Herbicidal triazolinones

BACKGROUND OF THE INVENTION
New compounds effective for controlling the growth of undesired vegetation are in constant demand. In the most common situation, such compounds are sought to selectively control the growth of weeds in useful crops such as cotton, rice, corn, wheat and soybeans, to name a few. Unchecked weed growth in such crops can cause significant losses, reducing profit to the farmer and increasing costs to the consumer. In other situations, herbicides are desired which will control all plant growth. Examples of areas in which complete control of all vegetation is desired are areas around railroad tracks, storage tanks and industrial storage areas. There are many products commercially available for these purposes, but the search continues for products which are more effective, less costly and environmentally safe.
U.S. Pat. No. 4,213,773 discloses herbicidal triazolinones which differ from the compounds of the present invention in that they lack a substituent on the left-hand ring.
SUMMARY OF THE INVENTION
The crop protection chemical compounds of this invention are compounds of Formula I: ##STR2## wherein the dashed line indicates that the left-hand ring contains only single bonds or one bond in the ring is a double bond;
n is 1 or 2;
R.sup.1 is selected from the group H, halogen; hydroxy, C.sub.1 -C.sub.3 alkoxy; C.sub.1 -C.sub.3 haloalkoxy; C.sub.2 -C.sub.5 alkylcarbonyloxy; or C.sub.2 -C.sub.5 haloalkylcarbonyloxy;
R.sup.2 is selected from the group H, hydroxy, and halogen; or
when R.sup.1 and R.sup.2 are bonded to the same carbon atom they can be taken together along with the carbon to which they are attached to form C.dbd.O; or
when R.sup.1 and R.sup.2 are bonded to adjacent carbon atoms they can be taken together along with the carbons to which they are attached to form ##STR3## Q is selected from the group ##STR4## R.sup.3 is selected from the group H and halogen; R.sup.4 is selected from the group H, C.sub.1 -C.sub.8 alkyl, C.sub.1 -C.sub.8 haloalkyl, halogen, OR.sup.9, S(O).sub.m R.sup.9, COR.sup.9, CO.sub.2 R.sup.9, C(O)SR.sup.9, C(O)NR.sup.11 R.sup.12, CHO, CR.sup.7 .dbd.CR.sup.7 CO.sub.2 R.sup.9, CO.sub.2 N.dbd.CR.sup.13 R.sup.14, NO.sub.2, CN, NHSO.sub.2 R.sup.15 and NHSO.sub.2 NHR.sup.15 ;
m is 0, 1 or 2;
R.sup.5 is selected from the group C.sub.1 -C.sub.2 alkyl, C.sub.1 -C.sub.2 haloalkyl, OCH.sub.3, SCH.sub.3, OCHF.sub.2, halogen, CN and NO.sub.2 ;
R.sup.6 is selected from the group H, C.sub.1 -C.sub.3 alkyl, C.sub.2 -C.sub.3 alkynyl, C.sub.2 -C.sub.3 haloalkynyl, CO.sub.2 (C.sub.1 -C.sub.4 alkyl), and halogen;
R.sup.7 is independently selected from the group H, C.sub.1 -C.sub.3 alkyl and halogen; or
when Q is Q-2 or Q-6, R.sup.6 and R.sup.7 together with the carbon to which they are attached can be C.dbd.O;
R.sup.8 is selected from the group C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 haloalkyl, C.sub.2 -C.sub.6 alkoxyalkyl, C.sub.3 -C.sub.6 alkenyl and C.sub.3 -C.sub.6 alkynyl;
R.sup.9 is selected from the group C.sub.1 -C.sub.8 alkyl; C.sub.3 -C.sub.8 cycloalkyl; C.sub.3 -C.sub.8 alkenyl; C.sub.3 -C.sub.8 alkynyl; C.sub.1 -C.sub.8 haloalkyl; C.sub.2 -C.sub.8 alkoxyalkyl; C.sub.2 -C.sub.8 alkylthioalkyl; C.sub.2 -C.sub.8 alkylsulfinylalkyl; C.sub.2 -C.sub.8 alkylsulfonylalkyl; C.sub.1 -C.sub.8 alkylsulfonyl; phenylsulfonyl optionally substituted on the phenyl ring with halogen or C.sub.1 -C.sub.4 alkyl; C.sub.4 -C.sub.8 alkoxyalkoxyalkyl, C.sub.4 -C.sub.8 cycloalkylalkyl; C.sub.4 -C.sub.8 alkenoxyalkyl; C.sub.4 -C.sub.8 alkynoxyalkyl; C.sub.6 -C.sub.8 cycloalkoxyalkyl; C.sub.4 -C.sub.8 alkenyloxyalkyl; C.sub.4 -C.sub.8 alkynyloxyalkyl; C.sub.3 -C.sub.8 haloalkoxyalkyl; C.sub.4 -C.sub.8 haloalkenoxyalkyl; C.sub.4 -C.sub.8 haloalkynoxyalkyl; C.sub.6 -C.sub.8 cycloalkylthioalkyl; C.sub.4 -C.sub.8 alkenylthioalkyl; C.sub.4 -C.sub.8 alkynylthioalkyl; C.sub.1 -C.sub.4 alkyl substituted a substituent selected from phenoxy and benzyloxy, each ring optionally substituted with a substituent selected from halogen, C.sub.1 -C.sub.3 alkyl and C.sub.1 -C.sub.3 haloalkyl; C.sub.4 -C.sub.8 trialkylsilylalkyl; C.sub.3 -C.sub.8 cyanoalkyl; C.sub.3 -C.sub.8 halocycloalkyl; C.sub.3 -C.sub.8 haloalkenyl; C.sub.5 -C.sub.8 alkoxyalkenyl; C.sub.5 -C.sub.8 haloalkoxyalkenyl; C.sub.5 -C.sub.8 alkylthioalkenyl; C.sub.3 -C.sub.8 haloalkynyl; C.sub.5 -C.sub.8 alkoxyalkynyl; C.sub.5 -C.sub.8 haloalkoxyalkynyl; C.sub.5 -C.sub.8 alkylthioalkynyl; C.sub.2 -C.sub.8 alkyl carbonyl; benzyl optionally substituted with a substituent selected from the group halogen, C.sub.1 -C.sub.3 alkyl and C.sub.1 -C.sub.3 haloalkyl; CHR.sup.16 COR.sup.10 ; CHR.sup.16 CO.sub.2 R.sup.10 ; CHR.sup.16 P(O)(OR.sup.10).sub.2 ; CHR.sup.16 P(S)(OR.sup.10).sub.2 ; CHR.sup.16 C(O)NR.sup.11 R.sup.12 ; and CHR.sup.16 C(O)NH.sub.2 ;
R.sup.10 is selected from the group C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkenyl and C.sub.1 -C.sub.6 alkynyl;
R.sup.11 and R.sup.13 are independently selected from the group H and C.sub.1 -C.sub.4 alkyl;
R.sup.12 and R.sup.14 are independently selected from the group C.sub.1 -C.sub.4 alkyl and phenyl optionally substituted with a substituent selected from the group halogen, C.sub.1 -C.sub.3 alkyl and C.sub.1 -C.sub.3 haloalkyl;
R.sup.11 and R.sup.12 may be taken together as --(CH.sub.2).sub.5 --, --(CH.sub.2).sub.4 -- or --CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 --, each ring optionally substituted with a substituent selected from the group C.sub.1 -C.sub.3 alkyl, phenyl and benzyl;
R.sup.13 and R.sup.14 may be taken together with the carbon to which they are attached to form C.sub.3 -C.sub.8 cycloalkyl;
R.sup.15 is selected from the group C.sub.1 -C.sub.4 alkyl and C.sub.1 -C.sub.4 haloalkyl;
R.sup.16 is selected from the group H and C.sub.1 -C.sub.3 alkyl; and
W is selected from the group O and S;
provided that R.sup.1 is other than H when the left-hand ring contains only single bonds.
In the above definitions, the terms "alkyl", "alkenyl" and "alkynyl" include straight and branched chain groups. "Halogen" means fluorine, chlorine, bromine or iodine. Further, when used in compound words such as "haloalkyl" said alkyl may be partially or fully saturated with halogen atoms, which may be the same or different.
The bonding in compounds of Formula I is such that the left-hand ring contains single bonds, except that at most one of the bonds may be a double bond. Examples of structures of Formula I are: ##STR5##
Preferred for reasons of better biological activity and/or ease of synthesis are: Preferred 1: Compounds of Formula I wherein the left-hand ring contains only single bonds. Such compounds are compounds of Formula Ia: ##STR6## wherein n is 1 or 2;
R.sup.1 is selected from the group halogen; hydroxy, C.sub.1 -C.sub.3 alkoxy; C.sub.1 -C.sub.3 haloalkoxy; C.sub.2 -C.sub.5 alkylcarbonyloxy; or C.sub.2 -C.sub.5 haloalkylcarbonyloxy;
R.sup.2 is selected from the group H, hydroxy, and halogen; or
when R.sup.1 and R.sup.2 are bonded to the same carbon atom they can be taken together along with the carbon to which they are attached to form C.dbd.O; or
when R.sup.1 and R.sup.2 are bonded to adjacent carbon atoms they can be taken together along with the carbons to which they are attached to form ##STR7## Q is selected from the group ##STR8## R.sup.3 is selected from the group H and halogen; R.sup.4 is selected from the group H, C.sub.1 -C.sub.8 alkyl, C.sub.1 -C.sub.8 haloalkyl, halogen, OR.sup.9, S(O).sub.m R.sup.9, COR.sup.9, CO.sub.2 R.sup.9, C(O)SR.sup.9, C(O)NR.sup.11 R.sup.12, CHO, CR.sup.7 .dbd.CR.sup.7 CO.sub.2 R.sup.9, CO.sub.2 N.dbd.CR.sup.13 R.sup.14, NO.sub.2, CN, NHSO.sub.2 R.sup.15 and NHSO.sub.2 NHR.sup.15 ;
m is 0, 1 or 2;
R.sup.5 is selected from the group C.sub.1 -C.sub.2 alkyl, C.sub.1 -C.sub.2 haloalkyl, OCH.sub.3, SCH.sub.3, OCHF.sub.2, halogen, CN and NO.sub.2 ;
R.sup.6 is selected from the group H, C.sub.1 -C.sub.3 alkyl, C.sub.2 -C.sub.3 alkynyl, C.sub.2 -C.sub.3 haloalkynyl, CO.sub.2 (C.sub.1 -C.sub.4 alkyl), and halogen;
R.sup.7 is independently selected from the group H, C.sub.1 -C.sub.3 alkyl and halogen; or
when Q is Q-2 or Q-6, R.sup.6 and R.sup.7 together with the carbon to which they are attached can be C.dbd.O;
R.sup.8 is selected from the group C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 haloalkyl, C.sub.2 -C.sub.6 alkoxyalkyl, C.sub.3 -C.sub.6 alkenyl and C.sub.3 -C.sub.6 alkynyl;
R.sup.9 is selected from the group C.sub.1 -C.sub.8 alkyl; C.sub.3 -C.sub.8 cycloalkyl; C.sub.3 -C.sub.8 alkenyl; C.sub.3 -C.sub.8 alkynyl; C.sub.1 -C.sub.8 haloalkyl; C.sub.2 -C.sub.8 alkoxyalkyl; C.sub.2 -C.sub.8 alkylthioalkyl; C.sub.2 -C.sub.8 alkylsulfmylalkyl; C.sub.2 -C.sub.8 alkylsulfonylalkyl; C.sub.1 -C.sub.8 alkylsulfonyl; phenylsulfonyl optionally substituted on the phenyl ring with halogen or C.sub.1 -C.sub.4 alkyl; C.sub.4 -C.sub.8 alkoxyalkoxyalkyl, C.sub.4 -C.sub.8 cycloalkylalkyl; C.sub.4 -C.sub.8 alkenoxyalkyl; C.sub.4 -C.sub.8 alkynoxyalkyl; C.sub.6 -C.sub.8 cycloalkoxyalkyl; C.sub.4 -C.sub.8 alkenyloxyalkyl; C.sub.4 -C.sub.8 alkynyloxyalkyl; C.sub.3 -C.sub.8 haloalkoxyalkyl; C.sub.4 -C.sub.8 haloalkenoxyalkyl; C.sub.4 -C.sub.8 haloalkynoxyalkyl; C.sub.6 -C.sub.8 cycloalkylthioalkyl; C.sub.4 -C.sub.8 alkenylthioalkyl; C.sub.4 -C.sub.8 alkynylthioalkyl; C.sub.1 -C.sub.4 alkyl substituted a substituent selected from phenoxy and benzyloxy, each ring optionally substituted with a substituent selected from halogen, C.sub.1 -C.sub.3 alkyl and C.sub.1 -C.sub.3 haloalkyl; C.sub.4 -C.sub.8 trialkylsilylalkyl; C.sub.3 -C.sub.8 cyanoalkyl; C.sub.3 -C.sub.8 halocycloalkyl; C.sub.3 -C.sub.8 haloalkenyl; C.sub.5 -C.sub.8 alkoxyalkenyl; C.sub.5 -C.sub.8 haloalkoxyalkenyl; C.sub.5 -C.sub.8 alkylthioalkenyl; C.sub.3 -C.sub.8 haloalkynyl; C.sub.5 -C.sub.8 alkoxyalkynyl; C.sub.5 -C.sub.8 haloalkoxyalkynyl; C.sub.5 -C.sub.8 alkylthioalkynyl; C.sub.2 -C.sub.8 alkyl carbonyl; benzyl optionally substituted with a substituent selected from the group halogen, C.sub.1 -C.sub.3 alkyl and C.sub.1 -C.sub.3 haloalkyl; CHR.sup.16 COR.sup.10 ; CHR.sup.16 CO.sub.2 R.sup.10 ; CHR.sup.16 P(O)(OR.sup.10).sub.2 ; CHR.sup.16 P(S)(OR.sup.10).sub.2 ; CHR.sup.16 C(O)NR.sup.11 R.sup.12 ; and CHR.sup.16 C(O)NH.sub.2 ;
R.sup.10 is selected from the group C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.6 alkenyl and C.sub.1 -C.sub.6 alkynyl;
R.sup.11 and R.sup.13 are independently selected from the group H and C.sub.1 -C.sub.4 alkyl;
R.sup.12 and R.sup.14 are independently selected from the group C.sub.1 -C.sub.4 alkyl and phenyl optionally substituted with a substituent selected from the group halogen, C.sub.1 -C.sub.3 alkyl and C.sub.1 -C.sub.3 haloalkyl;
R.sup.11 and R.sup.12 may be taken together as --(CH.sub.2).sub.5 --, --(CH.sub.2).sub.4 -- or --CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 --, each ring optionally substituted with a substituent selected from the group C.sub.1 -C.sub.3 alkyl, phenyl and benzyl;
R.sup.13 and R.sup.14 may be taken together with the carbon to which they are attached to form C.sub.3 -C.sub.8 cycloalkyl;
R.sup.15 is selected from the group C.sub.1 -C.sub.4 alkyl and C.sub.1 -C.sub.4 haloalkyl;
R.sup.16 is selected from the group H and C.sub.1 -C.sub.3 alkyl; and
W is selected from the group O and S.
Preferred 2: Compounds of Formula I wherein:
R.sup.1 is halogen;
R.sup.2 is selected from the group H, and halogen;
Q is selected from the group consisting of Q-1, Q-2 and Q-6;
R.sup.3 is halogen;
R.sup.5 is selected from the group C.sub.1 -C.sub.2 haloalkyl, OCH.sub.3, OCHF.sub.2, CN, NO.sub.2, and halogen;
R.sup.6 is selected from the group H, C.sub.1 -C.sub.3 alkyl, C.sub.2 -C.sub.3 alkynyl, C.sub.2 -C.sub.3 haloalkynyl, and halogen;
R.sup.7 is H; and
W is O.
Preferred 3: Compounds of Preferred 2 wherein:
R.sup.4 is selected from the group halogen, OR.sup.9, S(O).sub.m R.sup.9, COR.sup.9, CO.sub.2 R.sup.9, C(O)NR.sup.11 R.sup.12, CH.dbd.CHCO.sub.2 R.sup.9, NHSO.sub.2 R.sup.15 and NHSO.sub.2 NHR.sup.15 ;
R.sup.5 is halogen;
R.sup.6 is selected from the group H and C.sub.1 -C.sub.3 alkyl;
R.sup.7 is H; and
R.sup.9 is selected from the group C.sub.1 -C.sub.8 alkyl; C.sub.3 -C.sub.8 cycloalkyl; C.sub.3 -C.sub.8 alkenyl; C.sub.3 -C.sub.8 alkynyl; C.sub.1 -C.sub.8 haloalkyl; C.sub.2 -C.sub.8 alkoxyalkyl; C.sub.1 -C.sub.4 alkyl substituted with a substituent selected from phenoxy and benzyloxy, each ring optionally substituted with a substituent selected from halogen, C.sub.1 -C.sub.3 alkyl and C.sub.1 -C.sub.3 haloalkyl; C.sub.3 -C.sub.8 haloalkenyl; C.sub.3 -C.sub.8 haloalkynyl; C.sub.2 -C.sub.8 alkyl carbonyl; benzyl optionally substituted with a substituent selected from the group halogen, C.sub.1 -C.sub.3 alkyl and C.sub.1 -C.sub.3 haloalkyl; CHR.sup.16 COR.sup.10 ; CHR.sup.16 CO.sub.2 R.sup.10 ; CHR.sup.16 P(O)(OR.sup.10).sub.2 ; CHR.sup.16 C(O)NR.sup.11 R.sup.12 ; and CHR.sup.16 C(O)NH.sub.2.
Preferred compounds of the invention are:
2,5,6,7-tetrahydro-2-�2,4-dichloro-5-(2-propynyloxy)phenyl!-6-fluoro-3H-pyrrolo�2,1-c!-1,2,4-triazol-3-one; and
5,6,7,8-tetrahydro-2-�2,4-dichloro-5-(2-propynyloxy)phenyl!-8-chloro-1,2,4-triazolo�4,3-.alpha.!pyridin-3(2H)-one.
