Herbicidal pyrimidines

• US 8,802,597 B2
• Filed: 12/08/2010
• Issued: 08/12/2014
• Est. Priority Date: 12/19/2003
• Status: Active Grant

• Current Assignee: Corteva Agriscience LLC (Corteva, Inc.)
• Original Assignee: E. I. du Pont de Nemours and Company (Corteva, Inc.)
• Inventors: Clark, David Alan, Finkelstein, Bruce Lawrence, Armel, Gregory Russell, Wittenbach, Vernon Arie
• Primary Examiner(s): RAO, DEEPAK R
• Application Number:
  US12/963,231
• Publication Number:
  US 20110077156A1
• Time in Patent Office: 1,343 Days
• Field of Search: 544/122, 544/329, 504/225, 504/239, 504/242
• US Class Current: 504/225
• CPC Class Codes: A01N 2300/00 Combinations or mixtures of active ingredients covered by classes A01N27/00 - A01N65/48 with other active or formulation relevant ingredients, e.g. specific carrier materials or surfactants, covered by classes A01N25/00 - A01N65/48
• CPC Class Codes: A01N 43/54 1,3-Diazines; Hydrogenated 1,3-diazines
• CPC Class Codes: A01N 47/34 containing the groups , e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
• CPC Class Codes: A01N 47/36 containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
• CPC Class Codes: C07D 239/30 Halogen atoms or nitro radicals
• CPC Class Codes: C07D 239/42 One nitrogen atom nitro radicals C07D239/30
• CPC Class Codes: C07D 239/47 One nitrogen atom and one oxygen or sulfur atom, e.g. cytosine
• CPC Class Codes: C07D 239/48 Two nitrogen atoms
• CPC Class Codes: C07D 401/12 linked by a chain containing hetero atoms as chain links
• CPC Class Codes: C07D 405/04 directly linked by a ring-member-to-ring-member bond
• CPC Class Codes: C07D 405/12 linked by a chain containing hetero atoms as chain links

Abstract

Compounds of Formula I, and their N-oxides and agriculturally suitable salts, are disclosed which are useful for controlling undesired vegetation

wherein

• • R¹ is cyclopropyl optionally substituted with 1-5 R⁵, isopropyl optionally substituted with 1-5 R⁶, or phenyl optionally substituted with 1-3 R⁷;
  • R² is ((O)_jC(R¹⁵)(R¹⁶))_kR;
  • R is CO₂H or a herbicidally effective derivative of CO₂H;
  • R³ is halogen, cyano, nitro, OR²⁰, SR²¹ or N(R²²)R²³;
  • R⁴ is —N(R²⁴)R²⁵ or —NO₂;
  • j is 0 or 1; and k is 0 or 1; provided that when k is 0, then j is 0;
  • and R⁵, R⁶, R⁷, R¹⁵, R¹⁶, R²⁰, R²¹, R²², R²³, R²⁴ and R²⁵ are as defined in the disclosure.
    Also disclosed are compositions comprising the compounds of Formula I and a method for controlling undesired vegetation which involves contacting the vegetation or its environment with an effective amount of a compound of Formula I. Also disclosed are compositions comprising a compound of Formula I and at least one additional active ingredient selected from the group consisting of an other herbicide and a herbicide safener.

Claims

1. A compound selected from Formula I, an N-oxide or an agriculturally suitable salt thereof,

2. The compound of claim 1 wherein

R² is CO₂R¹², CH₂OR¹³, CH(OR⁴⁶)(OR⁴⁷), CHO, C(═

NOR¹⁴)H, C(═

NNR⁴⁸R⁴⁹)H, (O)_jC(R¹⁵)(R¹⁶)CO₂R¹⁷, C(═

O)N(R¹⁸)R¹⁹, C(═

S)OR⁵⁰, C(═

O)SR⁵¹, C(═

S)SR⁵² or C(═

NR⁵³)YR⁵⁴;

R¹² is H, —

CHC(O)O(CH₂)_m, —

N═

C(R⁵⁵)R⁵⁶;

or a radical selected from C₁-C₁₄ alkyl, C₃-C₁₂ cycloalkyl, C₄-C₁₂ alkylcycloalkyl, C₄-C₁₂ cycloalkylalkyl, C₂-C₁₄ alkenyl, C₂-C₁₄ alkynyl and phenyl, each radical optionally substituted with 1-3 R²⁷;

or

R¹² is a divalent radical linking the carboxylic ester function CO₂R¹² of each of two pyrimidine ring systems of Formula I, the divalent radical selected from —

