Substituted benzene compounds, process for their preparation, and herbicidal and defoliant compositions containing them

• US 6,355,799 B1
• Filed: 04/27/2000
• Issued: 03/12/2002
• Est. Priority Date: 10/27/1997
• Status: Expired

• Current Assignee: ISK Americas, Inc. (Ishihara Sangyo Kaisha Limited)
• Original Assignee: ISK Americas, Inc. (Ishihara Sangyo Kaisha Limited)
• Inventors: Gupta, Sandeep, Ying, Bai-Ping, Tsukamoto, Masamitsu, Pulman, David A., Wu, Shao-Yong
• Primary Examiner(s): Shah, Mukund J.
• Assistant Examiner(s): Patel, Sudhaker B
• Application Number:
  US09/530,373
• Time in Patent Office: 684 Days
• Field of Search: 544/242, 544/309, 544/311, 544/312
• US Class Current: 544/309
• CPC Class Codes: A01N 37/32 Cyclic imides of polybasic carboxylic acids or thio analogues thereof
• CPC Class Codes: A01N 37/34 Nitriles
• CPC Class Codes: A01N 43/40 six-membered rings
• CPC Class Codes: A01N 43/54 1,3-Diazines; Hydrogenated 1,3-diazines
• CPC Class Codes: A01N 43/56 1,2-Diazoles; Hydrogenated 1,2-diazoles
• CPC Class Codes: A01N 43/58 1,2-Diazines; Hydrogenated 1,2-diazines
• CPC Class Codes: A01N 43/64 having rings with three nitrogen atoms as the only ring hetero atoms
• CPC Class Codes: A01N 43/653 1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
• CPC Class Codes: A01N 43/713 having rings with four or more nitrogen atoms as the only ring hetero atoms
• CPC Class Codes: A01N 43/90 having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
• CPC Class Codes: A01N 47/06 containing —O—CO—O— groups; Thio analogues thereof
• CPC Class Codes: A01N 47/20 N-Aryl derivatives thereof
• CPC Class Codes: A01N 47/22 O-Aryl or S-Aryl esters thereof
• CPC Class Codes: A01N 47/24 containing the groups , or; Thio analogues thereof
• CPC Class Codes: A01N 47/30 Derivatives containing the group >N—CO—N aryl or >N—CS—N—aryl
• CPC Class Codes: A01N 47/34 containing the groups , e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
• CPC Class Codes: C07C 211/52 the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups
• CPC Class Codes: C07C 217/84 the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom
• CPC Class Codes: C07D 209/48 with oxygen atoms in positions 1 and 3, e.g. phthalimide
• CPC Class Codes: C07D 231/16 Halogen atoms or nitro radicals
• CPC Class Codes: C07D 237/14 : Oxygen atoms
• CPC Class Codes: C07D 239/54 : as doubly bound oxygen atoms or as unsubstituted hydroxy radicals
• CPC Class Codes: C07D 239/553 : with halogen atoms or nitro radicals directly attached to ring carbon atoms, e.g. fluorouracil
• CPC Class Codes: C07D 249/12 : Oxygen or sulfur atoms
• CPC Class Codes: C07D 257/04 : Five-membered rings
• CPC Class Codes: C07D 471/04 : Ortho-condensed systems
• CPC Class Codes: C07D 487/04 : Ortho-condensed systems

Abstract

Novel herbicidal and defoliant substituted aniline derived compounds represented by general structure (I)

are described. W, X, Y, Z, and Q are as defined in the disclosure. Also described are the processes for the manufacture of these compounds and agriculturally suitable compositions containing these as active ingredients which are useful as herbicides for general or selective pre-emergent or post-emergent control of undesired plant species and defoliants at very low concentrations of these biologically active compounds.

Claims

1. A compound represented by the formula I or its salts

wherein X is hydrogen, halogen, nitro, amino, NHR, N(R)₂, amide, thioatnide, cyano, alkylcarbonyl, alkoxycarbonyl, alkylsulfonamnde, unsubstituted or substituted alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonylalkoxy, benzyloxy, amyloxy, or heteroaryloxy;

Y is hydrogen, halogen, or nitro;

W is hydrogen, OR, SR, NHR, N(R)₂, CH₂R, CH(R)₂, C(R)₃, halogen, nitro, or cyano, where multiple R groups represent any possible combination of substituents described by R;

