NZ200394A

NZ200394A - 2,3-diarylthiophenes

Info

Publication number: NZ200394A
Application number: NZ20039480A
Authority: NZ
Inventors: S C Cherkofsky
Original assignee: Du Pont
Priority date: 1979-08-09
Filing date: 1980-08-08
Publication date: 1984-05-31

Description

New Zealand Paient Spedficaiion for Paient Number £00394 200394 Priority Daisfs): .PP.'.k: p, q Complo^Q Specification F«2sd: .. ? CIms:C?.T3???;. C°7?.«V2....

Publication Date: 3i. MAX .1984 P.O. Jsamat Me: !??A.. to Under the provisions of RegUKj lation 23 (!) the A. O-w Specification has been ante-dated sto _ 19^9 23 APR»« >V ; Patents Form No. 5 PATENTS ACT 1953 COMPLETE SPECIFICATION -SUBSTITUTED 2,3-DIARYLTHIOPHENES We, E.I. DU PONT DE NEMOURS AND COMPANY a corporation organized and existing under the laws of the State of Delaware, United States of America, located at 10th & Market Streets, Wilmington Delaware, United States of America, hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement - ]A - 200394 -S INSTITUTED 2, 3-DIARYLTHIOPHENES Background of the Invention This invention relates to diarylthiophenes A number of references, such as J. Schmitt, M. Suquet and R. Fellard, Compt. Rend., 242, 1738 (1956) and Z. Chem., 13, 57 (1973) disclosed 2,3-diarylthiophenes.

Haas and Hellwig in Chem. Ber. , 109 , 2475 (1976) disclose the reactions of alkylthiophenes and of halothiophenes with haloalkyl sulfenyl halides. (1962) disclose the reactions of alkylthiophenes with 2,4-dinitrobenzenesulfenyl chloride. They also describe solvolysis of the resulting sulfide to give the correspondin mercaptan.

Relyea et al., in U.S. patent 4174405 disclose 2,3-diaryl-(5-arylthio)thiophenes and their use as insecticides and miticides.

This invention relates to novel compounds, and processes of preparing them . These compounds are of the formula: Schuatz and Fredericks in J. Org. Chem. , 2J7, 1301 2oo 21 f where R3 and R4 independently = pyridyl or -P- X = H, F, CI, Br, N02, C1~C2 alkyl, C1-C2 alkoxy, di (C^C^lkyl)- 2 amino or S(0) R ; where m m = 0, 1 or 2; and 2 R = CH3 or C2H5; Y = H, F or CI with the proviso that when Y is F or CI, then X is F or CI; R = H, C^-C^ alkyl or allyl; Br R6 = Synthesis The compounds of the invention can be made by the following reactions: (1) 0 R3-C=C-R4 " R C-Cl 3 - 94 A diaryl acetylene in an inert solvent e.g., CH^Cl^ or CCl^, in the presence of a Lewis acid catalyst, e.g. AlCl^/ is reacted with an alkanoic acid chloride to give a compound of structure I (R^ ^ H).

Compounds of structure I (R~* = H) are prepared by the reaction of a desoxybenzoin with the Vilsmeier reagent (dimethylformamide/phosphorous oxychloride) (2) 0 \ / A compound of structure I is reacted with mercaptoacetic acid in pyridine in the presence of triethylamine to give thiophene II (R^ = H). The by-product carboxylic acid (III) produced in the reaction is converted to III (R^ = H) by heating at reflux in quinoline in the presence of copper powder. g 2-Bromo-4,5-diarylthiophenes (II, R =Br) are prepared by reaction of a 2,3-diarylthiophenes (II, R^= H) with bromine (1 equivalent) in a solvent such as methylene chloride, acetic acid or their mixture at a temperature from -20° to 30°C.

The compounds of this invention can be used to 100394 prepare antiinf lainmatory compounds described and claimed in our New Zealand Patent Specification No. 194607 from which this specification has been divided. 20039<f

Claims

WHAT WE CLAIM IS:

1. Compounds of the formula: R3. R5 3 4 where R and R independently are pyridyl or Y X = H, F, CI, Br, NC>2, C1~C2 alkyl, C^-C2 alkoxy, di(C1~C2 alkyl)- 2 amino or S(0) R ; where m m = 0, 1 or 2; and R2 = CH3 or C2H5; Y = H, F or CI with the proviso that when Y is F or CI, then X is F or CI; R~* = H, C^-C^ alkyl or allyl;;R6 = JSSSt Br ,;A process for preparing a compound as clained in claim 1, comprising reacting a compound of the formula :;- 6 -;2ooZcf'-(>;R~;O;V;CI;3 4 5;where R ,R and R are as defined in claim 1 with;f3;t me rcaptoacetic acid Lin. the presence of triethylamine;? ,ttS;to give a compound ofjjclaim 1 where R is hydrogen and then to obtain a compound of claim 1 where is bromine, reacting this compound with one equivalent of bromine in a solvent at a temperature of from - 20°C to 30°C.;A process as claimed in claim 2 where the compound of formula I where R5 is hydrogen is prepared by reacting desoxybenzoin with the Vilsmeier reagent (dimethylformarnide/phosphorus oxychloride) .;A process as claimed in claim 2 where the compound of;5;formula I in which R is alkyl or allyl is obtained by reacting a compound of the formula;3 4;R- C=C-R;3 4;where R and R are as defined in claim 1 with a compound of the formula ';^ R5-COCl;\ where R"* is cjl~C4 ^^yl or aHyl in an inert solvent in the presence of a Lewis acid catalyst. BSL.DWIN, SON & C/^REY