Compounds of General Formula I can be readily prepared by one skilled in the art by using the reactions and techniques described in Schemes 1 to 11 below. The substituents R.sup.1 -R.sup.16, n, m, and Q for the compounds illustrated are as defined as for compounds of Formula I. Compounds prepared by Schemes 1 to 11 that include compounds numbered II to XVI are intermediates or reagents for the ultimate preparation of compounds of Formula I. Compounds of Formulae Ia-It are subsets of compounds of Formula I. In cases where the substituent of a starting material is not compatible with the reaction conditions described for any of the reaction schemes, it can be assumed that the substituent is convened to a protected form prior to the described reaction scheme and then deprotected after the reaction using commonly accepted protecting/deprotecting techniques (as an example, see T. W. Greene and P. G. M. Wuts, "Protective Groups in Organic Synthesis", 2nd Edition, John Wiley and Sons, Inc., New York, 1991). Otherwise alternative approaches known to one skilled in the art are available.
One skilled in the art will recognize that compounds of Formula I may exist as multiple stereoisomers. This invention therefore, comprises racemic mixtures, enriched mixtures, and pure enantiomers of compounds of Formula I.
The compounds of this invention are made by the following processes.
A retrosynthetic analysis of compounds of Formula Ib (compounds of Formula I wherein n is 2) is shown below (Scheme 1). The formation of ring A can be accomplished by an intramolecular cyclization between the nitrogen in ring B and the terminal double bond of triazolinone of Formula II. ##STR9##
The synthesis of the triazolinone ring B in compounds of Formula II is known in the art and can be prepared by methods such as those described in U.S. Pat. No. 4,818,275 and U.S. Pat. No. 4,818,276. Acidic condensation of .alpha.-ketoacids of Formula III and phenyl hydrazine derivatives of Formula IV gives hydrazones of Formula V. Schmidt rearrangement of the acid of Formula V with diphenylphosphoryl azide followed by a ring cyclization gives triazolinones of Formula II as shown below (Scheme 2). ##STR10##
For the synthesis of the triazolinones of Formula IIa (compounds of Formula II wherein R.sup.2 is H), 2-oxo-5-hexanoic acid IIIa (compound of Formula III wherein R.sup.2 is H) can be used as the starting material (Scheme 3). 2-Oxo-5-hexanoic acid can be made by hydrolysis of the methyl ester of Formula VI with base, preferably one equivalent of potassium hydroxide in an aqueous alcohol solvent. The ester of Formula VI is made from methyl pyruvate as described in J. Org. Chem., (1983), 48, 158 (scheme 3) ##STR11##
The triazolinone of Formula IIa can be made by the method described in Scheme 2. The hydrazone of Formula Va (compound of Formula V wherein R.sup.2 is H) is made by treating 2-oxo-5-hexanoic acid IIIa with a phenyl hydrazine of Formula IV under acidic conditions using hydrochloric acid in an organic solvent such as ethyl or methyl alcohol at a temperature between room temperature and about 100.degree. C. Schmidt rearrangement of hydrazone of Formula Va using an azide such as diphenylphosphoryl azide followed by intramolecular cyclization at a temperature between about 0.degree. C. and about 100.degree. C. affords the intermediate of Formula IIa.
Treatment of the olefin of Formula II with MCPBA (m-chloroperoxybenzoic acid) in an inert solvent such as dichloromethane at a temperature between about 0.degree. C. and about 100.degree. C., preferably at room temperature, gives an epoxide of Formula VII (Scheme 4). Intramolecular cyclization of the epoxide using a base such as potassium carbonate in an inert solvent such as acetonitrile or acetone gives the 6-membered ring product of Formula Ic (compound of Formula I wherein R.sup.1 is 6-OH). Fluorination of the alcohol of Formula Ic with DAST (diethylaminosulfur trifluoride) at a temperature between about -78.degree. C. and about 100.degree. C. in an inert solvent such as dichloromethane gives the fluorinated product of Formula Id. ##STR12##
The alcohol of Formula Ic can also be prepared by hydroxybromination of the olefin of Formula II using N-bromosuccinimide (NBS) and water or N-bromoacetamide and water followed by cyclization of the resulting bromohydrin of Formula VIII using potassium carbonate in an inert solvent such as acetonitrile or acetone (Scheme 5). ##STR13##
Compounds of Formula Ic can also be convened to the chloro-, bromo-, and iodo-R.sup.1 substituted bicyclic triazolinones of Formula I using methods known to those skilled in the art. The hydroxy group in compounds of Formula Ic can be acylated by known methods to prepare the alkylcarbonyloxy and haloalkylcarbonyloxy derivatives. In addition, the hydroxy or halo group can be convened by known methods to afford the R.sup.1 .dbd.alkoxy and haloalkoxy derivatives (March, J., Advanced Organic Chemistry, (1992), 4th Ed., John Wiley and Sons, Inc., pp 386-389). In fact all the R.sup.1 .dbd.OH or halogen compounds in the following Schemes can be functionalized as is known in the art to prepare the other R.sup.1 substituted compounds. Compounds wherein R.sup.1 and R.sup.2 are taken together along with the carbon atom to which they are attached to form C.dbd.O can be prepared from the corresponding R.sup.1 .dbd.OH and R.sup.2 .dbd.H compounds by well-known methods for oxidizing secondary alcohols to ketones.
Compounds of Formulae Ie and If (compounds of Formula I wherein n is 1) can be prepared as illustrated in Scheme 6. Oxidative cleavage of the olefin of Formula II using sodium periodate and a catalytic amount of osmium tetroxide in an inert solvent mixture such as tetrahydrofuran (THF) and water, or using ozone in dichloromethane followed by reductive workup using dimethyl sulfide (DMS), affords the aldehyde of Formula IX. Intramolecular cyclization of the aldehyde under basic conditions using potassium carbonate or sodium hydride gives the 5-membered ring alcohol of Formula Ie. Treatment of the alcohol of Formula Ie with DAST in an inert solvent such as dichloromethane at a temperature between about -80.degree. C. and about 60.degree. C. produces the fluoride of Formula If. The fluoride If can also be made by direct cyclization and fluorination using DAST at a temperature range between about -100.degree. C. and about 60.degree. C. ##STR14##
Hydroboration of the olefin of Formula II with 9-borabicyclo�3.3.1!nonane (9-BBN) gives the alcohol of Formula X after oxidative workup (Scheme 7). Oxidation of alcohol X with oxidizing agents such as PDC (pyridinium dichlorochromate) produces the hemiaminal of Formula Ig presumably via the aldehyde intermediate of Formula XI. The fluoro compound of Formula Ih can be made by the treatment of the hemiaminal with DAST. ##STR15##
Triazolinones of Formula XII can be made from 2-oxo4-pentenoic acids and sustituted phenyl hydrazines of Formula IV by methods known to those skilled in the art and the methods taught herein (Scheme 8). The epoxide of Formula XIII can be prepared from the olefin of Formula XII using an oxidant such as MCPBA. Intramolecular cyclization of the epoxide with a base such as potassium carbonate affords the alcohol of Formula Ii. The fluoro compound of Formula Ij can be made from the alcohol using DAST at a temperature between about -70.degree. C. and about room temperature in an inert solvent such as dichloromethane. ##STR16##
Compounds of Formula Iq can be prepared from the unsubstituted compounds of Formula XIV as illustrated in Scheme 9. Treatment of the bicyclic triazolinone of Formula XIV with N-bromosuccinimide (NBS) under allylic bromination conditions affords the mono-bromo derivative of Formula Io. One skilled in the art will recognize that bromination may also occur on Q if an electron-rich phenyl ring is present. When Q is Q-1, we have found that bromination does not occur on the phenyl ring when R.sup.3 and R.sup.5 are Cl and R.sup.4 is acetyloxy. The acetyl group can be removed by known methods, and the liberated phenolic hydroxyl group can be functionalized by known methods to prepare the desired OR.sup.9 group.
Hydrolysis of the bromide in hot aqueous dimethyl sulfoxide (DMSO) affords the alcohol of Formula Ip. The fluoro compound of Formula Iq can be prepared by treatment of the alcohol with diethylaminosulfur trifluoride (DAST) as described above. ##STR17##
Compounds of Formula I wherein the left-hand ring is unsaturated can be prepared by treating the hydroxy-, bromo, or chloro-substituted compound of Formula Ir with a base such as 1,8-diazabicyclo�5.4.0!undec-7-ene (DBU) as illustrated in Scheme 10. The unsaturated compound is represented by Formula Is wherein the left-hand ring contains one double bond. The hydroxy, bromo and chloro compounds of Formula Ir can be prepared by the methods described in the Schemes above. In some cases, the elimination results in a mixture of double bond isomers which can be separated by chromatography. ##STR18##
Compounds of Formula I wherein R.sup.1 and R.sup.2 are taken together along with the carbon atoms to which they are attached to form an epoxide can be prepared from the corresponding unsaturated ring compound of Formula Is by well known methods for epoxidizing double bonds, for example using MCPBA in CH.sub.2 Cl.sub.2.
Compounds of Formula It can be prepared as illustrated in Scheme 11. Allylic oxidation of the terminal alkene of Formula II with t-butyl hydroperoxide and catalytic selenium (IV) oxide in an inert solvent such as dichloromethane produces the allylic alcohol of Formula XV. Protection of the secondary alcohol as the t-butyldimethylsilyl (TBS) ether is accomplished using t-butylchlorodimethylsilane and a base, preferably triethylamine and catalytic 4-(dimethylamino)pyridine. The terminal olefin is converted to the primary alcohol to afford compounds of Formula XVI using 9-BBN followed by treatment with sodium perborate. Ring cyclization is accomplished using the Martin sulfurane dehydrating agent �C.sub.6 H.sub.5 (CF.sub.3).sub.2 O!.sub.2 S(C.sub.6 H.sub.5).sub.2. Removal of the TBS group and liberation of the alcohol can be accomplished using tetrabutylammonium fluoride. The alcohol can be converted to the corresponding fluoro compound using DAST, or to other R.sup.1 substituted compounds as described above. ##STR19##
For some compounds of Formula I wherein R.sup.2 is other than hydrogen, the R.sup.2 substituent is more conveniently introduced after cyclization to form the bicyclic triazolinone. This is especially the case when R.sup.1 and R.sup.2 are attached to the same carbon atom.

EXAMPLE 1
Step 1
Preparation of 2-oxo-5-hexenoic acid, 2,4-dichloro-5-�(2-propynyl)oxy!-phenylhydrazone.
To a solution of 2.0 g (14.1 mmol) of methyl 2-oxo-5-hexanoate prepared as described in J. Org. Chem., (1983), 48, 158, in 2.5 mL of ethyl alcohol was added a solution of 788 mg (14.1 mmol) of potassium hydroxide in 2.5 mL of water in an ice bath. After 10 min, a mixture of 20 mL of 10% aqueous hydrochloric acid and 20 mL of ethyl alcohol and 3.25 g (14.0 mmol) of 2,4-dichloro-5-�(2-propynyl)oxy!phenylhydrazine were added in sequence. The mixture was then warmed at 40.degree. C. for 1h. The mixture was cooled to room temperature and filtered to give 3.78 g of the title product of Step 1 as a brown solid, m.p.: 152.degree.-153.degree. C.; .sup.1 H NMR (DMSO-d.sub.6, 400 MHz) .delta. 12.5 (s,1H), 7.6 (s,1H), 7.4 (s,1H), 5.9 (m,1H), 4.9-5.1 (m,2H), 4.9 (s,2H) 3.7 (s,1H), 2.6 (t,2H), 2.4 (q,2H).
Step 2
Preparation of 2-�2,4-dichloro-5-(2-propynyloxy)phenyl!-2,4-dihydro-5-(3-butenyl)-3H- 1,2,4-triazol-3-one
To a solution of 7.34 g (21.6 mmol) of 2-oxo-5-hexenoic acid, 2,4-dichloro-5-�(2-propynyl)oxyl!phenylhydrazone in 100 mL of toluene was added 6.54 g (23.7 mmol) of diphenylphosphoryl azide and 3.6 mL of triethylamine (25.9 mmol) in sequence. The reaction mixture was then warmed at reflux for 1h. The mixture was cooled to room temperature and the excess toluene and triethylamine were evaporated in vacuo. The crude product was purified by flash chromatography over silica gel, eluting with 95:5 v:v mixture of dichloromethane and methanol to give 6.64 g of the title compound of Step 2 as a brown solid, m.p.: 150.degree.-151.degree. C.; .sup.1 H NMR (CDCl.sub.3, 400 MHz) .delta. 11.7 (broad s,1H), 7.6 (s,1H), 7.2 (s,1H), 5.95-5.7 (m,1H), 5.2-5.0 (m,2H), 4.8 (s,2H), 2.7 (t,2) 2.6 (t,1H), 2.5 (q,2H).
Step 3
Preparation of 2-�2,4-dichloro-5-(2-propynyloxy)phenyl!-2.4-dihydro-5-(3.4epoxybutyl)-3H- 1,2,4-triazol-3-one
To a solution of 500 mg (1.48 mmol) of 2-�2,4-dichloro-5-(2-propynyloxy)-phenyl!-2,4-dihydro-5-(3-butenyl)-3H- 1,2,4-triazol-3-one in 20 mL of dichloromethane was added 172 mg (1.63 mmol) of sodium carbonate and 970 mg of m-chloroperoxybenzoic acid (50-60%, 2.81 mmol) in an ice bath. The reaction mixture was stirred at room temperature for 24h. The mixture was filtered and the filtrate was evaporated in vacuo to give 500 mg of the title compound of Step 3 as yellow solid. The crude product was used in the following reaction without further purification. .sup.1 H NMR (CDCl.sub.3, 400 MHz) .delta. 11.25 (s,1H), 7.55 (s,1H), 7.2 (s,1H), 4.8 (s,2H), 3.05 (m,1H), 2.8 (t,1H), 2.8 (t,2H), 2.6 (s,1H), 2.75 (d,1H), 2.2 (m,1H), 1.8 (m,1H).
Step 4
Preparation of 5,6,7,8-tetrahydro-2-�2,4-dichloro-5-(2-propynyloxy)phenyl!-6-hydroxy- 1,2,4-triazolo�4.3-.alpha.!pyridin-3(2H)-one
A mixture of 500 mg (1.41 mmol) of 2-�2,4-dichloro-5-(2-propynyloxy)-phenyl!-2,4-dihydro-5-(3,4-epoxybutyl)-3H-1,2,4-triazol-3-one and 563 mg (4.08 mmol) of potassium carbonate in 20 mL of acetonitrile was warmed at reflux for 2h. The mixture was cooled to room temperature and filtered. The filtrate was evaporated in vacuo. The crude product was purified by flash chromatography over silica gel, eluting with a 95:5 v:v mixture of dichloromethane and methanol to give 184 mg of the title product of Step 4 as a pale yellow foam, .sup.1 H NMR (CDCl.sub.3, 400 MHz) .delta. 7.5 (s,1H), 7.15 (s,1H), 4.8 (s,2H), 4.45 (broad t,1H), 3.8 (m,2H), 3.0 (m,1H), 2.8 (m,1H), 2.6 (s,1H), 2.2 (s,1H), 2.15 (m,1H), 1.95 (m,1H).
EXAMPLE 2
Step 1
Preparation of 2-�2,4-dichloro-5-(2-propynyloxy)phenyl!-2,4-dihydro-5-(4-bromo-3-hydroxybutyl )-3H- 1,2,4-triazol-3-one
To a solution of 200 mg (0.592 mmol) of 2-�2,4-dichloro-5-(2-propynyloxy)phenyl!-2,4-dihydro-5-(3-butenyl)-3H-1,2,4-triazol-3-one in 1.8 mL of dimethyl sulfoxide was added 30 mL (1.67 mmol) of water and 211 mg (1.18 mmol) of N-bromosuccinimide, in sequence, at room temperature. The mixture was stirred at room temperature for 10 min. The mixture was then poured into cold water and extracted with dichloromethane. The organic layer was dried (MgSO.sub.4) and concentrated in vacuo. The crude product was purified by flash chromatography over silica gel, eluting with a 97:3 v:v mixture of dichloromethane and methanol to give 200 mg of the title product of Step 1 as a pale yellow foam. .sup.1 H NMR (CDCl.sub.3, 400 MHz) .delta. 11.0 (s, 1H), 7.55 (s,1H), 7.15 (s,1H), 4.8 (s,2H), 3.8 (m,1H), 3.4 (m,2H), 2.8 (m,2H), 2.6 (t,1H), 2.1-1.8 (m,2H).
Step 2
Preparation of 5,6,7,8-tetrahydro-2-�2,4,-dichloro-5-(2-propynyloxy)phenyl!- 6-hydroxy-2,4-triazolo�4,3-.alpha.!pyridin-3(2H)-one
A mixture of 200 mg (0.460 mmol) of 2-�2,4-dichloro-5-(2-propynyloxy)-phenyl!-2,4-dihydro-5-(4-bromo-3-hydroxybutyl)-3H- 1,2,4-triazol-3-one and 127 mg (0.920 mmol) of potassium carbonate in 10 mL of acetonitrile was warmed at reflux for 2h. The mixture was cooled to room temperature and filtered. The filtrate was evaporated in vacuo. The crude product was purified by flash chromatography over silica gel, eluting with a 96:4 v:v mixture of dichloromethane and methanol to give 57 mg of the title product as a pale yellow foam, The .sup.1 H NMR spectrum of the product was identical to that obtained for the product of Step 4 in Example 1.
EXAMPLE 3
Preparation of 5,6,7,8 tetrahydro-2-�2,4-dichloro-5-(2-propynyloxy)phenyl!-6-fluoro-1,2,4-triazolo�4,3-.alpha.!pyridin-3(2H)-one
To a solution of 169 mg (0.477 mmol) of 5,6,7,8-tetrahydro-2-�2,4-dichloro-5-(2-propynyloxy)phenyl!-6-hydroxy-1,2,4-triazolo�4,3-a!pyridin-3(2H)-one in 5 mL of dichloromethane was added 76 .mu.l (0.573 mmol) of diethylaminosulfur trifluoride (DAST) at 0.degree. C. The reaction mixture was stirred at 0.degree. C. for 1h. The mixture was then quenched with ice and extracted with dichloromethane. The organic extracts were dried (MgSO.sub.4), and then concentrated in vacuo to give a pale red solid. The crude product was purified by flash chromatography over silica gel, eluting with a 95:5 v:v mixture of dichloromethane and methanol to give 64 mg of the title product as a pale yellow foam. .sup.19 F NMR (CDCl.sub.3, 400 MHz) .delta.-188 ppm, .sup.1 H NMR (CDCl.sub.3, 400 MHz) .delta. 7.5 (s,1H), 7.1 (s,1H), 5.2 (m,1H), 4.8 (s,2H), 4.2-3.6 (m,2H), 3.2-3.0 (m,1H), 3.0-2.6 (m,1H), 2.5 (s,1H), 2.3-1.8 (m,2H).
