2- Nitro-2- -propanediol

On dehydration, nitro alcohols yield nitro-olefins. The ester of the nitro alcohol is treated with caustic or is refluxed with a reagent, eg, phthaUc anhydride or phosphoms pentoxide. A mil der method involves the use of methane sulfonyl chloride to transform the hydroxyl into a better leaving group. Yields up to 80% after a reaction time of 15 min at 0°C have been reported (5). In aqueous solution, nitro alcohols decompose at pH 7.0 with the formation of formaldehyde. One mole of formaldehyde is released per mole of monohydric nitro alcohol, and two moles of formaldehyde are released by the nitrodiols. However, 2-hydroxymethyl-2-nitro-l,3-propanediol gives only two moles of formaldehyde instead of the expected three moles. The rate of release of formaldehyde increases with the pH or the temperature or both. 

The nitro alcohols in Table 1 are manufactured in commercial quantities however, three of the five of them are used only for the production of the corresponding amino alcohols. 2-Methyl-2-nitro-l-propanol (NMP) is available as the crystalline soHd or as a mixture with siHcon dioxide. 2-Hydroxymethyl-2-nitro-1,3-propanediol is available as the soHd ( 9.15/kg), a 50% solution in water ( 2.33/kg), a 25% solution in water ( 1.41/kg), or as... 

In a battery of tests, which determine the tendency of chemicals to inhibit aquatic organisms, accumulate in such organisms, and degrade in the environment, 2-hydroxy-2-nitro-l,3-propanediol was found to have low potential for harm in the environment (7). 

Polymers. AH nitro alcohols are sources of formaldehyde for cross-linking in polymers of urea, melamine, phenols, resorcinol, etc (see Amino RESINS AND PLASTICS). Nitrodiols and 2-hydroxymethyl-2-nitro-l,3-propanediol can be used as polyols to form polyester or polyurethane products (see Polyesters Urethane polymers). 2-Methyl-2-nitro-l-propanol is used in tires to promote the adhesion of mbber to tire cord (qv). Nitro alcohols are used as hardening agents in photographic processes, and 2-hydroxymethyl-2-nitro-l,3-propanediol is a cross-linking agent for starch adhesives, polyamides, urea resins, or wool, and in tanning operations (17—25). Wrinkle-resistant fabric with reduced free formaldehyde content is obtained by treatment with... 

Stabilizers. Nitro alcohols can be used to prevent the decomposition of phenylenediarnine color-developing agents (27). 2-Hydroxymethyl-2-nitro-l,3-propanediol and 2-nitro-1-butanol have been used as additives for the stabilization of 1,1,1-trichloroethane. 

Other. 2-Nitro-1-butanol is an excellent solvent for many polyamide resins, cellulose acetate butyrate, and ethylceUulose. It can be utilized in paint removers for epoxy-based coatings. 2-Hydroxymethyl-2-nitro-l,3-propanediol is usebil for control of odors in chemical toilets. Its slow release of formaldehyde ensures prolonged action to control odor, and there is no reodorant problem which sometimes is associated with the use of free formaldehyde. 2-Hydroxymethyl-2-nitro-l,3-propanediol solutions are effective preservative and embalming fluids. The slow Uberation of formaldehyde permits thorough penetration of the tissues before hardening. 

Nitromethane. The nitroparaffins are used widely as raw materials for synthesis. Nitromethane is used to produce the nitro alcohol (qv) 2-(hydroxymethyl)-2-nitro-l,3-propanediol, which is a registered biocide useful for control of bacteria in a number of industrial processes. This nitro alcohol also serves as the raw material for the production of the alkanolamine (qv) 2-amino-2-(hydroxymethyl)-l,3-propanediol, which is an important buffering agent useful in a number of pharmaceutical appHcations. 

Methyl-2-nitro-l,3-propanediol [77-49-6] M 135.1, m 145 . Crystd from n-butanol. 

Tris-(hydroxymethyl)nitromethane [2-(hydroxymethyl)-2-nitro-l,3-propanediol] [126-11-4] M 151.1, m 174-175°(dec, tech grade), 214°(pure). Crystd from CHCl3/ethyl acetate or ethyl acetate/ benzene. It is an acid and a O.IM sol in H2O has pH 4.5. IRRITANT. 

Replacement of one tosyloxy group m 2-fluoro-2-nitro-l,3-propanediol ditosylate by azide ion occurs easily [S5] (equation 75)... 

Nitroethane and formaldehyde are first reacted to give 2-methyl-2-nitro-1,3-propanediol. This is reacted with 2-ethylhexylamine and formaldehyde to give 5-nitro-1,3-bis(2-ethyl-hexyl)-5-methyl-hexahydropyrimidine. 

Methylnitropropanediol (2-Nitro-2-methyl-l, 3-propanediol). Clfe. C(N02)(CH20H)2 mw 135.12, N 10.37% monocl crysts mp 149— 51° bp decompn. Sol in w (80p in lOOp at 20°) and in ale. Can be prepd by treating a mixt of nitroethane and formaldehyde in w with a small amt of K bicarbonate as catalyst. On nitration, it yields an expl, 2-Methyl-2-nitro-1,3-propanediol dinitrate (see below)... 

