# US 10,479,777 B2 · Herbicidal azines

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- Number: US 10,479,777 B2
- Document ID: US10479777B2
- Status: Granted
- Kind: B2
- Application number: 14/903,892
- Filed: 2014-07-15
- Published: 2016-06-09
- Granted: 2019-11-19
- Earliest claimed: 2013-07-16
- Assignees: BASF SE
- Applicants: BASF SE
- Inventors: Julia Major; Florian Vogt; Frederick Calo; Matthias Witschel; Doreen Schachtschabel; Trevor William Newton; Thomas Seitz; Kristin Hanzlik
- Web page: https://patentgrep.com/patent/US10479777B2

## CPC

- C07D 401/12: linked by a chain containing hetero atoms as chain links
- A01N 43/68: with two or three nitrogen atoms directly attached to ring carbon atoms
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- A01N: PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF (preservation of food or foodstuff A23); BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES (preparations for medical, dental or toiletry purposes which kill or prevent the growth or proliferation of unwanted organisms A61K); PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS

## Abstract

The present invention relates to diaminotriazine compounds of the formula (I) wherein A and R1-R5 are as defined herein, and their use as herbicides. The present invention also relates to agrochemical compositions for crop protection and to a method for controlling unwanted vegetation.

## Claims

### Claim 1

An azine compound of formula (I)
wherein
A is a 6-membered heteroaryl having 1 to 3 nitrogen atoms,
which is substituted by one to four substituents RA, selected from the group consisting of halogen, CN, NO2, C1-C6-alkyl, C1-C6-haloalkyl, OH, C1-C6-alkoxy, C1-C6-alkylthio, (C1-C6-alkyl)sulfinyl, (C1-C6-alkyl)sulfonyl, amino, (C1-C6-alkyl)amino, di(C1-C6-alkyl)amino, (C1-C6-alkyl) ¬carbonyl, (C1-C6-alkoxy)carbonyl;
R1 is selected from the group consisting of H, OH, S(O)2NH2, CN, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, (C3-C6-cycloalkyl)-C1-C4-alkyl, C1-C6-alkoxy, (C1-C6-alkoxy)-C1-C6-alkyl, (C1-C6-alkyl)-carbonyl, (C1-C6-alkoxy) carbonyl, (C1-C6-alkyl)sulfonyl, (C1-C6-alkylamino)carbonyl, di(C1-C6-alkyl)aminocarbonyl, (C1-C6-alkylamino)sulfonyl, di(C1-C6-alkyl)aminosulfonyl and (C1-C6-alkoxy) sulfonyl, where the aliphatic and cycloaliphatic parts of the 14 aforementioned radicals are unsubstituted, partly or completely halogenated, phenyl, phenyl-C1-C6-alkyl, phenylsulfonyl, phenylaminosulfonyl, phenylcarbonyl and phenoxycarbonyl,
wherein phenyl in the last 6 mentioned radicals are unsubstituted or substituted by 1, 2, 3, 4 or 5 identical or different substituents selected from the group consisting of halogen, CN, NO2, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy and C1-C6-haloalkoxy;
R2 is H, halogen, OH, CN, C1-C6-alkyl, C2-C6-alkenyl, C3-C6-alkynyl, (C1-C6-alkoxy)-C1-C6-alkyl, C3-C6-cycloalkyl, C3-C6-cycloalkenyl, (C3-C6-cycloalkyl)-C1-C4-alkyl, C1-C6-alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, C3-C6-cycloalkoxy or (C3-C6-cycloalkyl)-C1-C4-alkoxy, where the aliphatic and cycloaliphatic parts of the 9 aforementioned radicals are unsubstituted, partly or completely halogenated,
phenyl, phenyl-C1-C6-alkyl,
wherein phenyl in the last 2 mentioned radicals are unsubstituted or substituted by 1, 2, 3, 4 or 5 identical or different substituents selected from the group consisting of halogen, CN, NO2, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy and C1-C6-haloalkoxy,