EXAMPLE 4
Step 1
Preparation of 2-�2,4-dichloro-5-(2-propynyloxy)phenyl!-2,4-dihydro-5-(3-oxo-propyl)-3H-1,2,4-triazol-3-one
To a solution of 500 mg (1.48 mmol) of 2-�2,4-dichloro-5-(2-propynyloxy)phenyl!-2,4-dihydro-5-(3-butenyl)-3H-1,2,4-triazol-3-one in a mixture of 10 mL of tetrahydrofuran and 10 mL of water was added 696 mg (3.25 mmol) of sodium periodate and 167 mL of 0.18M aqueous solution of osmium tetroxide at room temperature. The mixture was stirred at the room temperature for 2h, and then diluted with water and extracted with ethyl acetate. The organic layer was dried (MgSO.sub.4) and concentrated in vacuo. The crude product was purified by flash chromatography over silica gel, eluting with a 96:4 v:v mixture of dichloromethane and methanol to give 464 mg of the title product of Step 1 as a white foam. .sup.1 H NMR (CDCI.sub.3, 400 MHz) .delta. 11.5 (broad s,1H), 9.8 (s,1H), 7.55 (s,1H), 7.2 (s,1H), 4.8 (s,2H), 2.9 (m,4H).
Step 2
Preparation of 2,5,6,7-tetrahydro-2-�2,4-dichloro-(2-propynyloxy)phenyl!-5-fluoro-3H-pyrrolo�2,1-c!-1,2,4-triazol-3-one
To a solution of 40 mg (0.117 mmol) of 2-�2,4-dichloro-5-(2-propynyloxy)phenyl!-2,4-dihydro-5-(3-oxo-propyl)-3H-1,2,4-triazol-3-one in 5 mL of dichloromethane was added 22.7 mg (0.141 mmol) of diethylaminosulfur trifluoride at 0.degree. C. The mixture was stirred at room temperature for 30 minutes, and then quenched with cold water and extracted with dichloromethane. The organic layer was washed with brine and water, dried (MgSO.sub.4) and concentrated in vacuo. The crude product was purified by flash chromatography over silica gel, eluting with a 95:5 v:v mixture of dichloromethane and methanol to give 18 mg of 2-�2,4-dichloro-5-(2-propynyloxy)phenyl!-2,4-dihydro-5-(3,3-difluoropropyl)-3H-1,2,4-triazol-3-one as a white foam .sup.1 H NMR (CDCl.sub.3, 400 MHz) .delta. 12.0 (s,1H), 7.55 (s,1H), 7.2 (s,1H), 5.95 (t,1H, J=55 Hz), 4.8 (s,2H), 2.8 (t,2H), 2.6 (s,1H), 2.3 (m,2H), and 7 mg of the title product as a solid, .sup.1 H NMR (CDCl.sub.3, 400 MHz) .delta. 7.5 (s,1H), 7.2 (s,1H), 6.4 and 6.2 (q,1H, J=60 and 5 Hz), 4.8 (s,2H), 3.15 (m,1H), 3.0-2.6 (m,3H), 2.6 (s,1H).
EXAMPLE 5
Step 1
Preparation of 5,6,7,8-tetrahydro-2-(5-acetyloxy-2,4-dichlorophenyl)-8-bromo1,2,4-triazolo�4,3-.alpha.!pyridin-3(2H)-one
To a solution of 3.55 g (10.4 mmol) of 5,6,7,8-tetrahydro-2-(5-acetyloxy-2,4-dichlorophenyl)-1,2,4-triazolo�4,3-.alpha.!pyridin-3(2H)-one in 100 mL of carbon tetrachloride was added 2.03 g (11.4 mmol) of N-bromosuccinimide at room temperature. The mixture was warmed under reflux by irradiating with a sun lamp for 3h. The mixture was cooled to room temperature and concentrated under reduced pressure. The crude product was purified by flash chromatography over silica gel, eluting with a 1:1 v:v mixture of ethyl acetate and n-hexane to give 4.10 g of the title product of Step 1 as a white solid, m.p.: 75.degree.-83.degree. C.; .sup.1 H NMR (CDCl.sub.3, 300 MHz) .delta. 7.6 (s,1H), 7.35 (s,1H), 5.25 (m,1H), 4.0 (m,1H), 3.6 (m,1H), 2.75 (s,3H), 2.5-1.9 (m,4H).
Step 2
Preparation of 5,6,7,8-tetrahydro-2-(2,4-dichloro-5-hydroxyphenyl)-8-hydroxy-1,2,4-triazolo�4,3-alpyridin-3(2H)-one
A mixture of 4.10 g (9.74 mmol) of 5,6,7,8-tetrahydro-2-(5-acetyloxy-2,4-dichlorophenyl)-8-bromo-1,2,4-triazolo�4,3-.alpha.!pyridin-3 (2H)-one, 50 mL of DMSO, and 50 mL of water was warmed at 90.degree. C. for 5h. The mixture was cooled to room temperature and diluted with ethyl acetate. The organic layer was washed with water, dried (MgSO.sub.4) and concentrated under reduced pressure. The crude product was purified by flash chromatography over silica gel, eluting with a 95:5 v:v mixture of dichloromethane and methanol to give 1.70 g of the title product of Step 2 as a yellow oil. .sup.1 H NMR (CD.sub.3 SO, 300 MHz) .delta. 7.65 (s,1H), 7.05 (s,1H), 5.85 (br s,1H), 4.60 (m,1H), 3.6-3.4 (m,2H), 2.2-1.8 (m,4H).
Step 3
Preparation of 5,6,7,8-tetrahydro-2-�-2,4-dichloro-5-(2-propynyloxy)phenyl!-8-hydroxy-1,2,4-triazolo�4,3-.alpha.!pyridin-3(2H)-one
A mixture of 1.7 g (5.38 mmol) of 5,6,7,8-tetrahydro-2-(2,4-dichloro-5-hydroxyphenyl)-8-hydroxy-,1,2,4-triazolo�4,3-.alpha.!pyridin-3(2H)-one, 959 mL (10.7 mmol) of propargyl bromide (80% in toluene), and 1.48 g (10.7 mmol) of potassium carbonate in 20 mL of acetonitrile was warmed at reflux for 5h. The mixture was cooled to room temperature and filtered. The filtrate was evaporated under reduced pressure. The crude product was flash chromatographed over silica gel, eluting with a 97:3 v:v mixture of dichloromethane and methanol to give 1.36 g of the title product of Step 3 as a yellow solid, m.p. 168.degree.-170.degree. C.; .sup.1 H NMR (CDCl.sub.3, 300 MHz) .delta. 7.55 (s,1H), 7.15 (s,1H), 4.85 (m,1H), 4.8 (d,2H), 3.8-3.6 (m,2H), 2.6 (m,1H), 2.55 (s,1H), 2.6 (m,1H), 2.55 (s,1H), 2.3-1.9 (m,4H).
Step 4
Preparation of 5,6,7,8-tetrahydro-2-�2,4-dichloro-5-(2-propynyloxy)phenyl!-8-fluoro-1,2,4-triazolo�4,3-.alpha.!pyridin-3(2H )-one
To a solution of 300 mg (0.847 mmol) of 5,6,7,8-tetrahydro-2-�2,4-dichloro-5-(2-propynyloxy)phenyl!-8-hydroxy-1,2,4-triazolo�4,3-.alpha.!pyridin-3(2H)-one in 10 mL of dichloromethane was added 123 mL (0.930 mmol) of diethylaminosulfur trifluoride (DAST) at -78.degree. C. The reaction mixture was stirred at -78.degree. C. for 4h. The mixture was warmed to room temperature, quenched with ice, and extracted with dichloromethane. The organic layers were dried (MgSO.sub.4), and concentrated under reduced pressure. The crude product was flash chromatographed over silica gel, eluting with a 98:2 v:v mixture of dichloromethane and methanol to give 272 mg of the title product of Step 4 as a yellow solid. .sup.19 F NMR (CDCl.sub.3, 300 MHz) .delta.-172; .sup.1 H NMR (CDCl.sub.3, 300 MHz) .delta. 7.55 (s,1H), 7.2 (s,1H), 5.6, 5.5 (2m, J=70 Hz,1H), 4.8 (s,2H), 4.0 (m,1H), 3.55 (m,1H), 2.6 (m,1H), 2.5-1.8 (m,4H).
Using the procedures outlined in Schemes 1-11, the compounds of Tables 1-6 can be prepared. ##STR20##
The following abbreviations are used in the tables which follow.
______________________________________n = normal Ph = phenyl Me = methyl i = iso Pr = propyl______________________________________
TABLE 1__________________________________________________________________________Compounds of Formula Ik wherein Q = Q-1; R.sup.5 = ClR.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.1 R.sup.2 R.sup.3 R.sup.4__________________________________________________________________________5-F H Cl OCH.sub.2 C.tbd.CH 5-F H Cl OCH(CH.sub.3)C.tbd.CH6-F H Cl OCH.sub.2 C.tbd.CH 6-F H Cl OCH(CH.sub.3)C.tbd.CH7-F H Cl OCH.sub.2 C.tbd.CH 7-F H Cl OCH(CH.sub.3)C.tbd.CH5-F 5-F Cl OCH.sub.2 C.tbd.CH 5-F 5-F Cl OCH(CH.sub.3)C.tbd.CH6-F 6-F Cl OCH.sub.2 C.tbd.CH 6-F 6-F Cl OCH(CH.sub.3)C.tbd.CH7-F 7-F Cl OCH.sub.2 C.tbd.CH 7-F 7-F Cl OCH(CH.sub.3)C.tbd.CH5-F 6-F Cl OCH.sub.2 C.tbd.CH 5-F 6-F Cl OCH(CH.sub.3)C.tbd.CH7-F 6-F Cl OCH.sub.2 C.tbd.CH 7-F 6-F Cl OCH(CH.sub.3)C.tbd.CH5-F H F OCH.sub.2 C.tbd.CH 5-F H F OCH(CH.sub.3)C.tbd.CH6-F H F OCH.sub.2 C.tbd.CH 6-F H F OCH(CH.sub.3)C.tbd.CH7-F H F OCH.sub.2 C.tbd.CH 7-F H F OCH(CH.sub.3)C.tbd.CH5-F 5-F F OCH.sub.2 C.tbd.CH 5-F 5-F F OCH(CH.sub.3)C.tbd.CH6-F 6-F F OCH.sub.2 C.tbd.CH 6-F 6-F F OCH(CH.sub.3)C.tbd.CH7-F 7-F F OCH.sub.2 C.tbd.CH 7-F 7-F F OCH(CH.sub.3)C.tbd.CH5-F 6-F F OCH.sub.2 C.tbd.CH 5-F 6-F F OCH(CH.sub.3)C.tbd.CH7-F 6-F F OCH.sub.2 C.tbd.CH 7-F 6-F F OCH(CH.sub.3)C.tbd.CH5-F H Cl OCH(CH.sub.3).sub.2 5-F H Cl OCH.sub.2 CH.dbd.CH.sub.26-F H Cl OCH(CH.sub.3).sub.2 6-F H Cl OCH.sub.2 CH.dbd.CH.sub.27-F H Cl OCH(CH.sub.3).sub.2 7-F H Cl OCH.sub.2 CH.dbd.CH.sub.25-F 5-F Cl OCH(CH.sub.3).sub.2 5-F 5-F Cl OCH.sub.2 CH.dbd.CH.sub.26-F 6-F Cl OCH(CH.sub.3).sub.2 6-F 6-F Cl OCH.sub.2 CH.dbd.CH.sub.27-F 7-F Cl OCH(CH.sub.3).sub.2 7-F 7-F Cl OCH.sub.2 CH.dbd.CH.sub.25-F 6-F Cl OCH(CH.sub.3).sub.2 5-F 6-F Cl OCH.sub.2 CH.dbd.CH.sub.27-F 6-F Cl OCH(CH.sub.3).sub.2 7-F 6-F Cl OCH.sub.2 CH.dbd.CH.sub.25-Cl H Cl OCH.sub.2 C.tbd.CH 5-Cl H Cl OCH(CH.sub.3)C.tbd.CH6-Cl H Cl OCH.sub.2 C.tbd.CH 6-Cl H Cl OCH(CH.sub.3)C.tbd.CH7-Cl H Cl OCH.sub.2 C.tbd.CH 7-Cl H Cl OCH(CH.sub.3)C.tbd.CH5-Cl 5-Cl Cl OCH.sub.2 C.tbd.CH 5-Cl 5-Cl Cl OCH(CH.sub.3)C.tbd.CH6-Cl 6-Cl Cl OCH.sub.2 C.tbd.CH 6-Cl 6-Cl Cl OCH(CH.sub.3)C.tbd.CH7-Cl 7-Cl Cl OCH.sub.2 C.tbd.CH 7-Cl 7-Cl Cl OCH(CH.sub.3)C.tbd.CH5-Cl 6-Cl Cl OCH.sub.2 C.tbd.CH 5-Cl 6-Cl Cl OCH(CH.sub.3)C.tbd.CH7-Cl 6-Cl Cl OCH.sub.2 C.tbd.CH 7-Cl 6-Cl Cl OCH(CH.sub.3)C.tbd.CH5-Cl H F OCH.sub.2 C.tbd.CH 5-Cl H F OCH(CH.sub.3)C.tbd.CH6-Cl H F OCH.sub.2 C.tbd.CH 6-Cl H F OCH(CH.sub.3)C.tbd.CH7-Cl H F OCH.sub.2 C.tbd.CH 7-Cl H F OCH(CH.sub.3)C.tbd.CH5-Cl 5-Cl F OCH.sub.2 C.tbd.CH 5-Cl 5-Cl F OCH(CH.sub.3)C.tbd.CH6-Cl 6-Cl F OCH.sub.2 C.tbd.CH 6-Cl 6-Cl F OCH(CH.sub.3)C.tbd.CH7-Cl 7-Cl F OCH.sub.2 C.tbd.CH 7-Cl 7-Cl F OCH(CH.sub.3)C.tbd.CH5-Cl 6-Cl F OCH.sub.2 C.tbd.CH 5-Cl 6-Cl F OCH(CH.sub.3)C.tbd.CH7-Cl 6-Cl F OCH.sub.2 C.tbd.CH 7-Cl 6-Cl F OCH(CH.sub.3)C.tbd.CH5-Cl H Cl OCH(CH.sub.3).sub.2 5-Cl H Cl OCH.sub.2 CH.dbd.CH.sub.26-Cl H Cl OCH(CH.sub.3).sub.2 6-Cl H Cl OCH.sub.2 CH.dbd.CH.sub.27-Cl H Cl OCH(CH.sub.3).sub.2 7-Cl H Cl OCH.sub.2 CH.dbd.CH.sub.25-Cl 5-Cl Cl OCH(CH.sub.3).sub.2 5-Cl 5-Cl Cl OCH.sub.2 CH.dbd.CH.sub.26-Cl 6-Cl Cl OCH(CH.sub.3).sub.2 6-Cl 6-Cl Cl OCH.sub.2 CH.dbd.CH.sub.27-Cl 7-Cl Cl OCH(CH.sub.3).sub.2 7-Cl 7-Cl Cl OCH.sub.2 CH.dbd.CH.sub.25-Cl 6-Cl Cl OCH(CH.sub.3).sub.2 5-Cl 6-Cl Cl OCH.sub.2 CH.dbd.CH.sub.27-Cl 6-Cl Cl OCH(CH.sub.3).sub.2 7-Cl 6-Cl Cl OCH.sub.2 CH.dbd.CH.sub.2__________________________________________________________________________R.sup.1 R.sup.2 R.sup.3 R.sup.5 R.sup.4 R.sup.1 R.sup.2 R.sup.3 R.sup.5 R.sup.4__________________________________________________________________________5-F H Cl Br OCH.sub.2 C.tbd.CH 5-Br H Cl Cl OCH.sub.2 C.tbd.CH6-F H Cl Br OCH.sub.2 C.tbd.CH 6-Br H Cl Cl OCH.sub.2 C.tbd.CH7-F H Cl Br OCH.sub.2 C.tbd.CH 7-Br H Cl Cl OCH.sub.2 C.tbd.CH5-F 5-F Cl Br OCH.sub.2 C.tbd.CH 6-OMe H Cl Cl OCH.sub.2 C.tbd.CH6-F 6-F Cl Br OCH.sub.2 C.tbd.CH 6-OCF.sub.3 H Cl Cl OCH.sub.2 C.tbd.CH7-F 7-F Cl Br OCH.sub.2 C.tbd.CH 6-MeCO H Cl Cl OCH.sub.2 C.tbd.CH5-F 6-F Cl Br OCH.sub.2 C.tbd.CH 6-CF.sub.3 CO H Cl Cl OCH.sub.2 C.tbd.CH7-F 6-F Cl Br OCH.sub.2 C.tbd.CH 5-F 6-OH Cl Cl OCH.sub.2 C.tbd.CH6-carbonyl Cl Cl OCH.sub.2 C.tbd.CH 6-carbonyl Cl Cl OCH(CH.sub.3).sub.25-F H Cl Cl OCF.sub.2 C.tbd.CH 5-F H F Cl OCF.sub.2 C.tbd.CH6-F H Cl Cl OCF.sub.2 C.tbd.CH 6-F H F Cl OCF.sub.2 C.tbd.CH7-F H Cl Cl OCF.sub.2 C.tbd.CH 7-F H F Cl OCF.sub.2 C.tbd.CH5-F 5-F Cl Cl OCF.sub.2 C.tbd.CH 5-F 5-F F Cl OCF.sub.2 C.tbd.CH6-F 6-F Cl Cl OCF.sub.2 C.tbd.CH 6-F 6-F F Cl OCF.sub.2 C.tbd.CH7-F 7-F Cl Cl OCF.sub.2 C.tbd.CH 7-F 7-F F Cl OCF.sub.2 C.tbd.CH5-F 6-F Cl Cl OCF.sub.2 C.tbd.CH 5-F 6-F F Cl OCF.sub.2 C.tbd.CH7-F 6-F Cl Cl OCF.sub.2 C.tbd.CH 7-F 6-F F Cl OCF.sub.2 C.tbd.CH__________________________________________________________________________Compounds of Formula II wherein Q = Q-1; R.sup.5 = ClR.