3-nitro-1-propanol nitrate

MethyU2-Nitro-l-Propanol (2-Nitro-2-methyl-1 -propanol, /J-Nitroisobutylalcohol). (CH3)2.C(N02).CH20H, mw 119.12, N 11.76%, OB to C02 —127.60%, needles or plates from methanol, mp 90—91°, bp 94.5—95.5° at. 10mm. Easily sol in ethyl methyl ales, eth and w (350p in lOOp at 20°). May be prepd by treating 2-nitropropane with formaldehyde in the presence of an alkaline catalyst, such as K bicarbonate (Refs 1, 2, 3 4). On nitration, it yields an expl, 2-Methyl-2-Nitro-l-Propanol Nitrate (see below)... 

Methyl-2-Nitro-1-Propanol Nitrate (2-Nitro-2-methyl-l-propanol nitrate). 

Preparation of 2-nitro-2-methyl-1 -propanol-nitrate. 50g of the 2-nitro-2-methyl-1-propanol purified as above were sifted into a mixt of 58.5g of 90.5% nitric acid.and 241,5g of 103.1% sulfuric acid (oleum) while the well-agitated mixt was maintained close to 15°. Stirring was continued for 1 hour and the mixt allowed to stand for hour. No separation of the nitration product occurred and the mixt was poured over cracked ice. An oily layer separated. The mixt was transferred to a separatory funnel, washed with water, Na bicarbonate, and twice with water to neutrality. The separated diluted spent acid together with the washings were thoroughly extracted with ether, the ether extract washed to neutrality and added to the main product. 

Alkenes react with dinitrogen pentoxide in chlorinated solvents to give a mixture of /3-nitro-nitrate, vic-dinitro, vic-dinitrate ester and nitroalkene compounds. At temperatures between -30 °C and -10 °C the /3-nitro-nitrate is often the main product. The /3-nitro-nitrates are inherently unstable and readily form the corresponding nitroalkenes." Propylene reacts with dinitrogen pentoxide in methylene chloride between -10 °C and 0°C to form a mixture of l-nitro-2-propanol nitrate (27 %) and isomeric nitropropenes (12 %). The same reaction with cyclohexene is more complicated." ... 

Cyclopropane is reported to react with dinitrogen pentoxide in methylene chloride at subambient temperature to yield 3-nitro-l-propanol nitrate. ... 

In the improvement of DNPDOH (2,2-dinitro-1,3-propanediol) [66], used sodium nitrite was reduced from 4 times to the equal amount, the amounts of sodium persulfate and potassium ferricyanide were adjusted, which reduced the impact of carbon emission pollution on the environment, and the cost of synthesis was reduced. The synthesis yield was 68 % after improvement, and lower than the production cost is much lower than that of silver nitration method. Major improvement in electrochemical synthesis of DNPOH is that In the first step, sodium hydroxide solution was added to an aqueous solution of 2-nitropropanol after 45 min of stirring at room temperature, lithium perchlorate solution and sodium nitrite solution were added to prepare the deprotonated 2-nitropropanol solution in the second step, deprotonated 2-nitro-propanol solution is added into the working electrode chamber and the reference electrode chamber of the electrolytic cell, and electrolytic reaction is continued for about 1 h under nitrogen for 20 min. Finally DNPOH will be obtained with a yield of about 40 %. The reaction mechanism is ... 

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-... 

Nitroparaffins, Explosives Derived From. Although mononitroparaffms are generally not expl, they can be used for the prepn of expls Aaronson (Ref 1) nitrated nitroisobutyl-glycerin to Nitroisobutylgjycerintrinitrate, 2-nitro-2-methyl-l,3-propane diol to 2-Nitro-2-methyl-l, 3-propanedioIdinitrate, and 2-nitro-2-methyl-l-propanol to 2-Nitro-2-methyl-l-pro-panolnitrate. Their prepn and characterization follow ... 

Purification of 2-nitro-2-methyl-l-propanol. Material melting at 86—87° and made by the Commercial Solvents Corp was recrystd from benzene and dried in a vacuum desiccator. The mp was about 88° (not sharp). This materia was used for nitration... 

It was claimed by Henry(Ref 2) that 0. de Battice prepd nitroacetone in 1895 in Belgium by oxidation of nitroisopropanol with chromic mixture. Henry described the compd as a coi, mobile liq with a sharp odor, a 1.070 at 14°, bp 152° at 767 mm and insol in w. Lucas c]aimed(Ref 3) that the compd described by Henry was not nitroacetone, but this statement was disputed by Henry(Ref 4). Harries also claimed(Ref 5) that the compd described by Henry is not nitroacetone More recently, Hass Hudgin(Ref 7) claimed that they had isolated some nitroacetone from the high-boiling fraction of the vapor-phase nitration of acetone but it is not clear from their paper whether the substance was liq or solid. Hurd NilsonfRef 8) prepd nitroacetone as pale-green crysts, mp 47°, by oxidizing 1—nitro—2—propanol with sodium dichromate and sulfuric acid. The yield was (5% of theoretical. The explosifcility of this compd was not mentioned... 

The cyano biarylamine used in the synthesis was obtained from the commercially available 4-cyano biphenyl, 17 (Scheme 3). Nitration of 17 in trifluoroacetic anhydride resulted in a 3 1 mixture of 4 - and 2 -nitro compounds. From the mixture, the required 4 -nitro confound was separated by crystallization from acetone-uo-propanol. Reduction of the nitro groiqi was carried out with tin(II) chloride and cone. HCl to afford the required product in 90% yield. 

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