247. Derivatives of cyclo-2 : 5-dithia-3 : 4-dimethylenestibine

Clark, Robert E. D.

doi:10.1039/jr9320001826

Cited by 11 publications

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“…dihydrolipoic acid (PVI unpublished results). Antimony(III) chloride with excess ethyl mercaptan gave the dithiolate (EtS) 2 Sb-Cl [30], with 1,2ethanedithiol in concentrated hydrochloric acid gave the ditholate (SCH 2 CH 2 S)Sb-Cl [12], and with BAL in methanol under 1:1 molar ratio gave a solution most likely containing the BAL/Sb-Cl or -OMe. Aqueous work up, however, gave 2 (based on elemental analyses) insoluble in MeOH but soluble in DMSO a fact that precluded ESI mass spectral analysis.…”

Section: Reactions Of Bal With M(iii) (M = As Sb Bi) Compounds Thementioning

confidence: 99%

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The reaction of British Anti-Lewisite (dimercaprol) with As(III), Sb(III), and Bi(III) oxides and salts

Ioannou

Vachliotis

Kouli

2013

Main Group Chemistry

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The ␣,␤-dithiol 2,3-dimercapto-1-propanol (dimercaprol or British Anti-Lewisite, BAL) reacts with AsCl 3 , in a 1:1 molar ratio, giving the expected cyclic adduct 1 but with As 2 O 3 and with AsCl 3 , in 2:3 As/BAL molar ratios, gave gums composed of many compounds. BAL reacts with Sb 2 O 3 in DMSO but the products could not be isolated. With SbCl 3 two products 2 and 3 have been isolated in 1:1 and 2:3 Sb/BAL molar ratios. Bi 2 O 3 in 1:1 and 2:3 molar ratios gave compounds 4 and 5. However, BiCl 3 and Bi(NO 3 ) 3 ·5H 2 O in either 1:1 or 2:3 stoichiometries gave compounds 6 and 7, respectively, indicating that the >Bi-Cl and >Bi(NO 3 ) bonds were not reactive towards excess BAL. The 1 H and 13 C NMR spectra of the Sb(III) and Bi(III) complexes in DMSO-d 6 revealed broad signals attributed to the quadrupole relaxation of Sb and Bi nuclei. No relaxation was observed for the arsenic complex 1 in CD 3 OD. Other properties of the complexes are presented and discussed. Fig. 1. A: Proposed structure for the interaction of arsenite with closely spaced thiols in a steroid receptor [11]; B: A 6-membered ring in the adduct DHLA/As-Ph; C: Proposed formula for the adduct BAL/lewisite; D: Formula of the adduct BAL/As-Ph.Because monofunctional thiols in excess do not reverse the effect of lewisite or NaH 2 AsO 3 , Sir Rudolf Peters introduced the dithiol 2,3-dimercapto-1-propanol (dimercaprol or British Anti-Lewisite, BAL) as an antidote for lewisite [34,47,48]. BAL efficiently and quickly reversed the effects of lewisite in cells and keratin [34,47] and of (Ar-AsO) x on DHLA of E. coli [46]. Conversely, excess BAL is toxic because it can inactivate proteins and enzymes containing disulfide groups or heavy metal prosthetic groups, e.g. catalase, peroxidase, carbonic anhydrase [47] and has other drawbacks, e.g. the BAL-As(III) complexes are distributed to other organs such as the brain [48].An attempt was make in 1968 to measure the dissociation constant of the arsenite complex of DHLA [50] and in 2005 it was shown that a particularly stable 2:3 As:DHLA complex was formed [45] but a formula for it was not proposed. However, a model for the interaction of NaH 2 AsO 3 with closely spaced thiols in steroid receptor was proposed [11] (A in Fig. 1), while the phenyl dithioarsonate adduct of DHLA has been established as having a six-membered ring, (B in Fig. 1) [14,49]. The formula for the product of the reaction of BAL with lewisite was proposed by Peters (C in Fig. 1) [34,47] and the feasibility of forming a five-membered ring was proven with the adduct (D in Fig. 1) by X-ray and by 1 H and 13 C NMR for other organoarsenicals [1]. Because arsenite forms a stronger complex with BAL than with 1,3-dithioglycerol [50], the reversal of the inhibition of DHLA by arsenite and lewisite after administration of BAL can be understood. Antimony(III) resembles As(III) in its chemistry and biochemistry in that it has an affinity for -SH groups. Its sodium and potassium tartrate salts are powerful emetics [19]. These two salts and other antimoni...

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Section: Reactions Of Bal With M(iii) (M = As Sb Bi) Compounds Thementioning

confidence: 99%

“…2). Examples of E with 1,2-ethanedithiol are known with M = As, L = Cl [7,41], with M = Sb, L = Cl [12] and M = Bi, L = Cl [3,35] and with toluene-3,4-dithiol (H 2 tdt) with M = As, Sb, Bi, L = Cl [26,35]. With a 2:3 metal:dithiol molar ratio, compound H (Fig.…”

Section: Introductionmentioning

confidence: 99%

The reaction of British Anti-Lewisite (dimercaprol) with As(III), Sb(III), and Bi(III) oxides and salts

Ioannou

Vachliotis

Kouli

2013

Main Group Chemistry

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“…55 Unlike the acyclic analogues (XXXII) derived from monothiols they show great stability towards hydrolysis 56 (though cleavage to the dithiol can be effected with sodium-ethanol-ammonia) 4 and this property forms the basis of the chemotherapeutic use of BAL for the removal of arsenic from the body, since the dithiol is thereby able to abstract the metal from the less stable compounds formed between the arsenical and the thiol groups in the tissue proteins. Regeneration of the carbonyl compound can usually be effected with mercuric chloride, 50 though recovery of the dithiol may be far from quantitative.…”

Section: Reactions With Carbonyl Groupsmentioning

confidence: 99%