Mesitoyl chloride

Mesitaldehyde may be prepared from mesitylmagnesium bromide by the reaction with orthoformate esters3 or ethoxy-methyleneaniline 3 from acetylmesitylene by oxidation with potassium permanganate,4 from mesitoyl chloride by reduction,5 from mesityllithium by the reaction with iron pentacarbonyl and from mesitylene by treatment with formyl fluoride and boron trifluoride,7 by treatment with carbon monoxide, hydrogen chloride, and aluminum chloride,8 or by various applications of the Gatterman synthesis.9-11... 

The first iron-catalyzed acylation of Grignard reagents was described by Kharasch and coworkers in 1944 (Scheme 6). They reported only one example of reaction between methyknagnesium iodide and mesitoyl chloride in the presence of iron(III) chloride in diethyl ether. 

This mechanism explains much of the experimental evidence obtainedhfrom studies of the solvolysis of acyl chlorides, but it may not be in agreement (as was pointed out to Minato by a referee) with the linear relationship between electrophilic catalysis observed in the solvolysis of certain acid chlorides would possibly be explained by a simpler mechanism such as the SN1 or hydration-ionisation mechanism. However, it is of interest to see how the mechanism applies to acetyl, benzoyl and mesitoyl chlorides. For acetyl chloride, kY and k-Y would be very large and the rate would approximate to... 

The mechanism proposed by Minato is on no firmer ground when used to interpret the data for benzoyl and mesitoyl chlorides. The lsO exchange for these compounds implies k3 > 2[R OH] since kh ke. The kinetic equation thus reduces to... 

The method for the preparation of the chloride is the general method for preparing aromatic acid chlorides with thionyl chloride,10 which has been applied to the preparation of mesitoyl chloride.9... 

Reagents i, mesitoyl chloride ii, 03 iii, isopropenylMgBr iv, Ac20-py v, Bu"Li-isopropyl-cyclohexylamine-THF, -78°C vi, HMPA-t-butyldimethylsilyl chloride-THF vii, hydrolysis viii, LiAlH4. 

AflSnity Chromatography.—Uridine nucleotides have been immobilized via phos-phoramidate linkages by successive treatments of the nucleotide with mesitoyl chloride and with 1,6-diaminoethane to afford (39), which is then coupled to cyanogen bromide(CNBr)-Sepharose. ... 

The neutral and acid-catalysed hydrolysis of mesitoyl chloride in acetonitrile containing 1% 018-enriched water is not accompanied by O18 exchange (Bender and Chen, 1963). It is suggested that in both cases unimolecular heterolytic bond fission occurs with the formation of an acyl cation. In alkaline solution a tetracovalent intermediate is postulated on the basis of a comparison of the effect of substituents on the rate of hydrolysis of the corresponding benzoate esters. The exchange of O18 in alkaline solution was not determined experimentally. 

Me5C5Fe(CO)2P(SiMe3)2, a similar product results using mesitoyl chloride, but both benzoyl and pivaloyl chlorides displace both silyl groups to give the bis-acyl (-aroyl) derivatives 76 (Scheme 24)95, a reaction also observed for ruthenium and osmium96. With... 

Three additional protecting groups in this category are the mesitoate ester (OCOC6H22,4,6-trimethyl, O— Mes), the pivaloyl ester (OCO—f-Bu), and the para-methoxybenzoyl ester (OCO—C6H4-4-Me). The mesitoate ester is formed by reaction of an alcohol with mesitoyl chloride in the presence of pyridine or triethylamine. The main advantage of this ester is its stability to hydrolysis (pH 1-12), nucleophilic attack,... 

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