GB2327418A - Derivatives of 2-benzoylcyclohexane-1,3-dione - Google Patents
Derivatives of 2-benzoylcyclohexane-1,3-dione Download PDFInfo
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- GB2327418A GB2327418A GB9715162A GB9715162A GB2327418A GB 2327418 A GB2327418 A GB 2327418A GB 9715162 A GB9715162 A GB 9715162A GB 9715162 A GB9715162 A GB 9715162A GB 2327418 A GB2327418 A GB 2327418A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/06—Benzimidazoles; Hydrogenated benzimidazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/04—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/04—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles
- C07D249/06—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles with aryl radicals directly attached to ring atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
- C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D257/04—Five-membered rings
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Abstract
2-benzoylcyclohexane-1,3-dione derivatives of formula I: wherein XR 3 represents a nitrogen containing heterocycle (e.g. a diazole, triazole or tetrazole) attached directly or indirectly to the phenyl ring, z is 1 or 2 and R 1 is 2-cyclohexyl-1,3-dione or a derivative thereof; compositions containing them and their use as herbicides.
Description
Herbicides
This invention relates to novel 2-benzoylcyclohexane- 1,3-dione and related derivatives, compositions containing them, processes for their preparation, intermediates in their preparation and their use as herbicides.
Herbicidal 2-benzoylcyclohexane-1,3-diones are described in US
Publication numbers 4,780,127 and 5,536,703, and WO 9626192 as well as EP 0666254. amongst other references. However none of the above publications disclose or suggest the presence of an aromatic heterocyclic ring linked by a ring nitrogen atom (optionally via a methylene) to the benzoyl ring.
The present invention provides 2-benzoylcyclohexane-1,3-dione derivatives of formula (I):
wherein:
R1 represents a group of formula (II), (III), (IV) or (V):
or a corresponding formula (IVa) or (Va):
in which the position of the carbonyl group and the group Q are reversed and the double bond in the ring is attached to the carbon atom attached to the group Q;
R2 represents:
halogen;
lower alkyl which is substituted by one or more groups -OR10;
a cycloalkyl group containing from three to six carbon atoms; or a group selected from nitro, cyano, -CO2R10, -NR10R1 1, -S(O)pR12, -O(CH2)mOR10, -COR10, -N(R13)SO2R12, -OR12, -OH, -OSO2R12, -(CR14R1 S)tS(O)qRl 2, -CONR10Rl -N(R1 3)-C(Z)=Y, -C(R14R15)NR13R16, CH2P(O)Rl0aRlobX R17, SF5 and benzyl optionally substituted by from one to five groups R18 which may be the same or different;
or two groups R2, together with adjacent carbon atoms of the phenyl ring form a second phenyl ring or a 5- or 6-membered saturated or unsaturated heterocyclic ring which is fused to the first ring and contains one or two oxygen or sulphur atoms and is optionally substituted by one or more halogen, lower alkyl, lower haloalkyl or lower alkoxy groups, or one of the ring carbon atoms of the heterocyclic ring forms part of a carbonyl group or an oxime or lower alkoxyimine derivative thereof; (examples of the optionally substituted fused ring systems when formed include thiochroman, chroman, 2H-thiochromene, 2H-chromene, 4H-thiochromene, 4H-chromene, isothiochroman, isochroman, isothiochromene, isochromene, 1,3-benzodithiole, 1,3benzodioxole, 1,3-benzoxathiole, 1,4-benzodithiin, 1,4-benzoxathiin, 1,3benzoxathian, 3, l-benzoxathian and 1,3-benzodithian);
n represents zero or an integer from one to three; where n is greater than one the groups R2 may be the same or different;
m represents one, two or three;
p and q represent zero, one or two;
t represents one, two, three or four (preferably one);
X represents -(CR14Rl5)v-; v represents zero or one;
R3 represents a 5-membered heteroaromatic ring of formula (V')
in which D, E, G and J independently represent CR19 or a nitrogen atom, with at least one of D, E, G and J representing CR19 (when more than one R19 group is present they may be the same or different); or
two adjacent groups may form a phenyl or a 5- to 7- membered heteroaromatic ring which is fused to the first ring and is optionally substituted by one or more groups R20, and when present the 5- to 7membered heterocyclic ring may contain from one to four heteroatoms in the ring which may be the same or different selected from nitrogen, oxygen and sulphur;
z represents one or two; when z represents two the -XR3 groups may be the same or different;
Q represents hydroxy, lower alkoxy, OR21, SR21 or SR22;
L represents oxygen or NR14,
R4, R4a, R4b, R5, R5a, R5b, R6, R6, R6b, R7, R7a R7b R8, R8a, R8b, R9, R9a and R9b represent the same or different groups selected from hydrogen, R17, -(CH2)UCo2Rl4, halogen; cyano, lower alkoxy, -(CH2)x-[phenyl optionally substituted by from one to five groups R18 which may be the same or different], and cycloalkyl containing from three to six carbon atoms optionally substituted by lower alkyl or -S(O)pR22; u represents zero, one or two;
x represents zero or one;
R10 and R11 which may be the same of different, each represents hydrogen or R17; Rloa and Rl0b which may be the same or different, each represents lower alkyl or lower alkoxy;
R12 represents:
R17; or a cycloalkyl group containing from three to six carbon atoms; or a group -(CH2)w-[phenyl optionally substituted by from one to five groups R18 which may be the same or different];
w represents zero or one;
R13 represents:
hydrogen, R12 or OR22; R14 and R15 independently represent hydrogen, lower alkyl or lower haloalkyl (preferably containing up to three carbon atoms);
R16 represents -SO2R12 or -C(Z)=Y;
R17 represents:
lower alkyl, lower haloalkyl, lower alkyl, lower haloalkenyl, lower alkynyl or lower haloalkynyl;
R18 represents a group selected from halogen, R23, nitro, cyano, -CO2R10, -S(O)pR22, -OR22 and -NR10R11; R19 represents:
a group selected from hydrogen, halogen, R23, nitro, cyano, -CO2R10, -S(O)pR22, -OR22, -NR10R11 and cyclopropyl;
R20 represents halogen or R17;
R21 represents phenyl optionally substituted by from one to five groups selected from halogen, lower alkyl, lower haloalkyl, lower alkoxy and nitro;
R22 represents lower alkyl or lower haloalkyl;
R23 represents a straight- or branched- chain alkyl group containing one to three carbon atoms optionally substituted by one or more halogen atoms;
Y is oxygen or sulphur (preferably Y represents oxygen);
Z represents a group selected from R17, -NR24R25, -SR12 and -OR12; R24 and R25 independently represent hydrogen or R12;
and agriculturally acceptable salts and metal complexes thereof, which possess valuable herbicidal properties.
Compounds of formula (I) may exist in enolic tautomeric forms that may give rise to geometric isomers around the enolic double bond.
Furthermore in certain cases the above substituents may contribute to optical isomerism and/or stereoisomerism. All such forms are embraced by the present invention.
It is to be understood that in this specification compounds comprising a cyclohexane ring corresponding to formula ('V) or (V) or a precursor thereof include the compounds with the corresponding formula (IVa) or (Va) or precursors thereof.
In the description unless otherwise specified the following terms are generally defined thus:
'lower alkyl' means a straight- or branched- chain alkyl group having one to six carbon atoms;
'lower haloalkyl' means a straight- or branched- chain alkyl group having one to six carbon atoms, substituted by one or more halogens;
'lower alkoxy' means a straight- or branched- chain alkoxy group having one to six carbon atoms;
'lower haloalkoxy' means a straight- or branched- chain alkoxy group having one to six carbon atoms, substituted by one or more halogens;
'lower alkenyl' means a straight- or branched- chain alkenyl group having two to six carbon atoms;
'lower haloalkenyl' means a straight- or branched- chain alkenyl group having two to six carbon atoms, substituted by one or more halogens;
'lower alkynyl' means a straight- or branched- chain alkynyl group having three to six carbon atoms;
'lower haloalkynyl' means a straight- or branched- chain alkynyl group having three to six carbon atoms, substituted by one or more halogens;
'halogen' means a fluorine, chlorine, bromine or iodine atom.
By the term "agriculturally acceptable salts" is meant salts the cations or anions of which are known and accepted in the art for the formation of salts for agricultural or horticultural use. Preferably the salts are water-soluble. Suitable salts with bases include alkali metal (eg. sodium and potassium), alkaline earth metal (eg. calcium and magnesium), ammonium and amine (eg. diethanolamine, triethanolamine, octylamine, morpholine and dioctylmethylamine) salts. Suitable acid addition salts, formed by compounds of formula (I) containing an amino group, include salts with inorganic acids, for example hydrochlorides, sulphates, phosphates and nitrates and salts with organic acids, for example acetic acid.
By the term "metal complexes" is meant compounds wherein Q represents hydrogen (or a tautomer thereof) in which one or more of the oxygen atoms of the 2-benzoylcyclohexane-1,3-dione derivatives of formula (I) act as chelating agents to a metal cation. Examples of such cations include zinc, manganese, cupric, cuprous, ferric, ferrous, titanium and aluminium.
The compounds of the invention, in certain aspects of their properties, for example their high levels of herbicidal activity, show advantageous properties over known compounds.
Compounds wherein one XR3 group is present are preferred (preferably the XR3 group is at the 2- or 4- position of the phenyl ring).
Compounds wherein X represents -(CH2)V- are preferred (compounds in which v represents zero are especially preferred).
Compounds wherein Q represents hydroxy or -S-phenyl are preferred (compounds in which Q represents hydroxy are especially preferred).
Compounds of formula (I) in which the 2- and 4-positions of phenyl are substituted are also preferred.
Preferably R3 is selected from pyrazol-l-yl, imidazol- 1 -yl, 1,2,4-triazol-1-yl, 1,2,3-triazol-1-yl, 1,2,3-triazol-2-yl, 1,2,3, 4-tetrazol- 1 -yl and benzimidazol-l-yl.
Preferably R3 is a ring of formula (VI) wherein R19 represents hydrogen, halogen or R23.
In formula (I) above, preferably the 5- and 6- positions of phenyl are unsubstituted.
Preferably R1 represents a group of formula (II).
Preferably R2 represents halogen, a straight- or branched- chain alkyl group containing up to four carbon atoms optionally substituted by one or more halogen atoms; or a group selected from nitro, cyano, -S(O)pR12, -OR12, -CH2S(O)qR12 wherein R12 represents lower alkyl or lower haloalkyl; or benzyl optionally substituted by -S(O)pR22 wherein R22 represents lower alkyl; or two groups R2 together with adjacent carbon atoms of the phenyl ring form a second phenyl ring.
Preferably n represents one or two.
A preferred class of compounds of formula (I) above are those wherein:
R1 is selected from:
a group of formula (11) wherein R4, R5, R6, R7, R8 and R9 represent hydrogen or lower alkyl; or
a group of formula (III) wherein R4b, R5b R6b R7b R8b and
R9b represent hydrogen or lower alkyl; or
a group of formula (IV) wherein R8a and R9a represent hydrogen or lower alkyl; and
a group of formula (V) wherein R4a, R5a, R6a and R7a represent hydrogen or lower alkyl, and L represents NH;
Q represents hydroxy or -S-phenyl;
R2 represents:
a straight- or branched- chain alkyl group containing up to three carbon atoms optionally substituted by one or more halogen atoms; or
a group selected from halogen, nitro, -S(O)pR12, -OR12, -CH2S(O)qR12, -CH2NR13R16, -N(R13)SO2R12, -N(R13)CO2R12 and benzyl optionally substituted by S(O)22; n represents zero, one or two;
X represents -(CH2)v-;
R3 represents a 5 -membered heteroaromatic ring of formula (VI) which is selected from pyrazol-l-yl, imidazol-1-yl, l,2,4-triazol-1-yl, 1,2,3-triazol-1-yl, 1,2,3-triazol-2-yl, 1,2,3,4-tetrazol-1-yl and benzimidazol-1-yl, the ring systems of which are substituted by one or two R19 groups;
z represents one;
R12 and R13 independently represent lower alkyl or lower haloalkyl;
R16 represents -SO2R12 or C02R12;
R19 represents hydrogen or a straight- or branched- chain alkyl group containing up to three carbon atoms; and
R22 represents lower alkyl.
