1062-30-2

Upstream product

• 78089-44-8 n-Butyl 2,4,6-triisopropylphenyl sulfide 
• 22693-41-0 2,4,6-Triisopropylthiophenol 
• 6553-96-4 2,4,6-triisopropylphenylsulfonyl chloride 
• 78089-47-1 n-Butyl 2,4,6-triisopropylphenyl sulfoxide 

Downstream Products

• 20875-34-7 1,2-bis(2,4,6-triisopropylphenyl)disulfane 

Relevant academic research and scientific papers

An easy and practical synthesis of symmetrical thiosulfonic S-esters

Symmetrical alkyl and aryl thiosulfonic S-esters were prepared in good to excellent yields by the acetyl chloride-activated zinc reduction of sulfonyl chlorides.

STRUCTURE AND CONFORMATION OF SYMMETRIC ARYL THIOSULPHONIC ESTERS

The symmetric thiosulphonic esters R-SO2-S-R (R = CH3, C6H5, p-CH3-C6H4, p-CH3O-C6H4, p-Cl-C6H4, 2,4,6-(CH3)3-C6H2, 2,4,6-(i-C3H7)3-C6H2) have been prepared by a one-step synthesis partially reducing the sulphonyl chlorides with KI in the presence of catalytic amounts of pyridine.The crystal structures of the aryl derivatives X-C6H4-SO2-S-C6H4-X (X = H, CH3, Cl) have been determined using single crystal X-ray diffractometric data: C6H5-SO2-S-C6H5 (MoKα): P2/n, a = 12.413(4), b = 8.537(2), c = 12.649(5) Angstroem, β = 116.50(2) deg, Z = 4, final R = 0.0485; CH3-C6H4-SO2-S-C6H4-CH3 (CuKα): P21/n, a = 13.932(6), b = 12.076(6), c = 8.326(4) Angstroem, β = 93.40(6) deg, Z = 4, final R = 0.0425; Cl-C6H4-SO2-S-C6H4-Cl (MoKα): P21/n, a = 13.716(9), b = 11.932(8), c = 8.206(4) Angstroem, β = 92.47(2) deg, Z = 4, final R = 0.0493.The three structures are strictly similar with a conformation of the thiosulphonyl system essentially determined by the tendency of the non bonding electron pairs of S(II) to assume synclinal and antiperiplanar conformation with respect to the S(VI)-O bonds.The repulsion exerted by these pairs on the S(II)-C and S(II)-S(VI) bonding pairs justifies the narrowing of the S(VI)-S(II)-C angle with respect to the tetrahedral value.Electronic effects due to the para substituents in the phenyl rings superimpose that repulsion producing a different narrowing in the three derivatives.These effects influence also the S(VI)-S(II) distance which is shorter in the case of X = H, where the angle S(VI)-S(II)-C is larger.The angular deformations of the environment of S(VI) make the two oxygen atoms non equivalent, so that S(VI) is chiral.

Chemistry of Sulfenic Acids. 3. Studies of Sterically Hindered Sulfenic Acids Using Flash Vacuum Pyrolysis

Flash vacuum pyrolysis (FVP) of sulfoxides containing β-hydrogen atoms affords sulfenic acids (RSOH) in good concentration under conditions where they are stable.The application of this technique to the synthesis and study of sterically hindered sulfenic acids 12a-e is described.The principal or primary reaction of simple sulfenic acids prepared in this manner is dehydration to thiosulfinates 13 (eq 1).Steric inhibition to dehydration (eq 1) appears to only be of importance for 2-methyl-2-propanesulfenic acid (12a) which was trapped in good yield with methyl propiolate to afford 16a. 2,4,6-Tri-tert-butylbenzenesulfenic acid (12e) appears to be destabilized as a consequence of interaction between the SOH and adjacent tert-butyl groups.In the pyrolysis section of the apparatus, 12e decomposes to phenol 21 and aryl radical 22, which reacts further.Thermolysis of sulfoxides generates the sulfenic acids 12a-e in very low concentration at any one time.The products of sulfenic acids generated in this way result from secondary reactions of the corresponding thiosulfinates.

Sulphone Formation from 2,4,6-Tri-isopropylbenzenesulphinic Acid

2,4,6-Tri-isopropylbenzenesulphinic acid decomposed in the presence of oxygen giving 2,4,6-tri-isopropyl-1,α-sultone; a mechanism involving arylsulphonyl and peroxyarylsulphonyl radicals and intramolecular hydrogen atom abstraction is suggested.