Imenes most readily add amines and other nucleophilic reagents, such as water, alcohols, mercaptans, hydrogen sulphide, hydrocyanic add. Bismethylsulphonyl-N-methylimene, which was studied more extensively, proved to possess not only electrophilic but also nudeophilic properties.Thus it adds HCl and can be applied in the Friedel-Crafts reaction.In our previous publication 1) it was shown that imenes possess a pronounced addition power towards water. With the aid of this property it was easy to distinguish the imene from the accompanying carbo-methylation product in the case of phenylsulphonyl-methylsulphonyl-acetonitrile, reacting with diazomethane.
When reacting diazomethane on nitriles of the type RSO2‐CHXCN, where X is a negative group, methylation on the nitrogen atom often occurs. In the case of bis‐methylsulphonyl‐acetonitrile, the N‐methyl derivative is formed exclusively: (CH3SO2)2CCNCH3. The less acidic methylsulphoxyl‐methylsulphonyl‐acetonitrile forms only the C‐methyl derivative: (CH3SO)(CH3SO2)C(CH3)CN.
It could be derived from kinetic measurements that irradiation of an aqueous solution of ρ‐methoxybenzenediazosulphonate with ultra‐violet light causes a dissociation of the sulphonate ion to form a ρ‐methoxybenzene‐diazonium ion and a sulphite ion. The ions produced photochemically slowly recombine in the dark to form back the original sulphonate ion.
The reactions may be represented by the scheme:
The occurence of a labile or cis‐diazosulphonate can practically be precluded.
A description is given of the preparation of substituted methylsulphonylacetonitriles CH&02CHXCN, x being cH8s02, C0&2Ha, CeHaSOn, CH&O or CN.When reacting methanesulphochloride with methylsulphonylacetonitrile under the influence of a sodium alcoholate solution, the sodium salt of bis-methylsulphonyl-acetonitrile separates. Therefore two molecules of sodium alcoholate are required 2 ) .CH,SO,CH,CN + CH,SO,Cl + 2 C,H,ONa --f (CH,SO,) ,CNaCN + NaCl When using one molecule of sodium alcoholate instead of two in the reaction of cyanoacetic ester with methanesulphochloride, the yield of methylsulphonyl-carboxethyl-acetonitrile is reduced from 45% to 14%.Phenylsulphonyl-methylsulphonyl-acetonitrile has been synthesized along two lines. The introduction of a phenylsulphonyl group into methylsulphonyl-acetonitrile with the aid of benzenesulphochloride gives a poor yield (23%). From methanesulphochloride and phenylsulphonyl-acetonitrile a yield of 66% is obtained.Oxidation of methylthio-methylsulphonyl-acetonitrile with one molecule of hydrogen peroxide in acetic acid in the presence of a little sulphuric acid as a catalyst, leads, in poor yield, to the corresponding methylsulphoxyl compound. By oxidation with hydrogen peroxide alone ( 1 mol.) , bis-methylsulphonyl-acetonitrile is formed, the starting material remaining partly unchanged. In both cases the consumption of hydrogen peroxide is complete.Surprisingly the strongly acidic methylsulphonyl-malonitrile (pre- 565 (1954).2) The use of two molecules of NaOCnH5 has also been applied to the prepara-
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