# US 5,703,008 A · Pyrazolines for protecting crop plants against herbicides

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- Number: US 5,703,008 A
- Document ID: US5703008A
- Status: Granted
- Kind: A
- Application number: 08/476,065
- Filed: 1995-06-07
- Granted: 1997-12-30
- Earliest claimed: 1989-11-30
- Assignees: Hoechst Aktiengesellschaft
- Inventors: Wolfgang Rosch; Erich Sohn; Klaus Bauer; Hermann Bieringer
- Web page: https://patentgrep.com/patent/US5703008A

## CPC

- C07F 7/1896: {Compounds having one or more Si-O-acyl linkages}
- A01N 25/32: Ingredients for reducing the noxious effect of the active substances to organisms other than pests, e.g. toxicity reducing compositions, self-destructing compositions
- C07D 231/06: having one double bond between ring members or between a ring member and a non-ring member
- C07D 231/54: condensed with carbocyclic rings or ring systems
- C07F 7/0812: {comprising a heterocyclic ring}
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- 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
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)

## Abstract

Compounds of the formula (I) ##STR1## where X, n, R.sup.1, R.sup.2 and R.sup.3 are as defined in claim 1 are suitable as antidotes against phytotoxic secondary effects of herbicides in crop plants without adversely affecting the action of the herbicides against harmful plants.

## Claims

### Claim 1

A composition which protects crop plants and which contains as a safener an effective amount of a compound of formula (I). ##STR6## where X radicals independently of one another are halogen or haloalkyl,
n is an integer from 1 to 3,
R.sup.1 is hydrogen, alkyl, cycloalkyl, trialkylsilyl, trialkylsilylmethyl or alkyloxyalkyl,
R.sup.2 and R.sup.3 independently of one another are hydrogen, alkyl, C.sub.3 -C.sub.6 -cycloalkyl, alkenyl, alkynyl, haloalkyl, alkoxyalkyl, hydroxylalkyl, alkoxycarbonyl, alkylcarbonyl, alkylaminocarbonyl, optionally substituted phenyl, halogen or cyano, it being possible for the radicals R.sup.2 and R.sup.3 to form a ring with the 5-C atom
of the pyrazoline ring, and which, additionally, contains an herbicide.

### Claim 2 (depends on 1)

A composition as claimed in claim 1, wherein
X radicals independently of one another are halogen or C.sub.1 -C.sub.4 -haloalkyl,
n is an integer from 1 to 3,
R.sup.1 is C.sub.1 -C.sub.6 -alkyl, C.sub.3 -C.sub.6 -coycloalkyl, tri(C.sub.1 -C.sub.4 -alkyl)-silyl, tri(C.sub.1 -C.sub.4 -alkyl)silylmethyl or (C.sub.1 -C.sub.6 -alkyl-oxy)-C.sub.1 -C.sub.6 -alkyl,
R.sup.2 and R.sup.3 independently of one another are hydrogen, C.sub.1 -C.sub.6 -alkyl, C.sub.2 -C.sub.6 -alkenyl, C.sub.2 -C.sub.6 -alkynyl, C.sub.3 -C.sub.6 -cycloalkyl, C.sub.1 -C.sub.6 -haloalkyl, mono- or di-(C.sub.1 -C.sub.4 -alkoxy)-C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.6 -hydroxyalkyl, (C.sub.1 -C.sub.6 -alkyl)carbonyl, mono- or di-(C.sub.1 -C.sub.4 -alkyl)aminocarbonyl, cyano, halogen, (C.sub.1 -C.sub.12 -alkyl)oxycarbonyl, phenyl, or phenyl which is substituted by one or more radicals selected from the group comprising halogen, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy or cyano.

### Claim 3 (depends on 1)

A composition as claimed in claim 1, wherein
X radicals independently of one another are fluorine, chlorine, bromine or trifuoromethyl,
n is 2 or 3,
R.sup.1 is C.sub.1 -C.sub.4 -alkyl or (C.sub.1 -C.sub.4 -alkoxy)-C.sub.1 -C.sub.4 -alkyl,
R.sup.2 is hydrogen, C.sub.1 -C.sub.4 -alkyl or C.sub.2 -C.sub.4 -alkenyl,
R.sup.3 is C.sub.1 -C.sub.4 -alkyl, C.sub.3 -C.sub.4 -alkenyl, C.sub.2 -C.sub.4 -alkynyl, C.sub.1 -C.sub.4 -haloalkyl, mono- or di-(C.sub.1 -C.sub.4 -alkoxy)-C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -hydroxyalkyl, mono- or di-(C.sub.1 -C.sub.4 -alkyl)-amino-carbonyl, cyano, (C.sub.1 -C.sub.12 -alkyloxy)-carbonyl, phenyl, or phenyl which is monosubstituted or polysubstituted by halogen.

