52209-09-3

Upstream product

• 619-73-8 4-nitrobenzyl chloride 
• 38622-91-2 [(p-methylphenyl)sulfonylmethyl]isonitrile 
• 536-57-2 p-toluene sulfinic acid 
• 555-16-8 4-nitrobenzaldehdye 
• 1576-35-8 toluene-4-sulfonic acid hydrazide 
• 1747-50-8 4-methyl-N'-[(4-nitrophenyl)methylidene]benzene-1-sulfonohydrazide 
• 824-79-3 sodium 4-methylbenzenesulfinate 

Relevant academic research and scientific papers

N - P -Toluenesulfinylimidazole: A New in situ Reagent for the Mild and Efficient Synthesis of p -Toluenesulfinate Alkyl Esters and Aryl Esters

A new synthetic methodology has been developed for the synthesis of sulfinate alkyl and aryl esters. The methodology involves the combination of p -toluenesulfinic acid and 1,1′-carbonyldiimidazole (CDI) to create the putative reagent sulfinylimidazole. The process spontaneously releases carbon dioxide upon the addition of the CDI to the acid suggesting the rapid formation of the proposed reagent. Reaction of this reagent with a series of alcohols (primary, secondary, and tertiary) afforded the corresponding sulfinate alkyl esters in good to excellent yields by the addition of alcohols. It was also possible to form the related sulfinate aryl esters by treating the proposed sulfinylimidazole with selected phenols (phenol, p - tert -butylphenol, and thymol). The aryl esters were formed in excellent conversion based on analysis of the 500 MHz 1H NMR spectra of the crude reaction mixtures.

Base-Promoted Direct Synthesis of Sulfinates from N -Sulfonyl-hydrazones under Metal-Free Conditions

A base-promoted direct synthesis of sulfinates from N -sulfonylhydrazones is described. Various N -sulfonylhydrazones, derived from aldehydes and ketones, are converted into the corresponding sulfinates in moderate to good yields. This protocol possesses

Sodium Arenesulfinates-Involved Sulfinate Synthesis Revisited: Improved Synthesis and Revised Reaction Mechanism

Reaction of alcohols with sodium arenesulfinates could afford either sulfones or sulfinates, and O-attack of sulfinate anions onto the in situ generated carbocation intermediates from alcohols was the previous proposed reaction mechanism in many syntheses of sulfinates. This concept, which is often used consciously or unconsciously, was revised herein by using isotopic labeling experiments and development of an improved sulfinate synthesis. The improved sulfinate synthetic protocol possesses many advantages such as a high sulfinate/sulfone selectivity, a broad substrate scope, metal-free, and mild reaction conditions. The revised reaction mechanism necessitates revision of many previous proposed reaction mechanisms in literatures.

Efficient Synthesis of Sulfinate Esters and Sulfinamides via Activated Esters of p -Toluenesulfinic Acid

Sulfinate esters were prepared by the process of activating p -toluenesulfinic acid with either cyanuric chloride, methanesulfonyl chloride, or 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC-HCl). Activation of p -toluenesulfinic acid with cyanuric chloride led to the formation of sulfinate esters that were accompanied by the formation of the corresponding sulfones. The use of methanesulfonyl chloride for activation via methanesulfonic p -toluenesulfinic anhydride afforded mixtures of sulfinate esters and methanesulfonates. The use of the carbodiimide EDC proved to yield the best results with the highly selective formation of the target sulfinate esters. The use of trimethylacetic p -toluenesulfinic anhydride or cyanuric chloride to achieve the synthesis of sulfinamides proved to be ineffective due to poor chemoselectivity of the nucleophilic attack on the activated p -toluenesulfinic acid anhydride. Ultimately, the use of EDC-HCl to form the sulfinamides proved to be the best pathway for synthesis.

A mixed anhydride approach to the preparation of sulfinate esters and allylic sulfones: Trimethylacetic p-toluenesulfinic anhydride

A reagent combination of toluenesulfinic acid and trimethylacetyl chloride affords a putative trimethylacetic p-toluenesulfinic anhydride. This reagent has been used to prepare a series of sulfinate esters from primary and secondary alcohols. In addition, the reagent was used to convert Baylis-Hillman substrates into allylic sulfones. Attempts to use the reagent to convert amines to sulfinamides were unsuccessful. In contrast, the use of 2-pyrrolidinone afforded N-p-toluenesulfinyl pyrrolidinone in 64% yield. The use of a chiral 4-benzyl-1,3-oxazolidinone or 4-benzyl-1,3-oxazolidine-2-thione led to the isolation of S-p-tolyl p-toluenethiosulfonate.

Substrate- and temperature-controlled divergence in reactions of alcohols with TosMIC catalyzed by BF3 · Et2O: Facile access to sulfinates and sulfones

An efficient BF3 · Et2O-catalyzed divergent synthesis of sulfinate esters and sulfones through C–O and C–S bond formation has been achieved from alcohols and p-toluenesulfonylmethyl isocyanide (TosMIC). Various alcohols reacted smoothly with TosMIC under the present conditions at room temperature providing sulfinate esters exclusively. By tuning the reaction temperature, the alcohols that provide highly stabilized carbocation in the reaction medium afforded sulfones as sole products. This study was aimed at understanding the regioselectivity of ambidentate sulfinate ion and to elucidate the interpretation of sulfinate/sulfone scaffolds.

Sulfination of alcohols with sodium sulfinates promoted by BF3·OEt2: An unexpected access

A BF3·OEt2-promoted direct substitution of various alcohols with sodium sulfinates affording sulfinates under mild conditions has been developed. Further reaction of the hydroxysteroids achieves the highly complex sulfinates in good yields, which are two potential pharmacophores routinely encountered in drug discovery.

SULFINIC ACIDS AND RELATED COMPOUNDS. 21. PREPARATION OF CRYSTALLINE SULFINIC ESTERS

In a search for means of preparing stable crystalline esters of sulfinic acids, yields from p-toluenesulfinic acid as a model were 53-92 percent with 1,1'-carbonyldiimidazole (CDI, 2) as a coupling reagent for a variety of alcohols.The best coupling reagents were CDI and chlorotrimethylsilane (16).The agent 16 could be used with sulfinate salts, as could CDI with in situ acidification.The best alcohols were 1-adamantanol and p-nitrobenzyl alcohol.Among alkanesulfinic esters, methanesulfinates were unstable oils obtainable only in low yields, but 1-butanesulfinates were obtained in 52-56 percent yield (although still as oils).As a stable disulfinic acid, 1,4-butanedisulfinic acid gave a nicely crystalline di-1-adamantyl ester (mp 123-125 deg C), but another alkanedisulfinate salt or acid that contained a disulfide moiety gave no diester by use either of 2 or 16.Key words: 1,1'-Carbonyldiimidazole, chlorotrimethylsilane, sulfinic acids, sulfinic acid esters, sulfinic acid salts, p-toluenesulfinic acid.