A particularly preferred class of compounds of formula (I) above are those wherein:
R1 is selected from:
a group of formula (II) wherein R4, R5, R6, R7, R8 and R9 represent hydrogen, methyl or ethyl; or
a group of formula (III) wherein R4b, R5b, R6b, R7b R8b and
R9b represent hydrogen, methyl or ethyl; or
a group of formula (IV) wherein R8a and R9a represent hydrogen, methyl or ethyl; and
a group of formula (V) wherein R4a, R5a, R6a and R7a represent hydrogen, methyl or ethyl, and L represents NH;
Q represents hydroxy or -S-phenyl;
R represents:
halogen, a straight- or branched- chain alkyl group containing up to three carbon atoms optionally substituted by one or more halogen atoms; or a group selected from -S(O)pCH3, -CH2S(O)qCH3, -OCH3 and benzyl optionally substituted by -S(O)pCH3;
X represents a bond;
R3 represents a pyrazol-1-yl, imidazol-l-yl, 1,2,3-triazol-1-yl, 1,2,3-triazol-2-yl, 1 ,2,4-triazol- 1 -yl or 1,2,3,4-tetrazol-1-yl ring substituted by one or two R19 groups, wherein R19 represents hydrogen, halogen or optionally halogenated methyl;
z represents one; and
n represents 0, 1 or 2.
A further particularly preferred class of compounds of formula (I) above are those wherein:
R1 represents a group of formula (II) wherein R4, R5, R6, R7, R8 and R9 represent hydrogen, methyl or ethyl;
Q represents hydroxy or -S-phenyl;
R2 represents:
halogen, a straight- or branched- chain alkyl group containing up to three carbon atoms optionally substituted by one or more halogen atoms; or a group selected from -S(O)pCH3, -CH2S(O)qCH3, -OCH3 and benzyl optionally substituted by -S(O)pCH3;
X represents a bond;
R3 represents a pyrazol-l-yl, imidazol-1-yl, 1,2,3-triazol-l-yl, 1,2,3-triazol-2-yl, 1 ,2,4-triazol- 1 -yl or 1,2,3 ,4-tetrazol- 1 -yl ring substituted by one or two R19 groups, wherein R19 represents hydrogen, halogen or optionally halogenated methyl;
z represents one; and
n represents 0, 1 or 2.
A further particularly preferred class of compounds of formula (t) above are those wherein:
R1 represents a formula (II) wherein wherein R4, R5, R8 and R9 represent hydrogen;
R6 and R7 represent hydrogen or methyl;
R represents:
optionally halogenated methyl;
Q represents hydroxy or -S-phenyl;
X represents a bond;
R3 represents a 1,2,4-triazol-1-yl ring; and
z and n represent one.
Particularly preferred compounds of the invention include:
2-[4-(1,2,4-triazol-1-yl)-2-trifluoromethylbenzoyl]cyclohexane1,3-dione (Compound 1);
3-phenylthio-2-[4-(1,2,4-triazol-1-yl)-2trifluoromethylbenzoyl]cyclohex-2-ene-1-one (Compound 2); and
5,5-dimethyl-2-[4-(1,2,4-triazol-1-yl)-2trifluoromethylbenzoyl]cyclohexane-1,3-dione (Compound 3).
The following compounds of formula (I) in which R1 represents a group of formula (II); R4, R5, R8 and R9 represent hydrogen, and the group (XR3)z is attached either to the 4-position of the phenyl ring (Table 1), or to the 2-position ofthe phenyl ring (Table 2), or to the 3position of the phenyl ring (Table 3), form part of the present invention.
In the Tables that follow, Me means methyl, Et means ethyl, Pr means propyl, and Ph means phenyl. Where subscripts do not appear in the
Tables it will be understood that in appropriate cases they are present (e.g. CF3 means CF3 etc.).
TABLE 1
Cpd R6 R7 Q (R2)n (XR3)z No.
1 H H OH 2-CF3 1,2,4-triazol-1-yl 2 H H SPh 2-CF3 1,2,4-triazol-1- -yl 3 Me Me OH 2-CF3 1,2,4-triazol-1-yl 4 H H OH 2-CF3 1,2,3-triazol-1-yl 5 H H OH 2-CH2SMe 1,2,3-triazol-1-yl 6 H H OH 2-Cl 1 ,2,3-tri ol-1 -yl 7 H H OH 2-Me 1,2,3-triazol-1-yl 8 H H OH 2-SMe 1,2,3-triazol-1-yl 9 H H OH 2-SMe-3-Br 1,2,3-triazol-1-yl 10 H H OH 2-SMe-3-F 1 2,3-triazol-1-yl 11 H H OH 2-SMe-3-SMe 1,2,3-triazol-1-yl 12 H H OH 2-CF3 1,2,3-triazol-2-yl 13 H H OH 2-CH2SMe 1,2,3-triazol-2-yl 14 H H OH 2-Cl 1,2,3-triazol-2-yl 15 H H OH 2-Me 1,2,3-triazol-2-yl 16 H H OH 24Me 1,2,3-triazol-2-yl 17 H H OH 2-SMe-3-Br 1,2,3-triazol-2-yl 18 H H OH 2-SMe-3-F 1,2,3-triazol-2-yl 19 H H OH 2-SMe-3-SMe 1,2,3-triazol-2-yl 20 H H OH 2-Br 1,2,4-triazol-1-yl 21 H H OH 2-CH2[(2-MeS)Ph] 1,2,4-triazol-1-yl 22 H H OH 2-CH2[(2-MeSO)Ph] 1,2,4-triazol-1-yl 23 H H OH 2-CH2 2-MeSO2 Ph 1 ,2,4-triazol-1 -yl 24 H H OH 2-CH2N(Me)C02Me 1,2,4-triazol-1-yl 25 H H OH 2-CH2N(Me)SO2Me 1,2,4-triazol-1-yl
Cpd R6 R7 Q (R2)n (XR3)z No. ~ 26 H H OH 2-CH2Ph 1 1,2,4-triazol-1 -yl 27 H H OH 2-CH2SMe 1,2,4-triazol-1-yl 28 H H OH 2-CH2SMe 1,2,4-triazol-1-yl 29 H H OH 2-CH2502Me 1,2,4-triazol-1-yl 30 H H OH 2-CH2SOMe 1,2,4-triazol-1-yl 31 H H OH 2-CI 1,2,4-triazol-1-yl 32 H H OH 2-Me I ,2,4-triazol-1 - 33 H H OH 2-Me-3-SMe 1,2,4-triazol-1-yl 34 H H OH 2-Me-3-S02Me 1,2,4-triazol-1-yl 35 H H OH 2-Me-3-SOMe 1,2,4-triazol-1 -yl 36 H H OH 2-NMeC02Me ,1,2,4-triazol-1-yl 37 H H OH 2-NMeS02Me 1,2,4-triazol-1-yl 38 H H OH 2-OMe 1,2,4-triazol-1-yl 39 H H OH 2-OMe-3-SMe 1,2,4-triazol-1-yl 40 H H OH 2-OMe-3-S02Me 1,2,4-tri olUl 41 H H OH 2-OMe-3-SOMe 1,2,4-triazol-1-yl 42 H H OH 2-SMe 1,2,4-triazol-1-yl 43 H H OH 2-SMe-3-Br 1,2,4-triazol-1-yl 44 H H OH 2-SMe-3-CI 1,2,4-triazol-1 -yl 45 H H OH 2-SMe-3-F 1 ,214-triazol-1 - I 46 H H OH 2-SMe-3-OMe 1,2,4-triazol-I- I 47 H H OH 2-SMe-3-SMe 1,2,4-triazol-1-yl 48 H H OH 2-SO2Me 1,2,4-triazol-1-yl 49 H H OH 2-S02Me-3-CI 1,2,4-triazol-1-yl 50 H H OH 2-S02Me-3-OMe 1,2,4-triazol-1-yl 51 H H OH 2-SOMe 1,2,4-triazol-1-yl 52 H H OH 2-SOMe-3-CI 1,2,4-triazol-1-yl 53 H H OH 2-SOMe-3-OMe 1,2,4-triazol-1-yl 54 H H OH 2-NO2 1,2,4-triazol-1-yl 55 H H OH 2-CF3 imidazol-1 -yl 56 H H OH 2-CH2SMe imidazol-1-yl 57 H H OH 2-Cl imidazol-1-yl 58 H H OH 2-Me imidazol-1 - I 59 H H OH 2-SMe imidazol-I- -yl 60 H H OH 2-SMe-3-Br imidazol-1-yl 61 H H OH 2-SMe-3-F imidazol-1 -yl 62 H H OH 2-SMe-3-SMe imidazol-1 -yl 63 H H OH 2-CF3 pyr ol-1 -yl 64 H H OH 2-CH2SMe pyrazol-1- -yl 65 H H OH 2-Cl pyrazol-1-yl 66 H H OH 2-Me pyrazol-1-yl 67 H H OH 2-SMe pyrazol-1 -yl 68 H H OH 2-CF3 tetrazol-1-yl 69 H H OH 2-SMe tetrazol-1-yl
Cpd R6 R7 Q (R2)n (XR3)z No.
70 H H OH 2-SMe-3-SMe tetrazol-1 -yl 71 H Me OH 2-CF3 1,2,3-triazol-1- -yl 72 H Me OH 2-CH2SMe 1,2,3-triazol-1-yl 73 H Me OH 2-CI 1,2,3-triazol-1-yl 74 H Me OH 2-Me 1,2,3-triazol-1- -yl 75 H Me OH 2-SMe 1,2,3-triazol-1 -yl 76 H Me OH 2-SMe-3-Br 1,2,3-triazol-1 -y 77 H Me OH 2-SMe-3-F 1,2,3-triazol-1-yl 78 H Me OH 2-SMe-3-SMe 1,2,3-triazol-1-yl 79 H Me OH 2-CF3 1,2,3-triazol-2-yl 80 H Me OH 2-CH2SMe 1,2,3-triazol-2-yl 81 H Me OH 2-CI 1,2,3-triazol-2-yl 82 H Me OH 2-Me 1,2,3-triazol-2-yl 83 H Me OH 2-SMe 1,2,3-triazol-2-yl 84 H Me OH 2-SMe-3-Br 1,2,3-triazol-2-yl 85 H Me OH 2-SMe-3-F 1,2,3-triazol-2-yl 86 H Me OH 2-SMe-3-SMe 1,2,3-triazol-2-yl 87 H Me OH 2-Br 1,2,4-triazol-1 -yl 88 H Me OH 2-CF3 1,2,4-triazol-1 -yl 89 H Me OH 2-CH2 2-MeS Ph 1,2,4-triazol-1-yl 90 H Me OH 2-CH2 2-MeSO Ph 1,2,4-triazol-1-yl 91 H Me OH 2-CH2 2-MeSO2 Ph 1,2,4-triazol-1 -yl 92 H Me OH 2-CH2N(Me)CO2Me 1,2,4-triazol-1-yl 93 H Me OH 2-CH2N(Me)SO2Me 1,2,4-triazol-1-yl 94 H Me OH 2-CH2Ph 1,2,4-triazol-1-yl 95 H Me OH 2-CH2SMe 1,2,4-triazol-1 -yl 96 H Me OH 2-CH2SMe 1,2,4-triazol-1-yl 97 H Me OH 2-CH2S02Me 1,2,4-triazol-1-yl 98 H Me OH 2-CH2SOMe 1 ,2,4-triazol-1 -yl 99 H Me OH 2-CI 1,2,4-triazol-1-yl 100 H Me OH 2-Me 1,2,4-triazol-1-yl 101 H Me OH 2-Me-3-SMe 1,2,4-triazol-1-yl 102 H Me OH 2-Me-3-S02Me 1,2,4-triazol-1-yl 103 H Me OH 2-Me-3-SOMe 1,2,4-triazol-1 -yl 104 H Me OH 2-NMeC02Me 1,2,4-triazol-1-yl 105 H Me OH 2-NMeS02Me 1,2,4-triazol-1-yl 106 H Me OH 2-OMe 1,2,4-triazol-1-yl 107 H Me OH 2-OMe-3-SMe 1,2,4-triazol-1-yl 108 H Me OH 2-OMe-3-SO2Me 1,2,4-triazol-1-yl 109 H Me OH 2-OMe-3-SOMe 1,2,4-triazol-1-yl 110 H Me OH 2-SMe 1,2,4-triazol-1-yl 111 H Me OH 2-SMe-3-Br 1,2,4-triazol-1-yl 112 H Me OH 2-SMe-3-CI 1,2,4-triazol-1-yl 113 H Me OH 2-SMe-3-F 1,2,4-triazol-1-yl
Cpd R6 R7 Q (R2)n (XR3)z No.
