Substituted 2,4-diamino-1,3,5-triazines, processes for their use as herbicides and crop growth regulators
View Patent ↗Compounds of the formula (I) or salts thereof, in which in which R 1 is an optionally substituted amino group or analogous group, and R 2 to R 7 are each as described herein, are suitable as herbicides and crop growth regulators. The compounds (I) can be prepared by the processes described, via intermediates including novel intermediates for example of the formula (III).
1. A compound of the formula (I) or salt thereof, in which
R 1 is a radical of the formula —NH 2 , —NH(B 1 -D 1 ), or —N(B 1 -D 1 )(B 2 -D 2 ), in each of which B 1 , B 2 , D 1 and D 2 are each as defined below, or a group of the formula
where
L 1 is a direct bond, —O—, —S— or a group of the formula —NG 2 -,
U 1 , U 2 are each independently a group of the formula G 3 , OG 4 , SG 5 , NG 6 G 7 , NG 8 NG 9 G 10 , NG 11 OG 12 or NG 11 SG 12 ,
U 3 is a group of the formula G 13 , OG 14 , SG 15 , NG 16 G 17 , NG 18 NG 19 G 20 NG 21 OG 22 or NG 23 SG 24
U 4 is a group of the formula G 25 , OG 26 , SG 27 or NG 28 G 29 ,
where the G 1 to G 29 radicals are each independently hydrogen, aryl which is unsubstituted or substituted and has from 6 to 30 carbon atoms including substituents, or (C 3 -C 9 )cycloalkyl which is unsubstituted or substituted and has from 3 to 30 carbon atoms including substituents, or heterocyclyl which is substituted or unsubstituted and has from 2 to 30 carbon atoms including substituents, or
(C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl or (C 2 -C 6 )alkynyl,
where each of the 3 latter radicals is unsubstituted or substituted by one or more radicals from the group consisting of halogen, hydroxyl, cyano, nitro, thiocyanato, (C 1 -C 4 )alkoxy, (C 1 -C 4 )haloalkoxy, (C 2 -C 4 )alkenyloxy, (C 2 -C 4 )haloalkenyloxy, (C 1 -C 4 )alkylthio, (C 1 -C 4 )haloalkylthio, acyl, (C 3 -C 9 )cycloalkyl, which is unsubstituted or substituted, phenyl which is unsubstituted or substituted, and heterocyclyl which is unsubstituted or substituted, and has from 1 to 30 carbon atoms including substituents,
or the U 1 and U 3 or U 2 and U 4 or U 2 and G 1 or U 4 and G 1 radicals, in pairs with the atoms connecting them, are each a carbocyclic or heterocyclic ring having from 4 to 7 ring atoms, where the ring is unsubstituted or substituted, and has up to 30 carbon atoms including substituents,
B 1 and B 2 are each independently a divalent group of the formula —C(=Z*)-, —C(=Z*)-Z**-, —C(=Z*)-NH— or —C(=Z*)-NR*-,
where Z* is an oxygen or sulfur atom, Z** is an oxygen or sulfur atom and R* is (C 1 -C 6 )alkyl, aryl, aryl(C 1 -C 6 )alkyl, (C 3 -C 9 )cycloalkyl or (C 3 -C 9 )cycloalkyl(C 1 -C 6 )alkyl, where each of the 5 latter radicals is unsubstituted or substituted and has up to 30 carbon atoms including substituents,
D 1 and D 2 are each independently hydrogen, (C 1 -C 6 )alkyl, aryl, aryl(C 1 -C 6 )alkyl, (C 3 -C 9 )cycloalkyl or (C 3 -C 9 )cycloalkyl(C 1 -C 6 )alkyl, where each of the 5 latter radicals is unsubstituted or substituted and has up to 30 carbon atoms including substituents,