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.1 R.sup.2 R.sup.3 R.sup.4__________________________________________________________________________5-F H Cl OCH.sub.2 C.tbd.CH 5-F H Cl OCH(CH.sub.3)C.tbd.CH6-F H Cl OCH.sub.2 C.tbd.CH 6-F H Cl OCH(CH.sub.3)C.tbd.CH7-F H Cl OCH.sub.2 C.tbd.CH 7-F H Cl OCH(CH.sub.3)C.tbd.CH8-F H Cl OCH.sub.2 C.tbd.CH 8-F H Cl OCH(CH.sub.3)C.tbd.CH5-F 5-F Cl OCH.sub.2 C.tbd.CH 5-F 5-F Cl OCH(CH.sub.3)C.tbd.CH6-F 6-F Cl OCH.sub.2 C.tbd.CH 6-F 6-F Cl OCH(CH.sub.3)C.tbd.CH7-F 7-F Cl OCH.sub.2 C.tbd.CH 7-F 7-F Cl OCH(CH.sub.3)C.tbd.CH8-F 8-F Cl OCH.sub.2 C.tbd.CH 8-F 8-F Cl OCH(CH.sub.3)C.tbd.CH5-F 6-F Cl OCH.sub.2 C.tbd.CH 5-F 6-F Cl OCH(CH.sub.3)C.tbd.CH6-F 7-F Cl OCH.sub.2 C.tbd.CH 6-F 7-F Cl OCH(CH.sub.3)C.tbd.CH8-F 7-F Cl OCH.sub.2 C.tbd.CH 8-F 7-F Cl OCH(CH.sub.3)C.tbd.CH5-F H F OCH.sub.2 C.tbd.CH 5-F H F OCH(CH.sub.3)C.tbd.CH6-F H F OCH.sub.2 C.tbd.CH 6-F H F OCH(CH.sub.3)C.tbd.CH7-F H F OCH.sub.2 C.tbd.CH 7-F H F OCH(CH.sub.3)C.tbd.CH8-F H F OCH.sub.2 C.tbd.CH 8-F H F OCH(CH.sub.3)C.tbd.CH5-F 5-F F OCH.sub.2 C.tbd.CH 5-F 5-F F OCH(CH.sub.3)C.tbd.CH6-F 6-F F OCH.sub.2 C.tbd.CH 6-F 6-F F OCH(CH.sub.3)C.tbd.CH7-F 7-F F OCH.sub.2 C.tbd.CH 7-F 7-F F OCH(CH.sub.3)C.tbd.CH8-F 8-F F OCH.sub.2 C.tbd.CH 8-F 8-F F OCH(CH.sub.3)C.tbd.CH5-F 6-F F OCH.sub.2 C.tbd.CH 5-F 6-F F OCH(CH.sub.3)C.tbd.CH6-F 7-F F OCH.sub.2 C.tbd.CH 6-F 7-F F OCH(CH.sub.3)C.tbd.CH8-F 7-F F OCH.sub.2 C.tbd.CH 8-F 7-F F OCH(CH.sub.3)C.tbd.CH5-F H Cl OCH(CH.sub.3).sub.2 5-F H Cl OCH.sub.2 CH.tbd.CH.sub.26-F H Cl OCH(CH.sub.3).sub.2 6-F H Cl OCH.sub.2 CH.tbd.CH.sub.27-F H Cl OCH(CH.sub.3).sub.2 7-F H Cl OCH.sub.2 CH.tbd.CH.sub.28-F H Cl OCH(CH.sub.3).sub.2 8-F H Cl OCH.sub.2 CH.tbd.CH.sub.25-F 5-F Cl OCH(CH.sub.3).sub.2 5-F 5-F Cl OCH.sub.2 CH.tbd.CH.sub.26-F 6-F Cl OCH(CH.sub.3).sub.2 6-F 6-F Cl OCH.sub.2 CH.tbd.CH.sub.27-F 7-F Cl OCH(CH.sub.3).sub.2 7-F 7-F Cl OCH.sub.2 CH.tbd.CH.sub.28-F 8-F Cl OCH(CH.sub.3).sub.2 8-F 8-F Cl OCH.sub.2 CH.tbd.CH.sub.25-F 6-F Cl OCH(CH.sub.3).sub.2 5-F 6-F Cl OCH.sub.2 CH.tbd.CH.sub.26-F 7-F Cl OCH(CH.sub.3).sub.2 6-F 7-F Cl OCH.sub.2 CH.tbd.CH.sub.28-F 7-F Cl OCH(CH.sub.3).sub.2 8-F 7-F Cl OCH.sub.2 CH.tbd.CH.sub.25-F H F OCH(CH.sub.3).sub.2 5-F H F OCH.sub.2 CH.tbd.CH.sub.26-F H F OCH(CH.sub.3).sub.2 6-F H F OCH.sub.2 CH.tbd.CH.sub.27-F H F OCH(CH.sub.3).sub.2 7-F H F OCH.sub.2 CH.tbd.CH.sub.28-F H F OCH(CH.sub.3).sub.2 8-F H F OCH.sub.2 CH.tbd.CH.sub.25-F 5-F F OCH(CH.sub.3).sub.2 5-F 5-F F OCH.sub.2 CH.tbd.CH.sub.26-F 6-F F OCH(CH.sub.3).sub.2 6-F 6-F F OCH.sub.2 CH.tbd.CH.sub.27-F 7-F F OCH(CH.sub.3).sub.2 7-F 7-F F OCH.sub.2 CH.tbd.CH.sub.28-F 8-F F OCH(CH.sub.3).sub.2 8-F 8-F F OCH.sub.2 CH.tbd.CH.sub.25-F 6-F F OCH(CH.sub.3).sub.2 5-F 6-F F OCH.sub.2 CH.tbd.CH.sub.26-F 7-F F OCH(CH.sub.3).sub.2 6-F 7-F F OCH.sub.2 CH.tbd.CH.sub.28-F 7-F F OCH(CH.sub.3).sub.2 8-F 7-F F OCH.sub.2 CH.tbd.CH.sub.25-Cl H F OCH.sub.2 C.tbd.CH 5-Cl H F OCH(CH.sub.3)C.tbd.CH6-Cl H F OCH.sub.2 C.tbd.CH 6-Cl H F OCH(CH.sub.3)C.tbd.CH7-Cl H F OCH.sub.2 C.tbd.CH 7-Cl H F OCH(CH.sub.3)C.tbd.CH8-Cl H F OCH.sub.2 C.tbd.CH 8-Cl H F OCH(CH.sub.3)C.tbd.CH5-Cl 5-Cl F OCH.sub.2 C.tbd.CH 5-Cl 5-Cl F OCH(CH.sub.3)C.tbd.CH6-Cl 6-Cl F OCH.sub.2 C.tbd.CH 6-Cl 6-Cl F OCH(CH.sub.3)C.tbd.CH7-Cl 7-Cl F OCH.sub.2 C.tbd.CH 7-Cl 7-Cl F OCH(CH.sub.3)C.tbd.CH8-Cl 8-Cl F OCH.sub.2 C.tbd.CH 8-Cl 8-Cl F OCH(CH.sub.3)C.tbd.CH5-Cl 6-Cl F OCH.sub.2 C.tbd.CH 5-Cl 6-Cl F OCH(CH.sub.3)C.tbd.CH6-Cl 7-Cl F OCH.sub.2 C.tbd.CH 6-Cl 7-Cl F OCH(CH.sub.3)C.tbd.CH8-Cl 7-Cl F OCH.sub.2 C.tbd.CH 8-Cl 7-Cl F OCH(CH.sub.3)C.tbd.CH5-Cl H Cl OCH(CH.sub.3).sub.2 5-Cl H Cl OCH.sub.2 CH.dbd.CH.sub.26-Cl H Cl OCH(CH.sub.3).sub.2 6-Cl H Cl OCH.sub.2 CH.dbd.CH.sub.27-Cl H Cl OCH(CH.sub.3).sub.2 7-Cl H Cl OCH.sub.2 CH.dbd.CH.sub.28-Cl H Cl OCH(CH.sub.3).sub.2 8-Cl H Cl OCH.sub.2 CH.dbd.CH.sub.25-Cl 5-Cl Cl OCH(CH.sub.3).sub.2 5-Cl 5-Cl Cl OCH.sub.2 CH.dbd.CH.sub.26-Cl 6-Cl Cl OCH(CH.sub.3).sub.2 6-Cl 6-Cl Cl OCH.sub.2 CH.dbd.CH.sub.27-Cl 7-Cl Cl OCH(CH.sub.3).sub.2 7-Cl 7-Cl Cl OCH.sub.2 CH.dbd.CH.sub.28-Cl 8-Cl Cl OCH(CH.sub.3).sub.2 8-Cl 8-Cl Cl OCH.sub.2 CH.dbd.CH.sub.25-Cl 6-Cl Cl OCH(CH.sub.3).sub.2 5-Cl 6-Cl Cl OCH.sub.2 CH.dbd.CH.sub.26-Cl 7-Cl Cl OCH(CH.sub.3).sub.2 6-Cl 7-Cl Cl OCH.sub.2 CH.dbd.CH.sub.28-Cl 7-Cl Cl OCH(CH.sub.3).sub.2 8-Cl 7-Cl Cl OCH.sub.2 CH.dbd.CH.sub.2__________________________________________________________________________R.sup.1 R.sup.2 R.sup.3 R.sup.5 R.sup.4 R.sup.1 R.sup.2 R.sup.3 R.sup.5 R.sup.4__________________________________________________________________________5-F H Cl Br OCH.sub.2 C.tbd.CH 5-Br H Cl Cl OCH.sub.2 C.tbd.CH6-F H Cl Br OCH.sub.2 C.tbd.CH 6-Br H Cl Cl OCH.sub.2 C.tbd.CH7-F H Cl Br OCH.sub.2 C.tbd.CH 7-Br H Cl Cl OCH.sub.2 C.tbd.CH8-Br H Cl Br OCH.sub.2 C.tbd.CH 8-Br H Cl Cl OCH.sub.2 C.tbd.CH6-F 6-F Cl Br OCH.sub.2 C.tbd.CH 6-OMe H Cl Cl OCH.sub.2 C.tbd.CH7-F 7-F Cl Br OCH.sub.2 C.tbd.CH 7-OCF.sub.3 H Cl Cl OCH.sub.2 C.tbd.CH5-F 6-F Cl Br OCH.sub.2 C.tbd.CH 6-MeCO H Cl Cl OCH.sub.2 C.tbd.CH6-F 7-F Cl Br OCH.sub.2 C.tbd.CH 6-CF.sub.3 CO H Cl Cl OCH.sub.2 C.tbd.CH8-F 7-F Cl Br OCH.sub.2 C.tbd.CH 6-F 7-OH Cl Cl OCH.sub.2 C.tbd.CH7-carbonyl Cl Cl OCH.sub.2 C.tbd.CH 7-carbonyl Cl Cl OCH(CH.sub.3).sub.25-F H Cl Cl OCF.sub.2 C.tbd.CH 5-F H F Cl OCF.sub.2 C.tbd.CH6-F H Cl Cl OCF.sub.2 C.tbd.CH 6-F H F Cl OCF.sub.2 C.tbd.CH7-F H Cl Cl OCF.sub.2 C.tbd.CH 7-F H F Cl OCF.sub.2 C.tbd.CH8-Br H Cl Cl OCF.sub.2 C.tbd.CH 8-Br H F Cl OCF.sub.2 C.tbd.CH6-F 6-F Cl Cl OCF.sub.2 C.tbd.CH 6-F 6-F F Cl OCF.sub.2 C.tbd.CH7-F 7-F Cl Cl OCF.sub.2 C.tbd.CH 7-F 7-F F Cl OCF.sub.2 C.tbd.CH5-F 6-F Cl Cl OCF.sub.2 C.tbd.CH 5-F 6-F F Cl OCF.sub.2 C.tbd.CH6-F 7-F Cl Cl OCF.sub.2 C.tbd.CH 6-F 7-F F Cl OCF.sub.2 C.tbd.CH8-F 7-F Cl Cl OCF.sub.2 C.tbd.CH 8-F 7-F F Cl OCF.sub.2 C.tbd.CH__________________________________________________________________________
TABLE 2______________________________________Compounds of Formula Ik wherein Q = Q-2; R.sup.6 = H; W = OR.sup.1 R.sup.2 R.sup.3 R.sup.5 R.sup.7 R.sup.1 R.sup.2 R.sup.3 R.sup.5 R.sup.7______________________________________5-F H Cl Cl Me 5-F H F Cl Me6-F H Cl Cl Me 6-F H F Cl Me7-F H Cl Cl Me 7-F H F Cl Me5-F 5-F Cl Cl Me 5-F 5-F F Cl Me6-F 6-F Cl Cl Me 6-F 6-F F Cl Me7-F 7-F Cl Cl Me 7-F 7-F F Cl Me5-F 6-F Cl Cl Me 5-F 6-F F Cl Me7-F 6-F Cl Cl Me 7-F 6-F F Cl Me5-Cl H Cl Cl Me 5-Cl H F Cl Me6-Cl H Cl Cl Me 6-Cl H F Cl Me7-Cl H Cl Cl Me 7-Cl H F Cl Me5-Cl 5-Cl Cl Cl Me 5-Cl 5-Cl F Cl Me6-Cl 6-Cl Cl Cl Me 6-Cl 6-Cl F Cl Me7-Cl 7-Cl Cl Cl Me 7-Cl 7-Cl F Cl Me5-Cl 6-Cl Cl Cl Me 5-Cl 6-Cl F Cl Me7-Cl 6-Cl Cl Cl Me 7-Cl 6-Cl F Cl Me5-F H Cl Cl Me 5-F H F Cl Me6-F H Cl Cl Me 6-F H F Cl Me7-F H Cl Cl Me 7-F H F Cl Me8-F H Cl Cl Me 8-F H F Cl Me5-F 5-F Cl Cl Me 5-F 5-F F Cl Me6-F 6-F Cl Cl Me 6-F 6-F F Cl Me7-F 7-F Cl Cl Me 7-F 7-F F Cl Me8-F 8-F Cl Cl Me 8-F 8-F F Cl Me5-F 6-F Cl Cl Me 45-F 6-F F Cl Me6-F 7-F Cl Cl Me 6-F 7-F F Cl Me8-F 7-F Cl Cl Me 8-F 7-F F Cl Me5-Cl H Cl Cl Me 5-Cl H F Cl Me6-Cl H Cl Cl Me 6-Cl H F Cl Me7-Cl H Cl Cl Me 7-Cl H F Cl Me8-Cl H Cl Cl Me 8-Cl H F Cl Me5-Cl 5-Cl Cl Cl Me 5-Cl 5-Cl F Cl Me6-Cl 6-Cl Cl Cl Me 6-Cl 6-Cl F Cl Me7-Cl 7-Cl Cl Cl Me 7-Cl 7-Cl F Cl Me8-Cl 8-Cl Cl Cl Me 8-Cl 8-Cl F Cl Me5-Cl 6-Cl Cl Cl Me 5-Cl 6-Cl F Cl Me6-Cl 7-Cl Cl Cl Me 6-Cl 7-Cl F Cl Me8-Cl 7-Cl Cl Cl Me 8-Cl 7-Cl F Cl Me______________________________________
TABLE 3__________________________________________________________________________R.sup.1 R.sup.2 R.sup.3 R.sup.7 R.sup.8 R.sup.1 R.sup.2 R.sup.3 R.sup.7 R.sup.8__________________________________________________________________________Compounds of the formula Ik wherein Q = Q-6; W = O; R.sup.6 = H5-F H F H CH.sub.2 C.tbd.CH 5-F H F H CH(CH.sub.3)C.tbd.CH5-F H F CH.sub.3 CH.sub.2 C.tbd.CH 5-F H F CH.sub.3 CH(CH.sub.3)C.tbd.CH6-F H F H CH.sub.2 C.tbd.CH 6-F H F H CH(CH.sub.3)C.tbd.CH6-F H F CH.sub.3 CH.sub.2 C.tbd.CH 6-F H F CH.sub.3 CH(CH.sub.3)C.tbd.CH7-F H F H CH.sub.2 C.tbd.CH 7-F H F H CH(CH.sub.3)C.tbd.CH7-F H F CH.sub.3 CH.sub.2 C.tbd.CH 7-F H F CH.sub.3 CH(CH.sub.3)C.tbd.CH5-F 5-F F H CH.sub.2 C.tbd.CH 5-F 5-F F H CH(CH.sub.3)C.tbd.CH6-F 6-F F H CH.sub.2 C.tbd.CH 6-F 6-F F H CH(CH.sub.3)C.tbd.CH6-F 6-F F CH.sub.3 CH.sub.2 C.tbd.CH 6-F 6-F F CH.sub.3 CH(CH.sub.3)C.tbd.CH7-F 7-F F H CH.sub.2 C.tbd.CH 7-F 7-F F H CH(CH.sub.3)C.tbd.CH5-Cl H F H C.sub.2 C.tbd.CH 5-Cl H F H CH(CH.sub.3)C.tbd.CH5-Cl H F CH.sub.3 CH.sub.2 C.tbd.CH 5-Cl H F CH.sub.3 CH(CH.sub.3)C.tbd.CH6-Cl H F H CH.sub.2 C.tbd.CH 6-Cl H F H CH(CH.sub.3)C.tbd.CH6-Cl H F CH.sub.3 CH.sub.2 C.tbd.CH 6-Cl H F CH.sub.3 CH(CH.sub.3)C.tbd.CH7-Cl H F H CH.sub.2 C.tbd.CH 7-Cl H F H CH(CH.sub.3)C.tbd.CH7-Cl H F CH.sub.3 CH.sub.2 C.tbd.CH 7-Cl H F CH.sub.3 CH(CH.sub.3)C.tbd.CH5-Cl 5-Cl F H CH.sub.2 C.tbd.CH 5-Cl 5-Cl F H CH(CH.sub.3)C.tbd.CH6-Cl 6-Cl F H CH.sub.2 C.tbd.CH 6-Cl 6-Cl F H CH(CH.sub.3)C.tbd.CH6-Cl 6-Cl F CH.sub.3 CH.sub.2 C.tbd.CH 6-Cl 6-Cl F CH.sub.3 CH(CH.sub.3)C.tbd.CH7-Cl 7-Cl F H CH.sub.2 C.tbd.CH 7-Cl 7-Cl F H CH(CH.sub.3)C.tbd.CHCompounds of Formula Il wherein Q = Q-6; W = O; R.sup.6 =H5-F H F H CH.sub.2 C.tbd.CH 5-F H F H CH(CH.sub.3)C.tbd.CH5-F H F CH.sub.3 CH.sub.2 C.tbd.CH 5-F H F CH.sub.3 CH(CH.sub.3)C.tbd.CH6-F H F H CH.sub.2 C.tbd.CH 6-F H F H CH(CH.sub.3)C.tbd.CH6-F H F CH.sub.3 CH.sub.2 C.tbd.CH 6-F H F CH.sub.3 CH(CH.sub.3)C.tbd.CH7-F H F H CH.sub.2 C.tbd.CH 7-F H F H CH(CH.sub.3)C.tbd.CH7-F H F CH.sub.3 CH.sub.2 C.tbd.CH 7-F H F CH.sub.3 CH(CH.sub.3)C.tbd.CH8-F H F H CH.sub.2 C.tbd.CH 8-F H F H CH(CH.sub.3)C.tbd.CH8-F H F CH.sub.3 CH.sub.2 C.tbd.CH 8-F H F CH.sub.3 CH(CH.sub.3)C.tbd.CH5-F 5-F F H CH.sub.2 C.tbd.CH 5-F 5-F F H CH(CH.sub.3)C.tbd.CH6-F 6-F F H CH.sub.2 C.tbd.CH 6-F 6-F F H CH(CH.sub.3)C.tbd.CH7-F 7-F F H CH.sub.2 C.tbd.CH 7-F 7-F F H CH(CH.sub.3)C.tbd.CH7-F 7-F F CH.sub.3 CH.sub.2 C.tbd.CH 7-F 7-F F CH.sub.3 CH(CH.sub.3)C.tbd.CH8-F 8-F F H CH.sub.2 C.tbd.CH 8-F 8-F F H CH(CH.sub.3)C.tbd.CH5-Cl H F H CH.sub.2 C.tbd.CH 5-Cl H F H CH(CH.sub.3)C.tbd.CH5-Cl H F CH.sub.3 CH.sub.2 C.tbd.CH 5-Cl H F CH.sub.3 CH(CH.sub.3)C.tbd.CH6-Cl H F H CH.sub.2 C.tbd.CH 6-Cl H F H CH(CH.sub.3)C.tbd.CH6-Cl H F CH.sub.3 CH.sub.2 C.tbd.CH 6-Cl H F CH.sub.3 CH(CH.sub.3)C.tbd.CH7-Cl H F H CH.sub.2 C.tbd.CH 7-Cl H F H CH(CH.sub.3)C.tbd.CH7-Cl H F CH.sub.3 CH.sub.2 C.tbd.CH 7-Cl H F CH.sub.3 CH(CH.sub.3)C.tbd.CH8-Cl H F H CH.sub.2 C.tbd.CH 8-Cl H F H CH(CH.sub.3)C.tbd.CH8-Cl H F CH.sub.3 CH.sub.2 C.tbd.CH 8-Cl H F CH.sub.3 CH(CH.sub.3)C.tbd.CH5-Cl 5-Cl F H CH.sub.2 C.tbd.CH 5-Cl 5-Cl F H CH(CH.sub.3)C.tbd.CH6-Cl 6-Cl F H CH.sub.2 C.tbd.CH 6-Cl 6-Cl F H CH(CH.sub.3)C.tbd.CH7-Cl 7-Cl F H CH.sub.2 C.tbd.CH 7-Cl 7-Cl F H CH(CH.sub.3)C.tbd.CH7-Cl 7-Cl F CH.sub.3 CH.sub.2 C.tbd.CH 7-Cl 7-Cl F CH.sub.3 CH(CH.sub.3)C.tbd.CH8-Cl 8-Cl F H CH.sub.2 C.tbd.CH 8-Cl 8-Cl F H CH(CH.sub.3)C.tbd.CH__________________________________________________________________________