114 H Me OH 2-SMe-3-OMe 1,2,4-triazol-1 -yl 115 H Me OH 2-SMe-3-SMe 1,2,4-triazol-1 -yl 116 H Me OH 2-S02Me 1,2,4-triazol-1-yl 117 H Me OH 2-S02Me-3-CI 1,2,4-triazol-1-yl 118 H Me OH 2-S02Me-3-OMe 1,2,4-triazol-1 -yl 119 H Me OH 2-SOMe 1,2,4-triazol-1 -yl 120 H Me OH 2-SOMe-3-CI 1,2,4-triazol-1 -yl 121 H Me OH 2-SOMe-3-OMe 1,2,4-triazol-1-yl 122 H Me OH 2-NO2 1,2,4-triazol-1-yl 123 H Me OH 2-CF3 imidazol-1- -yl 124 H Me OH 2-CH2SMe imidazol-1-yl 125 H Me OH 2-CI imidazol-1-yl 126 H Me OH 2-Me imidazol-1-yl 127 H Me OH 2-SMe imidazol-1-yl 128 H Me OH 2-SMe-3-Br imidazol-1-yl 129 H Me OH 2-SMe-3-F imidazol-1-yl 130 H Me OH 2-SMe-3-SMe imidazol-1-yl 131 H Me OH 2-CF3 pyrazol-1- -yl 132 H Me OH 2-CH2SMe pyrazol-1-yl 133 H Me OH 2-Cl pyrazol-1-yl 134 H Me OH 2-Me pyrazol-1-yl 135 H Me OH 2-SMe pyrazol-1 -yl 136 H Me OH 2-CF3 tetrazol-1- -yl 137 H Me OH 2-SMe tetrazol-1 138 H Me OH 2-SMe-3-SMe tetrazol-1-yl 139 Me Me OH 2-CF3 1,2,3-triazol-1- -yl 140 Me Me OH 2-CH2SMe 1,2,3-tri ol-1 -yl 141 Me Me OH 2-CI 1,2,3-triazol-1- -yl 142 Me Me OH 2-Me 1,2, 3-triazol-1 -yl 143 Me Me OH 2-SMe 1,2,3-triazol-1-yl 144 Me Me OH 2-SMe-3-Br 1,2,3-triazol-1 -yl 145 Me Me OH 2-SMe-3-F 1,2,3-triazol-1-yl 146 Me Me OH 2-SMe-3-SMe 1,2,3-triazol-1-yl 147 Me Me OH 2-CF3 1,2,3-triazol-2-yl 148 Me Me OH 2-CH2SMe 1,2,3-
Cpd R6 R7 Q (R2)n (XR3)z No.
158 Me Me OH 2-CH2[(2-MeSO2)Ph] 1,2,4-triazol-1-yl 159 Me Me OH 2-CH2N(Me)CO2Me 1,2,4-triazol-1-yl 160 Me Me OH 2-CH2N(Me)SO2Me 1,2,4-triazol-1-yl 161 Me Me OH 2-CH2Ph 1,2,4-triazol-1-yl 162 Me Me OH 2-CH2SMe 1,2,4-triazol-1-yl 163 Me Me OH 2-CH2SMe 1,2,4-triazol-1-yl 164 Me Me OH 2-CH2SO2Me 1,2,4-triazol-1-yl 165 Me Me OH 2-CH2SOMe 1,2,4-triazol-1-yl 166 Me Me OH 2-Cl 1,2,4-triazol-1-yl 167 Me Me OH 2-Me 1,2,4-triazol-1-yl 168 Me Me OH 2-Me-3-SMe 1,2,4-triazol-1-yl 169 Me Me OH 2-Me-3-SO2Me 1,2,4-triazol-1-yl 170 Me Me OH 2-Me-3-SOMe 1,2,4-triazol-1-yl 171 Me Me OH 2-NMeCO2Me 1,2,4-triazol-1-yl 172 Me Me OH 2-NMeS02Me I 12,4-triazol-1 -yl 173 Me Me OH 2-OMe 1,2,4-triazol-1-yl 174 Me Me OH 2-OMe-3-SMe 1,2,4-triazol-1-yl 175 Me Me OH 2-OMe-3-S02Me 1,2,4-triazol-1 -yl 176 Me Me OH 2-OMe-3-SOMe 1,2,4-triazol-1-yl 177 Me Me OH 2-SMe 1,2,4-triazol-1-yl 178 Me Me OH 2-SMe-3-Br 1,2,4-triazol-1-yl 179 Me Me OH 2-SMe-3-CI 1,2,4-triazol-1 -yl 180 Me Me OH 2-SMe-3-F 1,2,4-triazol-1-yl 181 Me Me OH 2-SMe-3-OMe 1,2,4-triazol-1- -yi 182 Me Me OH 2-SMe-3-SMe 1,2,4-triazol-1-yl 183 Me Me OH 2-SO2Me 1,2,4-triazol-1-yl 184 Me Me OH 2-S02Me-3-CI 1,2,4-triazol-1-yl 185 Me Me OH 2-SO2Me-3-OMe 1,2,4-triazol-1-yl 186 Me Me OH 2-SOMe 1,2,4-triazol-1 -yl 187 Me Me OH 2-SOMe-3-CI 1,2,4-triazol-1 -yl 188 Me Me OH 2-SOMe-3-OMe 1,2,4-triazol-1-yl 189 Me Me OH 2-NO2 1,2,4-triazol-1-yl 190 Me Me OH 2-CF3 imidazol-1-yl 191 Me Me OH 2-CH2SMe imidazol-1-yl 192 Me Me OH 2-CI imidazol-1-yl 193 Me Me OH 2-Me imidazol-1 -yl 194 Me Me OH 2-SMe imidazol-1-yl 195 Me Me OH 2-SMe-3-Br imidazol-1-yl 196 Me Me OH 2-SMe-3-F imidazol-1- I 197 Me Me OH 2-SMe-3-SMe ~ imidazol-1- -yl 198 Me Me OH 2-CF3 yrazol-1- -yl 199 Me Me OH 2-CH2SMe razol-1 -yl 200 Me Me OH 2-CI pyrazol-1 -yl 201 Me Me OH 2-Me pyrazol-1-yl
Cpd R6 R7 Q (R2)n (XR3)z No.
202 Me Me OH 2-SMe pyrazol-1- I 203 Me Me OH 2-CF3 tetrazol-1-yl 204 Me Me OH 2-SMe tetrazol-1 -yl 205 Me Me OH 2-SMe-3-SMe tetrazol-1 -yl 206 H H OH 2-CF3 3-Me-112,4-triazol-1- -vl 207 H Me OH 2-CF3 3-Me-1,2,4-triazuol-1-yl 208 Me Me OH 2-CF3 3-Me-1,2,4-triazol-1 -yl TABLE 2
Cpd. R6 R7 Q (R2)n (XR3)z No.
209 H H OH 4-Br 1,2,3-triazol-1-yl 210 H H OH 4-CF3 1,2,3-triazol-1-yl 211 H H OH 4-Cl 1,2,3-triazol-1-yl 212 H H OH 4-F 1,2,3-triazol-1-yl 213 H H OH 4-SMe 1,2,3-triazol-1-yl 214 H H OH 4-Br 1,2,3-triazol-2-yl 215 H H OH 4-CF3 1,2,3-triazol-2-yl 216 H H OH 4-Cl 1,2,3-triazol-2-yl 217 H H OH 4-F 1,2,3-triazol-2-yl 218 H H OH 4-SMe 1,2,3-triazol-2-yl 219 H H OH 3,4-Cl2 1,2,4-triazol-1-yl 220 H H OH 3,4-F2 1,2,4-triazol-1-yl 221 H H OH 3-Br 1,2,4-triazol-1-yl 222 H H OH 3-CF3 1 ,2,4-triazol-1 - 223 H H OH 3-CH2SO2Me 1,2,4-triazol-1-yl 224 H H OH 3-CH2SO2Me 1,2,4-triazol-1 -yl 225 H H OH 3-CH2SOMe 1,2,4-triazol-1-yl 226 H H OH 3-Cl 1,2,4-triazol-1-yl 227H H OH 3-F 1,2,4-triazol-1-yl 228 H H OH 3-Me 1,2,4-triazol-1-yl 229 H H OH 3-Me-4-F 1,2,4-triazol-1-yl 230 H H OH 3-Me-4-SMe 1,2,4-triazol-1-yl 231 H H OH 3-OMe 1,2,4-triazol-1 -yl 232 H H OH 3-SMe 1,2,4-triazol-1-yl 233 H H OH 3-SMe-4-F 1,2,4-triazol-1-yl 234 H H OH 3-SMe-4-OMe 1,2,4-triazol-1- -yl 235 H H OH 3-SMe-4-SMe 1,2,4-triazol-1 -vl 236 H H OH 3-SO2Me 1,2,4-triazol-1- -yl 237 H H OH 3-SO2Me-4-F 1,2,4-triazol-1 -vl 238 H H OH 3-SO2Me-4-OMe 1,2,4-triazol-1-yl 239 H H OH 3-SO2Me-4-SO2Me 1,2,4-triazol-1-yl 240 H H OH 3-SOMe 1,2,4-triazol-1-yl
:pd. R6 R7 Q (R2)n (XR3)z Io.
241 H H OH 3-SOMe-4-F 1,2,4-triazol-1-yl 242 H H OH 3-SOMe4-OMe 1,2,4-triazol-1-yl 243 H H OH 4-Br 1,2,4-triazol-1-yl 244H H OH 4-CF3 1,2,4-triazol-1-yl 245 H H OH 4-Cl 1,2,4-triazol-1-yl 246 H H OH 4-F 1,2,4-triazol-1-yl 247 H H OH 4-Me 1,2,4-triazol-1 -yl 248 H H OH 4-OMe 1,2,4-triazol-1-yl 249 H H OH 4-SMe 1,2,4-triazol-1-yl 250 H H OH 4-SO2Me 1,2,4-triazol-1-yl 251 H H OH 4-SOMe 1,2,4-triazol-1-yl 252 H H OH - 1,2,4-triazol-1- -yl 253 H H OH 4-Br - imidazol-l -yl 254 H H OH 4-CF3 imidazol-1 -yl 255 H H OH 4-Cl imidazol-1 -yl 256 H H OH 4-F imidazol-1-yl 257 H H OH 4-SMe imidazol-1-yl 258 H H OH - pyrazol-1-yl 259 H H OH 4-Br tetrazol-I- I 260 H H OH 4-CF3 tetrazol-1-yl 261 H H OH 4-Cl tetrazol-1-vl 262 H H OH 4-F tetrazol-1-yl 263 H H OH 4-SMe tetrazol-1-yl 264 H H OH 4-Br benzimidazol-1-yl 265 H H OH 4-CF3 benzimidazol-1-yl 266 H H OH 4-Cl benzimidazol-1-yl 267 H H OH 4-F benzimidazol-1-yl 268 H H OH 4-SMe benzimidazol-I - 269 H Me OH 4-Br 1,2,3-triazol-1-yl 270 H Me OH 4-CF3 1,2,3-triazol-1-yl 271 H Me OH 4-Cl 1,2,3-triazol-1-yl 272 H Me OH 4-F 1,2,3-triazol-1-yl 273 H Me OH 4-SMe 1,2,3-triazol-1-yl 274 H Me OH 4-Br 1,2,3-triazol-2-yl 275 H Me OH 4-CF3 1,2,3-triazol-2-yl 276 H Me OH 4-Cl 1,2,3-triazol-2-yl 277 H Me OH 4-F 1,2,3-triazol-2-yl 278 H Me OH 4-SMe 1,2,3-triazol-2-yl 279 H Me OH 3,4-Cl2 1,2,4-triazol-1-yl 280 H Me OH 3,4-F2 1,2,4-triazol-1-yl 281 H Me OH 3-Br 1,2,4-triazol-1 -yl 282 H Me OH 3-CF3 1,2,4-triazol-1- -yl 283 H Me OH 3-CH2SO2Me 1,2,4-triazol-1 -yl 284 H Me OH 3-CH2SO2Me 1,2,4-triazol-1-yl
Cpd. R6 R7 Q (R2)n (XR3)z No.