Nitroisobutylglycerin (2-Nitro -2-me thylol-1,3-propanediol, 2-Nitro-2-oxymethyl-l, 3-propanediol). 02N.C(CH20H)3, mw 151.12, N 9.26%, OB to C02 79.4%, mp 144—180°. Note According to Beil 1, [596] it exists in two modifications, one melting (not sharply) at 144°, and the other at 180°. The second form is obtained by treating the first form with either sulfuryl-chloride or phosphorous trichloride. After ciystn from ethyl acetate chlf, a substance is obtained which melts sharply at 180°. On standing, the second form slowly reverts to the low melting modification. It is usually found in the form of needles and crysts, and is sol in w, ale and eth... 

Add 20.0g of 2-nitro-2-(3,5,-dinitrophenyl)-propanediol-1,3 in several portions to 130ml of fuming nitric acid (d 1.5g/cc) cooled to 5°. 

Notes 1) Nitration with mixed nitric-sulfuric acid gives a less satisfactory product and a lower yield (about 52%). 2) Attempts to prepare the product starting with 2-nitro-2-(m-nitrophenyl)-propanediol-1,3 or its dinitrate were unsuccessful Its expl props were detd by R. McGill et al at the NDRC Res Lab at Bruceton, Pa and were found to be as follows ... 

Nitro-2-(m-nitrophenyl)-propanediol-1,3 Dinitrate (2-Nitro-2-(3,-nitrophenyl)-propane-... 

The Polyurethane Polymer of 3,3,5,7,7-Penta-nitro-5-Aza-1,9-Nonane Diisocyanate and 2,2-Dinitro-1,3-propanediol. 

The Polyurethane Polymer of 2-Nitraza-1,4-Butane Diisocyanate and 2-Nitro-2-Methy 1-1,3-Propanediol. 

The Postnitrated Polyurethane Polymer of 3-Nitro-3-Aza-l,5-Pentane Diisocyanate and 2-Nitro-2-Methyl-1,3-Propanediol. 

Purification of 2-nitro-2-methyl- 1,3-propanediol. This material was purchased from the Commercial Solvents Corp and had a melting point of 135-136°. By recrystallizing twice from 95% ale the mp was raised to 151.2. This purified material was used for nitration... 

Nitro-2-(3-nitrophenyl)-propanediol-1,3-dinitrate (2-Nitro-2-(m-nitrophenyl)-propane-l, 3-diol-dinitrate). (02N)C6H4. C(N02) (CH20N02)2, mw 332, N 16 %, OB to C02 -57.8%, pale yel acicular prisms, mp 71—73.6°. Can be prepd by nitrating 2-nitro-2-(3 r-nitrophenyl)-propanediol-1, 3 with mixed nitric-sulfuric acid, as described in Ref 2, p 23. Sol in most common organic solvents... 

Note A mixt consisting chiefly of 1,2-Propanediol Dinitrate, but contg varying amts of ethylene glycol dinitrate and butylene glycol dinitrate was marketed under the trade name Nitro-byronel (Ref 8)... 

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). ... 

Frankel synthesized 2-nitro-3-acetoxy-l-propene (139) by heating l,3-diacetoxy-2-nitropropane (138) with sodium acetate under reduced pressure. The reaction of 2-nitro-3-acetoxy-l-propene with 1,1-dinitroethane yields 2,2,4,6,6-pentanitroheptane. The same reaction with nitroform provides 1,1,1,3,5,5,5-heptanitropentane (142), a powerful explosive (VOD 9230 m/s) with an excellent oxygen balance. The synthesis of 1,1,1,3,5,5,5-heptanitropentane from2-nitro-l,3-propanediol and 2-nitro-l-propen-3-ol has also been reported and involves a similar mechanism. 

Canfield and Rohrback ° reported on the reaction of some electron-deficient difluo-roaminoalkenes with dinitrogen pentoxide in chloroform at subambient temperatures. Contrary to previous work that the /3-nitro-nitrate ester should be the main product, the corresponding vtc-dinitrate esters were isolated from these reactions l,4-bis(iV,iV-difiuoroamino)-2,3-butanediol dinitrate (55), 3,4-bis(iV,iV-difluoroamino)-l,2-butanediol dinitrate (56) and 3-(iV,iV-difluoroamino)-1,2-propanediol dinitrate (57) were isolated in 30 %, 27 %, and 55 % yields respectively, from the parent alkenes. 

Chemical synthesis of racemates and subsequent resolution via crystallization of diastereomeric salts is employed in the preparation of rf-biotin and tocopherol (vitamins), dexchlorpheniramine (antihistaminic), levomepromazine (neuroleptic), levorphanol (analgesic), and naproxen (antiphlogistic), to note some examples4, threo-2-Amino-1 -(4-nitro-phenyl)-l,3-propanediol, an intermediate in the production of chloramphenicol, is resolved by crystallization with entrainment or via crystallization of the salt with camphorsulfonic acid4. Enzymatic resolutions are increasingly employed, normally via deacetylation of racemic acetates. This method has recently been used in the synthesis of carbacyclin derivatives5. 

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