CA1185974A - 1,3,5-triazinones and their use for controlling undesirable plant growth - Google Patents
1,3,5-triazinones and their use for controlling undesirable plant growthInfo
- Publication number
- CA1185974A CA1185974A CA000416267A CA416267A CA1185974A CA 1185974 A CA1185974 A CA 1185974A CA 000416267 A CA000416267 A CA 000416267A CA 416267 A CA416267 A CA 416267A CA 1185974 A CA1185974 A CA 1185974A
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- CA
- Canada
- Prior art keywords
- carbon atoms
- formula
- halogen
- alkyl
- hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/30—Only oxygen atoms
- C07D251/34—Cyanuric or isocyanuric esters
Abstract
Abstract of the disclosure: 1,3,5-Triazinones of the formula
Description
7 ~
o ~. r~50/356~7 1,3,5-Tri~inones and their use. ~or ccntrolli~g undesirable plant gro~th The present invention relates to 1~3,5~triazi-nones, herbicides containing these compounds as -the active ingredients1 and a method of controlling undesi-rable plant growth using these active ingredients.
German Laid-Open Application DOS 2,246,109 has disclosed the use of phenoxy~substituted N-phenyl-1,3,5-triazinones~ such as l-[4-(2'-chloro-4'-trifluoromethyl-phenoxy)-phenyl]-3-methyl-1,3,5-triazine 1-2,4,6-(lH,3H,-5H)-trione, as drugs, especially as coccidiostatics.
We have found that 1,~,5-triazinones of the formula 1 'J~ 2 O N3 0 (I) R
zl where R~ is ~ ~ Z3 where zl and z2 independently of one another are each hydrogen, halogen, nitro, cyano or carboxyl, or alkyl, haloalkyl or alkoxy, each of not more than 4 carbon atoms, Z3 is halogen, nitro or cyano, or alkyl, haloalkyl, alkoxy, haloalkoxy, alkylmercapto, haloalkylmercapto, alkylsulfinyl, halo-alkylsulfinyl, alkylsulfonyl or haloalkylsulfonyl, each of not more than 4 ca-bon atoms, and Y is hydrcgen, halogen, cyano or nitro~ and R2 is hydrogen or a J5~
~ 2 ~ ~j.'. O()'(j/356~
saturated or unsatura-ted, s-traight-chaln or branched aliphatic radical of not more than 20 carbon atoms, or R is a saturated 7 straight chain or branched allphatic radical of no-t more than 10 carbon atoms whi.ch is substituted by halogen, cyano, hydroxyl or mercapto, or by alkoxy or alkylmercapto 3 each of not more than 4 carbon atoms, or by phenylmercapto 7 or by alkylamino or dlalkylamino, where each alkyl is of 1 to 4 carbon atoms, or R2 is cycloalkyl of 3 to 7 carbon atoms l~hich lG is ~nsubstituted or substituted by alkoxy o~ 1 to 4 car-bon atoms, or R2 is phenyl which is unsubstituted or substituted by halogen, or by alkyl or alkoxy, each of 1 to 4 carbon atoms, or by nitro or cyano, or 'Dy halo-alkyl, haloalkoxy or haloalXylmercapto 9 each of 1 to 4 carbon atoms, or R~ is benzyl or halobenzyl, and R~ is hydrogen, alkyl of n~ more than 4 carbon atoms or acyl o~ not more than 7 carbcn atoms which is ~lsubstituted or substituted by halogen, or is an alkali metal ion or an ammonium ion, which may be alkylated, have very good herbicidal proper-ties and are selective in crops.
In formula I, if Rl is zl Y ~ o ~ z3 zl and z2 independently of one another can each ~e, for example, hydrogen, halogen, such as fluorine, chlorine, bromine or iodine, nitro, c-~ano or carboxyl, or al~yl, _ 3 _ O.Z. OO~(j/35~
haloalkyl or alkoxy 9 each of not more than 4 carbon atoms, eg, meth-yl, ethyl, n-propyl, i-propyl, n-out;l, tert.-butyl, trifluoromethyl, difluoromethyl, fluoromethyl, trichloromethyl, dichloromethyl 9 chloromethyl, difluoro~
chloromethyl, l-chloroe~hyl, 2 chloroe~thyl, l-fluoroethyl,
o ~. r~50/356~7 1,3,5-Tri~inones and their use. ~or ccntrolli~g undesirable plant gro~th The present invention relates to 1~3,5~triazi-nones, herbicides containing these compounds as -the active ingredients1 and a method of controlling undesi-rable plant growth using these active ingredients.
German Laid-Open Application DOS 2,246,109 has disclosed the use of phenoxy~substituted N-phenyl-1,3,5-triazinones~ such as l-[4-(2'-chloro-4'-trifluoromethyl-phenoxy)-phenyl]-3-methyl-1,3,5-triazine 1-2,4,6-(lH,3H,-5H)-trione, as drugs, especially as coccidiostatics.
We have found that 1,~,5-triazinones of the formula 1 'J~ 2 O N3 0 (I) R
zl where R~ is ~ ~ Z3 where zl and z2 independently of one another are each hydrogen, halogen, nitro, cyano or carboxyl, or alkyl, haloalkyl or alkoxy, each of not more than 4 carbon atoms, Z3 is halogen, nitro or cyano, or alkyl, haloalkyl, alkoxy, haloalkoxy, alkylmercapto, haloalkylmercapto, alkylsulfinyl, halo-alkylsulfinyl, alkylsulfonyl or haloalkylsulfonyl, each of not more than 4 ca-bon atoms, and Y is hydrcgen, halogen, cyano or nitro~ and R2 is hydrogen or a J5~
~ 2 ~ ~j.'. O()'(j/356~
saturated or unsatura-ted, s-traight-chaln or branched aliphatic radical of not more than 20 carbon atoms, or R is a saturated 7 straight chain or branched allphatic radical of no-t more than 10 carbon atoms whi.ch is substituted by halogen, cyano, hydroxyl or mercapto, or by alkoxy or alkylmercapto 3 each of not more than 4 carbon atoms, or by phenylmercapto 7 or by alkylamino or dlalkylamino, where each alkyl is of 1 to 4 carbon atoms, or R2 is cycloalkyl of 3 to 7 carbon atoms l~hich lG is ~nsubstituted or substituted by alkoxy o~ 1 to 4 car-bon atoms, or R2 is phenyl which is unsubstituted or substituted by halogen, or by alkyl or alkoxy, each of 1 to 4 carbon atoms, or by nitro or cyano, or 'Dy halo-alkyl, haloalkoxy or haloalXylmercapto 9 each of 1 to 4 carbon atoms, or R~ is benzyl or halobenzyl, and R~ is hydrogen, alkyl of n~ more than 4 carbon atoms or acyl o~ not more than 7 carbcn atoms which is ~lsubstituted or substituted by halogen, or is an alkali metal ion or an ammonium ion, which may be alkylated, have very good herbicidal proper-ties and are selective in crops.
In formula I, if Rl is zl Y ~ o ~ z3 zl and z2 independently of one another can each ~e, for example, hydrogen, halogen, such as fluorine, chlorine, bromine or iodine, nitro, c-~ano or carboxyl, or al~yl, _ 3 _ O.Z. OO~(j/35~
haloalkyl or alkoxy 9 each of not more than 4 carbon atoms, eg, meth-yl, ethyl, n-propyl, i-propyl, n-out;l, tert.-butyl, trifluoromethyl, difluoromethyl, fluoromethyl, trichloromethyl, dichloromethyl 9 chloromethyl, difluoro~
chloromethyl, l-chloroe~hyl, 2 chloroe~thyl, l-fluoroethyl,
2-fluoroethyl, 2,2,2-trichloroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, 1,1,2 trifluoro-2-chloroethyl, 9 2 3 2,2-pentafluoroethyl, methoxy, ethox~J, n-propoxy, i-propoxy or tert.-butoxy, and Z3 is ha].ogen, such as 0 fluorine, chlorine, bromine or iodine, or nitro or cyano, or alkyl, haloalkyl, alkoxy, haloalkoxy, alkylmercapto, haloalkylmercapto, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl or haloalkylsulfonyl, each of not more than 4 carbon atoms, eg. methyl 9 ethyl 9 n-propyl) i-propyl, n-butyl, -tert,-butyl, trifluoromethyl, di~luoro-methyl, fluoromethyl, trichloromethyl, dichloromethyl, chlorome-thyl, difluorochloromethyl, l-chloroethyl, 2~
chloroethyl, l~fluoroethyl, 2-fluoroethyl, 2,2,2-tri-chloroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-te-tralluoro-) ethyl, 1,1,2-trifluoro-2-chloroethyl, 1,1,2~2 t 2-penta-fluoroethyl, methoxy, n-propoxy, i-propoxy~ tert,-butoxy, trichlorometho~y, trifluoromethoxy, l-chloro-ethoxy, 2-chloroethoxy, l-fluoroethoxy, 2-fluoroethox~J, 2,2,2~trichloroethoxy, 2,2,2-trifluoroetkoxy, 1,1,2,2-tetrafluoroethoxy, 1,1,2,2,2-pentafluoroethoxy, methyl-mercapto, ethylmercapto, trickloromethylmercapto, tri-fluoromethylmercapto, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl or trifluoromethylsulfonyl, and Y can be, for example, halogen, such as fluorinet _ 4 _ o.z GG~,o/356~7 chlorine, bromine or iodine, or h~drogen, c~Jano or nitro.
R2 in formula I is hydrogen, or is a saturated or unsaturated, s-traight-chain or br~nched aliphatic radical of not more than 20 carbon atoms, for example alkyl of not more than 20 carbon atoms, preferably of not more than 12 and especially of not more than 4 carbon atoms, or alkenyl or alk~nyl of not more than 20 carbon atoms, preferably of not more than 12 and especially o~
not more than 4 carbon atoms, eg. methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec.-butyl, tert.-butyl, n-pentyl, tert -amyl, n-hexyl, pent-3-yl, l,2-dimethyl-n-propyl, l,3-dimethyl-n-butyl, l-ethyl-2-methyl-n propyl, l,2,2-trimethyl-n-propyl, l,2-dimethyl-4-hexyl, allyl, methallyl, crotyl, 2-ethyl-hex-2-enyl, hex-5-enyl, 2-methyl-but-2-enyl, 2-methyl-but-3-enyl, but-l-en-~-yl, 2-methyl-but-l-en-4~yl, 2-methyl-but- 2-en-4-yl, 3 methyl-but-l-en-3-yl, propargyl, but~ n-3-yl or bu-t-2-ynyl, or R is a saturated, straigh-t-chain or branched aliphatic radical of not more than lO carbon atoms, pre-2~) ferably of not more than 4 carbon atoms, which is sub-stituted by halogen, cyano, hydroxyl, mercapto or alkoxy o~ l to 4 carbon atoms, for example alkyl of not more than lO carbon atoms, preferably of l to 4 carbcn atoms, which is substituted by halogen, cyano, hydroxyl, mer-capto or alkoxy of not more than 4 carbon atoms~ eg.
