2.2- dinitro-l ,3-propanediol

The use of polynitroaliphatic alcohols as sources of the corresponding nitronate anions is common in addition reactions. However, polynitroaliphatic alcohols are useful in their own right. The hydroxy functionalities of 2,2-dinitroethanol, 2,2-dinitro-l,3-propanediol and... 

Formals and acetals prepared from the reaction of polynitroaliphatic alcohols with formaldehyde and acetaldehyde have found use as explosive plastisizers for nitrocellulose and in plastic bonded explosives (PBXs). Formals of polynitroaliphatic alcohols are commonly prepared via reaction with trioxane or paraformaldehyde in the presence of sulfuric acid as a condensing agent. Bis(2,2-dinitropropyl)formal (175) is prepared from the reaction of trioxane with 2,2-dinitropropanol (25). The reaction of 2,2,2-trinitroethanol (159) and 2,2-dinitro-l,3-propanediol (19) with formaldehyde in the presence of sulfu-... 

A large number of nitramine-based explosives have been synthesized via Mannich-type condensation reactions (Section 5.13.2). The amines generated from these reactions often have the powerful electron-withdrawing trinitromethyl or fluorodinitromethyl groups positioned on the carbon a to the amino group. This reduces amine basicity to an extent that A-nitration becomes facile. The energetic nitramines (17), (19) and (21) have been synthesized from the condensation of ethylenediamine with 2,2,2-trinitroethanol, 2-fluoro-2,2-dinitroethanol with ethanolamine, and 2-fluoro-2,2-dinitroethylamine with 2,2-dinitro-l,3-propanediol respectively, followed by A-nitration of the resulting amine bases (16), (18) and (20), respectively. 

Pentanitropiperidine (91) is prepared from the condensation of 2,2-dinitro-l,3-propanediol (89) with formaldehyde and f-butylamine under slightly acidic conditions, followed by nitrolysis of the f-butyl group of the resulting piperidine (90) with mixed acid or absolute nitric acid. ... 

Dinitro-l,3-propanediol diformate Novel low sensitivity, energetic plasticizer useful for composite and multi-base explosive and propellant formulations [175]. 

Note R.C.Elderfield et al [OSRD Rept 158 (1941), 7-8] prepd by condensing 2-amino-2-methyl-l,3-propanediol with 2,4-dinitro-chlorobenzene the product identified as 2,4-dinitrophenyl-bisfhydroxymethyl)-methylamine, mp 162—3°, which on nitration with mixed nitricsulfuric acid gave 2,4,6- trini trophenyl-( bi s- hydroxy )-tert-butylnitramine dinitrate, mp 159°,(See also under Anilinomethylpropanediol... 

The Polyester Polymer of 4,4-Dinitro-l,7-Heptanedioyl Chloride and 2,2-Dinitro-1,3-Propanediol. 

N 22.42%, OB to CO, -27.4%, OB to CO +5.5%. Lt yel crysts, mp 142-3° (with decomp) insol in w, ales, pet eth, chlf, CQ4, benz tol sol in acet, AcOH, NB pyridine. Can be prepd by nitrating either the corresponding dinitro- or trinitro- compds with fuming nitric acid (Ref 2). It is a powerful explosive Note According to Elderfield et al (Ref 3), the nitration of 2-(2, 4 -dinitrophenyl-amino)-1,3-propanediol with mixed nitric-sulfuric acid yielded a product which melted at 146.5° and exploded on further heating or on being stnick with a hammer on an iron surface. No analysis was made but it seems that this product was identical with the one prepd by den Otter Refs l)Beil—not found 2)H.P.den... 

Pentolite [8066-33-9] [2,2-bis(nitrooxy) methyl)-l,3-propanediol dinitrate mixed with 2-methyl-1,3,5-trinitrobenzene] Picramic acid (dry) [96-91-3] (4,6-Dinitro-2-aminophenol)... 

Axenrod and co-workers reported a synthesis of TNAZ (18) starting from 3-amino-l,2-propanediol (28). Treatment of (28) with two equivalents of p-toluenesulfonyl chloride in the presence of pyridine yields the ditosylate (29), which on further protection as a TBS derivative, followed by treatment with lithium hydride in THF, induces ring closure to the azetidine (31) in excellent yield. Removal of the TBS protecting group from (31) with acetic acid at elevated temperature is followed by oxidation of the alcohol (32) to the ketone (33). Treatment of the ketone (33) with hydroxylamine hydrochloride in aqueous sodium acetate yields the oxime (34). The synthesis of TNAZ (18) is completed on treatment of the oxime (34) with pure nitric acid in methylene chloride, a reaction leading to oxidation-nitration of the oxime group to em-dinitro functionality and nitrolysis of the A-tosyl bond. This synthesis provides TNAZ in yields of 17-21 % over the seven steps. 

Chloroanilino-propanediols or Chloropbenyl-amino-propanediols, C9H12C1N02. The 3-chloro isomer is mentioned in Ref 2. They may be considered as parent compds of the two dinitro derivs described below, although they were not used for their prepn Refs l)Beil - not found 2)J.B. Dickey ... 

---