Alkane nitration

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)... 

Efficient catalytic alkane nitrations can be performed with the assistance of N-hydroxyphthalimide (NHPI) with N02 in air [Eq. (10.57)]298 or with HNO3.299 NHPI may also be used to form alkanesulfonic acids by reacting alkanes with S02 300... 

Alkanes, nitration of 2l9.229 (F86. K9) Atkylamine nitrates in slurrv explosives. 549... 

Alkanes, nitration ol 2l9. 229 (I S6. S9) Alkviaminc nitriiies in slurrv explosives 549... 

The nitrate esters have also been used in human health and medicine fields [9, 10]. For example, single alkane nitrates play an important role in clearance and purification of energy and environment [11, 12]. There are about 20 liquid nitrate esters with most bright potential in application and production over the world. They will be introduced in the following sections. 

Thus, the rate-determining step of alkane nitration is the formation of free alkyl radicals in (Equation 5.1), as well as in reaction of alkanes with O, NO3, OH, Cl and other active radicals. The reactions of R with NO, NO, O, N O [19], Br [20] and other components of the reaction system (including solvents) results in a mixture of nitro compounds, nitrites, nitroso compounds, and nitrates. All these compounds with the exception of RNO depending on the conditions undergo further conversions, resulting in the different composition of the end products of nitration. 

Scheme 6.12 A possible reaction path for alkane nitration catalyzed by NHPI.

Adams catalyst, platinum oxide, Pt02 H20. Produced by fusion of H2PtCl6 with sodium nitrate at 500-550 C and leaching of the cooled melt with water. Stable in air, activated by hydrogen. Used as a hydrogenation catalyst for converting alkenes to alkanes at low pressure and temperature. Often used on Si02... 

The selection of solvents for quantitative work is not easy. Nitro-alkanes are sufficiently inert, but nitronium tetrafluoroborate is poorly soluble in them c. 0-3 %). Nitronium salts react rapidly with acetic anhydride, and less rapidly with acetic acid, A, A -dimethylformamide and acetonitrile, although the latter solvent can be used for nitration at low temperatures. Sulpholan was selected as the most suitable solvent ... 

Aliphatic Nitration. Alkanes undergo electrophilic nitration with nitronium salts such as (N02) piotic solvent such as CH2CI2... 

The only method utilized commercially is vapor-phase nitration of propane, although methane (70), ethane, and butane also can be nitrated quite readily. The data in Table 5 show the typical distribution of nitroparaffins obtained from the nitration of propane with nitric acid at different temperatures (71). Nitrogen dioxide can be used for nitration, but its low boiling point (21°C) limits its effectiveness, except at increased pressure. Nitrogen pentoxide is a powerful nitrating agent for alkanes however, it is expensive and often gives polynitrated products. 

Poly(vinyl nitrate) has been prepared and studied for use in explosives and rocket fuel (104,105). Poly(vinyl alcohol) and sulfur trioxide react to produce poly(vinyl sulfate) (106—111). Poly(vinyl alkane sulfonate)s have been prepared from poly(vinyl alcohol) and alkanesulfonyl chlorides (112—114). In the presence of urea, poly(vinyl alcohol) and phosphoms pentoxide (115) or phosphoric acid (116,117) yield poly(vinyl phosphate)s. 

Nitro-nitrate mit endstandiger Nitro-Gruppe liefern bei dcr Reduktion mit 3,5 Mol-Aquivalenten Natriumboranat4 die sonst nur schwierig zuganglichen terminalen Nitro-alkane. 

Alkanes can be nitrosated photochemically, by treatment with NOCl and UV light. For nitration at an activated carbon, see 14-12. 

Nitration of alkanes can be carried out in the gas phase at 400°C or in the liquid phase. The reaction is not practical for the production of pure products for any alkane except methane. For other alkanes, not only does the reaction produce mixtures of the mono-, di-, and polynitrated alkanes at every combination of positions, but extensive chain cleavage occurs. A free-radical mechanism is involved. ... 

The major reactions carried out by hydroxyl and nitrate radicals may conveniently be represented for a primary alkane RH or a secondary alkane RjCH. In both, hydrogen abstraction is the initiating reaction. 

A range of transformation products has been identified from simulated reactions of alkanes. These include alkyl nitrates by reactions that have already been given, but also include a range of hydroxy-carbonyls that are summarized in Table 1.2 (Reisen et al. 2005). 

Organic synthesis 51 [OS 51) Nitration of alkanes such as methane and hexane with... 

These quinoxalinylalkyl esters of alkane- or arenecarboxylic acids are sometimes used as intermediates (see, e.g., Section 3.4.2). The formation of an analogous quinoxalinylmethyl nitrate is included in this section. Examples follow. 

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