1.1- Dinitroethane derivative

It was also found that bromonitrophenylmethane (375) reacted with sodium aryl-methanenitronate (374) in DMSO to give the isoxazoline iV-oxide (369) in 60% yield. Both reactions probably involved the formation of a vicinal dinitroethane derivative (376), which lost nitrous acid to give cfs-a-nitrostilbene (368). As mentioned, the reaction of (368) with (374) gave the isoxazoline iV-oxide (369). 

The nitroparaffins are named as derivatives of the corresponding hydrocarbons by usiag the prefix "nitro" to designate the NO2 group (1), eg, 1,1-dinitroethane, CH2CH(N02)2- The salts obtained from nitroparaffins and the so-called nitronic acids are identical and may be named as derivatives of either, eg, sodium salt of i7ti-nitromethane, or sodium methanenitronate [25854-38-0]. 

At the same time, two different coupling constants J13 15 were observed in the spectrum of the SiMe3 derivative of 1,1 -dinitroethane, in which the sterically hindered Z isomer is present at very low concentration. By this reason, the process of 1,5-0,0-migration of the SiMe3 group is unobservable on the NMR time scale (272) (Scheme 3.79). 

Both 1,1-dinitroethane (26) and 1,1-dinitropropane, and their methylol derivatives, 2,2-dinitropropanol (25) and 2,2-dinitro-l-butanol respectively, have been synthesized via the Ter Meer reaction. - The formal and acetal of 2,2-dinitropropanol in the form of a 1 1 eutectic is an energetic plasticizer and so the synthesis of 2,2-dinitropropanol has been the subject of much investigation. On a pilot plant scale 2,2-dinitropropanol (25) is synthesized in 60 % overall yield from nitroethane (22). Thus, treatment of 1 -chloronitroethane (23) with potassium nitrite... 

A range of primary and secondary nitroalkanes and their derivatives have been converted to the corresponding gem-dinitroalkanes via oxidative nitration, including the conversion of nitroethane, 1-nitropropane, 2-nitropropane and 2-nitro-1,3-propanediol to 1,1-dinitroethane (78 %), 1,1-dinitropropane (86 %), 2,2-dinitropropane (93 %) and 2,2-dinitro-1,3-propanediol (77 %) respectively. The silver nitrate used in these reactions can be recovered quantitatively on a laboratory scale and this has led to a study where oxidative nitration has been considered for the large-scale production of 2,2-dinitropropanol (25) from the nitroethane (22). ... 

Primary and secondary nitroalkanes, dinitromethane, and terminal em-dinitroaliphatic compounds like 1,1-dinitroethane, all contain acidic protons and have been used to generate Mannich products. Formaldehyde is commonly used in these reactions although the use of other aliphatic aldehydes has been reported. The nitroalkane component is frequently generated in situ from its methylol derivative, a reaction which also generates formaldehyde. Ammonia, " aliphatic amines, " hydrazine, and even urea have been used as the amine component of Mannich reactions. 

Alkalsit is a Ger blasting expi which is described in PATR 2510(1958), p Ger 3 Alkanes, Nitrated Derivatives (Nitrated Aliphatic Hydrocarbons). The first nitro-alkane described in the literature was 1,2-dinitroethane, prepd in Russia by A.Semenov. Since then hundreds of nitroalkanes, some of them explosive, were obtained. The reference given below describes old and new methods of prepn of nitro alkanes. Most of expl nitro alkanes are described in this dictionary under their parent names, such as methane, ethane, propane, etc Ref 0. vonSchickh, AngewChem 62, 547-56 (1950)(Chemie und Technologie der Nitro-alkane)... 

H. -O. Structure, synthesis, and properties of some persubstituted 1,2-dinitroethanes. In quest of nitrocydopropyl-anion derivatives. Helv. Chim. Acta 1982, 65, 137-161. 

Chancel [80a] described another general method of preparing 1,1-dinitroparaf-fins and in particular 1,1-dinitroethane, starting from ethyl acetoacetate and its derivatives ... 

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