285 H Me OH 3-CH2SOMe 1,2,4-triazol-1-yl 286 H Me OH 3-Cl 1,2,4-triazol-1-yl 287 H Me OH 3-F 1,2,4-triazol-1-yl 288 H Me OH 3-Me 1,2,4-triazoi-1 -yl 289 H Me OH 3-Me-4-F 1,2,4-triazol-1-yl 290 H Me OH 3-Me-4-SMe 1,2,4-triazol-1-yl 291 H Me OH 3-OMe 1,2,4-triazol-1-yl 292 H Me OH 3-SMe 1,2,4-triazol-1-yl 293 H Me OH 3-SMe-4-F 1,2,4-triazol-1-yl 294 H Me OH 3-SMe-4-OMe 1,2,4-triazol-1-yl 295 H Me OH 3-SMe-4-SMe 1,2,4-triazol-1-yl 296 H Me OH 3-SO2Me 1,2,4-triazol-1-yl 297 H Me OH 3-SO2Me-4-F 1,2,4-triazol-1-yl 298 H Me OH 3-SO2Me-4-OMe 1,2,4-triazol-1-yl 299 H Me OH 3-SO2Me-4-SO2Me 1,2,4-triazol-1-yl 300 H Me OH 3-SOMe 1,2,4-triazol-1-yl 301 H Me OH 3-SOMe-4-F 1,2,4-triazol-1-yl 302 H Me OH 3-SOMe-4-OMe 1,2,4-triazol-1-yl 303 H Me OH 4-Br 1,2,4-triazol-1-yl 304 H Me OH 4-CF3 1,2,4-triazol-1 -yl 305 H Me OH 4-Cl 1,2,4-triazol-1-yl 306 H Me OH 4-F 1,2,4-triazol-1-yl 307 H Me OH 4-Me 1,2,4-triazol-1-yl 308 H Me OH 4-OMe 1,2,4-triazol-1-yl 309 H Me OH 4-SMe 1,2,4-triazol-1-yl 310 H Me OH 4-SO2Me 1,2,4-triazol-1-yl 311 H Me OH 4-SOMe 1,2,4-triazol-1-yl 312 H Me OH - 1,2,4-triazol-1-yl 313 z H Me OH 4-Br imidazol-1-yl 314 H Me OH 4-CF3 imidazol-1-yl 315 H Me OH 4-Cl imidazol-1-yl 316 H Me OH 4-F imidazol-1- -yi 317 H Me OH 4-SMe imidazol-1-yl 318 H Me OH - pyrazol-1-yl 319 H Me OH 4-Br tetrazol-1-yl 320 H Me OH 4-CF3 tetrazol-I- -yl 321 H Me OH 4-Cl tetrazol-1 -yl 322 H Me OH 4-F tetrazol-1 -yl 323 H Me OH 4-SMe tetrazol-1-yl 324 H Me OH 4-Br benzimidazol-1-yl 325 H Me OH 4-CF3 benzimidazol-1-yl 326 H Me OH 4-Cl benzimidazol-1-yl 327 H Me OH 4-F benzimidazol-1-yl 32E H Me OH 4-SMe benzimidazol-1- -yl
Cpd. R6 R7 Q (R2)n (XR3)z No.
329 Me Me OH 4-Br 1,2,3-triazol-1-yl 330 Me Me OH 4-CF3 I ,2,3-triazol-1 - 331 Me Me OH 4-Cl 1,2,3-triazol-1-yl 332 Me Me OH 4-F 1,2,3-triazol-1-yl 333 Me Me OH 4-SMe I ,2,3-triazol-I -yl 334 Me Me OH 4-Br 12,3-triazol-2-yl 335 Me Me OH 4-CF3 1,2,3-triazol-2-yl 336 Me Me OH 4-Cl 1,2,3-triazol-2-yl 337 Me Me OH 4-F 1,2,3-triazol-2-yl 338 Me Me OH 4-SMe 1,2,3-triazol-2-yl 339 Me Me OH 3,4-C12 1,2,4-triazol-1-yl 340 Me Me OH 3,4-F2 1,2,4-triazol-1-yl 341 Me Me OH 3-Br 1,2,4-triazol-1 -yl 342 Me Me OH 3-CF3 I 1214-triazol-I - 343 Me Me OH 3-CH2SO2Me 1,2,4-triazol-1-yl 344 Me Me OH 3-CH2SO2Me 1,2,4-triazol-1-yl 345 Me Me OH 3-CH2SOMe 1,2,4-triazol-1-yl 346 Me Me OH 3-Cl 1,2,4-triazol-1-yl 347 Me Me OH 3-F 1,2,4-triazol-1-yl 348 Me Me OH 3-Me 1,2,4-triazol-1-yl 349 Me Me OH 3-Me-4-F 1,2,4-triazol-1-yl 350 Me Me OH 3-Me-4-SMe I,2,4-triazol-1- I 351 Me Me OH 3-OMe 1,2,4-triazol-1 -yl 352 Me Me OH 3-SMe 1,2,4-triazol-1-yl 353 Me Me OH 3-SMe-4-F 1,2,4-triazol-1 -yl 354 Me Me OH 3-SMe-4-OMe 1,2,4-triazol-1 -yl 355 Me Me OH 3-SMe-4-SMe 1,2,4-triazol-1-yl 356 Me Me OH 3-SO2Me 1,2,4-triazol-1-yl 357 Me Me OH 3-SO2Me-4-F 1,2,4-triazol-1-yl 358 Me Me OH 3-SO2Me-4-OMe 1,2,4-triazol-1-yl 359 Me Me OH 3-SO2Me-4-SO2Me 1,2,4-triazol-1-yl 360 Me Me OH 3-SOMe 1,2,4-triazol-1-yl 361 Me Me OH 3-SOMe-4-F I ,2,4-triazol-1 - 362 Me Me OH 3-SOMe4-OMe 1,2,4-triazol-1 -yl 363 Me Me OH 4-Br 1,2,4-triazol-1 -yl 364 Me Me OH 4-CF3 1,2,4-triazol-1-yl 365 Me Me OH 4-Cl 1,2,4-triazol-1-yl 366 Me Me OH 4-F 1,2,4-triazol-1-yl 367 Me Me OH 4-Me 1,2,4-triazol-1-yl 368 Me Me OH 4-OMe 1,2,4-tri ol-1 -yl 369 Me Me OH 4-SMe 1,2,4-triazol-1-yl 370 Me Me OH 4-SO2Me 1 ,2,4-triazol-1 -yl 371 Me Me OH 4-SOMe 1,2,4-triazol-1 -yl 372 Me Me OH 1 1,2,4-triazol-1-yl
Cpd. R6 R7 Q (R2)n (XR3)z No.
373 Me Me OH 4-Br imidazol-1 374 Me Me OH 4-CF3 imidazol-1-yl 375 Me Me OH 4-CI imidazol-1 -yl 376 Me Me OH 4-F imidazol-1-yl 377 Me Me OH 4-SMe imidazol-1 -yl 378 Me Me OH - pyrazol-1-yl 379 Me Me OH 4-Br tetrazol-1-yl 380 Me Me OH 4-CF3 tetrazol-1 -yl 381 Me Me OH 4-Cl tetrazol-1-yl 382 Me Me OH 4-F tetrazol-I - 383 Me Me OH 4-SMe tetrazol-I - 384 Me Me OH 4-Br benzimidazol-1-yl 385 Me Me OH 4-CF3 benzimidazol-1 -yl 386 Me Me OH 4-CI benzimidazol-1 -yl 387 Me Me OH 4-F benzimidazol-1-yl 388 Me Me OH 4-SMe enzimidazol-1 -yl 389 H H OH 4-Br CH2-(triazol-1-yl 390 H H OH 4-Cl CH2-(triazol-1-yl) 391 H H OH 4-F CH2-(triazol-1-yl) 392 H H OH 4-CF3 CH2- triazol-I. -yl) 393 H H OH 4-OF3 CH2-(triazol-1-yl) 394 H H OH 4-Me CH2-(triazol-1-yl) TABLE 3
Cpd. R6 R7 Q (R2)n R3 No.
395 H H OH 2-Br 1.213-triazol-1- I 396 H H OH 2-CF3 1,2,3-triazol-1-y 397 H H OH 2-CH2SMe 1,2,3-triazol-1-y 398 H H OH 2-CI $1,2,3-triazol-1-yl 399 H H OH 2-F 1,2,3-triazol-1-yl 400 H H OH 2-SMe 1,2,3-triazol-1-y 401 H H OH 2-SMe-4-Br 1,2,3-triazol-1 -yl 402 H H OH 2-SMe-4-CF3 1,2,3-triazol-1-yl 403 H H OH 2-SMe-4-CI 1,2,3-triazol-1-y 404 H H OH 2-SMv4-F 1,2,3-triazol-1 -yl 405 H H OH 2-SMe-4-SMe 1,2,3-triazol-1 -yl 406 H H OH 2-SO2Me 1,2,3-triazol-1-yl 407 H H OH 2-SO2Me-4-SO2Me 1,2,3-triazol-1 -yl 408 H H OH 2-SOMe 1,2,3-triazol-1 -yl 409 H H OH 2-Br 1,2,4-triazol-1-yl 410 H H OH 2-CF3 1,2,4-triazol-1-yl 411 H H OH 2-CH2SMe 1,2,4-triazol-1-y
Cpd. R6 R7 Q (R2)n R3 No.
412 H H OH 2-CI 1,2,4-triazol-1-yl 413 H H OH 2-F 1,2,4-triazol-1-yl 414 H H OH 2-SMe 1,2,4-triazol-1-yl 415 H H OH 2-SMe-4-Br I,2,4-triazol-1- -yl 416 H H OH 2-SMe-4-CF3 1,2,4-triazol-1 -yl 417 H H OH 2-SMe-4-Cl 1,2,4-triazol-1-yl 418 H H OH 2-SMe-4-F 1,2,4-triazol-1-yl 419 H H OH 2-SMe-4-SMe 1,2,4-triazol-1-yl 420 H H OH 2-SO2Me 1,2,4-triazol-1-yl 421 H H OH 2-SO2Me-4-SO2Me 1,2,4-triazol-1-yl 422 H H OH 2-SOMe 1,2,4-triazol-1-yl 423 H H OH 2-Br imidazol-1-yl 424 H H OH 2-CF3 imidazol-1-yl 425 H H OH 2-CH2SMe imidazol-1-yl 427 H H OH 2-F imidazol-1-yl 428 H H OH 2-SMe imidazol-1-yl 429 H H OH 2-SMe-4-Br imidazol-1-yl 426 H H OH 2-CI imidazol-1- -yl 427 H H OH 2-F imidazol-1-yl 428 H H OH 2-SMe imidazol-1-yl 429 H H OH 2-SMe-4-Br imidazol-1-yl 430 H H OH 2-SMe-4-CF3 imidazol-1-yl 431 H H OH 2-SMe-4-Cl imidazol-1-yl 432 H H OH 2-SMe-4-F imidazol-1-yl 433 H H OH 2-SMe-4-SMe imidazol-1-yl 434 H H OH 2-SO2Me imidazol-1-yl 435 H H OH 2-SO2Me-4-SO2Me imidazol-1-yl 436 H H OH 2-SOMe imidazol-1 -yl 437 H H OH 2-Br ~~~~~~~~ tetrazol-1- -yl 438 H H OH 2-CF3 tetrazol-1-yl 439 H H OH 2-CH2SMe tetrazol-1 -yi 440 H H OH 2-CI tetrazol-1-yl 441 H H OH 2-F tetrazol-1-yl 442 H H OH 2-SMe tetrazol-1 -yl 443 H H OH 2-SMe-4-Br tetrazol-1-yl 444 H H OH 2-SMe-4-CF3 tetrazol-1-yl 445 H H OH 2-SMe-4-Cl tetrazol-1-yl 446 H H OH 2-SMe-4-F tetrazol-1-yl 447 H H OH 2-SMe4-SMe tetrazol-1-yl 448 H H OH 2-SO2Me tetrazol-1-yl 449 H H OH 2-SO2Me-4-SO2Me tetrazokl -yl 450 H H OH 2-SOMe tetrazol-1-yl 451 H Me OH 2-Br 1,2,3-triazol-1-yl 452 H Me OH 2-CF3 1,2,3-triazol-1 -yl 453 H Me OH 2-CH2SMe I 2,3-triazol-1-yl 454 H Me OH 2-Cl 1,2,3-triazol-1-yl 455 # H Me OH 2-F 1,2,3-triazol-1-yl
Cpd. R6 R7 Q (R2)n R3 No.
