Dinitroethanes

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]. 

Polynitroparaffkis are stronger acids than the corresponding mononitroparaffins. Thus 1,1-dinitroethane has an ionization constant of 5.6 x 10 in water at 20°C trinitromethane is a typical strong acid with an ionization constant ki the range of 10 to 10 . Neutralization of these substances occurs rapidly, and they may be titrated readily. 

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). 

Potassium Dinitroethane. See under 1,1-Dinitro-ethane in Vol 6, E164-L... 

Dinitro-1 -Propanol. CH.3.C(NO a)2-CH2OH crysts mp 88°. Can be prepd by the action of formaldehyde on 1,1-dinitroethane. It is an expl comparable in power to Tetryl and in sensitivity to TNT. It is slightly hygroscopic and fairly stable... 

Nitro Compounds, Feuer H. Nielsen A. T. (Eds), New York, VCH, 1990, 315 The crude product is too explosive to be worked up. Analogy with other olefins indicates that the final product will be ethylene glycol dinitrate, a known explosive though safe enough to have largely replaced nitroglycerine. That will be preceded by 1,2-dinitroethane and nitratonitroethane, more sensitive if less powerful. 

Silylation of Salts of AN a-Functionalized AN 52a-c (trinitro-methane, dinitroethane, dimethyl nitromalonate, nitroacetates, etc.) can form salts, which are quite stable. It should be noted that stability of silver and mercury salts can be increased by complexation with neutral molecules (e.g., with dioxane). Hence, for these AN it is advantageous to prepare salts A, which react with halosilanes to smoothly form the corresponding SENAs 51a—C (Scheme 3.51) (174-177). 

However, certain facts contradict this interpretation. For example, the silylation of AN with BSA was accelerated after addition of triethylamine, which facilitates AN ionization (185). Besides, the addition of 1,1-dinitroethane leads to an increase in the rate of silylation of methyl nitroacetate with a deficient amount of DPSU. At the same time, the silylation of 1,1-dinitroethane by itself, taken separately with DPSU, occurs faster than silylation of MeC>2CCH2NC>2 (204). Apparently, this is accounted for by the higher nucleophilicity of methyl nitroacetate compared to that of 1,1-dinitroethane. (A separate experiment demonstrated that silyl aci-dinitroethane does not react with methyl nitroacetate.)... 

Approximately at the same time, Shevelev and coworkers studied the reactions of trinitromethane and 1,1-dinitroethane salts with RCOC1 (R=Me or Ph) and detected the corresponding acyl nitronates on the basis of decomposition products and by trapping with various E—X reagents (222) (Scheme 3.64). 

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). 

Dinitroethane and 1,2-dinitrocyclohexane can be formed in this way from the corresponding alkenes in 42 % and 37 % yield respectively. ... 

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... 

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