2-chloroethyl, 2-chloro-n-propyl, 3-chloro-n-propyl, 2-chloro-sec,-butyl, 2-chloro-isobutyl, 2-fluoro-sec.-butyl, 2-fluoro-isobutyl, 2-fluoro-isopropyl, chloro-tert -butyl, 2,2,2-trifluoroethyl, l-cyanomethyl, ~ ~ ~ s~j~7~
-- 5 ~
2-cyanomethy],, 2-hydroxyethyl, 3-hydroxy~n~propyl, 2-mercapto-ethyl, 3-mercapto-n~propyl, 2-methoxye-thyl, 2-ethoxy-ethyl, 3-methoxy-n-propyl, 2-methoxy-lsopropyl, 3-methoxy-n-butyl, l-methoxy-sec.-butyl, methoxy-tert.-butyl, ethoxy-tert.-butyl, 2~methoxy-n-butyl or 4-methoxy-n-bu-tyl, or R
is cycloalkyl of 3 to 7 carbon atoms which is unsubstltuted or substituted by alkoxy of 1 to 4 carbon atoms, eg. cyclo propyl, cyclopentyl, cyclohexyl or q-ethoxycyclohexyl.
R can also be a satura-ted, straight-chain or branched aliphatic radical of not more than 10 carbon atoms which is substituted by phenylmercapto, by alkylmercapto of not more than 4 carbon atoms, or by alkyl- or dialkylamino, where alkyl is of 1 to 4 carbon atoms, for example alkyl of not more than 10 carbon atoms, preferably of 1 to 4 carbon atoms, which is substituted by phenylmercapto or alkyl-mercapto of 1 to 4 carbon atoms or by alkylamino or dialkyl-amino, where each alkyl is of 1 to 4 carbon atoms, eg.
2-methylmercapto-ethyl, 2-ethylmercapto-ethyl, 3-methyl-mercapto-n-propyl, 3-methylmercapto-n-butyl, l-methylmercapto-2t) sec.-butyl, methylmercapto-tert.~butyl, 2-methylmercapto-n-butyl, 2-methylaminoethyl, 2-ethylaminoethyl, 2-dimethyl-aminoethyl, 2-diethylaminoethyl, 2-dimethylamino-n-propyl,
chloroethyl, l~fluoroethyl, 2-fluoroethyl, 2,2,2-tri-chloroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-te-tralluoro-) ethyl, 1,1,2-trifluoro-2-chloroethyl, 1,1,2~2 t 2-penta-fluoroethyl, methoxy, n-propoxy, i-propoxy~ tert,-butoxy, trichlorometho~y, trifluoromethoxy, l-chloro-ethoxy, 2-chloroethoxy, l-fluoroethoxy, 2-fluoroethox~J, 2,2,2~trichloroethoxy, 2,2,2-trifluoroetkoxy, 1,1,2,2-tetrafluoroethoxy, 1,1,2,2,2-pentafluoroethoxy, methyl-mercapto, ethylmercapto, trickloromethylmercapto, tri-fluoromethylmercapto, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl or trifluoromethylsulfonyl, and Y can be, for example, halogen, such as fluorinet _ 4 _ o.z GG~,o/356~7 chlorine, bromine or iodine, or h~drogen, c~Jano or nitro.
R2 in formula I is hydrogen, or is a saturated or unsaturated, s-traight-chain or br~nched aliphatic radical of not more than 20 carbon atoms, for example alkyl of not more than 20 carbon atoms, preferably of not more than 12 and especially of not more than 4 carbon atoms, or alkenyl or alk~nyl of not more than 20 carbon atoms, preferably of not more than 12 and especially o~
not more than 4 carbon atoms, eg. methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec.-butyl, tert.-butyl, n-pentyl, tert -amyl, n-hexyl, pent-3-yl, l,2-dimethyl-n-propyl, l,3-dimethyl-n-butyl, l-ethyl-2-methyl-n propyl, l,2,2-trimethyl-n-propyl, l,2-dimethyl-4-hexyl, allyl, methallyl, crotyl, 2-ethyl-hex-2-enyl, hex-5-enyl, 2-methyl-but-2-enyl, 2-methyl-but-3-enyl, but-l-en-~-yl, 2-methyl-but-l-en-4~yl, 2-methyl-but- 2-en-4-yl, 3 methyl-but-l-en-3-yl, propargyl, but~ n-3-yl or bu-t-2-ynyl, or R is a saturated, straigh-t-chain or branched aliphatic radical of not more than lO carbon atoms, pre-2~) ferably of not more than 4 carbon atoms, which is sub-stituted by halogen, cyano, hydroxyl, mercapto or alkoxy o~ l to 4 carbon atoms, for example alkyl of not more than lO carbon atoms, preferably of l to 4 carbcn atoms, which is substituted by halogen, cyano, hydroxyl, mer-capto or alkoxy of not more than 4 carbon atoms~ eg.
2-chloroethyl, 2-chloro-n-propyl, 3-chloro-n-propyl, 2-chloro-sec,-butyl, 2-chloro-isobutyl, 2-fluoro-sec.-butyl, 2-fluoro-isobutyl, 2-fluoro-isopropyl, chloro-tert -butyl, 2,2,2-trifluoroethyl, l-cyanomethyl, ~ ~ ~ s~j~7~
-- 5 ~
2-cyanomethy],, 2-hydroxyethyl, 3-hydroxy~n~propyl, 2-mercapto-ethyl, 3-mercapto-n~propyl, 2-methoxye-thyl, 2-ethoxy-ethyl, 3-methoxy-n-propyl, 2-methoxy-lsopropyl, 3-methoxy-n-butyl, l-methoxy-sec.-butyl, methoxy-tert.-butyl, ethoxy-tert.-butyl, 2~methoxy-n-butyl or 4-methoxy-n-bu-tyl, or R
is cycloalkyl of 3 to 7 carbon atoms which is unsubstltuted or substituted by alkoxy of 1 to 4 carbon atoms, eg. cyclo propyl, cyclopentyl, cyclohexyl or q-ethoxycyclohexyl.
R can also be a satura-ted, straight-chain or branched aliphatic radical of not more than 10 carbon atoms which is substituted by phenylmercapto, by alkylmercapto of not more than 4 carbon atoms, or by alkyl- or dialkylamino, where alkyl is of 1 to 4 carbon atoms, for example alkyl of not more than 10 carbon atoms, preferably of 1 to 4 carbon atoms, which is substituted by phenylmercapto or alkyl-mercapto of 1 to 4 carbon atoms or by alkylamino or dialkyl-amino, where each alkyl is of 1 to 4 carbon atoms, eg.
2-methylmercapto-ethyl, 2-ethylmercapto-ethyl, 3-methyl-mercapto-n-propyl, 3-methylmercapto-n-butyl, l-methylmercapto-2t) sec.-butyl, methylmercapto-tert.~butyl, 2-methylmercapto-n-butyl, 2-methylaminoethyl, 2-ethylaminoethyl, 2-dimethyl-aminoethyl, 2-diethylaminoethyl, 2-dimethylamino-n-propyl,
3-dimethylamino~n~propyl or 4-dimethylamino-n-butyl, or R2 ls phenyl which is unsubstituted or substituted by halogen, or by alkyl or alkoxy of 1 to 4 carbon atoms, or by nitro or cyano, or by haloalkyl, haloalkoxy or haloalkylmercapto of 1 to 4 carbon a-toms, or is benzyl or halobenzyl, eg. phenyl,
4-chlorophenyl, 3,4-dichlorophenyl, o-, m- or p tert.-~ 0 Z. ~050/35~7bu-tylphenyl, o-, m- or p-metho.xyphen~l, o-, m- or p-methylphenyl, 4-methory-3-chlorophen~l, 2-methyl-4-chlorophenyl~ 4~nitrophenyl, 4-nitro-2-chlorophenyl, o-, m- or p-cyanophenyl, o- or m trifluoromethylphenyl, ~-chloro-4-triIluorome thylphenyl 9 4-trifluoromethoxy-phenyl, 4-trifluorometh~lmercaptophenyl, 3-trifluoro-methylmercaptophenyl, benzyl, 2 9 6-dichlorobenzyl, 2-chloro-6-fluorobenzyl, 2,6-diiluorobenzyl, or o~ or p-chlorobenzyl.
R3 can be hydrogen, al~yl of no~ more than 4 car-bon atoms, or acyl of not more than 7 carbon atoms, which may be substituted by halogen, or an alkali metal ion or an ammonium ion, l~hich may be alkylated~ eg~ methyl 9 ethyl, n-propyl, isopropyl, n-butyl, 2 butyl, formyl, acetyl, chloroacetyl, benzoyl, sodium, potassium, ammo-nium, methylammonium, dimethylammonium, trimethylammonium or tetramethylammonium.
Preferred 1,3,5-triazinones are those compounds of the formula I where Rl ls Z~
Y ~ ~ ~ z3 where zl and z2 independently of one another are hydro-gen, chlorine, bromine or cyano, Z3 ls chlorine, bromine, methyl, trifluoromethoxy, trifluoromethylmercapto or trifluoromethyl, preferably trifluoromethyl, ar.d ~ is bromine or nitro, in particular nitro, and R2 is al~yl of 1 to 4 carbon atoms, ~hich is ~substituted or sub-stituted by halogen, cyano, alko~y or alkylmercapto, or 7~
- / - o.Z~ 0050/35~87 is cycloalkyl of 3 to '7 car'oon atoms, or is phenyl which is substituted b~J haloalkyl of l to L, carbon atoms or by halogen, or i~ halobenzyl, preferabl~J methyl, ethyl, 2-chloroethyl, 2-cyanoethyl, 2~methoxyethyl, 2-methyl-mercaptoethyl, cyclohexyl, 3,4-dichlorophenyl, ~-tri-fluoromethylphenyl or 4-chlorobenzyl, in par-ticular methyl 9 2 chloroethyl, 2-methoxyethyl or 3,4-dichloro-phenyl, &nd R~ is hydrogen, methyl or sodium.