CH₂—

, —

(CH₂)₂—

, —

(CH₂)₃— and

—

CH(CH₃)CH₂—

;

R¹³ is H, C₁-C₁₀ alkyl optionally substituted with 1-3 R²⁸, or benzyl;

R¹⁴ is H, C₁-C₄ alkyl, C₁-C₄ haloalkyl or benzyl;

R¹⁷ is C₁-C₁₀ alkyl optionally substituted with 1-3 R²⁹, or benzyl;

R¹⁸ is H, C₁-C₄ alkyl, hydroxy, C₁-C₄ alkoxy or S(O)₂R⁵⁷;

R¹⁹ is H or C₁-C₄ alkyl;

each R²⁷ is independently halogen, cyano, hydroxycarbonyl, C₂-C₄ alkoxycarbonyl, hydroxy, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₁-C₄ alkylthio, C₁-C₄ haloalkylthio, amino, C₁-C₄ alkylamino, C₂-C₄ dialkylamino, —

CHO(CH₂)_n or phenyl optionally substituted with 1-3 R⁴⁴;

or

two R²⁷ are taken together as —

OC(O)O—

or —

O(C(R⁵⁸)(R⁵⁸))_1-2O—

;

or

two R²⁷ are taken together as an oxygen atom to form, with the carbon atom to which they are attached, a carbonyl moiety;

each R²⁸ is independently halogen, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₁-C₄ alkylthio, C₁-C₄ haloalkylthio, amino, C₁-C₄ alkylamino or C₂-C₄ dialkylamino;

or

two R²⁸ are taken together as an oxygen atom to form, with the carbon atom to which they are attached, a carbonyl moiety;

each R²⁹ is independently halogen, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₁-C₄ alkylthio, C₁-C₄ haloalkylthio, amino, C₁-C₄ alkylamino or C₂-C₄ dialkylamino;

each R⁴⁴ is independently halogen, C₁-C₄ alkyl, C₁-C₃ haloalkyl, hydroxy, C₁-C₄ alkoxy, C₁-C₃ haloalkoxy, C₁-C₃ alkylthio, C₁-C₃ haloalkylthio, amino, C₁-C₃ alkylamino, C₂-C₄ dialkylamino or nitro;

R⁴⁶ and R⁴⁷ are independently C₁-C₄ alkyl or C₁-C₃ haloalkyl;

or

R⁴⁶ and R⁴⁷ are taken together as —

CH₂CH₂—

, —

CH₂CH(CH₃)—

or —

(CH₂)₃—

;

R⁴⁸ is H, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₂-C₄ alkylcarbonyl, C₂-C₄ alkoxycarbonyl or benzyl;

R⁴⁹ is H, C₁-C₄ alkyl or C₁-C₄ haloalkyl;

R⁵⁰, R⁵¹ and R⁵² are H;

or a radical selected from C₁-C₁₄ alkyl, C₃-C₁₂ cycloalkyl, C₄-C₁₂ alkylcycloalkyl, C₄-C₁₂ cycloalkylalkyl, C₂-C₁₄ alkenyl and C₂-C₁₄ alkynyl, each radical optionally substituted with 1-3 R²⁷;

Y is O, S or NR⁶¹;

R⁵³ is H, C₁-C₃ alkyl, C₁-C₃ haloalkyl, C₂-C₄ alkoxyalkyl, OH or C₁-C₃ alkoxy;

R⁵⁴ is C₁-C₃ alkyl, C₁-C₃ haloalkyl or C₂-C₄ alkoxyalkyl;

or

R⁵³ and R⁵⁴ are taken together as —

(CH₂)₂—

, —

CH₂CH(CH₃)—

or —

(CH₂)₃—

;

R⁵⁵ and R⁵⁶ are independently C₁-C₄ alkyl;

R⁵⁷ is C₁-C₄ alkyl, C₁-C₃ haloalkyl or NR⁵⁹R⁶⁰;

each R⁵⁸ is independently selected from H and C₁-C₄ alkyl;

R⁵⁹ and R⁶⁰ are independently H or C₁-C₄ alkyl;

R⁶¹ is H, C₁-C₃ alkyl, C₁-C₃ haloalkyl or C₂-C₄ alkoxyalkyl;

m is an integer from 2 to 3; and

n is an integer from 1 to 4.

3. The compound of claim 2 wherein R³ is halogen.

4. The compound of claim 2 wherein R¹ is phenyl substituted with a halogen, methyl or methoxy radical in the para position and optionally with 1-2 radicals selected from halogen and methyl in other positions;

and R⁴ is —

N(R²⁴)R²⁵.

