Thiophene compounds and their manufacture

• US 4,239,897 A
• Filed: 09/15/1978
• Issued: 12/16/1980
• Est. Priority Date: 04/10/1976
• Status: Expired due to Term

• Current Assignee: BASF AG (BASF SE)
• Original Assignee: BASF AG (BASF SE)
• Inventors: Hoffmann, Werner, Rossy, Phillip
• Primary Examiner(s): Siegel, Alan
• Application Number:
  US05/942,655
• Time in Patent Office: 823 Days
• Field of Search: 260/332.2 C, 549/61, 549/64, 549/65, 549/66
• US Class Current: 549/61
• CPC Class Codes: C07D 333/32 Oxygen atoms
• CPC Class Codes: C07D 333/36 Nitrogen atoms
• CPC Class Codes: C07D 333/38 Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
• CPC Class Codes: C07D 495/04 Ortho-condensed systems

Abstract

New thiophene compounds and a new process for the manufacture of thiophene compounds by dehydrogenating dihydrothiophene with certain halogen compounds. The products are starting materials for the manufacture of pharmaceuticals, dyes and plant protection agents and, in particular, for the manufacture of additives to foodstuffs, feeds, beverages and pharmaceuticals.

Claims

1. A process for the manufacture of thiophene compounds of the formula ##STR85## the individual radicals R³ and R⁴ may be identical or different and each is an aliphatic, cycloaliphatic, araliphatic or aromatic radical, and R³ may also be hydrogen, R¹² has the meanings of R¹ or is ##STR86## wherein dihydrothiophenes of the formula ##STR87## where R¹, R² and R³ have the above meanings, are dehydrogenated with chlorides or bromides of phosphoric acid or sulfuric acid, with chlorine, bromine or iodine, or with N-halogen compounds of the formula ##STR88## where X is chlorine or bromine, R⁹ is hydrogen or ##STR89## the individual radicals R¹⁰ may be identical or different and each is an aliphatic, araliphatic or aromatic radical, the two radicals R¹⁰ may also together be ##STR90## where R³ and X have the above meanings and R¹¹ is alkylene, or when disulfide-(3,3'"'"')-bis-(dihydrothiophenes) of the formula ##STR91## where R² and R³ have the above meanings, or dihydrothiophenes of the formula ##STR92## where R¹³ has the meanings of R¹² or, if R¹² is ##STR93## R¹³ may also be ##STR94## are dehydrogenerated with chlorides or bromides of sulfuric acid or with chlorine.

2. A process as claimed in claim 1, wherein the dehydrogenation is carried out with from 1 to 2 equivalents of dehydrogenating agent per mole of starting material II, IIa or III.

3. A process as claimed in claim 1, wherein, for the case of the starting materials II, the reaction is carried out with sulfuryl chloride, sulfuryl bromide or chlorine.

4. A process as claimed in claim 1, wherein the reaction is carried out at from -30°

to +100°

C.

5. A process as claimed in claim 1, wherein the reaction is carried out at from +10°

to +40°

C.

6. A process as claimed in claim 1, wherein the reaction is carried out in the presence of organic solvents which are inert under the reaction conditions.

7. A process as claimed in claim 1, wherein the reaction is carried out in from 400 to 10,000% by weight--based on starting material II, IIa or III--of solvent.

8. A process as claimed in claim 1, wherein the reaction is carried out in the presence of an acid-binding compound.

9. A process as claimed in claim 1, wherein the reaction is carried out in the presence of from 1.9 to 2.1 equivalents of an acid-binding compound per mole of starting material II, IIa or III.