PROCESS FOR THE PREPARATION OF THIETANE DERIVATIVES

摘要

The present invention relates to processes for the preparation of thietane derivatives of the formula (IA) and thietane derivatives of the formula (IB) wherein R1, R2, A1, A2, A3, A4, B, and n are as defined in the claims. The invention also relates to intermediates useful in the processes, as well as the compounds of formula (IA) and (IB) and their use as pesticides.;

主权项

1. A process for the preparation of a compound of formula IAwherein
A1, A2, A3 and A4 are independently of one another C—H, C—R3, or nitrogen; B is O or CH2; R1 is C1-C8haloalkyl; R2 is aryl or aryl substituted by one to five R4, or heteroaryl or heteroaryl substituted by one to five R4; each R3 is independently halogen, cyano, nitro, C1-C8alkyl, C3-C8cycloalkyl, C1-C8haloalkyl, C2-C8alkenyl, C2-C8haloalkenyl, C2-C8alkynyl, C2-C8haloalkynyl, C1-C8alkoxy, C1-C8haloalkoxy, C1-C8alkoxycarbonyl-, amino, hydroxy, mercapto, C1-C8alkylthio, C1-C8haloalkylthio, C1-C8alkylsulfinyl, C1-C8haloalkylsulfinyl, C1-C8alkylsulfonyl, C1-C8haloalkylsulfonyl, C1-C8alkylcarbonyl, or two R3 on adjacent carbon atoms together form a —CH═CH—CH═CH— bridge or a —N═CH—CH═CH— bridge; each R4 is independently halogen, cyano, nitro, C1-C8alkyl, C1-C8haloalkyl, C2-C8alkenyl, C2-C8haloalkenyl, C2-C8alkynyl, C2-C8haloalkynyl, hydroxy, C1-C8alkoxy, C1-C8haloalkoxy, mercapto, C1-C8alkylthio, C1-C8haloalkylthio, C1-C8alkylsulfinyl, C1-C8haloalkylsulfinyl, C1-C8alkylsulfonyl, C1-C8haloalkylsulfonyl, C1-C8alkylcarbonyl, C1-C8alkoxycarbonyl, aryl or aryl substituted by one to five R5, or heterocyclyl or heterocyclyl substituted by one to five R5; each R5 is independently halogen, cyano, nitro, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy-, or C1-C4haloalkoxy-; n is 0, 1 or 2; comprising preparing a compound of formula IV by either a. reacting a compound of formula II with a source of cyanide in the presence of water to give a compound of formula III b. reducing the compound of formula III with a suitable reducing agent to give a compound of formula IV c-i. reacting the compound of formula IV with a compound of formula Vwherein R is OH, C1-C6alkoxy or Cl, F or Br, and R1, R2, B, A1, A2, A3 and A4 are as defined for compounds of formula IA to give a compound of formula I; or
A) reacting a compound of formula VII with CH3NO2 to give a compound of formula XI B) reducing the compound of formula XI with a suitable reducing agent to give a compound of formula IV; or 1) homologating a compound of formula VII to give an ester of formula XII wherein R is C1-C6alkyl; 2) reducing the compound of formula XII using a suitable reducing agent to give a compound of formula XIII 3) treating the compound of formula XIII with hydrazoic acid to give a compound of formula IV; and c-i. reacting the compound of formula IV with a compound of formula Vwherein R is OH, C1-C6alkoxy or Cl, F or Br, and R1, R2, B, A1, A2, A3 and A4 are as defined for compounds of formula I to give a compound of formula IA; or
c-ii reacting the compound of formula IV with a compound of formula VIwherein XB is a leaving group for example a halogen, such as bromo, and R1, R2, B, A1, A2, A3 and A4 are as defined for compounds of formula IAwith carbon monoxide in the presence of a suitable catalyst to give a compound of formula IA;and wherein the method optionally comprises oxidizing the sulfur atom of the thietane moiety.