R is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heteroaryl, alkoxy, cycloalkyloxy, aryloxy, heteroaryloxy, alkylsulfonyl, benzyl, alkylcarbonyl, alkenylcarbonyl, alkynylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, or heteroaryloxycarbonyl, where any of these groups may be unsubstituted or substituted with any of the functional groups represented by one or more of the following;

halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkylsilyl, alkylcarbonyl, haloalkylcarbonyl, alkoxy, alkoxybarbonyl, haloalkoxy, haloalkoxycarbonyl, alkylsulfonyl, haloalkylsulfonyl, aryl, heteroaryl, or cycloalkyl;

Q is a heterocycle;

 

wherein R₁ is hydrogen, alkyl, haloalkyl, alkenyl, alkynyl, amino, alkoxyalkyl, acetyl, alkoxycarbonylamino, alkylcarbonylamino, or alkoxycarbonyl;

R₂ is alkyl or haloalkyl;

R₁ and R₂ could combine to form a five- or six-membered heterocyclic ring;

R₃ is hydrogen, halogen, nitro, amino, alkylamino, haloalkylamino, cyano, or amide;

R₈ and R₉ are independently oxygen, or sulfur;

Q6, Q7, and Q10 may optionally be unsaturated containing one or two double bonds in the 6-membered ring;

Z is amino, hydroxyl, thiol, formyl, carboxyl, cyano, alkylcarbonyl, arylcarbonyl, azido, or one of the following;

 

wherein R₄ is alkyl, alkenyl, alkynyl, amino, cycloalkyl, heterocycloalkyl, alkylsulfonyl, arylsulfonyl, benzyl, aryl, heteroaryl, alkylcarbonyl, alkenylcarbonyl, alkynylcarbonyl, cycloalkylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkoxycarbonyl, alkylthiocarbonyl, cycloalkyloxycarbonyl, aryloxycarbonyl, arylthio-carbonyl, aryl-thiocarbonyl, heteroaryloxycarbonyl, aminocarbonyl, alkylaminocarbonyl, arylaminocarbonyl, heteroarylaminocarbonyl, alkoxycarbonylcarbonyl or arylcarbonylcarbonyl, where any of these groups may be unsubstituted or substituted with any of the functional groups represented by one or more of the following;

halogen, cyano, nitro, amino, dialkylamino, hydroxyl, carboxyl, alkyl, alkenyl, alkynyl, alkyklcarbonyl, alkylcarbonyloxy, alkoxy, alkoxycarbonyl, alkylthio, alkylthiocarbonyl, alkoxythiocarbonyl alkylaminocarbonyl, arylaminocarbonyl, alkylsulfonyl, alkenyloxycarbonyl, alkynyloxycarbonyl, aryl, arylcarbonyl, aryloxy, aryloxycarbonyl, arylthio, heteroaryl, heteroaryloxycarbonyl or methylenedioxy, wherein the alkyl moiety or aryl moiety may be substituted with halogen, cyano, nitro, alkyl, alkoxy, haloalkyl, haloalkoxy, alkoxycarbonyl, aryl, or heterocycloalkyl; and

R₅ is hydrogen or any one of the groups represented by R₄;

or R₄ and R₅ could combine to form a 4-8 membered heterocyclic ring;

 

wherein R₆ represents alkyl, haloalkyl, dialkylamino, unsubstituted or substituted aryl and heteroaryl; and

R₇ represents hydrogen, halogen or any of the groups represented by R₆;

—

OR₄,

—

SR₄,

—

CH₂R₁₀,

—

CH(R₁₀)₂,

—

C(R₁₀)₃, or

—

CH═

CHR₁₀

wherein R₁₀ is carboxyl, alkyl, alkenyl, alkynyl, amino, cycloalkyl, heterocycloalkyl, alkylsulfonyl, arylsulfonyl, benzyl, aryl, heteroaryl, alkylcarbonyl, alkenylcarbonyl, alkynylcarbonyl, cycloalkylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkoxycarbonyl, alkyithiocarbonyl, cycloalkyloxycarbonyl, aryloxycarbonyl, arylthio-carbonyl, aryl-thiocarbonyl, heteroaryloxycarbonyl, aminocarbonyl, alkylaminocarbonyl, arylaminocarbonyl, heteroarylaminocarbonyl, alkoxycarbonylcarbonyl or arylcarbonylcarbonyl, where any of these groups may be unsubstituted or substituted with any of the functional groups represented by one or more of the following;

