Thietan

Structural formula
General
Surname	Thietan
other names	Thiacyclobutane; Trimethylene sulfide;
Molecular formula	C 3 H 6 S
Brief description	colorless liquid
External identifiers / databases
EC number	206-015-0
ECHA InfoCard	100.005.469
PubChem	9251
Wikidata	Q127300
properties
Molar mass	74.14 g mol −1
Physical state	liquid
density	1.028 g cm −3 (20 ° C)
Melting point	−73 ° C
boiling point	94 ° C
Vapor pressure	199 h Pa (48 ° C)
solubility	soluble in ethanol, benzene
Refractive index	1.510 (20 ° C)
safety instructions
H and P phrases	H: 225-302
	P: 210
Thermodynamic properties
ΔH f 0	24.7 kJ / mol
	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

Thietane , also called trimethylene sulfide , is the simplest sulfur-containing saturated four-membered heterocycle .

presentation

Thietane can be obtained in very poor yield from the reaction between 1,3-dioxan-2-one and potassium thiocyanate . Potassium cyanate and carbon dioxide are produced as by-products .

{\ displaystyle \ mathrm {C_ {4} H_ {6} O_ {3} + \ KSCN \ longrightarrow \ C_ {3} H_ {6} S + \ KOCN + \ CO_ {2}}}

A better synthesis route is given by the reaction between 1,3-dibromopropane and sodium sulfide .

{\ displaystyle \ mathrm {Br {-} (CH_ {2}) _ {3} {-} Br + \ Na_ {2} S \ longrightarrow \ C_ {3} H_ {6} S + 2 \ NaBr}}

properties

Thietane is a colorless, unpleasantly smelling liquid that boils at 94.8 ° C under normal pressure. According to Antoine, the vapor pressure function results from log ₁₀ (P) = A− (B / (T + C)) (P in bar, T in K) with A = 4.14157, B = 1321.331 and C = −48.637 in the temperature range from 321.5 to 404.8 K. In the solid phase, two polymorphic crystal forms are formed, where crystal form II changes to crystal form I at −96 ° C. The melting point is then −73 ° C. The molecule is not built perfectly square, but has a distorted structure. The bond angle at the sulfur is 78 °, while the opposite carbon has a bond angle of 97 °. The CS bond length is 185.1 pm , the C – C bond length 154.9 pm.

Reactions

Thietane reacts with nucleophiles to open a ring. For example, the reaction with n -BuLi forms an unsymmetrical thioether .

{\ displaystyle \ mathrm {C_ {3} H_ {6} S + \ C_ {4} H_ {9} Li \ longrightarrow \ C_ {4} H_ {9} -S-C_ {3} H_ {7}}}

The reaction with elemental halogens enables the representation of halogenated open-chain disulfides at both chain ends .

Individual evidence

↑ ^a ^b ^c ^d data sheet Trimethylene sulfide from Sigma-Aldrich , accessed on April 24, 2011 ( PDF ).
↑ ^a ^b ^c ^d ^e entry on Thietane. In: Römpp Online . Georg Thieme Verlag, accessed on June 19, 2014.
^ DW Scott, HL Finke, WN Hubbard, JP McCullough, C. Katz, ME Gross, JF Messerly, RE Pennington, G. Waddington in: J. Am. Chem. Soc. 1953, 75, 2795-2800. doi : 10.1021 / ja01108a001
↑ David R. Lide (Ed.): CRC Handbook of Chemistry and Physics . 90th edition. (Internet version: 2010), CRC Press / Taylor and Francis, Boca Raton, FL, Standard Thermodynamic Properties of Chemical Substances, pp. 5-24.
↑ S. Searles, EF Lutz in: A new synthesis of small ring cyclic sulfides J. Am. Chem. Soc. 1958, 80, 3168. doi : 10.1021 / ja01545a071
↑ K. Nagasawa, A. Yoneta: Chemistry. II. Use of Dimethyl Sulfoxide - a Facile Synthesis of Cyclic Sulfides in Chem. Pharm. Bull. 1985 , 33 , 5048-5052, doi : 10.1248 / cpb.33.5048 , pdf .
↑ CRC Handbook of Data on Organic Compounds, 2nd Edition, Weast, RC and Grasselli, JG, ed (s)., CRC Press, Inc., Boca Raton, FL, 1989, 1.
^ Osborn, AG; Douslin, DR: Vapor Pressure Relations of 36 Sulfur Compounds Present in Petroleum in J. Chem. Eng. Data , 1966, 11, 4, 502-509, doi : 10.1021 / je60031a014 .
↑ ^a ^b Scott, DW; Finke, HL; Hubbard, WN; McCullough, JP; Katz, C .; Gross, ME; Messerly, JF; Pennington, RE; Waddington, G .: Thiacyclobutane: heat capacity, heats of transition, fusion and vaporization, vapor pressure, entropy, heat of formation and thermodynamic functions in J. Am. Chem. Soc. , 1953, 75, 2795-2800, doi : 10.1021 / ja01108a001 .
↑ Goldish in: J. Chem. Educ. 1959, 36, 408-411. ISSN 0021-9584
^ FG Bordwell, HM Andersen, MP Burnett: The reaction of thiacyclopropanes and thiacyclobutanes with organolithium compounds , in: J. Am. Chem. Soc. , 1954 , 76 , 1082-1085; doi : 10.1021 / ja01633a045 .
^ JM Stewart, CH Burnside: Reactions of trimethylenesulfide with chlorine and bromine , in: J. Am. Chem. Soc. , 1953 , 75 , 243-244; doi : 10.1021 / ja01097a517 .

