Thioethers
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Thioethers
In organic chemistry, an organic sulfide (British English sulphide) or thioether is an organosulfur functional group with the connectivity as shown on right. Like many other sulfur-containing compounds, volatile sulfides have foul odors. A sulfide is similar to an ether except that it contains a sulfur atom in place of the oxygen. The grouping of oxygen and sulfur in the periodic table suggests that the chemical properties of ethers and sulfides are somewhat similar, though the extent to which this is true in practice varies depending on the application. Nomenclature Sulfides are sometimes called thioethers, especially in the old literature. The two organic substituents are indicated by the prefixes. (CH3)2S is called dimethylsulfide. Some sulfides are named by modifying the common name for the corresponding ether. For example, C6H5SCH3 is methyl phenyl sulfide, but is more commonly called thioanisole, since its structure is related to that for anisole, C6H5OCH3. The modern ...
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Alkylation
Alkylation is the transfer of an alkyl group from one molecule to another. The alkyl group may be transferred as an alkyl carbocation, a free radical, a carbanion, or a carbene (or their equivalents). Alkylating agents are reagents for effecting alkylation. Alkyl groups can also be removed in a process known as dealkylation. Alkylating agents are often classified according to their nucleophilic or electrophilic character. In oil refining contexts, alkylation refers to a particular alkylation of isobutane with olefins. For upgrading of petroleum, alkylation produces a premium blending stock for gasoline. In medicine, alkylation of DNA is used in chemotherapy to damage the DNA of cancer cells. Alkylation is accomplished with the class of drugs called alkylating antineoplastic agents. Nucleophilic alkylating agents Nucleophilic alkylating agents deliver the equivalent of an alkyl anion ( carbanion). The formal "alkyl anion" attacks an electrophile, forming a new cova ...
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Dimethylsulfide
Dimethyl sulfide (DMS) or methylthiomethane is an organosulfur compound with the formula (CH3)2S. Dimethyl sulfide is a flammable liquid that boils at and has a characteristic disagreeable odor. It is a component of the smell produced from cooking of certain vegetables, notably maize, cabbage, beetroot, and seafoods. It is also an indication of bacterial contamination in malt production and brewing. It is a breakdown product of dimethylsulfoniopropionate (DMSP), and is also produced by the bacterial metabolism of methanethiol. Occurrence and production DMS originates primarily from DMSP, a major secondary metabolite in some marine algae. DMS is the most abundant biological sulfur compound emitted to the atmosphere. Emission occurs over the oceans by phytoplankton. DMS is also produced naturally by bacterial transformation of dimethyl sulfoxide (DMSO) waste that is disposed of into sewers, where it can cause environmental odor problems. DMS is oxidized in the marine atmosphere ...
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Thioanisole
Thioanisole is an organic compound with the formula CH3SC6H5. It is a colorless liquid that is soluble in organic solvents. It is the simplest alkyl– aryl thioether. The name indicates that this compound is the sulfur analogue—the thioether rather than the oxygen-centered ether—of anisole. It can be prepared by methylation of thiophenol. Reactions Alkyllithium reagents deprotonate thioanisole at the methyl group to afford C6H5SCH2Li, a strong nucleophile that can be alkylated to form more complex chains and structures. The resulting homologated thioether can be manipulated in a variety of ways. Oxidation of sulfur via addition of a single oxygen atom gives methyl phenyl sulfoxide Methyl phenyl sulfoxide is the organosulfur compound with the formula CH3S(O)C6H5. A low-melting white solid, it is an oxidized derivative of thioanisole. The compound is a prototypical chiral sulfoxide In organic chemistry, a sulfoxide, also c ..., a reaction useful for titration ...
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Methionine
Methionine (symbol Met or M) () is an essential amino acid in humans. As the precursor of other amino acids such as cysteine and taurine, versatile compounds such as SAM-e, and the important antioxidant glutathione, methionine plays a critical role in the metabolism and health of many species, including humans. It is encoded by the codon AUG. Methionine is also an important part of angiogenesis, the growth of new blood vessels. Supplementation may benefit those suffering from copper poisoning. Overconsumption of methionine, the methyl group donor in DNA methylation, is related to cancer growth in a number of studies. Methionine was first isolated in 1921 by John Howard Mueller. Biochemical details Methionine (abbreviated as Met or M; encoded by the codon AUG) is an α-amino acid that is used in the biosynthesis of proteins. It contains a carboxyl group (which is in the deprotonated −COO− form under biological pH conditions), an amino group (which is in the prot ...
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Tetrahydrothiophene
Tetrahydrothiophene is an organosulfur compound with the formula (CH2)4S. The molecule consists of a five-membered saturated ring with four methylene groups and a sulfur atom. It is the saturated analog of thiophene. It is a volatile, colorless liquid with an intensely unpleasant odor. It is also known as thiophane, thiolane, or THT. While THT is not particularly common, the vitamin biotin is essential for life in aerobic organisms. Synthesis and reactions Tetrahydrothiophene is prepared by the reaction of tetrahydrofuran with hydrogen sulfide. This vapor-phase reaction is catalyzed by alumina and other heterogenous acid catalysts. This compound is a ligand in coordination chemistry, an example being the complex chloro(tetrahydrothiophene)gold(I). Oxidation of THT gives the sulfone sulfolane, which is of interest as a polar, odorless solvent: : Sulfolane is, however, more conventionally prepared from butadiene. Natural occurrence Both unsubstituted and substituted tetra ...