R 2 is hydrogen, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl or (C 2 -C 6 )alkynyl where each of the three latter groups is unsubstituted or substituted by one or more of the radicals from the group which consists of halogen, hydroxyl, cyano, (C 1 -C 6 )alkoxy, (C 1 -C 6 )alkylthio, (C 1 -C 6 )haloalkoxy, (C 1 -C 4 )alkoxy-(C 1 -C 4 )alkoxy and optionally halogen-, cyano-, (C 1 -C 4 )alkyl- or (C 1 -C 4 )haloalkyl-substituted (C 3 -C 6 )cycloalkyl, or is (C 3 -C 6 )cycloalkyl which is unsubstituted or substituted by one or more radicals from the group consisting of halogen, cyano, (C 1 -C 4 )alkyl and (C 1 -C 4 )haloalkyl,
R 3 is cyclopropyl or cyclobutyl, where each of the latter two radicals is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C 1 -C 4 )alkyl, (C 1 -C 4 )haloalkyl, (C 2 -C 4 )alkenyl, (C 2 -C 4 )alkynyl, (C 1 -C 4 )alkoxy, (C 1 -C 4 )haloalkoxy and (C 1 -C 4 )alkylthio, where the cyclic R 3 radical, by its carbon atom in the 2 position,
(a) may be connected to the divalent R 4 group=methylene and may thus form, with the molecular moiety R 3 -C—C-R 4 , a bicycle composed of a five-membered ring and the three- or four-membered ring of R 3 , or
(b) may be bonded directly or via a methylene group to the carbon atom in the 2 position of the cyclic CR 4 R 5 radical and thus form a tricycle with the molecular moiety R 3 —C—CR 4 R 5 , and
R 4 and R 5 are each independently
(C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl or (C 2 -C 6 )alkynyl, where each of the latter three radicals is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C 1 -C 4 )alkoxy, (C 1 -C 4 )haloalkoxy and (C 1 -C 4 )alkylthio, or
cyclopropyl which is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C 1 -C 4 )alkyl, (C 1 -C 4 )haloalkyl, (C 2 -C 4 )alkenyl, (C 2 -C 4 )alkynyl, (C 1 -C 4 )alkoxy, (C 1 -C 4 )haloalkoxy and (C 1 -C 4 )alkylthio, or
R 4 and R 5 , together with the carbon atom bonded to them, are a 3- to 9-membered carbocyclic ring which is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C 1 -C 4 )alkyl, (C 1 -C 4 )haloalkyl, (C 1 -C 4 )alkoxy-(C 1 -C 4 )alkyl, (C 1 -C 4 )alkoxy, (C 1 -C 4 )haloalkoxy and (C 1 -C 4 )alkylthio,
where a cyclic CR 4 R 5 radical, by its carbon atom in the 2 position, may be bonded to the carbon atom in the 2 position of the cycle of the R 3 group directly or via a methylene group and may thus form a tricycle with the molecular moiety R 3 —C—CR 4 R 5 , or
R 4 is a divalent group of the formula —CH 2 — which is bonded to the carbon atom in the 2 position of the cyclic R 3 radical and may thus form, with the molecular moiety R 3 -C—C-R 4 , a bicycle composed of a five-membered ring and the three- or four-membered ring of R 3 , and
R 6 is hydrogen or (C 1 -C 4 )alkyl which is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C 1 -C 4 )alkoxy, (C 1 -C 4 )haloalkoxy and (C 1 -C 4 )alkylthio, and
R 7 is hydrogen, methyl, ethyl or cyclopropyl which is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C 1 -C 4 )alkyl, (C 1 -C 4 )haloalkyl, (C 1 -C 4 )alkoxy, (C 1 -C 4 )haloalkoxy and (C 1 -C 4 )alkylthio.
