6-(2-Aminophenyl)picolinates and their use as herbicides

• US 20130326735A1
• Filed: 12/12/2011
• Published: 12/05/2013
• Est. Priority Date: 12/16/2010
• Status: Active Grant

• Current Assignee: Bayer Intellectual Property GmbH (Bayer AG)
• Original Assignee: Bayer Intellectual Property GmbH (Bayer AG)
• Inventors: Dietrich, Hansjrg, Hoffmann, Michael Gerhard, Huser-Hahn, Isolde, Rosinger, Christopher Hugh, Gatzweiler, Elmar, Heinemann, Ines, Brnjes, Marco, Dller, Uwe
• Granted Patent: US 9,078,440 B2
• Time in Patent Office: Days
• US Class Current: 800/298
• CPC Class Codes: A01N 43/40 six-membered rings
• CPC Class Codes: C07D 213/79 Acids; Esters

Abstract

The present invention relates to novel herbicidally active 6-(2-aminophenyl)picoline derivatives and to processes for preparation thereof. The present invention further provides for the use thereof as a herbicide, especially as a herbicide for selective control of weed plants in useful plant crops, and as a plant growth regulator alone or in combination with safeners and/or in a mixture with other herbicides.

Claims

1. A 6-(2-Aminophenyl)picolinate of formula (I) and/or an N-oxide, salt, ester and/or agrochemically suitable derivative thereof:

3. The compound as claimed in claim 1, in which the radicals are each defined as follows:

n is an integer selected from the group consisting of 0, 1, 2, 3, and 4;

R¹ is, optionally independently of further R¹ radicals, selected from the group consisting of hydrogen, halogen, cyano, nitro, amino, (C₁-C₆)alkyl, (C₁-C₆)haloalkyl, (C₂-C₆)alkoxyalkyl, (C₂-C₆)haloalkoxyalkyl, (C₂-C₆)alkenyl, (C₂-C₆)haloalkenyl, (C₂-C₆)alkynyl, (C₁-C₆)alkoxy, (C₁-C₆)haloalkoxy, (C₂-C₆)haloalkenyloxy, (C₁-C₆)alkylthio, (C₂-C₆)alkylthioalkyl, (C₁-C₆)haloalkylthio, (C₁-C₆)alkylsulfonyl, (C₁-C₆)haloalkylsulfonyl, (C₂-C₆)alkenylthio, (C₂-C₆)haloalkenylthio, (C₁-C₆)alkylamino, (C₂-C₆)dialkylamino, (C₂-C₆)alkylaminoalkyl, (C₂-C₆)alkylcarbonyl, (C₂-C₆)alkoxycarbonyl, (C₂-C₆)aminocarbonyl, (C₂-C₆)alkylaminocarbonyl, (C₃-C₈)dialkylaminocarbonyl, or two adjacent R¹ radicals together form an —

OCH₂O—

, —

CH₂CH₂O—

, —

OCH₂CH₂O—

, —

OCH(CH₃)O—

, —

OC(CH₃)₂O—

, —

OCF₂O—

, —

CF₂CF₂O—

, —

OCF₂CF₂O—

or —

CH═

CH—

CH═

CH—

group;

R² is hydrogen, halogen, cyano;

R³ is hydrogen, (C₁-C₄)alkyl, (C₂-C₄)alkenyl, (C₂-C₄)alkynyl or C(═

O)R⁹, OR¹⁰, S(O)₂R¹¹, N(R¹²)R¹³ or N═

C(R¹⁴)R¹⁵;

R⁴ is hydrogen, (C₁-C₄)alkyl optionally substituted by one or two R⁶ radicals, or C(═

O)R⁹;

or

R³ and R⁴ together form a —

(CH₂)₄—

, —

(CH₂)₅, —

(CH₂)₂O(CH₂)—

or ═

C(R¹⁷)N(R¹⁸)R¹⁹ group;

each R⁶ radical, optionally independently of further R⁶ radicals, is selected from the group consisting of halogen, (C₁-C₃)alkoxy, (C₁-C₃)haloalkoxy, (C₁-C₃)alkylthio, (C₁-C₃)haloalkylthio, amino, (C₁-C₃)alkylamino, (C₂-C₄)dialkylamino and (C₂-C₄)alkoxycarbonyl;

R⁵ is hydrogen, halogen, cyano;