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Thiol
In organic chemistry, a thiol (; ), or thiol derivative, is any organosulfur compound of the form , where R represents an alkyl or other organic substituent. The functional group itself is referred to as either a thiol group or a sulfhydryl group, or a sulfanyl group. Thiols are the sulfur analogue of alcohols (that is, sulfur takes the place of oxygen in the hydroxyl () group of an alcohol), and the word is a blend of "''thio-''" with "alcohol". Many thiols have strong odors resembling that of garlic or rotten eggs. Thiols are used as odorants to assist in the detection of natural gas (which in pure form is odorless), and the "smell of natural gas" is due to the smell of the thiol used as the odorant. Thiols are sometimes referred to as mercaptans () or mercapto compounds, a term introduced in 1832 by William Christopher Zeise and is derived from the Latin ('capturing mercury')''Oxford American Dictionaries'' ( Mac OS X Leopard). because the thiolate group () bonds very str ...
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Methanogenesis
Methanogenesis or biomethanation is the formation of methane coupled to energy conservation by microbes known as methanogens. Organisms capable of producing methane for energy conservation have been identified only from the domain Archaea, a group phylogenetically distinct from both eukaryotes and bacteria, although many live in close association with anaerobic bacteria. Other forms of methane production that are not coupled to ATP synthesis exist within all three domains of life. The production of methane is an important and widespread form of microbial metabolism. In anoxic environments, it is the final step in the decomposition of biomass. Methanogenesis is responsible for significant amounts of natural gas accumulations, the remainder being thermogenic. Biochemistry Methanogenesis in microbes is a form of anaerobic respiration. Methanogens do not use oxygen to respire; in fact, oxygen inhibits the growth of methanogens. The terminal electron acceptor in methanogenesis i ...
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Methane
Methane ( , ) is a chemical compound with the chemical formula (one carbon atom bonded to four hydrogen atoms). It is a group-14 hydride, the simplest alkane, and the main constituent of natural gas. The relative abundance of methane on Earth makes it an economically attractive fuel, although capturing and storing it poses technical challenges due to its gaseous state under normal conditions for temperature and pressure. Naturally occurring methane is found both below ground and under the seafloor and is formed by both geological and biological processes. The largest reservoir of methane is under the seafloor in the form of methane clathrates. When methane reaches the surface and the atmosphere, it is known as atmospheric methane. The Earth's atmospheric methane concentration has increased by about 150% since 1750, and it accounts for 20% of the total radiative forcing from all of the long-lived and globally mixed greenhouse gases. It has also been detected on other pl ...
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Coenzyme M
Coenzyme M is a coenzyme required for methyl-transfer reactions in the metabolism of archaeal methanogens, and in the metabolism of other substrates in bacteria. It is also a necessary cofactor in the metabolic pathway of alkene-oxidizing bacteria. CoM helps eliminate the toxic epoxides formed from the oxidation of alkenes such as propylene. The structure of this coenzyme was discovered by CD Taylor and RS Wolfe in 1974 while they were studying methanogenesis, the process by which carbon dioxide is transformed into methane in some anaerobic bacteria. The coenzyme is an anion with the formula . It is named 2-mercaptoethanesulfonate and abbreviated HS–CoM. The cation is unimportant, but the sodium salt is most available. Mercaptoethanesulfonate contains both a thiol, which is the main site of reactivity, and a sulfonate group, which confers solubility in aqueous media. Biochemical role Methanogenesis The coenzyme is the C1 donor in methanogenesis. It is converted to methyl ...
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Polyphenylene Sulfide
Polyphenylene sulfide (PPS) is an organic polymer consisting of aromatic rings linked by sulfides. Synthetic fiber and textiles derived from this polymer resist chemical and thermal attack. PPS is used in filter fabric for coal boilers, papermaking felts, electrical insulation, film capacitors, specialty membranes, gaskets, and packings. PPS is the precursor to a conductive polymer of the semi-flexible rod polymer family. The PPS, which is otherwise insulating, can be converted to the semiconducting form by oxidation or use of dopants.David Parker, Jan Bussink, Hendrik T. van de Grampel, Gary W. Wheatley, Ernst-Ulrich Dorf, Edgar Ostlinning, Klaus Reinking, "Polymers, High-Temperature" in Ullmann's Encyclopedia of Industrial Chemistry 2002, Wiley-VCH: Weinheim. Polyphenylene sulfide is an engineering plastic, commonly used today as a high-performance thermoplastic. PPS can be molded, extruded, or machined to tight tolerances. In its pure solid form, it may be opaque white ...
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