456 H Me OH 2-SMe 1,2,3-triazol-1-yl 457 H Me OH 2-SMe4-Br 1,2,3-triazol-1-yl 458 H Me OH 2-SMe-4-CF3 1,2,3-triazol-1-yl 459 H Me OH 2-SMe-4-Cl 1,2,3-triazol-1-yl 460 H Me OH 2-SMe-4-F 1,2,3-triazol-1-yl 461 H Me OH 2-SMe-4-SMe 1,2,3-triazol-1-yl 462 H Me OH 2-SO
Cpd. R6 R7 Q (R2)n R3 No.
500 H Me OH 2-SMe-4-CF3 tetrazokl- -yl 501 H Me OH 2-SMe-4-CI tetrazol-1 -yl 502 H Me OH 2-SMe-4-F tetrazol-1-yl 503 H Me OH 2-SMe-4-SMe tetrazol-1 -yl 504 H Me OH 2-SO2Me tetrazol-1-yl 505 H Me OH 2-SO2Me-4-SO2Me tetrazol-1 -yl 506 H Me OH 2-SOMe tetrazol-1-yl 507 Me Me OH 2-Br 1,2,3-triazol-1 -yl 508 Me Me OH 2-CF3 1,2,3-triazol-1 -yl 509 Me Me OH 2-CH2SMe 1,2,3-triazol-1-yl 510 Me Me OH 2-Cl 1,2,3-triazol-1-yl 511 Me Me OH 2-F 1,2,3-triazol-1-yl 512 Me Me OH 2-SMe 1,2,3-triazol-1-yl 513 Me Me OH 2-SMe-4-Br 1,2,3-triazol-1-yl 514 Me Me OH 2-SMe-4-CF3 1,2,3-triazol-1-yl 515 Me Me OH 2-SMe-4-Cl 1,2,3-triazol-1-yl 516 Me Me OH 2-SMe4-F I ,2,3-triazol-1-yl 517 Me Me OH 2-SMeA-SMe 1,2,3-triazol-1-yl 518 Me Me OH 2-SO2Me 1,2,3-triazol-1-yl 519 Me Me OH 2-SO2Me-4-SO2Me 1,2,3-triazol-1-yl 520 Me Me OH 2-SOMe 1,2,3-triazol-1 -yl 521 Me Me OH 2-Br 1,2,4-triazol-1-yl 522 Me Me OH 2-CF3 1,2,4-triazol-1 -yl 523 Me Me OH 2-CH2SMe 1,2,4-triazol-1-yl 524 Me Me OH 2-Cl 1,2,4-triazol-1-yl 525 Me Me OH 2-F 1,2,4-triazol-1-yl 526 Me Me Me OH 2-SMe 1,2,4-triazol-1-yl 527 Me Me OH 2-SMe-4-Br 1,2,4-triazol-1-yl 528 Me Me OH 2-SMe-4-CF3 1,2,4-triazol-1 -yl 529 Me Me OH 2-SMe-4-Cl 1,2,4-triazol-1-yl 530 Me Me OH 2-SMe-4-F 1,2,4-triazol-1-yl 531 Me Me OH 2-SMe-4-SMe 1,2,4-triazol-1-yl 532 Me Me OH 2-SO2Me 1,2,4-triazol-1-yl 533 Me Me OH 2-SO2Me-4-SO2Me 1 ,2,4-triazol-1 - 534 Me Me OH 2-SOMe 1,2,4-triazol-1-yl 535 Me Me OH 2-Br imidazol-1-yl 536 Me Me OH 2-CF3 imidazol-1-yl 537 Me Me OH 2-CH2SMe imidazol-1-yl 538 Me Me OH 2-Cl imidazol-1-yl 539 Me Me OH 2-F imidazol-1-yl 540 Me Me OH 2-SMe imidazol-1-yl 541 Me Me OH 2-SMe-4-Br imidazol-1-yl 542 Me Me OH 2-SMe4-CF3 imidazol-1- -yl 543 Me Me OH 2-SMe-4-CI imidazol-1-yl
Cpd. R6 R7 Q (R2)n R3 No.
544 Me Me OH 2-SMe-4-F imidazol-1 -yl 545 Me Me OH 2-SMe-4-SMe imidazol-1 -yl 546 Me Me OH 2-SO2Me imidazol-1-yl 547 Me Me OH 2-SO2Me-4-SO2Me imidazol-1-yl 548 Me Me OH 2-SOMe imidazol-1 -yl 549 Me Me OH 2-Br tetrazol-1-yl 550 Me Me OH 2-CF3 tetrazol-1-yl 551 Me Me OH 2-CH2SMe tetrazol-1-yl 552 Me Me OH 2-CI tetrazol-1-yl 553 Me Me OH 2-F tetrazol-1-yl 554 Me Me OH 2-SMe tetrazol-1 -yl 555 Me Me OH 2-SMe4-Br tetrazokl -yl ~~~~~ 556 Me Me OH 2-SMe-4-CF3 tetrazol-1-yl 557 Me Me OH 2-SMe-4-CI tetrazol-1-yl 558 Me Me OH 2-SMe4-F tetrazol-1- -yl 559 Me Me OH 2-SMe4-SMe tetrazol-1-yl 560 Me Me OH 2-SO2Me tetrazol-1-yl 561 Me Me OH 2-SO2Me-4-SO2Me tetrazol-1-yl 562 Me Me ~ OH 2-SOMe tetrazol-1 -yl Compounds of formula (I) may be prepared by the application or adaptation of known methods (i.e. methods heretofore used or described in the literature), for example as hereinafter described.
In the following description where symbols appearing in formulae are not specifically defined, it is to be understood that they are "as hereinbefore defined" in accordance with the first definition of each symbol in the specification.
It is to be understood that in the descriptions of the following processes the sequences may be performed in different orders, and that suitable protecting groups may be required to achieve the compounds sought.
According to a feature of the present invention compounds of formula (I) wherein the various symbols are as defined above and Q represents hydroxy may be prepared by the rearrangement of a compound of formula (VII), (VIII), (IX) or (X):
wherein the various symbols are as defined above, by reaction with a source of cyanide in the presence of a base. Cyanide sources include metal cyanides for example alkali metal cyanides such as sodium cyanide, hydrogen cyanide, or cyanhydrins of dialkyl ketones preferably acetone cyanhydrin. Generally up to 0.5 equivalent (preferably 0.1 equivalent) of cyanide source is employed. Suitable bases include trialkylainines such as triethylamine, or pyridine or alkali metal carbonates such as potassium carbonate. Generally 1-4 equivalents (preferably 2 equivalents) of the base is used. Solvents which may be used include toluene, acetonitrile, dichloromethane or preferably 1,2-dichloroethane. The reaction is generally performed at a temperature of from 00C-600C (generally at 200C-300C).
The above ester intermediates of formula (VII), (VIII), (IX) or (X) may be prepared by the reaction of the corresponding cyclohexane-1,3dione derivatives of formula (XI), (XII), (XIII) or (XIV) (which are represented here as the enol tautomer forms):
wherein the various symbols are as defined above, with an acid chloride of formula (XV):
wherein R2, R3, X, z and n are as defined above. The reaction is generally performed in the presence of a base preferably a trialkylamine such as triethylamine, or an alkali metal carbonate such as potassium carbonate, in a solvent such as dichloromethane, dichloroethane, acetonitrile, N,N-dimethylformamide or tetrahydrofuran. One to 1.1 equivalents of the base is generally employed and the reaction is generally conducted at a temperature of from about -200C to about 500C (preferably 0 C to 300C). Compounds of formula (VII), (VIII), (IX) and (X) are novel and as such constitute a further feature of the invention.
Optionally the reaction to form a compound of formula (I) by the reaction of a compound of formula (XV) with a compound of formula (XI), (XII), (XIII) or (XIV) to give ester intermediates of formula (VII), (VIII), (IX) or (X), and the subsequent reaction with a source of cyanide may be performed in one pot. In such cases the intermediate esters are
not isolated but are treated in situ with the additional base and cyanide source required for the rearrangement process to occur, and according to the above process description.
It is understood that when unsymmetrical diones of formulae (XI), (XII), (XIII) and (XIV) are employed in the above reaction, that the isomeric esters in which the position of the ring carbonyl and ester groups is reversed may be formed, and that the process is applicable for the formation of all such isomeric forms.
According to a further feature of the present invention compounds of formula (I) wherein the various symbols are as defined above and Q represents SR21 or SR22 may be prepared by reaction of the corresponding compound of formula (I) wherein Q represents hydroxy with a chlorinating agent, generally oxalyl chloride, in an inert solvent such as dichloromethane and preferably in the presence of a catalyst such as N,N-dimethylformamide and at a temperature of from -200C to 500C (preferably from OOC to 300C) to give the intermediate chloride of formula (I) wherein Q is replaced by a chlorine atom. These intermediates are not generally isolated and are reacted in situ with a thiophenol of formula (XVI) or thiol of formula (XVII):
R21SH (XVI) R22SH (XVII) wherein R21 and R22 are as defined above, in the presence of a base such as a trialkylamine, for example triethylamine, in an inert solvent such as dichloromethane or tetrahydrofuran, and at a temperature of from -200C to 500C (preferably from 0 C to 30oC).
According to a further feature of the present invention compounds in which p or q is one or two may be prepared by the oxidation of the sulphur atom of the corresponding compounds in which p or q is 0 or 1.
The oxidation of the sulphur atom is generally carried out using for example 3-chloroperoxybenzoic acid in an inert solvent such as dichloromethane at a temperature from -400C to room temperature.
Compounds of formula (XV) may be prepared by the reaction of the corresponding benzoic acid derivative of formula (XVIII):
with a chlorinating agent such as thionyl chloride or oxalyl chloride according to known procedures. Certain benzoic acids of formula (XVIII) are novel and as such constitute a further feature of the invention.
Compounds of formula (XI), (XII), (XIII) and (XIV) are known or may be prepared by known methods.
The following non-limiting Examples illustrate the preparation of compounds of formula (I) and the Reference Examples illustrate the preparation of intermediates in their synthesis. NMR Spectra are recorded as d (ppm) in deuterochloroform as solvent (unless ortherwise stated).
