N-arylsulfilimine compounds and their use as catalysts in the preparation of N-arylarylsulfonamide compounds

• US 5,973,148 A
• Filed: 12/23/1998
• Issued: 10/26/1999
• Est. Priority Date: 11/13/1996
• Status: Expired due to Term

• Current Assignee: DowElanco Co.
• Original Assignee: Dow Agrosciences LLC (Corteva, Inc.)
• Inventors: Ringer, James W., Wallin, Anne P., Scott, Carmen A., Pearson, Douglas L.
• Primary Examiner(s): Dees, Jose' G.
• Assistant Examiner(s): QAZI, SABIHA NAIM
• Application Number:
  US09/220,304
• Time in Patent Office: 307 Days
• Field of Search: 544/263, 564/102, 564/440, 546/297, 546/304, 546/119
• US Class Current: 544/263
• CPC Class Codes: B01J 31/0222 comprising sulfonyl groups
• CPC Class Codes: B01J 31/0224 being perfluorinated, i.e. comprising at least one perfluorinated moiety as substructure in case of polyfunctional compounds
• CPC Class Codes: B01J 31/0229 also containing elements or functional groups covered by B01J31/0201 - B01J31/0214
• CPC Class Codes: B01J 31/0232 also containing elements or functional groups covered by B01J31/0201 - B01J31/0228 perfluorinated sulfonyl compounds or moieties B01J31/0224; perfluorosulfonic acids B01J31/0227
• CPC Class Codes: B01J 31/0235 Nitrogen containing compounds
• CPC Class Codes: B01J 31/0237 Amines
• CPC Class Codes: B01J 31/0244 with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
• CPC Class Codes: B01J 31/0271 also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
• CPC Class Codes: C07C 303/38 by reaction of ammonia or amines with sulfonic acids, or with esters, anhydrides, or halides thereof
• CPC Class Codes: C07C 311/21 having the nitrogen atom of at least one of the sulfonamide groups bound to a carbon atom of a six-membered aromatic ring
• CPC Class Codes: C07C 381/10 Compounds containing sulfur atoms doubly-bound to nitrogen atoms
• CPC Class Codes: C07D 213/76 to which a second hetero atom is attached nitro radicals C07D213/61
• CPC Class Codes: C07D 231/38 Nitrogen atoms nitro radicals C07D231/16
• CPC Class Codes: C07D 239/42 One nitrogen atom nitro radicals C07D239/30
• CPC Class Codes: C07D 487/04 Ortho-condensed systems

Abstract

N-arylsulfilimine compounds, such as S,S-dimethyl-N-(2,6-dichlorophenyl)sulfilimine, were prepared and found to catalyze the reaction of aromatic sulfonyl chloride compounds, such as 2-chlorosulfonyl-7-fluoro-5-ethoxy[1,2,4]triazolo[1,5-c]pyrimidine, with aromatic amine compounds, such as 2,6-dichloroaniline, to form N-arylarylsulfonamide compounds, such as N-(2,6-dichlorophenyl)-7-fluoro-5-ethoxy[1,2,4]triazolo[1,5-c]-pyrimidine-2-sulfonamide. The aryl moiety of the N-arylsulfilimine catalyst and the aryl moiety of the aromatic amine compound were generally chosen to be identical.

Claims

1. A process for the preparation of an N-arylarylsulfonamide compound of the formula:

space="preserve" listing-type="equation">Q-SO.sub.2 NH-AR

wherein

Q and AR each independently represents an aromatic hydrocarbyl or aromatic heterocyclyl moiety

which comprises combining a sulfonyl chloride compound of the formula;

space="preserve" listing-type="equation">Q-SO.sub.2 Cl

wherein Q is defined as above

with an amine compound of the formula;

space="preserve" listing-type="equation">AR-NH.sub.2

wherein AR is defined as above

in the presence of an aromatic tertiary amine base and an added catalytic amount of an N-arylsulfilimine compound of the formula;

##STR13## wherein R represents methyl, ethyl, or n-propyl;

R'"'"' represents R, benzyl, or phenyl;

or R and R'"'"' together represent tetramethylene; and

AR'"'"' represents an aromatic hydrocarbyl or aromatic heterocyclyl moiety.

