dichloroethane, etc.), ketones (e.g., acetone, ethyl methyl ketone, etc.), nitriles (e.g., acetonitrile, etc.), water, etc. These solvents can be used alone or in combination thereof.
The reaction temperature is normally -10.degree. C. to 200.degree. C., preferably 0.degree. C. to 180.degree. C. The reaction time varies with the compounds but is generally 0.5 to 48 hours.
The compound (IV) thus obtained can be used in the next step as the reaction mixture or crude product, or after purification by conventional methods (e.g., chromatography, recrystallization, etc.).
Route 1 (continued) ##STR15## wherein each symbol is as defined above.
The compound (VII) can be prepared by reacting the compound (IV) with a base or acid in an appropriate solvent to hydrolyze the compound (IV).
Examples of the base include metal hydroxides (e.g., sodium hydroxide, potassium hydroxide, etc.), metal carbonates (e.g., sodium carbonate, potassium carbonate, etc.), metal alkoxides (e.g., sodium methoxide, sodium ethoxide, potassium tert-butoxide, etc.), etc. Examples of the acid include hydrochloric acid, sulfuric acid, hydrobromic acid, p-toluenesulfonic acid, etc. The amount of the base or acid to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (IV).
Examples of the solvent include N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), hexamethylphosphoric triamide (HMPA), aromatic hydrocarbons (e.g., toluene, benzene, xylene, etc.), saturated hydrocarbons (e.g., cyclohexane, hexane, etc.), alcohols (e.g., methanol, ethanol, isopropanol, butanol, etc.), ethers (e.g., tetrahydrofuran (THF), dioxane, etc.), halogenated hydrocarbons (e.g., dichloromethane, 1,2-dichloroethane, etc.), ketones (e.g., acetone, ethyl methyl ketone, etc.), nitriles (e.g., acetonitrile, etc.), water, etc. These solvents can be used alone or in combination thereof.
The reaction temperature is normally -10.degree. C. to 150.degree. C., preferably 0.degree. C. to 120.degree. C. The reaction time varies with the compounds but is generally 0.1 to 48 hours.
The compound (VII) thus obtained can be used in the next step as the reaction mixture or crude product, or after purification by conventional methods (e.g., chromatography, recrystallization, etc.).
Route 1 (continued) ##STR16## wherein A is halogen, and the other symbols are as defined above.
Examples of the halogen represented by A include fluorine, chlorine, bromine and iodine. It is preferably chlorine or bromine.
The compound (VIII) can be prepared by reacting the compound (VII) with a halogenating agent in the absence of a solvent or in an appropriate solvent in the presence or absence of a catalyst.
Examples of the halogenating agent include thionyl halides (e.g., thionyl chloride, thionyl bromide, etc.), phosphoryl halides (e.g., phosphoryl chloride, phosphoryl bromide, etc.), phosphorus halides (e.g., phosphorus pentachloride, phosphorus trichloride, phosphorus pentabromide, phosphorus tribromide, etc.), phosgene, oxalyl halides (e.g., oxalyl chloride, etc.), etc. The amount of the halogenating agent to be used is 1 mol or more, preferably 1 to 10 mol per mol of the compound (VII).
Examples of the catalyst include DMF, DMSO, HMPA, pyridine, triethylamine, iodine, zinc chloride, Viismeier reagent, etc. The amount of the catalyst to be used is 0.005 to 3 mol, preferably 0.01 to 1 mol per mol of the compound
Examples of the reaction solvent include aromatic hydrocarbons (e.g., toluene, benzene, xylene, etc.), saturated hydrocarbons (e.g., cyclohexane, hexane, etc.), halogenated hydrocarbons (e.g., dichloromethane, 1,2-dichloroethane, etc.), etc. These solvents can be used alone or in combination thereof.
The reaction temperature is normally -10.degree. C. to 150.degree. C., preferably 0.degree. C. to 120.degree. C. The reaction time varies with the compounds but is generally 0.1 to 48 hours.
The compound (VIII) thus obtained can be used in the next step as the reaction mixture or crude product, or after purification by conventional methods (e.g., chromatography, recrystallization, etc.).
Route 1 (continued) ##STR17## wherein each symbol is as defined above.
The compound (X) can be prepared by reacting the compound (VIII) with the compound (IX) or a salt thereof (e.g., hydrochloric acid salt, sulfuric acid salt, etc.) in the presence of a base in the absence of a solvent or in an appropriate solvent.
The amount of the compound (IX) to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (VIII).
Examples of the base include metal hydroxides (e.g., sodium hydroxide, potassium hydroxide, etc.), metal carbonates (e.g., sodium carbonate, potassium carbonate, etc.), metal alkoxides (e.g., sodium methoxide, sodium ethoxide, potassium tert-butoxide, etc.), amines (e.g., pyridine, triethylamine, etc.), etc. The amount of the base to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (VIII).
Examples of the solvent include aromatic hydrocarbons (e.g., toluene, benzene, xylene, etc.), saturated hydrocarbons (e.g., cyclohexane, hexane, etc.), halogenated hydrocarbons (e.g., dichloromethane, 1,2-dichloroethane, etc.), ethers (e.g., THF, dioxane, etc.), water, etc. These solvents can be used alone or in combination thereof.
The reaction temperature is normally -30.degree. C. to 150.degree. C., preferably -10.degree. C. to 100.degree. C. The reaction time varies with the compounds but is generally 0.5 to 48 hours.
The compound (X) thus obtained can be used in the next step as the reaction mixture or crude product, or after purification by conventional methods (e.g., chromatography, recrystallization, etc.).
Route 1 (continued) ##STR18## wherein each symbol is as defined above.
The compound (XI) can be prepared by reacting the compound (X) with a halogenating agent in the absence of a solvent or in an appropriate solvent.
Examples of the halogenating agent include thionyl halides (e.g., thionyl chloride, thionyl bromide, etc.), phosphoryl halides (e.g., phosphoryl chloride, phosphoryl bromide, etc.), phosphorus halides (e.g., phosphorus pentachloride, phosphorus trichloride, phosphorus pentabromide, phosphorus tribromide, etc.), phosgene, oxalyl halides (e.g., oxalyl chloride, etc.), triphenylphosphine/carbon tetrachloride, triphenylphosphine/carbon tetrabromide, etc. The amount of the halogenating agent to be used is 1 mol or more, preferably 1 to 10 mol per mol of the compound (X).
Examples of the solvent include aromatic hydrocarbons (e.g., toluene, benzene, xylene, etc.), saturated hydrocarbons (e.g., cyclohexane, hexane, etc.), halogenated hydrocarbons (e.g., dichloromethane, 1,2-dichloroethane, etc.), nitriles (e.g., acetonitrile, propionitrile, etc.), etc. These solvents can be used alone or in combination thereof.
The reaction temperature is normally -30.degree. C. to 150.degree. C., preferably -10.degree. C. to 120.degree. C. The reaction time varies with the compounds but is generally 0.1 to 48 hours.
The compound (XI) thus obtained can be used in the next step as the reaction mixture or crude product, or after purification by conventional methods (e.g., chromatography, recrystallization, etc.).
Route 1 (continued) ##STR19## wherein each symbol is as defined above.
The compound of the formula (I) of the present invention can be prepared by reacting the compound (XI) with the compound (XII) in the presence or absence of a base in the absence of a solvent or in an appropriate solvent.
The amount of the compound (XII) to be used is 1 mol or more, preferably 1 to 6 mol per mol of the compound (XI).
Examples of the base include metal hydroxides (e.g., sodium hydroxide, potassium hydroxide, etc.), metal carbonates (e.g., sodium carbonate, potassium carbonate, etc.), metal alkoxides (e.g., sodium methoxide, sodium ethoxide, potassium tert-butoxide, etc.), metal hydrides (e.g., sodium hydrides, etc.), amines (e.g., triethylamine, etc.), etc. The amount of the base to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (XI).
Examples of the solvent include N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), hexamethylphosphoric triamide (HMPA), aromatic hydrocarbons (e.g., toluene, benzene, xylene, etc.), saturated hydrocarbons (e.g., cyclohexane, hexane, etc.), ethers (e.g., tetrahydrofuran (THF), dioxane, etc.), halogenated hydrocarbons (e.g., dichloromethane, 1,2-dichloroethane, etc.), ketones (e.g., acetone, ethyl methyl ketone, etc.), nitriles (e.g., acetonitrile, etc.), water, etc. These solvents can be used alone or in combination thereof.
The reaction temperature is normally -10.degree. C. to 200.degree. C., preferably 0.degree. C. to 180.degree. C. The reaction time varies with the compounds but is generally 0.5 to 48 hours.
The desired compound (I) thus obtained can be purified by conventional methods (e.g., chromatography, recrystallization, etc.).
Alternatively, the compound (I) of the present invention can be prepared by the following route.
Route 2 ##STR20## wherein R.sup.5 is hydrogen, C.sub.1-5 alkyl (e.g., methyl, ethyl, isopropyl, etc.) or halogen (e.g., fluorine, chlorine, bromine, iodine), and the other symbols are as defined above.
The compound (XIII) can be prepared by treating the compound (Ia) with a Lewis acid in an appropriate solvent.
Examples of the Lewis acid include aluminium chloride, aluminium bromide, boron trifluoride, boron tribromide, boron trichloride, ferric chloride, etc. In particular, aluminium chloride is preferred. The amount of the Lewis acid to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (Ia).
Examples of the solvent include anisole, nitromethane, nitroethene, etc. These solvents can be used alone or in combination thereof.
The reaction temperature is normally -50.degree. C. to 150.degree. C., preferably, -20.degree. C. to 100.degree. C. The reaction time varies with the compounds but is generally 0.5 to 48 hours.
The compound (XIII) thus obtained can be used in the next step as the reaction mixture or crude product, or after purification by conventional methods (e.g., chromatography, recrystallization, etc.).
Route 2 (continued) ##STR21## wherein each symbol is as defined above.
The compound of the formula (I) of the present invention can be prepared by reacting the compound (XIII) with the compound (III) in the presence of a base in the absence of a solvent or in an appropriate solvent.
The amount of the compound (III) to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (XIII).
Examples of the base include metal hydroxides (e.g., sodium hydroxide, potassium hydroxide, etc.), metal carbonates (e.g., sodium carbonate, potassium carbonate, etc.), metal alkoxides (e.g., sodium methoxide, sodium ethoxide, potassium tert-butoxide, etc.), metal hydrides (e.g., sodium hydrides, etc.), amines (e.g., pyridine, triethylamine, etc.), etc. The amount of the base to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (XIII).
Examples of the solvent include N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), hexamethylphosphoric triamide (HMPA), aromatic hydrocarbons (e.g., toluene, benzene, xylene, etc.), saturated hydrocarbons (e.g., cyclohexane, hexane, etc.), alcohols (e.g., methanol, ethanol, isopropanol, butanol, etc.), ethers (e.g., tetrahydrofuran (THF), dioxane, etc.), halogenated hydrocarbons (e.g., dichloromethane, 1,2-dichloroethane, etc.), ketones (e.g., acetone, ethyl methyl ketone, etc.), nitriles (e.g., acetonitrile, etc.), water, etc. These solvents can be used alone or in combination thereof.
The reaction temperature is normally -10.degree. C. to 200.degree. C., preferably 0.degree. C. to 180.degree. C. The reaction time varies with the compounds but is generally 0.5 to 48 hours.
The desired compound (I) thus obtained can be purified by conventional methods (e.g., chromatography, recrystallization, etc.).
Route 2 (continued) ##STR22## wherein each symbol is as defined above.
The compound of the formula (I) of the present invention can be prepared by reacting the compound (XIII) with the compound (XXIII) in the presence of triphenylphosphine and diethyl azodicarboxylate or dimethyl azodicarboxylate in the absence of a solvent or in an appropriate solvent.
The amount of the compound (XXIII) to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (XIII). The amount of the triphenylphosphine to be used is 1 to 5 mol, preferably 1 to 3 mol per mol of the compound (XIII). The amount of the diethyl azodicarboxylate or dimethyl azodicarboxylate to be used is 1 to 5 mol, preferably 1 to 3 mol per mol of the compound (XIII).
Examples of the solvent include aromatic hydrocarbons (e.g., toluene, benzene, xylene, etc.), saturated hydrocarbons (e.g., cyclohexane, hexane, etc.), ethers (e.g., tetrahydrofuran (THF), dioxane, etc.), nitriles (e.g., acetonitrile, etc.), etc. These solvents can be used alone or in combination thereof.
The reaction temperature is normally -10.degree. C. to 200.degree. C., preferably 0.degree. C. to 120.degree. C. The reaction time varies with the compounds but is generally 0.5 to 72 hours.
The desired compound (I) thus obtained can be purified by conventional methods (e.g., chromatography, recrystallization, etc.).
Alternatively, the compound (I) of the present invention can be prepared in one step from the intermediate (X) in the above Route 1 (Scheme 6) by the following reaction.
Route 3 ##STR23## wherein W is carbonyl or sulfinyl, Z is chlorine, bromine or ##STR24## and the other symbols are as defined above.
The compound of the formula (I) of the present invention can be prepared by reacting the compound (X) with the compound (XIV) in the absence of a solvent or in an appropriate solvent.
The amount of the compound (XIV) to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (X).
Examples of the solvent include aromatic hydrocarbons (e.g., toluene, benzene, xylene, etc.), saturated hydrocarbons (e.g., cyclohexane, hexane, etc.), halogenated hydrocarbons (e.g., dichloromethane, 1,2-dichloroethane, etc.), etc. These solvents can be used alone or in combination thereof.
The reaction temperature is normally -30.degree. C. to 150.degree. C., preferably -10.degree. C. to 120.degree. C. The reaction time varies with the compounds but is generally 0.1 to 48 hours.
The desired compound (I) thus obtained can be purified by conventional methods (e.g., chromatography, recrystallization, etc.).
The compound (XIII) in above Route 2 (Scheme 9) can also be prepared by the following reaction.
Route 4 ##STR25## wherein each symbol is as defined above.
The compound (XIII) can be prepared by reacting the compound (XV) with the compound (XIV) in the absence of a solvent or in an appropriate solvent.
The amount of the compound (XIV) to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (XV).
Examples of the solvent include aromatic hydrocarbons (e.g., toluene, benzene, xylene, etc.), saturated hydrocarbons (e.g., cyclohexane, hexane, etc.), halogenated hydrocarbons (e.g., dichloromethane, 1,2-dichloroethane, etc.), etc. These solvents can be used alone or in combination thereof.
The reaction temperature is normally -30.degree. C. to 150.degree. C., preferably -10.degree. C. to 120.degree. C. The reaction time varies with the compounds but is generally 0.1 to 48 hours.
Alternatively, the compound (I) of the present invention can be prepared by the following route.
Route 5 ##STR26## wherein each symbol is as defined above.
The compound (XVII) can be prepared by reacting the compound (XVI) with the compound (III) in the presence of a base in the absence of a solvent or in an appropriate solvent.
The amount of the compound (III) to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (XVI).
