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Phosphite
The general structure of a phosphite ester showing the lone pairs on the P In organic chemistry, a phosphite ester or organophosphite usually refers to an organophosphorous compound with the formula P(OR)3. They can be considered as esters of an unobserved tautomer phosphorous acid, H3PO3, with the simplest example being trimethylphosphite, P(OCH3)3. Some phosphites can be considered esters of the dominant tautomer of phosphorous acid (HP(O)(OH)2). The simplest representative is dimethylphosphite with the formula HP(O)(OCH3)2. Both classes of phosphites are usually colorless liquids. Synthesis ;From PCl3 Phosphite esters are typically prepared by treating phosphorus trichloride with an alcohol. For alkyl alcohols the displaced chloride ion can attack the phosphite, causing dealkylation to give a dialkylphosphite and an organochlorine compound. The overall reaction is as follows: :PCl3 + 3 C2H5OH → (C2H5O)2P(O)H + 2 HCl + C2H5Cl Alternatively, when the alcoh ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Triethylphosphite
Triethyl phosphite (TEP) is an organophosphorus compound, specifically a phosphite ester, with the formula P(OCH2CH3)3, often abbreviated P(OEt)3. It is a colorless, malodorous liquid. It is used as a ligand in organometallic chemistry and as a reagent in organic synthesis. The molecule features a pyramidal phosphorus(III) center bound to three ethoxide groups. Its 31P NMR spectrum features a signal at around +139 ppm vs phosphoric acid standard. Triethylphosphite is prepared by treating phosphorus trichloride with ethanol in the presence of a base, typically a tertiary amine: :PCl3 + 3 EtOH + 3 R3N → P(OEt)3 + 3 R3NH + 3 Cl− In the absence of the base, the reaction of ethanol and phosphorus trichloride affords diethylphosphite ((EtO)2P(O)H). Of the many related compounds can be prepared similarly, triisopropyl phosphite is an example (b.p. 43.5 °C/1.0 mm; CAS# 116-17-6). Reactions Triethyl phosphite can react with electrophiles in a Michaelis–Arbuzov rea ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Trimethyl Phosphite
Trimethyl phosphite is an organophosphorus compound with the formula P(OCH3)3, often abbreviated P(OMe)3. It is a colorless liquid with a highly pungent odor. It is the simplest phosphite ester and finds used as a ligand in organometallic chemistry and as a reagent in organic synthesis. The molecule features a pyramidal phosphorus(III) center bound to three methoxy groups. Synthesis Trimethyl phosphite is in principle obtainable by methanolysis of phosphorus trichloride, say in the presence of a proton accepting base. This method suffers from numerous side reactions however. The use of sodium methoxide is superior: : Reactions Trimethyl phosphite is susceptible to oxidation to trimethyl phosphate: : It reacts with a catalytic amount of methyl iodide in the Arbuzov reaction to give dimethyl methylphosphonate: :P(OCH3)3 → CH3P(O)(OCH3)2 As a ligand, trimethyl phosphite has a smaller cone angle and better acceptor properties relative to trimethylphosphine. A representati ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Trimethylphosphite
Trimethyl phosphite is an organophosphorus compound with the formula P(OCH3)3, often abbreviated P(OMe)3. It is a colorless liquid with a highly pungent odor. It is the simplest phosphite ester and finds used as a ligand in organometallic chemistry and as a reagent in organic synthesis. The molecule features a pyramidal phosphorus(III) center bound to three methoxy groups. Synthesis Trimethyl phosphite is in principle obtainable by methanolysis of phosphorus trichloride, say in the presence of a proton accepting base. This method suffers from numerous side reactions however. The use of sodium methoxide is superior: : Reactions Trimethyl phosphite is susceptible to oxidation to trimethyl phosphate: : It reacts with a catalytic amount of methyl iodide in the Arbuzov reaction to give dimethyl methylphosphonate: :P(OCH3)3 → CH3P(O)(OCH3)2 As a ligand, trimethyl phosphite has a smaller cone angle and better acceptor properties relative to trimethylphosphine. A representa ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Michaelis–Arbuzov Reaction
The Michaelis–Arbuzov reaction (also called the Arbuzov reaction) is the chemical reaction of a trivalent phosphorus ester with an alkyl halide to form a pentavalent phosphorus species and another alkyl halide. The picture below shows the most common types of substrates undergoing the Arbuzov reaction; phosphite esters (1) react to form phosphonates (2), phosphonites (3) react to form phosphinates (4) and phosphinites (5) react to form phosphine oxides (6). The reaction was discovered by August Michaelis in 1898, and greatly explored by Aleksandr Arbuzov soon thereafter. This reaction is widely used for the synthesis of various phosphonates, phosphinates, and phosphine oxides. Several reviews have been published. The reaction also occurs for coordinated phosphite ligands, as illustrated by the demethylation of 2+ to give −, which is called the Klaui ligand. Reaction mechanism file:Michaelis-Arbuzov Reaction Mechanism.png, center, 600px, The mechanism of the Michaelis–Arb ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Phosphorous Acid
Phosphorous acid (or phosphonic acid) is the Compound (chemistry), compound described by the chemical formula, formula . It is diprotic (readily ionizes two protons), not triprotic as might be suggested by its formula. Phosphorous acid is an intermediate in the preparation of other phosphorus compounds. Organic derivatives of phosphorous acid, compounds with the formula , are called phosphonic acids. Nomenclature and tautomerism Solid has tetrahedral geometry about the central phosphorus atom, with a bond of 132 picometer, pm, one double bond of 148 pm and two longer single bonds of 154 pm. In common with other phosphorus oxides with bonds (e.g.hypophosphorous acid and dialkyl phosphites), it exists in equilibrium with an extremely minor tautomer . (In contrast, arsenous acid's major tautomer is the trihydroxy form.) IUPAC recommends that the trihydroxy form be called phosphorous acid, and the dihydroxy form phosphonic acid.. Only the reduced phosphorus c ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Organophosphorous