TABLE 4__________________________________________________________________________R.sup.3 R.sup.4 R.sup.3 R.sup.4 R.sup.3 R.sup.4 R.sup.3 R.sup.4__________________________________________________________________________Compounds of Formula Ik wherein Q = Q-1; R.sup.1 = 6-F; R.sup.2 = H;R.sup.5 = ClCl H Cl SCH.sub.2 C.tbd.CH Cl CH.dbd.CHCO.sub.2 (i-Pr) Cl OCH.sub.2 OCH.sub.3F H F SCH.sub.2 C.tbd.CH F CH.dbd.CHCO.sub.2 (i-Pr) F OCH.sub.2 OCH.sub.3Cl O-(n-Pr) Cl SCH(CH.sub.3)C.tbd.CH Cl OCH.sub.2 CO.sub.2 (i-Pr) Cl SCH.sub.2 CO.sub.2 EtF O-(n-Pr) F SCH(CH.sub.3)C.tbd.CH F OCH.sub.2 CO.sub.2 (i-Pr) F SCH.sub.2 CO.sub.2 EtCl OCH.sub.2 CF.sub.3 Cl NHSO.sub.2 CH.sub.3 Cl OCH.sub.2 OPh Cl OCH.sub.2 CO(i-Pr)Cl CO.sub.2 (i-Pr) F NHSO.sub.2 CH.sub.3 F OCH.sub.2 OPh F OCH.sub.2 CO(i-Pr)F CO.sub.2 (i-Pr) Cl OCH.sub.2 CO.sub.2 (n-pentyl) F OCH.sub.2 CO.sub.2 (n-pentyl)Compounds of Formula Il wherein Q = Q-1; R.sup.1 = 6-F; R.sup.2 = H;R.sup.5 = ClCl H Cl SCH.sub.2 C.tbd.CH Cl CH.dbd.CHCO.sub.2 (i-Pr) Cl OCH.sub.2 OCH.sub.3F H F SCH.sub.2 C.tbd.CH F CH.dbd.CHCO.sub.2 (i-Pr) F OCH.sub.2 OCH.sub.3Cl O-(n-Pr) Cl SCH(CH.sub.3)C.tbd.CH Cl OCH.sub.2 CO.sub.2 (i-Pr) Cl SCH.sub.2 CO.sub.2 EtF O-(n-Pr) F SCH(CH.sub.3)C.tbd.CH F OCH.sub.2 CO.sub.2 (i-Pr) F SCH.sub.2 CO.sub.2 EtCl OCH.sub.2 CF.sub.3 Cl NHSO.sub.2 CH.sub.3 Cl OCH.sub.2 OPh Cl OCH.sub.2 CO(i-Pr)Cl CO.sub.2 (i-Pr) F NHSO.sub.2 CH.sub.3 F OCH.sub.2 OPh F OCH.sub.2 CO(i-Pr)F CO.sub.2 (i-Pr) Cl OCH.sub.2 CO.sub.2 (n-pentyl) F OCH.sub.2 CO.sub.2 (n-pentyl)__________________________________________________________________________
TABLE 5__________________________________________________________________________Compounds of Formula Ik wherein Q = Q-4; W = S;R.sup.1 R.sup.2 R.sup.3 R.sup.9 R.sup.1 R.sup.2 R.sup.3 R.sup.9 R.sup.1 R.sup.2 R.sup.3 R.sup.9__________________________________________________________________________5-F H F CH.sub.2 C.tbd.CH 5-Cl H F CH.sub.2 C.tbd.CH 6-F 6-F F CH.sub.2 C.tbd.CH5-F H F CH.sub.2 C.tbd.CH 5-Cl H F CH.sub.2 C.tbd.CH 6-F 6-F F CH.sub.2 C.tbd.CH6-F H F CH.sub.2 C.tbd.CH 6-Cl H F CH.sub.2 C.tbd.CH 7-F 7-F F CH.sub.2 C.tbd.CH6-F H F CH.sub.2 C.tbd.CH 6-Cl H F CH.sub.2 C.tbd.CH 6-Cl 6-Cl F CH.sub.2 C.tbd.CH7-F H F CH.sub.2 C.tbd.CH 7-Cl H F CH.sub.2 C.tbd.CH 6-Cl 6-Cl F CH.sub.2 C.tbd.CH7-F H F CH.sub.2 C.tbd.CH 7-Cl H F CH.sub.2 C.tbd.CH 7-Cl 7-Cl F CH.sub.2 C.tbd.CH5-F 5-F F CH.sub.2 C.tbd.CH 5-Cl 5-Cl F CH.sub.2 C.tbd.CH__________________________________________________________________________R.sup.1 R.sup.2 R.sup.3 R.sup.9 R.sup.1 R.sup.2 R.sup.3 R.sup.9__________________________________________________________________________5-F H F CH(CH.sub.3)C.tbd.CH 5-Cl H F CH(CH.sub.3)C.tbd.CH5-F H F CH(CH.sub.3)C.tbd.CH 5-Cl H F CH(CH.sub.3)C.tbd.CH6-F H F CH(CH.sub.3)C.tbd.CH 6-Cl H F CH(CH.sub.3)C.tbd.CH6-F H F CH(CH.sub.3)C.tbd.CH 6-Cl H F CH(CH.sub.3)C.tbd.CH7-F H F CH(CH.sub.3)C.tbd.CH 7-Cl H F CH(CH.sub.3)C.tbd.CH7-F H F CH(CH.sub.3)C.tbd.CH 7-Cl H F CH(CH.sub.3)C.tbd.CH5-F 5-F F CH(CH.sub.3)C.tbd.CH 5-Cl 5-Cl F CH(CH.sub.3)C.tbd.CH6-F 6-F F CH(CH.sub.3)C.tbd.CH 6-Cl 6-Cl F CH(CH.sub.3)C.tbd.CH6-F 6-F F CH(CH.sub.3)C.tbd.CH 6-Cl 6-Cl F CH(CH.sub.3)C.tbd.CH7-F 7-F F CH(CH.sub.3)C.tbd.CH 7-Cl 7-Cl F CH(CH.sub.3)C.tbd.CH__________________________________________________________________________Compounds of the Formula II wherein Q = Q-4; W = S;R.sup.1 R.sup.2 R.sup.3 R.sup.9 R.sup.1 R.sup.2 R.sup.3 R.sup.9 R.sup.1 R.sup.2 R.sup.3 R.sup.9__________________________________________________________________________5-F H F CH.sub.2 C.dbd.CH 5-Cl H F CH.sub.2 C.tbd.CH 7-F 7-F F CH.sub.2 C.tbd.CH5-F H F CH.sub.2 C.dbd.CH 5-Cl H F CH.sub.2 C.dbd.CH 7-F 7-F F CH.sub.2 C.dbd.CH6-F H F CH.sub.2 C.dbd.CH 6-Cl H F CH.sub.2 C.dbd.CH 8-F 8-F F CH.sub.2 C.dbd.CH6-F H F CH.sub.2 C.dbd.CH 6-Cl H F CH.sub.2 C.dbd.CH 7-Cl 7-Cl F CH.sub.2 C.dbd.CH7-F H F CH.sub.2 C.dbd.CH 7-Cl H F CH.sub.2 C.dbd.CH 7-Cl 7-Cl F CH.sub.2 C.dbd.CH7-F H F CH.sub.2 C.dbd.CH 7-Cl H F CH.sub.2 C.dbd.CH 8-Cl 8-C F CH.sub.2 C.dbd.CH8-F H F CH.sub.2 C.dbd.CH 8-Cl H F CH.sub.2 C.dbd.CH 6-F 6-F F CH.sub.2 C.dbd.CH8-F H F CH.sub.2 C.dbd.CH 8-Cl H F CH.sub.2 C.dbd.CH 6-Cl 6-Cl F CH.sub.2 C.dbd.CH5-F 4-F F CH.sub.2 C.dbd.CH 5-Cl 5-Cl F CH.sub.2 C.dbd.CH__________________________________________________________________________R.sup.1 R.sup.2 R.sup.3 R.sup.9 R.sup.1 R.sup.2 R.sup.3 R.sup.9__________________________________________________________________________5-F H F CH(CH.sub.3)C.tbd.CH 5-Cl H F CH(CH.sub.3)C.tbd.CH5-F H F CH(CH.sub.3)C.tbd.CH 5-Cl H F CH(CH.sub.3)C.tbd.CH6-F H F CH(CH.sub.3)C.tbd.CH 6-Cl H F CH(CH.sub.3)C.tbd.CH6-F H F CH(CH.sub.3)C.tbd.CH 6-Cl H F CH(CH.sub.3)C.tbd.CH7-F H F CH(CH.sub.3)C.tbd.CH 7-Cl H F CH(CH.sub.3)C.tbd.CH7-F H F CH(CH.sub.3)C.tbd.CH 7-Cl H F CH(CH.sub.3)C.tbd.CH8-F H F CH(CH.sub.3)C.tbd.CH 8-Cl H F CH(CH.sub.3)C.tbd.CH8-F H F CH(CH.sub.3)C.tbd.CH 8-Cl H F CH(CH.sub.3)C.tbd.CH5-F 5-F F CH(CH.sub.3)C.tbd.CH 5-Cl 5-Cl F CH(CH.sub.3)C.tbd.CH6-F 6-F F CH(CH.sub.3)C.tbd.CH 6-Cl 6-Cl F CH(CH.sub.3)C.tbd.CH7-F 7-F F CH(CH.sub.3)C.tbd.CH 7-Cl 7-Cl F CH(CH.sub.3)C.tbd.CH7-F 7-F F CH(CH.sub.3)C.tbd.CH 7-Cl 7-Cl F CH(CH.sub.3)C.tbd.CH8-F 8-F F CH(CH.sub.3)C.tbd.CH 8-Cl 8-Cl F CH(CH.sub.3)C.tbd.CH__________________________________________________________________________
TABLE 6______________________________________R.sup.1 R.sup.2 R.sup.3 R.sup.1 R.sup.2 R.sup.3 R.sup.1 R.sup.2 R.sup.3 R.sup.1 R.sup.2 R.sup.3______________________________________Compounds of Formula Ik wherein Q = Q-5; R.sup.6 = R.sup.7 = CF.sub.3 ;5-F H F 6-F 6-F F 7-Cl H F 5-F 5-F F5-F H Cl 6-F 6-F Cl 7-Cl H Cl 5-F 5-F Cl6-F H F 7-F 7-F F 5-Cl 5-Cl F 6-Cl H F6-F H Cl 7-F 7-F Cl 5-Cl 5-Cl Cl 6-Cl H Cl7-F H F 5-Cl H F 6-Cl 6-Cl F 7-Cl 7-Cl F7-F H Cl 5-Cl H Cl 6-Cl 6-Cl Cl 7-Cl 7-Cl ClCompounds of Formula Il wherein Q = Q-5; R.sup.6 = R.sup.7 = CF.sub.3 ;5-F H F 5-F 5-F F 5-Cl 5-Cl F 6-F 6-F F5-F H Cl 5-F 5-F Cl 5-Cl 5-Cl Cl 6-F 6-F Cl6-F H F 7-F 7-F F 8-Cl H F 7-Cl H F6-F H Cl 7-F 7-F Cl 8-Cl H Cl 7-Cl H Cl7-F H F 7-F 8-F F 6-Cl 6-Cl F 8-CL 8-Fl F7-F H Cl 8-F 8-F Cl 6-Cl 6-Cl Cl 8-Cl 8-Cl Cl8-F H F 6-Cl H F 7-Cl 7-Cl F8-F H Cl 6-Cl H Cl 7-Cl 7-Cl Cl______________________________________
Formulation/Utility
The compounds of this invention are useful as herbicides in agriculture. Typically, such compound(s) can be formulated in an effective amount with conventional additives including a carrier therefor (comprising a surfactant and/or a solid or liquid diluent) and applied by known methods to the locus to be protected.
Compounds of this invention will generally be used in formulation with an agriculturally suitable carrier comprising a liquid or solid diluent or an organic solvent. Useful formulations include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, dry flowables and the like, consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature. Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation. The formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up 100 weight percent.
______________________________________ Weight Percent Active Ingredient Diluent Surfactant______________________________________Wettable Powders 25-90 0-74 1-10Oil Suspensions, Emulsions, 5-50 40-95 0-15Solutions, (including EmulsifiableConcentrates)Dusts 1-25 70-99 0-5Granules and Pellets 0.01-99 5-99.99 0-15High Strength Compositrons 90-99 0-10 0-2______________________________________
Typical solid diluents are described in Watkins, et al., Handbook of insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, N.J. Typical liquid diluents and solvents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, (1950). McCutcheon's Detergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, N.J., as well as Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, (1964), list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth, etc.
Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer mill or fluid energy mill. Water-dispersible granules can be produced by agglomerating a free powder composition; see for example, Cross et al., Pesticide Formulations, Washington, D.C., (1988), pp 251-259. Suspensions are prepared by wet-milling; see, for example, U.S. Pat. No. 3,060,084. Granules and pellets can be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, Dec. 4, 1967, pp 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, (1963), pp 8-57 and following, and WO 91/13546. Pellets can be prepared as described in U.S. Pat. No. 4,172,714. Water-dispersible and water-soluble granules can also be prepared as taught in DE 3,246,493.
For further information regarding the art of formulation, see U.S. Pat. No. 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 10-41; U.S. Pat. No. 3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; U.S. Pat. No. 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, (1961), pp 81-96; and Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, (1989).
In the following Examples, all percentages are by weight and all formulations are worked up in conventional ways. The compound number refers to the compound in Index Table A hereinafter.
______________________________________Example AHigh Strength ConcentrateCompound 12 98.5%silica aerogel 0.5%synthetic amorphous fine silica 1.0%.Example BWettable PowderCompound 12 65.0%dodecylphenol polyethylene glycol ether 2.0%sodium ligninsulfonate 4.0%sodium silicoaluminate 6.0%montmorillonite (calcined) 23.0%.Example CGranuleCompound 12 10.0%attapulgite granules (low volatile 90.0%.matter, 0.71/0.30 mm; U.S.S. No.25-50 sieves)Example DExtruded PelletCompound 12 25.0%anhydrous sodium sulfate 10.0%crude calcium ligninsulfonate 5.0%sodium alkylnaphthalenesulfonate 1.0%calcium/magnesium bentonite 59.0%.______________________________________
The compounds of the present invention are highly active preemergent and/or postemergent herbicides and/or plant growth regulants. Many of them have utility for broad-spectrum pre- and/or postemergence weed control in areas where complete control of all vegetation is desired such as around fuel storage tanks, industrial storage areas, parking lots, drive-in theaters, around billboards and highway and railroad structures. Some of the compounds are useful for the control of selected grass and broadleaf weeds with tolerance to important agronomic crops which include but are not limited to barley, cotton, wheat, corn, soybeans, rice, citrus, peanut, and plantation crops such as sugarcane, coffee, banana, oil palm, rubber, grapes, fruit trees, nut trees, turf, pineapple and loblolly pine. The compounds of the instant invention are particularly useful on plantation crops such as sugarcane, coffee, banana, oil palm, rubber, grapes, fruit trees, nut trees, turf, pineapple and loblolly pine. Those skilled in the art will appreciate that not all compounds are equally effective against all weeds. Alternatively, the subject compounds are useful to modify plant growth.
