Pentaerythritol nitrates

J. W. F. Davidson, F. J. Dicarlo, and E. F. Szabo, Gas chromatographic separation and detection of pentaerythritol nitrates and other organic nitrate esters, J. Chromatogr., 57 345 (1971). 

Covalent nitrates. Apart from organic nitrates covalent nitrates of non-metals are limited to those of H, F, and Cl. (CINO3 has been prepared from anhydrous HNO3 and CIF as a liquid stable at —40°C in glass or stainless steel vessels. 9 Electron diffraction studies have been made of the explosive gas FN03 and of the (planar) methyl nitrate molecule. A refinement of the crystal structure of pentaerythritol nitrate, C(CH20N02)4, shows that the nitrate group has the same structure, (d), as in nitric acid. 

A number of explosives fit the latter mechanism. These include lead azide, ammonium nitrate and pentaerythritol nitrate.The critical strains needed to initiate explosion may be estimated. As expected, the sensitivity of explosives to shock can also be rationalized by estimating their initial HOMO-LUMO gaps, or E°g. For solids such as Pb(N3)2, the energy needed to excite an electron from the valence band to the conduction band can be found by spectroscopy. A small gap means high sensitivity. ... 

Pentaerythritol may be nitrated by a batch process at 15.25°C using concentrated nitric acid in a stainless steel vessel equipped with an agitator and cooling coils to keep the reaction temperature at 15—25°C. The PETN is precipitated in a jacketed diluter by adding sufficient water to the solution to reduce the acid concentration to about 30%. The crystals are vacuum filtered and washed with water followed by washes with water containing a small amount of sodium carbonate and then cold water. The water-wet PETN is dissolved in acetone containing a small amount of sodium carbonate at 50°C and reprecipitated with water the yield is about 95%. Impurities include pentaerythritol trinitrate, dipentaerythritol hexanitrate, and tripentaerythritol acetonitrate. Pentaerythritol tetranitrate is shipped wet in water—alcohol in packing similar to that used for primary explosives. 

After the removai of acid, the nitrate was dried by suction on the nutsch for about 15 minutes. The dried material was refined by means of acetone treatment or other suitabie refining means. About 210 parts refined pentaerythritol tetranitrate per charge was obtained. 

Pentaerythritol Dinitrate [2,2-Bis(hydroxy-methyll-1, 3-propanediol 1,3-di nitrate... 

Pentaerythritol Dichloride Di nitrate [2,2-Bis(ch oromethyl -1,3-propanediol Di nitrate (name preferred by CA)). CsH8C12N206, mw 263.04, N 10.65%. CH2C1... 

PETN was first prepared in 1894 by the nitration of pentaerythritol, PE (Ref 1). This is still the basic method used today. Commercial production of PETN could not be realized until the formaldehyde and acetaldehyde required in the synthesis of PE became readily available about a decade before WWII... 

Crystal Structure of the Tetraacetate and Tetra-nitrate of Pentaerythritol , ZKrist 66, 355—92... 

Mono and Diallyl Esthers (sic) of Pentaerythritol and some of the Properties of their Nitrates , Bulletin of 4th Army-Navy Solid Propellant Group Meeting, Chicago (19—20 Apr 1948), 83 3) R. Evans J.A. Callaghan, JACS 75, 1248 (1953)... 

PETN. Acronym for Pentaerythritol Tetra-nitrate. See under Pentaerythritol and its Derivatives in this Vol ... 

Pentaerythritol is made commercially by the reaction of formaldehyde and acetaldehyde in the presence of alkali. It can be nitrated by adding it to strong nitric acid at temperatures below about 30°C. An excess of nitric... 

The above mechanism of intramolecularly catalyzed cleavage is possible only for compounds with a N02 group close to the departing NO group. In other words, it can be postulated to follow nitro reduction in erythritol tetra-nitrate (9.8), mannitol hexanitrate (9.9), pentaerythritol tetranitrate (9.10), and perhaps trolnitrate (9.14), but not in isosorbide dinitrate (9.11). 

S. Y. P. King, H. L. Fung, Rapid Microbial Degradation of Organic Nitrates in Rat Excreta. Re-Examination of the Urinary and Fecal Profiles of Pentaerythritol Tetranitrate in the Rat , Drug Metab. Dispos. 1984, 12, 353-357. 

AN, ammonium nitrate HMTD, hexamethylene triperoxide diamine HMX, C4H8N8O8 NG, nitroglycerin PETN, pentaerythritol tetranitrate RDX, CsHgNgOg TATP, triacetone triperoxide ... 

Pentaerythritol tetranitrate (PETN) (3) is a powerful explosive which exhibits considerable brisance on detonation (VOD 8310 m/s at = 1.77 g/cm ). It is the most stable and least reactive of the common nitrate ester explosives. The relatively high sensitivity of PETN to friction and impact means that it is usually desensitized with phlegmatizers like wax and the product is used in detonation cord, boosters and as a base charge in detonators. Pentaerythritol tetranitrate can be mixed with synthetic polymers to form plastic bonded explosives (PBXs) like detasheet and Semtex-IA. A cast mixture of PETN and TNT in equal proportions is known as pentolite and has seen wide use as a military explosive and in booster charges. The physical, chemical and explosive properties of PETN commend its use as a high explosive. 

---