In organic chemistry, organophosphates (also known as phosphate esters, or OPEs) are a class of organophosphorus compounds with the general structure , a central phosphate molecule with alkyl or aromatic substituents. They can be considered as esters of phosphoric acid. Organophosphates are best known for their use as pesticides. Like most functional groups, organophosphates occur in a diverse range of forms, with important examples including key biomolecules such as DNA, RNA and ATP, as well as many insecticides, herbicides, nerve agents and flame retardants. OPEs have been widely used in various products as flame retardants, plasticizers, and performance additives to engine oil. The low cost of production and compatibility to diverse polymers made OPEs to be widely used in industry including textile, furniture, electronics as plasticizers and flame retardants. These compounds are added to the final product physically rather than by chemical bond. Due to this, OPEs leak into ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Abramov Reaction
The Abramov reaction is the related conversions of trialkyl to α-hydroxy phosphonates by the addition to carbonyl compounds. In terms of mechanism, the reaction involves attack of the nucleophilic phosphorus atom on the carbonyl carbon. It was named after the Russian chemist Vasilii Semenovich Abramov (1904–1968) in 1957. Introduction Electron-rich sources of phosphorus such as phosphites, phosphonites, and phosphinites may undergo nucleophilic addition to carbon atoms in simple carbonyl compounds. When fully esterified phosphites are used (Abramov reaction), neutralization of the resulting tetrahedral intermediate usually occurs via the transfer of an alkyl or silyl group from an oxygen attached to phosphorus to the newly created alkoxide center. Conjugate addition is also possible, and gives γ-functionalized carbonyl compounds or enol ethers after group transfer. The use of siloxy-containing phosphorus sources has greatly expanded the scope of this reaction, as the resulting ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Dimethylphosphite
Dimethylphosphite is an organophosphorus compound with the formula (CH3O)2P(O)H, known as dimethyl hydrogen phosphite (DMHP). Dimethylphosphite, is a minor tautomer of the phosphorus(V) derivative. It is a reagent for generating other organophosphorus compounds, exploiting the high reactivity of the P-H bond. The molecule is tetrahedral. It is a colorless liquid. The compounds can be prepared by methanolysis of phosphorus trichloride or by heating diethylphosphite in methanol. Although studies have not been reported for this compound, the closely related diethylphosphite exists predominantly as the phosphorus(V) tautomer. References {{Chemical agents Organophosphites Methyl esters ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Phosphate Ester
In organic chemistry, organophosphates (also known as phosphate esters, or OPEs) are a class of organophosphorus compounds with the general structure , a central phosphate molecule with alkyl or aromatic substituents. They can be considered as esters of phosphoric acid. Organophosphates are best known for their use as pesticides. Like most functional groups, organophosphates occur in a diverse range of forms, with important examples including key biomolecules such as DNA, RNA and ATP, as well as many insecticides, herbicides, nerve agents and flame retardants. OPEs have been widely used in various products as flame retardants, plasticizers, and performance additives to engine oil. The low cost of production and compatibility to diverse polymers made OPEs to be widely used in industry including textile, furniture, electronics as plasticizers and flame retardants. These compounds are added to the final product physically rather than by chemical bond. Due to this, OPEs leak into ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Phosphorus Trichloride
Phosphorus trichloride is an inorganic compound with the chemical formula PCl3. A colorless liquid when pure, it is an important industrial chemical, being used for the manufacture of phosphites and other organophosphorus compounds. It is toxic and reacts readily with water to release hydrogen chloride. History Phosphorus trichloride was first prepared in 1808 by the French chemists Joseph Louis Gay-Lussac and Louis Jacques Thénard by heating calomel (Hg2Cl2) with phosphorus. Later during the same year, the English chemist Humphry Davy produced phosphorus trichloride by burning phosphorus in chlorine gas. Preparation World production exceeds one-third of a million tonnes. Phosphorus trichloride is prepared industrially by the reaction of chlorine with white phosphorus, using phosphorus trichloride as the solvent. In this continuous process PCl3 is removed as it is formed in order to avoid the formation of PCl5. :P4 + 6 Cl2 → 4 PCl3 Structure and spectroscopy It has a t ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Perkow Reaction
The Perkow reaction is an organic reaction in which a trialkyl phosphite ester reacts with a haloketone to form a dialkyl vinyl group, vinyl phosphate and an alkyl halide. In the related Michaelis–Arbuzov reaction the same reactants are known to form a beta-keto phosphonate which is an important reagent in the Horner–Wadsworth–Emmons reaction on the road to alkenes. The Perkow reaction, in this respect is considered a side-reaction. Reaction mechanism The reaction mechanism of the Perkow reaction consists of a nucleophilic addition of the phosphite at the carbonyl carbon forming a zwitterionic intermediate. The zwitterionic intermediate rearranges to a cationic species while eliminating the halide. The cationic species then dealkylates through a second nucleophilic displacement in which the halide anion attacks one of the phosphite alkoxide substituents forming an enol phosphate.Organophosphorus chemistry. XVII. ''Kinetics and mechanism of the Perkow reaction'' Irving J ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
