5538-41-0Relevant articles and documents
para-Selective chlorination of cresols and m-xylenol using sulfuryl chloride in the presence of poly(alkylene sulfide)s
Smith, Keith,Hegazy, Amany S.,El-Hiti, Gamal A.
, p. 345 - 356 (2020/03/23)
Chlorination of o-cresol, m-cresol, and m-xylenol using sulfuryl chloride in the presence of a range of poly(alkylene sulfide)s and a Lewis acid (aluminum or ferric chloride) has been studied. The sulfur containing catalysts used led to the production of para-chlorophenols in high yields and higher para/ortho ratios than for reactions in the absence of such poly(alkylene sulfide)s. The effectiveness of the polymers was found to be dependent on the length of the spacer groups between the sulfur atoms. For example, polymers with shorter spacers provided high yields of 4-chloro-o-cresol (ca. 97%), while polymers with at least one longer spacer provided high yields of both 4-chloro-m-cresol (up to 94.6%) and 4-chloro-m-xylenol (up to 97.6%).
Regioselective synthesis of important chlorophenols in the presence of methylthioalkanes with remote SMe, OMe or OH substituents
Smith, Keith,Al-Zuhairi, Ali J.,Elliott, Mark. C.,El-Hiti, Gamal A.
, p. 607 - 621 (2018/07/13)
Various methylthio alcohols, methoxy(methylthio)alkanes and bis(methylthio)alkanes have been used as regioselectivity modifiers in the chlorination reactions of various phenols at room temperature. The process involves the use of a slight excess of sulfuryl chloride in the presence of aluminum or ferric chloride as an activator. Methylthio alcohols, methoxy(methylthio)alkanes and bis(methylthio)alkanes having 2 and 3 methylene groups as a spacer were found to be good for the para-selective chlorination of o-cresol and phenol. On the other hand, methylthio alcohols, methoxy(methylthio)alkanes and bis(methylthio)alkanes having 6 and 9 methylene groups were found to be good for the selective para-chlorination of m-xylenol and m-cresol. Calculations using density functional theory on bis(methylthio)alkanes have suggested two different types of stable chlorinated intermediates depending on the number of methylene units as a spacer.
Comparison of cyclic and polymeric disulfides as catalysts for the regioselective chlorination of phenols
Smith, Keith,Al-Zuhairi, Ali J.,El-Hiti, Gamal A.,Alshammari, Mohammed B.
, p. 74 - 85 (2015/10/20)
Two cyclic and two polymeric disulfides have been synthesized and established to be useful catalysts for the chlorination of m-xylenol, o-cresol, m-cresol and phenol using freshly distilled sulfuryl chloride in the presence of aluminum or ferric chloride as a co-catalyst at room temperature. The yields of p-isomers and para/ortho ratios were higher compared to cases where no catalyst was used with most catalysts for most phenols even when a very low concentration of disulfide was used.