Sulfonyl cyanide

Caution Since cyanogen chloride is highly toxic, the preparation and isolaiion of the sulfonyl cyanide should be condwted in a well-ventilated hood. 

When crude aulfonyl chlorides were used as starting materials, the reaction mixture was washed with a suitable solvent to remove organic impurities. In the case of higher-melting crystalline sulfonyl chlorides, heating to 50 may be necessary to complete their reduction. The solution of the sulfinate salt may be kept overnight, if desired, with no decrease in the yield of sulfonyl cyanide. 

The higher-melting sulfonyl cyanides which separate as solids should be dried when dissolved in a suitable solvent, e.g., benzene. p-Nitro-benzenesulfonyl cyanide is not readily extracted from the reaction mixture it is collected on a Buchner funnel, pressed as dry as possible, dissolved in benzene, washed with water, and dried over anhydrous calcium chloride. 

Solid sulfonyl cyanides now show a melting point not more than 1-2 below that of recrystallized material. They may be used with t further purification. Analytically pure samples are obtained by r crystallization from dry benzene, diy petroleum ether, or a mixture or the two. 

Whereas sulfonyl halides have been known for a long time and, especially the chlorides, have become of great synthetic value, sulfonyl cyanides were unknown until 1968. They were first prepared by van Leusen and co-workers from the reaction of sulfonylmethylenephos-phoranes with nitrosyl chloride. The same group also investigated part of their chemistry. Since then, two more, completely different, methods of synthesis were published from sulfinates with cyanogen chloride,and by the oxidation of thiocyanates. ... 

Cycloadditions to a cyano group are comparatively rare. The high-temperature reactions of 1,3-dienes, e.g. butadiene, isoprene and 2-chloro-l,3-butadiene, with dicyanogen, propionitrile or benzonitrile result in formation of pyridines (equation 80)70. Sulfonyl cyanides 147, obtained by the action of cyanogen chloride on sodium salts of sulfinic acids, add to dienes to give dihydropyridines 148, which are transformed into pyridines 149 by oxidation (equation 81)71. 

Excess sodium sulfite or sodium hydrogen carbonate should be avoided, since either would rSaet- irath the sulfonyl cyanide once formed. 

Some sulfinates are commercially available. They may be used as starting materials for the preparation of sulfonyl cyanides also. Yields, however, are not significantly better than when the much cheaper and more readily available sulfonyl chlorides are used as starting materials. Good to excellent results are obtained, even when starting from rather impure sulfonyl chlorides. Illustrative examples are given in Table I. 

Attempts to prepare sulfonyl cyanides from the corresponding sulfonyl chlorides according to the procedure described were unsuccessful when applied to mono-, di-, and trichloromethanesulfonyl chloride, to dimethylsulfamoyl chloride, and to ethylene- and 2,4-diiiitrophenylsulfonyl chloride. 

Sodium toluene dispersion of, 55, 65 Sodium p-toluenesulfinate, 57, 103 Spiro[4 n] alkenones, 58, 62 Spiro[cyclopentane-l,l -indene] 55, 94 Squalene, 56, 116 Squalene, 2,3-epoxy, 56, 116 Stannic chloride, 56, 97 Steroids synthesis, 58, 85 E Stilbene, 55, 115,58, 73 z-Stilbene, 58, 133 Styrene, 56, 35,58, 43 Styrene glycol, 55, 116 Styrene glycol dimesylate, 55, 116 Succinic acid, 58, 85 Succinic anhydride, 58, 85 Sucunimide, 56, 50, 58, 126 Succimmide, Vbromo, 55, 28, 56, 49 SULFIDE CONTRACTION, 55, 127 Sulfide, dimethyl-, 56, 37 SULFIDE SYNTHESIS, 58, 143,58, 138 SULFIDE SYNTHESIS ALKYL ARYL SULFIDES, 58, 143 SULFIDE SYNTHFSIS DIALKYL SULFIDES, 58, 143 SULFIDE SYNTHESIS UNSYMMETRI-CAL DIALKYL DISULFIDES, 58, 147 SULFONYL CYANIDES, 57, 88 Sulfur tetrafluoride, 57, 51... 

Preparative Methods from reaction of Cyclopentadiene with either sulfonyl cyanides or Chlorosulfonyl Isocyanate Both enantiomers can be obtained via enzymic kinetic resolution of the racemate. ... 

A chiral camphoisulfonic acid-derived sulfonyl cyanide reacts with cyclopentadiene to give a produa with only 13% ee C. Caamono, A. Eirfn, F. Femtindez, G. G6mez and E. Uriarte, Heterocycles, 1988, 27,2839. 

In 1974, Jagt and Van Leusen (74JOC564) found that sulfonyl cyanides are good dienophiles. At room temperature, tosyl cyanide (67) dissolved in cyclopentadiene 68 is converted into 3-tosyl-2-azabicyclo [2.2.1 ]hepta-2,5-diene (69) (95%). This is the first example of the formation of a primary Diels-Alder cycloadduct of a nitrile. Adduct 69 was hydrolyzed with acetic acid and water to the lactam 70. Daluge and Vince (73JOC2311) used 70 to synthesize puromycin analog 76 (Scheme 9). Lactam 70 was hydrolyzed to the cis-amino... 

SULFIDE SYNTHESIS UNSYMMETRI-CAL DIALKYL DISULFIDES, 58, 147 SULFONYL CYANIDES, 57, 88 Sulfur tetrafluoride, 57,51... 

Sulfonyl cyanides, which are readily prepared by reaction of an alkyl or aryl sodium sulfinate with cyanogen chloride [Eq. (3)],... 

Sulfonyl cyanides. The compounds can be prepared from sulfonyl chlorides by reduction to sodium sulfinates followed by reaction with cyanogen chloride. Example ... 

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