Carbyl sulfate

Structural formula
General
Surname	Carbyl sulfate
other names	1,3,2,4-dioxadithiane-2,2,4,4-tetraoxide
Molecular formula	C 2 H 4 O 6 S 2
Brief description	colorless, crystalline solid that dissolves in moist air
External identifiers / databases
EC number	207-968-5
ECHA InfoCard	100.007.244
PubChem	68151
Wikidata	Q1035566
properties
Molar mass	188.18 g mol −1
Physical state	firmly
density	1.85 g cm −3
Melting point	102-108 ° C
boiling point	327.5 ° C at 1013 hPa
safety instructions
GHS hazard labeling ; no classification available
GHS hazard labeling ; no classification available
	As far as possible and customary, SI units are used. Unless otherwise noted, the data given apply to standard conditions .

Carbyl sulfate (1,3,2,4-dioxadithiane-2,2,4,4-tetroxide) is an addition compound of ethylene and sulfur trioxide , which was first used in 1838 by Regnault and in 1839 by Heinrich Gustav Magnus as a product of the conversion of anhydrous ethanol and anhydrous sulfuric acid reported.

Extraction and presentation

Carbyl sulfate is formed in the strongly exothermic ( reaction enthalpy approx. 3,350 kJ / kg) reaction of ethylene and sulfur trioxide in the vapor phase in almost quantitative yield.

The industrial production process is carried out in one or two tube bundle reactors connected in series with dry ethylene and gaseous sulfur trioxide in a mixing ratio of 1: 2.2 to 1: 2.4 at 115 ° C to 140 ° C and liquid carbyl sulfate is continuously drawn off at the bottom of the reactor. The reaction conversion is already at least 80% in the first reactor. Disulfonic acid or oleum or chlorosulfonic acid can also be used as sulfonating agents; instead of ethylene, compounds which form ethylene with the sulfonating agent, e.g. B. ethanol or diethyl ether .

properties

Carbyl sulfate is a colorless, crystalline, hygroscopic substance with a pungent odor of sulfur dioxide and high reactivity, which can lead to explosive decomposition when heated above 170 ° C. In accordance with DS Breslow (107.5–109 ° C), the carbyl sulphate obtained as a water-clear melt in the industrial process has a melting range of 102 to 108 ° C. The melting point of approx. 80 ° C given as early as 1839 is due to the adhering sulfur trioxide. Due to its unpleasant properties, carbyl sulfate is difficult to handle and is usually not isolated, but processed directly into secondary products.

use

Carbyl sulfate is used as the starting material for vinyl sulfonic acid or sodium vinyl sulfonate ( English sodium vinyl sulfonate , SVS), which are important activated alkenes and u. a. are used as anionic comonomers. By nucleophilic addition to the activated double bond of vinyl sulfonic acid and its derivatives, a number of functional compounds with diverse applications are accessible.

Derived connections

Vinyl sulfonic acid
Sodium vinyl sulfonate
Isethionic acid
Sodium isethionate

Individual evidence

↑ ^a ^b ^c ^d patent application DE2509738A1 : Process for the production of carbyl sulfate. Registered on March 6, 1975 , published on September 23, 1976 , applicant: BASF, inventor: Rudolf Irnich, Rolf Schneider. ‌
↑ Adolph Strecker: Short textbook of organic chemistry . 4th improved edition, printed and published by Friedrich Vieweg and Son, Braunschweig 1863, p. 336.
↑ ^a ^b Entry 1,3,2,4-Dioxadithiane, 2,2,4,4-tetraoxide from Guidechem , accessed on June 21, 2013.
↑ This substance has either not yet been classified with regard to its hazardousness or a reliable and citable source has not yet been found.
^ Regnault, Ann., 25 , 32 (1838).
↑ Magnus, Ann., 31 , 249 (1839) and G. Magnus, "Ueber das Carbylsulfat und die Aethionäure", Pogg. Ann. (= Annalen der Physik), XLVII, 609 (1839).
↑ ^a ^b "In memory of Gustav Magnus". After a lecture given on December 14, 1870 at the General Assembly of the German Chemical Society in Berlin, August Wilhelm Hofmanns , Berlin, Ferd. Dümmler's Verlagbuchhandlung, 1871 (p. 32).
↑ ^a ^b ^c ^d David S. Breslow, Robert R. Hough: The Synthesis of Sodium Ethylenesulfonate from Ethylene . In: Journal of the American Chemical Society . tape 79 , no. September 18 , 1957, p. 5000–5002 , doi : 10.1021 / ja01575a046 .

↑ H. Distler: On the chemistry of vinyl sulfonic acid . In: Angewandte Chemie . tape 77 , no. 7 , April 7, 1965, pp. 291-302 , doi : 10.1002 / anie.19650770704 .

[Irnich-1] tent application DE2509738A1 : Process for the production of carbyl sulfate. Registered on March 6, 1975 , published on September 23, 1976 , applicant: BASF, inventor: Rudolf Irnich, Rolf Schneider. ‌

[2] Adolph Strecker: Short textbook of organic chemistry . 4th improved edition, printed and published by Friedrich Vieweg and Son, Braunschweig 1863, p. 336.

[guidechem-3] Entry 1,3,2,4-Dioxadithiane, 2,2,4,4-tetraoxide from Guidechem , accessed on June 21, 2013.

[NV-4] This substance has either not yet been classified with regard to its hazardousness or a reliable and citable source has not yet been found.

[5] Regnault, Ann., 25 , 32 (1838).

[6] Magnus, Ann., 31 , 249 (1839) and G. Magnus, "Ueber das Carbylsulfat und die Aethionäure", Pogg. Ann. (= Annalen der Physik), XLVII, 609 (1839).

[Magnus-7] "In memory of Gustav Magnus". After a lecture given on December 14, 1870 at the General Assembly of the German Chemical Society in Berlin, August Wilhelm Hofmanns , Berlin, Ferd. Dümmler's Verlagbuchhandlung, 1871 (p. 32).

[Breslow-8] David S. Breslow, Robert R. Hough: The Synthesis of Sodium Ethylenesulfonate from Ethylene . In: Journal of the American Chemical Society . tape 79 , no. September 18 , 1957, p. 5000–5002 , doi : 10.1021 / ja01575a046 .

[9] H. Distler: On the chemistry of vinyl sulfonic acid . In: Angewandte Chemie . tape 77 , no. 7 , April 7, 1965, pp. 291-302 , doi : 10.1002 / anie.19650770704 .