halogen, cyano, nitro, amino, dialkylamino, hydroxyl, carboxyl, alkyl, alkenyl, alkynyl, cycloalkyl, alkylcarbonyl, alkylcarbonyloxy, alkoxy, alkoxycarbonyl, alkylthio, alkylthiocarbonyl, alkoxythiocarbonyl alkylaminocarbonyl, arylaminocarbonyl, alkylsulfonyl, alkenyloxycarbonyl, alkynyloxycarbonyl, aryl, arylcarbonyl, aryloxy, aryloxycarbonyl, arylthio, heteroaryl, heteroaryloxycarbonyl or methylenedioxy, wherein the alkyl moiety or aryl moiety may be substituted with halogen, cyano, nitro, alkyl, alkoxy, haloalkyl, haloalkoxy, alkoxycarbonyl, cycloalkyl, aryl, or heterocycloalkyl;

provided that (1) Z is not alkyl, alkoxy, haloalkyl, haloalkoxy, alkylthio, haloalkythio, alkenyl, haloalkenyl, amino, monoalkylamino, dialkylamino, alkoxyalkoxy or cyano, when Q is Q1 and R₂ is haloalkyl.

2. The compound according to claim 1 wherein Z is represented by the following:

wherein R₄ and R₅ are the same as defined in claim 1;

or —

CH₂R₁₀,

wherein R₁₀ is the same as defined in claim 1.

3. The compound according to claims 1 or 2 wherein X is halogen or cyano;

Y is halogen;

W is OR;

R is alkyl, alkenyl, or alkynyl, where any of these groups may be unsubstituted or substituted with any of the functional groups represented by one or more of the following;

halogen, cyano, nitro, amino, or carboxyl.

4. The compound according to claim 1 wherein Q is

wherein R₁ is alkyl, amino, or haloalkyl;

R₂ is haloalkyl;

R₃ is hydrogen;

R₈ and R₉ are independently oxygen, or sulfur.

5. The compound according to claim 1 wherein X is a halogen;

Y is fluorine;

W is OR;

R is alkyl, alkenyl, or alkynyl, where any of these groups may be unsubstituted or substituted with halogen or cyano;

Q is

 

wherein R₁ is alkyl, amino, or haloalkyl;

R₂ is haloalkyl;

R₃ is hydrogen;

R₈ and R₉ are independently oxygen, or sulfur;

Z is represented by the following;

 

wherein R₄ is alkylcarbonyl, alkenylcarbonyl, alkynylcarbonyl, cycloalkylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkoxycarbonyl, alkylthiocarbonyl, cycloalkyloxycarbonyl, aryloxycarbonyl, arylthio-carbonyl, aryl-thiocarbonyl, heteroaryloxycarbonyl, aminocarbonyl, alkylaminocarbonyl, arylaminocarbonyl, heteroarylaminocarbonyl, alkoxycarbonylcarbonyl, or arylcarbonylcarbonyl, where any of these groups may be unsubstituted or substituted with any of the functional groups represented by one or more of the following;

halogen, cyano, nitro, amino, dialkylamino, hydroxyl, carboxyl, alkyl, alkenyl, alkynyl, alkylcarbonyl, alkylcarbonyloxy, alkoxy, alkoxycarbonyl, alkylthio, alkylthiocarbonyl, alkoxythiocarbonyl alkylaminocarbonyl, arylaminocarbonyl, alkylsulfonyl, alkenyloxycarbonyl, alkynyloxycarbonyl, aryl, arylcarbonyl, aryloxy, aryloxycarbonyl, arylthio, heteroaryl, heteroaryloxycarbonyl, or methylenedioxy, wherein the alkyl moiety or aryl moiety may be substituted with halogen, cyano, nitro, alkyl, alkoxy, haloalkyl, haloalkoxy, alkoxycarbonyl, aryl, or heterocyclcoalkyl; and

R₅ is hydrogen;

or —

CH₂R₁₀,

wherein R₁₀ is carboxyl, alkyl, alkenyl, or alkynyl, where any of these groups may be unsubstituted or substituted with any of the functional groups represented by one or more of the following;

halogen, cyano, nitro, amino, dialkylamino, hydroxyl, carboxyl, alkyl, alkenyl, alkynyl, cycloalkyl, alkylcarbonyl, alkylcarbonyloxy, alkoxy, alkoxycarbonyl, alkylthio, alkylthiocarbonyl, alkoxythiocarbonyl alkylaminocarbonyl, arylaminocarbonyl, alkylsulfonyl, alkenyloxycarbonyl, alkynyloxycarbonyl, aryl, arylcarbonyl, aryloxy, aryloxycarbonyl, arylthio, heteroaryl, heteroaryloxycarbonyl, or methylenedioxy, wherein teh alkyl moiety or aryl moiety may be substituted with halogen, cyano, nitro, alkyl, alkoxy, haloalkyl, haloalkoxy, alkoxycarbonyl, cycloalkyl, aryl, or heterocycloalkyl.