~le compounds of the formula I where R3 is hydrogen can be prepared, for example, by the following process:
~ phenoxy-substituted urea of the formula zl O
~2 NHCNHR
where zl, z2, z3, y and R2 have the above rneanings, is reacted with a substituted carbonyl isocyanate of the form~la o R --C-~=C-0 (III) where R4 is halogen, alXoxy or arylo~cy, in an inert organic solvent, with or without addition of an acid acceptcr, at from -20 to +180C 3 preferably from +20 to +150C, at atmospheric or superatmospheric pressure, l continuously or batchwise, to give a substituted 1,3J5-triazinone of the formula ~.L~
o . z . o~ 5(j/356~7 ,$ ' i P
where zl, z2~ z3, y and R2 have the above meanings.
If desired, this product can then be acylated or al~ylated with an acyl halide of the ~ormula R3CoX, an alkyl halide of the formula R3~ or a dîalkylsulfate of the formula (R30)2So2, where R3 in each case has the above meanings, with the exception of hydrogen, and X is halogen 9 or converted into a salt of the formula I with an alkali metal alcoholate, an alkali metal hydro~ide, ammonium hydroxide or an alkylated ammonium hydroxide.
If N-3-(2'-chloro-4'-trifluoromethylpheno~3)-6-nitro-phenyl-N'-methylurea and chlorocarbonylisocyanate ~re used as the starting substances and dimeth~31sulfate .is used as the a~kylating agent, the course OL the reac-tion can be represented by the following equa~ion:
o ~
HC~IHC~_ 1 C= ~12 0 ~ - H C 1 ~ ,~
F C ~0 / ~ C~
3C4~'~' 0~1~) C1 ~ H
( C~30 ) 2SOG/
9 ~ O.Z. 0050/356~7 F C- ~ 0 0 N o 3 ~ CH3 Cl The reaction is carried out in organic sol~ents which are inert under the partic~lar conditi.ons) ~or example halohydrocarbons, in particular aromatic or aliphatic chlorohydrocarbons, eg~ tetrachloroethylene, 1,1,2,2- or 19~ 2-tetrachloroethane, dichloropropane, methylene chloride,dichlorobutane, chloro~orm9 chloro-naphthalene, dichloronaphthalene 9 carbon tetrachloride, 1,1,1- or 1,1,2-trichloroethane, trichloroethylene, pentachloroethane, o-, m- or p di~luorobenzene, 1,2-I() dichloroethane, 1,l-dichloroethane, 1,2-cis-dichloro-ethylene, chlorobenzene, fluorobenzene, bromobenzene, iodobenzene, o-, m- or p-dichlorobenzene, o- 9 m- or p-dibromo~.enzene, o- 9 m- or p-chlorotoluene or 1,2 9 4-trichlorobenzene,ethers, eg. ethtJl propyl ether, me-thyl tert.-butyl ether, n-butyl ethyl ether, di~n-butyl ether, diisobutyl ether, diisoamyl ether, diisopropyl ether, anisole, phenetole, cyclohexyl methyl ether, diethyl ether, ethylene glycol dimeth~Jl ether, tetrah~Jdrofuran, dioxane or ~,3'-dichlorodiethyl ether, nitrohydrocarbons, eg~ nitromethane, nitroethane, nitrobenzene, o~, m- or p-chloronitrobenzene and o-nitrotoluene, nitriles, acetonitrile, butyronitrile, isobutyronitrile, benzo~
nitrile and m-chloroben70ni-trile, aliphatic or c~Jclo-~ f~
- 10 - 0.~ )()50/350~
aliphatic hydrocarbons, eg~ heptarle, plnane, nonane, o-, m- or p-c~Jmene, gasoline fractions ~ thin a boiling point range of from 70 to 190C, cyclohexane, methyl-cyclohexane, decalin, petroleum ether, hexane, naphtha, 2 9 2,4-trimethylpentane, 2,2,3-trimethylpentane, 2,3,3-trlmethylpentane and octane, esters, eg. e-thyl acetate, ethyl acetoacetate and isobutyl ace-tate, amides, egq formamide, methylformamide and dime-thylformamlde, and ketones, egu acetone and methyl ethyl ketone, and app~op_ riat~ mixtures. The solvent is advantageously used in an amount of from 100 to 2,000% by weight, preferably from 200 to 700% by ~eight, based on the starting substances~
l~e hydrochloric acid formed during the reaction escapes as a gas, or is bonded by acid acceptors. ~ny o~ the conventional acid acoeptors can be used, pre-ferably tertiary amines, alkaline earth metal compounds 7 al~monium compounds and alkali metal compounds or appro-priate miYtures9 Zinc compounds can also be used.
'0 Examples o~ suitab].e basic compounds are potassium hydroxide, sodium carbonate~ lithium hydroxide 9 lithium carbonate, sodium bicarbonate 9 potassium bicarbonate, calcium hydroxide, calcium oxide, barium oxide~ magnesium hydroxide 9 magnesium oxide, barium hydroxide, calcium carbonat~, magnesium carbonate, magnesium bicarbonate 9 magnesium acetate 9 zinc hydroxide 9 zinc oxide, zinc carbonate, zinc bicarbonate, zinc acetate, sodium formate~
sodium acetate 7 trimethylamine, triethylamine t trlpropyl-amine, triisopropylamine, tributylamine, -triisobutylamine 7 rj~f~r~
~ .Z. ()050/35~7 tri-sec butylamine, tri-~ert -bu~tylamine, tribenzylamine, tricyclohexylamine~ ~riamylamine~ diisopropylethylamine, trihexylamine, N,M~dimethyl~niline, N,N-diethylaniline, N,N dipropyltoluidine, N,N-dimethyl-p-aminopyridine, N-methylpyrrolidone, N-ethylpyrrolidone, N~methylpiperi-dine, N-ethylpiperidine 7 N-methyl-pyrrolidine, N-ethyl-pyrrolidine, N~methylimidazole, N-ethylirnidazoIe, N-methylpyrrole, N-ethylpyrrole, N-methylmorpholine, N-ethylmorpholine, N-methylhexamethyleneimine, N-ethyl-hexamethyleneimine, pyridine, quinoline, a-picoline, ~-picoline 9 ~-picoline, isoquinoline~ pyrimidine, acridine, N,N,N',N'-tetramethyleth~Jlenediamine, N,N,N',-N'-tetraethylethylenediamine, quinoxaline, quinazoline, N-propyldiisopropylamine, N,N-dimethylcyclohex~lamine, 2,6-lutidine, 2,4-lutidine, trifurfurylamine and tri-ethylenediamine.
The starting substances are reacted in, for e~-ample, approcimately the stoichiometric ratio, iec starting substance III can be employed in, for example 9 an eccess of not more than 20 mole%, based on II.
The process for the preparation of the compounds of the formula I is advantageously carried out by taking the starting substance II, if appropriate in one of ~he above diluents, and then adding t~e starting substance III and, where appropriate, an acid acceptor, at the s~me time or successively. However, it is also pos-sible to take the starting substance III in a diluent and then to add the starting substance II and an acid acceptor by -two separate lines, at the same tlme or in 12 - ~J Z ~,050/356?,7 ~ither order.
In many cases, the reaction has ende~-once the components ha~re been brought ~o~ether, other~ise ~he mixture is sti~red for a ~ur~her period o~ from 10 minutes to 10 hours at from ~20 to 180C, pre~f~rably from 20 to 150C and in particular from 40 tc lOO~C, until the reac-tlon has ended If an inert gas is used to remove the hydrogen halide, stirring is adv~ltageously continued for from O~2 to 10 hours at from 40 to 100C.
~ he end product I is isolated from the reaction mixture in a conventional manner, for example a~ter distilling off solvents or excess starting substance III
or directly by filtration with suction~ In this case, the residue which remains is washed with water or dilute alkali, to remove acid impurities, and dried. If water-immiscible diluents are used, the reaction mi~ture can also be extracted directly with water or with dilute alkali and the extract then dried and concentrated.
~) However, it is also possible to dissolve the residue in a water-immiscible solvent and to wash the solution as described. m e desired end products are thereby obtained in a pure form, and if necessary they can be purified by recrysta lization, chromatography or distil-lation.
The compounds of the formula I where R' is alkyl, acyl, an alkali metal ion or an ammonium ion which may be alkylated can be prepared from the correspo~ding com-pounds of the ~ormula I where R3 is hydrogen , in a
R3 can be hydrogen, al~yl of no~ more than 4 car-bon atoms, or acyl of not more than 7 carbon atoms, which may be substituted by halogen, or an alkali metal ion or an ammonium ion, l~hich may be alkylated~ eg~ methyl 9 ethyl, n-propyl, isopropyl, n-butyl, 2 butyl, formyl, acetyl, chloroacetyl, benzoyl, sodium, potassium, ammo-nium, methylammonium, dimethylammonium, trimethylammonium or tetramethylammonium.
Preferred 1,3,5-triazinones are those compounds of the formula I where Rl ls Z~
Y ~ ~ ~ z3 where zl and z2 independently of one another are hydro-gen, chlorine, bromine or cyano, Z3 ls chlorine, bromine, methyl, trifluoromethoxy, trifluoromethylmercapto or trifluoromethyl, preferably trifluoromethyl, ar.d ~ is bromine or nitro, in particular nitro, and R2 is al~yl of 1 to 4 carbon atoms, ~hich is ~substituted or sub-stituted by halogen, cyano, alko~y or alkylmercapto, or 7~
- / - o.Z~ 0050/35~87 is cycloalkyl of 3 to '7 car'oon atoms, or is phenyl which is substituted b~J haloalkyl of l to L, carbon atoms or by halogen, or i~ halobenzyl, preferabl~J methyl, ethyl, 2-chloroethyl, 2-cyanoethyl, 2~methoxyethyl, 2-methyl-mercaptoethyl, cyclohexyl, 3,4-dichlorophenyl, ~-tri-fluoromethylphenyl or 4-chlorobenzyl, in par-ticular methyl 9 2 chloroethyl, 2-methoxyethyl or 3,4-dichloro-phenyl, &nd R~ is hydrogen, methyl or sodium.
