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Thioesters
In organic chemistry, thioesters are organosulfur compounds with the functional group . They are analogous to carboxylate esters () with the sulfur in the thioester playing the role of the linking oxygen in the carboxylate ester, as implied by the '' thio-'' prefix. They are the product of esterification between a carboxylic acid () and a thiol (). In biochemistry, the best-known thioesters are derivatives of coenzyme A, e.g., acetyl-CoA.Matthys J. Janssen "Carboxylic Acids and Esters" in PATAI's Chemistry of Functional Groups: Carboxylic Acids and Esters, Saul Patai, Ed. John Wiley, 1969, New York: pp. 705–764. Synthesis The most typical route to thioester involves the reaction of an acid chloride with an alkali metal salt of a thiol: :RSNa + R'COCl -> R'COSR + NaCl Another common route entails the displacement of halides by the alkali metal salt of a thiocarboxylic acid. For example, thioacetate esters are commonly prepared by alkylation of potassium thioacetate: :CH3COS ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Organosulfur Compounds
Organosulfur compounds are organic compounds that contain sulfur. They are often associated with foul odors, but many of the sweetest compounds known are organosulfur derivatives, e.g., saccharin. Nature abounds with organosulfur compounds—sulfur is vital for life. Of the 20 common amino acids, two (cysteine and methionine) are organosulfur compounds, and the antibiotics penicillin and sulfa drugs both contain sulfur. While sulfur-containing antibiotics save many lives, sulfur mustard is a deadly chemical warfare agent. Fossil fuels, coal, petroleum, and natural gas, which are derived from ancient organisms, necessarily contain organosulfur compounds, the removal of which is a major focus of oil refineries. Sulfur shares the chalcogen group with oxygen, selenium, and tellurium, and it is expected that organosulfur compounds have similarities with carbon–oxygen, carbon–selenium, and carbon–tellurium compounds. A classical chemical test for the detection of sulfur compoun ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Coenzyme A
Coenzyme A (CoA, SHCoA, CoASH) is a coenzyme, notable for its role in the synthesis and oxidation of fatty acids, and the oxidation of pyruvate in the citric acid cycle. All genomes sequenced to date encode enzymes that use coenzyme A as a substrate, and around 4% of cellular enzymes use it (or a thioester) as a substrate. In humans, CoA biosynthesis requires cysteine, pantothenate (vitamin B5), and adenosine triphosphate (ATP). In its acetyl form, coenzyme A is a highly versatile molecule, serving metabolic functions in both the anabolic and catabolic pathways. Acetyl-CoA is utilised in the post-translational regulation and allosteric regulation of pyruvate dehydrogenase and carboxylase to maintain and support the partition of pyruvate synthesis and degradation. Discovery of structure Coenzyme A was identified by Fritz Lipmann in 1946, who also later gave it its name. Its structure was determined during the early 1950s at the Lister Institute, London, together by L ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Acetyl-CoA
Acetyl-CoA (acetyl coenzyme A) is a molecule that participates in many biochemical reactions in protein, carbohydrate and lipid metabolism. Its main function is to deliver the acetyl group to the citric acid cycle (Krebs cycle) to be oxidized for energy production. Coenzyme A (CoASH or CoA) consists of a β-mercaptoethylamine group linked to the vitamin pantothenic acid (B5) through an amide linkage and 3'-phosphorylated ADP. The acetyl group (indicated in blue in the structural diagram on the right) of acetyl-CoA is linked to the sulfhydryl substituent of the β-mercaptoethylamine group. This thioester linkage is a "high energy" bond, which is particularly reactive. Hydrolysis of the thioester bond is exergonic (−31.5 kJ/mol). CoA is acetylated to acetyl-CoA by the breakdown of carbohydrates through glycolysis and by the breakdown of fatty acids through β-oxidation. Acetyl-CoA then enters the citric acid cycle, where the acetyl group is oxidized to carbon dioxid ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
N,N'-Dicyclohexylcarbodiimide
''N'',''N''′-Dicyclohexylcarbodiimide (DCC or DCCD) is an organic compound with the chemical formula (C6H11N)2C. It is a waxy white solid with a sweet odor. Its primary use is to couple amino acids during artificial peptide synthesis. The low melting point of this material allows it to be melted for easy handling. It is highly soluble in dichloromethane, tetrahydrofuran, acetonitrile and dimethylformamide, but insoluble in water. Structure and spectroscopy The C−N=C=N−C core of carbodiimides (N=C=N) is linear, being related to the structure of allene. The molecule has idealized C2 symmetry. The N=C=N moiety gives characteristic IR spectroscopic signature at 2117 cm−1. The 15N NMR spectrum shows a characteristic shift of 275 ppm upfield of nitric acid and the 13C NMR spectrum features a peak at about 139 ppm downfield from TMS. Preparation DCC is produced by the decarboxylation of cyclohexyl isocyanate using phosphine oxides as a catalyst: :2 C6H11N ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Propanephosphonic Acid Anhydride
Propanephosphonic acid anhydride (PPAA, T3P) is an anhydride of propane phosphonic acid. Its structure is a cyclic trimer, with a phosphorus–oxygen core and propyl groups and additional oxygens attached. The chemical is a useful reagent for peptide synthesis reactions, where it activates the carboxylic acid partner for subsequent reaction with amines. It is commercially available as 50 % solution in DMF or ethyl acetate Ethyl acetate ( systematically ethyl ethanoate, commonly abbreviated EtOAc, ETAC or EA) is the organic compound with the formula , simplified to . This colorless liquid has a characteristic sweet smell (similar to pear drops) and is used in glues ... as a slightly yellow mixture. References Reagents for organic chemistry Phosphonates {{organic-compound-stub ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Cyclopentanone
