Process for the preparation of pyrazole carboxylic acid amides
View Patent ↗The invention relates to a process for the preparation of 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (9-dichloromethylene-1,2,3,4-tetrahydro-1,4-methano-naphthalen-5-yl)-amide by acylating the oxime oxygen of the compound of formula (VIII), in the presence of a solvent and an acylating agent of formula (XI) R 1 C(X)—CI (XI); wherein X is oxygen or sulfur; R 1 is chloro if X is oxygen or sulfur; or R1 is C 1 -C 6 alkoxy, CH 3 —C(═CH 2 )—O—, phenoxy or trichloromethoxy if X is oxygen; and a) if R 1 is chloro and the compound of formula (XI) was added to the compound of formula (VIII); reacting the so obtained product of formula (XIIa) wherein X is oxygen or sulfur; with the compound of formula (IX) b) if R 1 is chloro and the compound of formula (VIII) was added to the compound of formula (XI); or R 1 is C 1 -C 6 alkoxy, CH 3 —C(═CH 2 )—O—, phenoxy or trichloromethoxy if X is oxygen; reacting the so obtained product of formula (XII) wherein X is oxygen or sulfur; R 1 is chloro if X is oxygen or sulfur; or R 1 is C 1 -C 6 alkoxy, CH 3 —C(═CH 2 )—O—, phenoxy or trichloromethoxy if X is oxygen; with the compound of formula (IX).
1. A process for the preparation of the compound of formula I
which process comprises
acylating the oxime oxygen of the compound of formula VIII
in the presence of a solvent and an acylating agent of formula XI
R 1 —C(X)—Cl (XI),
wherein X is oxygen or sulfur;
R 1 is chloro if X is oxygen or sulfur; or
R 1 is C 1 -C 6 alkoxy, CH 3 —C(═CH 2 )—O—, phenoxy or trichloromethoxy if X is oxygen;
and
a) if R 1 is chloro and the compound of formula XI was added to the compound of formula VIII;
reacting the so obtained product of formula XIIa
wherein X is oxygen or sulfur;
with the compound of formula IX
or
b) if R 1 is chloro and the compound of formula VIII was added to the compound of formula XI;
or R 1 is C 1 -C 6 alkoxy, CH 3 —C(═CH 2 )—O—, phenoxy or trichloromethoxy if X is oxygen;
reacting the so obtained product of formula XII
wherein X is oxygen or sulfur;
R 1 is chloro if X is oxygen or sulfur; or
R 1 is C 1 -C 6 alkoxy, CH 3 —C(═CH 2 )—O—, phenoxy or trichloromethoxy if X is oxygen;
with the compound of formula IX
2. A process according to claim 1 , wherein the acylating agent is selected from a compound of formula XI, wherein R 1 is methoxy, ethoxy, isopropoxy, isopropenyloxy or phenoxy and X is oxygen.
3. A process according to claim 2 , wherein the acylating agent is ethyl-chloroformate.
4. A process according to claim 1 , wherein the acylated agent is reacted with the compound of formula IX in the presence of an acid.
5. A process according to claim 1 , wherein the acylated agent is reacted with the compound of formula IX in the presence of CH 3 SO 3 H.
6. A process according to claim 1 , wherein the acylating agent is ethyl-chloroformate and the acylated derivative is reacted with the compound of formula IX in the presence of CH 3 SO 3 H.
7. A compound of formula XII
wherein X is oxygen or sulfur;
R 1 is chloro if X is oxygen or sulfur; or
R 1 is C 1 -C 6 alkoxy, CH 3 —C(═CH 2 )—O—, phenoxy or trichloromethoxy if X is oxygen.
8. A compound of formula XIIa
wherein X is oxygen or sulfur.