Halides phosphoric acid ester

Amongst heat stabilisers are copper salts, phosphoric acid esters,phenyl-3-naphthylamine, mercaptobenzothiazole and mercaptobenzimidazole. Of these, copper salts in conjunction with halides have been found particularly effective, and some automotive specifications require the use of copper for heat stabilisation. Light stabilisers include carbon black and various phenolic materials. 

The Arbuzov reaction,also called the Michaelis-Arbuzov reaction, allows for the synthesis of pentavalent alkyl phosphoric acid esters 4 from trivalent phosphoric acid esters 1 (Z,Z = R,OR) by treatment with alkyl halides 2. 

The reaction mechanism outlined below for phosphorous acid esters analogously applies for the other two cases. The first step is the addition of the alkyl halide 2 to the phosphite 1 to give a phosphonium salt 3 ... 

Various sulfuric and phosphoric acid esters have sometimes been used instead of alcohols as starting materials for the preparation of nitriles. Of more general importance are sulfonates, particularly from methane- or p-toluene-sulfonic acid, which react in an 5N2-type substitution with cyanide ions. The most common starting materials are, as described in Section 1.8.1.2.1, alkyl halides, and if their preparation creates problems, the use of sulfonates may be advantageous. The addition of crown ethers or the... 

A number of other methods have also been used to generate nitrile ylides. Access to this 1,3-dipole has been realized by (a) treatment of imidoyl halides (5) with base, (b) thermal or photochemical elimination of phosphoric acid ester from 4,5-dihydro-1,3,5-oxazaphospholes (6), (c) 1,3-dipolar cycloreversion of 1-azetidines (7), (d)loss of carbon dioxide from 3-oxazolin-5-ones (g)44-47 treatment of boron-containing isonitriles (9) with base ... 

Pinner cleavage—Halides and mixed phosphoric acid esters s. lA, 605... 

Metal ions have been shown to catalyze the hydrolysis of phosphate esters, phosphoric and phosphonic acid halides, and various phosphoric acid anhydrides including acyl phosphates, pyrophosphate derivatives, and ATP. 

Primary alkyl halides (chlorides, bromides, and iodides) can be oxidized to aldehydes easily and in good yields with dimethyl sulfoxide.311 Tosyl esters of primary alcohols can be similarly converted to aldehydes,312 and epoxides313 give a-hydroxy ketones or aldehydes.314 The reaction with tosyl esters is an indirect way of oxidizing primary alcohols to aldehydes (9-3). This type of oxidation can also be carried out without isolation of an intermediate ester The alcohol is treated with dimethyl sulfoxide, dicyclohexylcarbodiimide (DCC),315 and anhydrous phosphoric acid.316 In this way a primary alcohol can be converted to the aldehyde with no carboxylic acid being produced. 

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