Hexamethylenetetramine Properties

In a 500 ml. flask, fitted with a reflux condenser, place 53 g. of 1-chloro-methylnaphthalene (Section IV.23), 84 g, of hexamethylenetetramine and 250 ml. of 1 1 acetic acid [CAUTION 1-Chloromethylnaphtha-lene and, to a lesser degree, a-naphthaldehyde have lachrymatory and vesicant properties adequate precautions should therefore be taken to avoid contact with these substances.] Heat the mixture under reflux for 2 hours it becomes homogeneous after about 15 minutes and then an oil commences to separate. Add 100 ml. of concentrated hydrochloric acid and reflux for a further 15 minutes this will hydrolyse any SchifiF s bases which may be formed from amine and aldehyde present and will also convert any amines into the ether-insoluble hydrochlorides. Cool, and extract the mixture with 150 ml. of ether. Wash the ether layer with three 50 ml. portions of water, then cautiously with 50 ml. of 10 per cent, sodium carbonate solution, followed by 50 ml. of water. Dry the ethereal solution with anhydrous magnesium sulphate, remove the ether by distillation on a steam bath, and distil the residue under reduced pressure. Collect the a-naphthaldehyde at 160-162718 mm. the yield is 38 g. 

Acid—Base Chemistry. Acetic acid dissociates in water, pK = 4.76 at 25°C. It is a mild acid which can be used for analysis of bases too weak to detect in water (26). It readily neutralizes the ordinary hydroxides of the alkaU metals and the alkaline earths to form the corresponding acetates. When the cmde material pyroligneous acid is neutralized with limestone or magnesia the commercial acetate of lime or acetate of magnesia is obtained (7). Acetic acid accepts protons only from the strongest acids such as nitric acid and sulfuric acid. Other acids exhibit very powerful, superacid properties in acetic acid solutions and are thus useful catalysts for esterifications of olefins and alcohols (27). Nitrations conducted in acetic acid solvent are effected because of the formation of the nitronium ion, NO Hexamethylenetetramine [100-97-0] may be nitrated in acetic acid solvent to yield the explosive cycl o trim ethyl en etrin itram in e [121 -82-4] also known as cyclonit or RDX. 

Compound 225 can be recrystallized from a large volume of water but gradually decomposes into starting materials, especially in the presence of aqueous mineral acids in a process similar to that for hexamethylenetetramine. When treated with concentrated nitric acid, it yields hexogen (cyclotrimethylenetrinitroamine, an explosive).245 Similar properties can be expected for 226, which is characterized by its high toxicity.246... 

The author did not cite the product as an explosive — he recommended its use in medicine — but in later patents [3] he proposed the use of cyclonite in the manufacture of smokeless propellant. In 1921 Herz [4] modified Henning s method by nitrating hexamethylenetetramine itself, not its nitrate. Hale [5] described in detail the preparation of cyclonite by nitrating hexamethylenetetramine, and reported its explosive properties. 

Hexamethylenetriperoxidediamine is the only organic peroxide which has been considered seriously as an explosive. Its explosive properties commend it, but it is too reactive chemically and too unstable to be of practical use. It is most conveniently prepared by treating hexamethylenetetramine with hydrogen peroxide in the presence of citric acid which promotes the reaction by combining with the ammonia which is liberated. 

Hexamine is also known as hexamethylenetetramine, aminoform, crystamine, methenamine or formin. It was first prepared in 1859 by Butlerov of Russia. It is a white, crystalline powder with a slight amine odor. It is soluble in water, alcohol, and chloroform, but it is insoluble in ether. However the aqueous solutions exhibit inverse solubility, i.e., less hexamine dissolves as the temperature increases. The hydrate, (CHi N O can be crystallized from the aqueous solution at temperatures below 14°C. Some additional properties are listed in Table 17.1. 

Among its other properties, hexamethylenetetramine combines with one molecular equivalent of an aliphatic... 

Turbidity is a measure of the light-transmitting properties of water. The measurement of turbidity is based on comparison of the intensity of light scattered by a sample to the light scattered by a reference suspension under the same conditions. The most widely used standards are prepared with hydrazine sulfate and hexamethylenetetramine in water, and give rise to the Formazin Turbidity Units (FTU). 

Figure 14. Dynamic properties of a phenol-formaldehyde novolak cross-linked with various amounts of hexamethylenetetramine by heating for one hour at 175 C,...

Hydrazine nitrace Fluoiine nitrate Mcthylamine nitrate Tetramethylammonium nitrate Guanidine nitrate Properties Manufacture Urea nitrate Thiourea nitrate Ethylene diamine dinitritc Hexamethylenetetramine diniirate Nitrates of ethanolamine nitric esters Ethanolamine nitric ester nitrate (ethanolamine dinitrate) Diethanolamine dinitric ester nitrate (diethanolamine trinitrate) Trictham amine trimtnc ester nitrate (triethanolamine tetranitrate) Oxontum nitrate Literature... 

Now according to the present Invention it has been found that hexamethylenetetramine, the well know n condensation product obtained from formaldehyde and ammonia, yields, when suitably treated with concentrated nitric acid, an extraordinarily powerful explosive compound, which combines in itself in an absolutely ideal manner the favourable properties of the ethereal salts of nitric acid and the aromatic nitro compounds. 

Properties White, crystalline solid. D 1.82, mp 203,5C. Soluble in acetone insoluble in water, alcohol, carbon tetrachloride, and carbon disulfide slightly soluble in methanol and ether. Derivation Reaction of hexamethylenetetramine with concentrated nitric acid. 

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