2. A process according to claim 1 wherein AR'"'"' of the N-arylsulfilimine compound is selected to be identical with AR in the amine compound.

3. A process according to claim 1 wherein R and R'"'"' each represent methyl.

4. A process according to claim 1 wherein AR represents a substituted phenyl moiety, a substituted pyridinyl moiety, or a substituted pyrazolyl moiety.

5. A process according to claim 4 wherein AR represents an aromatic moiety selected from

a) a substituted phenyl moiety of the formula:

##STR14## wherein A represents F, Cl, Br, NO₂, CN, C₁ -C₄ fluoroalkyl, CO₂ (C₁ -C₄ alkyl), CONH(C₁ -C₄ alkyl), CON(C₁ -C₄ alkyl)₂, SO₂ (C₁ -C₄ alkyl), or SO₂ (C₁ -C₄ fluoroalkyl);

B represents C₁ -C₄ alkyl, F, Cl, Br, O(C₁ -C₄ alkyl), O(C₁ -C₄ fluoroalkyl), S(C₁ -C₄ alkyl), S(C₁ -C₄ fluoroalkyl), N(C₁ -C₄ alkyl)₂ ;

or phenyl, phenoxy, or phenylthio each optionally possessing 1 to 3 substituents selected from the group consisting of F, Cl, Br, CN, CF₃, NO₂, and CH₃ ; and

D and J each independently represents H or CH₃ ;

b) a substituted 3-pyridinyl moiety of the formula;

##STR15## wherein L and M each independently represents H, C₁ -C₄ alkyl, C₁ -C₄ fluoroalkyl, O(C₁ -C₄ alkyl), O(C₁ -C₄ fluoroalkyl), O(C₂ -C₄ alkoxyalkyl), O(C₃ -C₄ alkenyl), O(C₃ -C₄ alkynyl), S(C₁ -C₄ alkyl), S(C₁ -C₄ fluoroalkyl), SO₂ (C₁ -C₄ alkyl), SO₂ (C₁ -C₄ fluoroalkyl), F, C₁, Br, I, CN, NO₂, C₆ H₅, CO₂ (C₁ -C₄ alkyl), CO₂ (C₃ -C₄ alkenyl), CO₂ (C₃ -C₄ alkynyl), CON(C₁ -C₄ alkyl)₂, or CONH(C₁ -C₄ alkyl); and

T represents H, F, Cl, Br, I, CH₃, or CF₃ ;

or

c) a 3-, 4-, or 5-pyrazolyl moiety substituted with a C₁ -C₃ alkyl group in the 1-position, with at least one Cl, Br, I, or CF₃ and, optionally, with one OCH₃ or CH₃ group.

6. A process according to claim 5 wherein AR is a substituted phenyl moiety and A represents F, Cl, Br, CF₃, NO₂, or CO₂ CH₃ ;

B represents F, Cl, Br, CH₃, OCH₃ ;

D represents H or CH₃ ; and

J represents H.

7. A process according to claim 5 wherein AR is a substituted pyridinyl moiety and T represents H and a) M represents Br or Cl and L represents O(C₁ -C₃ alkyl), b) M represents F and L represents C₁ -C₂ alkyl, or c) M represents H and L represents methoxycarbonyl.

8. A process according to claim 5 wherein AR is a substituted pyrazolyl moiety selected from 1-methyl-4-halo-3-pyrazolyl, 1-methyl-4-halo-5-pyrazolyl, and 1-ethyl-3-(trifluoromethyl)-5-(methyl, methoxy, or halo)-4-pyrazolyl.

9. A process according to claim 6 wherein AR is selected from 2,6-dichloro-3-methylphenyl, 2,6-dichlorophenyl, 2,6-difluorophenyl, and 2-methoxycarbonyl-6-chlorophenyl.

10. A process according to claim 1 wherein Q represents a substituted phenyl, substituted pyridinyl, substituted [1,2,4]triazolo[1,5-c]pyrimidine-2-yl, substituted [1,2,4]triazolo[1,5-a]pyrimidine-2-yl, or substituted [1,2,4]triazolo[1,5-a]pyridine-2-yl moiety.

