26910-40-7Relevant articles and documents
Aldehyde to Ketone Homologation Enabled by Improved Access to Thioalkyl Phosphonium Salts
Fragis, Meghan,Deobald, Jackson L.,Dharavath, Srinivas,Scott, Jeffrey,Magolan, Jakob
supporting information, p. 4548 - 4552 (2021/06/28)
Phosphines were previously unusable as Pummerer-type nucleophiles due to competing redox chemistry with sulfoxides. Here we circumvent this problem to achieve a formal phosphine Pummerer reaction that offers thioalkyl phosphonium salts that, in turn, give rise to diverse vinyl sulfides via Wittig olefinations. Thirty vinyl sulfides are thus prepared from (alkylthioalkyl)triphenyl phosphonium salts and aldehydes. The hydrolysis of these vinyl sulfides offers an efficient and versatile two-step one-carbon homologation of aldehydes to ketones.
Pyrolysis of α- and β-heteroatoms substituted ethyl phenyl sulfoxides
Yoshimura, Toshiaki,Sakae, Hironori,Yoshizawa, Masaki,Hasegawa, Kiyoshi,Tsukurimichi, Eiichi
experimental part, p. 1162 - 1173 (2010/08/06)
A study on the mechanism of the thermal decomposition of α- and β-heteroatoms substituted ethyl phenyl sulfoxides was carried out using 1-chloroethyl phenyl sulfoxide (1); two diastereomeric 1-acetoxyethyl (substituted phenyl) sulfoxides (2a) and (2b); and 2-chloroethyl phenyl, 2-bromoethyl phenyl, and 2-methoxyethyl phenyl sulfoxides (3, 4, 5). The rate of pyrolysis of 1 was 4.8 times faster at 160°C than that of ethyl phenyl sulfoxide used as a reference, while those of 2a and 2b were 107 and 155 times faster, respectively. The results indicate that the lone pair of electrons on the α-heteroatoms has a larger rate acceleration effect than the electronegativity of them. The substituent effects of the phenyl group of 2a and 2b gave positive Hammett ρ-values (ρa= 0.76 and ρb= 0.80 vs. σ). Activation parameters for 2a and 2b are as follows: 2a, ΔH?= 112 kJmol-1, ΔS?= -20 JK-1mol-1; 2b, ΔH?= 107 kJmol-1, ΔS?= -29 JK-1mol-1. Large deuterium kinetic isotope effects for 1-acetoxyethyl-2,2,2-d3 phenyl sulfoxides (2ad and 2bd) were observed (kH/kD= 3.5 ~ 4.1). These results suggest that the pyrolysis of -heteroatom substituted ethyl phenyl sulfoxides proceeds via a five-membered transition state deviated to E1-like in character. On the other hand, from the results of kinetics for the pyrolysis of 3, 4, and 5, no effect by the β-halogen atoms or some deceleration effect by the β-methoxy group was observed. Thus the reaction seems to proceed via an E1-like mechanism. Copyright Taylor & Francis Group.
Facile one-pot synthesis of α-chloro sulfoxides from sulfides
Kim,Shin,Park
, p. 209 - 210 (2007/10/02)
Various sulfides 1 reacted with sulfuryl chloride in the presence of metal nitrates in acetonitrile under mild conditions to give the corresponding α-chloro sulfoxides 2 in good yields.