R3 is selected from the group consisting of H, halogen, CN, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy and C1-C6-haloalkoxy;
R4 is selected from the group consisting of H, halogen, CN, C1-C6-alkyl, C2-C6-alkenyl, C3-C6-alkynyl, C3-C6-cycloalkyl, (C3-C6-cycloalkyl)-C1-C4-alkyl, C3-C6-cycloalkenyl and C1-C6-alkoxy-C1-C6-alkyl, where the aliphatic and cycloaliphatic parts of the 7 aforementioned radicals are unsubstituted, partly or completely halogenated; or
R3 and R4 together with the carbon atom to which they are attached form a moiety selected from the group consisting of carbonyl, C2-C6-alkenyl, C3-C6-cycloalkyl, C3-C6-cycloalkenyl and three- to six-membered heterocyclyl,
wherein the C3-C6-cycloalkyl, C3-C6-cycloalkenyl, or three- to six-membered heterocyclyl is unsubstituted or substituted by one to six substituents selected from halogen, CN, C1-C6-alkyl and C1-C6-alkoxy, and wherein the heterocyclyl is a monocyclic saturated or partially unsaturated hydrocarbon having three to six ring members, which contains in addition to the carbon atoms one or two heteroatoms selected from O, S and N; and
R5 is selected from the group consisting of H, OH, S(O)2NH2, CN, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, (C3-C6-cycloalkyl)-C1-C4-alkyl, C1-C6-alkoxy, (C1-C6-alkoxy)-C1-C6-alkyl, (C1-C6-alkyl)-carbonyl, (C1-C6-alkoxy)carbonyl, (C1-C6-alkyl)sulfonyl, (C1-C6-alkylamino)carbonyl, di(C1-C6-alkyl)aminocarbonyl, (C1-C6-alkylamino)sulfonyl, di(C1-C6-alkyl)aminosulfonyl and (C1-C6-alkoxy)sulfonyl, where the aliphatic and cycloaliphatic parts of the 14 aforementioned radicals are unsubstituted, partly or completely halogenated, phenyl, phenyl-C1-C6-alkyl, phenyl sulfonyl, phenylaminosulfonyl, phenylcarbonyl and phenoxycarbonyl,
wherein phenyl in the last 6 mentioned radicals are unsubstituted or substituted by 1, 2, 3, 4 or 5 identical or different substituents selected from the group consisting of halogen, CN, NO2, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy and C1-C6-haloalkoxy;
including their agriculturally acceptable salts or N-oxides,
with the proviso that the following compounds are excluded:
4-amino-6-[(2-methyl-1H-benzimidazol-5-yl)amino]-1,3,5-triazine-2-carboxylic acid,
Methyl-4-amino-6-[(2-methyl-1H-benzimidazol-5-yl)amino]-1,3,5-triazine-2-carboxylate,
Ethyl-4-amino-6-[(2-methyl-1H-benzimidazol-5-yl)amino]-1,3,5-triazine-2-carboxylate,
N2-(4-methylthiazol-2-yl)-6-pentyl-1,3,5-triazine-2,4-diamine,
N2-[(5-ethylthio)-1,3,4-thiadiazol-2-yl)]-6-methyl-N4-(2,4,6-trimethylphenyl)-1,3,5-triazine-2,4-diamine,
6-methyl-N2-(4-methyl-1,3-benzothiazol-2-yl)-N4-(2,4,6-trimethylphenyl)-1,3,5-triazine-2,4-diamine,
2-amino-4-(5-chloro-8-isoquinolylamino)-6-(p-isobutylbenzyl)1,3,5-triazine.

### Claim 2 (depends on 1)

The compound of claim 1, wherein RA is selected from the group consisting of halogen, CN, NO2, C1-C6-alkyl, C1-C6-haloalkyl, OH, C1-C6-alkoxy, C3-C6-cycloalkyl, C3-C6-cycloalkoxy, (C3-C6-cycloalkyl)methoxy, C2-C6-alkynyl, C2-C6-alkenyl, C2-C6-alkynyloxy, C2-C6-alkenyloxy, C1-C6-alkylthio, (C1-C6-alkyl)sulfinyl, (C1-C6-alkyl)sulfonyl, amino, (C1-C6-alkyl)amino, di(C1-C6-alkyl)amino, (C1-C6-alkyl)carbonyl, (C1-C6-alkoxy)carbonyl and C1-C6-haloalkoxy.

### Claim 3 (depends on 1)

The compound of claim 1, wherein RA is halogen, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy and CN.

