In organic chemistry, episulfides are a class of organic compounds that contain a saturated, heterocyclic ring consisting of two carbon atoms and one sulfur atom. It is the sulfur analogue of an epoxide or aziridine. They are also known as thiiranes, olefin sulfides, thioalkylene oxides, and thiacyclopropanes. Episulfides are less common and generally less stable than epoxides. The most common derivative is ethylene sulfide (C2H4S). [1] [2]
According to electron diffraction, the C−C and C−S distances in ethylene sulfide are respectively 1.473 and 1.811 Å. The C−C−S and C−S−C angles are respectively 66.0 and 48.0°. [1]
A number of chemists in the early 1900s, including Staudinger and Pfenninger (1916), as well as Delepine (1920) studied episulfides. [3] I 1934 Dachlauer and Jackel devised a general synthesis of episulfides from epoxides using alkali thiocyanates and thiourea.
Following the lead of Dachlauer and Jackel, contemporary routes to episulfides utilize a two-step method, converting an olefin to an epoxide followed by thiation using thiocyanate or thiourea. [3]
Episulfides can also be prepared from cyclic carbonates, hydroxy mercaptans, hydroxyalkyl halides, dihaloalkanes, and halo mercaptans. [3] The reaction of ethylene carbonate and KSCN gives ethylene sulfide: [4]
The metal-catalyzed reaction of sulfur with alkenes has been demonstrated. [5]
Common uses of episulfides in both academic and industrial settings most often involve their use as monomers in polymerization reactions. Episulfides have an innate ring strain due to the nature of three-membered rings. Therefore, most reactions of episulfides involve ring-opening. Most commonly, nucleophiles are employed for the ring-opening process. [3] For terminal episulfide, nucleophiles attack the primary carbon. Nucleophiles include hydrides, thiolates, alkoxides, amines, and carbanions.
Thiiranes occur very rarely in nature and are of no significance medicinally. [1]
Very few commercial applications exist, although the polymerization of episulfide has been reported. [6]
Dithiiranes are three membered rings containing two sulfur atoms and one carbon. One example was prepared by oxidation of a 1,3-dithietane. [7]
In organic chemistry, an alkene is a hydrocarbon containing a carbon–carbon double bond. The double bond may be internal or in the terminal position. Terminal alkenes are also known as α-olefins.
In chemistry, an ester is a compound derived from an acid in which the hydrogen atom (H) of at least one acidic hydroxyl group of that acid is replaced by an organyl group. Analogues derived from oxygen replaced by other chalcogens belong to the ester category as well. According to some authors, organyl derivatives of acidic hydrogen of other acids are esters as well, but not according to the IUPAC.
In organic chemistry, an epoxide is a cyclic ether, where the ether forms a three-atom ring: two atoms of carbon and one atom of oxygen. This triangular structure has substantial ring strain, making epoxides highly reactive, more so than other ethers. They are produced on a large scale for many applications. In general, low molecular weight epoxides are colourless and nonpolar, and often volatile.
In chemistry, an electrophile is a chemical species that forms bonds with nucleophiles by accepting an electron pair. Because electrophiles accept electrons, they are Lewis acids. Most electrophiles are positively charged, have an atom that carries a partial positive charge, or have an atom that does not have an octet of electrons.
Thiophene is a heterocyclic compound with the formula C4H4S. Consisting of a planar five-membered ring, it is aromatic as indicated by its extensive substitution reactions. It is a colorless liquid with a benzene-like odor. In most of its reactions, it resembles benzene. Compounds analogous to thiophene include furan (C4H4O), selenophene (C4H4Se) and pyrrole (C4H4NH), which each vary by the heteroatom in the ring.
In organic chemistry, a carbene is a molecule containing a neutral carbon atom with a valence of two and two unshared valence electrons. The general formula is R−:C−R' or R=C: where the R represents substituents or hydrogen atoms.
Polysulfides are a class of chemical compounds derived from anionic chains of sulfur atoms. There are two main classes of polysulfides: inorganic and organic. The inorganic polysulfides have the general formula S2−
n. These anions are the conjugate bases of polysulfanes H2Sn. Organic polysulfides generally have the formulae R1SnR2, where R = alkyl or aryl.
Thiourea is an organosulfur compound with the formula SC(NH2)2 and the structure H2N−C(=S)−NH2. It is structurally similar to urea, except that the oxygen atom is replaced by a sulfur atom ; however, the properties of urea and thiourea differ significantly.