~le compounds of the formula I where R3 is hydrogen can be prepared, for example, by the following process:
~ phenoxy-substituted urea of the formula zl O
~2 NHCNHR
where zl, z2, z3, y and R2 have the above rneanings, is reacted with a substituted carbonyl isocyanate of the form~la o R --C-~=C-0 (III) where R4 is halogen, alXoxy or arylo~cy, in an inert organic solvent, with or without addition of an acid acceptcr, at from -20 to +180C 3 preferably from +20 to +150C, at atmospheric or superatmospheric pressure, l continuously or batchwise, to give a substituted 1,3J5-triazinone of the formula ~.L~
o . z . o~ 5(j/356~7 ,$ ' i P
where zl, z2~ z3, y and R2 have the above meanings.
If desired, this product can then be acylated or al~ylated with an acyl halide of the ~ormula R3CoX, an alkyl halide of the formula R3~ or a dîalkylsulfate of the formula (R30)2So2, where R3 in each case has the above meanings, with the exception of hydrogen, and X is halogen 9 or converted into a salt of the formula I with an alkali metal alcoholate, an alkali metal hydro~ide, ammonium hydroxide or an alkylated ammonium hydroxide.
If N-3-(2'-chloro-4'-trifluoromethylpheno~3)-6-nitro-phenyl-N'-methylurea and chlorocarbonylisocyanate ~re used as the starting substances and dimeth~31sulfate .is used as the a~kylating agent, the course OL the reac-tion can be represented by the following equa~ion:
o ~
HC~IHC~_ 1 C= ~12 0 ~ - H C 1 ~ ,~
F C ~0 / ~ C~
3C4~'~' 0~1~) C1 ~ H
( C~30 ) 2SOG/
9 ~ O.Z. 0050/356~7 F C- ~ 0 0 N o 3 ~ CH3 Cl The reaction is carried out in organic sol~ents which are inert under the partic~lar conditi.ons) ~or example halohydrocarbons, in particular aromatic or aliphatic chlorohydrocarbons, eg~ tetrachloroethylene, 1,1,2,2- or 19~ 2-tetrachloroethane, dichloropropane, methylene chloride,dichlorobutane, chloro~orm9 chloro-naphthalene, dichloronaphthalene 9 carbon tetrachloride, 1,1,1- or 1,1,2-trichloroethane, trichloroethylene, pentachloroethane, o-, m- or p di~luorobenzene, 1,2-I() dichloroethane, 1,l-dichloroethane, 1,2-cis-dichloro-ethylene, chlorobenzene, fluorobenzene, bromobenzene, iodobenzene, o-, m- or p-dichlorobenzene, o- 9 m- or p-dibromo~.enzene, o- 9 m- or p-chlorotoluene or 1,2 9 4-trichlorobenzene,ethers, eg. ethtJl propyl ether, me-thyl tert.-butyl ether, n-butyl ethyl ether, di~n-butyl ether, diisobutyl ether, diisoamyl ether, diisopropyl ether, anisole, phenetole, cyclohexyl methyl ether, diethyl ether, ethylene glycol dimeth~Jl ether, tetrah~Jdrofuran, dioxane or ~,3'-dichlorodiethyl ether, nitrohydrocarbons, eg~ nitromethane, nitroethane, nitrobenzene, o~, m- or p-chloronitrobenzene and o-nitrotoluene, nitriles, acetonitrile, butyronitrile, isobutyronitrile, benzo~
nitrile and m-chloroben70ni-trile, aliphatic or c~Jclo-~ f~
- 10 - 0.~ )()50/350~
aliphatic hydrocarbons, eg~ heptarle, plnane, nonane, o-, m- or p-c~Jmene, gasoline fractions ~ thin a boiling point range of from 70 to 190C, cyclohexane, methyl-cyclohexane, decalin, petroleum ether, hexane, naphtha, 2 9 2,4-trimethylpentane, 2,2,3-trimethylpentane, 2,3,3-trlmethylpentane and octane, esters, eg. e-thyl acetate, ethyl acetoacetate and isobutyl ace-tate, amides, egq formamide, methylformamide and dime-thylformamlde, and ketones, egu acetone and methyl ethyl ketone, and app~op_ riat~ mixtures. The solvent is advantageously used in an amount of from 100 to 2,000% by weight, preferably from 200 to 700% by ~eight, based on the starting substances~
l~e hydrochloric acid formed during the reaction escapes as a gas, or is bonded by acid acceptors. ~ny o~ the conventional acid acoeptors can be used, pre-ferably tertiary amines, alkaline earth metal compounds 7 al~monium compounds and alkali metal compounds or appro-priate miYtures9 Zinc compounds can also be used.
'0 Examples o~ suitab].e basic compounds are potassium hydroxide, sodium carbonate~ lithium hydroxide 9 lithium carbonate, sodium bicarbonate 9 potassium bicarbonate, calcium hydroxide, calcium oxide, barium oxide~ magnesium hydroxide 9 magnesium oxide, barium hydroxide, calcium carbonat~, magnesium carbonate, magnesium bicarbonate 9 magnesium acetate 9 zinc hydroxide 9 zinc oxide, zinc carbonate, zinc bicarbonate, zinc acetate, sodium formate~
sodium acetate 7 trimethylamine, triethylamine t trlpropyl-amine, triisopropylamine, tributylamine, -triisobutylamine 7 rj~f~r~
~ .Z. ()050/35~7 tri-sec butylamine, tri-~ert -bu~tylamine, tribenzylamine, tricyclohexylamine~ ~riamylamine~ diisopropylethylamine, trihexylamine, N,M~dimethyl~niline, N,N-diethylaniline, N,N dipropyltoluidine, N,N-dimethyl-p-aminopyridine, N-methylpyrrolidone, N-ethylpyrrolidone, N~methylpiperi-dine, N-ethylpiperidine 7 N-methyl-pyrrolidine, N-ethyl-pyrrolidine, N~methylimidazole, N-ethylirnidazoIe, N-methylpyrrole, N-ethylpyrrole, N-methylmorpholine, N-ethylmorpholine, N-methylhexamethyleneimine, N-ethyl-hexamethyleneimine, pyridine, quinoline, a-picoline, ~-picoline 9 ~-picoline, isoquinoline~ pyrimidine, acridine, N,N,N',N'-tetramethyleth~Jlenediamine, N,N,N',-N'-tetraethylethylenediamine, quinoxaline, quinazoline, N-propyldiisopropylamine, N,N-dimethylcyclohex~lamine, 2,6-lutidine, 2,4-lutidine, trifurfurylamine and tri-ethylenediamine.
The starting substances are reacted in, for e~-ample, approcimately the stoichiometric ratio, iec starting substance III can be employed in, for example 9 an eccess of not more than 20 mole%, based on II.
The process for the preparation of the compounds of the formula I is advantageously carried out by taking the starting substance II, if appropriate in one of ~he above diluents, and then adding t~e starting substance III and, where appropriate, an acid acceptor, at the s~me time or successively. However, it is also pos-sible to take the starting substance III in a diluent and then to add the starting substance II and an acid acceptor by -two separate lines, at the same tlme or in 12 - ~J Z ~,050/356?,7 ~ither order.
In many cases, the reaction has ende~-once the components ha~re been brought ~o~ether, other~ise ~he mixture is sti~red for a ~ur~her period o~ from 10 minutes to 10 hours at from ~20 to 180C, pre~f~rably from 20 to 150C and in particular from 40 tc lOO~C, until the reac-tlon has ended If an inert gas is used to remove the hydrogen halide, stirring is adv~ltageously continued for from O~2 to 10 hours at from 40 to 100C.
~ he end product I is isolated from the reaction mixture in a conventional manner, for example a~ter distilling off solvents or excess starting substance III
or directly by filtration with suction~ In this case, the residue which remains is washed with water or dilute alkali, to remove acid impurities, and dried. If water-immiscible diluents are used, the reaction mi~ture can also be extracted directly with water or with dilute alkali and the extract then dried and concentrated.
~) However, it is also possible to dissolve the residue in a water-immiscible solvent and to wash the solution as described. m e desired end products are thereby obtained in a pure form, and if necessary they can be purified by recrysta lization, chromatography or distil-lation.
The compounds of the formula I where R' is alkyl, acyl, an alkali metal ion or an ammonium ion which may be alkylated can be prepared from the correspo~ding com-pounds of the ~ormula I where R3 is hydrogen , in a
5~
-- 13 ~ O Z. 0~50/35687 conventional manner Alkylation is ef~ected by means of alkylating agents, such as alkyl halides (eg~ methyl bromide or ethyl iodide), dialXylsulfates (eg. dimethyl-sulfate or diethylsulfate) or OXOIliUm salts (eg tri-methyloxoniumtetrafluoborate), in the presence or absence of an inert orga~ic solvent and i^n the presence or absence of an acid acceptor, at from -20C -to 100C, preferably from O to 100C, under atmospheric or super-atmospheric pressure, continuously or batchwise.
Acylation is effected by means of acyl halides (eg.
acetyl chloride or benzyl chloride), in the presence orabsence of an inert organic solvent and in the presence or absence of an acid acceptor, at from -20C to 150C, pre~erably from 20 to 120C, under atmospheric or super-atmospheric pressure, continuously or batchwise To prepare a salt, a compound of the formula I
where R3 is hydrogen is advantageously dissolved in an or~anic solvent, eg. methanol, approximately the stoi-chiometric amount of alkali metal alcoholate, eg. sodium .~0 methylate, alkali metal hydroxide, eg. sodium hydroxide, ammonium hydroxide or alkylated ammonium hydroxide is added,and the mi~ture is concentrated to dryness m e starting compounds can be prepared in a con-ventional ma~ner ~hus, the phenoxy-substituted ureas of the formula II are prepared by, for example, the pro-cedure described in German Laid-O~en Application DOS
2,942,3~0. The co~pounds of the formula III can be prepared by ~ethods disclosed in tne literatuLre (AnOe~.
Chem. 89 (1977), 789).