Example 1
To a solution of 3-[4-(1,2,4-triazol-1-yl)-2 trifiuoromethylbenzoyloxy] cyclohex-2-en- 1-one (2.90g) in acetonitrile was added triethylamine (1.67g) and acetone cyanohydrin (0.3ml) at 200C. The mixture was stirred for 3 days, evaporated and the residue diluted (ethyl acetate and aqueous citric acid). The organic layer was dried (magnesium sulfate), evaporated and the residue purified by chromatography eluting with ethyl acetate/hexane to give 2-[4-(1,2,4 triazol- 1 -yl)-2-trifluoromethylbenzoyl] cyclohexane- 1,3 -dione as a colourless solid (Compound 1, 1.75g), NMR 2.06(m,2H), 2.42(t,2H), 2.82(t,1H), 7.36(d,1H), 7.90(m,1H), 8.05(s,1H), 8.15(s,1H), 8.65(s,1H).
By proceeding in a similar manner the following compound was also prepared: 5,5 -dimethyl-2-[4-( 1 ,2,4-triazol- 1 -yl)-2 trifluoromethylbenzoyl]cyclohexane-1,3-dione (Compound 3), NMR 1.24(6H,s), 2.29(2H,s), 2.68(2H,s), 7.34(1H,d), 7.89(1H,d), 8.05(1H,s), 8.14(1H,s), 8.66(1H,s).
Example 2
To a solution of 2-[4-(1,2,4-triazol-1-yl)-2 trifluoromethylbenzoyl] cyclohexane- 1,3 -dione (1.42g) in dry dichloromethane was added a catalytic amount of N, N- dimethylformamide followed by oxalyl chloride (0.9ml) dropwise at 200C. The mixture was stirred until a clear solution was obtained and then evaporated. To a suspension of the residue in dry tetrahydrofuran was added thiophenol (0.51g) and triethylamine (0.93g) dropwise at 0 OC. The mixture was stirred at 200C for one day, then aqueous citric acid and ethyl acetate added. The organic layer was dried (magnesium sulfate), evaporated and the residue purified by chromatography eluting with ethyl acetate/hexane to give 3-phenylthio-2-[4-(1,2,4-triazol-1-yl)- 2-trifluoromethylbenzoyl]cyclohex-2-ene-1-one (Compound 2, 0.93 g) as a yellow solid, NMR 1.92(m,2H), 2.36(t,2H), 2.48(t,2H), 7.407.62(m,6H), 7.92(dd,1H), 8.04(d,1H),8.15(s,1H),8.66(s,1H).
Reference Example 1
To a suspension of 4-(1,2,Striazol-1-yl)-2-trifluoromethylbenzoic acid (3.32g) and a catalytic amount of N,N-dimethylformamide in dichloromethane was added oxalyl chloride (2.5ml) dropwise at 200C.
The mixture was stirred for 3 hours and evaporated. To a suspension of the residue in dichloromethane was added a solution of 1,3 cyclohexanedione (1 .52g) in dichloromethane and triethylamine (4.16g) dropwise at OOC. The reaction mixture was warmed to 200C, stirred for 0.5 hour, diluted (ethyl acetate) and washed with aqueous citric acid.
The organic layer was dried (magnesium sulfate), evaporated and the residue purified by chromatography to give 3-[4-(1,2,4-triazol-1-yl)-2 trifluoromethylbenzoyloxy]cyclohex-2-en-l-one as a yellow solid (3.05g), NMR 2.1 5(m,2H), 2.50(t,2H), 2.70(t,2H), 6.10(s,1H), 8.03(m,1H), 8.12(d,1H), 8.19(s,1H), 8.22 (s,lH), 8.73(s,1H).
By proceeding in a similar manner the following compound was also prepared:
5,5-dimethyl-3-[4-(1,2,4-triazol- 1-yl)-2 trifiuoromethylbenzoyloxy] cyclohex-2-en- 1-one, which was used directly in the following stage.
Reference Example 2
To a solution of methyl 4
(1,2,4-triazol-1-yl)-2-trifluoromethylbenzoate (5.07g) in methanol was added aqueous sodium hydroxide (1.50g) at 200C. The mixture was stirred for 4 hours, partially evaporated and extracted with ether. The aqueous layer was acidified (aqueous citric acid) and extracted with ethyl acetate. The organic layer was dried (magnesium sulfate), and evaporated to give 4-(1,2,4-triazol-1-yl)-2-trifiuoromethylbenzoic acid (3.32g), NMR 8.25(1H), 8.34-8.42(3H), 10.00(s, 1H).
Reference Example 3
To a solution of methyl 4-fluoro-2-trifluoromethylbenzoate (4.95g) in N,N-dimethylformamide was added 1,2,4-triazole (2.0g) and potassium carbonate (4.0g) at 200C and the mixture stirred for 4 hours at 600C. The mixture was diluted (ether), washed (aqueous citric acid) and dried (magnesium sulfate). The residue was purified by chromatography to give methyl 4-(1,2,4-triazol-1-yl)-2- trifluoromethylbenzoate (5.07g), NMR 3.98(s,3H),7.94 8.05(2H),8.15(2H),8.71(s,1H).
According to a feature of the present invention, there is provided a method for controlling the growth of weeds (i.e. undesired vegetation) at a locus which comprises applying to the locus a herbicidally effective amount of at least one 2-benzoylcyclohexane-1,3-dione derivative of formula (I) or an agriculturally acceptable salt thereof. For this purpose, the 2-benzoylcyclohexane-1,3-dione derivatives are normally used in the form of herbicidal compositions (i.e. in association with compatible diluents or carriers and/or surface active agents suitable for use in herbicidal compositions), for example as hereinafter described.
The compounds of formula (I) show herbicidal activity against dicotyledonous (i.e. broad-leafed) and monocotyledonous (i.e. grass) weeds by pre- and/or post-emergence application.
By the term "pre-emergence application" is meant application to the soil in which the weed seeds or seedlings are present before emergence of the weeds above the surface of the soil. By the term "postemergence application" is meant application to the aerial or exposed portions of the weeds which have emerged above the surface of the soil.
For example, the compounds of formula (I) may be used to control the growth of:
broad-leafed weeds, for example, Abutilon theophrasti,
Amaranthus retroflexus, Bidens pilosa, Chenopodium album, Galium aparine, Ipomoea spp. e.g. Ipomoea purpurea, Sesbania exaltata, Sinapis arvensis, Solanum nigrum and Xanthium strumarium, and
grass weeds, for example Alopecurus myosuroides, Avena fatua,
Digitaria sangunalis, Echinochloa crus-galli, Sorghum bicolor, Eleusine indica and Setaria spp e.g. Setaria faberii or Setaria viridis, and
sedges, for example, Cyprus esculentus.
The amounts of compounds of formula (I) applied vary with the nature of the weeds, the compositions used, the time of application, the climatic and edaphic conditions and (when used to control the growth of weeds in crop-growing areas) the nature of the crops. When applied to a crop-growing area, the rate of application should be sufficient to control the growth of weeds without causing substantial permanent damage to the crop. In general, talking these factors into account, application rates from 0.01kg to 2kg of active material per hectare give good results.
However, it is to be understood that higher or lower application rates may be used, depending upon the particular problem of weed control encountered.
The compounds of formula (I) may be used to control selectively the growth of weeds, for example to control the growth of those species hereinbefore mentioned, by pre- or post-emergence application in a directional or non-directional fashion, e.g. by directional or nondirectional spraying, to a locus of weed infestation which is an area used, or to be used, for growing crops, for example cereals, e.g. wheat, barley, oats, maize and rice, soya beans, field and dwarf beans, peas, lucerne, cotton, peanuts, flax, onions, carrots, cabbage, oilseed rape, sunflower, sugar beet, and permanent or sown grassland before or after sowing of the crop or before or after emergence of the crop. For the selective control of weeds at a locus of weed infestation which is an area used, or to be used, for growing of crops, e.g. the crops hereinbefore mentioned, application rates from 0.01kg to 1.0kg, and preferably from 0.025kg to 0.25kg, of active material per hectare are particularly suitable.
The compounds of formula (I) may also be used to control the growth of weeds, especially those indicated above, by pre- or postemergence application in established orchards and other tree-growing areas, for example forests, woods and parks, and plantations, e.g. sugar cane, oil palm and rubber plantations. For this purpose they may be applied in a directional or non- directional fashion (e.g. by directional or non-directional spraying) to the weeds or to the soil in which they are expected to appear, before or after planting of the trees or plantations at application rates from 0.25kg to 2.0kg, and preferably from 0.25kg to 1.0kg of active material per hectare.
The compounds of formula (I) may also be used to control the growth of weeds, especially those indicated above, at loci which are not crop-growing areas but in which the control of weeds is nevertheless desirable.
Examples of such non-crop-growing areas include airfields, industrial sites, railways, roadside verges, the verges of rivers, irrigation and other waterways, scrublands and fallow or uncultivated land, in particular where it is desired to control the growth of weeds in order to reduce fire risks. When used for such purposes in which a total herbicidal effect is frequently desired, the active compounds are normally applied at dosage rates higher than those used in crop-growing areas as hereinbefore described. The precise dosage will depend upon the nature of the vegetation treated and the effect sought.
Pre- or post-emergence application, and preferably pre-emergence application, in a directional or non-directional fashion (e.g. by directional or non-directional spraying) at application rates from 0.5kg to 2.0kg, and preferably from 0.5kg to 1. Okg, of active material per hectare are particularly suitable for this purpose.
When used to control the growth of weeds by pre-emergence application, the compounds of formula (I) may be incorporated into the soil in which the weeds are expected to emerge. It will be appreciated that when the compounds of formula (I) are used to control the growth of weeds by post-emergence application, i.e. by application to the aerial or exposed portions of emerged weeds, the compounds of formula (I) will also normally come into contact with the soil and may also then exercise a pre-emergence control on later-germinating weeds in the soil.
Where especially prolonged weed control is required, the application of the compounds of formula (I) may be repeated if required.
According to a further feature of the present invention, there are provided compositions suitable for herbicidal use comprising one or more of the 2-benzoylcyclohexane- 1,3-dione derivatives of formula (I), in association with, and preferably homogeneously dispersed in, one or more compatible agriculturally- acceptable diluents or carriers and/or surface active agents [i.e. diluents or carriers and/or surface active agents of the type generally accepted in the art as being suitable for use in herbicidal compositions and which are compatible with compounds of formula (I)]. The term "homogeneously dispersed" is used to include compositions in which the compounds of formula (I) are dissolved in other components. The term "herbicidal compositions" is used in a broad sense to include not only compositions which are ready for use as herbicides but also concentrates which must be diluted before use.
Preferably, the compositions contain from 0.05 to 90% by weight of one or more compounds of formula (I).
The herbicidal compositions may contain both a diluent or carrier and surface-active (e.g. wetting, dispersing, or emulsifying) agent.
Surface-active agents which may be present in herbicidal compositions of the present invention may be of the ionic or non-ionic types, for example sulphoricinoleates, quatemary ammonium derivatives, products based on condensates of ethylene oxide with alkyl and polyaryl phenols, e.g. nonyl- or octyl-phenols, or carboxylic acid esters of anhydrosorbitols which have been rendered soluble by etherification of the free hydroxy groups by condensation with ethylene oxide, alkali and alkaline earth metal salts of sulphuric acid esters and sulphonic acids such as dinonyland dioctyl-sodium sulphonosuccinates and alkali and alkaline earth metal salts of high molecular weight sulphonic acid derivatives such as sodium and calcium lignosulphonates and sodium and calcium alkylbenzene sulphonates.
Suitably, the herbicidal compositions according to the present invention may comprise up to 10% by weight, e.g. from 0.05% to 10% by weight, of surface-active agent but, if desired, herbicidal compositions according to the present invention may comprise higher proportions of surface-active agent, for example up to 15% by weight in liquid emulsifiable suspension concentrates and up to 25% by weight in liquid water soluble concentrates.