### Claim 4 (depends on 1)

A composition as claimed in claim 1, wherein
X radicals independently of one another are fluorine, chlorine, bromine or trifluoromethyl,
n is 2 or 3,
R.sup.2 is hydrogen, C.sub.1 -C.sub.4 -alkyl, C.sub.2 -C.sub.4 -alkenyl or C.sub.2 -C.sub.4 -alkynyl, and
R.sup.3 is C.sub.1 -C.sub.4 -alkyl which is unsubstituted or monosubstituted or polysubstituted by halogen, or is (C.sub.1 -C.sub.12 -alkyl)oxycarbonyl or cyano.

### Claim 5 (depends on 1)

A composition as claimed in claim 1, wherein
X radicals independent of one another is halogen or haloalkyl
n is 1, 2 or 3,
R.sup.1 is H or C.sub.1 -C.sub.4 -alkyl,
R.sup.2 is H or C.sub.1 -C.sub.4 -alkyl,
R.sup.3 is C.sub.1 -C.sub.4 -alkyl or (C.sub.1 -C.sub.4 -alkoxy)-carbonyl.

### Claim 6 (depends on 5)

A composition as claimed in claim 5, wherein
(X).sub.n is 2,4-dichloro,
R.sup.1 is C.sub.1 -C.sub.4 -alkyl,
R.sup.2 is hydrogen or methyl,
R.sup.3 is (C.sub.1 -C.sub.4 -alkoxy)-carbonyl.

### Claim 7 (depends on 1)

A composition as claimed in claim 1, wherein the molar ratio of safener and herbicide is between 1:10 and 10:1.

### Claim 8 (depends on 7)

A composition as claimed in claim 7, which additionally contains common formulation auxiliaries.

### Claim 9 (depends on 1)

A composition as claimed in claim 1, wherein the herbicide is selected from the group consisting of carbamates, thiocarbamates, haloacetanilides, substituted phenoxycarboxylic acid derivatives, substituted naphthoxycarboxylic acid derivatives, substituted phenoxyphenoxycarboxylic acid derivatives, heteroaryloxyphenoxycarboxylic acid derivative and cyclohexandione derivatives.

### Claim 10 (depends on 9)

A composition as claimed in claim 9, wherein the herbicide is selected from the group consisting of substituted phenoxyphenoxycarboxylic acid derivatives and heteroaryloxphenoxycarboxylic acid derivatives.

### Claim 11 (depends on 1)

A composition as claimed in claim 1, which additionally contains common formulation auxiliaries.

### Claim 12 (depends on 1)

A composition as claimed in claim 1, wherein
X radicals independently of one another are halogen or haloalkyl,
n is 1, 2 or 3,
R.sup.1 is cycloalkyl, trialkylsilyl, trimethylsilylmethyl or alkoxyalkyl,
R.sup.2 and R.sup.3 independently of one another are hydrogen, alkyl, C.sub.3 -C.sub.6 -cycloalkyl, alkenyl, alkynyl, haloalkyl, alkoxyalkyl, hydroxyalkyl, alkoxycarbonyl, alkylcarbonyl, alkylaminocarbonyl, optionally substituted phenyl, halogen or cyano, it being possible for the radicals R.sup.2 and R.sup.3 to form a ring with the 5-C atom of the pyrazoline ring.

### Claim 13

A plant protection composition which contains an effective amount of a combination of a herbicide, selected from the group consisting of fenoxaprop-ethyl and fenoxaprop-P-ethyl, and a safener selected from the compounds of formula (I) ##STR7## where X radicals independently of one another are halogen or haloalkyl,
n is an integer from 1 to 3,
R.sup.1 is hydrogen, alkyl, cycloalkyl, trialkylsilyl, trialkylsilylmethyl or alkyloxyalkyl,
R.sup.2 and R.sup.3 independently of one another are hydrogen, alkyl, C.sub.3 -C.sub.6 -cycloalkyl, alkenyl, alkynyl, haloalkyl, alkoxyalkyl, hydroxyalkyl, alkoxycarbonyl, alkylcarbonyl, alkylaminocarbonyl, optionally substituted phenyl, halogen or cyano, it being possible for the radicals R.sup.2 and R.sup.3 to form a ring with the 5-C atom of the pyrazoline ring.