~ 14 ~ (~ z 0050/35687 The Examples which follow illus-tra-te the pre-paration of the compounds oi the formula I by the 2rocess described. Parts by weight bear the same relation to parts by volume as that of the kilogram to the liter.
EXAMPI~:E 1 A solution of 6 t 4 parts by weight of M~chloro-carbonyl isocyanate in 5 parts by volume of ab~o'.ute toluene is added to a suspension of~ 19 4 5 parts by weight of N-3-(2'~chloro-4'-trifluoromethylphenox~J)-6-nitro-phenyl~N'-methylurea in 25 parts by volume of absolute toluene. The reaction mixture is heated, and is then - stirred under reflux for two hours. After cooling, n-pentane is added ~nd the precipitate formed is filtered off with suctionO 19 parts by weight (83C~o of theory) o~ 3'~(2"-chloro-4"-trifluoromethylphenoxy)-6'-nitro-phenyl]-3-methyl-1,3,5-triazine-2,4,6-(lH~3H,5H)-trione (compound No. 1) of melting point 208-211C &~e obtained.
A solution of 8 parts by weight of compound No. 1 in 100 parts by volume cf acetone is stirred under reflux with 2.4 parts by weight of potassium carbonate and 2.2 parts by weight of dimethylsulfate for two hours.
m e reaction mixt~re is filtered, the filtrate is evapo-rated under reduced pressure~ &nd the residue is recrys-tallized from diisopropyl ether. 8 parts by weiOht (970,6 of theory) of 1-[3'-(2'7-chloro-4"-trifluoromethyl-phenoxy)-o'-nitrophenyl]-3,5-dimethyl~1,3,5-triazine-2,4,6-(lH,3H75H)-trione (compound No. 2) of melting - 15 - o.z. 0050/356~7 point 200-205 C are obtained.
~ EX~PLE 3 5 parts by weight of compound No. 1 are suspended in 50 par-ts by volume of absolute methanol, and 1.96 parts by weight of 30~0 strength methanolic sodium methylate solu-tion ar~ added. The mi~ture is stirred at room temperature for 30 mlnutes and is evaporated under reduced pressure~ 5 parts by weight (99% o~ theory) of the sodium sal-t o~ 3'~(2'7-chloro-4"-trifllloromethyl-phenoxy)-6'-nitrophenyl] 3-methyl-1,3,5-triazine-2,4~6-lo (lH,3H,5H)-trione (compound No, 3) of melting point 220-225C are obtained.
The compounds listed in the Ta~l~ below are prepared in a manner similar to that in the above Examples.
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O ~r ~ ~r ~r ~ ~ ~r Z ~1 ~ ~ ~ ~ ~ r~l ~1 - 25 - O.Z. 0050/35687 The compounds of -the formula I, or herbicidal agents con-taining them, may be applied for instance in the form of directly sprayable solutions, powders, suspensions (inclucliny high-percen-tage aqueous, oily or other suspensions), dispersions, emulslons, oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering. The forms of applicatlon depend enti.rely on the purpose for which the agents are being used, but they must ensure as fine a distribution of the active ingredients according to the invention as possible.
For the pre2aration of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal tar oils, and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, chloro-form, carbon tetrachloride, cyclohexanol, cyclohexanone, chloro-benzene, i.sophorone, etc~, and strongly polar solvents such as dimethylformamide, dimethyl sulfoxi.de, N-methylpyrrolidone, water, 2~ ~tc. are suitable.
Aqueous formulations may be prepared from emulsion concen-trates, pastes, oil dispersions or wettable powders by adding water. To prepare emulsions, pastes and oil dispersions the ingre-dients as such or dissolved in an oil or solvent may be homoge-nized in water by means of wetting or dispersing agents, adherents or emulsifiers. Concentrates which are suitable for dilution with -- 26 - O.Z. 0050/35687 water may be prepared from active ingredient, wettiny agent, ad-herent, emulsifying or dlspersing agent and possibly solvent or oil.
Examples of surfactants are: alkali metal, alkaline earth metal and alnmonium salts of ligninsulfonic acid, naphthalenesul-fonic acids, phenolsulfonic acids, alkylaryl sulfonates, alkyl sul~ates, and alkyl sulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether sul-fate, fatty alcohol sulfates, alkali metal and alkaline earth metal salts of fatty acids, salts of sulfated hexadecanols, hepta-decanols, and octadecanols, salts of sulfated fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene deri~atives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and form-aldehyde, polyoxyethylene octylphenol ethers, ethoxylated isocctyl-phenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkyl-phenol polyglycol ethers, tributylphenyl polyglycol ethers, alkyl-aryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyo~y ethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin, sulfite waste liquors and methyl cellulose.
Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.
Gxanules, e.g., coated, impregnated or homogeneous granules, may be prepared ~y bonding the active ingredients to solid car-riers. Examples of solid carriers are mineral earths such as - ~7 ~ O.Z. 0050/35687 silicic acid, sillca gels, silicates, talc, kaolin, ~ttaclay, limestone, lime, chalk, bole, loess, clay, dclomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertili2ers such as ammonium sulfate, arnmonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain flours, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.
The formulations contain from 0.1 to 95, and preferably 0.5 to 90~ % by weight of active ingredient.
~xamples of formulations are given below:
I. 90 parts by weight of compound no. 1 is mixed with 10 parts by weight of N~methyl-alpha-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.
II. 20 parts by weight of compound no. 38 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduc-t of 8 to 10 moles of ethylene oxide and 1 mole o~ oleic acid-N-ntonoethanolamidel 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the aclduct of 40 moles of ethylene oxide and 1 mole of castor oil. By ~ pou~lng the solution into 100,000 parts by weight of water and urliformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.
III. 20 parts by weight of compound no. 3 is dissolved in a mix-ture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide and 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide and r j t~
- 28 -- o. æ . 0050/35687 1 mole of castor oil~ By pouring the solution into lO0,000 parts by weight of water and finely dis~rlhuting it -therein, an aqueous dispersion is obtained containing 0.02~ by weight of the active ingredient.
IVo 20 parts by weight of compound noO 3 is dissolved in a mix-ture consisting of 25 parts by weight of cyc]ohexanol, 65 parts by weight of a mineral oil fraction havlng a boiling point between 210 and 280C, and 10 parts by weight of the adduct of 40 moles of e-thylene oxide and l mole of castor oil~ By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained contain-ing 0.02% by weight of the active ingredient.
V. 80 parts by weight of compound no. 37 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene--alpha-sulfonic acid, lO parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 7 parts by welght of powdered silica gel, and triturated in a hammer mill.
VI. 3 parts by weight of compound no. 36 is intimately mi~ed with ~l7 parts by weight of particulate kaolin. A dust is obtained con-taining 3~ by weight of the active ingredient.
VII. 30 parts by weight of compound no. l is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingre-dient is obtained having good adherence.
35 ~ ~ ~
- 29 - O.Z. 0050/35687 VIII. 20 parts of compound no. 1~6 is intima~ely mixed wlth 2 parts of the calcium salt of dodecylbenzenesulfonic acidt 8 parts of a fatty alcohol polyqlycol ether, 2 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a parafflnic ~ineral oil. A stable oily dispersion is obtained.
The herblcidal agents may be applied pre- or postemergence.
If certain crop plants tolerate the active ingredients less well, application techniques may be used in wh:ich the herbicidal agents are spray~d from suitable equipment in such a manner that the leaves of sensitive crop plants are if possible not touched, and the agents reach the soil or the unwanted plants growiny beneath the crop plants (post-directed, lay-by treatment).
The amount of active ingredient applied depends on the time of the year and the growth stage of the plants, and varies from 0.025 to 10 kg/ha and more, but is preferably from 0.1 to 4 kg/ha.
The higher application rates are particularly suitable for total elimination of vegetation.
The herbicidal action of compounds of the formula I or herbicidal agents containiny them is demonstrated in greenhouse experiments.
The vessels employed were plastic flowerpots having a volume of 300 cm3, and which were filled with a sandy loam containing about 1.5% humus. The seeds of the test plants were sown shallow, and separately, according to species. For the preemergence treat-ment, the active ingredients were applied to the surface of the soil immediately after the seeds had been sown. The compounds were g5~
- 30 - O.Z. ~050/356~7 emulsified or suspended in water as vehicle, ,~nd spra~ed through finely distributing nozzles. After the agents had been applied, the vessels were lightly sprinkler-irrigated to induce germination and growth and to activate the chemical ayents~ Txansparent plastic covers were then placed on the vessels until the plants had taken root. The cover ensured uniform germination of the plants, insofar as this was not impaired by the chemicals.
For the postemergence treatment~ the plants were Eirst grown in the vessels to a height of from 3 to lS cm, depending on growth form, before ~eing treated. The rice plants used for the postemer-gence treatment were grown in a peat-enriched substrate. Peat was also added to the soybeans to ensure better growth than in the abovementioned soil. For this treatment, either plants which had been sown directly in the pots and grown there were selected~ or plants which had been grown separately as seedlings and trans-planted to the experiment vessels a few days before treatment.
The pots were set up in the greenhouse - species from warmer areas at from 20 to 35C, and species from moderate climates at L5 to 25C. The experiments were run for from 3 to 4 weeks. During this period, the plants were tended and their reactions to the various treatments assessed. The scale used for assessment was 0 to 100, 0 denoting no damage or normal emerc~ence, and 100 denoting nonemergence or complete destruction of at least the visible plant parts.
The test plants employed were Abutilon theophrasti, Amaranthus spp., Arachis hypogaea, Chenopodium album, Datura ~f,~
O.Z. 0050/35687 stra.monium, Echinochloa crus~galli, Galeopsis ~etrahit, Glycine max., Oryza sativa, Sesbania exaltata, Sida spinosa, Sinapis alba, Solanum nigrum, Triticum aestivum, and Zea mays.
The prior art compound usecl for comparison purposes was 1-[4'~(2"-chloro-4"-trlfluoromethyl-phenoxy)-phenyl]-3-methyl--1,3,-5-triazine-2,4~6-trione (German Laid Open Appllcation DE-OS 22 46 109).
The results of the greenhouse exper:iments reveal that for instance compounds nos. 1, 36 and 37, applied preemergence at a rate of, for example, 3.0 kg/ha, have a good herbicidal actlon.
