Thietan
Structural formula | ||||||||||||||||
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General | ||||||||||||||||
Surname | Thietan | |||||||||||||||
other names |
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Molecular formula | C 3 H 6 S | |||||||||||||||
Brief description |
colorless liquid |
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properties | ||||||||||||||||
Molar mass | 74.14 g mol −1 | |||||||||||||||
Physical state |
liquid |
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density |
1.028 g cm −3 (20 ° C) |
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Melting point |
−73 ° C |
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boiling point |
94 ° C |
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Vapor pressure |
199 h Pa (48 ° C) |
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solubility |
soluble in ethanol, benzene |
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Refractive index |
1.510 (20 ° C) |
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safety instructions | ||||||||||||||||
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Thermodynamic properties | ||||||||||||||||
ΔH f 0 |
24.7 kJ / mol |
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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 .
A better synthesis route is given by the reaction between 1,3-dibromopropane and sodium sulfide .
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 .
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 .