5. The compound of claim 4 wherein R² is CO₂R¹², CH₂OR¹³, CHO or CH₂CO₂R¹⁷.

6. The compound of claim 5 wherein R²⁴ is H, C(O)R³³ or C₁-C₄ alkyl optionally substituted with R³⁰;

R²⁵ is H or C₁-C₂ alkyl;

or R²⁴ and R²⁵ are taken together as ═

C(R³⁹)N(R⁴⁰)R⁴¹.

7. The compound of claim 6 wherein R² is CO₂R¹²;

and R²⁴ and R²⁵ are H.

8. The compound of claim 7 wherein R¹² is H, C₁-C₄ alkyl or benzyl.

9. The compound of claim 1 selected from the group consisting of:

methyl 6-amino-5-chloro-2-(4-chlorophenyl)-4-pyrimidinecarboxylate,

ethyl 6-amino-5-chloro-2-(4-chlorophenyl)-4-pyrimidinecarboxylate,

6-amino-5-chloro-2-(4-chlorophenyl)-4-pyrimidinecarboxylic acid,

ethyl 6-amino-2-(4-bromophenyl)-5-chloro-4-pyrimidinecarboxylate,

methyl 6-amino-2-(4-bromophenyl)-5-chloro-4-pyrimidinecarboxylate, and

6-amino-2-(4-bromophenyl)-5-chloro-4-pyrimidinecarboxylic acid.

10. A herbicidal mixture comprising a herbicidally effective amount of a compound of claim 1 and an effective amount of at least one additional active ingredient selected from the group consisting of an other herbicide and a herbicide safener.

11. A herbicidal mixture comprising synergistically effective amounts of a compound of claim 1 and an auxin transport inhibitor.

12. A herbicidal composition comprising a herbicidally effective amount of a compound of claim 1 and at least one of a surfactant, a solid diluent or a liquid diluent.

13. A method for controlling the growth of undesired vegetation comprising contacting the vegetation or its environment with a herbicidally effective amount of a compound of claim 1.

14. A herbicidal composition comprising a herbicidally effective amount of a compound of claim 1, an effective amount of at least one additional active ingredient selected from the group consisting of an other herbicide and a herbicide safener, and at least one of a surfactant, a solid diluent or a liquid diluent.

15. The compound of claim 1 selected from the group consisting of:

methyl 6-amino-5-chloro-2-(4-chlorophenyl)-4-pyrimidinecarboxylate,

ethyl 6-amino-5-chloro-2-(4-chlorophenyl)-4-pyrimidinecarboxylate,

6-amino-5-chloro-2-(4-chlorophenyl)-4-pyrimidinecarboxylic acid,

ethyl 6-amino-2-(4-bromophenyl)-5-chloro-4-pyrimidinecarboxylate,

methyl 6-amino-2-(4-bromophenyl)-5-chloro-4-pyrimidinecarboxylate, and

6-amino-2-(4-bromophenyl)-5-chloro-4-pyrimidinecarboxylic acid.

16. The compound of claim 15 selected from the group consisting of:

methyl 6-amino-5-chloro-2-(4-chlorophenyl)-4-pyrimidinecarboxylate,

ethyl 6-amino-5-chloro-2-(4-chlorophenyl)-4-pyrimidinecarboxylate,

6-amino-5-chloro-2-(4-chlorophenyl)-4-pyrimidinecarboxylic acid,

ethyl 6-amino-2-(4-bromophenyl)-5-chloro-4-pyrimidinecarboxylate,

6-amino-2-(4-bromophenyl)-5-chloro-4-pyrimidinecarboxylic acid, and

methyl 6-amino-2-(4-bromophenyl)-5-chloro-4-pyrimidinecarboxylate.

17. A compound of claim 1 which is methyl 6-amino-5-chloro-2-(4-chlorophenyl)-4-pyrimidinecarboxylate.

18. A compound of claim 1 which is ethyl 6-amino-5-chloro-2-(4-chlorophenyl)-4-pyrimidinecarboxylate.

19. A compound of claim 1 which is 6-amino-5-chloro-2-(4-chlorophenyl)-4-pyrimidinecarboxylic acid.

20. A herbicidal mixture comprising a herbicidally effective amount of a compound of claim 15, and an effective amount of at least one additional active ingredient selected from the group consisting of an other herbicide and a herbicide safener.