On investigations into selective herbicidal properties on postemergence application, compound no. 4, at 0.5 kg/ha, proves to have a better action on the broadleaved weed Chenopodium than the comparative agent, without damaging soybean and Indian corn plants.
For instance compounds nos. 1, 3, 36, 37, 38, 44, 45, 69, 90, 93, 146 and 148, applied postemergence at rates of 0.06, 0.125, 0.25 and 0.5 kg/ha, combat a number of unwanted broadleaved plants, depending on the active ingredient, in crops such as rice, O wheat and groundnuts.
In view of the good tolerance of the active ingredients and the many application methods possible, the compounds according to the invention may be used in a large number of crop plants for removing unwanted plant growth.
The following crop plants may be mentioned by way of example:
DI~
32 - O.Z. 0050/35687 Botanical name Common name Allium cepa onions Ananas comosus pineapples Arachis hypogaea peanuts (groundnuts) Asparagus officinalis asparagus Avena sativa oats Beta vulgaris spp. altissima sugarbeets Beta vulgaris spp. rapa fodder beets Beta vulgaris spp. esculenta table beets, red beets Brassica napus var~ napus rape Brassica napus var. napobrassica Brassica napus var. rapa turnips Brassica rapa var. silvestris Camellia sinensis tea plants Carthamus tinctorius safflower Carya illinoinensls pecan trees Ci.trus limon lemons Citrus maxima grapefruits Citrus reticulata mandarins Citrus slnensis orange trees Coffea arabica (Coffea canephora, CofEea liberica) coffee plants Cucumis melo melons CUCUmiS sativus cucumbers Cynodon dactylon Bermudagrass in turf and lawns Daucus carota carrots Elais guineensis oil palms Fragaria vesca strawberries ~ ¢~'~t~
~ 33 - O.Z. 0050/35~87 Botanical_name _ _ Common name Glycine max soybeans Gossypium hirsutum (Gossypium arboreum cotton ~ossypium herbaceum Gossypium vitifolium) ~elianthus annuus sunflowers Helianthus tuberosus Hevea brasiliensis ruhber plants Hordeum vulgare barley ~umulus lupulus hops Ipomoea batatas sweet potatoes Juglans regia walnut trees Lactuca sativa lettuce Lens culinaris lentils Linum usitatissimum flax Lycopexsicon lycopersicum tomatoes Malus spp. apple trees Manihot esculenta cassava ~le~icago sativa alfalfa (lucerne) Mentha pi.perita peppermint Musa spp. banana plants Nlcothiana tabacum tobacco (N. rustica) Olea europaea olive trees Oryza sativa rice Panicum miliaceum Phaseolus lunatus limabeans Phaseolus mungo munybeans Phaseolus vulgaris snapbeans, green beans, dry beans Pennisetum glaucum r3~
- 34 - O.Z. 0050/356~7 Botanical name Common narne Petroselinum crispum parsley spp. tuberosum Picea abies ~orway spruce Abies alba fir trees Pinus spp. pine trees Pisum sativum English peas Prunus avium cherry trees Prunus domestica plum trees Prunus dulcis almond trees Prunus persica peach trees Pyrus cornmunis pear trees Ribes sylvestre redcurrants Ribes uva-crispa gooseberries Rlcinus communis castor-oil plants Saccharum oEficinarum sugar cane Secale cereale rye Sesamllm indicum sesame Solanum tuberosum Irish potatoes Sorghum bicolor (s. vulgare) sorghum ~0 Sorghum dochna Spinacia oleracea spinach Theobroma cacao cacao plants Trifolium pratense red clover Triticum aestivum wheat Vaccinium corymbosum blueberries Vaccinium vitis-idaea cranberries Vicia faba tick beans Vigna sinensis (V. unguiculata) cow peas Vitis vinifera grapes Zea mays Indian corn, sweet corn, maize ~ 35 - O.Z. 00~0/35687 To increase the spec-trum of action and to achieve synergistic effects, the novel compounds according to the invention may be mixed and applied together with numerous representatives of other herbicidal or growth-regulating actlve inyredient groups~ Examples of suitable mixture components are diAzlnes, 4H-3,1-benzoxazine derivatives, benzothiadiazinones, 2,6-dinitroanilines, N~phenyl-carbamates, thiolcarbamates, halocarboxylic acids, triazines, amides, ureas, diphenyl ethers, triazinones, uxacils, benzofuran derivatives, cyclohexane-1,3-dione derivatives, etc.
It may also be useful to apply the agents according to the invention, either alone or in combination with other herbicides, in admixture with other crop protection agents, e.g., agents for combating pests or phytopathogenic fungi or bacteria. The com-pounds may also be mixed with solutions of mineral salts used to remedy n~ltritional or trace element deficiencies. Non-phytotoxic oils and oil concentrates may also be added.
)o
-- 13 ~ O Z. 0~50/35687 conventional manner Alkylation is ef~ected by means of alkylating agents, such as alkyl halides (eg~ methyl bromide or ethyl iodide), dialXylsulfates (eg. dimethyl-sulfate or diethylsulfate) or OXOIliUm salts (eg tri-methyloxoniumtetrafluoborate), in the presence or absence of an inert orga~ic solvent and i^n the presence or absence of an acid acceptor, at from -20C -to 100C, preferably from O to 100C, under atmospheric or super-atmospheric pressure, continuously or batchwise.
Acylation is effected by means of acyl halides (eg.
acetyl chloride or benzyl chloride), in the presence orabsence of an inert organic solvent and in the presence or absence of an acid acceptor, at from -20C to 150C, pre~erably from 20 to 120C, under atmospheric or super-atmospheric pressure, continuously or batchwise To prepare a salt, a compound of the formula I
where R3 is hydrogen is advantageously dissolved in an or~anic solvent, eg. methanol, approximately the stoi-chiometric amount of alkali metal alcoholate, eg. sodium .~0 methylate, alkali metal hydroxide, eg. sodium hydroxide, ammonium hydroxide or alkylated ammonium hydroxide is added,and the mi~ture is concentrated to dryness m e starting compounds can be prepared in a con-ventional ma~ner ~hus, the phenoxy-substituted ureas of the formula II are prepared by, for example, the pro-cedure described in German Laid-O~en Application DOS
2,942,3~0. The co~pounds of the formula III can be prepared by ~ethods disclosed in tne literatuLre (AnOe~.
Chem. 89 (1977), 789).
~ 14 ~ (~ z 0050/35687 The Examples which follow illus-tra-te the pre-paration of the compounds oi the formula I by the 2rocess described. Parts by weight bear the same relation to parts by volume as that of the kilogram to the liter.
EXAMPI~:E 1 A solution of 6 t 4 parts by weight of M~chloro-carbonyl isocyanate in 5 parts by volume of ab~o'.ute toluene is added to a suspension of~ 19 4 5 parts by weight of N-3-(2'~chloro-4'-trifluoromethylphenox~J)-6-nitro-phenyl~N'-methylurea in 25 parts by volume of absolute toluene. The reaction mixture is heated, and is then - stirred under reflux for two hours. After cooling, n-pentane is added ~nd the precipitate formed is filtered off with suctionO 19 parts by weight (83C~o of theory) o~ 3'~(2"-chloro-4"-trifluoromethylphenoxy)-6'-nitro-phenyl]-3-methyl-1,3,5-triazine-2,4,6-(lH~3H,5H)-trione (compound No. 1) of melting point 208-211C &~e obtained.
A solution of 8 parts by weight of compound No. 1 in 100 parts by volume cf acetone is stirred under reflux with 2.4 parts by weight of potassium carbonate and 2.2 parts by weight of dimethylsulfate for two hours.
m e reaction mixt~re is filtered, the filtrate is evapo-rated under reduced pressure~ &nd the residue is recrys-tallized from diisopropyl ether. 8 parts by weiOht (970,6 of theory) of 1-[3'-(2'7-chloro-4"-trifluoromethyl-phenoxy)-o'-nitrophenyl]-3,5-dimethyl~1,3,5-triazine-2,4,6-(lH,3H75H)-trione (compound No. 2) of melting - 15 - o.z. 0050/356~7 point 200-205 C are obtained.
~ EX~PLE 3 5 parts by weight of compound No. 1 are suspended in 50 par-ts by volume of absolute methanol, and 1.96 parts by weight of 30~0 strength methanolic sodium methylate solu-tion ar~ added. The mi~ture is stirred at room temperature for 30 mlnutes and is evaporated under reduced pressure~ 5 parts by weight (99% o~ theory) of the sodium sal-t o~ 3'~(2'7-chloro-4"-trifllloromethyl-phenoxy)-6'-nitrophenyl] 3-methyl-1,3,5-triazine-2,4~6-lo (lH,3H,5H)-trione (compound No, 3) of melting point 220-225C are obtained.
The compounds listed in the Ta~l~ below are prepared in a manner similar to that in the above Examples.
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O ~r ~ ~r ~r ~ ~ ~r Z ~1 ~ ~ ~ ~ ~ r~l ~1 - 25 - O.Z. 0050/35687 The compounds of -the formula I, or herbicidal agents con-taining them, may be applied for instance in the form of directly sprayable solutions, powders, suspensions (inclucliny high-percen-tage aqueous, oily or other suspensions), dispersions, emulslons, oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering. The forms of applicatlon depend enti.rely on the purpose for which the agents are being used, but they must ensure as fine a distribution of the active ingredients according to the invention as possible.
For the pre2aration of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal tar oils, and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, chloro-form, carbon tetrachloride, cyclohexanol, cyclohexanone, chloro-benzene, i.sophorone, etc~, and strongly polar solvents such as dimethylformamide, dimethyl sulfoxi.de, N-methylpyrrolidone, water, 2~ ~tc. are suitable.
Aqueous formulations may be prepared from emulsion concen-trates, pastes, oil dispersions or wettable powders by adding water. To prepare emulsions, pastes and oil dispersions the ingre-dients as such or dissolved in an oil or solvent may be homoge-nized in water by means of wetting or dispersing agents, adherents or emulsifiers. Concentrates which are suitable for dilution with -- 26 - O.Z. 0050/35687 water may be prepared from active ingredient, wettiny agent, ad-herent, emulsifying or dlspersing agent and possibly solvent or oil.