Cyclopentanone is the organic compound with the formula (CH2)4CO. This cyclic ketone is a colorless volatile liquid. Preparation Upon treatment with barium hydroxide at elevated temperatures, adipic acid undergoes ketonization to give cyclopentanone: :(CH2)4(CO2H)2 → (CH2)4CO + H2O + CO2 Uses Cyclopentanone is common precursor to fragrances, especially those related to jasmine and jasmone Jasmone is an organic compound, which is a volatile portion of the oil from jasmine flowers. It is a colorless to pale yellow liquid. Jasmone can exist in two isomeric forms with differing geometry around the pentenyl double bond, ''cis''-jasmon .... Examples include 2-pentyl- and 2-heptylcyclopentanone.Johannes Panten and Horst Surburg "Flavors and Fragrances, 2. Aliphatic Compounds" in Ullmann's Encyclopedia of Industrial Chemistry, 2015, Wiley-VCH, Weinheim. It is a versatile synthetic intermediate, being a precursor to cyclopentobarbital. Cyclopentanone is also used to mak ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Acid Anhydride
An acid anhydride is a type of chemical compound derived by the removal of water molecules from an acid. In organic chemistry, organic acid anhydrides contain the functional group R(CO)O(CO)R'. Organic acid anhydrides often form when one equivalent of water is removed from two equivalents of an organic acid in a dehydration reaction. In inorganic chemistry, an acid anhydride refers to an acidic oxide, an oxide that reacts with water to form an oxyacid (an inorganic acid that contains oxygen or carbonic acid), or with a base to form a salt. Nomenclature The nomenclature of organic acid anhydrides is derived from the names of the constituent carboxylic acids which underwent dehydration to form the compound. In symmetrical acid anhydrides, where only one constituent carboxylic acid was used to form the compound (such as the dehydration of propanoic acid, 2CH3CH2COOH → CH3CH2C(O)OC(O)CH2CH3 + H2O), only the prefix of the original carboxylic acid is used and the suffix " ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Mitsunobu Reaction
The Mitsunobu reaction is an organic reaction that converts an alcohol into a variety of functional groups, such as an ester, using triphenylphosphine and an azodicarboxylate such as diethyl azodicarboxylate (DEAD) or diisopropyl azodicarboxylate (DIAD). Although DEAD and DIAD are most commonly used, there are a variety of other azodicarboxylates available which facilitate an easier workup and/or purification and in some cases, facilitate the use of more basic nucleophiles. It was discovered by Oyo Mitsunobu (1934–2003). Typical protocol is to add the phosphine and azodicarboxylate together at −10 °C, typically in THF or toluene, until a white precipitate forms. This white, cloudy suspension is the ylide. Then a solution of the nucleophile and alcohol are added together and the reaction can be, and in many cases is, heated to reflux. The alcohol reacts with the phosphine to create a good leaving group then undergoes an inversion of stereochemistry in classic SN2 fashion ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Lactone
Lactones are cyclic carboxylic esters, containing a 1-oxacycloalkan-2-one structure (), or analogues having unsaturation or heteroatoms replacing one or more carbon atoms of the ring. Lactones are formed by intramolecular esterification of the corresponding hydroxycarboxylic acids, which takes place spontaneously when the ring that is formed is five- or six-membered. Lactones with three- or four-membered rings (α-lactones and β-lactones) are very reactive, making their isolation difficult. Special methods are normally required for the laboratory synthesis of small-ring lactones as well as those that contain rings larger than six-membered. Nomenclature Lactones are usually named according to the precursor acid molecule (''aceto'' = 2 carbon atoms, ''propio'' = 3, ''butyro'' = 4, ''valero'' = 5, ''capro'' = 6, etc.), with a ''-lactone'' suffix and a Greek letter prefix that specifies the number of carbon atoms in the heterocycle — that is, the distance between the relevant -OH ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Mannich Base
A Mannich base is a beta-amino-ketone, which is formed in the reaction of an amine, formaldehyde (or an aldehyde) and a carbon acid. The Mannich base is an endproduct in the Mannich reaction, which is nucleophilic addition reaction of a non-enolizable aldehyde and any primary or secondary amine to produce resonance stabilized imine (iminium ion or imine salt). The addition of a carbanion from a CH acidic compound (any enolizable carbonyl compound, amide, carbamate, hydantoin or urea) to the imine gives the Mannich base.Mannich base applied in this example: Reactivity With primary or secondary amines, Mannich bases react with additional aldehyde and carbon acid to larger adducts HN(CH2CH2COR)2 and N(CH2CH2COR)3. With multiple acidic hydrogen atoms on the carbon acid higher adducts are also possible. Ammonia can be split off in an elimination reaction An elimination reaction is a type of organic reaction in which two substituents are removed from a molecule in either a one- or t ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Thioacetic Acid
Thioacetic acid is an organosulfur compound with the molecular formula . It is the sulfur analogue of acetic acid (), as implied by the ''thio-'' prefix. It is a yellow liquid with a strong thiol-like odor. It is used in organic synthesis for the introduction of thiol groups () in molecules. Synthesis and properties Thioacetic acid is prepared by the reaction of acetic anhydride with hydrogen sulfide: :(CH3C(O))2O + H2S -> CH3C(O)SH + CH3C(O)OH It has also been produced by the action of phosphorus pentasulfide on glacial acetic acid, followed by distillation. :CH3C(O)OH + P2S5 -> CH3C(O)SH + P2OS4 Thioacetic acid is typically contaminated by acetic acid. The compound exists exclusively as the thiol tautomer, consistent with the strength of the double bond. Reflecting the influence of hydrogen-bonding, the boiling point (93 °C) and melting points are 20 and 75 K lower than those for acetic acid. Reactivity Acidity With a p''K''a near 3.4, thioacetic acid is about 1 ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
