Organic N‐Sulfinyl Compounds

Abstract

The nitrogen-sulfur linkage in compounds of the type R-NSO is capable of undergoing addition. For N-sulfinylsulfonamides in particular, the reactivity is increased so greatly that new types of compounds may be obtained by cyclic addition or migration of the sulfinyl group.In 1890, Michaelis and Herz [l) identified "thionylaniline" C~HSNSO as a product of the reaction of aniline with SOC4:(1) QHsNHz + SOClz + GHsNSO + 2 HCL This substance has been described earlier by Bottinger [2] but with no statement concerning its structure. In a large number of subsequent publications, Michaelis has described the preparation of approximately seventy-five N-sulfinylamines of the type R-NSO and their reactions. This thorough exploration of the field, as well as the fact that the described reactions either led back to the amines, or else to products which could be obtained more easily by another route, explains why very little work was done with the N-sulfinyl compounds in the subsequent period. Only in the last few years have various groups made renewed studies of the structure and behavior of the organic N-sulfinyl compounds, and it is these studies in particular which are described here. The literature up to June 1958 is summarized in Houben-Weyl [3a] and is therefore only treated briefly; a survey of earlier works is also given by Kennard [3 b]. A summary of the properties of the unsubstituted thionylimide has been given by Goehring [4].Most N-sulhyl compounds known up to the present time are amine or bydrazine derivatives and are prepared from them.

Catalysis of H‐D Exchange in Cyclooctatetraene by Cycloocta‐1,3,5‐triene

“…101-102°C (from ethanol). ( I ) and (2) are identical with authentic specimens prepared by a different route [2]. The present synthesis is based on an electrophilic attack of the carbon disulfide and a simultaneous nucleophilic influence of the sulfur which is incorporated.…”

“…Thus, 1-morpholinocyclopent-I-ene forms 4,s-trimethylenetrithione ( I ) in 50 %, yield, m. p. 123 "C, and l-morpholinocyclohex-I-ene gives 45 % of 4,5-tetramethylenetrithione (2), m.p. 101-102°C (from ethanol).…”

“…Thus, a mixture of (I) and alkoxide/alcohol at 140 "C gives cycloocta-1.3.5-tricne in yields of up to 30 %, together with a brown polymeric powder [l]. A dimer of ( I ) , tricyclo[8,4,2,0*,9]hexadeca-3,5,7, I I ,I3,lShexaene (2), described by Jones [2], reduces ( I ) to cycloocta-1,3,5-triene under the catalytic effect of alkoxide. We have found that H-D exchange in ( I ) is catalysed by cycloocta-1,3,5-triene in a basic medium [3].…”

“…Deuterated ( I ) is obtained by way of the anion radical stage from the deuterated dianion, and non-deuterated dianion is obtained from non-deuterated ( I ) , whereby the latter is again reconverted into deuterated dianion in the system ROK/ROD. [3] Compound (2) is even more suitable as a catalyst than cycloocta-1,3,5-triene. [4] Compound ( I ) was separated from the reaction mixture by distillation (oil pump vacuum: 0.1 mm), passed through a condenser (0 "C), and condensed in a cold trap (-75 "C).…”

Analysis of the High-Resolution Fourier Transform Infrared Spectra of the ν3and ν5Bands of Thionylimide (HNSO)

“…The FTIR spectrometer was a Bomem DA3.002 interferometric spectrophotometer equipped with a globar light lamines (R-NSO) are a large class of organic nitrogensulfur compounds with a rich and varied chemistry (5). The source and a Wilks-type multiple reflection cell set for a pathlength of 8.25 m. The n 3 band (980-1200 cm 01 ) was simplest member of this class, thionylimide (HNSO), is a semi-stable molecule that adopts a cis-planar structure of recorded with a KBr beamsplitter, an MCT detector, and an HNSO pressure of 0.4 Torr.…”