Examples of the base include metal hydroxides (e.g., sodium hydroxide, potassium hydroxide, etc.), metal carbonates (e.g., sodium carbonate, potassium carbonate, etc.), metal alkoxides (e.g., sodium methoxide, sodium ethoxide, potassium tert-butoxide, etc.), metal hydrides (e.g., sodium hydrides, etc.), amines (e.g., pyridine, triethylamine, etc.), etc. The amount of the base to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (XVI).
Examples of the solvent include N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), hexamethylphosphoric triamide (HMPA), aromatic hydrocarbons (e.g., toluene, benzene, xylene, etc.), saturated hydrocarbons (e.g., cyclohexane, hexane, etc.), alcohols (e.g., methanol, ethanol, isopropanol, butanol, etc.), ethers (e.g., tetrahydrofuran (THF), dioxane, etc.), halogenated hydrocarbons (e.g., dichloromethane, 1,2-dichloroethane, etc.), ketones (e.g., acetone, ethyl methyl ketone, etc.), nitriles (e.g., acetonitrile, etc.), water, etc. These solvents can be used alone or in combination thereof.
The reaction temperature is normally -10.degree. C. to 200.degree. C., preferably 0.degree. C. to 180.degree. C. The reaction time varies with the compounds but is generally 0.5 to 48 hours.
The compound (XVII) thus obtained can be used in the next step as the reaction mixture or crude product, or after purification by conventional methods (e.g., chromatography, recrystallization, etc.).
Alternatively, the compound (XVII) can also be prepared by the following reaction.
Route 5 (continued) ##STR27## wherein each symbol is as defined above.
The compound (XVII) can be prepared by reacting the compound (XVIII) with the compound (VI) in the presence of a base in the absence of a solvent or in an appropriate solvent.
The amount of the compound (VI) to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (XVIII).
Examples of the base include metal hydroxides (e.g., sodium hydroxide, potassium hydroxide, etc.), metal carbonates (e.g., sodium carbonate, potassium carbonate, etc.), metal alkoxides (e.g., sodium methoxide, sodium ethoxide, potassium tert-butoxide, etc.), metal hydrides (e.g., sodium hydrides, etc.), amines (e.g., pyridine, triethylamine, etc.), etc. The amount of the base to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (XVIII).
Examples of the solvent include N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), hexamethylphosphoric triamide (HMPA), aromatic hydrocarbons (e.g., toluene, benzene, xylene, etc.), saturated hydrocarbons (e.g., cyclohexane, hexane, etc.), alcohols (e.g., methanol, ethanol, isopropanol, butanol, etc.), ethers (e.g., tetrahydrofuran (THF), dioxane, etc.), halogenated hydrocarbons (e.g., dichloromethane, 1,2-dichloroethane, etc.), ketones (e.g., acetone, ethyl methyl ketone, etc.), nitriles (e.g., acetonitrile, etc.), water, etc. These solvents can be used alone or in combination thereof.
The reaction temperature is normally -10.degree. C. to 200.degree. C., preferably 0.degree. C. to 180.degree. C. The reaction time varies with the compounds but is generally 0.5 to 48 hours.
The compound (XVII) thus obtained can be used in the next step as the reaction mixture or crude product, or after purification by conventional methods (e.g., chromatography, recrystallization, etc.).
Route 5 (continued) ##STR28## wherein each symbol is as defined above.
The compound (XIX) can be prepared by reacting the compound (XVII) with hydroxylamine or a salt thereof (e.g., hydrochloric acid salt, sulfuric acid salt, etc.) in the presence or absence of a base in the absence of a solvent or in an appropriate solvent.
The amount of the hydroxylamine to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (XVII).
Examples of the base include metal hydroxides (e.g., sodium hydroxide, potassium hydroxide, etc.), metal carbonates (e.g., sodium carbonate, potassium carbonate, etc.), metal alkoxides (e.g., sodium methoxide, sodium ethoxide, potassium tert-butoxide, etc.), amines (e.g., pyridine, triethylamine, etc.), etc. The amount of the base to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (XVII).
Examples of the solvent include aromatic hydrocarbons (e.g., toluene, benzene, xylene, etc.), saturated hydrocarbons (e.g., cyclohexane, hexane, etc.), alcohols (e.g., methanol, ethanol, isopropanol, butanol, etc.), ethers (e.g., tetrahydrofuran (THF), dioxane, etc.), halogenated hydrocarbons (e.g., dichloromethane, 1,2-dichloroethane, etc.), water, etc. These solvents can be used alone or in combination thereof.
The reaction temperature is normally -30.degree. C. to 150.degree. C., preferably -10.degree. C. to 100.degree. C. The reaction time varies with the compounds but is generally 0.5 to 48 hours.
The compound (XIX) thus obtained can be used in the next step as the reaction mixture or crude product, or after purification by conventional methods (e.g., chromatography, recrystallization, etc.).
Route 5 (continued) ##STR29## wherein each symbol is as defined above.
The compound (XX) can be prepared by reacting the compound (XIX) with a halogenating agent in the absence of a solvent or in an appropriate solvent.
Examples of the halogenating agent include halogen (e.g., chlorine, bromine, etc.), N-halosuccinimide (e.g., N-bromosuccinimide, N-chlorosuccinimide, etc.), etc. The amount of the halogenating agent to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (XIX).
Examples of the solvent include aromatic hydrocarbons (e.g., toluene, benzene, xylene, etc.), saturated hydrocarbons (e.g., cyclohexane, hexane, etc.), halogenated hydrocarbons (e.g., dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, etc.), ethers (e.g., diethyl ether, dioxane, tetrahydrofuran (THF), etc.), etc. These solvents can be used alone or in combination thereof.
The reaction temperature is normally -30.degree. C. to 150.degree. C., preferably -10.degree. C. to 120.degree. C. The reaction time varies with the compounds but is generally 0.1 to 48 hours.
The compound (XX) thus obtained can be used in the next step as the reaction mixture or crude product, or after purification by conventional methods (e.g., chromatography, recrystallization, etc.).
Route 5 (continued) ##STR30## wherein each symbol is as defined above.
The compound (Ib) of the present invention can be prepared by reacting the compound (XX) with the compound (XII) in the presence or absence of a base in the absence of a solvent or in an appropriate solvent.
The amount of the compound (XII) to be used is 1 mol or more, preferably 1 to 6 mol per mol of the compound (XX).
Examples of the base include metal hydroxides (e.g., sodium hydroxide, potassium hydroxide, etc.), metal carbonates (e.g., sodium carbonate, potassium carbonate, etc.), metal alkoxides (e.g., sodium methoxide, sodium ethoxide, potassium tert-butoxide, etc.), metal hydrides (e.g., sodium hydrides, etc.), amines (e.g., triethylamine, etc.), etc. The amount of the base to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (XX).
Examples of the solvent include N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), hexamethylphosphoric triamide (HMPA), aromatic hydrocarbons (e.g., toluene, benzene, xylene, etc.), saturated hydrocarbons (e.g., cyclohexane, hexane, etc.), alcohols (e.g., methanol, ethanol, isopropanol, butanol, etc.), ethers (e.g., tetrahydrofuran (THF), dioxane, etc.), halogenated hydrocarbons (e.g., dichloromethane, 1,2-dichloroethane, etc.), ketones (e.g., acetone, methyl ethyl ketone, etc.), nitriles (e.g., acetonitrile, etc.), etc. These solvents can be used alone or in combination thereof.
The reaction temperature is normally -10.degree. C. to 200.degree. C., preferably 0.degree. C. to 180.degree. C. The reaction time varies with the compounds but is generally 0.5 to 48 hours.
The compound (Ib) can be purified by conventional methods (e.g., chromatography, recrystallization, etc.). When the compound (Ib) is used in the next step, it can be used as the reaction mixture or crude product, or after purification by conventional methods (e.g., chromatography, recrystallization, etc.).
Route 5 (continued) ##STR31## wherein each symbol is as defined above.
The compound (I) of the present invention can be prepared by reacting the compound (Ib) with the compound (XXII) in the presence of a base in the absence of a solvent or in an appropriate solvent.
The amount of the compound (XXII) to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (Ib).
Examples of the base include metal hydroxides (e.g., sodium hydroxide, potassium hydroxide, etc.), metal carbonates (e.g., sodium carbonate, potassium carbonate, etc.), metal alkoxides (e.g., sodium methoxide, sodium ethoxide, potassium tert-butoxide, etc.), metal hydrides (e.g., sodium hydrides, etc.), amines (e.g., pyridine, triethylamine, etc.), etc. The amount of the base to be used is 1 mol or more, preferably 1 to 3 mol per mol of the compound (Ib).
Examples of the solvent include N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), hexamethylphosphoric triamide (HMPA), aromatic hydrocarbons (e.g., toluene, benzene, xylene, etc.), saturated hydrocarbons (e.g., cyclohexane, hexane, etc.), alcohols (e.g., methanol, ethanol, isopropanol, butanol, etc.), ethers (e.g., tetrahydrofuran (THF), dioxane, etc.), halogenated hydrocarbons (e.g., dichloromethane, 1,2-dichloroethane, etc.), ketones (e.g., acetone, ethyl methyl ketone, etc.), nitriles (e.g., acetonitrile, etc.), water, etc. These solvent can be used alone or in combination thereof.
The reaction temperature is normally -10.degree. C. to 200.degree. C., preferably 0.degree. C. to 180.degree. C. The reaction time varies with the compounds but is generally 0.5 to 48 hours.
The desired compound (I) thus obtained can be purified by conventional methods (e.g., chromatography, recrystallization, etc.).
The compounds of the formula (I) of the present invention show a strong fungicidal activity against a wide variety of phytopathogenic fungi on crop plants (e.g., rice, wheat, barley, rye, corn, common millet, millet, buckwheat, soybean, redbean, peanut, etc.), fruit trees (e.g., citrus fruits, grape, apple, pear, peach, etc.), vegetables (e.g., cucumber, eggplant, tomato, pumpkin, kidney bean, etc.), etc. They also show fungicidal activity against phytopathogenic fungi in soil. Examples of the phytopathogenic fungi on which the compounds of the formula (I) of the present invention exert their fungicidal activity are Pyricularia oryzae, Rhizoctonia solani, Erysiphe graminis, Sphaerotheca fuliginea, Erysiphe cichoracearum, Phytophthora infestans, Pseudoperonospora cubensis, Peronospora manshurica, Plasmopara viticola, Botrytis cinerea of vegetables, grape, etc., Pythium aphanidermatum, Sclerotinia sclerotiorum of buckwheat, soybean, colza, etc., Corticium rolfsii of soybean, redbean, potato, peanut, etc., Pseudocercosporella herpotrichoides, etc. Therefore, the compounds (I) of the present invention are useful as agricultural fungicides.
Application of the compounds (I) of the present invention may be made to plants by any conventional procedure such as atomizing, scattering or spreading. Application may also be made through treatment of seeds of plants, soil where plants grow, paddy field for seedling or water for perfusion with the compounds (I). Application may be performed before and/or after the infection with phytopathogenic fungi on plants.
For the practical usage, the compounds (I) may be applied as such or in a formulation form suitable for agricultural fungicides such as solutions, wettable powders, emulsions, suspensions, concentrated liquid preparations, tablets, granules, aerosols, powders, pastes, dusts, etc. Such formulation form can be prepared in a conventional manner by mixing at least one of the compounds (I) with an appropriate solid or liquid carrier(s) and, if necessary, an appropriate adjuvant(s) (e.g., surfactants, spreaders, dispersants, stabilizers, etc.) for improving the dispersibility and other properties of the active ingredient.
Examples of the solid carriers or diluents include botanical materials (e.g., flour, tobacco stalk powder, soybean powder, walnut-shell powder, vegetable powder, saw dust, bran, bark powder, cellulose powder, vegetable extract residue, etc.), fibrous materials (e.g., paper, corrugated cardboard, old rags, etc.), artificial plastic powders, clays (e.g., kaolin, bentonire, fuller's earth, etc.), talc, other inorganic materials (e.g., pyrophyllite, sericite, pumice, sulfur powder, active carbon, etc.), chemical fertilizers (e.g., ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, ammonium chloride, etc.), etc.
Examples of the liquid carriers or diluents include water, alcohols (e.g., methanol, ethanol, etc.), ketones (e.g., acetone, ethyl methyl ketone, etc.), ethers (e.g., diethyl ether, dioxane, cellosolve, tetrahydrofuran, etc.), aromatic hydrocarbons (e.g., benzene, toluene, xylene, methylnaphthalene, etc.), aliphatic hydrocarbons (e.g., gasoline, kerosene, lamp oil, etc.), esters, nitriles, acid amides (e.g., N,N-dimethylformamide, N,N-dimethylacetamide, etc.), halogenated hydrocarbons (e.g., dichloroethane, carbon tetrachloride, etc.), etc.
Examples of the surfactants include alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates, polyethylene glycol ethers, polyhydric alcohol esters, etc.
Examples of the spreaders or dispersants include casein, gelatin, starch powder, carboxymethyl cellulose, gum arabic, alginic acid, lignin, bentonite, molasses, polyvinyl alcohol, pine oil, agar, etc.
Examples of the stabilizers include PAP (a mixture of isopropylphosphate), tricresyl phosphate (TCP), tolu oil, epoxidized oil, surfactants, fatty acids and their esters, etc.
The composition of the present invention may contain other fungicides, insecticides, herbicides, fertilizers, etc., in addition to the above components.
When the compounds (I) are used as fungicidal compositions, each of such compositions contains at least one of the compounds (I) in a concentration of normally 0.1 to 95% by weight, preferably 2.0 to 80% by weight. These compositions can be used as such or in a diluted form. The concentration to be used depends upon a particular purpose, subject and plant to be treated, and it is generally in the range of about 1 to 50,000 ppm, preferably about 100 to 5,000 ppm. The amount of the compound (I) to be used is generally about 1.0 g to 5 kg/hectare, preferably about 2 g to 100 g/hectare.
Further, the compounds (I) of the present invention have excellent herbicidal activity against gramineous and broad-leaved weeds such as Digitaria ciliaris, Setaria viridis, Echinochloa crus-galli, Amaranthus lividus, Chenopodium album, Cyperus microiria, Mollugo stricta, Stellaria neglecta, Sagina japonica, Stellaria Alsine GRIMM var. undulata, Capsella bursa-pastoris, Alopecurus aequalis SOBOL var. amurensis, Poa annua, Polygonum longisetum, Polygonum lapathifolium, Trigonotis peduncularis, upland weeds such as Gnaphalium affine, paddy weeds such as Echinochloa oryzicola, Monochoria vaginalis, Cyperus difformis, Rotala indica, Dopatrium junceum, etc.
Further, the compounds (I) also have growth regulating activity (e.g., growth inhibiting activity) against gramineous and broad-leaved weeds, particularly lawns and balk weeds, and can inhibit the growth of grasses in paddy balks or lawns of golf courses for a long term.