### Claim 4 (depends on 1)

The compound of claim 1, wherein A is a 6-membered heteroaryl having 1 to 3 nitrogen atoms,
which is substituted by one to four substituents RA, selected from the group consisting of halogen, CN, C1-C6-alkyl and C1-C6-alkoxy.

### Claim 5 (depends on 1)

The compound of claim 1, wherein A is pyridyl, which is substituted by 1, 2, 3 or 4 identical or different radicals RA.

### Claim 6 (depends on 5)

The compound of claim 5, wherein A is 2,3,5,6-tetraflouro-4-pyridyl or 4-chloro-3,5,6-trifluoro-2-pyridyl.

### Claim 7 (depends on 1)

The compound of claim 1, wherein R1 and R5 independently of one another are selected from the group consisting of H, CN, C1-C6-alkyl, C1-C6-alkoxy-C1-C6-alkyl, C1-C6-alkoxy, (C1-C6-alkyl)carbonyl and (C1-C6-alkyl)sulfonyl.

### Claim 8 (depends on 7)

The compound of claim 7, wherein R1 and R5 are H.

### Claim 9 (depends on 1)

The compound of claim 1, wherein R2 is selected from the group consisting of H, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C4-alkoxy and, C1-C6-haloalkoxy.

### Claim 10 (depends on 1)

The compound of claim 1, wherein
R3 is selected from the group consisting of hydrogen, fluorine, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C6-haloalkoxy;
R4 is selected from the group consisting of C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C3-C6-alkynyl, C3-C6-cycloalkyl, C3-C6-cycloalkenyl, and C1-C6-alkoxy-C1-C6-alkyl;
or
R3 and R4 together with the carbon atom to which they are attached form a moiety selected from the group consisting of C3-C6-cycloalkyl, C3-C6-cycloalkenyl and three- to six-membered saturated or partially unsaturated heterocyclyl.

### Claim 11 (depends on 1)

A process for preparing an azine of claim 1, wherein R1 and R5 independently of one another are H, C1-C6-alkyl, C1-C6-alkoxy-C1-C6-alkyl or C1-C6-alkoxy; and A, R2, R3 and R4 are as defined in claim 1;
comprising reacting a halotriazine of formula (II),
wherein R5 is H, C1-C6-alkyl, C1-C6-alkoxy-C1-C6-alkyl or C1-C6-alkoxy; and
Hal is halogen;
with an amine of formula (III),
A-NHR1 (III),
wherein R1 is H, C1-C6-alkyl, C1-C6-alkoxy-C1-C6-alkyl or C1-C6-alkoxy;
in the presence of a base and a catalyst.

### Claim 12 (depends on 1)

A process for preparing an azine of claim 1, wherein R5 is CN, (C1-C6-alkyl)carbonyl, (C1-C6-alkoxy)carbonyl, (C1-C6-alkyl)sulfonyl or phenylsulfonyl,
wherein the phenyl is unsubstituted or substituted by one to five substituents selected from the group consisting of halogen, CN, NO2, C1-C6-alkyl, C1-C6-haloalkyl and C1-C6-alkoxy;
comprising reacting an azine of formula (I), wherein R5 is hydrogen,
with a compound of formula (VII)
R5—X (VII)
wherein
R5 is CN, (C1-C6-alkyl)carbonyl, (C1-C6-alkoxy)carbonyl, (C1-C6-alkyl)sulfonyl or phenylsulfonyl,
wherein the phenyl is unsubstituted or substituted by one to five substituents selected from the group consisting of halogen, CN, NO2, C1-C6-alkyl, C1-C6-haloalkyl and C1-C6-alkoxy; and
X is halogen or oxycarbonyl-C1-C6-alkyl.

### Claim 13 (depends on 1)

A process for preparing an azine of claim 1, wherein R1 is CN, (C1-C6-alkyl)carbonyl, (C1-C6-alkoxy)carbonyl, (C1-C6-alkyl)sulfonyl or phenyl sulfonyl,
wherein the phenyl is unsubstituted or substituted by one to five substituents selected from the group consisting of halogen, CN, NO2 , C1-C6 -alkyl, C1-C6-haloalkyl and C1-C6-alkoxy;
comprising reacting an azine of formula (I), wherein R1 is hydrogen, with a compound of formula (VIII)
R1—X (VIII),
wherein
R1 is CN, (C1-C6-alkyl)carbonyl, (C1-C6-alkoxy)carbonyl, (C1-C6-alkyl)sulfonyl or phenylsulfonyl,
wherein the phenyl is unsubstituted or substituted by one to five substituents selected from the group consisting of halogen, CN, NO2, C1-C6-alkyl, C1-C6-haloalkyl and C1-C6-alkoxy; and
X is halogen or oxycarbonyl-C1-C6-alkyl.