11. A process according to claim 10 wherein the substituents are selected from F, Cl, Br, I, NO₂, CN, O(C₃ -C₄ alkenyl), or O(C₃ -C₄ alkynyl);

C₁ -C₄ alkyl, O(C₁ -C₄ alkyl), N(C₁ -C₄ alkyl)₂, S(C₁ -C₄ alkyl), SO₂ (C₁ -C₄ alkyl), CO₂ (C₁ -C₄ alkyl), CONH(C₁ -C₄ alkyl), or CON(C₁ -C₄ alkyl)₂, each alkyl optionally mono to completely substituted with fluorine;

or phenyl or phenoxy, each optionally possessing 1 to 3 substituents selected from the group consisting of F, Cl, Br, CN, CF₃, NO₂, and CH₃.

12. A process according to claim 11 wherein the sulfonyl chloride compound is selected from 2-chlorosulfonyl-5-ethoxy-7-fluoro[1,2,4]triazolo[1,5-c]pyrimidine, 2-chlorosulfonyl-5-methoxy-8-fluoro[1,2,4]triazolo[1,5-c]pyrimidine, 2-chlorosulfonyl-5-methoxy-7-methyl[1,2,4]triazolo[1,5-c]pyrimidine, 2-chlorosulfonyl-5-ethoxy-7-methyl[1,2,4]triazolo[1,5-c]pyrimidine, 2-chlorosulfonyl-5-methyl[1,2,4]triazolo[1,5-a]pyrimidine, 2-chlorosulfonyl-5,7-dimethoxy[1,2,4]triazolo[1,5-a]pyrimidine, 2-chlorosulfonyl-5,7-dimethyl[1,2,4]triazolo[1,5-a]pyrimidine, 2-chlorosulfonyl-5-methoxy-7-methyl[1,2,4]triazolo[1,5-a]pyridine, and 2-chlorosulfonyl-5-methoxy-8-chloro[1,2,4]triazolo[1,5-a]pyridine.

13. A process according to claim 3 wherein the catalytic compound is S,S-dimethyl-N-(2,6-dichloro-3-methylphenyl)sulfilimine, S,S-dimethyl-N-(2,6-dichlorophenyl)sulfilimine, S,S-dimethyl-N-(2,6-difluorophenyl)sulfilimine, or S,S-dimethyl-N-(2-methoxycarbonyl-6-chlorophenyl)sulfilimine.

14. A process according to claim 1 wherein the aromatic tertiary amine base is selected from pyridine, a picoline, nicotinamide, and quinoline.

15. A process according to claim 1 wherein the sulfilimine catalyst is prepared essentially immediately before use and is used in the form of the reaction mixture in which it was prepared or in a partially purified form.

16. A process according to claim 1 wherein the temperature is maintained at between about -20 and about 50°

C.

17. A process according to claim 1 wherein the amount of catalyst used is between about 2 and about 30 mole percent of the aromatic sulfonyl chloride compound.

18. The method of use of an N-arylsulfilimine compound of the formula:

##STR16## wherein R represents methyl, ethyl, or n-propyl;

R'"'"' represents R, phenyl or benzyl or R and R'"'"' together represent tetramethylene; and

AR'"'"' represents an aromatic hydrocarbyl or aromatic heterocyclyl moiety

to catalyze the reaction between an aromatic sulfonyl chloride compound of the formula;

space="preserve" listing-type="equation">Q-SO.sub.2 Cl

wherein Q represents an aromatic hydrocarbyl or aromatic heterocyclyl moiety

with an aromatic amine compound of the formula;

space="preserve" listing-type="equation">AR-NH.sub.2

wherein AR represents an aromatic hydrocarbyl or aromatic heterocyclyl moiety

to obtain an N-arylarylsulfonamide compound of the formula;

space="preserve" listing-type="equation">Q-SO.sub.2 NH-AR

wherein Q and AR are as defined above.

19. A method of use according to claim 18 wherein AR'"'"' of the N-arylsulfilimine compound is selected to be identical with AR of the aromatic amine compound.

20. A method of use according to claim 18 wherein R and R'"'"' each represent methyl.