The compounds (I) in certain amounts (e.g., 1 to 40 g/a) cause no or little damage to useful plants such as corn, sugarcane, sorghum, rice, wheat, barley, rye, soybean, peanut, cotton, etc. Even when the damage is caused, the damage is so slight that the damaged plants can readily recovered. Therefore, the compounds (I) can be used as selective or nonselective herbicides or growth regulating compositions (e.g., growth inhibiting compositions, compositions for reducing cutting frequency, and compositions for making felling easy, etc.) in arables such as plowed fields, paddy fields, fruit gardens, tea gardens, mulberry fields, arable lands not being used, pastures, and untillable lands such as railroads, roads, lawns, factory sites, riverbeds, housing lands, green tracts in parks, forests, created lands, vacant lands, etc.
The compounds (I) are harmless to humans, domestic animals and birds, and the toxicity to fishes is extremely low. Therefore the herbicides and growth regulating compositions are safe and the residual toxicity does not become a problem.
The compounds (I) can be used as herbicides or growth regulating compositions in various manners depending on the purpose, subject plants, term for use, etc. In general, treatment of soil or foliage application are preferred for the use as herbicides and foliage application is preferred for the use as growth regulating compositions. Each of such herbicidal compositions and growth regulating compositions contains at least one of the compounds (I) in a concentration of normally 0.1 to 95% by weight, preferably 2 to 80% by weight. These compositions can be used as such or in a diluted form. The concentration to be used depends upon a particular purpose, subject and plant to be treated, and it is generally in the range of about 1 to 50,000 ppm, preferably about 100 to 5,000 ppm. The amount of the compounds (I) to be used is generally about 10 g to 5 kg/hectare, preferably about 100 g to 1,000 g/hectare.
When the compounds (I) are used as herbicides or growth regulating compositions, the compounds (I) are used as such or in a formulation form such as powders, wettable powders, emulsions, etc., prepared by mixing various carriers depending on the sites where the compounds are applied. The carriers may be solid, liquid or combinations thereof. Examples of the solid carriers include clays, talc, diatomaceous earth, bentonite, etc. Examples of the liquid carriers include water, alcohols (e.g., methanol, ethanol, etc.), acetone, benzene, toluene, xylene, solvent naphtha, cyclohexane, etc. In addition, agriculturally acceptable emulsifying agents, stabilizers, dispersants, suspending agents, spreaders, penetrating agents, wetting agents, etc., can be formulated.
To increase the activity or obtain additive or synergistic action, the herbicides can be used in combination with other herbicides such as diuron, MCP, CNP, IPC, asulam, alachlor, trifluralin, etc. The herbicides or the growth regulating compositions of the present invention can also be used as a mixture with insecticides, fungicides, fertilizers, soil treating (improving) agents, etc.
Further, the benzaldehyde oxime derivatives of the present invention also have strong fungicidal activity against pathogenic fungi such as Candida, Aspergillus, Trichophyton, etc., and can be used as antifungal agents for treating such infectious diseases.
As described hereinabove, according to the present invention, there are provided novel benzaldehyde oxime derivatives, processes for producing them, and fungicidal, herbicidal and growth regulating compositions containing them as active ingredients.

The following examples and experiments further illustrate the present invention in detail, but are not to be construed to limit the scope thereof.
Example 1
Synthesis of 2-(2,4-dichlorobenzyloxy)benzoic acid
Dimethylformamide (DMF)(100 ml), potassium carbonate (17.97 g) and 2,4-dichlorobenzyl chloride (21.50 g) were added to methyl salicylate (15.22 g), and the mixture was stirred at room temperature overnight. Ethyl acetate (1000 ml) was added to the reaction mixture, and the resulting mixture was washed with brine (700 ml) twice, dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give crude methyl 2-(2,4-dichlorobenzyloxy)benzoate. Methanol (100 ml), THF (100 ml), water (20 ml) and 85% potassium hydroxide (7.92 g) were added to the crude product thus obtained, and the mixture was stirred at 60.degree. C. for 2 hours. After completion of the reaction, the mixture was concentrated under reduced pressure. Water (300 ml) was added to the residue, and the pH of the mixture was adjusted to not more than 2, and the resulting crystals were separated by filtration, dried to give 2-(2,4-dichlorobenzyloxy)benzoic acid (29.30 g) as colorless crystals.
Example 2
Synthesis of 2-(2,4-dichlorobenzyloxy)-N-methoxybenzamide
Dry dichloroethane (80 ml), thionyl chloride (3.16 ml) and DMF (0.2 ml) were added to 2-(2,4-dichlorobenzyloxy)benzoic acid (11.89 g), and the mixture was stirred under reflux for 1 hour. After completion of the reaction, the mixture was concentrated under reduced pressure, the residue was dissolved in dry methylene chloride (80 ml), the solution was added dropwise to a mixture of methoxyamine hydrochloride (6.68 g), pyridine (9.49 g) and methylene chloride (40 ml) under ice-cooling over 15 minutes, and the resulting mixture was stirred at room temperature for 1 hour. To the reaction mixture was added 1N hydrochloric acid (300 ml), and the resulting mixture was extracted with methylene chloride (150 ml) twice, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The resulting crude crystals were recrystallized from ethyl acetate/n-hexane to give 2-(2,4-dichlorobenzyloxy)-N-methoxybenzamide (10.81 g) as colorless crystals. mp 100.degree.-101.5.degree. C.
Example 3
Synthesis of .alpha.-chloro-2-(2,4-dichlorobenzyloxy)benzaldehyde O-methyloxime
2-(2,4-Dichlorobenzyloxy)-N-methoxybenzamide (10.44 g) was dissolved in dry methylene chloride (100 ml), phosphorus pentachloride (6.66 g) was added under ice-cooling over about 3 minutes to the solution, and the mixture was stirred at 0.degree. C. for 1 hour. After completion of the reaction, a saturated aqueous solution of sodium bicarbonate (150 ml) was added slowly, and the mixture was extracted with methylene chloride (150 ml) twice, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The resulting crude product was purified by silica gel chromatography to give .alpha.-chloro-2-(2,4-dichlorobenzyloxy)benzaldehyde O-methyloxime (9.52 g) as crystals. A part of the crystals was recrystallized from ethyl acetate/n-hexane to give colorless crystals. mp 91.degree.-92.degree. C.
Example 4
Synthesis of 2-(2,4-dichlorobenzyloxy)-.alpha.-(1-imidazolyl)benzaldehyde O-methyloxime (Compound 31)
Imidazole (2.04 g) was dissolved in DMF (30 ml), and 60% sodium hydride (1.20 g) was added. The mixture was stirred at room temperature for 10 minutes, then .alpha.-chloro-2-(2,4-dichlorobenzyloxy)benzaldehyde O-methyloxime (5.17 g) was added, and the mixture was stirred at 120.degree. C. for 2 hours. After completion of the reaction, ether (200 ml) was added, and the mixture was washed with brine (200 ml) twice, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The resulting crude product was purified by silica gel chromatography and recrystallized from ethyl acetate/n-hexane to give 2-(2,4-dichlorobenzyloxy)-.alpha.-(1-imidazolyl)benzaldehyde O-methyloxime (2.74 g) as colorless crystals. mp. 122.degree.-123.degree. C.
Example 5
Synthesis of 2-(4-chlorobenzylthio)-.alpha.-(1-imidazolyl)benzaldehyde O-ethyloxime (Compound No. 155)
DMF (3 ml) and imidazole (0.41 g) were added to .alpha.-chloro-2-(4-chlorobenzylthio)benzaldehyde O-ethyloxime (0.68 g), and the mixture was stirred at 170.degree. C. for 21 hours. After completion of the reaction, ether (100 ml) was added, and the mixture was washed with brine (80 ml) twice, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The resulting crude product was purified by silica gel chromatography and recrystallized from ethyl acetate/n-hexane to give 2-(4-chlorobenzylthio)-.alpha.-(1-imidazolyl)benzaldehyde O-ethyloxime (0.11 g) as colorless crystals. mp. 96.5.degree.-97.5.degree. C.
Example 6
Synthesis of 2-hydroxy-.alpha.-(1-imidazolyl)benzaldehyde O-methyloxime
Dry anisole (6 ml) and aluminium chloride (0.59 g) were added to 2-(2,4-dichlorobenzyloxy)-.alpha.-(1-imidazolyl)benzaldehyde O-methyloxime (0.75 g), and the mixture was stirred under ice-cooling for 2 hours. After completion of the reaction, a half-saturated aqueous solution of sodium bicarbonate (100 ml) was added slowly, and the mixture was extracted with ether (50 ml) and ethyl acetate (50 ml), dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The resulting crude product was purified by silica gel chromatography and recrystallized from ethyl acetate/n-hexane to give 2-hydroxy-.alpha.-(1-imidazolyl)benzaldehyde O-methyloxime (0.34 g) as colorless crystals. mp. 103.5.degree.-104.5.degree. C.
Example 7
Synthesis of .alpha.-(1-imidazolyl)-2-(4-methylbenzyloxy)benzaldehyde O-methyloxime (Compound 3)
DMF (3 ml), potassium carbonate (0.22 g) and 4-methylbenzyl chloride (0.20 g) were added to 2-hydroxy-.alpha.-(1-imidazolyl)benzaldehyde O-methyloxime (0.26 g), and the mixture was stirred at room temperature overnight. After completion of the reaction, ether (100 ml) was added, and the mixture was washed with brine (80 ml) twice, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The resulting crude product was purified by silica gel chromatography and recrystallized from ethyl acetate/n-hexane to give .alpha.-(1-imidazolyl)-2-(4-methylbenzyloxy)benzaldehyde O-methyloxime (0.22 g) as colorless crystals. mp. 70.5.degree.-72.0.degree. C.
Example 8
Synthesis of 2-(4-chlorobenzyloxy)-.alpha.-(1-imidazolyl)benzaldehyde O-methyloxime (Compound 9)
Thionyl chloride (0.16 ml) was added to a suspension of imidazole (0.63 g) and methylene chloride (6 ml) under ice-cooling, and the mixture was stirred under ice-cooling for 30 minutes. Then 2-(4-chlorobenzyloxy)-N-methoxybenzamide (0.44 g) was added, and the mixture was stirred under reflux for 2 hours. After completion of the reaction, water (100 ml) was added, and the mixture was extracted with methylene chloride (50 ml) twice, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The resulting crude product was purified by silica gel chromatography to give 2-(4-chlorobenzyloxy)-.alpha.-(1-imidazolyl)benzaldehyde O-methyloxime (0.01 g) as colorless crystals. mp. 92.5.degree.-93.5.degree. C.
Example 9
Synthesis of 2-(4-chlorobenzyloxy)benzaldehyde oxime
Potassium carbonate (33.17 g) and DMF (180 ml) were added to salicylaldehyde (24.42 g), and the mixture was stirred at room temperature for 10 minutes. Then a mixture of 4-chlorobenzyl chloride (33.82 g) and DMF (20 ml) was added at room temperature over 15 minutes, and the mixture was stirred at 60.degree. C. for 3 hours. After completion of the reaction, ether (500 ml) was added, and the mixture was washed with water (400 ml) three times, dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give crude 2-(4-chlorobenzyloxy)benzaldehyde. The ethanol (200 ml) and hydroxylamine hydrochloride (27.80 g) was added to the crude product, and the mixture was stirred at 80.degree. C. overnight. After completion of the reaction, water (400 ml) was added, and the mixture was extracted with methylene chloride (200 ml) three times, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The resulting crude product was recrystallized from ethyl acetate/n-hexane to give 2-(4-chlorobenzyloxy)benzaldehyde oxime (32.06 g) as colorless crystals. mp. 122.5.degree.-123.5.degree. C.
Example 10
Synthesis of 2-(4-chlorobenzyloxy)-.alpha.-(1-imidazolyl)benzaldehyde oxime
2-(4-Chlorobenzyloxy)benzaldehyde oxime (26.17 g) was dissolved in ether (200 ml) and methylene chloride (50 ml), and chlorine (6.0 ml) was introduced at -10.degree. C. or below, and then the temperature was raised from -10.degree. C. to room temperature over 2 hours. After completion of the reaction, the mixture was concentrated under reduced pressure to give crude .alpha.-chloro-2-(4-chlorobenzyloxy)benzaldehyde oxime. The resulting crude product was dissolved in acetonitrile (150 ml), a mixture of imidazole (17.02 g) and acetonitrile (100 ml) was added at room temperature over 15 minutes, and then the resulting mixture was stirred at 65 to 70.degree. C. for 2 hours. After completion of the reaction, water and methylene chloride were added. The resulting crystals were separated by filtration to give 2-(4-chlorobenzyloxy)-.alpha.-(1-imidazolyl)benzaldehyde oxime (11.05 g) as colorless crystals. mp. 196.degree.-197.degree. C.
Example 11
Synthesis of 2-(4-chlorobenzyloxy)-.alpha.-(1-imidazolyl)benzaldehyde O-benzyloxime
Potassium carbonate (0.21 g), benzyl chloride (0.15 g) and DMF (2 ml) were added to 2-(4-chlorobenzyloxy)-.alpha.-(1-imidazolyl)benzaldehyde oxime (0.33 g), and the mixture was stirred at 60.degree. C. for 2 hours. After completion of the reaction, ether (100 ml) was added, and the mixture was extracted with brine (80 ml) twice, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The resulting crude product was purified by silica gel chromatography to give 2-(4-chlorobenzyloxy)-.alpha.-(1-imidazolyl)benzaldehyde O-benzyloxime (0.38 g) as colorless crystals. mp. 94.degree.-95.5.degree. C.
Example 12
Synthesis of .alpha.-(1-imidazolyl)-2-(1-phenylpropyloxy)benzaldehyde O-methyloxime
Triphenylphosphine (1.05 g), 1-phenylpropyl alcohol (0.54 g) and THF (20 ml) were added to 2-hydroxy-.alpha.-(1-imidazolyl)benzaldehyde O-methyloxime (0.43 g), and diethyl azodicarboxylate (0.70 g) was added under ice-cooling over 10 minutes. Then the mixture was stirred at room temperature for 2 hours. After completion of the reaction, ether (100 ml) was added, the mixture was washed with water (80 ml) twice, and the ether layer was concentrated under reduced pressure. The resulting crude product was purified by silica gel chromatography to give .alpha.-(1-imidazolyl)-2-(1-phenylpropyloxy)benzaldehyde O-methyloxime (0.63 g) as a colorless oil.
Example 13
According the same manner as that described above, the compounds in the following tables (Compound Nos. 1 to 1130) were prepared.
The physical properties of the representative compounds obtained are in Tables 1 to 156. In the tables, the physical properties of the compounds obtained in Examples 4, 5, 7 and 8 are also listed. In the tables, Me means methyl, Et means ethyl, n-Pr means n-propyl, i-Pr means isopropyl, i-Bu means isobutyl, t-Bu means t-butyl, Ph means phenyl, and Bn means benzyl.
The .sup.1 H-NMR values were determined on 270 MHz and are indicated in terms of .delta. values (ppm) using tetramethylsilane in CDCl.sub.3 as the internal standard. The spin coupling constants (J) are indicated in terms of Hz. In the NMR data, s means a singlet, d means a doublet, t means a triplet, q means a quartet, quint means a quintet, sext means a sextet, sept means a septet, and m means a multiplet.
