2.2- dinitropropanol

Jensen, The Preparation of 2,2,2-Trinitroethyl- 4,4-dinitropentanoate , NAVORD 2498 (1952) 4) M. Hill, Preparation and Properties of 2,2-Dinitropropanol Esters , NAVORD 2497 (1952)... 

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). ... 

Shackelford and co-workers studied the 1,2-addition of 2,2-dinitropropanol, 2,2,2-trinitroethanol, and 2-fluoro-2,2-dinitroethanol across the double bonds of vinyl ethers. These reactions are Lewis acid catalyzed because of the weak nucleophilic character of alcohols which contain two or three electron-withdrawing groups on the carbon p to the hydroxy functionality. Base catalysis is precluded since alkaline conditions lead to deformylation with the formation of formaldehyde and the nitronate salt. 

Frankel and Klager have reported using the Mannich reaction for the condensation of 2,2-dinitroalkanols with ammonia and hydrazine. This method was used to synthesize 2,2,6,6-tetranitro-4-azaheptane (100%) and bis(2,2-dinitropropyl)hydrazine (162) (73%) from the reaction of 2,2-dinitropropanol (25) with ammonia and hydrazine hydrate respectively. This work was later extended to using polynitroaliphatic amines and diamines. " ... 

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-... 

Sulfuric acid cannot be used for the synthesis of acetals and so bis(2,2-dinitropropyl)acetal (179) is prepared from the reaction of paraldehyde with 2,2-dinitropropanol (25) in the presence of boron trifluoride.333 323 50 50 eutectic mixture of bis(2,2-dinitropropyl)formal (175) and bis(2,2-dinitropropyl)acetal (179) has found use as an energetic liquid plastisizer for nitrocellulose. 

N 14.68%, crysts (from MeOH), mp 85—85.6° sp gr 1.51. It was prepd by the Al chloride. catalyzed esterification of 2,2-dinitropropanol with succinyl chloride in methylene chloride soln (Refs 3 Sc 6). It is an insensitive compd (50% Impact Sensitivity, 2.5kg wt >320cm),... 

A good illustration of the relationship between the acidity of alcohols and their reactivity towards sulfur tetrafluoride can be found in the reaction of nitro alcohols. The conversion of 2,2,2-trinitroethanol into 2-fluoro-l,l,l-trinitroethane (la) proceeds at ambient temperature, while 2,2-dinitropropanol and 2,2-dinitropropane-l,3-diol are less reactive and require elevated temperatures for their conversion into l-fluoro-2,2-dinitropropane (lb) and 1.3-difluoro-2,2-dinitropropane(2), respectively. 2-Methyl-2-nitropropanol, however, does not react with sulfur tetrafluoride.43... 

H8C.CH2.NH.CH2.C(N02)2.CH8.HN03 mw 240.17, N23.33%, OB to CO2-60% crysts, mp 111-112°. Prepd by condensing ethylamine with 2,2-dinitropropanol to give the free base (which tends to revert to starting material), followed by addition of 70% HN03 in eth Refs l)Beil, not found 2)H.E.Ungfiade ... 

A reactor was charged with 2,2-dinitropropanol (0.1 mol), formaldehyde (0.11 mol), allyl alcohol (0.3 mol), and CH2CI2 (40 g) and treated with the slow addition of boron trifluoride etherate (0.3 mol) at 5°C. After the addition the mixture was stirred at 5°C for 40 minutes. Thereafter 100 ml of water was slowly added to the mixture, which was then stirred and the aqueous component discarded. The organic layer was washed 3 times with NaOH, once with water, once with brine, and again with water. The organic phase was then dried, concentrated, and the product was isolated in 73% yield. 

Tile monomer was prepared by dissolving 2,2-dinitropropanol and acrylic chloride in carbon tetrachloride and heating for 12 hours at 55 C. The dried product was mixed with powdered silver and vacuum distilled. It can be used as a binder in propellants burning readily at a pressure of ca. 70 kg/cm. It can be polymerized in toluene in the presettee of azobisisobutyroniiriic as a free radical catalyst, under dry nitrogen at SO C for 45 min. The conversion of. 25% was obtained to yield the polymer ... 

Acetal from the formed multi-nitro alcohol is the main energetic ingredient in liquid mixed explosives [19], and can be used as a rocket propellant. Formaldehyde and 2,2-dinitropropanol can generate acetal through addition reaction. The condensation reaction can be catalyzed by 96 % H2SO4, calcium chloride, zinc chloride, ferric chloride or boron trifluoride via catalytic polycondensation. 

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