Method for producing alkenylthiophenols and their esters

Details Method for producing alkenylthiophenols and their esters Method for producing alkenylthiophenols and their esters

1986-12-10

1988-12-27

Rotman, Alan L.

Organic compounds -- part of the class 532-570 series

Organic compounds

Esters having the thiocarboxylate group, -cx-, wherein the...

568 67, 568 68, C07C15311, C07C14800

Patent

active

047942053

ABSTRACT:
A method is provided for preparing alkenylthiophenols, e.g., para-vinylthiophenol, or their esters, e.g., para-vinylthiophenol acetate by reacting a hydroxy aromatic ketone, e.g., 4-hydroxyacetophenone (4-HAP) with an N,N-di(organo)thiocarbamoyl halide, e.g., N,N-dimethylthiocarbamoyl chloride (DMTC) to form an O-(acylaryl) N,N-di(organo)thiocarbamate, e.g., O-(4'-acetophenyl) N,N-dimethylthiocarbamate, and pyrolytically rearranging the latter compound to form an S-(acylaryl) N,N-di(organo)thiocarbamate, e.g., S-(4-4- -acetophenyl) N,N-dimethylthiocarbamate. In one procedure, the latter compound is directly reduced to form an S-(1-hydroxyalkylaryl) N,N-di(organo) thiocarbamate, e.g., S-[4'-(1-hydroxyethyl)phenyl] N,N-dimethylthiocarbamate, which is either hydrolyzed to form a (1-hydroxyalkyl) thiophenol, e.g., 4'-(1-hydroxyethyl) thiophenol, which optionally after acylation of its thiol group, is dehydrated to form the alkenylthiophenol wherein the double bond is at the ring-bonded carbon atom, e.g., para-vinylthiophenol, or the S-(1-hydroxyalkylaryl) N,N-di(organo) thiocarbamate is dehydrated to form an S-(alkenylaryl) N,N-di(organo) thiocarbamate, e.g., S-(4-vinylphenyl) N,N-dimethylthiocarbamate which is hydrolyzed to form the alkenylthiophenol. In an alternative procedure, the S-(acylaryl) N,N-di(organo)thiocarbamate is hydrolyzed and the resulting thiol acylated with an acylating agent, e.g., acetyl chloride, to produce an acylthiophenol ester, e.g., 4-acetothiophenol acetate, which is then reduced and hydrolyzed to produce the (1-hydroxyalkyl) thiophenol. The latter compound is then dehydrated to produce the alkenylthiophenol, or acylated and dehydrated to produce alkenylthiophenol thioester, as described in the first procedure.

REFERENCES:
patent: 3475251 (1969-10-01), Widmer
patent: 3476791 (1969-11-01), Newman et al.
P. A. Schweitzer, Handbook of Separation Techniques for Chemical Engineers (McGraw-Hill) pp. 1-386 (one page).
Newman et al., Journal of Organic Chemistry 31, 3980-3984 (1966).
Kwart et al., Journal of Organic Chemistry 31, 410-413 (1966).
Overberger et al., Journal of the American Chemical Society 78, 4792-4797 (1956).
Nuyken et al., Polymer Bulletin 4, 75-82 (1981).
Reid, Organic Chemistry of Bivalent Sulfur, vol. III, Chem. Pub. Co., Ive., N.Y., 1962 pp. 27 & 31.

Affiliated with

Also associated with

Rating

Method for producing alkenylthiophenols and their esters does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Method for producing alkenylthiophenols and their esters, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Method for producing alkenylthiophenols and their esters will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-868816