Compounds of this invention can be used alone or in combination with other commercial herbicides, insecticides or fungicides. A mixture of one or more of the following herbicides with a compound of this invention can be particularly useful for weed control: acetochlor, acifluorfen, acrolein, 2-propenal, alachlor, ametryn, amidosulfuron, ammonium sulfamate, amitrole, anilofos, asulam, atrazine, barban, benefin, bensulfuron methyl, bensulide, bentazon, benzofluor, benzoylprop, bifenox, bromacil, bromoxynil, bromoxynil heptanoate, bromoxynil octanoate, butachlor, buthidazole, butralin, butylate, cacodylic acid, 2-chloro-N,N-di-2-propenyl-acetamide, 2-chloroallyl diethyldithiocarbamate, chloramben, chlorbromuron, chloridazon, chlorimuron ethyl, chlormethoxynil, chlornitrofen, chloroxuron, chlorpropham, chlorsulfuron, chlortoluron, cinmethylin, cinosulfuron, clethodim, clomazone, cloproxydim, clopyralid, calcium salt of methylarsonic acid, cyanazine, cycloate, cycluron, cyperquat, cyprazine, cyprazole, cypromid, dalapon, dazomet, dimethyl 2,3,5,6-tetrachloro-1,4-benzenedicarboxylate, desmedipham, desmetryn, dicamba, dichlobenil, dichlorprop, diclofop, diethatyl, difenzoquat, diflufenican, dimepiperate, dinitramine, dinoseb, diphenamid, dipropetryn, diquat, diuron, 2-methyl-4,6-dinitrophenol, disodium salt of methylarsonic acid, dymron, endothall, S-ethyl dipropylcarbamothioate, esprocarb, ethalfluralin, ethametsulfuron methyl, ethofumesate, fenac, fenoxaprop, fenuron, salt of fenuron and trichloroacetic acid, flamprop, fluazifop, fluazifop-P, fluchloralin, flumesulam, flumipropyn, fluomemron, fluorochloridone, fluorodifen, fluoroglycofen, flupoxam, fluridone, fluroxypyr, fluzasulfuron, fomesafen, fosamine, glyphosate, glyphosate salts, haloxyfop, hexaflurate, hexazinone, imazamethabenz, imazapyr, imazaquin, imazamethabenz methyl, imazethapyr, imazosulfuron, ioxynil, isopropalin, isoproturon, isouron, isoxaben, karbutilate, lactofen, lenacil, linuron, metobenzuron, metsulfuron methyl, methylarsonic acid, monoammonium salt of methylarsonic acid, (4-chloro-2-methylphenoxy)acetic acid, S,S'-dimethyl-2-(difluoromethyl)-4-(2-methylpropyl)-6-(trifluoromethyl)-3,5-pyridinedicarbothioate, mecoprop, mefenacet, mefluidide, methalpropalin, methabenzthiazuron, metham, methazole, methoxuron, metolachlor, metribuzin, 1,2-dihydropyridazine-3,6-dione, molinate, monolinuron, monuron, monuron salt and trichloroacetic acid, monosodium salt of methylarsonic acid, napropamide, naptalam, neburon, nicosulfuron, nitralin, nitrofen, nitrofluorfen, norea, norflurazon, oryzalin, oxadiazon, oxyfluorfen, paraquat, pebulate, pendimethalin, perfluidone, phenmedipham, picloram, 5-�2-chloro-4-(trifluoromethyl)phenoxy!-2-nitroacetophenone oxime-O-acetic acid methyl ester, pretilachlor, primisulfuron, procyazine, profluralin, prometon, prometryn, pronamide, propachlor, propanil, propazine, propham, prosulfalin, prynachlor, pyrazolate, pyrazon, pyrazosulfuron ethyl, quinchlorac, quizalofop ethyl, rimsulfuron, secbumeton, sethoxydim, siduron, simazine, 1-(.alpha.,.alpha.-dimethylbenzyl)-3-(4-methylphenyl)urea, sulfometuron methyl, trichloroacetic acid, tebuthiuron, terbacil, terbuchlor, terbuthylazine, terbutol, terbutryn, thifensulfuron methyl, thiobencarb, tri-allate, trialkoxydim, triasulfuron, tribenuron methyl, triclopyr, tridiphane, trifluralin, trimeturon, (2,4-dichlorophenoxy)acetic acid, 4-(2,4-dichlorophenoxy)butanoic acid, vernolate, and xylachlor.
In certain instances, combinations with other herbicides having a similar spectrum of control but a different mode of action will be particularly advantageous for resistance management.
A herbicidally effective amount of the compounds of this invention is determined by a number of factors. These factors include: formulation selected, method of application, amount and type of vegetation present, growing conditions, etc. In general, a herbicidally effective amount of a compound(s) of this invention is applied at rates from about 0.005 to 5.0 kg/ha with a preferred rate range of 0.010 to 2.0 kg/ha. One skilled in the art can easily determine application rates necessary for the desired level of weed control.
The following Tests demonstrate the control efficacy of the compounds of this invention against specific weeds. The weed control afforded by the compounds is not limited, however, to these species. See Index Tables A and B for compound descriptions.
__________________________________________________________________________Index Table A ##STR21##Compound of Formula Im wherein:Cmpd No. R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 m.p. (.degree.C.).sup.1,2__________________________________________________________________________ 1 6-OH H Cl OCH.sub.2 C CH Cl oil 2 8-OH H Cl OCH.sub.2 C CH Cl 168-170 3 8-Br H Cl OC(O)Me Cl 75-83 4 8-Br H Cl OC(O)Me Cl 77-82 5 8-Br H Cl OS(O).sub.2 (4-CH.sub.3 Ph) Cl oil 6 8-Br 8-Br Cl OS(O).sub.2 (4-CH.sub.3 Ph) Cl 161-162 d 7 6-Br H Cl OCH.sub.2 C CH Cl oil 8 6-F H Cl OCH.sub.2 C CH Cl oil 9 6-(O) Cl OCH.sub.2 C CH Cl oil10 6-OC(O)Me H Cl OCH.sub.2 C CH Cl oil11 8-F H Cl OCH.sub.2 C CH Cl oil12 8-Cl H Cl OCH.sub.2 C CH Cl oil13 7-OH 8-OH Cl OS(O).sub.2 (4-CH.sub.3 Ph) Cl glass14 8-OC(O)Me H Cl OCH.sub.2 C CH Cl oil15 7-OH 8-OH Cl OCH.sub.2 C CH Cl oil16 8-OH H Cl OS(O).sub.2 (4-CH.sub.3 Ph) Cl oil17 8-(O) Cl OS(O).sub.2 (4-CH.sub.3 Ph) Cl oil18 8-(O) Cl OCH.sub.2 C CH Cl oil19 7-OH H Cl OCH.sub.2 C CH Cl oil20 8-F H Cl OCH.sub.3 Cl 148-15121 6-OH H H H F oil22 6-Cl H Cl OCH.sub.2 C CH Cl oil23 8-OH H Cl OCH.sub.3 Cl 245-24724 6-OH H Cl OCH.sub.2 C CH Cl 186-18725 6-F H Cl OCH.sub.2 C CH Cl oil26 6-Cl H Cl OCH.sub.2 C CH Cl oil27 7-Cl H Cl OCH.sub.2 C CH Cl oil28 7-F H Cl OCH.sub.2 C CH Cl oil29 8-OH H Cl OH Cl 238-240 d30 8-Br H Cl OH Cl 187-19031 7-OH 8-OH Cl OH Cl 215-21832 8-OH H Cl OH Cl oil33 8-(O) Cl OH Cl oil__________________________________________________________________________
______________________________________Index Table B ##STR22##Compound of Formula In wherein:Cmpd No. R.sup.1 R.sup.3 R.sup.4 R.sup.5 m.p. (.degree.C.).sup.1______________________________________36 H Cl OS(O).sub.2 (4-CH.sub.3 Ph) Cl oil37 H Cl OH Cl oil38 Br Cl OH Cl 246-24739 Br Cl OC(O)Me Cl oil ##STR23## ##STR24##______________________________________ .sup.1 .sup.1 H NMR data for oils and glass in Index Table C. .sup.2 d = decomposed
INDEX TABLE C______________________________________ .sup.1 HNMR DataCmpd (solvent = CDCl.sub.3 unless otherwise indicated,No. in ppm downfield from tetramethylsilane)______________________________________ 1 7.55(s, 1H), 7.2(s, 1H), 4.8(s, 2H), 4.4(m, 1H), 3.75(m, 2H), 3.2 (s, 1H), 3.0(m, 1H), 2.75(m, 1H), 2.6(s, 1H), 2.1(m, 1H), 1.9 (m, 1H). 5 7.78(d, 2H), 7.55(s, 1H), 7.50(s, 1H), 7.35(d, 2H), 5.27(t, 1H), 4.0(m, 1H), 3.61(m, 1H), 2.45(s, 3H), 2.1-2.5(m, 4H). 7 7.6(s, 1H), 7.1(s, 1H), 4.8(q, 2H), 4.6(m, 1H), 4.0(m, 1H), 3.8 (m, 1H), 3.2(m, 1H), 3.0(m, 1H), 2.6(m, 1H), 2.4(m, 2H). 8 7.55(s, 1H), 7.2(s, 1H), 5.4, 5.2(2m, 1H), 4.8(d, 2H), 4.1(m, 1H), 3.8-3.6(4d, 1H), 2.95(m, 2H), 2.6(m, 1H), 2.5(m, 1H), 2.0 (m, 1H). 9 7.55(s, 1H), 7.2(s, 1H), 4.8(s, 2H), 4.4(s, 2H), 3.15(m, 2H), 2.8 (m, 2H), 2.6(s, 1H).10 7.55(s, 1H), 7.2(s, 1H), 5.4(m, 1H), 4.8(s, 2H), 3.95(m, 1H), 3.8 (dd, 1H), 2.9(m, 2H), 2.6(s, 1H), 2.3(m, 1H), 2.1(s, 3H), 2.0 (m, 1H).11 7.55(s, 1H), 7.2(s, 1H), 5.6, 5.5(2m, 1H), 4.8(s, 2H), 4.0(m, 1H), 3.55(m, 1H), 2.6(m, 1H), 2.5-1.8(m, 4H).12 7.55(s, 1H), 7.2(s, 1H), 5.15(t, 1H), 4.8(s, 2H), 3.95(m, 1H), 3.6(m, 1H), 2.6(m, 1H), 2.5-2.0(m, 4H).13 7.81(d, 2H), 7.63(s, 1H), 7.50(s, 1H), 7.35(d, 2H), 4.62(dd, 1H), 4.15(m, 1H), 3.89(m, 1H), 3.71(m, 1H), 3.55(d, 1H), 2.77(d, 1H), 2.46(s, 3H), 2.36(m, 1H), 2.1(m, 1H).14 7.55(s, 1H), 7.15(m, 1H), 5.95(m, 1H), 4.8(s, 2H), 3.85(m, 1H), 3.6(m, 1H), 2.6(s, 1H), 2.2-2.0(m, 4H), 2.15(s, 3H).15 (solvent = (CD.sub.3).sub.2 SO) 7.85(s, 1H), 7.35(s, 1H), 6.13(d, 1H), 5.44(d, 1H), 4.97(d, 2H), 4.35(m, 1H), 3.95(m, 1H), 3.70(t, 1H), 3.65(m, 1H), 3.5(m, 1H), 2.15(m, 1H), 1.9(m, 1H).16 7.78(d, 2H), 7.60(s, 1H), 7.50(s, 1H), 7.34(d, 2H), 4.85(m, 1H), 2.78(d, 1H), 2.45(s, 3H), 2.25(m, 1H), 2.0(m, 3H).17 7.77(d, 2H), 7.60(s, 1H), 7.53(s, 1H), 7.30(d, 2H), 4.00(m, 2H), 2.86(m, 2H), 2.46(s, 3H), 2.42(m, 2H).18 (solvent = (CD.sub.3).sub.2 SO) 7.92(s, 1H), 7.42(s, 1H), 4.98(d, 2H), 3.8(t, 2H), 3.70(t, 1H), 2.75(t, 2H), 2.25(m, 2H).19 7.54(s, 1H), 7.16(s, 1H), 4.77(d, 2H), 4.40(m, 1H), 3.75-3.90 (m, 2H), 3.6(t, 1H), 2.9-3.0(m, 2H), 2.6(m, 1H), 2.0-2.2(m, 2H).21 7.9(m, 2H), 7.1(m, 2H), 4.5(m, 1H), 3.8(m, 2H), 3.0(m, 1H), 2.8(m, 1H), 2.2(m, 1H), 1.9(m, 1H), 1.6(hr s, 1H).22 7.55(s, 1H), 7.2(s, 1H), 4.8(s, 2H), 4.6(m, 1H), 4.0(m, 2H), 3.15 (m, 1H), 2.9(m, 1H), 2.6(m, 1H), 2.3(m, 2H).25 7.55(s, 1H), 7.2(s, 1H), 6.3, 6.15(2t, 1H), 4.8(d, 2H), 3.0(m, 1H), 2.7(m, 1H), 2.6(m, 1H), 2.5(m, 1H), 2.2-1.8(m, 3H).26 7.55(s, 1H), 7.2(s, 1H), 6.2(m, 1H), 4.8(t, 2H), 3.0(m, 1H), 2.8 (m, 1H), 2.6(m, 1H), 2.6-2.0(m, 4H)27 7.55(s, 1H), 7.2(s, 1H), 4.8(d, 2H), 4.6(m, 1H), 4.0-3.8(m, 2H), 3.2(m, 2H), 2.65(m, 1H), 2.6(m, 1H), 2.4(m, 1H).28 7.6(s, 1H), 7.2(s, 1H), 5.4, 5.2(2q, 1H), 4.8(d, 2H), 4.0-3.75 (m, 2H), 3.3-2.8(m, 2H), 2.6(m, 1H), 2.5(m, 1H), 2.2-2.0(m, 1H).32 (solvent = (CD.sub.3).sub.2 SO) 10.9(s, 1H), 7.65(s, 1H), 7.02(s, 1H), 5.22 (d, 1H), 4.17(m, 1H), 3.55(m, 2H), 2.80(m, 1H), 2.59(dd, 1H), 1.95(m, 2H).33 (solvent = (CD.sub.3).sub.2 SO) 11.1(s, 1H), 7.75(s, 1H), 7.09(s, 1H), 3.78 (t, 2H), 2.74(d, 2H), 2.25(m, 2H).34 7.55(s, 1H), 7.2(s, 1H), 6.4, 6.2(2d, 1H), 4.8(s, 2H), 3.2-2.6(m, 4H), 2.6(s, 1H).35 7.55(s, 1H), 7.2(s, 1H), 5.2(d, 1H), 4.8(d, 2H), 4.0(m, 2H), 2.8 (m, 2H), 2.6(m, 1H).36 7.80(d, 2H), 7.62(s, 1H), 7.48(s, 1H), 7.34(d, 2H), 6.43(m, 2H), 3.89(t, 2H), 2.69(dt, 2H), 2.45(s, 3H).37 7.46(s, 1H), 7.10(s, 1H), 6.4(m, 2H), 3.89(t, 2H), 2.65(m, 2H).39 7.6(s, 1H), 7.35(s, 1H), 6.7(t, 1H), 3.9(t, 2H), 2.7(q, 2H), 2.35 (s, 3H).______________________________________
TEST A
Seeds of barley (Hordeum vulgare), barnyardgrass (Echinochloa crus-galli), bedstraw (Gatlum aparine), blackgrass (Alopecurus myosuroides), cheatgrass (Bromus secalinus), chickweed (Stellaria media), cocklebur (Xanthium pensylvanicum), corn (Zea mays), cotton (Gossypium hirsutum), crabgrass (Digitaria spp.), downy brome (Bromus rectorurn), giant foxtail (Setaria faberii), lambsquarters (Chenopodium album), morningglory (Ipomoea hederacea), rape (Brassica napus), rice (Oryza sativa), sorghum (Sorghum bicolor), soybean (Glycine max), sugar beet (Beta vulgaris), velvetleaf (Abutilon theophrasti), wheat (Triticum aestivum), wild buckwheat (Polygonum convolvulus), wild oat (Avena fatua) and purple nutsedge (Cyperus rotundus) tubers were planted and treated preemergence with test chemicals dissolved in a non-phytotoxic solvent. At the same time, these crop and weed species were also treated with postemergence applications of test chemicals. Plants ranged in height from two to eighteen cm (one to four leaf stage) for postemergence treatments. Treated plants and controls were maintained in a greenhouse for twelve to sixteen days, after which all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table A, are based on a scale of 0 to 10 where 0 is no effect and 10 is complete control. A dash (-) response means no test result.
