Imines 9-sulphonylated

Diphenyl cyclopropenone reacts readily with isocyanates activated by p-toluene-sulphonyl, trichloroacetyl, and chlorosulphonyl116 or benzenesulphonyl117 groups giving rise to cyclopropenone imines 152 and carbon dioxide ... 

Allylic phenyl tellurides are converted into the corresponding allylic amines by imination with [iV-(p-toluene-sulphonyl)imino] phenyliodinane. The reaction proceeds via [2,31-sigma-tropic rearrangement of a tellurimide intermediate. 

As intended, C2 carbanion 7.47 attacked the nitrile giving 7.48, which unexpectedly attacked the adjacent sulphonyl group giving indolyl anion 7.49. During the acidic aqueous workup this anion is quenched and the reactive N-sulphonyl imine functionality is readily hydrolysed affording ketone 7.44 and sulphonamide 7.45. 

Photolysis of sulphonyl azides in the presence of nucleophilic trapping agents such as dimethyl sulphoxide or dimethyl sulphide gave imine derivatives. For example, irradiation of -toluenesulphonyl azide in dimethyl sulphide gave a 54% yield of iV-( -toluenesulphonyl) dimethylsulphimine (375) The use of dimethyl sulphoxide resulted in lower yields of the trapped nitrene (377) (13-32%), and... 

As shown in Scheme 4, a new approach to 3-methylene-azetidin-2-ones has been described. The reaction of the acrylamide (16) with n-butyl-lithium, followed by the addition of toluene-4-sulphonyl chloride, gives the azetidinone (17), in 60% yield. In the same paper it is reported that lithium phenylethynolate reacts with imines (in a highly stereoselective manner) to form azetidinones, in a promising new approach to functionalized azetidinones. 

Acyl and sulphonyl isocyanates react with diphenylcyclopropenone, presumably via initial attack on the ketone group, providing cyclo-propenone imines [197] ... 

Neooctams, such as the unsubstituted parent compound (191), are easily obtained in cycloadditions. Isocyanates [125,126], sulphonyl isocyanates (43) [29,127] and especially chlorosulphonyl isocyanate (189) [128] react with alkenes to form variously-substituted j3-lactams [129—135]. Synthesis of compound (191) is an example of this reaction which has been discussed in detail [52]. The same compound (192) can be obtained in the photolytic rearrangement of the pyrazolone (194) [136]. Compound (196) is neooctam-5,7-diene, obtained from the azocine (195) and hydrogen bromide [137]. Lactam (196)is a partly saturated form of (199). The latter is an unstable neooctam derivative, formed in an intramolecular ketene-imine cycloaddition reaction (see (198))... 

However, definitive evidence for the existence of the title compounds has been given by Tamagaki and Oae, who recently reported the isolation of the compounds (112), obtained from the reaction of l,2-dithiole-3-thiones with bis(toluene-p-sulphonyl)diazomethane. The reaction of l,2-dithiole-3-thiones with Chloramine T produced thiocarbonyl imines (113) in a similar manner. ... 

Iminosulphuranes usually hydrolyse slowly to amines and sulphoxides. Kobayashi et al reported the abnormal methanolysis of (97) to 2-methoxythiophane. For the imine (97 R = toluene-p-sulphonyl) the... 

The sulphurdi-imines are hydrolysed in acidic media to sulphur dioxide and two equivalents of amine. Oxidation with ozone afforded a nitrocompound and sulphinylamine. Pyrolysis of the diphenyl derivative (100 R = Ph) gave azobenzene, but pyrolysis of the di-t-butyl derivative (100 R = t-butyl) resulted in an intramolecular elimination to isobutylene, hydrogen sulphide, and ammonia. The bis-tosyl imine (100 R = toluene-p-sulphonyl) reacted with diamines (1,2----------1,6-) in an... 

Primary and secondary amines are also oxidized to aldehydes and ketones, via imines, using sulphonyl peroxides. The first reports of high-yield selective oxidative conversions of unbranched primary amines into em-dihalides (masked aldehydes) have appeared (Scheme 9), and the cleavage of tertiary amines to carbamates with ethyl chloroformate has been examined. ... 

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