R⁹ is, optionally independently of further R⁹ radicals, selected from the group consisting of hydrogen, (C₁-C₄)alkyl, (C₁-C₄)haloalkyl, (C₁-C₄)alkoxy, phenyl, phenoxy, benzyl and benzyloxy;

R¹⁰ is hydrogen, (C₁-C₄)alkyl or (C₁-C₃)haloalkyl;

R¹¹ is (C₁-C₄)alkyl or phenyl optionally substituted by one, two or three radicals selected independently from the group consisting of CH₃, Cl and OCH₃;

R¹² is hydrogen, (C₁-C₄)alkyl or C(═

O)R²⁴;

R¹³ is hydrogen or (C₁-C₄)alkyl;

R¹⁴ is hydrogen or (C₁-C₄)alkyl;

R¹⁵ is hydrogen or (C₁-C₄)alkyl;

or

R¹⁴ and R¹⁵ together form a —

(CH₂)₄—

or —

(CH₂)₅—

group;

R¹⁷ is hydrogen or (C₁-C₄)alkyl;

R¹⁸ and R¹⁹ are each independently hydrogen or (C₁-C₄)alkyl;

or R¹⁸ and R¹⁹ together form a —

(CH₂)₄—

, —

(CH₂)₅—

, —

CH₂CH═

CHCH₂—

or —

(CH₂)₂O(CH₂)₂—

group;

R²⁴ is hydrogen, (C₁-C₄) alkyl or benzyl.

4. The compound as claimed in claim 1, in which the radicals are each defined as follows:

n is an integer selected from the group consisting of 0, 1, 2, 3, and 4,

R¹ is, optionally independently of further R¹ radicals, selected from hydrogen, fluorine, chlorine, bromine, iodine, methyl, cyclopropyl, trifluoromethyl, methoxymethyl, methoxy, methylthio, methoxycarbonyl, dimethylamino;

R² is hydrogen, fluorine or chlorine;

R³ is hydrogen, methyl, ethyl or C(═

O)CH₃ (acetyl);

R⁴ is hydrogen, methyl, ethyl or C(═

O)CH₃ (acetyl);

R⁵ is hydrogen, fluorine or chlorine.

5. A process for preparing a compound as claimed in claim 1, comprising:

(A) reacting a halogen compound of formula (II) where R′

=(C₁-C₁₂)alkyl or hydrogen and R² to R⁵ are

R² is hydrogen, halogen, cyano, nitro, (C₁-C₆)alkyl, (C₁-C₆)haloalkyl, (C₁-C₆)alkoxy, (C₁-C₆)alkylamino, (C₁-C₆)dialkylamino, (C₁-C₆)thioalkoxy, (C₂-C₆)alkenyl, (C₂-C₆)haloalkenyl, (C₂-C₆)alkynl;

R³ is hydrogen, (C₁-C₄)alkyl optionally substituted by one or two R⁶ radicals, (C₂-C₄)alkenyl optionally substituted by 1-2 R⁷ radicals, or (C₂-C₄)alkynyl optionally substituted by one or two R⁸ radicals;

or R³ is C(═

O)R⁹, NO₂, OR¹⁰, S(O)₂R¹¹, N(R¹²)R¹³ or N═

C(R¹⁴)R¹⁵;

R⁴ is hydrogen, (C₁-C₄)alkyl optionally substituted by one or two R⁶ radicals, or C(═

O)R⁹;

or

R³ and R⁴ together form a —

(CH₂)₄—

, —

(CH₂)₅—

, —

CH₂CH═

CHCH₂—

or —

(CH₂)₂O(CH₂)₂—

group which is optionally substituted by one or two R¹⁶ radicals;

or R³ and R⁴ together form a ═

C(R¹⁷)N(R¹⁸)R¹⁹ or ═

C(R²⁰)OR²¹ group;

where each R⁶, R⁷ and R⁸ radical is independently selected from halogen, (C₁-C₃)alkoxy, (C₁-C₃)haloalkoxy, (C₁-C₃)alkylthio, (C₁-C₃)haloalkylthio, amino, (C₁-C₃)alkylamino, (C₂-C₄)dialkylamino and (C₂-C₄)alkoxycarbonyl;