Examples of surfactants are: alkali metal, alkaline earth metal and alnmonium salts of ligninsulfonic acid, naphthalenesul-fonic acids, phenolsulfonic acids, alkylaryl sulfonates, alkyl sul~ates, and alkyl sulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether sul-fate, fatty alcohol sulfates, alkali metal and alkaline earth metal salts of fatty acids, salts of sulfated hexadecanols, hepta-decanols, and octadecanols, salts of sulfated fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene deri~atives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and form-aldehyde, polyoxyethylene octylphenol ethers, ethoxylated isocctyl-phenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkyl-phenol polyglycol ethers, tributylphenyl polyglycol ethers, alkyl-aryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyo~y ethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin, sulfite waste liquors and methyl cellulose.
Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.
Gxanules, e.g., coated, impregnated or homogeneous granules, may be prepared ~y bonding the active ingredients to solid car-riers. Examples of solid carriers are mineral earths such as - ~7 ~ O.Z. 0050/35687 silicic acid, sillca gels, silicates, talc, kaolin, ~ttaclay, limestone, lime, chalk, bole, loess, clay, dclomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertili2ers such as ammonium sulfate, arnmonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain flours, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.
The formulations contain from 0.1 to 95, and preferably 0.5 to 90~ % by weight of active ingredient.
~xamples of formulations are given below:
I. 90 parts by weight of compound no. 1 is mixed with 10 parts by weight of N~methyl-alpha-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.
II. 20 parts by weight of compound no. 38 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduc-t of 8 to 10 moles of ethylene oxide and 1 mole o~ oleic acid-N-ntonoethanolamidel 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the aclduct of 40 moles of ethylene oxide and 1 mole of castor oil. By ~ pou~lng the solution into 100,000 parts by weight of water and urliformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.
III. 20 parts by weight of compound no. 3 is dissolved in a mix-ture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide and 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide and r j t~
- 28 -- o. æ . 0050/35687 1 mole of castor oil~ By pouring the solution into lO0,000 parts by weight of water and finely dis~rlhuting it -therein, an aqueous dispersion is obtained containing 0.02~ by weight of the active ingredient.
IVo 20 parts by weight of compound noO 3 is dissolved in a mix-ture consisting of 25 parts by weight of cyc]ohexanol, 65 parts by weight of a mineral oil fraction havlng a boiling point between 210 and 280C, and 10 parts by weight of the adduct of 40 moles of e-thylene oxide and l mole of castor oil~ By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained contain-ing 0.02% by weight of the active ingredient.
V. 80 parts by weight of compound no. 37 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene--alpha-sulfonic acid, lO parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 7 parts by welght of powdered silica gel, and triturated in a hammer mill.
VI. 3 parts by weight of compound no. 36 is intimately mi~ed with ~l7 parts by weight of particulate kaolin. A dust is obtained con-taining 3~ by weight of the active ingredient.
VII. 30 parts by weight of compound no. l is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingre-dient is obtained having good adherence.
35 ~ ~ ~
- 29 - O.Z. 0050/35687 VIII. 20 parts of compound no. 1~6 is intima~ely mixed wlth 2 parts of the calcium salt of dodecylbenzenesulfonic acidt 8 parts of a fatty alcohol polyqlycol ether, 2 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a parafflnic ~ineral oil. A stable oily dispersion is obtained.
The herblcidal agents may be applied pre- or postemergence.
If certain crop plants tolerate the active ingredients less well, application techniques may be used in wh:ich the herbicidal agents are spray~d from suitable equipment in such a manner that the leaves of sensitive crop plants are if possible not touched, and the agents reach the soil or the unwanted plants growiny beneath the crop plants (post-directed, lay-by treatment).
The amount of active ingredient applied depends on the time of the year and the growth stage of the plants, and varies from 0.025 to 10 kg/ha and more, but is preferably from 0.1 to 4 kg/ha.
The higher application rates are particularly suitable for total elimination of vegetation.
The herbicidal action of compounds of the formula I or herbicidal agents containiny them is demonstrated in greenhouse experiments.
The vessels employed were plastic flowerpots having a volume of 300 cm3, and which were filled with a sandy loam containing about 1.5% humus. The seeds of the test plants were sown shallow, and separately, according to species. For the preemergence treat-ment, the active ingredients were applied to the surface of the soil immediately after the seeds had been sown. The compounds were g5~
- 30 - O.Z. ~050/356~7 emulsified or suspended in water as vehicle, ,~nd spra~ed through finely distributing nozzles. After the agents had been applied, the vessels were lightly sprinkler-irrigated to induce germination and growth and to activate the chemical ayents~ Txansparent plastic covers were then placed on the vessels until the plants had taken root. The cover ensured uniform germination of the plants, insofar as this was not impaired by the chemicals.
For the postemergence treatment~ the plants were Eirst grown in the vessels to a height of from 3 to lS cm, depending on growth form, before ~eing treated. The rice plants used for the postemer-gence treatment were grown in a peat-enriched substrate. Peat was also added to the soybeans to ensure better growth than in the abovementioned soil. For this treatment, either plants which had been sown directly in the pots and grown there were selected~ or plants which had been grown separately as seedlings and trans-planted to the experiment vessels a few days before treatment.
The pots were set up in the greenhouse - species from warmer areas at from 20 to 35C, and species from moderate climates at L5 to 25C. The experiments were run for from 3 to 4 weeks. During this period, the plants were tended and their reactions to the various treatments assessed. The scale used for assessment was 0 to 100, 0 denoting no damage or normal emerc~ence, and 100 denoting nonemergence or complete destruction of at least the visible plant parts.
The test plants employed were Abutilon theophrasti, Amaranthus spp., Arachis hypogaea, Chenopodium album, Datura ~f,~
O.Z. 0050/35687 stra.monium, Echinochloa crus~galli, Galeopsis ~etrahit, Glycine max., Oryza sativa, Sesbania exaltata, Sida spinosa, Sinapis alba, Solanum nigrum, Triticum aestivum, and Zea mays.
The prior art compound usecl for comparison purposes was 1-[4'~(2"-chloro-4"-trlfluoromethyl-phenoxy)-phenyl]-3-methyl--1,3,-5-triazine-2,4~6-trione (German Laid Open Appllcation DE-OS 22 46 109).
The results of the greenhouse exper:iments reveal that for instance compounds nos. 1, 36 and 37, applied preemergence at a rate of, for example, 3.0 kg/ha, have a good herbicidal actlon.
On investigations into selective herbicidal properties on postemergence application, compound no. 4, at 0.5 kg/ha, proves to have a better action on the broadleaved weed Chenopodium than the comparative agent, without damaging soybean and Indian corn plants.
For instance compounds nos. 1, 3, 36, 37, 38, 44, 45, 69, 90, 93, 146 and 148, applied postemergence at rates of 0.06, 0.125, 0.25 and 0.5 kg/ha, combat a number of unwanted broadleaved plants, depending on the active ingredient, in crops such as rice, O wheat and groundnuts.
In view of the good tolerance of the active ingredients and the many application methods possible, the compounds according to the invention may be used in a large number of crop plants for removing unwanted plant growth.
The following crop plants may be mentioned by way of example:
DI~
32 - O.Z. 0050/35687 Botanical name Common name Allium cepa onions Ananas comosus pineapples Arachis hypogaea peanuts (groundnuts) Asparagus officinalis asparagus Avena sativa oats Beta vulgaris spp. altissima sugarbeets Beta vulgaris spp. rapa fodder beets Beta vulgaris spp. esculenta table beets, red beets Brassica napus var~ napus rape Brassica napus var. napobrassica Brassica napus var. rapa turnips Brassica rapa var. silvestris Camellia sinensis tea plants Carthamus tinctorius safflower Carya illinoinensls pecan trees Ci.trus limon lemons Citrus maxima grapefruits Citrus reticulata mandarins Citrus slnensis orange trees Coffea arabica (Coffea canephora, CofEea liberica) coffee plants Cucumis melo melons CUCUmiS sativus cucumbers Cynodon dactylon Bermudagrass in turf and lawns Daucus carota carrots Elais guineensis oil palms Fragaria vesca strawberries ~ ¢~'~t~
~ 33 - O.Z. 0050/35~87 Botanical_name _ _ Common name Glycine max soybeans Gossypium hirsutum (Gossypium arboreum cotton ~ossypium herbaceum Gossypium vitifolium) ~elianthus annuus sunflowers Helianthus tuberosus Hevea brasiliensis ruhber plants Hordeum vulgare barley ~umulus lupulus hops Ipomoea batatas sweet potatoes Juglans regia walnut trees Lactuca sativa lettuce Lens culinaris lentils Linum usitatissimum flax Lycopexsicon lycopersicum tomatoes Malus spp. apple trees Manihot esculenta cassava ~le~icago sativa alfalfa (lucerne) Mentha pi.perita peppermint Musa spp. banana plants Nlcothiana tabacum tobacco (N. rustica) Olea europaea olive trees Oryza sativa rice Panicum miliaceum Phaseolus lunatus limabeans Phaseolus mungo munybeans Phaseolus vulgaris snapbeans, green beans, dry beans Pennisetum glaucum r3~
- 34 - O.Z. 0050/356~7 Botanical name Common narne Petroselinum crispum parsley spp. tuberosum Picea abies ~orway spruce Abies alba fir trees Pinus spp. pine trees Pisum sativum English peas Prunus avium cherry trees Prunus domestica plum trees Prunus dulcis almond trees Prunus persica peach trees Pyrus cornmunis pear trees Ribes sylvestre redcurrants Ribes uva-crispa gooseberries Rlcinus communis castor-oil plants Saccharum oEficinarum sugar cane Secale cereale rye Sesamllm indicum sesame Solanum tuberosum Irish potatoes Sorghum bicolor (s. vulgare) sorghum ~0 Sorghum dochna Spinacia oleracea spinach Theobroma cacao cacao plants Trifolium pratense red clover Triticum aestivum wheat Vaccinium corymbosum blueberries Vaccinium vitis-idaea cranberries Vicia faba tick beans Vigna sinensis (V. unguiculata) cow peas Vitis vinifera grapes Zea mays Indian corn, sweet corn, maize ~ 35 - O.Z. 00~0/35687 To increase the spec-trum of action and to achieve synergistic effects, the novel compounds according to the invention may be mixed and applied together with numerous representatives of other herbicidal or growth-regulating actlve inyredient groups~ Examples of suitable mixture components are diAzlnes, 4H-3,1-benzoxazine derivatives, benzothiadiazinones, 2,6-dinitroanilines, N~phenyl-carbamates, thiolcarbamates, halocarboxylic acids, triazines, amides, ureas, diphenyl ethers, triazinones, uxacils, benzofuran derivatives, cyclohexane-1,3-dione derivatives, etc.
