Organic sulfide
In
Nomenclature
Sulfides are sometimes called thioethers, especially in the old literature. The two organic substituents are indicated by the prefixes. (CH3)2S is called
The modern systematic nomenclature in chemistry for the trival name thioether is sulfane.[2]
Structure and properties
Sulfide is an angular functional group, the C–S–C angle approaching 90° The C–S bonds are about 180
Sulfides are characterized by their strong odors, which are similar to thiol odor. This odor limits the applications of volatile sulfides. In terms of their physical properties they resemble ethers, but are less volatile, higher melting, and less hydrophilic. These properties follow from the polarizability of the divalent sulfur center, which is greater than that for oxygen in ethers.
Thiophenes
Occurrence and applications
Sulfides are important in biology, notably in the amino acid methionine and the cofactor biotin. Petroleum contains many organosulfur compounds, including sulfides. Polyphenylene sulfide is a useful high temperature plastic. Coenzyme M, CH
3SCH
2CH
2SO−
3, is the precursor to methane (i.e. natural gas) via the process of methanogenesis.
Preparation
Sulfides are typically prepared by
- RBr + HSR' → RSR' + HBr
Such reactions are usually conducted in the presence of a base, which converts the thiol into the more nucleophilic thiolate.[5] Analogously, the reaction of disulfides with organolithium reagents produces thioethers:
- R3CLi + R1S-SR2 → R3CSR1 + R2SLi
Analogous reactions are known starting with Grignard reagents.
Alternatively, sulfides can be synthesized by the addition of a thiol to an alkene in the thiol-ene reaction:
- R-CH=CH2 + H-SR' → R-CH2-CH2-S-R'
This reaction is often catalysed by
Sulfides can also be prepared by many other methods, such as the Pummerer rearrangement. Trialkysulfonium salts react with nucleophiles with a dialkyl sulfide as a leaving group:
- Nu− + R3S+ → Nu-R + R2SR1
This reaction is exploited in biological systems as a means of transferring an
An unusual but well tested method for the synthesis of thioethers involves addition of alkenes, especially ethylene across the S-Cl bond of sulfur dichloride. This method has been used in the production of bis(2-chloroethyl)sulfide, a mustard gas:[7]
- SCl2 + 2 C2H4 → (ClC2H4)2S
Reactions
The
- S(CH3)2 + CH3I → [S(CH3)3]+I−
Sulfides also oxidize easily to sulfoxides (R−S(=O)−R), which can themselves be further oxidized to sulfones (R−S(=O)2−R). Hydrogen peroxide is a typical oxidant—for example, with dimethyl sulfide (S(CH3)2):[9]
- S(CH3)2 + H2O2 → OS(CH3)2 + H2O
- OS(CH3)2 + H2O2 → O2S(CH3)2 + H2O
In analogy to their easy alkylation, sulfides bind to metals to form
Sulfides undergo hydrogenolysis in the presence of certain metals:
- R-S-R' + 2 H2 → RH + R'H + H2S
Raney nickel is useful for stoichiometric reactions in organic synthesis[11] whereas molybdenum-based catalysts are used to "sweeten" petroleum fractions, in the process called hydrodesulfurization.
Unlike
References
- ISBN 0-471-95512-4.
- ISBN 978-3-64256765-0. p. 131:
Individual species of the genus thioether can again most uniformly be named as ...sulfane and ...sulfanyl derivatives, respectively (formerly: ...sulfides and ...thio derivatives, respectively). [...] Cyclic sulfides (thioethers) are treated as heterocycles, in the same way as their ether counterparts. Polysulfides substituted at both ends are named substitutively as ...polysulfanes (formerly: ...polysulfides).
(230 pages) - .
- .
- .
- PMID 20166107.
- ISBN 0-7637-2425-4.
- ^ Brendsma & Arens 1967, p. 596.
- ^ Brendsma & Arens 1967, p. 601.
- ^ Brendsma & Arens 1967, p. 587.
- ^ Brendsma & Arens 1967, pp. 576–578.
- ^ Brendsma & Arens 1967, p. 581.
- ^ Brendsma & Arens 1967, pp. 555–559.
- Brendsma, L.; Arens, J. F. (1967). "The chemistry of thioethers; differences and analogies with ethers". In Patai, Saul (ed.). The Chemistry of the Ether Linkage. The Chemistry of Functional Groups. London: Interscience / William Clowes and Sons. pp. 555–559. LCCN 66-30401.