TABLE 1__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________ ##STR32## Me H O CH ##STR33##2 ##STR34## Me H O CH3 ##STR35## Me H O CH 70.5-72 ##STR36##4 ##STR37## Me H O CH5 ##STR38## Me H O CH6 ##STR39## Me H O CH7 ##STR40## Me H O CH 91.5-92.5 ##STR41##__________________________________________________________________________
TABLE 2__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________ 8 ##STR42## Me H O CH 9 ##STR43## Me H O CH 92.5-93.5 ##STR44##10 ##STR45## Me H O CH11 ##STR46## Me H O CH12 ##STR47## Me H O CH13 ##STR48## Me H O CH14 ##STR49## Me H O CH15 ##STR50## Me H O CH ##STR51##__________________________________________________________________________
TABLE 3__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________16 ##STR52## Me H O CH17 ##STR53## Me H O CH18 ##STR54## Me H O CH19 ##STR55## Me H O CH20 ##STR56## Me H O CH21 ##STR57## Me H O CH22 ##STR58## Me H O CH__________________________________________________________________________
TABLE 4__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________23 ##STR59## Me H O CH24 ##STR60## Me H O CH25 ##STR61## Me H O CH26 ##STR62## Me H O CH ##STR63##27 ##STR64## Me H O CH28 ##STR65## Me H O CH29 ##STR66## Me H O CH30 ##STR67## Me H O CH__________________________________________________________________________
TABLE 5__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________31 ##STR68## Me H O CH 122-123 ##STR69##32 ##STR70## Me H O CH 110.5-111.5 ##STR71##33 ##STR72## Me H O CH34 ##STR73## Me H O CH35 ##STR74## Me H O CH ##STR75##36 ##STR76## Me H O CH37 ##STR77## Me H O CH__________________________________________________________________________
TABLE 6__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________38 ##STR78## Me H O CH39 ##STR79## Me H O CH40 ##STR80## Me H O CH41 ##STR81## Me H O CH42 ##STR82## Me H O CH43 ##STR83## Me H O CH44 ##STR84## Me H O CH45 ##STR85## Me H O CH__________________________________________________________________________
TABLE 7__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________46 ##STR86## Me H O CH47 ##STR87## Me H O CH48 ##STR88## Me H O CH49 ##STR89## Me H O CH 118-119 ##STR90##50 ##STR91## Me H O CH51 ##STR92## Me H O CH 128-129 ##STR93##52 PhOCH.sub.2 CH.sub.2 Me H O CH ##STR94##__________________________________________________________________________
TABLE 8__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________53 MeOCOCH.sub.2 Me H O CH 3.72(3H, s), 4.05(3H, s), 4.50(2H, s), 6.78- 7.53(6H, m), 8.03(1H, s)54 PhCOCH.sub.2 Me H O CH 4.04(3H, s), 5.15(2H, s), 6.79-7.86(11H, m), 8.04(1H, s)55 ##STR95## Me H S CH ##STR96##56 ##STR97## Me H S CH57 ##STR98## Me H S CH58 ##STR99## Me H S CH 74.5-75.559 ##STR100## Me H S CH60 ##STR101## Me H S CH__________________________________________________________________________
TABLE 9__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________61 ##STR102## Me H S CH62 ##STR103## Me H O N 91.5-92.563 ##STR104## Me H O N 124-12564 ##STR105## Me H O N65 ##STR106## Me H O N ##STR107##66 ##STR108## Me H O N 130-131 ##STR109##67 ##STR110## Me H O CH68 ##STR111## Me H O CH ##STR112##__________________________________________________________________________
TABLE 10__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________69 ##STR113## Me H O CH70 ##STR114## Me H O CH 75.5-76.5 ##STR115##71 ##STR116## Me H O CH 147-148 ##STR117##72 ##STR118## Me H O CH 76-77 ##STR119##73 ##STR120## Me H O CH74 ##STR121## Me H O CH75 ##STR122## Me H O CH__________________________________________________________________________
TABLE 11__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________76 ##STR123## Me H O CH 42-49 ##STR124##77 ##STR125## Me H O CH78 ##STR126## Me H O CH79 ##STR127## Me H O CH 80-81 ##STR128##80 ##STR129## Me H O CH81 ##STR130## Me H O CH ##STR131##82 ##STR132## Me H O CH ##STR133##__________________________________________________________________________
TABLE 12__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________83 ##STR134## Me H O CH 94.5-95.5 ##STR135##84 ##STR136## Me H O CH85 ##STR137## Me H O CH86 ##STR138## Me H O CH ##STR139##87 ##STR140## Me H O CH ##STR141##88 ##STR142## Me H O CH89 ##STR143## Me H O CH ##STR144##90 ##STR145## Me H O CH__________________________________________________________________________
TABLE 13__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________91 ##STR146## Me H O CH92 ##STR147## Me H O CH ##STR148##93 ##STR149## Me H O CH94 ##STR150## Me H O CH95 ##STR151## Me H O CH96 ##STR152## Me H O CH ##STR153##97 ##STR154## Me H O CH__________________________________________________________________________
TABLE 14__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________98 ##STR155## Me H O CH ##STR156##99 ##STR157## Me H O CH100 ##STR158## Me H O CH__________________________________________________________________________
TABLE 15__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________101 ##STR159## Et H O CH ##STR160##102 ##STR161## Et H O CH103 ##STR162## Et H O CH 80-82 ##STR163##104 ##STR164## Et H O CH ##STR165##105 ##STR166## Et H O CH106 ##STR167## Et H O CH 77-79 ##STR168##107 ##STR169## Et H O CH 67-70 ##STR170##__________________________________________________________________________
TABLE 16__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________108 ##STR171## Et H O CH 73.5-75 ##STR172##109 ##STR173## Et H O CH 99.5-100.5 ##STR174##110 ##STR175## Et H O CH ##STR176##111 ##STR177## Et H O CH112 ##STR178## Et H O CH113 ##STR179## Et H O CH114 ##STR180## Et H O CH115 ##STR181## Et H O CH ##STR182##__________________________________________________________________________
TABLE 17__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________116 ##STR183## Et H O CH117 ##STR184## Et H O CH118 ##STR185## Et H O CH ##STR186##119 ##STR187## Et H O CH120 ##STR188## Et H O CH 104.5-106.5 ##STR189##121 ##STR190## Et H O CH122 ##STR191## Et H O CH__________________________________________________________________________
TABLE 18__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________123 ##STR192## Et H O CH124 ##STR193## Et H O CH ##STR194##125 ##STR195## Et H O CH126 ##STR196## Et H O CH ##STR197##127 ##STR198## Et H O CH 88.0-89.5128 ##STR199## Et H O CH ##STR200##129 ##STR201## Et H O CH 72-73.5 ##STR202##130 ##STR203## Et H O CH__________________________________________________________________________
TABLE 19__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________131 ##STR204## Et H O CH 106.5-107.5 ##STR205##132 ##STR206## Et H O CH 97-98 ##STR207##133 ##STR208## Et H O CH 113-114 ##STR209##134 ##STR210## Et H O CH135 ##STR211## Et H O CH136 ##STR212## Et H O CH137 ##STR213## Et H O CH__________________________________________________________________________
TABLE 20__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________138 ##STR214## Et H O CH139 ##STR215## Et H O CH140 ##STR216## Et H O CH141 ##STR217## Et H O CH142 ##STR218## Et H O CH143 ##STR219## Et H O CH144 ##STR220## Et H O CH145 ##STR221## Et H O CH__________________________________________________________________________
TABLE 21__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________146 ##STR222## Et H O CH147 ##STR223## Et H O CH148 ##STR224## Et H O CH149 ##STR225## Et H O CH 84.5-85.5 ##STR226##150 ##STR227## Et H O CH151 ##STR228## Et H O CH152 PhOCH.sub.2 CH.sub.2 Et H O CH ##STR229##__________________________________________________________________________
TABLE 22__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________153 ##STR230## Et H O CH ##STR231##154 PhCOCH.sub.2 Et H O CH155 ##STR232## Et H S CH 96.5-97.5 ##STR233##156 ##STR234## Et H S CH157 ##STR235## Et H S CH158 ##STR236## Et H S CH159 ##STR237## Et H S CH160 ##STR238## Et H S CH__________________________________________________________________________
TABLE 23__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________161 ##STR239## Et H O CH ##STR240##162 PhO(CH.sub.2).sub.3 Et H O CH163 ##STR241## Et H O N164 ##STR242## Et H O N165 ##STR243## Et H O N ##STR244##166 ##STR245## Et H O N167 ##STR246## Et H O CH168 ##STR247## Et H O CH ##STR248##__________________________________________________________________________
TABLE 24__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________169 ##STR249## Et H O CH170 ##STR250## Et H O CH 65-66 ##STR251##171 ##STR252## Et H O CH 131-132.5 ##STR253##172 ##STR254## Et H O CH 81-82 ##STR255##173 ##STR256## Et H O CH174 ##STR257## Et H O CH175 ##STR258## Et H O CH__________________________________________________________________________
TABLE 25__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________176 ##STR259## Et H O CH177 ##STR260## Et H O CH178 ##STR261## Et H O CH ##STR262##179 ##STR263## Et H O CH ##STR264##180 ##STR265## Et H O CH181 ##STR266## Et H O CH ##STR267##182 ##STR268## Et H O CH__________________________________________________________________________
TABLE 26__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________183 ##STR269## Et H O CH ##STR270##184 ##STR271## Et H O CH ##STR272##185 ##STR273## Et H O CH186 ##STR274## Et H O CH 71-73 ##STR275##187 ##STR276## Et H O CH ##STR277##188 ##STR278## Et H O CH189 ##STR279## Et H O CH ##STR280##190 ##STR281## Et H O CH__________________________________________________________________________
TABLE 27__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________191 ##STR282## Et H O CH ##STR283## ##STR284##192 ##STR285## Et H O CH ##STR286##193 ##STR287## Et H O CH194 ##STR288## Et H O CH195 ##STR289## Et H O CH196 ##STR290## Et H O CH ##STR291##197 ##STR292## Et H O CH__________________________________________________________________________
TABLE 28__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________198 ##STR293## Et H O CH199 ##STR294## Et H O CH ##STR295##200 ##STR296## Et H O CH__________________________________________________________________________
TABLE 29__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________201 ##STR297## Allyl H O CH202 ##STR298## Allyl H O CH203 ##STR299## Allyl H O CH ##STR300##204 ##STR301## Allyl H O CH205 ##STR302## Allyl H O CH206 ##STR303## Allyl H O CH207 ##STR304## Allyl H O CH ##STR305##__________________________________________________________________________
TABLE 30__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________208 ##STR306## Allyl H O CH209 ##STR307## Allyl H O CH ##STR308## ##STR309##210 ##STR310## Allyl H O CH211 ##STR311## Allyl H O CH212 ##STR312## Allyl H O CH213 ##STR313## Allyl H O CH214 ##STR314## Allyl H O CH215 ##STR315## Allyl H O CH__________________________________________________________________________
TABLE 31__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________216 ##STR316## Allyl H O CH217 ##STR317## Allyl H O CH218 ##STR318## Allyl H O CH219 ##STR319## Allyl H O CH220 ##STR320## Allyl H O CH221 ##STR321## Allyl H O CH222 ##STR322## Allyl H O CH__________________________________________________________________________
TABLE 32__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________223 ##STR323## Allyl H O CH224 ##STR324## Allyl H O CH225 ##STR325## Allyl H O CH226 ##STR326## Allyl H O CH ##STR327##227 ##STR328## Allyl H O CH228 ##STR329## Allyl H O CH229 ##STR330## Allyl H O CH230 ##STR331## Allyl H O CH__________________________________________________________________________
TABLE 33__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________231 ##STR332## Allyl H O CH232 ##STR333## Allyl H O CH233 ##STR334## Allyl H O CH 92.5- 93.5 4.72-4.75(2H, m), 4.88(2H, s), 5.25- 5.40(2H, m), 5.98-6.12(1H, m), 6.85(1H, dd, J=8.6, 2.4), 6.94(1H, d, =8.5), 7.06-7.54(7H, m), 7.96(1H, s)234 ##STR335## Allyl H O CH235 ##STR336## Allyl H O CH236 ##STR337## Allyl H O CH237 ##STR338## Allyl H O CH__________________________________________________________________________
TABLE 34__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________238 ##STR339## Allyl H O CH239 ##STR340## Allyl H O CH240 ##STR341## Allyl H O CH241 ##STR342## Allyl H O CH242 ##STR343## Allyl H O CH243 ##STR344## Allyl H O CH244 ##STR345## Allyl H O CH245 ##STR346## Allyl H O CH__________________________________________________________________________
TABLE 35__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________246 ##STR347## Allyl H O CH247 ##STR348## Allyl H O CH248 ##STR349## Allyl H O CH249 ##STR350## Allyl H O CH250 ##STR351## Allyl H O CH251 ##STR352## Allyl H O CH252 PhOCH.sub.2 CH.sub.2 Allyl H O CH__________________________________________________________________________
TABLE 36__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________253 ##STR353## Allyl H O CH ##STR354## ##STR355##254 PhCOCH.sub.2 Allyl H O CH255 ##STR356## Allyl H S CH256 ##STR357## Allyl H S CH257 ##STR358## Allyl H S CH258 ##STR359## Allyl H S CH259 ##STR360## Allyl H S CH260 ##STR361## Allyl H S CH__________________________________________________________________________
TABLE 37__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________261 ##STR362## Allyl H O CH262 PhO(CH.sub.2).sub.3 Allyl H O CH263 ##STR363## Allyl H O N264 ##STR364## Allyl H O N265 ##STR365## Allyl H O N266 ##STR366## Allyl H O N267 ##STR367## Allyl H O CH__________________________________________________________________________
TABLE 38__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________268 ##STR368## Allyl H O CH269 ##STR369## Allyl H O CH270 ##STR370## Allyl H O CH 57-58 ##STR371##271 ##STR372## Allyl H O CH272 ##STR373## Allyl H O CH273 ##STR374## Allyl H O CH274 ##STR375## Allyl H O CH275 ##STR376## Allyl H O CH__________________________________________________________________________
TABLE 39__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________276 ##STR377## Allyl H O CH277 ##STR378## Allyl H O CH278 ##STR379## Allyl H O CH279 ##STR380## Allyl H O CH280 ##STR381## Allyl H O CH281 ##STR382## Allyl H O CH ##STR383##282 ##STR384## Allyl H O CH__________________________________________________________________________
TABLE 40__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________283 ##STR385## Allyl H O CH ##STR386##284 ##STR387## Allyl H O CH285 ##STR388## Allyl H O CH286 ##STR389## Allyl H O CH ##STR390##287 ##STR391## Allyl H O CH288 ##STR392## Allyl H O CH289 ##STR393## Allyl H O CH290 ##STR394## Allyl H O CH__________________________________________________________________________