Examples of suitable solid diluents or carriers are aluminium silicate, talc, calcined magnesia, kieselguhr, tricalcium phosphate, powdered cork, absorbent carbon black and clays such as kaolin and bentonite. The solid compositions (which may take the form of dusts, granules or wettable powders) are preferably prepared by grinding the compounds of formula (I) with solid diluents or by impregnating the solid diluents or carriers with solutions of the compounds of formula (I) in volatile solvents, evaporating the solvents and, if necessary, grinding the products so as to obtain powders. Granular formulations may be prepared by absorbing the compounds of formula (I) (dissolved in suitable solvents, which may, if desired, be volatile) onto the solid diluents or carriers in granular form and, if desired, evaporating the solvents, or by granulating compositions in powder form obtained as described above. Solid herbicidal compositions, particularly wettable powders and granules, may contain wetting or dispersing agents (for example of the types described above), which may also, when solid, serve as diluents or carriers.
Liquid compositions according to the invention may take the form of aqueous, organic or aqueous-organic solutions, suspensions and emulsions which may incorporate a surface-active agent. Suitable liquid diluents for incorporation in the liquid compositions include water, glycols, tetrahydrofurfuryl alcohol, acetophenone, cyclohexanone, isophorone, toluene, xylene, mineral, animal and vegetable oils and light aromatic and naphthenic fractions of petroleum (and mixtures of these diluents). Surface-active agents, which may be present in the liquid compositions, may be ionic or non-ionic (for example of the types described above) and may, when liquid, also serve as diluents or carriers.
Powders, dispersible granules and liquid compositions in the form of concentrates may be diluted with water or other suitable diluents, for example mineral or vegetable oils, particularly in the case of liquid concentrates in which the diluent or carrier is an oil, to give compositions ready for use.
Liquid concentrates in which the diluent or carrier is an oil may be used without further dilution using the electrostatic spray technique.
Herbicidal compositions according to the present invention may also contain, if desired, conventional adjuvants such as adhesives, protective colloids, thickeners, penetrating agents, spreading agents, stabilisers, sequestering agents, anti-caking agents, colouring agents and corrosion inhibitors. These adjuvants may also serve as carriers or diluents.
Herbicidal compositions according to the present invention may also comprise the compounds of formula I in association with, and preferably homogeneously dispersed in, one or more other pesticidally active compounds and, if desired, one or more compatible pesticidally acceptable diluents or carriers, surface-active agents and conventional adjuvants as hereinbefore described.
Examples of other pesticidally active compounds which may be included in, or used in conjunction with, the herbicidal compositions of the present invention include herbicides, for example to increase the range of weed species controlled for example alachlor [2-chloro-2,6'diethyl-N-(methoxy-methyl)-acetanilide], atrazine [2-chloro4- ethylamino-6-isopropylamino- 1,3,5 -triazine], bromoxynil [3,5-dibromo4-hydroxybenzonitrile], chiortoluron [N'-(3 -chloro-4-methylphenyl)- N,N-dimethylurea], <RT dimethylurea], isoproturon [N'-(4-isopropylphenyl)-N,N-dimethylurea], insecticides, e.g. synthetic pyrethroids, e.g permethrin and cypermethrin, and fungicides, e.g. carbamates, e.g. methyl N-(l-butyl-carbamoyl benzimidazol-2-yl)carbamate, and triazoles e.g. 1 -(4-chloro-phenoxy)- 3,3-dimethyl- 1 -(1,2,4-triazol- 1 -yl)-butan-2-one.
Pesticidally active compounds and other biologically active materials which may be included in, or used in conjunction with, the herbicidal compositions of the present invention, for example those hereinbefore mentioned, and which are acids, may, if desired, be utilised in the form of conventional derivatives, for example alkali metal and amine salts and esters.
The following Examples illustrate herbicidal compositions according to the present invention. The following trade marks appear in the Examples: Synperonic, Solvesso, Arylan, Arkopon, Sopropon,
Tixosil, Soprophor, Attagel, Rhodorsil.
Example Cl:
An emulsifiable concentrate is formed from:
Active ingredient (Compound 1) 20% w/v
N-Methylpyrrolidinone (NMP) 25% w/v
Calcium dodecylbenzenesulphonate (70%)
(CaDDBS) (Arylan CA) 4% w/v
Nonylphenol ethylene oxide propylene oxide
condensate (NPEOPO) (Synperonic NPE 1800) 6% w/v
Aromatic solvent (Solvesso) to 100 volumes
by stirring NMP, active ingredient (Compound 1), CaDDBS,
NPEOPO and Aromatic solvent until a clear solution is formed, and adjusting to volume with Aromatic solvent.
Example C2
A wettable powder is formed from:
Active ingredient (Compound 1) 50% w/w
Sodium dodecylbenzenesulphonate
(Arylan SX85) 3% w/w
Sodium methyl oleoyl taurate
(Arkopon T) 5% w/w
Sodium polycarboxylate (Sopropon T36) 1% wlw Microfine silicon dioxide (Tixosil 38) 3% w/w
China clay 38% w/w
by blending the above ingredients together and grinding the
mixture in an air jet mill.
Example C3
A suspension concentrate is formed from:
Active ingredient (Compound 1) 50% w/v
Antifreeze (Propylene glycol) 5% w/v
Ethoxylated tristyrylphenol phosphate
(Soprophor FL) 0.5% w/v
Nonyl phenol 9 mole ethoxylate
(Ethylan BCP) 0.5% w/v
Sodium polycarboxylate (Sopropon T36) 0.2% w/v
Attaclay (Attagel) 1.5% w/v
Antifoam (Rhodorsil AF426R) 0.003% w/v
Water to 100 volumes
by stirring the above ingredients together and milling in a bead mill.
Example C4
A water dispersible granule is formed from:
Active ingredient (Compound 1) 50% w/w
Sodium dodecylbenzenesulphonate
(Arylan SX 85) 3% w/w
Sodium methyl oleoyl taurate (Arkopon T) 5% w/w
Sodium polycarboxylate (Sopropon T36) 1% w/w
Binder (Sodium lignosulphonate) 8% w/w
China clay 30% w/w
Microfine silicon dioxide (Tixosil 38) 3% w/w
by blending the above ingredients together, grinding the mixture in an air jet mill and granulating by addition of water in a suitable granulation plant (e.g. Fluid bed drier) and drying. Optionally the active ingredient may be ground either on its own or admixed with some or all of the other ingredients.
The compounds of the invention have been used in herbicidal applications according to the following procedures.
METHOD OF USE OF HERBICIDAL COMPOUNDS:
TEST METHOD A
a) General
Appropriate quantities of the compounds used to treat the plants were dissolved in acetone to give solutions equivalent to application rates of up to 250g test compound per hectare (g/ha). These solutions were applied from a standard laboratory herbicide sprayer delivering the equivalent of 290 litres of spray fluid per hectare.
b) Weed control: Pre-emergence
The seeds were sown in 70 mm square, 75 mm deep plastic pots in non-sterile soil The quantities of seed per pot were as follows:
Weed species Approx number of seeds/pot
1) Broad-leafed weeds
Abutilon theophrasti 10
Amaranthus retroflexus 20
Galium aparine 10
Ipomoea purpurea 10
Xanthium strumarium 2
2) Grass weeds
Alopecurus myosuroides 15
Avena fatua 10 Echinochloa crus-galli 15
Setaria viridis 20
3) Sedges
Cyperus esculentus 3
Crop
1) Broad-leafed
Cotton 3
Soya 3
2) Grass
Maize 2
Rice 6
Wheat 6
The compounds of the invention were applied to the soil surface, containing the seeds, as described in (a). A single pot of each crop and each weed was allocated to each treatment, with unsprayed controls and controls sprayed with acetone alone.
After treatment the pots were placed on capillary matting kept in a glass house, and watered overhead. Visual assessment of crop damage was made 20-24 days after spraying. The results were expressed as the percentage reduction in growth or damage to the crop or weeds, in comparison with the plants in the control pots.
c) Weed control : Post-emergence
The weeds and crops were sown directly into John Innes potting compost in 75 mm deep, 70 mm square pots except for Amaranthus which was pricked out at the seedling stage and transferred to the pots one week before spraying. The plants were then grown in the greenhouse until ready for spraying with the compounds used to treat the plants. The number of plants per pot were as follows :
1) Broad leafed weeds
Weed species Number of plants per pot Growth stale Abutilon theophrasti 3 1-2 leaves
Amaranthus retroflexus 4 1-2 leaves
Galium aparine 3 1 st whorl
Ipomoea purpurea 3 1-2 leaves
Xanthium strumarium 1 2-3 leaves
2) Grass weeds
Weed species Number of plants per pot Growth state
Alopecurus myosuroides 8-12 1-2 leaves Avenafatua 12-18 1-2 leaves Echinochloa crus-galli 4 2-3 leaves
Setaria viridis 15-25 1-2 leaves.
3) Sedges
Weed species Number of plants per pot Growth stage Cyperus esculentus 3 3 leaves.
1) Broad leafed
Crops Number of plants per pot Growth stave
Cotton 2 1 leaf
Soya 2 2 leaves.
2) Grass
Crops Number of plants per pot Growth stage
Maize 2 2-3 leaves
Rice 4 2-3 leaves
Wheat 5 2-3 leaves.
The compounds used to treat the plants were applied to the plants as described in (a). A single pot of each crop and weed species was allocated to each treatment, with unsprayed controls and controls sprayed with acetone alone.
After treatment the pots were placed on capillary matting in a glass house, and watered overhead once after 24 hours and then by controlled sub-irrigation. Visual assessment of crop damage and weed control was made 20-24 days after spraying. The results were expressed as the percentage reduction in growth or damage to the crop or weeds, in comparison with the plants in the control pots.
TEST METHOD B
Paddv Dost-emereence apolication in greenhouse Paddy field soil was filled in 170 cm2 plastic pots, a suitable amount of water and chemical fertilisers were added thereto and kneaded to convert it to a state of a paddy.
Paddy rice plants (variety; Koshihikari), that had been grown in advance in a greenhouse to a stage of two leaves, were transplanted to each pot (two seedlings per pot). Then in each pot there were sown predetermined amounts of seeds of Echinochloa orvzicola, Monochoria vaginalis, Lindernia procumbens and Scirpus juncoides respectively, and water was added to a depth of3 cm.
After having grown the plants in a greenhouse until Echinochipa orvzicola reached a stage of 1.5 leaves, solutions were prepared in 100% acetone using compounds described in the Examples so that they contained active ingredients in an amount equivalent to 75, 300 and 1200 glha. The solutions were applied by dropping with a pipette.
After 21 days from the application with the chemicals, herbicidal effects on each weed and phytotoxicity on paddy rice plants were visually assessed, and the results expressed as the percentage reduction in growth or damage to the crop or weeds in comparison with the plants in the control pots.
When applied pre- or post-emergence in Test Method A at 250g/ha or less compound 1 of the invention gave at least 90% reduction in growth of one or more of the weed species; at levels of application toxic to the weeds this compound was selective in at least one of the crop species.
When applied at 1200 glha or less, in Test Method B, compounds 1-3 of the invention gave at least 90% reduction in growth of one or more of the weed species listed above.
