Salt rebellion

Organic thiosulfates are salts and esters of organic thiosulfuric acids with the general formula RSSO ₂ X, where R = Alk, Ar; X = OMe (Me - metal), OR. S-alkyl and S-arylthiosulfates of alkali and alkaline earth metals are called Bunte salts in honor of the German chemist-technologist Hans Bunte , who investigated this class of compounds.

Content

Nomenclature

The name of the compound of organic thiosulfates is formed in accordance with the name of the organic radical, to which the suffix "-thiosulfate" is attached, it is necessary to indicate the atom with which the organic radical binds. For example, C ₆ H ₅ SSO ₂ OCH ₃ - S-phenylmethylthiosulfate, C ₂ H ₅ SSO ₂ ONa - S-ethylthiosulfate sodium.

Getting

The synthesis of Bunte salts consists in the interaction of alkyl halides, dialkyl sulfates, alkylaryl sulfonates with alkali metal thiosulfates in equimolar amounts in an aqueous-organic medium (in particular, a 50% ethanol solution):

{\mathsf {AlkX+Na_{2}S_{2}O_{3}\rightarrow AlkSSO_{2}ONa+NaX\ (X=Hal,OSO_{2}OAl,OSO_{2}Ar)}}

{\ displaystyle {\ mathsf {AlkX + Na_ {2} S_ {2} O_ {3} \ rightarrow AlkSSO_ {2} ONa + NaX \ (X = Hal, OSO_ {2} OAl, OSO_ {2} Ar)}} }

Another method of synthesizing Bunte salts is to attach alkali metal thiosulfates to activated alkenes or quinones in an acidic environment:

{\mathsf {CH_{3}OSO_{2}CH=CH_{2}+Na_{2}S_{2}O_{3}{\xrightarrow[{}]{H^{+}}}CH_{3}OSO_{2}CH_{2}CH_{2}SSO_{2}ONa}}

{\ displaystyle {\ mathsf {CH_ {3} OSO_ {2} CH = CH_ {2} + Na_ {2} S_ {2} O_ {3} {\ xrightarrow [{}] {H ^ {+}}} CH_ {3} OSO_ {2} CH_ {2} CH_ {2} SSO_ {2} ONa}}}

Arylthiosulfates are synthesized by the reaction of diaryldisulfides with potassium hydrosulfite:

{\mathsf {2ArSSAr+6KHSO_{3}\rightarrow 4ArSSO_{3}OK+K_{2}S_{2}O_{3}+3H_{2}O}}

{\ displaystyle {\ mathsf {2ArSSAr + 6KHSO_ {3} \ rightarrow 4ArSSO_ {3} OK + K_ {2} S_ {2} O_ {3} + 3H_ {2} O}}}

Properties

Bunte salts are solid crystalline substances that are highly soluble in water.

The chemical properties of organic thiosulfates are determined by the presence of the SS disulfide group, which is easily broken down by electrophilic and nucleophilic reagents. With acid hydrolysis of organic thiosulfates, thiols are formed, with alkaline - disulfides:

{\mathsf {NaOSO_{2}SCH_{2}COOH{\xrightarrow[{-NaHSO_{4}}]{H_{2}O,H^{+}}}HSCH_{2}COOH}}

{\ displaystyle {\ mathsf {NaOSO_ {2} SCH_ {2} COOH {\ xrightarrow [{- NaHSO_ {4}}] {H_ {2} O, H ^ {+}}} HSCH_ {2} COOH}}}

{\mathsf {RSSO_{2}ONa{\xrightarrow[{-NaHSO_{4}}]{H_{2}O,OH^{-}}}RS^{-}{\xrightarrow[{-NaSO_{3}^{-}}]{RSSO_{2}ONa}}RSSR}}

{\ displaystyle {\ mathsf {RSSO_ {2} ONa {\ xrightarrow [{- NaHSO_ {4}}] {H_ {2} O, OH ^ {-}}} RS ^ {-} {\ xrightarrow [{- NaSO_ {3} ^ {-}}] {RSSO_ {2} ONa}} RSSR}}}

The interaction of organic thiosulfates with thiolates is used in the synthesis of asymmetric disulfides:

{\mathsf {CH_{3}SSO_{2}ONa+NaSC_{6}H_{5}\rightarrow CH_{3}SSC_{6}H_{5}+Na_{2}SO_{3}}}

{\ displaystyle {\ mathsf {CH_ {3} SSO_ {2} ONa + NaSC_ {6} H_ {5} \ rightarrow CH_ {3} SSC_ {6} H_ {5} + Na_ {2} SO_ {3}}} }

Depending on the oxidizing agent, organic thiosulfates are oxidized to alkanesulfonic acids, alkanesulfonyl halides or dialkyl disulfides:

{\mathsf {CH_{3}SSO_{2}ONa{\xrightarrow[{}]{HNO_{3}}}RSO_{2}OH}}

{\ displaystyle {\ mathsf {CH_ {3} SSO_ {2} ONa {\ xrightarrow [{}] {HNO_ {3}}} RSO_ {2} OH}}}

{\mathsf {CH_{3}SSO_{2}ONa{\xrightarrow[{}]{Cl_{2},H_{2}O}}RSO_{2}Cl}}

{\ displaystyle {\ mathsf {CH_ {3} SSO_ {2} ONa {\ xrightarrow [{}] {Cl_ {2}, H_ {2} O}} RSO_ {2} Cl}}}

{\mathsf {CH_{3}SSO_{2}ONa{\xrightarrow[{}]{I_{2},H_{2}O}}RSSR}}

{\ displaystyle {\ mathsf {CH_ {3} SSO_ {2} ONa {\ xrightarrow [{}] {I_ {2}, H_ {2} O}} RSSR}}}

Application

Organic thiosulfates are used in organic synthesis as intermediates in the preparation of various organic sulfur compounds.

Literature

Zefirov N.S. et al. 4 Half-Three // Chemical Encyclopedia. - M .: Big Russian Encyclopedia, 1995 .-- 639 p. - 20,000 copies. - ISBN 5-85270-092-4 .
D. Barton, W. D. Ollis. General Organic Chemistry = Derek Barton, W. David Ollis. Comprehensive Organic Chemistry, vol. 3, Sulfur Compounds. - M .: Chemistry, 1983. - V. 5. - S. 479-480. - 720 s. - 15,000 copies.