Trichloromethanesulfenyl chloride

Structural formula
General
Surname	Trichloromethanesulfenyl chloride
other names	Trichloromethylsulfenyl chloride; Trichloromethyl sulfur chloride; Trichloromethanesulfenic acid chloride; Perchloromethyl mercaptan; Thiocarbonyl tetrachloride; Trichloromethyl sulfochloride; Chloroform thiohypochlorite;
Molecular formula	CCl 4 S
Brief description	yellowish, oily, foul-smelling liquid
External identifiers / databases
EC number	209-840-4
ECHA InfoCard	100,008,948
PubChem	11666
Wikidata	Q680191
properties
Molar mass	185.89 g mol −1
Physical state	liquid
density	1.69 g cm −3 (20 ° C)
Melting point	−78 ° C
boiling point	147-149 ° C
Vapor pressure	2.36 h Pa at 20 ° C
solubility	almost insoluble in water
Refractive index	1.5395
safety instructions
H and P phrases	H: 301-312-330-314
	P: 280-301 + 330 + 331-310-302 + 352-304 + 340-305 + 351 + 338-310
MAK	Switzerland: 0.1 ml m −3 or 0.8 mg m −3
Toxicological data	296 mg m −3 2 h −1 ( LC 50 , mouse , inh. ) ; 400 mg kg −1 ( LD 50 , mouse , oral ) ; 11 ppm 1h −1 ( LD 50 , rat , inh. ) ; 82.6 mg kg −1 ( LD 50 , rat , oral ) ;
	As far as possible and customary, SI units are used. Unless otherwise noted, the data given apply to standard conditions . Refractive index: Na-D line , 20 ° C

Trichloromethanesulfenyl chloride is a highly toxic chemical compound with the molecular formula CCl ₄ S.

Presentation and extraction

The compound can be prepared from the reaction of carbon disulfide with molecular chlorine in the presence of iodine or hydrogen chloride . Further synthesis possibilities exist in the chlorination of dimethyl sulfide or of thiophosgene .

properties

Trichloromethanesulfenyl chloride is a foul smelling, toxic liquid that boils at 147–149 ° C. In benzene it has a dipole moment of 0.65 D .

use

The substance can be used for the synthesis of thiophosgene . For this purpose, it is with iron (III) chloride - catalyst at 140 ° C in xylene implemented.

Trichloromethanesulfenyl chloride was used under the code name " Clairsite " by French and Russian armed forces as a chemical warfare agent during the First World War .

The dichlorofluoromethylsulfenyl chloride , which is required for the production of the fungicides dichlofluanid and tolylfluanid , can be obtained through a chlorine-fluorine exchange using mercury (II) fluoride or silver (I) fluoride .

safety instructions

Trichloromethanesulfenyl chloride can be absorbed through the respiratory tract, dermally or orally. It irritates the eyes, throat, bronchi and alveoli. It causes liver and kidney damage in the human organism. Animal experiments with rats and mice showed high inhalation and oral toxicity with symptoms such as diarrhea, skin irritation and changes, and dyspnoea.

Individual evidence

↑ ^a ^b ^c ^d ^e ^f ^g ^h Entry on trichloromethylsulfenyl chloride in the GESTIS substance database of the IFA , accessed on January 9, 2019(JavaScript required) .
^ IB Douglass, FT Martin, R. Addor: Sulfenyl Chloride studies. II. Mono-, di-, and tri-chloromethanesulfenyl Chlorides and Certain of their Derivatives , in: J. Org. Chem. , 1951 , 16 , pp. 1297-1302, doi : 10.1021 / jo50002a018 .
↑ Swiss Accident Insurance Fund (Suva): Limit values - current MAK and BAT values (search for 594-42-3 or trichloromethanesulfenyl chloride ), accessed on November 2, 2015.
↑ ^a ^b Toxicometric parameter of Industrial Toxic Chemicals Under Single Exposure, Izmerov, NF, et al., Moscow, Center of International Projects, GKNT, p 97 1982.
↑ ^a ^b ^c ^d ^e Entry on trichloromethanesulfenyl chloride in the ChemIDplus database of the United States National Library of Medicine (NLM) .
^ ^A ^b National Technical Information Service. Vol. OTS0533569.
↑ ^a ^b Toxicology and Applied Pharmacology . Vol. 42, p. 417, 1977.
↑ ^a ^b Sbornik Vysledku Toxixologickeho Vysetreni Latek A Pripravku, Marhold, JV, Institut Pro Vychovu Vedoucicn Pracovniku Chemickeho Prumyclu Praha, Czechoslovakia, p. 13, 1972.
↑ W. Autenrieth, H. Hefner: About experiments with thiophosgene , in: Chem. Ber. , 1925 , 58 , pp. 2151-2156, doi : 10.1002 / cber.19250580935 .
↑ GKS Prakash, J. Hu, J. Simon, DR Bellew, GA Olah: Preparation of α, α-difluoroalkanesulfonic acids in J. Fluorine Chem. , 2004 , 125 , 595-602, doi : 10.1016 / j.jfluchem. 2003.11 .031 .
↑ Patent DE Schering 416,603th
↑ JW James: The action of chlorine on organic thiocyanates. Part I. Methyl thiocyanate in J. Chem. Soc. , 1887 , 51 , 268-274, doi : 10.1039 / CT8875100268 .
↑ P. Klason: About some sulfur-containing derivatives of carbonic acid ester in Chem. Ber. , 1887 , 20 , 2384-2385, doi : 10.1002 / cber.18870200256 .
^ MT Rogers and KJ Gross: The Electric Moments of Some Sulfur and Selenium Compounds , in: J. Am. Chem. Soc. , 1952 , 74 , pp. 5294-5296, doi : 10.1021 / ja01141a018 .
↑ EF Orwoll, US Patent 2,668,853th
^ AT Schäfer: Lexicon of biological and chemical warfare agents. Köster, Berlin, 2003. ( ISBN 3-89574-515-4 ).
↑ Kober, E .: A New Class of Sulfenyl Derivatives; Perhalogenated Aliphatic Sulfenyl Fluorides in J. Am. Chem. Soc. 81 (1959) 4810-4812, doi : 10.1021 / ja01527a016 .
↑ Ham, NS: Dichlorofluoromethanesulfenyl chloride in J. Am. Chem. Soc. 83 (1961) 751-752, doi : 10.1021 / ja01464a052 .
↑ Jürgen Fritze: The medical assessment: legal questions, functional tests, assessments. 7th edition, Springer, 2008, ISBN 978-3-7985-1563-5 , p. 296.