TABLE A______________________________________ COMPOUNDRate 400 g/ha 8 10 11 12 14 20 21 22 23 35 36 38______________________________________POSTEMERGENCEBarley 9 6 7 8 8 9 0 6 2 4 4 2 Barnyardgrass 10 3 10 10 10 10 0 10 5 9 3 2 Bedstraw 10 5 10 9 8 9 2 10 2 9 1 1 Blackgrass 10 4 10 9 9 10 0 10 2 9 3 2 Chickweed 10 4 10 2 4 3 0 9 0 5 1 2 Cocklebur 9 7 9 8 8 8 0 10 4 7 4 2 Corn 9 5 8 8 9 9 0 7 3 5 3 2 Cotton 10 10 10 10 10 10 0 10 9 10 9 9 Crabgrass 10 4 9 8 8 10 0 9 3 8 4 2 Downy brome 9 4 8 6 5 9 0 8 1 5 2 1 Giant foxtail 10 3 9 9 9 9 0 9 3 8 3 2 Lambsquarter 10 7 10 10 10 10 0 10 9 10 6 4 Morningglory 10 9 10 10 10 10 0 10 7 9 4 2 Nutsedge 10 8 -- 5 6 10 0 6 1 5 0 1 Rape 10 6 10 10 9 9 0 10 7 8 5 1 Rice 10 5 9 8 8 9 0 9 5 6 3 3 Sorghum 10 4 9 9 9 10 0 9 3 6 3 3 Soybean 9 7 9 9 9 9 1 9 5 9 5 3 Sugar beet 10 7 10 10 10 10 0 10 7 10 6 3 Velvetleaf 10 10 10 10 10 10 0 10 9 10 8 2 Wheat 9 6 9 9 8 9 0 6 2 5 4 1 Wild 10 10 10 10 10 10 2 10 9 10 3 2 buckwheat Wild oat 10 5 9 8 9 9 0 9 1 8 3 2PREMERGENCEBarley 6 0 8 8 7 8 0 2 2 0 0 0 Barnyardgrass 10 7 10 9 10 10 0 9 7 4 0 0 Bedstraw 10 3 10 7 9 7 0 10 3 9 2 0 Blackgrass 8 1 10 9 9 10 0 9 2 6 0 0 Chickweed 10 2 10 4 8 4 0 10 0 2 0 0 Cocklebur 10 0 10 5 9 10 0 7 3 2 0 2 Corn 8 3 7 5 10 7 0 9 2 3 0 0 Cotton 9 0 10 7 9 8 0 9 3 1 0 0 Crabgrass 10 1 10 10 10 10 0 10 4 10 0 2 Downy brome 10 0 9 7 10 10 0 8 3 5 1 0 Giant foxtail 10 4 10 9 10 10 0 9 8 10 0 0 Lambsquarter 10 8 10 10 10 10 3 10 10 10 4 0 1 Morningglory 10 1 10 10 10 7 0 10 5 10 0 5 Nutsedge 3 2 3 1 8 4 0 2 8 1 3 0 Rape 10 2 10 10 10 10 0 10 8 8 1 0 Rice 9 5 9 5 8 9 0 5 3 2 0 0 Sorghum 10 2 10 10 9 10 0 7 2 4 0 0 Soybean 9 2 10 7 9 9 0 10 4 1 0 3 Sugar beet 10 4 10 10 10 10 0 10 9 10 3 0 Velvetleaf 10 10 10 10 10 10 0 10 9 10 0 0 Wheat 7 0 10 9 9 9 0 4 6 1 0 0 Wild 10 2 10 10 10 10 0 10 8 10 0 0 buckwheat Wild oat 9 0 10 10 9 10 0 9 6 6 0 0______________________________________ COMPOUNDRate 200 g/ha 6 24 40______________________________________POSTEMERGENCEBarley 2 3 0Barnyardgrass 2 3 1Bedstraw 1 3 2Blackgrass 2 4 3Chickweed 1 2 0Cocklebur 2 3 2Corn 2 2 1Cotton 9 9 2Crabgrass 5 4 1Downy brome 2 3 0Giant foxtail 3 3 2Lambsquarter 4 4 3Morningglory 3 5 1Nutsedge 1 1 --Rape 3 3 0Rice 3 3 1Sorghum 3 4 1Soybean 3 2 3Sugar beet 5 8 0Velvetleaf 6 7 4Wheat 5 4 0Wild buckwheat 4 3 3Wild oat 3 3 2PREEMERGENCEBarley 1 0 0Barnyardgrass 0 0 0Bedstraw 2 0 0Blackgrass 1 0 2Chickweed 0 0 0Cocklebur 0 0 0Corn 0 0 0Cotton 0 0 0Crabgrass 3 0 0Downy brome 1 0 2Giant foxtail 0 0 0Lambsquarter 0 0 0Morningglory 0 0 0Nutsedge 0 0 0Rape 1 0 0Rice 0 0 0Sorghum 0 0 0Soybean 0 0 0Sugar beet 0 0 0Velvetleaf 3 0 0Wheat 0 0 0Wild buckwheat 2 0 0Wild oat 0 0 0______________________________________ COMPOUNDRate 50 g/ha 6 24 37 40______________________________________POSTEMERGENCEBarley 1 3 1 0Barnyardgrass 2 3 2 1Bedstraw 1 3 0 2Blackgrass 1 3 2 2Chickweed 1 0 0 0Cocklebur 1 2 0 2Corn 2 2 1 1Cotton 5 9 4 2Crabgrass 3 4 2 1Downy brome 0 2 0 0Giant foxtail 2 2 2 1Lambsquarter 2 3 0 3Morningglory 2 2 0 1Nutsedge 1 0 0 --Rape 2 0 0 0Rice 2 3 0 1Sorghum 2 3 2 1Soybean 3 2 1 2Sugar beet 4 7 2 0Velvetleaf -- 7 0 3Wheat 4 3 2 0Wild buckwheat 3 2 0 1Wild oat 3 3 2 2PREEMERGENCEBarley 1 0 0 0Barnyardgrass 0 0 0 0Bedstraw 0 0 0 0Blackgrass 1 0 0 0Chickweed 0 0 0 0Cocklebur 0 0 0 0Corn 0 0 2 0Cotton 0 0 0 0Crabgrass 0 0 3 0Downy brome 0 0 0 0Giant foxtail 0 0 2 0Lambsquarter 0 0 0 0Morningglory 0 0 0 0Nutsedge 0 0 0 0Rape 1 0 2 0Rice 0 0 0 0Sorghum 0 0 0 0Soybean 0 0 0 0Sugar beet 0 0 0 0Velvetleaf 0 0 0 0Wheat 0 0 0 0Wild buckwheat 0 0 0 0Wild oat 0 0 0 0______________________________________Rate COMPOUND100 g/ha 8 9 10 11 12 14 20 21 22 23 35 36 38______________________________________Barley 7 4 3 7 5 5 7 0 4 1 4 3 1 Barnyard- 9 2 2 9 9 9 9 0 9 3 9 3 1 grass Bedstraw 9 7 4 10 9 6 9 0 9 2 6 1 1 Blackgrass 9 4 4 9 8 4 7 0 5 1 4 2 1 Chick- 9 5 4 7 1 3 3 0 6 0 4 1 1 weed Cocklebur 9 4 6 10 7 7 7 0 7 3 7 3 1 Corn 8 2 2 7 5 5 5 0 6 3 2 3 1 Cotton 10 9 9 10 10 10 10 0 10 9 9 9 6 Crabgrass 7 3 3 8 8 3 6 0 8 3 4 3 2 Downy 7 3 3 8 5 3 7 0 3 1 4 2 brome Giant 6 3 3 9 8 5 7 0 9 3 6 3 1 foxtail Lambs- 10 4 6 10 10 10 9 0 10 8 10 4 2 quarter Morning- 9 7 9 10 10 9 10 0 9 7 8 4 2 glory Nutsedge 10 1 4 4 3 2 2 0 3 1 2 0 1 Rape 9 4 6 9 9 8 8 0 10 5 7 3 1 Rice 8 5 4 9 7 5 7 0 9 3 4 3 2 Sorghum 9 4 3 8 7 8 9 0 9 3 4 3 3 Soybean 9 6 6 8 8 9 8 0 9 4 5 3 2 Sugar beet 10 7 7 10 8 10 10 0 9 6 8 4 2 Velvetleaf 10 7 7 10 9 9 10 0 10 5 8 5 1 Wheat 9 5 3 9 7 7 8 0 6 1 5 4 1 Wild 10 8 7 10 10 10 9 0 10 7 9 2 2 buckwheat Wild oat 8 3 3 8 4 6 8 0 8 0 5 2 1PREEMERGENCEBarley 6 1 0 6 2 4 4 0 1 0 0 0 0 Barnyard- 9 0 1 10 8 9 10 0 8 2 1 0 0 grass Bedstraw 9 1 2 10 10 0 3 0 8 0 1 0 0 Blackgrass 7 2 1 9 7 5 9 0 8 0 3 1 0 Chick- 10 0 0 9 2 0 2 0 10 0 3 0 0 weed Cocklebur 3 0 0 6 2 4 5 0 5 2 0 0 1 Corn 7 0 0 6 4 6 3 0 5 0 1 0 0 Cotton 10 0 -- 7 0 2 1 0 2 0 0 0 0 Crab- 10 0 -- 10 8 9 10 0 10 2 6 0 0 grass Downy 6 2 0 6 7 5 8 0 6 1 3 0 0 brome Giant 9 0 0 10 8 9 10 0 9 8 6 0 0 foxtail Lambs- 10 6 4 10 10 10 10 0 10 9 10 2 0 quarter Morning- 10 0 0 8 3 6 6 0 10 4 10 0 0 glory Nutsedge 1 -- 0 2 0 1 2 0 1 0 0 0 0 Rape 8 1 2 10 5 8 9 0 9 3 2 1 0 Rice 7 0 2 8 4 6 7 0 3 2 0 0 0 Sorghum 9 0 0 4 3 7 5 0 3 0 0 0 0 Soybean 10 0 2 8 4 9 6 0 9 2 0 0 1 Sugar beet 10 6 2 10 10 10 10 0 10 7 10 2 0 Velvetleaf 10 4 5 10 9 10 10 0 10 9 9 0 0 Wheat 7 1 0 7 1 7 5 0 2 1 2 0 0 Wild 10 1 0 10 8 10 9 0 6 3 7 0 0 buckwheat Wild oat 8 0 0 9 5 7 7 0 9 2 3 0 0______________________________________ COMPOUNDRate 20 g/ha 9______________________________________POSTEMERGENCEBarley 3Barnyardgrass 2Bedstraw 5Blackgrass 1Chickweed 3Cocklebur 4Corn 2Cotton 7Crabgrass 4Downy brome 1Giant foxtail 4Lambsquarter 4Morningglory 6Nutsedge --Rape 3Rice 4Sorghum 3Soybean 5Sugar beet 4Velvetleaf 5Wheat 4Wild buckwheat 7Wild oat 3PREEMERGENCEBarley 0Barnyardgrass 0Bedstraw 1Blackgrass 0Chickweed 0Cocklebur 0Corn 0Cotton 0Crabgrass 0Downy brome 0Giant foxtail 0Lambsquarter 0Morningglory 0Nutsedge 0Rape 1Rice 0Sorghum 0Soybean 0Sugar beet 2Velvetleaf 3Wheat 0Wild buckwheat 1Wild oat 0______________________________________ COMPOUNDRate 10 g/ha 37______________________________________POSTEMERGENCEBarley 0Barnyardgrass 0Bedstraw 0Blackgrass 0Chickweed 0Cocklebur 0Corn 0Cotton 0Crabgrass 1Downy brome 0Giant foxtail --Lambsquarter 0Morningglory --Nutsedge 0Rape 0Rice 0Sorghum 0Soybean 0Sugar beet 0Velvetleaf 0Wheat 1Wild buckwheat 0Wild oat 1PREEMERGENCEBarley 0Barnyardgrass 0Bedstraw 0Blackgrass 0Chickweed 0Cocklebur 0Corn 0Cotton 0Crabgrass 0Downy brome 0Giant foxtail 0Lambsquarter 0Morningglory 0Nutsedge 0Rape 0Rice 0Sorghum 0Soybean 0Sugar beet 0Velvetleaf 0Wheat 0Wild buckwheat 0Wild oat 0______________________________________
TEST B
Seeds of barnyardgrass (Echinochloa crus-galli), cheatgrass (Bromus secalinus), cocklebur (Xanthium pensylvanicum), crabgrass (Digitaria spp.), giant foxtail (Setaria faberii), morningglory (Ipomoea spp.), sorghum (Sorghum bicolor), velvetleaf (Abutilon theophrasti), and wild oat (Avenafatua) were planted into a sandy loam soil and treated preemergence, or with a soil drench(PDRN), with test chemicals dissolved in a non-phytotoxic solvent. At the same time, these crop and weed species were also treated postemergence, or sprayed to runoff(STRO), with test chemicals. Plants ranged in height from two to eighteen cm and were in the two to three leaf stage for the postemergence treatment. Treated plants and untreated controls were maintained in a greenhouse for approximately eleven days, after which all treated plants were compared to untreated controls and visually evaluated for injury. Plant response ratings, summarized in Table B, are based on a 0 to 10 scale where 0 is no effect and 10 is complete control. A dash (-) response means no test results.
TABLE B______________________________________ COMPOUNDRate 2000 g/ha 7______________________________________PDRNBarnyardgrass 0Cocklebur 0Crabgrass 0Downy brome 0Giant foxtail 0Morningglory 0Sorghum 0Velvetleaf 0Wild oats 0STROBarnyardgrass 1Cocklebur 0Crabgrass 1Downy brome 1Giant foxtail 2Morningglory 1Sorghum 1Velvetleaf 5Wild oats 2______________________________________ COMPOUNDRate 800 g/ha 3 4 13 30______________________________________PREEMERGENCEBarnyardgrass 0 0 0 0Cocklebur 0 0 0 0Crabgrass 0 0 0 0Downy brome 0 0 0 0Giant foxtail 0 0 0 0Morningglory 0 0 0 0Sorghum 0 0 0 0Velvetleaf 0 0 0 0Wild oats 0 0 0 0POSTEMERGENCEBarnyardgrass 2 2 1 2Cocklebur 2 1 0 1Crabgrass 1 1 1 1Downy brome 1 1 0 1Giant foxtail 1 1 0 2Morningglory 0 0 1 0Sorghum 3 2 1 2Velvetleaf 3 2 1 2Wild oats 1 1 0 2______________________________________
TEST C
The compounds evaluated in this test were formulated in a non- phytoxic solvent and applied to the soil surface before plant seedlings emerged (preemergence application), to water that covered the soil surface (flood application), and to plants that were in the one-to-four leaf stage (postemergence application). A sandy loam soil was used for the preemergence and postemergence tests, while a silt loam soil was used in the flood test. Water depth was approximately 2.5 cm for the flood test and was maintained at this level for the duration of the test.
Plant species in the preemergence and postemergence tests consisted of barnyardgrass (Echinochloa crus-galli), barley (Hordeum vulgare), bedstraw (Galium aparine), blackgrass (Alopecurus myosuroides), chickweed (Stellaria media), cocklebur (Xanthium pensylvanicum), corn (Zea mays), cotton (Gossypium hirsutum), crabgrass (Digitaria sanguinalis), downy brome (Bromus tectorum), giant foxtail (Setaria faberii), johnsongrass (Sorghum halpense), lambsquarters (Chenopodium album), morningglory (Ipomoea hederacea), pigweed (Amaranthus retroflexus), rape (Brassica napus), ryegrass (Lolium multiflorum), sorghum (Sorghum bicolor), soybean (Glycine max), speedwell (Veronica persica), sugar beet (Beta vulgaris), velvetleaf (Abutilon theophrasti), wheat (Triticum aestivum), wild buckwheat (Polygonum convolvulus), and wild oat (Avena fatua). All plant species were planted one day before application of the compound for the preemergence portion of this test. Plantings of these species were adjusted to produce plants of appropriate size for the postemergence portion of the test. Plant species in the flood test consisted of rice (Oryza sativa), umbrella sedge (Cyperus difformis), duck salad (Heteranthera limosa), barnyardgrass (Echinochloa crus-galli) and Late watergrass (Echinocloa oryzicola) grown to the 1 and 2 leaf stage for testing.
All plant species were grown using normal greenhouse practices. Visual evaluations of injury expressed on treated plants, when compared to untreated controls, were recorded approximately fourteen to twenty one days after application of the test compound. Plant response ratings, summarized in Table C, were recorded on a 0 to 100 scale where 0 is no effect and 100 is complete control. A dash (-) response means no test result.