[sigma-1] ta sheet Trimethylene sulfide from Sigma-Aldrich , accessed on April 24, 2011 ( PDF ).

[Römpp-2] ↑ ^a ^b ^c ^d ^e entry on Thietane. In: Römpp Online . Georg Thieme Verlag, accessed on June 19, 2014.

[3] DW Scott, HL Finke, WN Hubbard, JP McCullough, C. Katz, ME Gross, JF Messerly, RE Pennington, G. Waddington in: J. Am. Chem. Soc. 1953, 75, 2795-2800. doi : 10.1021 / ja01108a001

[CRC90_5_24-4] David R. Lide (Ed.): CRC Handbook of Chemistry and Physics . 90th edition. (Internet version: 2010), CRC Press / Taylor and Francis, Boca Raton, FL, Standard Thermodynamic Properties of Chemical Substances, pp. 5-24.

[5] S. Searles, EF Lutz in: A new synthesis of small ring cyclic sulfides J. Am. Chem. Soc. 1958, 80, 3168. doi : 10.1021 / ja01545a071

[6] K. Nagasawa, A. Yoneta: Chemistry. II. Use of Dimethyl Sulfoxide - a Facile Synthesis of Cyclic Sulfides in Chem. Pharm. Bull. 1985 , 33 , 5048-5052, doi : 10.1248 / cpb.33.5048 , pdf .

[7] CRC Handbook of Data on Organic Compounds, 2nd Edition, Weast, RC and Grasselli, JG, ed (s)., CRC Press, Inc., Boca Raton, FL, 1989, 1.

[8] Osborn, AG; Douslin, DR: Vapor Pressure Relations of 36 Sulfur Compounds Present in Petroleum in J. Chem. Eng. Data , 1966, 11, 4, 502-509, doi : 10.1021 / je60031a014 .

[Scott-9] Scott, DW; Finke, HL; Hubbard, WN; McCullough, JP; Katz, C .; Gross, ME; Messerly, JF; Pennington, RE; Waddington, G .: Thiacyclobutane: heat capacity, heats of transition, fusion and vaporization, vapor pressure, entropy, heat of formation and thermodynamic functions in J. Am. Chem. Soc. , 1953, 75, 2795-2800, doi : 10.1021 / ja01108a001 .

[10] Goldish in: J. Chem. Educ. 1959, 36, 408-411. ISSN 0021-9584

[11] FG Bordwell, HM Andersen, MP Burnett: The reaction of thiacyclopropanes and thiacyclobutanes with organolithium compounds , in: J. Am. Chem. Soc. , 1954 , 76 , 1082-1085; doi : 10.1021 / ja01633a045 .

[12] JM Stewart, CH Burnside: Reactions of trimethylenesulfide with chlorine and bromine , in: J. Am. Chem. Soc. , 1953 , 75 , 243-244; doi : 10.1021 / ja01097a517 .