7. A herbicidal composition, characterized in that it contains at least one compound according to claim 1 and an agricultural adjuvant.

10. A method for controlling undesired vegetation which comprises applying to a locus to be protected a herbicidally effective amount of a compound of claim 1.

11. The method of claim 10 wherein the locus to be protected is a cereal crop field.

12. The method of claim 11 wherein the compound of claim 1 is applied to soil as a preemergent herbicide.

13. The method of claim 11 wherein the compound of claim 1 is applied to plant foliage.

14. A method to defoliate potato and cotton using a compound of claim 1.

6. A compound selected from the group consisting of 3-(2-amino-4-chloro-6-fluoro-3-methoxyphenyl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)pyrimidinedione and 3-(²-amino-4-chloro-6-fluoro-3-methoxyphenyl)-1-amino-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione.

8. A process for preparing a compound represented by the formula I-1 or its salts:

wherein X is hydrogen, halogen, nitro, amino, NHR, N(R)₂, ainide, thioamide, cyano, alkylcarbonyl, alkoxycarbonyl, alkylsulfonamide, unsubstituted or substituted alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxycarbonylalkoxy, benzloxy, aryloxy, or heteroaryloxy;

Y is hydrogen, halogen, or nitro;

W is hydrogen, OR, SR, NHR, N(R)₂, CH₂R, CH(R)₂, C(R)₃, halogen, nitro, or cyano, where multiple R groups represent any possible combination of substituents described by R;

R is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heteroaryl, alkoxy, cycloalkyloxy, aryloxy, heteroaryloxy, alkylsulfonyl, benzyl, alkylcarbonyl, alkenylcarbonyl, alkynylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, or heteroaryloxycarbonyl, where any of these groups may be unsubstituted or substituted with any of the functional groups represented by one or more of the following;

halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkylsilyl, alkylcarbonyl, haloalkylcarbonyl, alkoxy, alkoxycarbonyl, haloalkoxy, haloalkoxycarbonyl, alkylsulfonyl, haloalkylsulfonyl, aryl, heteroaryl, or cycloalkyl;

Q is a heterocycle;

 

wherein R₁ is hydrogen, alkyl, haloalkyl, alkenyl, alkynyl, amino, alkoxyalkyl, acetyl, alkoxycarbonylamino, alkylcarbonylamino, or alkoxycarbonyl;

R₂ is alkyl or haloalkyl;

R₁ and R₂ could combine to form a five- or six-membered heterocyclic ring;

R₃ is hydrogen, halogen, nitro, amino, alkylamino, haloalkylamino, cyano, or amide;

R₈ and R₉ are independently oxygen, or sulfur;

Q6, Q7, and Q10 may optionally be unsaturated containing one or two double bonds in the 6-membered ring;

Z′

is one of the following;

 

wherein R₄ is alkyl, alkenyl, alkynyl, amino, cycloalkyl, heterocycloalkyl, alkylsulfonyl, arylsulfonyl, benzyl, aryl, heteroaryl, alkylcarbonyl, alkenylcarbonyl, alkynylcarbonyl, cycloalkylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkoxycarbonyl, alkylthiocarbonyl, cycloalkyloxycarbonyl, aryloxycarbonyl, arylthio-carbonyl, aryl-thiocarbonyl, heteroaryloxycarbonyl, aminocarbonyl, alkylaminocarbonyl, arylaminocarbonyl, heteroarylaminocarbonyl, alkoxycarbonylcarbonyl, or arylcarbonylcarbonyl, where any of these groups may be unsubstituted or substituted with any of the functional groups represented by one or more of the following;

halogen, cyano, nitro, amino, dialkylamino, hydroxyl, carboxyl, alkyl, alkenyl, alkynyl, alkylcarbonyl, alkylcarbonyloxy, alkoxy, alkoxycarbonyl, alkylthio, alkyithiocarbonyl, alkoxythiocarbonyl alkylaminocarbonyl, arylaminocarbonyl, alkylsulfonyl, alkenyloxycarbonyl, alkynyloxycarbonyl, aryl, arylcarbonyl, aryloxy, aryloxycarbonyl, arylthio, heteroaryl, heteroaryloxycarbonyl, or methylenedioxy, wherein the alkyl moiety or aryl moiety may be substituted with halogen, cyano, nitro, alkyl, alkoxy, haloalkyl, haloalkoxy, alkoxycarbonyl, aryl, or heterocycloalkyl; and

R₅ is hydrogen or any one of the groups represented by R₄;

or R₄ and R₅ could combine to form a 4-8 membered heterocyclic ring;