### Claim 14 (depends on 13)

A composition as claimed in claim 13, wherein
X radicals independently of one another are halogen or C.sub.1 -C.sub.4 -haloalkyl,
n is an integer from 1 to 3,
R.sup.1 is C.sub.1 -C.sub.6 -alkyl, C.sub.3 -C.sub.6 -cycloalkyl, tri(C.sub.1 -C.sub.4 -alkyl)-silyl, tri(C.sub.1 -C.sub.4 -alkyl)silylmethyl or (C.sub.1 -C.sub.6 -alkyl-oxy)-C.sub.1 -C.sub.6 -alkyl,
R.sup.2 and R.sup.3 independently of one another are hydrogen, C.sub.1 -C.sub.6 -alkyl, C.sub.2 -C.sub.6 -alkenyl, C.sub.2 -C.sub.6 -alkynyl, C.sub.3 -C.sub.6 -cycloalkyl, C.sub.1 -C.sub.6 -haloalkyl, mono- or di-(C.sub.1 -C.sub.4 -alkoxy)-C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.6 -hydroxyalkyl, (C.sub.1 -C.sub.6 -alkyl)carbonyl, mono- or di-(C.sub.1 -C.sub.4 -alkyl)aminocarbonyl, cyano, halogen, (C.sub.1 -C.sub.12 -alkyl)oxycarbonyl, phenyl, or phenyl which is substituted by one or more radicals selected from the group comprising halogen, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy or cyano.

### Claim 15 (depends on 14)

A composition as claimed in claim 14, wherein the molar ration of a safener and herbicide is between 1:10 and 10:1.

### Claim 16 (depends on 13)

A composition as claimed in claim 13, wherein
X radicals independently of one another are fluorine, chlorine, bromine or trifuoromethyl,
n is 2 or 3,
R.sup.1 is C.sub.1 -C.sub.4 -alkyl or (C.sub.1 -C.sub.4 -alkoxy)-C.sub.1 -C.sub.4 -alkyl,
R.sup.2 is hydrogen, C.sub.1 -C.sub.4 -alkyl or C.sub.2 -C.sub.4 -alkenyl,
R.sup.3 is C.sub.1 -C.sub.4 -alkyl, C.sub.3 -C.sub.4 -alkenyl, C.sub.2 -C.sub.4 -alkynyl, C.sub.1 -C.sub.4 -haloalkyl, mono- or di-(C.sub.1 -C.sub.4 -alkoxy)-C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -hydroxyalkyl, mono- or di-(C.sub.1 -C.sub.4 -alkyl)-amino-carbonyl, cyano, (C.sub.1 -C.sub.12 -alkyloxy)-carbonyl, phenyl, or phenyl which is monosubstituted or polysubstituted by halogen.

### Claim 17 (depends on 16)

A composition as claimed in claim 16, wherein the molar ratio of safener and herbicide is between 1:10 and 10:1.

### Claim 18 (depends on 13)

A composition as claimed in claim 13, wherein
X radicals independently of one another are fluorine, chlorine, bromine or trifluoromethyl,
n is 2 or 3,
R.sup.2 is hydrogen, C.sub.1 -C.sub.4 -alkyl, C.sub.2 -C.sub.4 -alkenyl or C.sub.2 -C.sub.4 -alkynyl, and
R.sup.3 is C.sub.1 -C.sub.4 -alkyl which is unsubstituted or monosubstituted or polysubstituted by halogen, or is (C.sub.1 -C.sub.12 -alkyl)oxycarbonyl or cyano.

### Claim 19 (depends on 18)

A composition as claimed in claim 18, wherein the molar ratio of safener and herbicide is between 1:10 and 10:1.

### Claim 20 (depends on 13)

A composition as claimed in claim 13, wherein
X radicals independent of one another is halogen or haloalkyl
n is 1, 2 or 3,
R.sup.1 is H or C.sub.1 -C.sub.4 -alkyl,
R.sup.2 is H or C.sub.1 -C.sub.4 -alkyl,
R.sup.3 is C.sub.1 -C.sub.4 -alkyl or (C.sub.1 -C.sub.4 -alkoxy)-carbonyl.

### Claim 21 (depends on 20)

A composition as claimed in claim 20, wherein
(X).sub.n is 2,4-dichloro,
R.sup.1 is C.sub.1 -C.sub.4 -alkyl,
R.sup.2 is hydrogen or methyl,
R.sup.3 is (C.sub.1 -C.sub.4 -alkoxy)-carbonyl.

### Claim 22 (depends on 21)

A composition as claimed in claim 21, wherein the molar ration of safener and herbicide is between 1:10 and 10:1.

