Esters, nitrate, from alkyl halides

Notable examples of general synthetic procedures in Volume 47 include the synthesis of aromatic aldehydes (from dichloro-methyl methyl ether), aliphatic aldehydes (from alkyl halides and trimethylamine oxide and by oxidation of alcohols using dimethyl sulfoxide, dicyclohexylcarbodiimide, and pyridinum trifluoro-acetate the latter method is particularly useful since the conditions are so mild), carbethoxycycloalkanones (from sodium hydride, diethyl carbonate, and the cycloalkanone), m-dialkylbenzenes (from the />-isomer by isomerization with hydrogen fluoride and boron trifluoride), and the deamination of amines (by conversion to the nitrosoamide and thermolysis to the ester). Other general methods are represented by the synthesis of 1 J-difluoroolefins (from sodium chlorodifluoroacetate, triphenyl phosphine, and an aldehyde or ketone), the nitration of aromatic rings (with ni-tronium tetrafluoroborate), the reductive methylation of aromatic nitro compounds (with formaldehyde and hydrogen), the synthesis of dialkyl ketones (from carboxylic acids and iron powder), and the preparation of 1-substituted cyclopropanols (from the condensation of a 1,3-dichloro-2-propanol derivative and ethyl-... 

Synthesis of nitrate esters from the reaction of alkyl halides with silver nitrate... 

McKillop and Ford synthesized a range of primary and secondary alkyl nitrates in excellent yields by treating alkyl bromides with mercury (I) nitrate in 1,2-dimethoxyethane at reflux (Equation 3.9). This method has been used to synthesize substituted nitrate esters from both a-bromocarboxylic acid and a-bromoketone substrates. Unlike metathesis with silver salts, which are widely known to promote SnI reactions, this method is not useful for the synthesis of nitrate esters from tertiary alkyl halides. 

Alkyl azides are conveniently prepared from the reaction of alkali metal azides with an alkyl halide, tosylate, mesylate, nitrate ester or any other alkyl derivative containing a good leaving group. Reactions usually work well for primary and secondary alkyl substrates and are best conducted in polar aprotic solvents like DMF and DMSO. The synthesis and chemistry of azido compounds is the subject of a functional group series. ... 

Reaction of alkyl halides with sodium nitrite Nitromercuration of alkcncs Formation of nitroalkancs from nitrate esters Chemical properties of nitroalkancs Nitronic acids... 

A re-investigation of the reaction between diketen and amides has shown that N-acetoacetylcarboxamides are formed most efficiently in the presence of trimethylsilyliodide. Olefins react with primary amides in the presence of mercury(ii) nitrate to give iV-substituted amides after NaBH4 reduction. The method provides a convenient procedure for the Markovnikov amidation of double bonds yields vary from 17 to 99% over 11 examples. Direct C-alkylation of secondary thioamides is achieved by the reaction of the dianion (177) with an activated halide to give (178). Esters of malonic, cyanoacetic, and /8-keto acids are readily C-amidoethylated by N-acylaziridines in the presence of triethylamine. ... 

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