 

wherein R₆ represents alkyl, haloallcyl, dialkylamino, unsubstituted or substituted aryl and heteroaryl; and

R₇ represents hydrogen, halogen or any of the groups represented by R₆;

—

CH₂R₁₀,

—

CH(R₁₀)₂,

—

C(R₁₀)₃, or

—

CH═

CHR₁₀

wherein R₁₀ is carboxyl, alkyl, alkenyl, alkynyl, amino, cycloalkyl, heterocycloalkyl, 25 alkylsulfonyl, arylsulfonyl, benzyl, aryl, heteroaryl, alkylcarbonyl, alkenylcarbonyl, alkynylcarbonyl, cycloalkylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkoxycarbonyl, alkylthiocarbonyl, cycloalkyloxycarbonyl, aryloxycarbonyl, arylthio-carbonyl, aryl-thiocarbonyl, heteroaryloxycarbonyl, aminocarbonyl, alkylaminocarbonyl, arylaminocarbonyl, heteroarylaminocarbonyl, alkoxycarbonylcarbonyl or arylcarbonylcarbonyl, where any of these groups may be unsubstituted or substituted with any of the functional groups represented by one or more of the following;

halogen, cyano, nitro, amino, dialkylamino, hydroxyl, carboxyl, alkyl, alkenyl, alkynyl, cycloalkyl, alkylcarbonyl, alkylcarbonyloxy, alkoxy, alkoxycarbonyl, alkylthio, alkylthiocarbonyl, alkoxythiocarbonyl alkylaminocarbonyl, arylaminocarbonyl, alkylsulfonyl, alkenyloxycarbonyl, alkynyloxycarbonyl, aryl, arylcarbonyl, aryloxy, aryloxycarbonyl, arylthio, heteroaryl, heteroaryloxycarbonyl or methylenedioxy, wherein the alkyl moiety or aryl moiety may be substituted with halogen, cyano, nitro, alkyl, alkoxy, haloalkyl, haloalkoxy, alkoxycarbonyl, cycloalkyl, aryl, or heterocycloalkyl;

provided that (1) Z′

is not alkyl, haloalkyl, alkenyl, haloalkenyl, monoalkylamino, or dialkylamino, when Q is Q1 and R₂ is haloalkyl,

which comprises of reacting a compound represented by the formula II;

with a compound selected from the group consisting of an alkyl halide, alkyl acid halide, aryl acid halide, alkyl acid anhydride, aryl acid anhydride, alkylhaloformate, alkyl isocyanate, aryl isocyanate, alkyl dihalide, aliphatic aldehyde, aliphatic ketone, aromatic aldehyde, and aromatic ketone.

9. A compound represented by the formula III:

wherein X is hydrogen, halogen, nitro, amino, NHR, N(R)₂, amide, thioamide, cyano, alkylcarbonyl, alkoxycarbonyl, alkylsulfonamide, unsubstituted or substituted alkyl, haloalkyl, alkoxy, haloalkoxy,alkoxycarbonylalkoxy, benzyloxy, aryloxy, or heteroaryloxy;

Y is hydrogen, halogen, or nitro;

W is hydrogen, OR, SR, NHR, N(R)₂, CH₂R, CH(R)₂, C(R)₃, halogen, nitro, or cyano, where multiple R groups represent any possible combination of substituents described by R;

R is hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heteroaryl, alkoxy, cycloalkyloxy, aryloxy, heteroaryloxy, alkylsulfonyl, benzyl, alkylcarbonyl, alkenylcarbonyl, alkynylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, or heteroaryloxycarbonyl, where any of these groups may be unsubstituted or substituted with any of the functional groups represented by one or more of the following;

halogen, cyano, nitro, amino, carboxyl, alkyl, haloalkyl, alkylsilyl, alkylcarbonyl, haloalkylcarbonyl, alkoxy, alkoxycarbonyl, haloalkoxy, haloalkoxycarbonyl, alkylsulfonyl, haloalkylsulfonyl, aryl, heteroaryl, or cycloalkyl;

Q is a heterocycle;

 

wherein R₁ is hydrogen, alkyl, haloalkyl, alkenyl, alkynyl, amino, alkoxyalkyl, acetyl, alkoxycarbonylamino, alkylcarbonylamino, or alkoxycarbonyl;

R₂ is alkyl or haloalkyl;

R₁ and R₂ could combine to form a five- or six-membered heterocyclic ring;

R₃ is hydrogen, halogen, nitro, amino, alkylamino, haloaklylamino, cyano, or amide;

R₈ and R₉ are independently oxygen or sulIfur;

M is nitro.