### Claim 23 (depends on 22)

A composition as claimed in claim 22, wherein (X).sub.n is two radicals selected from the group comprising
halogen and C.sub.1 -C.sub.4 -haloalkyl.

### Claim 24 (depends on 22)

A composition as claimed in claim 22, wherein
(X).sub.n is 2,4-Cl.sub.2, 2,4-F.sub.2, 2,4-Br.sub.2, 2-Cl-4-F, 2-F-4-Cl, 2,4-(CF.sub.3).sub.2,2-CF.sub.3 -4-Cl, 2-Cl-4-CF.sub.3, 2-F-4-CF.sub.3, 2-CF.sub.3 -4-F, 2-CF.sub.3 -4-Br or 2-Br-4-CF.sub.3.

### Claim 25 (depends on 21)

A composition as claimed in claim 21, wherein the molar ratio of safener and herbicide is between 1:10 and 10:1.

### Claim 26 (depends on 25)

A composition as claimed in claim 25, wherein
X radicals independently of one another are halogen or C.sub.1 -C.sub.4 -haloalkyl,
n is 1, 2 or 3,
R.sup.1 is C.sub.3 -C.sub.6 -cycloalkyl, tri(C.sub.1 -C.sub.4 -alkyl)silyl, trimethylsilylmethyl or C.sub.1 -C.sub.6 -alkoxy-C.sub.1 -C.sub.6 -alkyl,
R.sup.2 and R.sup.3 independently of one another are hydrogen, C.sub.1 -C.sub.6 -alkyl, C.sub.2 -C.sub.6 -alkenyl, C.sub.2 -C.sub.6 -alkynyl, C.sub.3 -C.sub.6 -cycloalkyl, C.sub.1 -C.sub.6 -haloalkyl, mono- or di-(C.sub.1 -C.sub.4 -alkoxy)-C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.6 -hydroxyalkyl, (C.sub.1 -C.sub.6 -alkyl)carbonyl, mono- or di-(C.sub.1 -C.sub.4 -alkyl)aminocarbonyl, cyano, halogen, (C.sub.1 -C.sub.12 -alkyl)-oxycarbonyl, phenyl, or phenyl which is substituted by one or more radicals selected from the group comprising halogen, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy or cyano.

### Claim 27 (depends on 13)

A composition as claimed in claim 13, wherein the molar ratio of safener and herbicide is between 1:10 and 10:1.

### Claim 28

A composition which protects crop plants and which contains as a safener an effective amount of a compound of formula (I) ##STR8## where X radicals independently of one another are halogen or haloalkyl,
n is an integer from 1 to 3,
R.sup.1 is hydrogen, alkyl, cycloalkyl, trialkylsilyl, trialkylsilylmethyl or alkyloxyalkyl,
R.sup.2 and R.sup.3 independently of one another are hydrogen, alkyl, C.sub.3 -C.sub.6 -cycloalkyl, alkenyl, alkynyl, haloalkyl, alkoxyalkyl, hydroxyalkyl, alkoxycarbonyl, alkylcarbonyl, alkylaminocarbonyl, optionally substituted phenyl, halogen or cyano, it being possible for the radicals R.sup.2 and R.sup.3 to form a ring with the 5-C atom of the pyrazoline ring, and which, additionally, contains an herbicide and wherein the herbicide is fenoxaprop-ethyl or fenoxaprop-P-ethyl.

### Claim 29

A composition which protects crop plants and which contains as a safener an effective amount of a compound of formula (I) ##STR9## where (X).sub.n is 2,4-dichloro,
R.sup.1 is C.sub.1 -C.sub.4 -alkyl,
R.sup.2 is hydrogen or methyl,
R.sup.3 is (C.sub.1 -C.sub.4 -alkoxy)-carbonyl, and which, additionally, contains an herbicide, and wherein the herbicide is fenoxapropethyl or fenoxaprop-P-ethyl.

### Claim 30

A composition which protects crop plants and which contains as a safener an effective amount of a compound of formula (I) ##STR10## where (X).sub.n is 2,4-dichloro,
R.sup.1 is C.sub.1 -C.sub.4 -alkyl,
R.sup.2 is hydrogen or methyl,
R.sup.3 is (C.sub.1 -C.sub.4 -alkoxy)-carbonyl, and which, additionally, contains an herbicide, and wherein the herbicide is fenoxapropethyl or fenoxaprop-P-ethyl, which additionally contains common formulation auxiliaries and wherein the molar ratio of safener and herbicide is between 1:10 and 10:1.