Alkenes oxalyl chloride

Halogenation of 106 with triphenylphosphine, iodine, and imidazole provided the iodo derivative 109. On treatment with lithium aluminum hydride, 109 was converted into two endocyclic alkenes, 110 and di-O-isopro-pylidenecyclohexanetetrol, in the ratio of 2 1. Oxidation of 110 with dimethyl sulfoxide - oxalyl chloride afforded the enone 111.1,4-Addition of ethyl 2-lithio-l,3-dithiane-2-carboxylate provided compound 112. Reduction of 112 with lithium aluminum hydride, and shortening of the side-chain, gave compound 113, which was converted into 114 by deprotection. ... 

Boyes and Wild reported the manganese-mediated regioselective chlorination of allenes [14]. For the dichlorination of cyclo-l,2-nonadiene, the dichloride was obtained as the major product whereas the reaction of monosubstituted allene afforded a mixture of regiosomers of the dichlorination products with 2,3-dichloro-1-alkene 12 being the major one. The yield with oxalyl chloride is better than that with TMSC1. 

On the pages which follow, general methods are illustrated for the synthesis of a wide variety of classes of organic compounds including acyl isocyanates (from amides and oxalyl chloride p. 16), epoxides (from reductive coupling of aromatic aldehydes by hexamethylphosphorous triamide p. 31), a-fluoro acids (from 1-alkenes p. 37), 0-lactams (from olefins and chlorosulfonyl isocyanate p. 51), 1 y3,5-triketones (from dianions of 1,3-diketones and esters p. 57), sulfinate esters (from disulfides, alcohols, and lead tetraacetate p. 62), carboxylic acids (from carbonylation of alcohols or olefins via carbonium-ion intermediates p. 72), sulfoxides (from sulfides and sodium periodate p. 78), carbazoles... 

Our catalyst for the isomerization of alkenes is going to be HC1 absorbed on to solid alumina (aluminium oxide, AI2O3) and the isomerization is to occur during a reaction, the addition of HC1 to an alkyne, in which the alkenes are formed as products. In this reaction the oxalyl chloride is first mixed with dried alumina. The acid chloride reacts with residual water on the surface (it is impossible to remove all water from alumina) to generate HC1, which remains on the surface. 

Cycloaddition of vinylketenes, produced in situ from the dehydrohalogenation of appropriately substituted unsaturated acid chlorides, with alkenes provides a convenient source of 2-vinyl-cyclobutanones. Oxidation with ruthenium(III) chloride trihydrate gave the corresponding P-oxo acid, which by treatment with oxalyl chloride and diazomethane, successively, led to the desired 2-(2-diazoacetyl)cyclobutanones. These diazo ketones are thermally labile and rearrange upon brief heating in refluxing xylene to give the spiro[cyclopropane-l,5 -furan-2 (5 i/)-ones] 2 (Table 2). ... 

The iron tricarbonyl unit has been described as a protecting group for a 1,3-diene, as in the acetylation of the complex of myrcene at low temperature (Scheme 20). The usual combinations of a,p- and p,"y-un-saturated ketones were formed. At higher temperatures, some acylation at the terminus of the diene complex was also observed. In an interesting extension, reaction of the complex with oxalyl chloride resulted in cyclization of the acid chloride initially formed by reaction at the alkene. ... 

In 1997, Marko and co-workers (423) followed up on their initial report of the KMn04 and oxalyl chloride system. This new system consists of KMn04, MesSiCl, benzytriethylammonium chloride with dichloromethane as the solvent. It gives good delds of dichlorinated alkenes. The permanganate anion is brought into solution by the ben-... 

Chlorination of Alkenes. A novel stereospecific dichlorination of electron rich alkenes has been reported using a manganese reagent generated from Benzyltriethylammonium Chloride and oxalyl chloride (eqs 13-17). No oxygenation b)q)roducts are observed. 

Certain alkenes such as 1-methylcyclohexene and styrene react with oxalyl chloride, under ionic conditions without added catalyst, to give alkenoic acid chlorides in variable yields. Alkenes such as octene and stilbene did not react under these conditions. Reactions of aromatic compounds with oxalyl chloride/Lewis acid catalysts have been reviewed. Anthracene is unusual as it undergoes substitution without added catalyst (eq 10). ... 

The oxidation of a secondary alcohol to a ketone or a primary alcohol to an aldehyde using dimethyl sulfoxide (DMSO) with oxalyl chloride at low temperature is called the Swern oxidation. Oxidation of an alkene with osmium tetroxide or potassium permanganate gives a cis-l,2-diol. 

Typical procedure. [1012] On refluxing 1,1-diphenylethylene 1338 (6.5 g) with oxalyl chloride (4.5 g) for 3-4 h, the acid chloride 1339 was obtained in 50% yield. The yield of this reaction could be raised to 95% by using 5 mol of oxalyl chloride per mol of alkene. Neither light nor peroxides have any effed on this reaction, which is apparently ionic. 

Dilithiobutadiene undergoes dimerization smoothly in the presence of CuCl to linear alkenes and cyclooctatetraenes through octasubstituted semibullvalenes (eq 32). Cyclopenta-dienone derivatives are produced with oxalyl chloride in the presence of CuCl in DMPU (eq 33). ... 

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