It may also be useful to apply the agents according to the invention, either alone or in combination with other herbicides, in admixture with other crop protection agents, e.g., agents for combating pests or phytopathogenic fungi or bacteria. The com-pounds may also be mixed with solutions of mineral salts used to remedy n~ltritional or trace element deficiencies. Non-phytotoxic oils and oil concentrates may also be added.
)o
Claims (6)
1. A 1,3,5-triazinone of the formula (I) where R1 is , where Z1 and Z2 independently of one another are each hydrogen, halogen, nitro, cyano or carboxyl, or alkyl, haloalkyl or alkoxy, each of not more than 4 carbon atoms, Z3 is halogen, nitro or cyano, or alkyl, haloalkyl, alkoxy, haloalkoxy, alkylmercapto, haloalkylmercapto, alkylsulfinyl, halo-alkylsulfinyl, alkylsulfonyl or haloalkylsulfonyl, each of not more than 4 carbon atoms, and Y i 5 hydrogen, halogen, cyano or nitro, and R2 is hydrogen or a saturated or unsaturated, straight-chain or branched aliphatic radical of not more than 20 carbon atoms, or R2 is a saturated, straight-chain or branched aliphatic radical of not more than 10 carbon atoms which is substituted by halogen, cyano, hydroxyl or mercapto, or by alkoxy or alkylmercapto, each of not more than 4 carbon atoms, or by phenylmercapto, or by alkylamino or dialkylamino, where each alkyl is of 1 to 4 carbon atoms, or R2 is cycloalkyl of 3 to 7 carbon atoms which is unsubstituted or substituted by alkoxy of 1 to 4 car-bon atoms, or R2 is phenyl which is unsubstituted or substituted by halogen, or by alkyl or alkoxy, each of 1 to 4 carbon atoms, or by nitro or cyano, or by halo-alkyl, haloalkoxy or haloalkylmercapto, each of 1 to 4 carbon atoms, or R2 is benzyl or halobenzyl, and R3 is hydrogen, alkyl of not more than 4 carbon atoms or acyl of not more than 7 carbon atoms which is unsubstituted or substituted by halogen, or is an alkali metal ion or an ammonium ion, which may be alkylated,
2. A 1,3,5-triazinone of the formula I as claimed in claim 1, where R1 is where Z1 and Z2 independently of one another are each hydrogen, chlorine, bromine or cyano, Z3 is chlorine, bromine, methyl, trifluoromethoxy, trifluoromethylmercapto or trifluoromethyl and Y
is bromine or nitro, R2 is alkyl, haloalkyl, cyanoalkyl, alkoxy-or alkylmercaptoalkyl, each of not more than 4 carbon atoms, cycloalkyl of 3 to 7 carbon atoms, phenyl substituted by haloalkyl of 1 to 4 carbon atoms or by halogen, or benzyl substituted by halogen, and R3 is hydrogen, methyl or sodium.
is bromine or nitro, R2 is alkyl, haloalkyl, cyanoalkyl, alkoxy-or alkylmercaptoalkyl, each of not more than 4 carbon atoms, cycloalkyl of 3 to 7 carbon atoms, phenyl substituted by haloalkyl of 1 to 4 carbon atoms or by halogen, or benzyl substituted by halogen, and R3 is hydrogen, methyl or sodium.
3. A 1,3,5-triazinone of the formula I as claimed in claim 1, where R1 is where Z1 and Z2 independently of one another are each hydrogen, chlorine, bromine or cyano, Z3 is chlorine, bromine, methyl, trifluoromethoxy, trifluoromethylmercapto or trifluoromethyl, and Y is nitro, R2 is methyl, 2-chloroethyl, 3,4-dichlorophenyl or 2-methoxyethyl, and R3 is hydrogen, methyl or sodium.
4. 1-[3'-(2"-Chloro-4"-trifluoromethylphenoxy)-6'-nitro-phenyl]-3-methyl-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione.
5. A process for the manufacture of 1,3,5-triazinones of the formula I as claimed in claim 1, wherein a phenoxy-substituted urea of the formula (II) where Z1, Z2, Z3, Y and R2 have the meanings given in claim 1, is reacted with a substituted carbonyl isocyanate of the formula (III), where R4 is halogen, alkoxy or aryloxy, in an inert organic solvent, with or without addition of an acid acceptor, at from -20 to +180°C, to give a 1,3,5-triazinone of the formula where Z1, Z2, Z3, Y and R2 have the meanings given in claim 1, and, if desired, this product is then acylated or alkylated with an acyl halide of the formula R3COX, an alkyl halide of the formula R3X or a dialkylsulfate of the formula (R3O)2SO2, where R3 in each case has the meanings given in claim 1, with the exception of hydrogen, and X is halogen, or converted into a salt of the formula I with an alkali metal alcoholate, an alkali metal hyroxide, ammonium hydroxide or an alkylated ammonium hydroxide.
6. A process for controlling unwanted plant growth, wherein the unwanted plants and/or the area to be kept free from unwanted plant growth are treated with a herbicidally effective amount of a 1,3,5-triazinone of the formula I as claimed in claim 1.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3147879.4 | 1981-12-03 | ||
| DE19813147879 DE3147879A1 (en) | 1981-12-03 | 1981-12-03 | 1,3,5-TRIAZINONE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR CONTROLLING UNWANTED PLANT GROWTH |
| DEP3201229.2 | 1982-01-16 | ||
| DE19823201229 DE3201229A1 (en) | 1982-01-16 | 1982-01-16 | 1,3,5-Triazinones, processes for their preparation, and their use for controlling undesired plant growth |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1185974A true CA1185974A (en) | 1985-04-23 |
Family
ID=25797739
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000416267A Expired CA1185974A (en) | 1981-12-03 | 1982-11-24 | 1,3,5-triazinones and their use for controlling undesirable plant growth |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0081142B1 (en) |
| BR (1) | BR8206946A (en) |
| CA (1) | CA1185974A (en) |
| DE (1) | DE3271848D1 (en) |
| HU (1) | HU188336B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11352332B2 (en) | 2018-02-26 | 2022-06-07 | AlzeCure Pharma AB | Triazine derivatives for treating diseases relating to neurotrophins |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3300793A1 (en) * | 1983-01-12 | 1984-07-12 | Bayer Ag, 5090 Leverkusen | Coccidiosis |
| US5219853A (en) * | 1983-01-12 | 1993-06-15 | Bayer Aktiengesellschaft | Agent for coccidiosis |
| DE3618662A1 (en) * | 1986-06-03 | 1987-12-10 | Bayer Ag | TRISUBSTITUTED 1,3,5-TRIAZINE-2,4,6-TRIONE |
| DE3920325C2 (en) * | 1988-06-24 | 2001-04-12 | Sunstar Engineering Inc | Masked polyisocyanurate compound and plastisol composition containing it |
| CZ146296A3 (en) * | 1995-06-02 | 1997-04-16 | American Cyanamid Co | 3-(3-aryloxyphenyl)-1-(substituted methyl)-s-triazine-2,4,6-oxo or thiotriones, process of their preparation and herbicidal agents |
| WO2004064730A2 (en) * | 2003-01-14 | 2004-08-05 | Cytokinetics, Inc. | Compounds, compositions and methods |
| RU2410384C2 (en) | 2004-06-17 | 2011-01-27 | Цитокинетикс, Инк. | Compounds, compositions and methods of their application |
| US7538223B2 (en) | 2005-08-04 | 2009-05-26 | Cytokinetics, Inc. | Compounds, compositions and methods |
| EP1959960B1 (en) | 2005-12-15 | 2013-04-10 | Cytokinetics, Inc. | Certain chemical entities, compositions and methods |
| US7825120B2 (en) | 2005-12-15 | 2010-11-02 | Cytokinetics, Inc. | Certain substituted ((piperazin-1-ylmethyl)benzyl)ureas |
| WO2007078815A2 (en) | 2005-12-16 | 2007-07-12 | Cytokinetics, Inc. | Certain chemical entities, compositions, and methods |
| WO2007078839A2 (en) | 2005-12-19 | 2007-07-12 | Cytokinetics, Inc. | Compounds, compositions and methods |
| GB201810669D0 (en) | 2018-06-28 | 2018-08-15 | Stiftelsen Alzecure | New compounds |
| GB201810668D0 (en) | 2018-06-28 | 2018-08-15 | Stiftelsen Alzecure | New compounds |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2246109A1 (en) * | 1972-09-20 | 1974-03-28 | Bayer Ag | 1- (4-PHENOXY-PHENYL) -1,3,5-TRIAZINE DERIVATIVES, A METHOD FOR THEIR MANUFACTURE AND THEIR USE AS A MEDICINAL PRODUCT |
| DE2718799A1 (en) * | 1977-04-27 | 1978-11-09 | Bayer Ag | 1- (4-PHENOXY-PHENYL) -1,3,5-TRIAZINE DERIVATIVES, THE METHOD FOR THEIR MANUFACTURING AND THEIR USE AS A MEDICINAL PRODUCT AND GROWTH PROMOTER |
-
1982
- 1982-11-24 DE DE8282110859T patent/DE3271848D1/en not_active Expired
- 1982-11-24 EP EP82110859A patent/EP0081142B1/en not_active Expired
- 1982-11-24 CA CA000416267A patent/CA1185974A/en not_active Expired
- 1982-11-30 BR BR8206946A patent/BR8206946A/en unknown
- 1982-12-02 HU HU823882A patent/HU188336B/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11352332B2 (en) | 2018-02-26 | 2022-06-07 | AlzeCure Pharma AB | Triazine derivatives for treating diseases relating to neurotrophins |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0081142B1 (en) | 1986-06-25 |
| BR8206946A (en) | 1983-10-11 |
| DE3271848D1 (en) | 1986-07-31 |
| HU188336B (en) | 1986-04-28 |
| EP0081142A2 (en) | 1983-06-15 |
| EP0081142A3 (en) | 1984-04-11 |
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