Diphenyl N-halosulfilimines : Preparation, decomposition, and reactions with nucleophiles

doi:10.1016/0040-4020(77)80226-3

Tetrahedron

Volume 33, Issue 9, 1977, Pages 1061-1067

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Abstract

Diphenyl N chloro (l)-N bromo (2) and N-iodo-sulfilimines (3) were prepared by halogenation of diphenyl free sulfilimine. Compound 1 decomposed in benzene at room temperature. The decomposition of 1 is a chain reaction since the reaction was induced by chlorine or t-butyl hypochlorite affording diphenyl(diphenylsulfilimino) sulfonium chloride(4a) while it was inhibited by styrene or stilbene. Compound 4a was also obtained by the reaction of 1 with diphenyl sulfide in benzene. Decomposition of 1 in acetic acid proceeded smoothly affording various products. Compound 1 reacted with sulfides sulfoxides triarylphosphines and triethylamine affording the N-substituted iminosulfonium salts. Compounds 1 and 2 were hydrolyzed with sodium hydroxide affording diphenyl sulfoximine. The reaction of 1 with sodium cyanide gave diphenyl N cyanosulfilimine(17). The reaction of 1 with Grignard reagent gave diphenyl free sulfilimine. Compounds 2 and 3 are more stable than 1. Decomposition of 2 in benzene or acetic acid gave diphenyl(diphenylsulfilimino)sulfonium perbromide(4c)

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New synthesis of the mixed bis-acetylacetonate complexes of Co, Ni and Zn bearing 1 or 2 diphenylsulfilimine ligands Ph₂S → NH (2) is described. Improved synthetic protocol towards anhydrous ligand 2 was developed. Earlier known Ph₂S = NTs forms upon acid hydrolysis easily extractable, air-stable and non-hygroscopic tosylate salt [Ph₂SNH₂]⁺TsO^‾ (1), that crystallize as dimer stabilized by hydrogen bonds in the solid state and can serve as stable and storable precursor for preparation on demand of labile ligand 2. Non-nucleophilic bases in dry ether or aromatic solvents when reacted with 1 provide 2 in high yields. Monomeric Co^II (4), Zn^II (5) and Ni^II (6) bis-acetylacetonate dihydrates when reacted with 2 form mixed complexes M(acac)₂(Ph₂SNH) 7, M = Zn; 8, M = Co and Ni(acac)₂(Ph₂SNH)₂ 9 in up to 90 % yields. Molecular structure of dimeric {Co^II(acac)₂(Ph₂SNH)}₂ complex (8) reveals strong donor Co-N interactions stabilized by intramolecular O···HN hydrogen bonds between acac-ligands and the HN group of Ph₂S → NH (2).
Alkaline hydrolysis of N-bromoiminothianthrene derivatives
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Citation Excerpt :
N-Halosulfilimines are interesting derivatives that can be obtained easily by treating the corresponding N-unsubstituted sulfilimines with halogenating reagents.1–4
5-(N-Bromo)iminothianthrene (2) and 5-(N-bromo)iminothianthrene 10-oxide (5) and 10,10-dioxide (8) were prepared and their alkaline hydrolyses were studied. The compound 2 and cis-5-(N-bromo)iminothianthrene 10-oxide (cis-5) afforded the corresponding sulfoximine exclusively. While, unexpectedly, both trans-5-(N-bromo)iminothianthrene 10-oxide (trans-5) and 8 afforded mainly de-brominated products, trans-5-iminothianthrene 10-oxide (trans-4) and 5-iminothianthrene 10,10-dioxide (7), respectively. In these cases, 5-iminothianthrene 5,10-dioxide (6) (Z- and E-mixture) and 5-iminothianthrene 5,10,10-trioxide (9) and further de-iminated products were also formed respectively as minor products. The stereochemical considerations on the S_N reactions are described in view of the steric effect and ‘flip-flap’ motion of the thianthrene framework.
A new method for the preparation of fluoro-λ<sup>6</sup>-sulfanenitriles: Reaction of sulfimides with Selectfluor™
2003, Tetrahedron Letters
The structures of [Ph<inf>2</inf>XS-N-SPh<inf>2</inf>NH]<sup>+</sup> cations (X=NH, O)
2000, Journal of Organometallic Chemistry
Diphenyl(diphenylsulfodiimidoyl)(nitrido)sulfur(VI) (2) and diphenyl(diphenylsulfoximidoyl)(nitrido)sulfur(VI) (3) (Ph₂XSNSNPh₂N, X=NH, O) were prepared by the reaction of diphenyl(fluoro)(nitrido)sulfur(VI) (Ph₂FSN) with sodium salts of diphenyl-sulfodiimide (Ph₂S(NH)₂) and -sulfoximide (Ph₂OSNH). The nitrido-sulfur complexes 2 and 3 are considerably basic (pK_a=7.86 and 7.60, respectively). Treatment of 2 and 3 with perchloric acid afforded quantitatively the corresponding μ-aza-bis[diphenyl(imido)sulfur(V)] perchlorate (4) and μ-aza-[diphenyl(imido)]-[diphenyl(oxo)]disulfur(V) perchlorate (5) ([Ph₂XSNSPh₂NH]⁺[ClO₄]⁻, X=NH, O). The crystal structures of 4 and 5 were determined by X-ray crystallographic analysis. The former has essentially C₂ symmetry with an SNS bond angle of 120.3(2)°, bridging SN bond lengths of 1.595(3) and 1.604(3) Å, and terminal SN bond lengths of 1.509(3) and 1.497(3); the latter cation is an unsymmetrically substituted oxygen analog with an SNS bond angle of 123.1(2)°, and bridging SN bond lengths of 1.607(4) and 1.568(4) Å, terminal SN and SO bond lengths of 1.501(3) and 1.438(2) Å. Single-point ab initio calculations were also carried out using the data from the crystal structures of 4 and 5.
Formation of S,S-diphenyl-S-methoxythiazyne Ph<inf>2</inf>S(OMe)(N) in the alkaline hydrolysis of S,S-diphenyl-N-halosulfilimines
1989, Tetrahedron Letters
Role of Hydrogen Bond in the Synthesis and Complexation of Diphenylsulfilimine Ph2s→Nh
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Diphenyl N-halosulfilimines : Preparation, decomposition, and reactions with nucleophiles

Abstract

Tetrahedron Letters

Tetrahedron Letters

Tetrahedron Letters

Int J. Sulfur. Chem. Part A

Synthesis

J. Org. Chem.

Chem. Ser.

J. Am. Chem. Soc.

Chem. Ind.

J. Org. Chem.

Chem. Ber.

J. Am. Chem. Soc.

J. Am. Chem. Soc.