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

• US 9,078,440 B2
• Filed: 12/12/2011
• Issued: 07/14/2015
• Est. Priority Date: 12/16/2010
• Status: Expired due to Fees

• Current Assignee: Bayer Intellectual Property GmbH (Bayer AG)
• Original Assignee: Bayer Intellectual Property GmbH (Bayer AG)
• Inventors: Brnjes, Marco, Dller, Uwe, Dietrich, Hansjrg, Hoffmann, Michael Gerhard, Huser-Hahn, Isolde, Rosinger, Christopher Hugh, Gatzweiler, Elmar, Heinemann, Ines
• Primary Examiner(s): Oswecki, Jane C
• Application Number:
  US13/994,557
• Publication Number:
  US 20130326735A1
• Time in Patent Office: 1,310 Days
• Field of Search: 504/100, 504/244, 504/260, 514/277, 514/352, 514/354, 546/304, 546/309, 546/310, 560/48, 560/102, 562/405, 562/426, 562/432, 562/433
• US Class Current: 1/1
• 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)

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

n is 0, 1, 2, 3, or 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)alkoxy-alkyl, (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)amino-carbonyl, (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)halo-alkylthio, 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; and

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 0, 1, 2, 3, or 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); and

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′

is (C₁-C₁₂)alkyl or hydrogen,

n is 0, 1, 2, 3, or 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)haloalkyl-sulfinyl, (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-C

     6)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 one to three R²⁵radicals;

or where two adjacent R¹ radicals may 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, 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)alkynyl;

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

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; and

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

with a boron compound 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 optionally also form cyclic structures,

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 of 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)