R⁵ is hydrogen, halogen, cyano, nitro, formyl, (C₁-C₆)alkyl, (C₂-C₆)alkenyl, (C₂-C₆)alkynyl, (C₁-C₆)haloalkyl, (C₂-C₆)haloalkenyl, (C₁-C₆)alkoxy, (C₁-C₆)thioalkoxy, (C₂-C₆)alkoxyalkyl, (C₂-C₆)thioalkoxyalkyl;

with boron compounds of formula (III) where the R^X and R^Y radicals are both hydrogen or where the R^X and R^Y radicals are each independently (C₁-C₆)alkyl or (C₆-C₁₂)aryl or where R^X and R^Y together with the boron atom to which they are bonded may also form cyclic structures, and R¹ and n are

n is an integer selected from 0, 1, 2, 3, 4;

R¹ is selected from the group consisting of hydrogen, halogen, cyano, nitro, amino, hydroxyl, (C₁-C₆)alkyl, (C₁-C₆)haloalkyl, (C₁-C₄)hydroxyalkyl, (C₂-C₆)alkoxyalkyl, (C₂-C₆)haloalkoxyalkyl, (C₂-C₆)alkenyl, (C₂-C₆)haloalkenyl, (C₂-C₆)alkynyl, (C₃-C₆)haloalkynyl, (C₁-C₆)alkoxy, (C₁-C₆)haloalkoxy, (C₂-C₆)alkenyloxy, (C₂-C₆)haloalkenyloxy, (C₂-C₆)alkynyloxy, (C₃-C₆)haloalkynyloxy, (C₁-C₆)alkylthio, (C₂-C₆)alkylthioalkyl, (C₁-C₆)haloalkylthio, (C₁-C₆)alkylsulfinyl, (C₁-C₆)haloalkylsulfinyl, (C₁-C₆)alkylsulfonyl, (C₁-C₆)haloalkylsulfonyl, (C₂-C₆)alkenylthio, (C₂-C₆)haloalkenylthio, (C₂-C₆)alkenylsulfinyl, (C₂-C₆)haloalkenylsulfinyl, (C₂-C₆)alkenylsulfonyl, (C₂-C₆)haloalkenylsulfonyl, (C₂-C₆)alkynylthio, (C₃-C₆)haloalkynylthio, (C₃-C₆)alkynylsulfinyl, (C₃-C₆)haloalkynylsulfinyl, (C₃-C₆)alkynylsulfonyl, (C₃-C₆)haloalkynylsulfonyl, (C₁-C₆)alkylamino, (C₂-C₆)dialkylamino, (C₂-C₆)alkylaminoalkyl, (C₂-C₆)alkylcarbonyl, (C₂-C₆)alkoxycarbonyl, (C₂-C₆)aminocarbonyl, (C₂-C₆)alkylaminocarbonyl, (C₃-C₈)dialkylaminocarbonyl, (C₃-C₆)trialkylsilyl, phenyl, phenoxy and 5- or 6-membered heteroaromatic rings, where each phenyl ring, phenoxy ring or 5- or 6-membered heteroaromatic ring may optionally be substituted by 1-3 R²⁵ radicals;

or where two adjacent R¹ radicals may together form an —

OCH₂O—

, —

CH₂CH₂O—

, —

OCH₂CH₂O—

, —

OCH(CH₃)O—

, —

OC(CH₃)O—

, —

OCF₂O—

, —

CF₂CF₂O—

, —

OCF₂CF₂O—

or —

CH═

CH—

CH═

CH—

group;

or with a trifluoroborate salt thereof in the presence of a palladium catalyst;

6. An agrochemical composition comprising a) at least one compound claim 1, and one or more b) auxiliaries and/or additives customary in crop protection.

7. An agrochemical composition comprising

a) at least one compound as defined in claim 1,

b) at least one active agrochemical ingredient other than component a), and optionally

c) one or more auxiliaries and/or additives customary in crop protection.

8. A method for controlling an unwanted plant and/or for regulating growth of a plant, comprising applying an effective amount of at least one compound as defined in claim 1, to a plant, seed and/or an area on which a plant grows.

9. The compound as defined in claim 1, capable of being used as a herbicide and/or plant growth regulator.

10. The compound capable of being used as claimed in claim 9, wherein said compound is capable of being used to control a weed plant and/or to regulate growth in a plant crop.

11. The compound capable of being used as claimed in claim 10, wherein said crop plant comprises a transgenic or nontransgenic crop plant.

12. A crop plant which has been treated with a compound of claim 1.

2. A compound of at least one of the formulae (I-a) to (I-c)