Method and preparing fused oxazinones

1. A method for preparing a benzo[1,3]oxazinone, comprising:

contacting a pyrrole or pyrazole carboxylic acid with a sulfonyl chloride and an isatoic anhydride in the presence of a tertiary amine to form the benzo[1,3]oxazinone, the nominal mole ratio of said sulfonyl chloride to said carboxylic acid being from about 1.0 to 1.5 and the nominal mole ratio of said isatoic anhydride to said carboxylic acid is from about 0.8 to 1.2.

2. The method of claim 1 wherein the benzo[1,3]oxazinone is a compound of Formula 1

wherein

J is an optionally substituted pyrrole or pyrazole; and

K is, together with the two contiguous linking carbon atoms, a fused phenyl ring optionally substituted;

the carboxylic acid is a compound of Formula 2

J-CO 2 H  2

 wherein J is defined as in Formula 1;

the sulfonyl chloride is a compound of Formula 4

LS(O) 2 Cl  4

 wherein L is selected from alkyl, haloalkyl, and phenyl optionally substituted with from one to three substituents independently selected from alkyl or halogen; and

the isatoic anhydride is a compound of Formula 5

 wherein K is defined as in Formula 1.

3. The method of claim 2 wherein the nominal mole ratio of the isatoic anhydride to carboxylic acid is from about 0.9 to 1.1.

4. The method of claim 3 wherein the nominal mole ratio of the tertiary amine to carboxylic acid is from about 2.0 to 4.0.

5. The method of claim 2 wherein

K is, together with the two contiguous linking carbon atoms, a fused phenyl ring optionally substituted with from one to four substituents independently selected from G, U, W or or R 13 ;

J is a pyrrole or pyrazole, each optionally substituted with from one to two substituents independently selected from G, U, W or R 13 ;

each G is a 5- or 6-membered nonaromatic heterocyclic ring optionally including one or two ring members selected from the group consisting of C(═O), SO or S(O) 2 , each optionally substituted with from one to four substituents independently selected from W;

each U is a phenyl ring, a benzyl group, a beazoyl group, a 5- or 6-membered heteroaromnatic ring, an aromatic 8-, 9- or 10-membered fused carbobicyclic ring system, an aromatic 8-, 9- or 10-membered fused heterobicyclic ring system, each optionally substituted with from one to four substituents independently selected from W;

each W is independently C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 4 haloalkyl, C 2 -C 4 haloalkenyl, C 2 -C 4 haloalkenyl, C 3 -C 6 halocycloalkyl, halogen, CN, NO 2, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkcylsulfinyl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 alkylamino, C 2 -C 8 dialkylamino, C 3 -C 6 cycloalkylamino, (C 1 -C 4 alkyl)(C 3 -C 6 cycloalkyl)amino or C 3 -C 6 trialkylsilyl;

each R 13 is B(OR 17 ) 2 ; NH 2 ; SH; thiocyanato; C 3 -C 8 trialkylsilyloxy; C 1 -C 4 alkyldisulfide; SF 5 ; R 19 C(=E)-; R 19 C(=E)M-; R 19 MC(=E)-; (R 19 )MC(=E)M-; —OP(=Q)(OR 19 ) 2 ; —S(O) 2 MR 19 ; R 19 S(O) 2 M-;

each E is independently O, S, NR 15 , NOR 15 , NN(R 15 ) 2 , N—S═O, N—ON or N—NO 2 ;

each M is independently O, NR 18 or S;

Q is O or S;

each R 15 and each R 19 is independently H; C 1 -C 6 alkyl optionally substituted with one or more substituents selected from the group consisting of CN, NO 2 , hydroxy, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 haloalkylthio, C 1 -C 4 haloalkylsulfinyl, C 1 -C 4 haloalkylsulfonyl, C 1 -C 4 alkylamino, C 2 -C 8 dialkylamino, CO 2 H, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylcarbonyl, C 3 -C 6 trialkylsilyl, and a phenyl ring optionally substituted with one to three substituents independently selected from W; C 1 -C 6 haloalkyl; C 3 -C 6 cycloalkyl; or a phenyl ring optionally substituted with from one to three substituents independently selected from W;

each R 17 is independently H or C 1 -C 4 alkyl; or

B(OR 17 ) 2 can form a ring wherein the two oxygen atoms are linked by a chain of two to three carbons optionally substituted with one or two substituents independently selected from methyl or C 2 -C 6 alkoxycarbonyl; and

each R 18 is independently H, C 1 -C 6 alkyl or C 1 -C 6 haloalkyl.

6. The method of claim 5 wherein K is, together with the two contiguous linking carbon atoms, a fused phenyl ring optionally substituted with from one to four substituents independently selected from W or R 13 .

7. The method of claim 2 wherein the compound of Formula 1 is a compound of Formula 1a

wherein

X is N or CR 6 ;

Y is N or CH;

R 4 is C 1 -C 4 alkyl or halogen;

R 5 is H, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, CN or halogen;

R 6 and R 7 are independently H, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, halogen, CN or C 1 -C 4 haloalkoxy;

R 8 is H, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 4 haloalkyl, C 2 -C 4 haloalkenyl, C 2 -C 4 haloalkynyl, C 3 -C 6 halocycloalkyl, halogen, CN, NO 2 , C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 alkylamino, C 2 -C 8 dialkylamino, C 3 -C 6 cycloalkylamino, (C 1 -C 4 alkyl)(C 3 -C 6 cycloalkyl)amino, C 2 -C 4 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylaminocarbonyl, C 3 -C 8 dialkylaminocarbonyl or C 3 -C 6 trialkylsilyl;

R 9 is CF 3 , OCF 3 , OCHF 2 , OCH 2 CF 3 , S(O) p CF 3 , S(O) p CHF 2 or halogen; and

p is 0, 1 or 2;

 the compound of Formula 2 is a compound of Formula 2′ and the compound of Formula 5 is a compound of Formula 5′

 wherein the definitions of X, Y, R 4 , R 5 , R 7 , R 8 and R 9 are the same as for Formula 1a.

8. The method of claim 7 wherein

X is N;

Y is N;

R 4 is CH 3 , F, Cl or Br;

R 5 is CF 3 , CN, F, Cl, Br or I;

R 7 is Cl or Br;

R 8 is H; and

R 9 is CF 3 , OCHF 2 , OCH 2 CF 3 , Cl or Br.