Trinitrate esters

Tris(hydroxymethyl)ethane (metriol) (63) and 1,1,1 -tris(hydroxymethyl)propane (64) are commercially available and yield the trinitrate esters (4) (metriol trinitrate) and (65) ... 

Dihydroxylation of the allyl groups of (70) with hydrogen peroxide and catalytic osmium tetroxide, followed by 0-nitration of the product (72), yields the hexanitrate ester (73). Similar treatment of the mono-allyl ether (74) affords the pentanitrate ester (76). Evans and Callaghan also 0-nitrated the hydroxy groups of (70) and (74) to yield the dinitrate and trinitrate esters, (71) and (75), respectively. The dinitrate ester (71) may find use as a monomer for the synthesis of energetic binders. 

Pentaerythritol trinitrate esters of nitrobenzoic acid have been also obtained by Marans, Elrick and Preckel [52] who have esterified pentaerythritol trinitrate by means of the corresponding nitrobenzoyl chloride. 

Triethanolamine trinitric ester nitrate (triethanolamine tetranitrate)... 

Its properties resemble those of the preceding substance. One molecule of nitric acid is readily lost by the compound, which is then transformed into triethanolamine trinitrate. The latter is also unstable and inclined to undergo decomposition. Diphosphoric salt of the trinitric ester was claimed to be an effective remedy against angina pectoris, instead of nitroglycerine. 

Merck (1976), 1241 (No 9347) Triethanolamine Tetranitrate. (Triethanolamine trinitric ester nitrate, Tris (j3-nitroxyethyl)-amine nitrate or Trinitroxy triethane amine nitrate). N(CH2. CH2.0N02)3. HN03 or [HN(CH2.CH2.0N02)3] N03, C6 Hj 3 N5 Oi 3 mw 347.24 N 20.17% OB to C02 —29.95% mp 74° (decompn), 62.7°, 62° (sep values). Hydrolyzed by w. Sol in hot ethanol insol in eth. Prepn is by nitration of triethanolamine nitrate with 97% nitric acid at —5°, removing the excess nitric acid in vacuo, pptg the product at —10° with eth, and recrystn from ethanol... 

Chemical Name Ethanol, 2,2, 2"-nitrilotris-, trinitrate (ester), phosphate (1 2) (salt)... 

Glycerine is obtained as a co-product from the hydrolysis of vegetable oils or animal fats. From the esterification of glycerine with nitric acid, the inorganic trinitrate ester (trinitroglycerine) is produced. 

Properly and Preparation of Trinitrate Esters 5.4.1 Property and Preparation of Nitroglycerine [1, 84-87]... 

Property and Preparation of Trinitrate Esters Table 5.43 pH values of nitroglycerine in water at 110 °C... 

The historical emphasis on the trinitrate ester as the derivative of choice for early experimental work on the SEC analysis of cellulose and cellulosics and the continued use of the trinitrate in this capacity are readily understandable. Cellulose nitrate was known to be soluble in organic solvents, and a mild method for its preparation with a high nitrogen content (approximately 13.4% N compared to 14.1% N theoretically) was reported (130). In addition, cellulose trinitrate was extensively used in previous studies of cellulose by viscometry, osmometry, ultracentrifugation, and fractional precipitation. Thus, SEC data could be readily compared with existing data for the trinitrate derivative. 

The use of cellulose derivatives as the basis for analysis was seen as a means of overcoming the difficulties in using cellulose solvents. Early on, SEC analysis of cellulose as its trinitrate ester became the preferred method. This method continues to be used with success. Although the tricarbanilate derivative was tried in some initial experiments, only recently has this cellulose derivative been extensively used because of several reported advantages over the trinitrate derivative. 

The structures of the mineral acids suggest that replacing one or more OH units will lead to acid derivatives. Esters are possible for all three mineral acids. Nitric acid gives a nitrate ester, 197. Nitrate esters are often unstable, and the trinitrate ester of glycerol (198) is the well-known explosive nitroglycerin. However, highly specialized nitrate esters are known to relax vascular smooth muscle, which leads to vasodilation (relaxation of the muscle wall of blood vessels that leads to widening of those vessels), and they are important compounds used in the treatment of heart disease. Nonetheless, nitrate esters will not be discussed further or used in this book. Amide derivatives O3N-NR2 are known as nitramides, but they will not be discussed. 

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