TABLE 41__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________291 ##STR395## Allyl H O CH292 ##STR396## Allyl H O CH293 ##STR397## Allyl H O CH294 ##STR398## Allyl H O CH295 ##STR399## Allyl H O CH296 ##STR400## Allyl H O CH297 ##STR401## Allyl H O CH__________________________________________________________________________
TABLE 42__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________298 ##STR402## Allyl H O CH ##STR403##299 ##STR404## Allyl H O CH300 ##STR405## Allyl H O CH__________________________________________________________________________
TABLE 43__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________301 ##STR406## i-Bu H O CH302 ##STR407## i-Bu H O CH303 ##STR408## i-Bu H O CH 84-86 ##STR409##304 ##STR410## i-Bu H O CH305 ##STR411## i-Bu H O CH306 ##STR412## i-Bu H O CH 73-74 ##STR413##307 ##STR414## i-Bu H O CH ##STR415##__________________________________________________________________________
TABLE 44__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________308 ##STR416## i-Bu H O CH309 ##STR417## i-Bu H O CH 84-85 ##STR418##310 ##STR419## i-Bu H O CH311 ##STR420## i-Bu H O CH312 ##STR421## i-Bu H O CH313 ##STR422## i-Bu H O CH314 ##STR423## i-Bu H O CH315 ##STR424## i-Bu H O CH ##STR425##__________________________________________________________________________
TABLE 45__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________316 ##STR426## i-Bu H O CH317 ##STR427## i-Bu H O CH318 ##STR428## i-Bu H O CH319 ##STR429## i-Bu H O CH320 ##STR430## i-Bu H O CH321 ##STR431## i-Bu H O CH322 ##STR432## i-Bu H O CH__________________________________________________________________________
TABLE 46__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________323 ##STR433## i-Bu H O CH324 ##STR434## i-Bu H O CH325 ##STR435## i-Bu H O CH326 ##STR436## i-Bu H O CH 81-82 ##STR437##327 ##STR438## i-Bu H O CH328 ##STR439## i-Bu H O CH329 ##STR440## i-Bu H O CH330 ##STR441## i-Bu H O CH__________________________________________________________________________
TABLE 47__________________________________________________________________________No. R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________331 ##STR442## i-Bu H O CH332 ##STR443## i-Bu H O CH333 ##STR444## i-Bu H O CH 95.5-96.5 ##STR445##334 ##STR446## i-Bu H O CH335 ##STR447## i-Bu H O CH336 ##STR448## i-Bu H O CH337 ##STR449## i-Bu H O CH__________________________________________________________________________
TABLE 48__________________________________________________________________________No. R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________338 ##STR450## i-Bu H O CH339 ##STR451## i-Bu H O CH340 ##STR452## i-Bu H O CH341 ##STR453## i-Bu H O CH342 ##STR454## i-Bu H O CH343 ##STR455## i-Bu H O CH344 ##STR456## i-Bu H O CH345 ##STR457## i-Bu H O CH__________________________________________________________________________
TABLE 49__________________________________________________________________________No. R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________346 ##STR458## i-Bu H O CH347 ##STR459## i-Bu H O CH348 ##STR460## i-Bu H O CH349 ##STR461## i-Bu H O CH350 ##STR462## i-Bu H O CH351 ##STR463## i-Bu H O CH352 PhOCH.sub.2 CH.sub.2 i-Bu H O CH__________________________________________________________________________
TABLE 50__________________________________________________________________________No. R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________353 ##STR464## i-Bu H O CH354 PhCOCH.sub.2 i-Bu H O CH355 ##STR465## i-Bu H S CH356 ##STR466## i-Bu H S CH357 ##STR467## i-Bu H S CH358 ##STR468## i-Bu H S CH359 ##STR469## i-Bu H S CH360 ##STR470## i-Bu H S CH__________________________________________________________________________
TABLE 51__________________________________________________________________________No. R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________361 ##STR471## i-Bu H O CH362 PhO(CH.sub.2).sub.3 i-Bu H O CH363 ##STR472## i-Bu H O N364 ##STR473## i-Bu H O N365 ##STR474## i-Bu H O N366 ##STR475## i-Bu H O N367 ##STR476## i-Bu H O CH__________________________________________________________________________
TABLE 52__________________________________________________________________________No. R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________368 ##STR477## i-Bu H O CH369 ##STR478## i-Bu H O CH370 ##STR479## i-Bu H O CH 92-93 ##STR480##371 ##STR481## i-Bu H O CH372 ##STR482## i-Bu H O CH373 ##STR483## i-Bu H O CH374 ##STR484## i-Bu H O CH375 ##STR485## i-Bu H O CH__________________________________________________________________________
TABLE 53__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________376 ##STR486## i-Bu H O CH ##STR487##377 ##STR488## i-Bu H O CH378 ##STR489## i-Bu H O CH379 ##STR490## i-Bu H O CH380 ##STR491## i-Bu H O CH381 ##STR492## i-Bu H O CH ##STR493##382 ##STR494## i-Bu H O CH__________________________________________________________________________
TABLE 54__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________383 ##STR495## i-Bu H O CH ##STR496##384 ##STR497## i-Bu H O CH385 ##STR498## i-Bu H O CH386 ##STR499## i-Bu H O CH 81.5-82.5 ##STR500##387 ##STR501## i-Bu H O CH388 ##STR502## i-Bu H O CH389 ##STR503## i-Bu H O CH390 ##STR504## i-Bu H O CH__________________________________________________________________________
TABLE 55__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________391 ##STR505## i-Bu H O CH392 ##STR506## i-Bu H O CH393 ##STR507## i-Bu H O CH394 ##STR508## i-Bu H O CH395 ##STR509## i-Bu H O CH396 ##STR510## i-Bu H O CH397 ##STR511## i-Bu H O CH__________________________________________________________________________
TABLE 56__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________398 ##STR512## i-Bu H O CH399 ##STR513## i-Bu H O CH400 ##STR514## i-Bu H O CH__________________________________________________________________________
TABLE 57__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________401 ##STR515## Me 4-MeO O CH 97.5-98.5 ##STR516##402 ##STR517## Me 4-MeO O CH403 ##STR518## Me 4-MeO O CH 79.5-80.5 ##STR519##404 ##STR520## Me 4-MeO O CH405 ##STR521## Me 4-MeO O CH406 ##STR522## Me 4-MeO O CH 71-72 ##STR523##407 ##STR524## Me 4-MeO O CH 121.5-122.5 ##STR525##__________________________________________________________________________
TABLE 58__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________408 ##STR526## Me 4-MeO O CH409 ##STR527## Me 4-MeO O CH 106-107 ##STR528##410 ##STR529## Me 4-MeO O CH411 ##STR530## Me 4-MeO O CH412 ##STR531## Me 4-MeO O CH413 ##STR532## Me 4-MeO O CH414 ##STR533## Me 4-MeO O CH415 ##STR534## Me 4-MeO O CH ##STR535##__________________________________________________________________________
TABLE 59__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________416 ##STR536## Me 4-MeO O CH417 ##STR537## Me 4-MeO O CH418 ##STR538## Me 4-MeO O CH419 ##STR539## Me 4-MeO O CH420 ##STR540## Me 4-MeO O CH421 ##STR541## Me 4-MeO O CH422 ##STR542## Me 4-MeO O CH423 ##STR543## Me 4-MeO O CH__________________________________________________________________________
TABLE 60__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________424 ##STR544## Me 4-MeO O CH425 ##STR545## Me 4-MeO O CH426 ##STR546## Me 4-MeO O CH ##STR547## ##STR548##427 ##STR549## Me 4-MeO O CH428 ##STR550## Me 4-MeO O CH429 ##STR551## Me 4-MeO O CH430 ##STR552## Me 4-MeO O CH__________________________________________________________________________
TABLE 61__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________431 ##STR553## Me 4-MeO O CH432 ##STR554## Me 4-MeO O CH433 ##STR555## Me 4-MeO O CH ##STR556## ##STR557##434 ##STR558## Me 4-MeO O CH435 ##STR559## Me 4-MeO O CH436 ##STR560## Me 4-MeO O CH437 ##STR561## Me 4-MeO O CH__________________________________________________________________________
TABLE 62__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________438 ##STR562## Me 4-MeO O CH439 ##STR563## Me 4-MeO O CH440 ##STR564## Me 4-MeO O CH441 ##STR565## Me 4-MeO O CH442 ##STR566## Me 4-MeO O CH443 ##STR567## Me 4-MeO O CH444 ##STR568## Me 4-MeO O CH445 ##STR569## Me 4-MeO O CH__________________________________________________________________________
TABLE 63__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________446 ##STR570## Me 4-MeO O CH447 ##STR571## Me 4-MeO O CH448 ##STR572## Me 4-MeO O CH449 ##STR573## Me 4-MeO O CH450 ##STR574## Me 4-MeO O CH451 ##STR575## Me 4-MeO O CH452 PhOCH.sub.2 CH.sub.2 Me 4-MeO O CH 3.85(3H, s), 3.92(2H, t, J=4.9), 4.00 (3H, s), 4.15(2H, t, J=4.9), 6.51-7.33 (9H, m), 7.46(1H, d, J=8.5), 7.84 (1H, s)__________________________________________________________________________
TABLE 64__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________453 MeOCOCH.sub.2 Me 4-MeO O CH454 PhCOCH.sub.2 Me 4-MeO O CH455 ##STR576## Me 4-MeO S CH456 ##STR577## Me 4-MeO S CH457 ##STR578## Me 4-MeO S CH458 ##STR579## Me 4-MeO S CH459 ##STR580## Me 4-MeO S CH460 ##STR581## Me 4-MeO S CH__________________________________________________________________________
TABLE 65__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________461 ##STR582## Me 4-MeO S CH462 ##STR583## Me 4-MeO O N463 ##STR584## Me 4-MeO O N464 ##STR585## Me 4-MeO O N465 ##STR586## Me 4-MeO O N466 ##STR587## Me 4-MeO O N467 ##STR588## Me 4-MeO O CH468 ##STR589## Me 4-MeO O CH__________________________________________________________________________
TABLE 66__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________469 ##STR590## Me 4-MeO O CH470 ##STR591## Me 4-MeO O CH 98.5-99.5 ##STR592##471 ##STR593## Me 4-MeO O CH472 ##STR594## Me 4-MeO O CH473 ##STR595## Me 4-MeO O CH474 ##STR596## Me 4-MeO O CH475 ##STR597## Me 4-MeO O CH__________________________________________________________________________
TABLE 67__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________476 ##STR598## Me 4-MeO O CH477 ##STR599## Me 4-MeO O CH478 ##STR600## Me 4-MeO O CH479 ##STR601## Me 4-MeO O CH480 ##STR602## Me 4-MeO O CH481 ##STR603## Me 4-MeO O CH ##STR604##482 ##STR605## Me 4-MeO O CH__________________________________________________________________________
TABLE 68__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________483 ##STR606## Me 4-MeO O CH ##STR607##484 ##STR608## Me 4-MeO O CH485 ##STR609## Me 4-MeO O CH486 ##STR610## Me 4-MeO O CH487 ##STR611## Me 4-MeO O CH488 ##STR612## Me 4-MeO O CH489 ##STR613## Me 4-MeO O CH490 ##STR614## Me 4-MeO O CH__________________________________________________________________________
TABLE 69__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________491 ##STR615## Me H O CH ##STR616##492 ##STR617## Me H O CH ##STR618##493 ##STR619## Me H O CH494 ##STR620## Me H O CH ##STR621##495 ##STR622## Me H O CH ##STR623##496 ##STR624## Me H O CH ##STR625##497 ##STR626## Me H O CH ##STR627##__________________________________________________________________________
TABLE 70__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________498 ##STR628## Me 4-MeO O CH499 ##STR629## Me 4-MeO O CH500 ##STR630## Me 4-MeO O CH__________________________________________________________________________
TABLE 71__________________________________________________________________________No R.sup.1 R.sup.2 R.sup.3 X Y mp(.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________501 ##STR631## Me 5-Cl O CH 107-108.5 ##STR632##502 ##STR633## Me 5-Cl O CH503 ##STR634## Me 5-Cl O CH 112-113 ##STR635##504 ##STR636## Me 5-Cl O CH505 ##STR637## Me 5-Cl O CH506 ##STR638## Me 5-Cl O CH 107-108 ##STR639##507 ##STR640## Me 5-Cl O CH 126-127 ##STR641##__________________________________________________________________________
TABLE 72__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________508 ##STR642## Me 5-Cl O CH509 ##STR643## Me 5-Cl O CH ##STR644## ##STR645##510 ##STR646## Me 5-Cl O CH511 ##STR647## Me 5-Cl O CH512 ##STR648## Me 5-Cl O CH513 ##STR649## Me 5-Cl O CH514 ##STR650## Me 5-Cl O CH515 ##STR651## Me 5-Cl O CH ##STR652## ##STR653##__________________________________________________________________________
TABLE 73__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________516 ##STR654## Me 5-Cl O CH517 ##STR655## Me 5-Cl O CH518 ##STR656## Me 5-Cl O CH519 ##STR657## Me 5-Cl O CH520 ##STR658## Me 5-Cl O CH521 ##STR659## Me 5-Cl O CH522 ##STR660## Me 5-Cl O CH__________________________________________________________________________
TABLE 74__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________523 ##STR661## Me 5-Cl O CH524 ##STR662## Me 5-Cl O CH525 ##STR663## Me 5-Cl O CH526 ##STR664## Me 5-Cl O CH ##STR665## ##STR666##527 ##STR667## Me 5-Cl O CH528 ##STR668## Me 5-Cl O CH529 ##STR669## Me 5-Cl O CH530 ##STR670## Me 5-Cl O CH__________________________________________________________________________
TABLE 75__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________531 ##STR671## Me 5-Cl O CH ##STR672## ##STR673##532 ##STR674## Me 5-Cl O CH533 ##STR675## Me 5-Cl O CH ##STR676## ##STR677##534 ##STR678## Me 5-Cl O CH535 ##STR679## Me 5-Cl O CH536 ##STR680## Me 5-Cl O CH537 ##STR681## Me 5-Cl O CH__________________________________________________________________________
TABLE 76__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________538 ##STR682## Me 5-Cl O CH539 ##STR683## Me 5-Cl O CH540 ##STR684## Me 5-Cl O CH541 ##STR685## Me 5-Cl O CH542 ##STR686## Me 5-Cl O CH543 ##STR687## Me 5-Cl O CH544 ##STR688## Me 5-Cl O CH545 ##STR689## Me 5-Cl O CH__________________________________________________________________________
TABLE 77__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________546 ##STR690## Me 5-Cl O CH547 ##STR691## Me 5-Cl O CH548 ##STR692## Me 5-Cl O CH549 ##STR693## Me 5-Cl O CH550 ##STR694## Me 5-Cl O CH551 ##STR695## Me 5-Cl O CH552 PhOCH.sub.2 CH.sub.2 Me 5-Cl O CH ##STR696## ##STR697##__________________________________________________________________________
TABLE 78__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________553 MeOCOCH.sub.2 Me 5-Cl O CH554 PhCOCH.sub.2 Me 5-Cl O CH555 ##STR698## Me 5-Cl S CH556 ##STR699## Me 5-Cl S CH557 ##STR700## Me 5-Cl S CH558 ##STR701## Me 5-Cl S CH559 ##STR702## Me 5-Cl S CH560 ##STR703## Me 5-Cl S CH__________________________________________________________________________