### Claim 14 (depends on 1)

An agrochemical composition comprising a herbicidally active amount of at least one azine of claim 1 and at least one inert liquid and/or solid carrier and, if appropriate, at least one surface-active substance.

### Claim 15 (depends on 1)

A process for the preparation of herbicidal active agrochemical compositions, which comprises mixing an herbicidally active amount of at least one azine of claim 1 and at least one inert liquid and/or solid carrier and, if desired, at least one surface-active substance.

### Claim 16 (depends on 1)

A method of controlling undesired vegetation, which comprises allowing an herbicidally active amount of at least one azine of claim 1 to act on plants, their environment or on seed.

### Claim 17 (depends on 1)

A method for desiccating/defoliating a plant comprising allowing an azine of claim 1 to act on plants, their environment or on seed.

### Claim 18 (depends on 16)

The method of claim 16, wherein, in the azine of formula (I), RA is selected from the group consisting of halogen, CN, NO2, C1-C6-alkyl, C1-C6-haloalkyl, OH, C1-C6-alkoxy, C3-C6-cycloalkyl, C3-C6-cycloalkoxy, (C3-C6-cycloalkyl)methoxy, C2-C6-alkynyl, C2-C6-alkenyl, C2-C6-alkynyloxy, C2-C6-alkenyloxy, C1-C6-alkylthio, (C1-C6-alkyl)sulfinyl, (C1-C6-alkyl)sulfonyl, amino, (C1-C6-alkyl)amino, di(C1-C6-alkyl)amino, (C1-C6-alkyl)carbonyl, (C1-C6-alkoxy)carbonyl and C1-C6-haloalkoxy.

### Claim 19 (depends on 16)

The method of claim 16, wherein, in the azine of formula (I), RA is halogen, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy and CN.

### Claim 20 (depends on 16)

The method of claim 16, wherein, in the azine of formula (I), A is a 6-membered heteroaryl having 1 to 3 nitrogen atoms,
which is substituted by one to four substituents RA, selected from the group consisting of halogen, CN, C1-C6-alkyl and C1-C6-alkoxy.

### Claim 21 (depends on 16)

The method of claim 16, wherein, in the azine of formula (I), A is pyridyl, which is substituted by 1, 2, 3 or 4 identical or different radicals RA.

### Claim 22 (depends on 21)

The method of claim 21, wherein A is 2,3,5,6-tetraflouro-4-pyridyl or 4-chloro-3,5,6-trifluoro-2-pyridyl.

### Claim 23 (depends on 16)

The method of claim 16, wherein, in the azine of formula (I), R1 and R5 independently of one another are selected from the group consisting of H, CN, C1-C6-alkyl, C1-C6-alkoxy-C1-C6-alkyl, C1-C6-alkoxy, (C1-C6-alkyl)carbonyl and (C1-C6-alkyl)sulfonyl.

### Claim 24 (depends on 16)

The method of claim 16, wherein, in the azine of formula (I), R2 is selected from the group consisting of H, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C4-alkoxy and, C1-C6-haloalkoxy.

### Claim 25 (depends on 16)

The method of claim 16, wherein
R3 is selected from the group consisting of hydrogen, fluorine, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C6-haloalkoxy;
R4 is selected from the group consisting of C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C3-C6-alkynyl, C3-C6-cycloalkyl, C3-C6-cycloalkenyl, and C1-C6-alkoxy-C1-C6-alkyl;
or
R3 and R4 together with the carbon atom to which they are attached form a moiety selected from the group consisting of C3-C6-cycloalkyl, C3-C6-cycloalkenyl and three- to six-membered saturated or partially unsaturated heterocyclyl.

### Claim 26 (depends on 23)

The method of claim 23, wherein R1 and R5 are H.