Polyol nitrates

Uses of NG. Aside from die expl uses discussed under Dynamite and Smokeless Powder (NG gelled with NC), the only extensive use for NG is as a decrease of blood pressure in the treatment of angina pectoris where It is in competition with other polyol nitrates. There is voluminous literature on the pros, aons, and wherefores of this subject... 

Determination of NG by Gas Liquid Chromatography. This technique is useful for measuring NG or other polyol nitrates present in air. Bubble a 10-liter sample thro two 10-ml containers of ale, then inject some of the ale soln onto a siliconized Chromosorb P column coated with 10% Igepal CO-880. Run the analysis at 160° under nitrogen carrier to detect a min of 2mg (Ref 14)... 

Alkyl nitrates (V), particularly polyol nitrates (V) such as nitrocellulose and nitroglycerine Alkyl and acyl nitrites (III)... 

Alkyl nitrates, particularly polyol nitrates such as nitrocellulose and nitroglycerine... 

Nitration of low molecular weight polyols, rather than polysaccharides, was initiated by Sobrero, who produced glyceryl trinitrate (nitroglycerin) in 1846 and mannitol hexanitrate in 1847, although the explosive properties of hexani-tromannitol were not examined until 1878, by Sokolov.During the various arms races between the Crimean War and the end of World War II, a host of polyol nitrates were investigated some of the compounds that have remained... 

By the use of very fast photodetectors, it has recently become possible to analyse intermediates in the deflagrations and detonations of polyol nitrates. Although data are still limited, it seems as if detonations are initiated by 5 nI departure of nitrate, followed by carbenium ion reactions, whereas deflagrations are initiated by thermal homolysis of the O-N bond. 

Separated polyols are detected by a variety of reagents, including ammoniacal silver nitrate (175), concentrated sulfuric acid, potassium permanganate (163), lead tetraacetate, and potassium teUuratocuprate (176). A mixture of sodium metaperiodate and potassium permanganate can be used to detect as htde as 5—8 ).tg of mannitol or erythritol (177). 

Polyhydric Alcohols. (Polyols). An alcohol with three or more hydroxyl groups, each attached to a different carbon atom. They are w-sol and of sweetish taste, which tends to intensify with increasing hydroxyl content. Examples of polyols of ordn interest are listed below. Polyvinyl alcohol is considered in a separate entry as a polymer although it is defined as a polyhydric alcohol. Polyols, when nitrated, make excellent expls, proplnt binders, plasticizers, etc. Prepn can follow the procedure of Lenth DuPuis (Ref 3) which uses a methanol suspension of either sucrose or dextrose and a special Cu-Al oxide catalyst to yield 60-65% distillable polyols at 240° and 1500psi Refs 1) Beil — refs found under individual compds 2) CA, under Alcohols, Polyhydric for compds of current ordn interest 3) C.W. Lenth R.N. DuPuis, "Polyhydric Alcohol Production by Hydrogenolysis of Sugars in the Presence of Copper-Aluminum Oxide , IEC 37, 152-57 (1945) CA 39, 1391 (1945)... 

Hawley, Glossary of Chemical Terms , Van-Nostrand-Reinhold,NY (1976), 217 Addnl Refs 1) K.S. Warren, Study Nitrates of Polyhydric Alcohols as Explosives , PATR 1103 (1941) la) D.B. Bright et al, Development of Polyol Prepolymers Containing High Energy Oxidizing Groups , Report No S-13843, Contract AF 04(611>5690, Shed Devel Co, Emeryville (1961) (limited distribution) 2) A.D. McElroy, Basic Approach to Incorporation of NP Propellants , Rept No RPL TDR 6448, Contract AF 04(611)-9059, Callery Chem Co, Phlla (1964) 3)... 

Gyttorp [Named after a small Swedish town] A continuous process for nitrating polyols to form nitrate esters, used as explosives. Similar to the Biazzi process. 

Nitro Nobel A process for making nitrate esters such as nitroglycerol. A special injector is used to mix the liquid polyol with the nitrating acid. 

Henry reactions have been extensively exploited for the synthesis of nitrate ester explosives. The condensation of nitroalkanes with aldehydes, followed by esterification of the hydroxy groups with nitric acid, leads to a number of nitrate ester explosives (see Chapter 3). The two examples given above (166 and 167) are synthesized from the C-nitration of the polyols obtained from the condensation of formaldehyde with nitromethane and nitroethane respectively. 

Olah and co-workers ° conducted a comprehensive study into the use of N-nitropyridinium salts for nitration. Such salts are easily prepared from the slow addition of the appropriate heterocyclic base to an equimolar suspension of nitronium tetrafluoroborate in acetonitrile. Olah studied the effect on nitration of changing both the structure of the heterocyclic base and the counter ion. Three of these salts (20, 21, 22) illustrated above have been synthesized and used for the 0-nitration of alcohols with success. Transfer nitrations with Al-nitropyridinium salts are particularly useful for the preparation of nitrate esters from acid-sensitive alcohols and polyols because conditions are essentially neutral. 

SYNTHETIC ROUTES TO SOME POLYOLS AND THEIR NITRATE ESTER DERIVATIVES... 

The reaction between formaldehyde and compounds containing acidic protons is probably the most important route to polyols. Some of these polyols have been 0-nitrated and used as practical explosives. The condensation of nitromethane and nitroethane with excess formaldehyde in the presence of potassium hydrogen carbonate yields tris(hydroxymethyl)nitromethane (58) and l,l-bis(hydroxymethyl)nitroethane (60) respectively. The nitration of (58) and (60) with either absolute nitric acid or mixed acid gives the secondary high explosives, (59) and (61) respectively. 

The dihydroxylation of alkenes is a useful sttategy for the synthesis of polyols and these can be nitrated to the corresponding nitrate esters. Evans and Gallaghan " synthesized both the mono- (74) and di- (70) allyl ethers of pentaerythritol and used these for the synthesis of some novel nitrate ester explosives. 

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