21. The herbicidal mixture of claim 10 wherein the additional active ingredient is selected from the group consisting of:

amidosulfuron, azimsulfuron, bensulfuron-methyl, bispyribac, bispyribac-sodium, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cloransulam-methyl, cyclosulfamuron, diclosulam, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, florasulam, flucarbazone, flucarbazone-sodium, flucetosulfuron, flumetsulam, flupyrsulfuron-methyl, flupyrsulfuron-methyl-sodium, foramsulfuron, halosulfuron-methyl, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin, imazaquin-ammonium, imazethapyr, imazosulfuron, iodosulfuron-methyl, mesosulfuron-methyl, metosulam, metsulfuron-methyl, nicosulfuron, oxasulfuron, penoxsulam, primisulfuron-methyl, propoxycarbazone, propoxycarbazone-sodium, prosulfuron, pyrazosulfuron-ethyl, pyribenzoxim, pyriftalid, pyriminobac-methyl, pyrithiobac, pyrithiobac-sodium, rimsulfuron, sulfometuron-methyl, sulfosulfuron, thifensulfuron-methyl, triasulfuron, tribenuron-methyl, trifloxysulfuron, triflusulfuron-methyl and tritosulfuron.

22. The herbicidal mixture of claim 21 wherein the additional active ingredient is in combination with at least one other active ingredient to form a combination of active ingredients selected from the group consisting of:

chlorsulfuron and flucarbazone-sodium;

chlorsulfuron and sulfometuron-methyl;

flumetsulam, nicosulfuron and rimsulfuron;

mesosulfuron-methyl and iodosulfuron-methyl;

metsulfuron-methyl and chlorsulfuron;

metsulfuron-methyl and sulfometuron-methyl;

metsulfuron-methyl, thifensulfuron-methyl and tribenuron-methyl;

imazapyr and metsulfuron-methyl;

imazapyr, metsulfuron-methyl and sulfometuron-methyl;

imazapyr and sulfometuron-methyl;

rimsulfuron and nicosulfuron;

rimsulfuron and thifensulfuron-methyl;

thifensulfuron-methyl and metsulfuron-methyl;

tribenuron-methyl and metsulfuron-methyl;

tribenuron-methyl and thifensulfuron-methyl;

bensulfuron-methyl and metsulfuron-methyl; and

metsulfuron-methyl and chlorimuron-ethyl.

23. The herbicidal mixture of claim 20 wherein the additional active ingredient is selected from the group consisting of:

amidosulfuron, azimsulfuron, bensulfuron-methyl, bispyribac, bispyribac-sodium, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cloransulam-methyl, cyclosulfamuron, diclosulam, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, florasulam, flucarbazone, flucarbazone-sodium, flucetosulfuron, flumetsulam, flupyrsulfuron-methyl, flupyrsulfuron-methyl-sodium, foramsulfuron, halosulfuron-methyl, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin, imazaquin-ammonium, imazethapyr, imazosulfuron, iodosulfuron-methyl, mesosulfuron-methyl, metosulam, metsulfuron-methyl, nicosulfuron, oxasulfuron, penoxsulam, primisulfuron-methyl, propoxycarbazone, propoxycarbazone-sodium, prosulfuron, pyrazosulfuron-ethyl, pyribenzoxim, pyriftalid, pyriminobac-methyl, pyrithiobac, pyrithiobac-sodium, rimsulfuron, sulfometuron-methyl, sulfosulfuron, thifensulfuron-methyl, triasulfuron, tribenuron-methyl, trifloxysulfuron, triflusulfuron-methyl and tritosulfuron.

24. The herbicidal mixture of claim 23 wherein the additional active ingredient is in combination with at least one other active ingredient to form a combination of active ingredients selected from the group consisting of:

chlorsulfuron and flucarbazone-sodium;

chlorsulfuron and sulfometuron-methyl;

flumetsulam, nicosulfuron and rimsulfuron;

mesosulfuron-methyl and iodosulfuron-methyl;

metsulfuron-methyl and chlorsulfuron;

metsulfuron-methyl and sulfometuron-methyl;

metsulfuron-methyl, thifensulfuron-methyl and tribenuron-methyl;

imazapyr and metsulfuron-methyl;

imazapyr, metsulfuron-methyl and sulfometuron-methyl;

imazapyr and sulfometuron-methyl;

rimsulfuron and nicosulfuron;

rimsulfuron and thifensulfuron-methyl;

thifensulfuron-methyl and metsulfuron-methyl;

tribenuron-methyl and metsulfuron-methyl;

tribenuron-methyl and thifensulfuron-methyl;

bensulfuron-methyl and metsulfuron-methyl; and

metsulfuron-methyl and chlorimuron-ethyl.

25. A herbicidal mixture comprising synergistically effective amounts of a compound of claim 15 and an auxin transport inhibitor.