Claims (17)
1. A 2-benzoylcyclohexane-1,3-dione derivative of formula (I)
wherein:
R1 represents a group of formula (II), (III), (IV), (V), (IVa) or (Va):
it being understood that in groups (II) to (Va) above the bond extending from the carbon atom adjacent to Q is a point of attachment between the respective group and the carbonyl group in formula (I);
R2 represents:
halogen;
lower alkyl which is substituted by one or more groups -OR10;
a cycloalkyl group containing from three to six carbon atoms; or a group selected from nitro, cyano, -CO2R10, -NR10R1 1, -S(O)pR12, -O(CH2)mOR1 0, -COR1 0, -N(R13)SO2R 2, -OR12, -OH, -OSO2R1 2, -(CR14R15)tS(O)qR12, -CONR10R11, -N(R13)-C(Z)=Y, -C(R14R15)NR13R16, CH2P(O)RlOaRlOb, R17, SF5 and benzyl optionally substituted by from one to five groups R18 which may be the same or different;
or two groups R2, together with adjacent carbon atoms of the phenyl ring form a second phenyl ring or a 5- or 6-membered saturated or unsaturated heterocyclic ring which is fused to the first ring and contains one or two oxygen or sulphur atoms and is optionally substituted by one or more halogen, lower alkyl, lower haloalkyl or lower alkoxy groups, or one of the ring carbon atoms of the heterocyclic ring forms part of a carbonyl group or an oxime or lower alkoxyimine derivative thereof;
n represents zero or an integer from one to three; where n is greater than one the groups R2 may be the same or different;
m represents one, two or three;
p and q represent zero, one or two;
t represents one, two, three or four;
X represents -(CR14R15)v-; v represents zero or one;
R3 represents a 5-membered heteroaromatic ring of formula (VI):
in which D, E, G and J independently represent CR19 or a nitrogen atom, with at least one of D, E, G and J representing CR19 (when more than one R19 group is present they may be the same or different);
or two adjacent groups may form a phenyl or a 5- to 7- membered heteroaromatic ring which is flised to the first ring and is optionally substituted by one or more groups R20, and when present the 5- to 7membered heterocyclic ring may contain from one to four heteroatoms in the ring which may be the same or different selected from nitrogen, oxygen and sulphur;
z represents one or two; when z represents two the -XR3 groups may be the same or different;
Q represents hydroxy, lower alkoxy, OR21, SR21 or SR22;
L represents oxygen or NR14;
R4, R4a, R4b, R5, R5a, R5b, R6, R6a, R6b, R7 R7a, R7b R8
R8a, R8b, R9, R9a and R9b represent the same or different groups selected from hydrogen, R17, -(CH2)UCo2Rl4, halogen, cyano, lower alkoxy, -(CH2)x-[phenyl optionally substituted by from one to five groups R18 which may be the same or different], and cycloalkyl containing from three to six carbon atoms optionally substituted by lower alkyl or S(O)pR22; u represents zero, one or two;
x represents zero or one;
R10 and R1 1 which may be the same of different, each represents hydrogen or R17; R1oa and R10b which may be the same or different, each represents lower alkyl or lower alkoxy;
R12 represents:
R17; or a cycloalkyl group containing from three to six carbon atoms; or a group -(CH2)w-[phenyl optionally substituted by from one to five groups R18 which may be the same or different];
w represents zero or one;
R13 represents:
hydrogen, R12 or OR22; R14 and R15 independently represent hydrogen, lower alkyl or lower haloalkyl;
R16 represents -SO2R12 or -C(Z)=Y;
R17 represents:
lower alkyl, lower haloalkyl, lower alkenyl, lower haloalkenyl, lower alkynyl or lower haloalkynyl;
R18 represents a group selected from halogen, R23, nitro, cyano, -CO2R1 0, -S(O)pR22, -OR22 and -NR10R11; R19 represents:
a group selected from hydrogen, halogen, R23, nitro, cyano, -C02R10, -S(o)pR22 -OR22, -NR10R11 and cyclopropyl;
R20 represents halogen or R1 7; R21 represents phenyl optionally substituted by from one to five groups selected from halogen, lower alkyl, lower haloalkyl, lower alkoxy and nitro;
R22 represents lower alkyl or lower haloalkyl;
R23 represents a straight- or branched- chain alkyl group containing one to three carbon atoms optionally substituted by one or more halogen atoms;
Y is oxygen or sulphur;
Z represents a group selected from R17, -NR24R25 -SR12 and -OR12; and R24 and R25 independently represent hydrogen or R12;
or an agriculturally acceptable salt or metal complex thereof.
2. A compound according to claim 1 wherein X represents -(CH2)v-.
3. A compound according to claim 1 or 2 wherein v is zero.
4. A compound according to claim 1, 2 or 3 in which the XR3 group is at the 2- or 4- position of the phenyl ring.
5. A compound according to any one of the preceding claims in which Q represents hydroxy or -S-phenyl.
6. A compound according to any one of the preceding claims in which R3 is selected from pyrazol-l-yl, imidazol- 1 -yl, 1,2,4-triazol-1-yl, 1,2,3 -triazol- 1 -yl, 1,2,3-triazol-2-yl, 1,2,3 ,4-tetrazol- 1 -yl and benzimidazol- 1 -yl.
7. A compound according to any one of the preceding claims in which R3 is a ring of formula (VI) wherein R19 represents hydrogen, halogen or R23.
8. A compound according to any one of the preceding claims in which R1 represents a group of formula (II) as defined in claim 1.
9. A compound according to any one of the preceding claims in which R2 represents halogen, a straight- or branched- chain alkyl group containing up to four carbon atoms optionally substituted by one or more halogen atoms; or a group selected from nitro, cyano, -S(O)pR12, -OR12, -CH2S(O)qR12 wherein R12 represents lower alkyl or lower haloalkyl; or benzyl optionally substituted by -S(O)pR22 wherein R22 represents lower alkyl; or two groups R2 together with adjacent carbon atoms of the phenyl ring form a second phenyl ring.
10. A compound according to any one of the preceding claims in which n represents one or two.
11. A composition comprising at least one 2-benzoylcyclohexane-1,3-dione derivative of formula (I) as defined in any one of claims 1 to 10 or an agriculturally acceptable salt or metal complex thereof, in association with an agriculturally acceptable diluent or carrier.
12. A method for controlling the growth of weeds at a locus which comprises applying to said locus an effective amount of at least one 2-benzoylcyclohexane- 1,3-dione derivative of formula (I) as defined in any one of claims 1 to 10, or an agriculturally acceptable salt or metal complex thereof or a composition according to claim 11.
13. A compound of formula (VII), (VIII), (IX) or (X):
wherein the various symbols are as defined in claim 1.
14. A compound of formula (XV):
wherein R2, R3, X n and z are as defined in claim 1.
15. A compound of formula (I) as defined in claim 1 substantially as hereinbefore defined.
16. A composition according to claim 11 substantially as hereinbefore defined.
17. A method according to claim 12 substantially as hereinbefore defined.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9715162A GB2327418A (en) | 1997-07-18 | 1997-07-18 | Derivatives of 2-benzoylcyclohexane-1,3-dione |
| PCT/EP1998/004951 WO1999003845A1 (en) | 1997-07-18 | 1998-07-15 | 2-benzoylcyclohexane-1,3-dione derivatives as herbicides and intermediates |
| AU93399/98A AU9339998A (en) | 1997-07-18 | 1998-07-15 | 2-benzoylcyclohexane-1,3-dione derivatives as herbicides and intermediates |
| TW087111593A TW508215B (en) | 1997-07-18 | 1998-07-16 | Novel compound, herbicidal composition comprising it and method for the control of weeds by using it |
| ARP980103507A AR016356A1 (en) | 1997-07-18 | 1998-07-17 | COMPOUNDS OF 2-BENZOILCICLOHEXAN-1,3-DIONA, PROCEDURE TO PREPARE THEM, HERBICIDE COMPOSITIONS FORMULATED WITH SUCH COMPOUNDS, METHOD FOR PARACONTROLING THE SCALES OF A PLACE WITH APPLICATION OF SUCH HERBICIDES AND INTERMEDIATE APPLICATION COMPOUNDS |
| US09/118,367 US5977376A (en) | 1997-07-18 | 1998-07-17 | Herbicidal 2-benzoylcyclohexane-1,3-diones and related compounds |
| ZA986381A ZA986381B (en) | 1997-07-18 | 1998-07-17 | Herbicides |
| US09/377,244 US6048984A (en) | 1997-07-18 | 1999-08-19 | Intermediates to herbicidal 2-benzoylcyclohexane-1,3-diones and related compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9715162A GB2327418A (en) | 1997-07-18 | 1997-07-18 | Derivatives of 2-benzoylcyclohexane-1,3-dione |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB9715162D0 GB9715162D0 (en) | 1997-09-24 |
| GB2327418A true GB2327418A (en) | 1999-01-27 |
Family
ID=10816068
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9715162A Withdrawn GB2327418A (en) | 1997-07-18 | 1997-07-18 | Derivatives of 2-benzoylcyclohexane-1,3-dione |
Country Status (6)
| Country | Link |
|---|---|
| AR (1) | AR016356A1 (en) |
| AU (1) | AU9339998A (en) |
| GB (1) | GB2327418A (en) |
| TW (1) | TW508215B (en) |
| WO (1) | WO1999003845A1 (en) |
| ZA (1) | ZA986381B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6376429B1 (en) | 1998-10-10 | 2002-04-23 | Hoechst Schering Agrevo Gmbh | Benzoylcyclohexanediones, process for their preparation and their use as herbicides and plant growth regulators |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2373137A1 (en) | 1999-05-07 | 2000-11-16 | Basf Aktiengesellschaft | Benzohetero cyclylcyclo hexenones and their use as herbicides |
| TWI382020B (en) | 2004-10-20 | 2013-01-11 | Kumiai Chemical Industry Co | 3-triazolylphenyl sulfide derivative and insecticide/acaricide/nematicide containing the same as active ingredient |
| JP5300225B2 (en) | 2007-08-03 | 2013-09-25 | バイエル・クロップサイエンス・アーゲー | Herbicide triazolyl pyridine ketones |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4780127A (en) * | 1982-03-25 | 1988-10-25 | Stauffer Chemical Company | Certain 2-(substituted benzoyl)-1,3-cyclohexanediones and their use as herbicides |
| EP0666254A1 (en) * | 1994-02-07 | 1995-08-09 | Basf Aktiengesellschaft | 2-Aroylcydohexanediones, process for their preparation and their use as herbicide or as plant growth regulating agent |
| US5536703A (en) * | 1995-01-13 | 1996-07-16 | Sandoz Ltd. | Herbicidal substituted benzoyl bicycloalkanediones |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4797150A (en) * | 1986-06-09 | 1989-01-10 | Stauffer Chemical Company | Certain 2-(2-substituted benzoyl)-1,3,5-cyclohexanetriones |
| DE3474297D1 (en) * | 1983-09-16 | 1988-11-03 | Stauffer Chemical Co | Certain 2-(2-substituted benzoyl)-1,3-cyclohexanediones |
| DE3839480A1 (en) * | 1988-11-23 | 1990-05-31 | Bayer Ag | N-ARYL NITROGEN HETEROCYCLES, METHOD AND NEW INTERMEDIATE PRODUCTS FOR THEIR PRODUCTION AND THEIR USE AS HERBICIDES AND PLANT GROWTH REGULATORS |
| US5189036A (en) * | 1990-06-20 | 1993-02-23 | Schering Ag | Imidazolylbenzoyl substituted heterocycles |
| US5834402A (en) * | 1995-02-24 | 1998-11-10 | Basf Aktiengesellschaft | Isoxazolylbenzoyl derivatives |
-
1997
- 1997-07-18 GB GB9715162A patent/GB2327418A/en not_active Withdrawn
-
1998
- 1998-07-15 AU AU93399/98A patent/AU9339998A/en not_active Abandoned
- 1998-07-15 WO PCT/EP1998/004951 patent/WO1999003845A1/en active Application Filing
- 1998-07-16 TW TW087111593A patent/TW508215B/en active
- 1998-07-17 AR ARP980103507A patent/AR016356A1/en unknown
- 1998-07-17 ZA ZA986381A patent/ZA986381B/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4780127A (en) * | 1982-03-25 | 1988-10-25 | Stauffer Chemical Company | Certain 2-(substituted benzoyl)-1,3-cyclohexanediones and their use as herbicides |
| EP0666254A1 (en) * | 1994-02-07 | 1995-08-09 | Basf Aktiengesellschaft | 2-Aroylcydohexanediones, process for their preparation and their use as herbicide or as plant growth regulating agent |
| US5536703A (en) * | 1995-01-13 | 1996-07-16 | Sandoz Ltd. | Herbicidal substituted benzoyl bicycloalkanediones |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6376429B1 (en) | 1998-10-10 | 2002-04-23 | Hoechst Schering Agrevo Gmbh | Benzoylcyclohexanediones, process for their preparation and their use as herbicides and plant growth regulators |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1999003845A1 (en) | 1999-01-28 |
| AU9339998A (en) | 1999-02-10 |
| TW508215B (en) | 2002-11-01 |
| GB9715162D0 (en) | 1997-09-24 |
| ZA986381B (en) | 1999-02-23 |
| AR016356A1 (en) | 2001-07-04 |
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