Transformation of thiosulphonates into α-sulphonyldisulphides, a new class of thioaldehyde precursors

Kirby, G. W.; Lochead, Alistair W.; Sheldrake, Gary N.

doi:10.1039/c39840001469

Cited by 28 publications

(16 citation statements)

References 3 publications

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“…A similar effect has been observed for the base-catalyzed cleavage of sodium S-benzylthiosulfates to thioaldehydes. 17 The structure of 74 is obvious from its analytical and spectroscopic data. It was corroborated by an X-ray structural analysis ( Figure 3).…”

Section: Introductionmentioning

confidence: 99%

Preparation of New Dialkyl Benzene-, Biphenyl-, and Naphthalene-bis(α-oxoethanedithioates)

Voß

Sarafidis

Sawluk

et al. 2010

Phosphorus, Sulfur, and Silicon and the Related Elements

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Novel arene-bis-and -tris(α-oxoethanedithioate) esters of the benzene, the biphenyl, and, in particular, the naphthalene series were prepared by reaction of the corresponding diazoacetyl or bromoacetyl derivatives with elemental sulfur in the presence of triethylamine in dry DMF, and subsequent direct alkylation of the produced dithiocarboxylate anions. The thiolation reaction of the diazoketones was significantly promoted by the addition of anhydrous calcium chloride (calcium chloride-activated thiolation, or CAT). Certain carbonyl-activated methylene and methyl compounds exhibiting no bromo or diazo substituents could be also transformed into dithioesters by the CAT reaction. The structure of three dithioesters was corroborated by X-ray structural analyses.

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Section: Introductionmentioning

confidence: 99%

Preparation of New Dialkyl Benzene-, Biphenyl-, and Naphthalene-bis(α-oxoethanedithioates)

Voß

Sarafidis

Sawluk

et al. 2010

Phosphorus, Sulfur, and Silicon and the Related Elements

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“…This study stimulated further interest in the spectroscopic properties of formyl cyanide, since rotationally resolved electronic and infrared spectra could be obtained for this molecule. [2][3][4][5][6][7][8] The analogous thioformyl cyanide has been formed as a transient species by a number of routes, including treatment of the appropriate Bunte salt, NCCH 2 SSO 3 Na, with triethylamine and calcium chloride 9 and photolysis of C 6 H 5 COCH 2 SCH 2 CN. 10 The existence of thioformyl cyanide in these studies was inferred from the formation of cycloadducts with an appropriate 1,3-diene.…”

Section: Introductionmentioning

confidence: 99%

“…10 The existence of thioformyl cyanide in these studies was inferred from the formation of cycloadducts with an appropriate 1,3-diene. 9,11 More recently, thioformyl cyanide was formed by thermal decomposition of CH 2 CHCH 2 SCH 2 CN and characterized in detail with the use of photoelectron spectroscopy. 12 The experimental observation of formyl cyanide as a stable species stimulated also theoretical studies of its spectroscopic properties, such as the vibrational frequencies, rotational constants, and the dipole moment of the electronic ground state.…”

Section: Introductionmentioning

confidence: 99%

Experimental Determination of the Enthalpies of Formation of Formyl Cyanide and Thioformyl Cyanide in the Gas Phase

1996

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The enthalpies of formation of formyl cyanide (HC(O)CN) and thioformyl cyanide (HC(S)CN) in the gas phase have been determined with the use of Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. The enthalpy of formation, ∆H f°( 298 K), of formyl cyanide is determined to be 26 ( 20 kJ mol -1 , whereas the value for thioformyl cyanide is 222 ( 30 kJ mol -1 . These enthalpies of formation are derived from experimental values of (i) the gas-phase acidities of the methylene groups in the CH 3 OCH 2 CN and CH 3 SCH 2 CN species (∆H°a cid (CH 3 OCH 2 CN) ) 1556 ( 8 kJ mol -1 and ∆H°a cid (CH 3 SCH 2 CN) ) 1494 ( 8 kJ mol -1 ), (ii) the enthalpy change for the dissociation of the CH 3 OC h HCN and CH 3 SC h HCN carbanions into a methyl radical and the radical anion of formyl cyanide and thioformyl cyanide, respectively (BDE-(CH 3 OC h HCN) ) 116 ( 10 kJ mol -1 and BDE(CH 3 SC h HCN) ) 133 ( 10 kJ mol -1 ), and (iii) the electron affinities of the neutral formyl species (EA(HC(O)CN) ) 65 ( 3 kJ mol -1 and EA(HC(S)CN) ) 159 ( 15 kJ mol -1 ). The structures of the two carbanions and the radical anions of the (thio)formyl species have been ascertained by high kinetic energy (8 keV) collision-induced charge-reversal (CR) experiments performed with the use of a double-focusing quadrupole hybrid mass spectrometer.

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“…19 The thiocarbonyl group is a good dienophile and will trap 1,3-dienes at low temperatures. 20 The resulting cycloadducts can be rearranged stereoselectively under basic conditions to cyclopentenyl sulfides (eq 3). 21 …”

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confidence: 99%

Sodium Thiosulfate

Larsen¹

2001

Encyclopedia of Reagents for Organic Synthesis

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Transformation of thiosulphonates into α-sulphonyldisulphides, a new class of thioaldehyde precursors

Abstract: Toluene-p-thiosulphonates, RCH2SS02Tol (1) where R is an electron-withdrawing group, are transformed readily into wsulphonyldisulphides (2) which, with triethylamine, undergo fragmentation-elimination to give 2 moles of t h ioa Me hydes, RCH S.

Cited by 28 publications

References 3 publications

Preparation of New Dialkyl Benzene-, Biphenyl-, and Naphthalene-bis(α-oxoethanedithioates)

Preparation of New Dialkyl Benzene-, Biphenyl-, and Naphthalene-bis(α-oxoethanedithioates)

Experimental Determination of the Enthalpies of Formation of Formyl Cyanide and Thioformyl Cyanide in the Gas Phase

Sodium Thiosulfate

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