In organic chemistry, the Michael reaction or Michael 1,4 addition is a reaction between a Michael donor and a Michael acceptor to produce a Michael adduct by creating a carbon-carbon bond at the acceptor's β-carbon. It belongs to the larger class of conjugate additions and is widely used for the mild formation of carbon-carbon bonds.
In organic chemistry, olefin metathesis is an organic reaction that entails the redistribution of fragments of alkenes (olefins) by the scission and regeneration of carbon-carbon double bonds. Because of the relative simplicity of olefin metathesis, it often creates fewer undesired by-products and hazardous wastes than alternative organic reactions. For their elucidation of the reaction mechanism and their discovery of a variety of highly active catalysts, Yves Chauvin, Robert H. Grubbs, and Richard R. Schrock were collectively awarded the 2005 Nobel Prize in Chemistry.
In organic chemistry, hydroboration refers to the addition of a hydrogen-boron bond to certain double and triple bonds involving carbon. This chemical reaction is useful in the organic synthesis of organic compounds.
Ring-closing metathesis (RCM) is a widely used variation of olefin metathesis in organic chemistry for the synthesis of various unsaturated rings via the intramolecular metathesis of two terminal alkenes, which forms the cycloalkene as the E- or Z- isomers and volatile ethylene.
The Shi epoxidation is a chemical reaction described as the asymmetric epoxidation of alkenes with oxone and a fructose-derived catalyst (1). This reaction is thought to proceed via a dioxirane intermediate, generated from the catalyst ketone by oxone. The addition of the sulfate group by the oxone facilitates the formation of the dioxirane by acting as a good leaving group during ring closure. It is notable for its use of a non-metal catalyst and represents an early example of organocatalysis. The reaction was first discovered by Yian Shi of Colorado State University in 1996.
A halonium ion is any onium ion containing a halogen atom carrying a positive charge. This cation has the general structure R−−R′ where X is any halogen and no restrictions on R, this structure can be cyclic or an open chain molecular structure. Halonium ions formed from fluorine, chlorine, bromine, and iodine are called fluoronium, chloronium, bromonium, and iodonium, respectively. The 3-membered cyclic variety commonly proposed as intermediates in electrophilic halogenation may be called haliranium ions, using the Hantzsch-Widman nomenclature system.
The Ramberg–Bäcklund reaction is an organic reaction converting an α-halo sulfone into an alkene in presence of a base with extrusion of sulfur dioxide. The reaction is named after the two Swedish chemists Ludwig Ramberg and Birger Bäcklund. The carbanion formed by deprotonation gives an unstable episulfone that decomposes with elimination of sulfur dioxide. This elimination step is considered to be a concerted cycloelimination.
In organic chemistry, aziridines are organic compounds containing the aziridine functional group, a three-membered heterocycle with one amine and two methylene bridges. The parent compound is aziridine, with molecular formula C2H4NH. Several drugs feature aziridine rings, including mitomycin C, porfiromycin, and azinomycin B (carzinophilin).
The Boord olefin synthesis is an organic reaction forming alkenes from ethers carrying a halogen atom 2 carbons removed from the oxygen atom (β-halo-ethers) using a metal such as magnesium or zinc. The reaction, discovered by Cecil E. Boord in 1930 is a classic named reaction with high yields and broad scope.
An oxaziridine is an organic molecule that features a three-membered heterocycle containing oxygen, nitrogen, and carbon. In their largest application, oxaziridines are intermediates in the industrial production of hydrazine. Oxaziridine derivatives are also used as specialized reagents in organic chemistry for a variety of oxidations, including alpha hydroxylation of enolates, epoxidation and aziridination of olefins, and other heteroatom transfer reactions. Oxaziridines also serve as precursors to amides and participate in [3+2] cycloadditions with various heterocumulenes to form substituted five-membered heterocycles. Chiral oxaziridine derivatives effect asymmetric oxygen transfer to prochiral enolates as well as other substrates. Some oxaziridines also have the property of a high barrier to inversion of the nitrogen, allowing for the possibility of chirality at the nitrogen center.
An insertion reaction is a chemical reaction where one chemical entity interposes itself into an existing bond of typically a second chemical entity e.g.:
Allyl glycidyl ether is an organic compound used in adhesives and sealants and as a monomer for polymerization reactions. It is formally the condensation product of allyl alcohol and glycidol via an ether linkage. Because it contains both an alkene and an epoxide group, either group can be reacted selectively to yield a product where the other functional group remains intact for future reactions.