26. The herbicidal mixture of claim 11 wherein the compound is selected from the group consisting of :

methyl 6-amino-5-chloro-2-(4-chlorophenyl)-4-pyrimidinecarboxylate,

ethyl 6-amino-5-chloro-2-(4-chlorophenyl)-4-pyrimidinecarboxylate,

6-amino-5-chloro-2-(4-chlorophenyl)-4-pyrimidinecarboxylic acid,

ethyl 6-amino-2-(4-bromophenyl)-5-chloro-4-pyrimidinecarboxylate,

6-amino-2-(4-bromophenyl)-5-chloro-4-pyrimidinecarboxylic acid, and

methyl 6-amino-2-(4-bromophenyl)-5-chloro-4-pyrimidinecarboxylate

and the auxin transport inhibitor is diflufenzopyr.

27. The herbicidal mixture of claim 11 wherein the compound is ethyl 6-amino-5-bromo-2-cyclopropyl-4-pyrimidinecarboxylate and the auxin transport inhibitor is diflufenzopyr.

28. The herbicidal mixture of claim 20 further comprising at least one of a surfactant, a solid diluent or a liquid diluent.

29. The herbicidal mixture of claim 25 further comprising at least one of a surfactant, a solid diluent or a liquid diluent.

30. The herbicidal mixture of claim 28 wherein the additional active ingredient is selected from the group consisting of:

amidosulfuron, azimsulfuron, bensulfuron-methyl, bispyribac, bispyribac-sodium, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cloransulam-methyl, cyclosulfamuron, diclosulam, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, florasulam, flucarbazone, flucarbazone-sodium, flucetosulfuron, flumetsulam, flupyrsulfuron-methyl, flupyrsulfuron-methyl-sodium, foramsulfuron, halosulfuron-methyl, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin, imazaquin-ammonium, imazethapyr, imazosulfuron, iodosulfuron-methyl, mesosulfuron-methyl, metosulam, metsulfuron-methyl, nicosulfuron, oxasulfuron, penoxsulam, primisulfuron-methyl, propoxycarbazone, propoxycarbazone-sodium, prosulfuron, pyrazosulfuron-ethyl, pyribenzoxim, pyriftalid, pyriminobac-methyl, pyrithiobac, pyrithiobac-sodium, rimsulfuron, sulfometuron-methyl, sulfosulfuron, thifensulfuron-methyl, triasulfuron, tribenuron-methyl, trifloxysulfuron, triflusulfuron-methyl and tritosulfuron.

31. The herbicidal mixture of claim 30 wherein the additional active ingredient is in combination with at least one other active ingredient to form a combination of active ingredients selected from the group consisting of:

chlorsulfuron and flucarbazone-sodium;

chlorsulfuron and sulfometuron-methyl;

flumetsulam, nicosulfuron and rimsulfuron;

mesosulfuron-methyl and iodosulfuron-methyl;

metsulfuron-methyl and chlorsulfuron;

metsulfuron-methyl and sulfometuron-methyl;

metsulfuron-methyl, thifensulfuron-methyl and tribenuron-methyl;

imazapyr and metsulfuron-methyl;

imazapyr, metsulfuron-methyl and sulfometuron-methyl;

imazapyr and sulfometuron-methyl;

rimsulfuron and nicosulfuron;

rimsulfuron and thifensulfuron-methyl;

thifensulfuron-methyl and metsulfuron-methyl;

tribenuron-methyl and metsulfuron-methyl;

tribenuron-methyl and thifensulfuron-methyl;

bensulfuron-methyl and metsulfuron-methyl; and

metsulfuron-methyl and chlorimuron-ethyl.

32. A method for controlling the growth of undesired vegetation comprising contacting the vegetation or its environment with the herbicidal mixture of claim 23.

33. A method for controlling the growth of undesired vegetation comprising contacting the vegetation or its environment with the herbicidal mixture of claim 24.

34. A method for controlling the growth of undesired vegetation comprising contacting the vegetation or its environment with the herbicidal mixture of claim 25.

35. A herbicidal mixture comprising a herbicidally effective amount of a compound of claim 16, and an effective amount of at least one additional active ingredient selected from the group consisting of an other herbicide and a herbicide safener.

36. A herbicidal mixture comprising synergistically effective amounts of a compound of claim 16 and an auxin transport inhibitor.

37. A compound of claim 1 wherein each R⁷ is independently selected from halogen, C₁-C₂ alkyl, C₁ fluoroalkyl, C₁-C₂ alkoxy or C₁ fluoroalkoxy.

38. A compound of claim 1 wherein each R⁷ is independently selected from halogen, methyl and methoxy.