[GESTIS-1] ↑ ^a ^b ^c ^d ^e ^f ^g ^h Entry on trichloromethylsulfenyl chloride in the GESTIS substance database of the IFA , accessed on January 9, 2019(JavaScript required) .

[2] IB Douglass, FT Martin, R. Addor: Sulfenyl Chloride studies. II. Mono-, di-, and tri-chloromethanesulfenyl Chlorides and Certain of their Derivatives , in: J. Org. Chem. , 1951 , 16 , pp. 1297-1302, doi : 10.1021 / jo50002a018 .

[3] Swiss Accident Insurance Fund (Suva): Limit values - current MAK and BAT values (search for 594-42-3 or trichloromethanesulfenyl chloride ), accessed on November 2, 2015.

[tox1-4] Toxicometric parameter of Industrial Toxic Chemicals Under Single Exposure, Izmerov, NF, et al., Moscow, Center of International Projects, GKNT, p 97 1982.

[chemid-5] Entry on trichloromethanesulfenyl chloride in the ChemIDplus database of the United States National Library of Medicine (NLM) .

[tox2-6] A ^b National Technical Information Service. Vol. OTS0533569.

[tox3-7] Toxicology and Applied Pharmacology . Vol. 42, p. 417, 1977.

[tox4-8] Sbornik Vysledku Toxixologickeho Vysetreni Latek A Pripravku, Marhold, JV, Institut Pro Vychovu Vedoucicn Pracovniku Chemickeho Prumyclu Praha, Czechoslovakia, p. 13, 1972.

[9] W. Autenrieth, H. Hefner: About experiments with thiophosgene , in: Chem. Ber. , 1925 , 58 , pp. 2151-2156, doi : 10.1002 / cber.19250580935 .

[10] GKS Prakash, J. Hu, J. Simon, DR Bellew, GA Olah: Preparation of α, α-difluoroalkanesulfonic acids in J. Fluorine Chem. , 2004 , 125 , 595-602, doi : 10.1016 / j.jfluchem. 2003.11 .031 .

[11] Patent DE Schering 416,603th

[12] JW James: The action of chlorine on organic thiocyanates. Part I. Methyl thiocyanate in J. Chem. Soc. , 1887 , 51 , 268-274, doi : 10.1039 / CT8875100268 .

[13] P. Klason: About some sulfur-containing derivatives of carbonic acid ester in Chem. Ber. , 1887 , 20 , 2384-2385, doi : 10.1002 / cber.18870200256 .

[14] MT Rogers and KJ Gross: The Electric Moments of Some Sulfur and Selenium Compounds , in: J. Am. Chem. Soc. , 1952 , 74 , pp. 5294-5296, doi : 10.1021 / ja01141a018 .

[15] EF Orwoll, US Patent 2,668,853th

[16] AT Schäfer: Lexicon of biological and chemical warfare agents. Köster, Berlin, 2003. ( ISBN 3-89574-515-4 ).

[17] Kober, E .: A New Class of Sulfenyl Derivatives; Perhalogenated Aliphatic Sulfenyl Fluorides in J. Am. Chem. Soc. 81 (1959) 4810-4812, doi : 10.1021 / ja01527a016 .

[18] Ham, NS: Dichlorofluoromethanesulfenyl chloride in J. Am. Chem. Soc. 83 (1961) 751-752, doi : 10.1021 / ja01464a052 .

[19] Jürgen Fritze: The medical assessment: legal questions, functional tests, assessments. 7th edition, Springer, 2008, ISBN 978-3-7985-1563-5 , p. 296.