2. A compound of the formula (I) or salts thereof as claimed in claim 1 , wherein
R 1 is a radical of the formula —NH 2 , —NH(B 1 -D 1 ), or —N(B 1 -D 1 )(B 2 -D 2 ), in each of which B 1 , B 2 , D 1 and D 2 are as defined below, or a group of the formula
where
L 1 is a direct bond, —O—, —S— or a group of the formula —NG 2 -, preferably a direct bond,
U 1 , U 2 are each independently a group of the formula G 3 , OG 4 , SG 5 , NG 6 G 7 , NG 8 NG 9 G 10 , NG 11 OG 12 or NG 11 SG 12 ,
U 3 is a group of the formula G 13 , OG 14 SG 15 NG 16 G 17 , NG 18 NG 19 G 20 NG 21 OG 22 or NG 23 SG 24 ,
U 4 is a group of the formula G 25 , OG 26 , SG 27 or NG 28 G 29 ,
where the G 1 to G 29 radicals are each independently hydrogen or phenyl which is unsubstituted or substituted and has from 6 to 30 carbon atoms including substituents, or (C 3 -C 8 )cycloalkyl which is unsubstituted or substituted and has from 3 to 30 carbon atoms including substituents, or heterocyclyl which is substituted or unsubstituted and has from 2 to 30 carbon atoms including substituents, or
(C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl or (C 2 -C 6 )alkynyl,
where each of the 3 latter radicals is unsubstituted or substituted by one or more radicals from the group of halogen, hydroxyl, cyano, nitro, thiocyanato, (C 1 -C 4 )alkoxy, (C 1 -C 4 )haloalkoxy, (C 2 -C 4 )alkenyloxy, (C 2 -C 4 )haloalkenyloxy, (C 1 -C 4 )alkylthio, (C 1 -C 4 )alkylsulfinyl, (C 1 -C 4 )alkylsulfonyl, (C 1 -C 4 )haloalkylthio, (C 1 -C 4 )haloalkylsulfinyl, (C 1 -C 4 )haloalkylsulfonyl, (C 3 -C 9 )cycloalkyl which is unsubstituted or substituted, phenyl which is unsubstituted or substituted, and heterocyclyl which is unsubstituted or substituted, and radicals of the formulae R′-C(=Z′)-, R′-C(=Z′)-Z-, R′-Z-C(=Z′)-, R′R″N—C(=Z′)-, R′-Z-C(=Z′)-O—, R′R″N—C(=Z′)-Z-, R′-Z-C(=Z′)-NR″— and R′R″N—C(=Z′)-NR′″—,
in which R′, R″ and R′″ are each independently (C 1 -C 6 )alkyl, phenyl, phenyl(C 1 -C 6 )alkyl, (C 3 -C 9 )cycloalkyl or (C 3 -C 9 )cyclo-alkyl(C 1 -C 6 )alkyl, where each of the 5 latter radicals is unsubstituted or substituted, and in which Z and Z′ are each independently an oxygen or sulfur atom,
or the U 1 and U 3 or U 2 and U 4 or U 2 and G 1 or U 4 and G 1 radicals, in pairs with the atoms connecting them, are each a carbocyclic or heterocyclic ring having from 4 to 7 ring atoms, where the ring is unsubstituted or substituted,
B 1 and B 2 are each independently a divalent group of the formula —C(=Z*)-, —C(=Z*)-Z**-, —C(=Z*)-NH— or —C(=Z*)-NR*-,
where Z* is an oxygen or sulfur atom, Z** is an oxygen or sulfur atom and R* is (C 1 -C 6 )alkyl, phenyl, phenyl(C 1 -C 6 )alkyl, (C 3 -C 9 )cycloalkyl or (C 3 -C 9 )cycloalkyl(C 1 -C 6 )alkyl, where each of the 5 latter radicals is unsubstituted or substituted and has up to 20 carbon atoms, including substituents,
D 1 and D 2 are each independently hydrogen, (C 1 -C 6 )alkyl, phenyl, phenyl(C 1 -C 6 )alkyl, (C 3 -C 9 )cycloalkyl or (C 3 -C 9 )cycloalkyl(C 1 -C 6 )alkyl, where each of the 5 latter radicals is unsubstituted or substituted and has up to 20 carbon atoms, including substituents.
3. A compound of the formula (I) or salts thereof as claimed in claim 1 , wherein
R 1 is amino, acylamino having from 1 to 6 carbon atoms, di(C 1 -C 4 )alkylamino-(C 1 -C 4 )alkylideneamino or N-heterocyclylamino-(C 1 -C 4 )alkylideneamino, where the N-heterocycle is a saturated heterocyclic ring having from 1 to 3 ring heteroatoms from the group of N, O and S and at least one nitrogen atom as a ring heteroatom which is bonded to the alkylidene group.