TABLE 79__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________561 ##STR704## Me 5-Cl S CH562 ##STR705## Me 5-Cl O N563 ##STR706## Me 5-Cl O N ##STR707##564 ##STR708## Me 5-Cl O N565 ##STR709## Me 5-Cl O N ##STR710## ##STR711##566 ##STR712## Me 5-Cl O N567 ##STR713## Me 5-Cl O CH568 ##STR714## Me 5-Cl O CH ##STR715##__________________________________________________________________________
TABLE 80__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________569 ##STR716## Me 5-Cl O CH570 ##STR717## Me 5-Cl O CH ##STR718## ##STR719##571 ##STR720## Me 5-Cl O CH572 ##STR721## Me 5-Cl O CH573 ##STR722## Me 5-Cl O CH574 ##STR723## Me 5-Cl O CH575 ##STR724## Me 5-Cl O CH__________________________________________________________________________
TABLE 81__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________576 ##STR725## Me 5-Cl O CH577 ##STR726## Me 5-Cl O CH578 ##STR727## Me 5-Cl O CH579 ##STR728## Me 5-Cl O CH580 ##STR729## Me 5-Cl O CH581 ##STR730## Me 5-Cl O CH ##STR731##582 ##STR732## Me 5-Cl O CH__________________________________________________________________________
TABLE 82__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________583 ##STR733## Me 5-Cl O CH ##STR734##584 ##STR735## Me 5-Cl O CH585 ##STR736## Me 5-Cl O CH586 ##STR737## Me 5-Cl O CH587 ##STR738## Me 5-Cl O CH588 ##STR739## Me 5-Cl O CH589 ##STR740## Me 5-Cl O CH590 ##STR741## Me 5-Cl O CH__________________________________________________________________________
TABLE 83__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________591 ##STR742## Me 5-Cl O CH592 ##STR743## Me 5-Cl O CH ##STR744##593 ##STR745## Me 5-Cl O CH594 ##STR746## Me 5-Cl O CH595 ##STR747## Me 5-Cl O CH596 ##STR748## Me 5-Cl O CH597 ##STR749## Me 5-Cl O CH__________________________________________________________________________
TABLE 84__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________598 ##STR750## Me 5-Cl O CH599 ##STR751## Me 5-Cl O CH600 ##STR752## Me 5-Cl O CH__________________________________________________________________________
TABLE 85__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________601 ##STR753## n-Pr H O CH602 ##STR754## n-Pr H O CH603 ##STR755## n-Pr H O CH ##STR756## ##STR757##604 ##STR758## n-Pr H O CH605 ##STR759## n-Pr H O CH606 ##STR760## n-Pr H O CH ##STR761##607 ##STR762## n-Pr H O CH__________________________________________________________________________
TABLE 86__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________608 ##STR763## n-Pr H O CH609 ##STR764## n-Pr H O CH ##STR765## ##STR766##610 ##STR767## n-Pr H O CH611 ##STR768## n-Pr H O CH612 ##STR769## n-Pr H O CH613 ##STR770## n-Pr H O CH614 ##STR771## n-Pr H O CH615 ##STR772## n-Pr H O CH ##STR773##__________________________________________________________________________
TABLE 87__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________616 ##STR774## i-Pr H O CH617 ##STR775## i-Pr H O CH618 ##STR776## i-Pr H O CH ##STR777##619 ##STR778## i-Pr H O CH620 ##STR779## i-Pr H O CH621 ##STR780## i-Pr H O CH ##STR781## ##STR782##622 ##STR783## i-Pr H O CH ##STR784## ##STR785##__________________________________________________________________________
TABLE 88__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________623 ##STR786## i-Pr H O CH624 ##STR787## i-Pr H O CH ##STR788## ##STR789##625 ##STR790## i-Pr H O CH626 ##STR791## i-Pr H O CH627 ##STR792## i-Pr H O CH628 ##STR793## i-Pr H O CH629 ##STR794## i-Pr H O CH630 ##STR795## i-Pr H O CH ##STR796##__________________________________________________________________________
TABLE 89__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________631 ##STR797## n-Pr H O N632 ##STR798## n-Pr H O CH633 ##STR799## n-Pr H O CH634 ##STR800## n-Pr H O CH ##STR801##635 ##STR802## n-Pr H O CH ##STR803## ##STR804##636 ##STR805## n-Pr H O CH637 ##STR806## n-Pr H O CH638 ##STR807## n-Pr H O CH__________________________________________________________________________
TABLE 90__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________639 ##STR808## n-Pr H O CH640 ##STR809## n-Pr H O CH ##STR810##641 ##STR811## n-Pr H O CH642 ##STR812## n-Pr H O CH643 ##STR813## n-Pr H O CH644 ##STR814## n-Pr H O CH645 ##STR815## n-Pr H O CH__________________________________________________________________________
TABLE 91__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________646 ##STR816## i-Pr H O N647 ##STR817## i-Pr H O CH648 ##STR818## i-Pr H O CH649 ##STR819## i-Pr H O CH ##STR820##650 ##STR821## i-Pr H O CH ##STR822## ##STR823##651 ##STR824## i-Pr H O CH652 ##STR825## i-Pr H O CH__________________________________________________________________________
TABLE 92__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________653 ##STR826## i-Pr H O CH654 ##STR827## i-Pr H O CH655 ##STR828## i-Pr H O CH ##STR829##656 ##STR830## i-Pr H O CH657 ##STR831## i-Pr H O CH658 ##STR832## i-Pr H O CH659 ##STR833## i-Pr H O CH660 ##STR834## i-Pr H O CH__________________________________________________________________________
TABLE 93__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________661 ##STR835## Benzyl H O CH ##STR836## ##STR837##662 ##STR838## Benzyl H O CH663 ##STR839## Benzyl H O CH664 ##STR840## Benzyl H O CH665 ##STR841## FCH.sub.2 CH.sub.2 H O CH ##STR842## ##STR843##666 ##STR844## FCH.sub.2 CH.sub.2 H O CH667 ##STR845## FCH.sub.2 CH.sub.2 H O CH__________________________________________________________________________
TABLE 94__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________668 ##STR846## FCH.sub.2 CH.sub.2 H O CH669 ##STR847## ##STR848## H O CH ##STR849## ##STR850##670 ##STR851## ##STR852## H O CH671 ##STR853## ##STR854## H O CH672 ##STR855## ##STR856## H O CH673 ##STR857## H O CH ##STR858##674 ##STR859## H O CH675 ##STR860## H O CH__________________________________________________________________________
TABLE 95__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________676 H O CH ##STR861## ##STR862##677 H O CH678 H O CH679 H O CH680 H O CH ##STR863## ##STR864##681 H O CH682 H O CH__________________________________________________________________________
TABLE 96__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________683 ##STR865## H O CH684 CICHCHCH.sub.2 H O CH ##STR866##685 CICHCHCH.sub.2 H O CH686 CICHCHCH.sub.2 H O CH687 CICHCHCH.sub.2 H O CH688 Me H O CH ##STR867##689 Et H O CH690 i-Bu H O CH ##STR868##
TABLE 97__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________691 Me 5-Me O CH ##STR869##692 Me 5-Me O CH ##STR870##693 Me 5-Me O CH694 Me 5-Me O CH ##STR871##695 Me 5-Me O CH696 Me 5-Me O CH ##STR872##697 Me 5-Me O CH__________________________________________________________________________
TABLE 98__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________698 Me 5-Me O CH ##STR873##699 Me 5-Me O N700 Me 5-Me O N__________________________________________________________________________
TABLE 99__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________701 Me 5-F O CH ##STR874## ##STR875##702 Me 5-F O CH703 Me 5-F O CH ##STR876## ##STR877##704 Me 5-F O CH705 Me 5-F O CH706 Me 5-F O CH ##STR878## ##STR879##707 Me 5-F O CH ##STR880## ##STR881##__________________________________________________________________________
TABLE 100__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________708 Me 5-F O CH709 Me 5-F O CH ##STR882## ##STR883##710 Me 5-F O CH711 Me 5-F O CH712 Me 5-F O CH713 Me 5-F O CH714 Me 5-F O CH715 Me 5-F O CH ##STR884## ##STR885##__________________________________________________________________________
TABLE 101__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________716 Me 5-F O CH717 Me 5-F O CH718 Me 5-F O CH719 Me 5-F O CH720 Me 5-F O CH721 Me 5-F O CH722 Me 5-F O CH__________________________________________________________________________
TABLE 102__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________723 Me 5-F O CH724 Me 5-F O CH725 Me 5-F O CH726 Me 5-F O CH ##STR886## ##STR887##727 Me 5-F O CH728 Me 5-F O CH729 Me 5-F O CH730 Me 5-F O CH__________________________________________________________________________
TABLE 103__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________731 ##STR888## Me 5-F O CH ##STR889## ##STR890##732 ##STR891## Me 5-F O CH733 ##STR892## Me 5-F O CH ##STR893## ##STR894##734 ##STR895## Me 5-F O CH735 ##STR896## Me 5-F O CH736 ##STR897## Me 5-F O CH737 ##STR898## Me 5-F O CH__________________________________________________________________________
TABLE 104__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________738 ##STR899## Me 5-F O CH739 ##STR900## Me 5-F O CH740 ##STR901## Me 5-F O CH741 ##STR902## Me 5-F O CH742 ##STR903## Me 5-F O CH743 ##STR904## Me 5-F O CH744 ##STR905## Me 5-F O CH745 ##STR906## Me 5-F O CH__________________________________________________________________________
TABLE 105__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________746 ##STR907## Me 5-F O CH747 ##STR908## Me 5-F O CH748 ##STR909## Me 5-F O CH749 ##STR910## Me 5-F O CH750 ##STR911## Me 5-F O CH751 ##STR912## Me 5-F O CH752 PhOCH.sub.2 CH.sub.2 Me 5-F O CH ##STR913## ##STR914##__________________________________________________________________________
TABLE 106__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________753 MeOCOCH.sub.2 Me 5-F O CH754 PhCOCH.sub.2 Me 5-F O CH755 ##STR915## Me 5-F S CH756 ##STR916## Me 5-F S CH757 ##STR917## Me 5-F S CH758 ##STR918## Me 5-F S CH759 ##STR919## Me 5-F S CH760 ##STR920## Me 5-F S CH__________________________________________________________________________
TABLE 107__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________761 ##STR921## Me 5-F S CH762 ##STR922## Me 5-F O N763 ##STR923## Me 5-F O N ##STR924##764 ##STR925## Me 5-F O N765 ##STR926## Me 5-F O N ##STR927## ##STR928##766 ##STR929## Me 5-F O N767 ##STR930## Me 5-F O CH768 ##STR931## Me 5-F O CH ##STR932##__________________________________________________________________________
TABLE 108__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________769 ##STR933## Me 5-F O CH770 ##STR934## Me 5-F O CH ##STR935## ##STR936##771 ##STR937## Me 5-F O CH772 ##STR938## Me 5-F O CH773 ##STR939## Me 5-F O CH774 ##STR940## Me 5-F O CH775 ##STR941## Me 5-F O CH__________________________________________________________________________
TABLE 109__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________776 ##STR942## Me 5-F O CH777 ##STR943## Me 5-F O CH778 ##STR944## Me 5-F O CH779 ##STR945## Me 5-F O CH ##STR946##780 ##STR947## Me 5-F O CH781 ##STR948## Me 5-F O CH ##STR949##782 ##STR950## Me 5-F O CH__________________________________________________________________________
TABLE 110__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________783 ##STR951## Me 5-F O CH ##STR952##784 ##STR953## Me 5-F O CH785 ##STR954## Me 5-F O CH786 ##STR955## Me 5-F O CH787 ##STR956## Me 5-F O CH788 ##STR957## Me 5-F O CH789 ##STR958## Me 5-F O CH790 ##STR959## Me 5-F O CH__________________________________________________________________________
TABLE 111__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________791 ##STR960## Me 5-F O CH792 ##STR961## Me 5-F O CH ##STR962##793 ##STR963## Me 5-F O CH794 ##STR964## Me 5-F O CH795 ##STR965## Me 5-F O CH796 ##STR966## Me 5-F O CH797 ##STR967## Me 5-F O CH__________________________________________________________________________
TABLE 112__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________798 ##STR968## Me 5-F O CH799 ##STR969## Me 5-F O CH800 ##STR970## Me 5-F O CH__________________________________________________________________________
TABLE 113__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________801 ##STR971## Me 3-Me O CH ##STR972##802 ##STR973## Me 3-Me O CH803 ##STR974## Me 3-Me O CH ##STR975##804 ##STR976## Me 3-Me O CH805 ##STR977## Me 3-Me O CH806 ##STR978## Me 3-Me O CH ##STR979##807 ##STR980## Me 3-Me O CH ##STR981##__________________________________________________________________________
TABLE 114__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________808 ##STR982## Me 3-Me O CH809 ##STR983## Me 3-Me O CH ##STR984##810 ##STR985## Me 3-Me O CH811 ##STR986## Me 3-Me O CH ##STR987##812 ##STR988## Me 3-Me O CH813 ##STR989## Me 3-Me O CH814 ##STR990## Me 3-Me O CH815 ##STR991## Me 3-Me O CH ##STR992##__________________________________________________________________________
TABLE 115__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________816 ##STR993## Me 4-Me O CH ##STR994## ##STR995##817 ##STR996## Me 4-Me O CH818 ##STR997## Me 4-Me O CH ##STR998## ##STR999##819 ##STR1000## Me 4-Me O CH820 ##STR1001## Me 4-Me O CH821 ##STR1002## Me 4-Me O CH ##STR1003## ##STR1004##822 ##STR1005## Me 4-Me O CH ##STR1006## ##STR1007##__________________________________________________________________________
TABLE 116__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________823 ##STR1008## Me 4-Me O CH824 ##STR1009## Me 4-Me O CH ##STR1010##825 ##STR1011## Me 4-Me O CH826 ##STR1012## Me 4-Me O CH ##STR1013## ##STR1014##827 ##STR1015## Me 4-Me O CH828 ##STR1016## Me 4-Me O CH829 ##STR1017## Me 4-Me O CH830 ##STR1018## Me 4-Me O CH ##STR1019##__________________________________________________________________________
TABLE 117__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________831 ##STR1020## Me 3-Me O N ##STR1021##832 ##STR1022## Me 3-Me O CH ##STR1023##833 ##STR1024## Me 3-Me O CH834 ##STR1025## Me 3-Me O CH835 ##STR1026## Me 3-Me O CH ##STR1027##836 ##STR1028## Me 3-Me O N ##STR1029##837 ##STR1030## Me 3-Me O CH__________________________________________________________________________
TABLE 118__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________838 ##STR1031## Me 3-Me O CH ##STR1032##839 ##STR1033## Me 3-Me O CH840 ##STR1034## Me 3-Me O CH ##STR1035##841 ##STR1036## Me 3-Me O CH ##STR1037##842 ##STR1038## Me 3-Me O CH ##STR1039##843 ##STR1040## Me 3-Me O CH844 ##STR1041## Me 3-Me O CH845 ##STR1042## Me 3-Me O CH__________________________________________________________________________
TABLE 119__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________846 ##STR1043## Me 4-Me O N ##STR1044##847 ##STR1045## Me 4-Me O CH ##STR1046##848 ##STR1047## Me 4-Me O CH849 ##STR1048## Me 4-Me O CH850 ##STR1049## Me 4-Me O CH ##STR1050##851 ##STR1051## Me 4-Me O N ##STR1052##852 ##STR1053## Me 4-Me O CH__________________________________________________________________________
