Nitroalcohol esters

Nitroalcohols are produced when nitroparaffins react with formaldehyde in an alkaline medium (Henry [75]). In the case of primary paraffins, the reaction proceeds as below  

With nitromethane, a trihydric alcohol, trimethylolnitromethane, so called nitroisobutylglycerine, is formed  

Opinions about the chemical stability of nitroisobutylglycerine trinitrate do 

Trimethylolnitromethane trinitrate has attracted considerable interest as an explosive owing to its ideal oxygen balance. Explosive decomposition results in production of heat exceeding that produced by nitroglycerine by 7% 

Its sensitiveness to impact is of the same order as that of nitroglycerine. The initiation temperature is 180°C. 

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The nitroaldol-lipase DCR process could not only amplify specific (3-nitroalcohol derivatives, but also lead to their asymmetric discrimination. HPLC analysis proved that the enantioselectivity of the process is very high, resulting in products of very high optical purity. The R-enantiomer of the ester 45 was resolved to 99% ee, and the R-enantiomer of the ester 46 to 98% ee. 

Alkenes can react with nitric acid, either neat or in a chlorinated solvent, to give a mixture of compounds, including v/c-dinitroalkane, jS-nitro-nitrate ester, v/c-dinitrate ester, /3-nitroalcohol, and nitroalkeneproducts. Cyclohexene reacts with 70 % nitric acid to yield a mixture of 1,2-dinitrocyclohexane and 2-nitrocyclohexanol nitrate. Frankel and Klager investigated the reactions of several alkenes with 70 % nitric acid, but only in the case of 2-nitro-2-butene (1) was a product identified, namely, 2,2,3-trinitrobutane (2). 

The reaction of fuming nitric acid with 2-methyl-2-butene (3) is reported to yield 2-methyl-3-nitro-2-butene (4). The reaction of alkenes with fuming nitric acid, either neat or in chlorinated solvents, is an important route to unsaturated nitrosteroids, which assumedly arise from the dehydration of /3-nitroalcohols or the elimination of nitric acid from /3-nitro-nitrate esters. Temperature control in these reactions is important if an excess of oxidation by-products is to be avoided. 

Nitroalcohols X and XI may be utilized as starting materials for the manufacture of nitric acid esters having explosive properties (see Vol. II). In the presence of primary or secondary amines or ammonia the reaction leads to formation of aminonitroalcohols (XII)... 

To investigate the lipase enantiomeric specificity, HPLC was used to monitor the enantiomeric ratios of products 22C and 22A. From these analyses, 99% and 98% ee of ester products 22C and 22A, respectively, were obtained and shown to have -configuration. This revealed that lipase-catalyzed transesterification is an efficient resolution technique since only two products were selected from 20 p-nitroalcohol substrates. 

Dehydration of nitroalcohols and their esters. Nitroalcoliols obtained by the Henry rnethod can be readily dehydrated with phthalic anhydride (Vol. t. 

In some instances it has been found that esters can give purer substances [103). According to Cold [104a] nitroalkenes can be obtained in good yield (up to 85%) by vapour phase catalytic cleavage of esters of nitroalcohols. for example ... 

Esters of nitroalcohol and unsaturated acids Industrial mcth(xls of nitrating alkanes German method tjf nitration of lower alkanes Method of Commercial Stdvcnis Corporation, Inc. 

Aliphatic dinitro compounds, nitronitric acid esters, and nitroalcohols from olefins... 

Nitroalcohols from nitric acid esters CHC C CCONOg) Functionalization of non-activated groups... 

Aminoalcohols from aminocarboxylic acids via acylaminocarboxylic acids, acylaminocarboxylic acid esters, and acylaminoalcohols s. 11, 115 Nitroalcohols from nitrocarboxylic acid esters s. 11, 116... 

Direct oxidation of primary nitroalkanes to carboxylic acids is rarely useful since strong reaction conditions are needed and often result in low yields. Lately, a mild and efficient condition using sodium nitrite and acetic acid in DMSO is developed to directly transform the nitro group to carboxylic acid 46. ° Under similar conditions, 2-nitroalcohol 47 is transformed into carboxylic acid methyl ester 48 in good yield without epimerization of the adjacent stereogenic center. 

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