TABLE C______________________________________ COMPOUNDRate 125 g/ha 11 12 14 20______________________________________POSTEMERGENCEBarley Igri 65 35 45 85Barnyardgrass 100 95 85 80Blackgrass 100 40 50 45Chickweed 85 45 30 35Cocklebur 55 65 65 70Corn 50 65 35 50Cotton 100 100 100 100Crabgrass 35 65 80 90Downy Brome 90 55 45 90Duck salad 35 20 50 90Galium 100 60 65 70Giant foxtail 95 95 80 95Italn. Rygrass 100 55 75 100Johnsongrass 100 95 100 100Lambsquarters 100 100 100 95Morningglory 100 100 100 95Rape 100 100 100 100Redroot Pigweed 100 90 100 100Rice Japonica 95 80 95 90Soybean 85 75 90 90Speedwell 100 100 100 --Sugar beet 100 100 100 100Umbrella sedge 100 60 45 90Velvetleaf 100 100 100 100Watergrass 2 100 100 90 95Wheat 100 35 45 100Wild buckwheat 100 100 100 100Wild oat 100 60 65 952 Leaf BYG 100 100 100 95PREEMERGENCEBarley Igri 70 15 25 55Barnyardgrass 95 100 100 100Blackgrass 100 80 60 95Chickweed 100 0 25 60Cocklebur 35 0 85 65Corn 65 0 85 70Cotton 95 0 90 85Crabgrass 100 95 100 100Downy Brome 90 01 30 55Galium 100 80 90 30Giant foxtail 100 100 100 100Italn. Rygrass 100 90 80 100Johnsongrass 100 95 100 100Lambsquarters 100 100 100 100Morningglory 85 30 65 95Rape 100 95 95 100Redroot Pigweed 100 100 90 100Soybean 60 25 40 90Speedwell 100 55 100 100Sugar beet 100 100 100 100Velvetleaf 100 100 100 100Wheat 80 45 35 95Wild buckwheat 100 100 100 100Wild oat 100 55 60 70POSTEMERGENCEBarley Igri 65 35 45 85Barnyardgrass 100 95 85 80Blackgrass 100 40 50 45Chickweed 85 45 30 35Cocklebur 55 65 65 70Corn 50 65 35 50Cotton 100 100 100 100Crabgrass 35 65 80 90Downy Brome 90 55 45 90Duck salad 35 20 50 90Galium 100 60 65 70Giant foxtail 95 90 80 95Italn. Rygrass 100 55 75 100Johnsongrass 100 95 100 100Lambsquarters 100 100 100 95Morningglory 100 100 100 95Rape 100 100 100 100Redroot Pigweed 100 90 100 100Rice Japonica 95 80 95 90Soybean 85 75 90 90Speedwell 100 100 100 --Sugar beet 100 100 100 100Umbrella sedge 100 60 45 90Velvetleaf 100 100 100 100Watergrass 2 100 100 90 95Wheat 100 35 45 100Wild buckwheat 100 100 100 100Wild oat 100 60 65 952 Leaf BYG 100 100 100 95PREEMERGENCEBarley Igri 70 15 25 55Barnyardgrass 95 100 100 100Blackgrass 100 80 60 95Chickweed 100 0 25 60Cocklebur 35 0 85 65Corn 65 0 85 70Cotton 95 0 90 85Crabgrass 100 95 100 100Downy Brome 90 10 30 55Galium 100 80 90 30Giant foxtail 100 100 100 100Italn. Rygrass 100 90 80 100Johnsongrass 100 95 100 100Lambsquarters 100 100 100 100Morningglory 85 30 65 95Rape 100 95 95 100Redroot Pigweed 100 100 90 100Soybean 60 25 40 90Speedwell 100 55 100 100Sugar beet 100 100 100 100Velvetleaf 100 100 100 100Wheat 80 45 35 95Wild buckwheat 100 100 100 100Wild oat 100 55 60 70______________________________________ COMPOUNDRate 62 g/ha 11 12 14 20 22______________________________________POSTEMERGENCEBarley Igri 65 35 45 85 0Barnyardgrass 100 65 45 80 95Blackgrass 95 40 50 35 65Chickweed 80 30 30 20 95Cocklebur 50 45 45 45 95Corn 35 30 35 50 60Cotton 100 100 100 100 100Crabgrass 35 35 25 70 35Downy Brome 85 50 45 40 65Duck salad 30 0 0 85 60Galium 100 55 65 20 100Giant foxtail 95 90 45 95 100Italn. Rygrass 95 50 60 90 75Johnsongrass 90 95 90 100 100Lambsquarters 100 100 100 95 100Morningglory 100 95 100 95 95Rape 100 100 95 80 100Redroot Pigweed 100 90 100 100 100Rice Japonica 95 70 80 80 75Soybean 80 75 80 85 75Speedwell 100 95 100 -- 100Sugar beet 100 100 100 100 100Umbrella sedge 95 30 30 90 80Velvetleaf 100 90 100 100 100Watergrass 2 100 100 75 95 95Wheat 95 30 45 95 65Wild buckwheat 100 95 100 95 100Wild oat 95 60 30 85 852 Leaf BYG 100 100 85 90 95PREEMERGENCEBarley Igri 50 0 0 35 25Barnyardgrass 95 85 80 90 95Blackgrass 100 45 30 80 65Chickweed 40 0 0 30 95Cocklebur 10 0 30 50 30Corn 50 0 65 50 65Cotton 55 0 60 75 0Crabgrass 100 85 90 100 100Downy Brome 70 0 30 55 35Galium 80 40 10 10 100Giant foxtail 100 95 50 100 90Italn. Rygrass 95 65 40 95 90Johnsongrass 100 95 100 95 95Lambsquarters 100 90 100 100 100Morningglory 40 0 30 0 80Rape 100 24 0 80 80Redroot Pigweed 100 100 75 100 100Soybean -- 25 35 70 95Speedwell 100 40 95 100 100Sugar beet 100 0 100 100 95Velvetleaf 100 100 100 100 100Wheat 65 0 0 90 40Wild buckwheat 100 45 95 95 100Wild oat 85 10 0 70 70______________________________________ COMPOUNDRate 31 g/ha 11 12 14 20 22______________________________________POSTEMERGENCEBarley Igri 55 35 40 50 0Barnyardgrass 85 25 40 80 65Blackgrass 50 35 35 25 60Chickweed 65.230 30 20 80Cocklebur 0 40 40 45 50Corn 0 30 25 50 35Cotton 100 100 100 100 100Crabgrass 0 30 25 65 10Downy Brome 75 40 35 40 35Duck salad 0 0 0 0 10Galium 95 45 45 15 100Giant foxtail 65 70 45 95 55Italn. Rygrass 85 45 45 80 55Johnsongrass 60 90 90 95 95Lambsquarters 100 95 100 95 100Morningglory 90 95 90 90 85Rape 95 100 95 65 100Redroot Pigweed 100 65 100 100 100Rice Japonica 85 65 55 35 70Soybean 60 75 50 75 75Speedwell 100 85 100 -- 100Sugar beet 100 100 100 85 100Umbrella sedge 75 20 0 75 80Velvetleaf 100 90 100 100 100Watergrass 2 100 85 65 50 80Wheat 60 25 45 90 45Wild buckwheat 100 90 100 80 100Wild oat 40 35 20 80 302 Leaf BYG 100 60 50 30 80PREEMERGENCEBarley Igri 35 0 0 0 0Barnyardgrass 85 75 75 65 85Blackgrass 95 20 0 45 50Chickweed 40 0 0 0 65Cocklebur 0 0 10 25 20Corn 35 0 20 35 60Cotton 25 0 0 35 0Crabgrass 90 55 40 100 95Downy Brome 60 0 30 10 0Galium 35 0 0 0 50Giant foxtail 100 85 15 100 70Italn. Rygrass 95 20 20 45 80Johnsongrass 100 55 95 95 85Lambsquarters 100 90 90 100 100Morningglory 40 0 0 0 65Rape 100 0 0 45 35Redroot Pigweed 100 100 75 100 100Soybean 60 10 30 25 65Speedwell 100 0 30 100 100Sugar beet 90 0 45 100 80Velvetleaf 100 100 100 100 100Wheat 50 0 0 0 0Wild buckwheat 95 0 35 90 75Wild oat 75 0 0 35 30______________________________________ COMPOUNDRate 16 g/ha 11 12 14 20 22______________________________________POSTEMERGENCEBarley Igri 45 25 35 50 0Barnyardgrass 70 0 35 0 40Blackgrass 35 30 25 25 50Chickweed 45 20 20 20 80Cocklebur 0 40 35 -- 50Corn 0 25 20 35 10Cotton 65 100 80 100 95Crabgrass 0 30 25 45 10Downy Brome 60 40 30 25 30Duck salad 0 0 0 0 0Galium -- 45 45 0 0Giant foxtail 20 20 40 50 45Italn. Rygrass 80 30 45 40 25Johnsongrass 20 70 85 50 90Lambsquarters 100 90 95 95 100Morningglory 80 65 90 85 85Rape 80 100 85 50 100Redroot Pigweed 85 50 85 -- 20Rice Japonica 70 55 35 35 20Soybean 55 75 45 55 75Speedwell 100 85 100 -- 100Sugar beet 100 100 100 40 100Umbrella sedge 70 0 0 65 70Velvetleaf 90 85 100 100 100Watergrass 2 70 30 0 35 65Wheat 55 25 35 50 30Wild buckwheat 95 90 70 35 100Wild oat 30 30 10 65 252 Leaf BYG 80 40 25 20 60PREEMERGENCEBarley Igri 35 0 0 0 0Barnyardgrass 65 0 0 65 30Blackgrass 95 0 0 25 40Chickweed 0 0 0 0 40Cocklebur 0 0 0 0 0Corn 20 0 0 0 0Cotton 25 0 0 10 0Crabgrass 85 50 40 60 95Downy Brome 50 0 30 10 0Galium 0 0 0 0 0Giant foxtail 95 0 10 50 70Italn. Rygrass 85 0 0 35 10Johnsongrass 95 30 35 90 75Lambsquarters 100 70 80 100 100Morningglory 35 0 0 0 65Rape 100 0 0 25 0Redroot Pigweed 100 70 45 100 100Soybean 30 0 0 10 40Speedwell 100 0 0 0 90Sugar beet -- 0 0 95 80Velvetleaf 100 40 100 0 100Wheat 30 0 0 0 0Wild buckwheat 75 0 30 80 60Wild oat 40 0 0 35 15______________________________________ COMPOUNDRate 8 g/ha 22______________________________________POSTEMERGENCEBarley Igri 0Barnyardgrass 35Blackgrass 35Chickweed 70Cocklebur 35Corn 10Cotton 95Crabgrass 0Downy Brome 30Duck salad 0Galium 0Giant foxtail 30Italn. Rygrass 0Johnsongrass 75Lambsquarters 95Morningglory 85Rape 85Redroot Pigweed 10Rice Japonica 5Soybean 65Speedwell 40Sugar beet 80Umbrella sedge 10Velvetleaf 100Watergrass 2 20Wheat 30Wild buckwheat 75Wild oat 202 Leaf BYG 10PREEMERGENCEBarley Igri 0Barnyardgrass 10Blackgrass 0Chickweed 0Cocklebur 0Corn 0Cotton 0Crabgrass 95Downy Brome 0Galium 0Giant foxtail 55Italn. Rygrass 0Johnsongrass 50Lambsquarters 95Morningglory 60Rape 0Redroot Pigweed 90Soybean 10Speedwell 0Sugar beet 35Velvetleaf 65Wheat 0Wild buckwheat 45Wild oat 0______________________________________
TEST D
Seeds of barnyardgrass (Echinochloa crus-galli), bindweed (Convolvolus erubescens), black nightshade (Solanum ptycanthum dunal), cassia (Cassia unifloria), cocklebur (Xanthium pensylvanicum), common ragweed (Ambrosia artemisiifolia), corn (Zea mays), cotton (Gossypium hirsutam), crabgrass (Digitaria spp.), fall panicum (Panicum dichotomifiorum), giant foxtail (Setaria faberii), green foxtail (Setaria viridis), jimsonweed (Datura stramonium), johnson grass (Sorghum halepense), lambsquarter (Chenpopdium album), morningglory (Ipomoea spp.), pigweed (Amaranthus retroflexus), prickly sida (Sida spinosa), shattercane (Sorghum vulgare), signalgrass (Brachiaria platyphylla), smartweed (Polygonum persicaria), soybean (Glycine max), sunflower (Helianthus annuus), velvetleaf (Abutilon theophrasti), wild proso (Pancium miliaceum), wooly cup grass (Eriochloa villosa), yellow foxtail (Setaria lutescens) and purple nutsedge (Cyperus rotundus) tubers were planted into a matapeake sandy loam soil. These crops and weeds were grown in the greenhouse until the plants ranged in height from two to eighteen cm (one to four leaf stage), then treated postemergence with the test chemicals dissolved in a non-phytotoxic solvent. Pots receiving these postemergence treatments were placed in the greenhouse and maintained according to routine greenhouse procedures. Treated plants and untreated controls were maintained in the greenhouse approximately 14-21 days after application of the test compound. Visual evaluations of plant injury responses were then recorded. Plant response ratings, summarized in Table D, are reported on a 0 to 100 scale where 0 is no effect and 100 is complete control.
TABLE D______________________________________PREEMERGENCE COMPOUNDRate 280 g/ha 12______________________________________Barnyardgrass 100Bindweed 100Blk Nightshade 100Cassia 70Cocklebur 55Corn 80Cotton 90Crabgrass 100Fall Panicum 100Giant Foxtail 100Green Foxtail 100Jimson Weed 100Johnson Grass 100Lambsquarter 100Morningglory 100Nustedge 25Pigweed 100Prickly Sida 100Ragweed 90Shattercane 95Signalgrass 100Smartweed 100Soybean 100Sunflower 80Velvetleaf 100Wild Proso 100Wolly Cup Grass 95Yellow Foxtail 100______________________________________ COMPOUNDRate 17.5 g/ha 12______________________________________Barnyardgrass 65Bindweed 0Blk Nightshade 0Cassia 100Cocklebur 0Corn 0Cotton 0Crabgrass 60Fall Panicum 65Giant Foxtail 60Green Foxtail 55Jimson Weed 15Johnson Grass 80Lambsquarter 100Morningglory 0Nustedge 0Pigweed 65Prickly Sida 50Ragweed 15Shattercane 15Signalgrass 20Smartweed 70Soybean 0Sunflower 0Velvetleaf 50Wild Proso 20Wolly Cup Grass 10Yellow Foxtail 55______________________________________ COMPOUNDRate 140 g/ha 12______________________________________Barnyardgrass 100Bindweed 100Blk Nightshade 100Cassia 50Cocklebur 25Corn 70Cotton 65Crabgrass 100Fall Panicum 100Giant Foxtail 100Green Foxtail 100Jimson Weed 100Johnson Grass 100Lambsquarter 100Morningglory 45Nustedge 15Pigweed 100Prickly Sida 100Ragweed 90Shattercane 80Signalgrass 90Smartweed 100Soybean 65Sunflower 65Velvetleaf 100Wild Proso 100Wolly Cup Grass 80Yellow Foxtail 90______________________________________ COMPOUNDRate 70 g/ha 12______________________________________Barnyardgrass 95Bindweed 100Blk Nightshade 100Cassia 30Cocklebur 15Corn 55Cotton 15Crabgrass 100Fall Panicum 100Giant Foxtail 100Green Foxtail 100Jimson Weed 70Johnson Grass 100Lambsquarter 100Morningglory 30Nustedge 0Pigweed 100Prickly Sida 100Ragweed 50Shattercane 60Signalgrass 90Smartweed 100Soybean 15Sunflower 25Velvetleaf 100Wild Proso 80Wolly Cup Grass 65Yellow Foxtail 85______________________________________ COMPOUNDRate 35 g/ha 12______________________________________Barnyardgrass 75Bindweed 15Blk Nightshade 100Cassia 0Cocklebur 0Corn 25Cotton 0Crabgrass 65Fall Panicum 100Giant Foxtail 75Green Foxtail 75Jimson Weed 55Johnson Grass 85Lambsquarter 100Morningglory 0Nustedge 0Pigweed 80Prickly Sida 65Ragweed 50Shattercane 15Signalgrass 60Smartweed 95Soybean 0Sunflower 15Velvetleaf 70Wild Proso 40Wolly Cup Grass 10Yellow Foxtail 65______________________________________
TEST E
Seeds, rhizomes, or plant parts of alfalfa (Medicago sativa), annual bluegrass (Poa annua), bermudagrass (Cynodon dactylon), broadleaf signalgrass (Brachiaria platyphylia), common purslane (Portulaca oleracea), common ragweed (Ambrosia artemisiifolia), dallisgrass (Paspalum dilatatum), goosegrass (Eleusine indica), guineagrass (Panicum maximum), itchgrass (Rottboellia cochinchinensis), johnsongrass (Sorghum halepense), large crabgrass (Digitaria sanguinalis), peanut (Arachis hypoagaea), pitted momingglory (Ipomoea lacunosa), purple nutsedge (Cyperus rotundus), sandbur (Southern sandbur), smooth crabgrass (Digitaria ischaemum) were planted into greenhouse pots containing greenhouse planting medium. Each pot contained only one plant species.
The test compound was dissolved in a non-phytotoxic solvent and applied preemergence and/or postemergence to the plants. Preemergence applications were made within one day of planting the seeds or plant parts. Postemergence applications were applied when the plants were in the two to four leaf stage (three to twenty cm). Untreated control plants and treated plants were placed in the greenhouse and visually evaluated for injury at 14 to 28 days after herbicide application. Plant response ratings, summarized in Table E, are based on a 0 to 100 scale where 0 is no injury and 100 is complete control. A dash (-) response indicates no test result.
TABLE 3______________________________________ COMPOUNDRate 0500 g/ha 11______________________________________POSTEMERGENCEAlfalfa Var. 100Ann Bluegrass 100Bermudagrass 100Brdlf Sgnlgrass 100Cmn Purslane 100Cmn Ragweed 100Dallisgrass 100Goosegrass 100Guineagrass 100Itchgrass 100Johnsongrass 98Large Crabgrass 95Peanuts 95Pit Morninglory 70Purple Nustedge 75S. Sandbur 100Smooth Crabgras 90PREEMERGENCEAlfalfa Var. 100Ann Bluegrass 100Bermudagrass 100Brdlf Sgnlgrass 100Cmn Purslane 100Cmn Ragweed 100Dallisgrass 100Goosegrass 100Guineagrass 100Itchgrass 98Johnsongrass 100Large Crabgrass 100Peanuts 60Pit Morninglory 10Purple Nustedge 90S. Sandbur 100Smooth Crabgras 100______________________________________ COMPOUNDRate 0250 g/ha 1 8 11______________________________________Alfalfa Var. 0 20 98Ann Bluegrass 0 50 95Bermudagrass 0 40 98Brdlf Sgnlgrass 0 70 100Cmn Purslane 30 50 100Cmn Ragweed -- -- 100Dallisgrass 0 0 100Goosegrass 20 40 90Guineagrass 0 90 75Itchgrass 0 60 95Johnsongrass 0 70 100Large Crabgrass 0 50 80Peanuts 0 60 98Pit Morninglory 0 70 75Purple Nustedge 0 40 80S. Sandbur -- 50 95Smooth Crabgras 0 70 75PREEMERGENCEAlfalfa Var. 30 100 100Ann Bluegrass 0 80 100Bermudagrass 20 100 100Brdlf Sgnlgrass 0 100 100Cmn Purslane 0 100 100Cmn Ragweed -- -- 100Dallisgrass 40 100 100Goosegrass 50 100 100Guineagrass 80 100 100Itchgrass 0 90 100Johnsongrass 0 100 100Large Crabgrass 60 100 100Peanuts 0 20 60Pit Morninglory 0 0 100Purple Nustedge 0 0 80S. Sandbur 50 100 100Smooth Crabgras 30 100 100______________________________________ COMPOUNDRate 0125 g/ha 8 11 34______________________________________POSTEMERGENCEAlfalfa Var. 0 50 20Ann Bluegrass 0 65 20Bermudagrass 0 98 60Brdlf Sgnlgrass 50 20 10Cmn Purslane 50 80 10Cmn Ragweed -- 95 --Dallisgrass 0 65 0Goosegrass 20 50 10Guineagrass 70 20 0Itchgrass 60 40 0Johnsongrass 20 40 10Large Crabgrass 0 30 0Peanuts 30 60 30Pit Morninglory 30 20 90Purple Nustedge -- 20 60S. Sandbur 30 30 0Smooth Crabgras 30 15 0PREEMERGENCEAlfalfa Var. 30 100 60Ann Bluegrass 80 90 0Bermudagrass 100 90 100Brdlf Sgnlgrass 80 100 40Cmn Purslane 100 100 100Cmn Ragweed -- 100 --Dallisgrass 100 100 80Goosegrass 100 100 100Guineagrass 100 100 100Itchgrass 90 80 20Johnsongrass 100 100 30Large Crabgrass 100 100 80Peanuts 20 10 0Pit Morninglory 0 10 50Purple Nustedge 0 20 0S. Sandbur 100 90 60Smooth Crabgras 100 90 80______________________________________

Herbicidal triazolinones

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