TABLE 120__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________853 ##STR1054## Me 4-Me O CH ##STR1055##854 ##STR1056## Me 4-Me O CH855 ##STR1057## Me 4-Me O CH ##STR1058##856 ##STR1059## Me 4-Me O CH ##STR1060##857 ##STR1061## Me 4-Me O CH ##STR1062##858 ##STR1063## Me 4-Me O CH859 ##STR1064## Me 4-Me O CH860 ##STR1065## Me 4-Me O CH__________________________________________________________________________
TABLE 121__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________861 ##STR1066## Me H O CH862 ##STR1067## Me H O CH863 ##STR1068## Me H O CH ##STR1069##864 ##STR1070## Me H O CH865 ##STR1071## Me H O CH866 ##STR1072## Me H O CH ##STR1073##867 ##STR1074## Et H O CH__________________________________________________________________________
TABLE 122__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________868 ##STR1075## Et H O CH869 ##STR1076## Et H O CH ##STR1077##870 ##STR1078## Et H O CH871 ##STR1079## Et H O CH872 ##STR1080## Et H O CH ##STR1081##873 ##STR1082## Me H S N874 ##STR1083## Me H S N ##STR1084##875 ##STR1085## Me H S N__________________________________________________________________________
TABLE 123__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________876 ##STR1086## Et H O CH ##STR1087##877 ##STR1088## Me 5-Cl O CH878 ##STR1089## Me 5-Cl O CH879 ##STR1090## Me 5-Cl O CH880 ##STR1091## Me 5-Cl O CH881 ##STR1092## Me 5-Cl O CH882 ##STR1093## Me 5-Cl O CH__________________________________________________________________________
TABLE 124__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________883 ##STR1094## Me 5-F O CH884 ##STR1095## Me 5-F O CH885 ##STR1096## Me 5-F O CH ##STR1097##886 ##STR1098## Me 5-F O CH887 ##STR1099## Me 5-F O CH888 ##STR1100## Me 5-F O CH ##STR1101##889 ##STR1102## Me 5-F O CH ##STR1103##890 ##STR1104## Me 5-F O CH__________________________________________________________________________
TABLE 125__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________891 ##STR1105## Me 5-Me O CH892 ##STR1106## Me 5-Me O CH893 ##STR1107## Me 5-Me O CH894 ##STR1108## Me 5-Me O CH895 ##STR1109## Me 5-Me O CH896 ##STR1110## Me 5-Me O CH897 ##STR1111## Me 5-Me O CH ##STR1112##__________________________________________________________________________
TABLE 126__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________898 ##STR1113## Me 5-Me O CH899 ##STR1114## Me 5-Me O CH900 ##STR1115## Me 6-Me O CH901 ##STR1116## Me 6-Me O CH902 ##STR1117## Me 6-Me O CH ##STR1118##903 ##STR1119## Me 6-Me O CH904 ##STR1120## Me 6-Me O CH905 ##STR1121## Me 6-Me O CH__________________________________________________________________________
TABLE 127__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________906 ##STR1122## Me H O CH ##STR1123##907 ##STR1124## Me 5-Cl O CH908 ##STR1125## Me 5-F O CH909 ##STR1126## Me 5-Me O CH910 ##STR1127## Et H O CH ##STR1128##911 ##STR1129## n-Pr H O CH912 ##STR1130## i-Pr H O CH__________________________________________________________________________
TABLE 128__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________913 ##STR1131## Me 5-Me O CH ##STR1132##914 ##STR1133## Me 5-Me O CH ##STR1134##915 ##STR1135## Me 5-F O CH916 ##STR1136## Me 5-Cl O CH ##STR1137##917 ##STR1138## Me 5-Cl O CH ##STR1139##918 ##STR1140## Me 5-Me O CH919 ##STR1141## Me 5-Me O CH920 ##STR1142## Me 5-Me O CH ##STR1143##__________________________________________________________________________
TABLE 129__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________921 ##STR1144## Me 5-MeO O CH ##STR1145##922 ##STR1146## Me 5-MeO O CH923 ##STR1147## Me 5-MeO O CH924 ##STR1148## Me 5-MeO O CH925 ##STR1149## Me 5-MeO O CH926 ##STR1150## Me 5-MeO O CH ##STR1151##927 ##STR1152## Me 5-MeO O CH__________________________________________________________________________
TABLE 130__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________928 ##STR1153## Me 5-MeO O CH929 ##STR1154## Me 5-MeO O CH ##STR1155##930 ##STR1156## Me 5-MeO O CH931 ##STR1157## Me 5-MeO O CH932 ##STR1158## Me 5-MeO O CH933 ##STR1159## Me 5-MeO O CH934 ##STR1160## Me 5-MeO O CH935 ##STR1161## Me 5-MeO O CH ##STR1162##__________________________________________________________________________
TABLE 131__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________936 ##STR1163## Me 5-MeO O CH937 ##STR1164## Me 5-MeO O CH ##STR1165##938 ##STR1166## Me 5-MeO O CH ##STR1167##939 ##STR1168## Me 5-MeO O CH940 ##STR1169## Me 5-MeO O CH ##STR1170##941 ##STR1171## Me 5-MeO O CH942 ##STR1172## Me 5-MeO O CH__________________________________________________________________________
TABLE 132__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________943 ##STR1173## Me 5-MeO O CH ##STR1174##944 ##STR1175## Me 5-MeO O CH945 ##STR1176## Me 5-MeO O CH946 ##STR1177## Me 5-MeO O CH ##STR1178##947 ##STR1179## Me 5-MeO O CH948 ##STR1180## Me 5-MeO O CH949 ##STR1181## Me 5-MeO O CH950 ##STR1182## Me 5-MeO O CH__________________________________________________________________________
TABLE 133__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________951 ##STR1183## Et 5-MeO O CH ##STR1184##952 ##STR1185## Et 5-MeO O CH953 ##STR1186## Et 5-MeO O CH954 ##STR1187## Et 5-MeO O CH955 ##STR1188## Et 5-MeO O CH956 ##STR1189## Et 5-MeO O CH ##STR1190##957 ##STR1191## Et 5-MeO O CH__________________________________________________________________________
TABLE 134__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________958 ##STR1192## Et 5-MeO O CH959 ##STR1193## Et 5-MeO O CH ##STR1194##960 ##STR1195## Et 5-MeO O CH961 ##STR1196## Et 5-MeO O CH962 ##STR1197## Et 5-MeO O CH963 ##STR1198## Et 5-MeO O CH964 ##STR1199## Et 5-MeO O CH965 ##STR1200## Et 5-MeO O CH ##STR1201##__________________________________________________________________________
TABLE 135__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________966 ##STR1202## Et 5-MeO O CH967 ##STR1203## Et 5-MeO O CH ##STR1204##968 ##STR1205## Et 5-MeO O CH ##STR1206##969 ##STR1207## Et 5-MeO O CH970 ##STR1208## Et 5-MeO O CH ##STR1209##971 ##STR1210## Et 5-MeO O CH972 ##STR1211## Et 5-MeO O CH__________________________________________________________________________
TABLE 136__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________973 ##STR1212## Et 5-MeO O CH ##STR1213##974 ##STR1214## Et 5-MeO O CH975 ##STR1215## Et 5-MeO O CH976 ##STR1216## Et 5-MeO O CH ##STR1217##977 ##STR1218## Et 5-MeO O CH978 ##STR1219## Et 5-MeO O CH979 ##STR1220## Et 5-MeO O CH980 ##STR1221## Et 5-MeO O CH__________________________________________________________________________
TABLE 137__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________981 ##STR1222## Et 5-Me O CH982 ##STR1223## Et 5-Me O CH983 ##STR1224## Et 5-Me O CH984 ##STR1225## Et 5-Me O CH985 ##STR1226## Et 5-Me O CH986 ##STR1227## Et 5-Me O CH ##STR1228##987 ##STR1229## Et 5-Me O CH__________________________________________________________________________
TABLE 138__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________988 ##STR1230## Et 5-Me O CH989 ##STR1231## Et 5-Me O CH ##STR1232##990 ##STR1233## Et 5-Me O CH991 ##STR1234## Et 5-Me O CH992 ##STR1235## Et 5-Me O CH993 ##STR1236## Et 5-Me O CH994 ##STR1237## Et 5-Me O CH995 ##STR1238## Et 5-Me O CH ##STR1239##__________________________________________________________________________
TABLE 139__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________996 ##STR1240## Et 5-Me O CH997 ##STR1241## Et 5-Me O CH ##STR1242##998 ##STR1243## Et 5-Me O CH ##STR1244##999 ##STR1245## Et 5-Me O CH1000 ##STR1246## Et 5-Me O CH ##STR1247##1001 ##STR1248## Et 5-Me O CH1002 ##STR1249## Et 5-Me O CH__________________________________________________________________________
TABLE 140__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________1003 ##STR1250## Et 5-Me O CH ##STR1251##1004 ##STR1252## Et 5-Me O CH1005 ##STR1253## Et 5-Me O CH1006 ##STR1254## Et 5-Me O CH ##STR1255##1007 ##STR1256## Et 5-Me O CH1008 ##STR1257## Et 5-Me O CH1009 ##STR1258## Et 5-Me O CH1010 ##STR1259## Et 5-Me O CH__________________________________________________________________________
TABLE 141__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________1011 ##STR1260## Et 5-F O CH1012 ##STR1261## Et 5-F O CH1013 ##STR1262## Et 5-F O CH1014 ##STR1263## Et 5-F O CH1015 ##STR1264## Et 5-F O CH1016 ##STR1265## Et 5-F O CH ##STR1266##1017 ##STR1267## Et 5-F O CH__________________________________________________________________________
TABLE 142__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________1018 ##STR1268## Et 5-F O CH1019 ##STR1269## Et 5-F O CH ##STR1270##1020 ##STR1271## Et 5-F O CH1021 ##STR1272## Et 5-F O CH1022 ##STR1273## Et 5-F O CH1023 ##STR1274## Et 5-F O CH1024 ##STR1275## Et 5-F O CH1025 ##STR1276## Et 5-F O CH ##STR1277##__________________________________________________________________________
TABLE 143__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________1026 ##STR1278## Et 5-F O CH1027 ##STR1279## Et 5-F O CH ##STR1280##1028 ##STR1281## Et 5-F O CH ##STR1282##1029 ##STR1283## Et 5-F O CH1030 ##STR1284## Et 5-F O CH ##STR1285##1031 ##STR1286## Et 5-F O CH1032 ##STR1287## Et 5-F O CH__________________________________________________________________________
TABLE 144__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________1033 ##STR1288## Et 5-F O CH ##STR1289##1034 ##STR1290## Et 5-F O CH1035 ##STR1291## Et 5-F O CH1036 ##STR1292## Et 5-F O CH ##STR1293##1037 ##STR1294## Et 5-F O CH1038 ##STR1295## Et 5-F O CH1039 ##STR1296## Et 5-F O CH1040 ##STR1297## Et 5-F O CH__________________________________________________________________________
TABLE 145__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________1041 ##STR1298## Et 5-Cl O CH ##STR1299##1042 ##STR1300## Et 5-Cl O CH1043 ##STR1301## Et 5-Cl O CH1044 ##STR1302## Et 5-Cl O CH1045 ##STR1303## Et 5-Cl O CH1046 ##STR1304## Et 5-Cl O CH ##STR1305##1047 ##STR1306## Et 5-Cl O CH__________________________________________________________________________
TABLE 146__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________1048 ##STR1307## Et 5-Cl O CH1049 ##STR1308## Et 5-Cl O CH ##STR1309##1050 ##STR1310## Et 5-Cl O CH1051 ##STR1311## Et 5-Cl O CH1052 ##STR1312## Et 5-Cl O CH1053 ##STR1313## Et 5-Cl O CH1054 ##STR1314## Et 5-Cl O CH1055 ##STR1315## Et 5-Cl O CH ##STR1316##__________________________________________________________________________
TABLE 147__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________1056 ##STR1317## Et 5-Cl O CH1057 ##STR1318## Et 5-Cl O CH ##STR1319##1058 ##STR1320## Et 5-Cl O CH ##STR1321##1059 ##STR1322## Et 5-Cl O CH1060 ##STR1323## Et 5-Cl O CH ##STR1324##1061 ##STR1325## Et 5-Cl O CH1062 ##STR1326## Et 5-Cl O CH__________________________________________________________________________
TABLE 148__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________1063 ##STR1327## Et 5-Cl O CH ##STR1328##1064 ##STR1329## Et 5-Cl O CH1065 ##STR1330## Et 5-Cl O CH1066 ##STR1331## Et 5-Cl O CH ##STR1332##1067 ##STR1333## Et 5-Cl O CH1068 ##STR1334## Et 5-Cl O CH1069 ##STR1335## Et 5-Cl O CH1070 ##STR1336## Et 5-Cl O CH__________________________________________________________________________
TABLE 149__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________1071 ##STR1337## Allyl 5-Cl O CH1072 ##STR1338## Allyl 5-Cl O CH1073 ##STR1339## Allyl 5-Cl O CH1074 ##STR1340## Allyl 5-Cl O CH1075 ##STR1341## Allyl 5-Cl O CH1076 ##STR1342## Allyl 5-Cl O CH1077 ##STR1343## Allyl 5-F O CH__________________________________________________________________________
TABLE 150__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________1078 ##STR1344## Allyl 5-F O CH1079 ##STR1345## Allyl 5-F O CH1080 ##STR1346## Allyl 5-F O CH1081 ##STR1347## Allyl 5-F O CH1082 ##STR1348## Allyl 5-F O CH1083 ##STR1349## Allyl 5-Me O CH1084 ##STR1350## Allyl 5-Me O CH1085 ##STR1351## Allyl 5-Me O CH__________________________________________________________________________
TABLE 151__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________1086 ##STR1352## Allyl 5-Me O CH1087 ##STR1353## Allyl 5-Me O CH1088 ##STR1354## Allyl 5-Me O CH1089 ##STR1355## Allyl 5-MeO O CH1090 ##STR1356## Allyl 5-MeO O CH1091 ##STR1357## Allyl 5-MeO O CH1092 ##STR1358## Allyl 5-MeO O CH__________________________________________________________________________
TABLE 152__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________1093 ##STR1359## Allyl 5-MeO O CH1094 ##STR1360## Allyl 5-MeO O CH1095 ##STR1361## i-Bu 5-Cl O CH1096 ##STR1362## i-Bu 5-Cl O CH1097 ##STR1363## i-Bu 5-Cl O CH1098 ##STR1364## i-Bu 5-Cl O CH1099 ##STR1365## i-Bu 5-Cl O CH1100 ##STR1366## i-Bu 5-Cl O CH__________________________________________________________________________
TABLE 153__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________1101 ##STR1367## Me 5-F O CH ##STR1368##1102 ##STR1369## Me 5-Cl O CH1103 ##STR1370## Me 5-Cl O CH1104 ##STR1371## Me 5-MeO O CH ##STR1372##1105 ##STR1373## Me 5-Me O CH1106 ##STR1374## Me 5-Me O CH1107 ##STR1375## Me 5-Me O CH__________________________________________________________________________
TABLE 154__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________1108 ##STR1376## Me 5-Me O CH1109 ##STR1377## Me 5-Me O CH1110 ##STR1378## Me H O CH1111 ##STR1379## Me 5-F O CH1112 ##STR1380## Me 5-Cl O CH1113 ##STR1381## Me 5-Me O CH1114 ##STR1382## Me 5-MeO O CH1115 ##STR1383## Et H O CH__________________________________________________________________________
TABLE 155__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________1116 ##STR1384## Me 5-F O CH1117 ##STR1385## Me 5-Cl O CH1118 ##STR1386## Me 5-F O CH1119 ##STR1387## Me 5-Me O CH1120 ##STR1388## Me 5-Cl O CH1121 ##STR1389## Allyl H O CH1122 ##STR1390## Me 5-Me O CH1123 ##STR1391## Me 5-Me O CH1124 ##STR1392## Me 5-Me O CH__________________________________________________________________________
TABLE 156__________________________________________________________________________ mpNo R.sup.1 R.sup.2 R.sup.3 X Y (.degree.C.) .sup.1 H-NMR(CDCl.sub.3)__________________________________________________________________________1125 ##STR1393## Me 5-Me O CH1126 ##STR1394## Et H O CH ##STR1395##1127 ##STR1396## Et 5-F O CH1128 ##STR1397## Et 5-Cl O CH ##STR1398##1129 ##STR1399## Et 5-Me O CH ##STR1400##1130 ##STR1401## Et 5-MeO O CH ##STR1402##__________________________________________________________________________
The following examples illustrate the production of the fungicidal compositions of the present invention.
