Sulfonyl halides synthesis

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. ... 

Sulfonate esters are especially useful substrates in nucleophilic substitution reactions used in synthesis. They have a high level of reactivity, and, unlike alkyl halides, they can be prepared from alcohols by reactions that do not directly involve bonds to the carbon atom imdeigoing substitution. The latter aspect is particularly important in cases in which the stereochemical and structural integrity of the reactant must be maintained. Sulfonate esters are usually prepared by reaction of an alcohol with a sulfonyl halide in the presence of pyridine ... 

A reaction which is related to hydroxy-de-diazoniations is the formation of aryl trifluoromethylsulfonic esters (aryl triflates, ArOSC CFs) which became widely used reagents because of their leaving-group properties. The classical method of synthesis by esterification of phenols with trifluoromethane-sulfonic anhydride or -sulfonyl halide is, however, not applicable for the preparation of aryl triflates bearing a (free)... 

In the early solution-phase synthesis of oligonucleotides, coupling of phosphate chesters was used. A mixed 3 -ester with one aryl substituent, usually o-chlorophenyl, was coupled with a deprotected 5 -OH. The coupling reagents used were sulfonyl halides, particularly 2,4,6-triisopropylbenzenesulfonyl chloride.153 The reactions proceed by... 

The single-monomer route (eq. 5) is preferred as it proves to give more linear and para-linked repeat unit structures than the two-monomer route. Other sulfone-based polymers can be similarly produced from sulfonyl halides with aromatic hydrocarbons. The key step in these polymerizations is the formation of the carbon—sulfur bond. High polymers are achievable via this synthesis route although the resulting polymers are not always completely linear. 

A very reactive halogen atom, such as that of mi acyl or sulfonyl halide, is replaced by fluorine by the action of almost any inorganic fluoride. The most convenient method consists in heating gently a mixture of an acyl or sulfonyl chloride with zinc or antimony fluoride in an apparatus which permits the acyl fluoride to distil as it is formed. The acyl fluoride usually boils about 40° lower than the chloride, and its removal from the reaction mixture results in quantitative yields. Com- plete interchange also can be effected with hydrogen fluoride, but more elaborate equipment is required. Good results have been reported for the synthesis of formyl and acetyl fluorides from mixtures of fonnic or... 

Sulfonimidothiazolines, 317, 318 Sulfonyl halides, with 2-aminothiazoles, 69 Sulfur (Sg), in synthesis of, A-4-thiazoline-2-thione, 373 Sulfur compounds, 69 Sulfuric acid, with alcohols, 38, 47, 80, 90 in bromination, 77 dealkylation by, 39 deuterated, 92 diazotization with, 66 in nitrations, 72 rearrangements in, 73, 113 Sulfuryl chloride, 432 Symbiotic behavior, see HSAB theory Symmetry. C2v and C2p, 120 Synthetic fibers, 154... 

Amino-l,2,4-thiadiazoles (16) readily yield monoacylated derivatives of type (129) under the usual conditions whereas both monoacyl and diacyl derivatives (130 and 131, respectively) are easily obtained from the 3-amino isomers (65AHC(5)119, 70CB1805). In a similar manner the 3-amino-l,2,4 thiadiazoles produce mono- and di-sulfenamide derivatives when treated with sulfenyl halides. In general, the reactions of 3-amino- and 5-amino-1,2,4-thiadiazoles with sulfonyl halides under basic conditions produce only low yields of the desired derivatives. Sulfonamides of type (132) are best prepared by ring synthesis methods as illustrated in Scheme 55 (75LA1961). 

Many other functional groups are reduced by Sml. For example, sulfonyl halides are converted to disulfides. The reduction of nitro compounds by this reagent enables synthesis of 1,2-diamines based on a reaction sequence initiated by nitronate addition to aldimines, and in the presence of nitriles it furnishes amidines, and that of isothiocyanates in the presence of conjugated esters, the half thioamide derivatives of succinic esters. 

Synthesis and Stability. Sulfonate esters are conveniently prepared from precursor sulfonyl halides and the appropriate alcohol or alkoxide [Eq. (3) ] this synthetic pathway is particularly suitable for the introduction of a C label into the alkylating moiety since radioactive primary alcohols can be readily synthesized. ... 

In summary, sulfonamides are most commonly prepared by the reaction of amines with sulfonyl halides. Aryl sulfonyl chlorides may be accessed from C-H bonds by chlorosulfonylation, from C-S bonds by oxidation, from C-N bonds by diazotization, or from C-X bonds by metalation. Approaches to all l sulfonamides are more limited as they are typically prepared by either oxidative chlorination of thiols or addition of organometallic nucleophiles to sulfur electrophiles. Traditional sulfonamide preparation has frequently necessitated harsh reagents and conditions, but the development of Pd-catalysed approaches and discovery of new sulfur dioxide sources allow for operationally simple sulfonamide synthesis under mild conditions. Future directions in sulfonamide synthesis will likely involve the direct C-H installation of sulfonamides without the use of hazardous reagents. 

Pyrimidine-2-sulfonyl chloride, 4,6-dimethyl-reactions, 3, 97 Pyrimidinesulfonyl halides reactions, 3, 97 Pyrimidinethiols S-acylation, 3, 95 S-alkylation, 3, 94 oxidation, 3, 94 synthesis, 3, 135 Pyrimidine-5-thiols oxidation, 3, 94 synthesis, 3, 136... 

The synthesis of sulfones included electrophilic substitution, specifically, Frie-del-Crafts catalysis by A1C13, FeCl3, SbCl5, AlBr3 and BF3, and so on, which are efficient catalysts for the sulfonylation by arenesulfonyl halides.1 22... 

M. G. Ambrose and R. W. Binkley, Synthesis of deoxyhalogeno sugars. Reaction of halide ions with l,23,4-tetra-0-acetyl-6-0-[(trifiuoromethyl)sulfonyl-p-D-glucopyranose, J. Org. Chem. 48 674 (1983). 

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