4. A compound of the formula (I) or salts thereof as claimed in claim 1 , wherein
R 2 is hydrogen, (C 1 -C 6 )alkyl, (C 2 -C 6 )alkenyl or (C 2 -C 6 )alkynyl, where each of the three latter groups is unsubstituted or substituted by one or more radicals from the group which consists of halogen, (C 1 -C 4 )alkoxy, (C 1 -C 4 )alkylthio, (C 1 -C 4 )haloalkoxy, (C 1 -C 2 )alkoxy(C 1 -C 2 )alkoxy and optionally halogen- or (C 1 -C 4 )alkyl-substituted (C 3 -C 6 )cycloalkyl, or is (C 3 -C 6 )cycloalkyl which is unsubstituted or substituted by one or more radicals from the group consisting of halogen and (C 1 -C 4 )alkyl,
R 3 is cyclopropyl or cyclobutyl, where each of the two latter radicals is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C 1 -C 4 )alkyl, (C 2 -C 4 )alkenyl and (C 2 -C 4 )alkynyl,
R 4 and R 5 are each independently
(C 1 -C 4 )alkyl, (C 2 -C 4 )alkenyl or (C 2 -C 4 )alkynyl, where each of the latter three radicals is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C 1 -C 4 )alkoxy, (C 1 -C 4 )haloalkoxy and (C 1 -C 4 )alkylthio, or
cyclopropyl which is unsubstituted or substituted by one or more radicals from the group consisting of halogen and (C 1 -C 4 )alkyl, or
R 4 and R 5 , together with the carbon atom bonded to them, is a 3- to 6-membered carbocyclic ring which is unsubstituted or substituted by one or more radicals from the group consisting of halogen and (C 1 -C 4 )alkyl,
R 6 is hydrogen or (C 1 -C 4 )alkyl which is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C 1 -C 4 )alkoxy, (C 1 -C 4 )haloalkoxy and (C 1 -C 4 )alkylthio,
R 7 is hydrogen, methyl, ethyl or cyclopropyl which is unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C 1 -C 4 )alkyl and (C 1 -C 4 )haloalkyl.
5. A compound of the formula (I) or salts thereof as claimed in claim 1 , which are compounds of the formula (I-A) and salts thereof
in which
R 1 to R 7 are each as defined in formula (I), where the R 4 and R 5 groups may be connected in a cyclic system, but the R 3 and R 4 groups are not connected in a cyclic system.
6. A process for preparing compounds of the formula (I) or salts thereof as claimed in claim 1 , which comprises
a) reacting a compound of the formula (II)
R 2 -Fu (II)
in which Fu is a functional group from the group of carboxylic ester, carboxylic orthoester, carbonyl chloride, carboxamide, carboxylic anhydride and trichloromethyl with a compound of the formula (III) or an acid addition salt thereof
or
b) reacting a compound of the formula (IV)
in which Z 1 is an exchangeable radical or a leaving group, for example chlorine, trichloromethyl, (C 1 -C 4 )alkylsulfonyl, unsubstituted or substituted phenyl-(C 1 -C 4 )alkylsulfonyl or (C 1 -C 4 )alkylphenylsulfonyl with an amine of the formula (V) or an acid addition salt thereof
or
c) derivatizing a compound of the formula (I′) or salt thereof
on the amino group to give the compound of the formula (I),
where, in the formulae (II), (III), (IV), (V) and (I′), the R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each as defined in formula (I).
7. A herbicidal or crop growth-regulating composition, which comprises one or more compounds of the formula (I) or salts thereof as claimed in claim 1 and formulation assistants customary in crop protection.
8. A method for controlling harmful plants or for regulating the growth of plants, which comprises applying an effective amount of one or more compounds of the formula (I) or salts thereof as claimed in claim 1 to the plants, plant seeds or the area under cultivation.
9. The method as claimed in claim 8 , wherein the compounds of the formula (I) or salts thereof are applied to control harmful plants in crops of useful or ornamental plants.
10. The method as claimed in claim 9 , wherein the crop plants are transgenic crop plants.
11. The method as claimed in claim 9 , wherein the crop plants are selected from plantation crops.