Example 14
A mixture of 2 parts of the Compound No. 9 and 98 parts of talc was pulverized to obtain a powder.
Example 15
A suspension was prepared by mixing 40 parts of Compound No. 9, 10 parts of sodium lignin sulfonate and 50 parts of water.
Example 16
A solution was prepared by mixing 10 parts of Compound No. 9, 1 part of Tween 20 (trade mark) and 89 parts of isopropyl alcohol.
Example 17
A wettable powder was prepared by mixing 50 parts of Compound No. 83, 6 parts of sodium alkylbenzenesulfonate, 4 parts of sodium lignin sulfonate and 40 parts of clay and pulverizing the mixture.
Example 18
Granules were prepared by mixing 5 parts of Compound No. 83, 90 parts of a mixture of equal amounts of bentonite and talc and 5 parts of sodium alkylbenzene sulfonate, pulverizing the mixture and granulating the pulverized mixture.
Example 19
An emulsion was prepared by mixing and dispersing 25 parts of Compound No. 83, 8 parts of polyoxyethylene alkylphenyl ether, 2 parts of sodium alkylbenzene sulfonate and 65 parts of xylene.
The following examples illustrate the production of the herbicidal and growth regulating compositions.
Example 20
______________________________________ Parts by weight______________________________________Compound No. 9 50Clay 45Emal (trade mark, spreader 5manufactured by Kao Corp.)______________________________________
The above ingredients were mixed to give a wettable powder.
Example 21
______________________________________ Parts by weight______________________________________Compound No. 9 20Xylene 65Sorpol 3005X (trade mark, spreader 15manufacutured by Tohoh Kagaku Kogyo K.K.)______________________________________
Compound No. 9 was dissolved in xylene and Sorpol was added to give an emulsifiable concentrate.
Example 22
______________________________________ Parts by weight______________________________________Compound No. 83 3Sorpol 5060 (trade mark, spreader 3manufactured by Tohoh Kagaku Kogyo K.K.)Bentonite 40Talc 20Clay 34______________________________________
The above ingredients were mixed homogeneously and binded by adding water and subjected to extrusion to give granules.
Example 23
______________________________________ Parts by weight______________________________________Compound No. 83 3Emulgen 910 (trade mark, nonionic surfactant 1manufactured by Kao Corp.)Solvent naphtha 5Granular bentonite 91______________________________________
Compound No. 83 and Emulgen were dissolved in solvent naphtha. The granular bentonite was spray-coated with this solution to obtain granules.
Test Examples
The following pot experiments show controlling effect of the various compounds of the present invention on plant diseases by foliar treatment.
Experimental Method
In experiments for determination of preventive effect, a liquid sample to be tested was sprayed to test plants and pathogens were inoculated after 24 hours. In experiments for determination of curative effect, the test plants were inoculated with each pathogen, and when slight lesions were observed (24 to 48 hours after the inoculation), a liquid sample to be tested was sprayed to the test plants.
The liquid sample was prepared by dissolving the test compound in a small amount of N,N-dimethylformamide and diluting the solution with distilled water containing a spreader to a given concentration.
The percent control was calculated according to the following equation: ##EQU1##
Test Example 1
Controlling effect on Pyricularia oryzae
Two-week rice seedlings (var.: AICHIASAHI) were transplanted in plastic cups (each 9 cm.phi.) and cultivated another 2 weeks. The test compound in the form of a solution or a suspension was sprayed to the foliage of the rice seedlings, to which a conidia suspension of Pyricularia oryzae cultured in an oatmeal medium was inoculated by spraying. The test plant was kept in a moist chamber (28.degree. C., 100% R.H.) for 24 hours, followed by cultivation in a greenhouse for 5 days. As the control, fthalide (4,5,6,7-tetrachlorophthalide) was used. Six days after inoculation, the number of lesions of the plant was measured and the preventive effect was calculated. The results are shown in Tablea 157 to 159.
In the following Tables 157 to 164, P.o. means Pyricularia oryzae, S.f. means Sphaerotheca fuliginea., B.c. means Botrytis cinerea, E.g. means Erysiphe graminis f. sp. frifici, pre means preventive treatment, and sup means curative treatment.
TABLE 157______________________________________ P.o. (%)Compound No. (125 ppm) pre sup______________________________________ 3 90 97 7 90 97 9 70 97 55 90 97 58 95 97 68 90 97 70 90 97 83 97 97103 90 97106 90 97109 90 97115 90 97131 70 90152 100155 97 97168 90 97170 90 97183 97 97184 93 90189 90 90196 97 70203 90 90233 90 90270 90 90______________________________________
TABLE 158______________________________________ P.o. (%)Compound No. (125 ppm) pre sup______________________________________283 90 90306 90 90315 90 90492 90 97494 90 97495 95 97552 95 97581 95 95583 95 95609 90 90624 95 90640 93 95655 90 90665 90 95669 95 95698 90 90703 95 90731 95 90803 90 90866 90 90869 90 90872 90 90876 97 97885 90 97______________________________________
TABLE 159______________________________________ P.o. (%)Compound No. (125 ppm) pre sup______________________________________888 90 90889 97 90937 90 90940 97 97946 90 90959 95 97970 90 90986 90 901016 93 971030 93 971046 95 901066 95 97Control 90 97______________________________________
Test Example 2
Controlling effect on cucumber powdery mildew (Sphaerotheca fuliginea)
Seeds of cucumber (var.: TSUKUBASHIROIBO) were sown in plastic cups (each 9 cm in diameter), followed by cultivation for 2 to 3 weeks. A liquid test sample in the form of a solution or suspension was sprayed on the surface of their first leaves. The pathogen was inoculated by spraying to the leaves a conidia suspension of Sphaerotheca fuliginea which had been cultured on the cucumber leaves. The plants were kept in a greenhouse at 20.degree. C. for 10 days. The infected area on the leaf was observed, and the percent control was calculated. As the control, fenarimol {2,4'-dichloro-2-(pyrimidin-5-yl)benzhydryl alcohol} was used. The results are shown in Table 160.
TABLE 160______________________________________ S.f. (%)Compound No. (125 ppm) pre sup______________________________________ 1 100 100 3 100 100 7 100 100 9 100 100 15 100 100 51 100 100 52 100 100 55 85 95 65 85 90 68 100 100 70 100 100 83 100 100107 100 100109 100 100131 100 100152 100155 100 100165 95 100168 100 100170 100 100183 100 100Control 100 100______________________________________
Test Example 3
Controlling effect on Botrytis cinerea
The seeds of cucumber (var.: TSUKUBASHIROIBO) were sown in plastic cups (9 cm.phi.), followed by cultivation for 2 to 3 weeks. The test compound in the form of a solution or suspension was sprayed to the surface of their first leaves, and the cucumber seedlings were inoculated with mycelial disks (4 mm.phi.) of Botrytis cinerea cultured on the potato sucrose agar medium by putting the disks on the leaf surfaces. The plants were kept in a moist chamber at 20.degree. C. for 2 days. The diameter of the lesions on the leaves was measured and the percent control was calculated. As the control, iprodione {3-(3,5-dichlorophenyl)-N-isopropyl-2,4-dioxoimidazolidine-1-carboxamide} was used. The results are shown in Table 161.
TABLE 161______________________________________ B.c.Compound No. (125 ppm) pre sup______________________________________ 1 100 70 3 100 70 7 100 50 15 100 70 68 90 50106 100 50109 70 30152 70 50501 100 30503 100 30526 70 30691 100 30694 70 30701 90 70707 100 30715 90 50726 100 30926 90 50935 100 30940 90 70965 70 30995 70 30Control 90 87______________________________________
Test Example 4
Controlling effect on Erysiphe graminis f. sp. frifici
The seeds of wheat (var.: NORIN No. 61) were sown in plastic cups (9 cm.phi.), followed by cultivation for 2 to 3 weeks. The test compound in the form of a solution or suspension was sprayed to the seedlings, and the seedlings were inoculated with conidia of Erysiphe graminis f. sp. frifici cultured on the wheat leaves by putting the conidia on the test plants. The plants were kept in a greenhouse at 20.degree. C. for 10 days. The infected area on the leaf was observed, and the percent control was calculated. As the control, fenarimol was used. The results are shown in Tables 162 to 164.
TABLE 162______________________________________ E.g.Compound No. (125 ppm) pre sup______________________________________ 62 90 90 63 90 90209 97 97253 97 97483 97 97491 97 97492 100 97494 90 97496 90 97497 97 97531 90 97563 97 90568 97 90581 97 90592 90 70603 90 90606 97 90621 97 97622 97 90635 90 90649 97 90650 97 90______________________________________
TABLE 163______________________________________ E.g.Compound No. (125 ppm) pre sup______________________________________692 90 90706 97 97707 90 90752 90 97765 90 90768 97 97770 97 97779 97 97781 97 90783 90 90831 97 90838 97 70855 97 90889 90 97902 90 97913 90 90914 90 97916 97 97929 97 90938 97 97943 90 97956 70 97______________________________________
TABLE 164______________________________________ E.g.Compound No. (125 ppm) pre sup______________________________________ 967 90 97 968 90 97 973 90 97 976 70 97 997 97 97 998 97 701000 97 701003 97 971025 97 971027 97 971028 97 971033 97 971036 97 901057 97 971058 90 971063 90 971101 97 971104 90 901126 90 971128 70 971129 97 97Control 97 97______________________________________
The following experiment shows herbicidal and growth regulating activities of the compounds of the present invention.
Test Example 5 (herbicidal activity)
As the test plants, Echinochloa oryzicola, Monochoria vaginalis and Scirpus juncoides were used.
A square-shaped pot (7.1.times.7.1 cm) was charged with paddy soil. The seeds (10 seeds/pot) of the above plants were sown in the soil and submerged in water (2 cm). Immediately after that, the test compound (40 g ai/a) was diluted with water (0.7 ml/pot) and treated on the water surface of each pot.
Three weeks after the treatment, the effects of the compound (inhibition of germination and growth, deformation, leaf dying, withering, etc.) were observed. The criteria for the evaluation were grouped into the following six grades: 0 (harmless) to 5 (withering).
The second screening was carried out when the maximum activity (5) was observed in the gramineous plant, broad-leaved plant and cyperaceous plant.
The results are shown in Tables 165 and 166. In the tables, E.o. means Echinochloa oryzicola, M.v. means Monochoria vaginalis, and S.J. means Scirpus juncoides.
TABLE 165______________________________________Compound No. E.o. M.v. S.j.______________________________________ 3 5 5 4 9 5 5 3 15 4 5 3 52 4 5 5 55 5 5 5 68 4 5 3 72 5 5 4 83 4 4 4109 5 5 4152 4 5 4698 5 5 5706 5 5 5709 5 5 4783 5 5 5806 5 5 5842 5 5 5866 5 5 2872 5 5 5885 5 5 4888 5 5 5897 5 5 3902 5 5 5920 5 5 4921 5 5 3938 5 5 5______________________________________
TABLE 166______________________________________Compound No. E.o. M.v. S.j.______________________________________ 951 5 5 4 956 5 5 4 968 5 5 4 986 5 5 2 998 5 5 41006 5 5 31016 5 5 41025 5 5 41028 5 5 51030 5 5 51036 5 5 41046 5 5 41057 5 5 51058 5 5 51060 5 5 31066 5 5 5______________________________________
Test Example 6
Growth inhibiting effect on weeds
As the test plants, Polygonum lapathifolium and Amaranthus viridis were used.
A square-shaped pot (7.1.times.7.1 cm) was charged with upland soil. The seeds (10 seeds/pot) of the above plants were sown on the soil and grown in a greenhouse for 7 days. Seven days after sowning, the test compound (20 g ai/a) was sprayed on the plant using a pressure-type sprayer.
Three weeks after spraying, the height of the plant was measured, and the growth inhibiting ratio was calculated according to the following equation: ##EQU2## The results are shown in Table 167. In the table, P.1. means Polygonum lapathifolium and A.v. means Amaranthus viridis.
TABLE 167______________________________________Compound No. P.1. A.v.______________________________________127 63 48863 52 66968 54 34970 57 48976 64 551036 67 671066 66 57______________________________________

Number	Date	Country
0142653	May 1985	EPX
0513397	Nov 1992	EPX
1-308260	Dec 1989	JPX
3-68559	Mar 1991	JPX
5-1046	Jan 1993	JPX
5-331011	Dec 1993	JPX
5-331012	Dec 1993	JPX
2250511	Jun 1992	GBX

Benzaldehyde oxime derivatives, production and use thereof

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Chemical Abstracts, vol. 116, No. 1, 6 Jan. 1992, Columbus, Ohio, U.S.; Abstract No. 2318x, Hokari Hiroshi et al., "Preparation of Hydroximoylimidazoles Or-Triazoles As Insecticides".
Chemical Abstracts, vol. 112, No. 23, 4 Jun. 1990, Columbus, Ohio, U.S.; Abstract No. 216938r, Hokari Hiroshi et al., "Preparation of N-Benzolazole O-Alkyloxime Derivatives As Insecticides".