Hexamethylenetetramine compounds

From ehloromethyl or bromomethyl aromatic compounds by heating with hexamethylenetetramine (hexamine) in aqueous alcohol or aqueous acetic acid. A quaternary ammonium compound is formed, which yields the aldehyde upon treatment with water in the presence of hexamine for example... 

The benzylchloride compound made in the previous recipe can be converted to piperonal or benzaldehyde using a chemical called hexamine [137 p817, 37 p700, 136]. Hexamine, also known as methenamine or hexamethylenetetramine, is a weird looking chemical that is easily made from formaldehyde but is better off being purchased. 

The production of hexamethylenetetramine consumes about 6% of the U.S. formaldehyde supply (115). Its principal use is as a thermosetting catalyst for phenoHc resins. Other significant uses are for the manufacture of RDX (cyclonite) high explosives, in mol ding compounds, and for mbber vulcanisation accelerators. Some hexamethylenetetramine is made as an unisolated intermediate in the manufacture of nitfilotriacetic acid. 

Uncured resins are skin sensitizers and contact should be avoided, as weU as breathing the vapor, mist, or dust. Novolak-based pulverized products generally contain hexamethylenetetramine, which may cause rashes and dermatitis. PhenoHc molding compounds and pulverized phenoHc adhesives must be controUed as potentially explosive dusts. In addition, they contain irritating or toxic additives. 

Methylene chloride is easily reduced to methyl chloride and methane by alkaU metal ammonium compounds in Hquid ammonia. When the vapor is contacted with reduced nickel at 200°C in the presence of excess hydrogen, hydrogen chloride and elementary carbon are produced. Heating with alcohoHc ammonia at 100—125°C results in hexamethylenetetramine, (CH2) N4, a heterocycHc compound with aqueous ammonia at 200°C, hydrogen chloride, formic acid, and methylamine are produced. 

Although in the dry state carbon tetrachloride may be stored indefinitely in contact with some metal surfaces, its decomposition upon contact with water or on heating in air makes it desirable, if not always necessary, to add a smaH quantity of stabHizer to the commercial product. A number of compounds have been claimed to be effective stabHizers for carbon tetrachloride, eg, alkyl cyanamides such as diethyl cyanamide (39), 0.34—1% diphenylamine (40), ethyl acetate to protect copper (41), up to 1% ethyl cyanide (42), fatty acid derivatives to protect aluminum (43), hexamethylenetetramine (44), resins and amines (45), thiocarbamide (46), and a ureide, ie, guanidine (47). 

A number of disinfectants apparentiy owe their activity to formaldehyde, although there is argument on whether some of them function by other mechanisms. In this category, the dmg with the longest history is hexamethylenetetramine (hexamine, urotropin) [100-97-0] which is a condensation product of formaldehyde and ammonia that breaks down by acid hydrolysis to produce formaldehyde. Hexamine was first used for urinary tract antisepsis. Other antimicrobials that are adducts of formaldehyde and amines have been made others are based on methylolate derivations of nitroalkanes. The apphcations of these compounds are widespread, including inactivation of bacterial endotoxin preservation of cosmetics, metal working fluids, and latex paint and use in spin finishes, textile impregnation, and secondary oil recovery (117). 

The novolak resins themselves contain no reactive methylol groups and do not form cross-linked structures on heating. If, however, they are mixed with compounds capable of forming methylene bridges, e.g. hexamethylenetetramine or paraformaldehyde, they cross-link on heating to form infusible, thermoset structures. 

Sand has been treated with oil-soluble organosilicon compounds to form a hydrophobic proppant (77). A double layer resin coating has also been developed. The inner layer coating the sand particle is a cured gamma-aminopropyltriethoxvsilane - hexamethylenetetramine. The outer layer is an uncured mixture of the same two chemicals which cures within the fracture to form a consolidated permeable mass holding the fracture open (78). 

Hexamethylenetetramine this ammonia precursor does not cause fibre swelling and the unfixed dyes are removed efficiently at pH 6.5, compared with pH 8.5 with ammonia, thus causing less damage to the wool. However, the hydrolysis of this compound (Scheme 12.6) results in the formation of formaldehyde and this can modify the hue of certain dyes [2]. 

Only 1,3,5,7-tetraazaadamantane is known. It is also called hexamethylenetetramine (93) (HMT), hexamine, aminoform, ammoform, cyctamin, cystogen, formin, uritone, urotropin, and methenamine. It is listed by the last name in the Merck Index. It is prepared from formaldehyde and ammonia. The chemistry of this well-known compound is not discussed in this review. 

Paquin in 1948 found that a strongly exothermic reaction occurred when 40% formaldehyde was added to a solution of sulfamide in 25% aqueous ammonia. At once beautiful crystals precipitated they were recrystallized from 96% alcohol to give a compound, C5H10N4SO2, mp 224-225 "C, in 88% yield.245 From the similar character to hexamethylenetetramine, he named this product pentamethylenetetramine sulfone it is 225. One year later, in 1949, Hecht and Henecka at Bayer research laboratory reported that a condensation product from one mole of sulfamide in strong mineral acid and two moles of formaldehyde showed very strong toxicity and was five times more toxic than strychnine. They called this product (226) tetra-methylenedisulfotetramine. 246... 

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... 

Sommelet process org chem The preparation of thiophene aldehydes by treatment of thiophene with hexamethylenetetramine.. so-mal ya, pra-s3s ) Sonnenschein s reagent analychem A solution of phosphomolybdicadd that forms a yellow precipitate with alkaloid sulfates. z6n-3n,shTnz r5,a-j3nt) sonocatalysis chem 1. Initiation of a catalytic reaction by irradiation with sound or ultrasound. 2. Use of sound to impart catalytic activity to a chemical compound. san-3-k3 tal-3-s3s)... 

Cs) and the magnesium dichromate hexahydrate-hexamethylenetetramine addition compound, MgCr207,6H20,2[(CH2)6N4], have been solved. 

Shan et al. first illustrated this solid-state enhancement technique in the context of cocrystals of the compound cyclohexane-l,3cfs,5cfs-tricarboxylic acid (CTA) 28 [55]. CTA readily formed phase-pure cocrystal material with hexamethylenetetramine (HMTA) 29 upon grinding for 20 min (as judged from powder XRD data). 

Methylamine occurs in herring brine 2 in crude methyl alcohol from wood distillation,3 and in the products obtained by the dry distillation of beet molasses residues.4 It has been prepared synthetically by the action of alkali on methyl cyanate or iso-cyanurate 5 by the action of ammonia on methyl iodide,6 methyl chloride,7 methyl nitrate,8 or dimethyl sulfate 9 by the action of methyl alcohol on ammonium chloride,10 on the addition compound between zinc chloride and ammonia,11 or on phos-pham 12 by the action of bromine and alkali on acetamide 13 by the action of sodamide on methyl iodide 14 by the reduction of chloropicrin,15 of hydrocyanic or of ferrocyanic acid,16 of hexamethylenetetramine,17 of nitromethane,18 or of methyl nitrite 19 by the action of formaldehyde on ammonium chloride.20... 

Hexamethylenetetramine and cyclohexylamine are both tasteless solutions. Hexamethylenetetramine, a highly water soluble compound, is tasteless even diough it is compost of a AH-X component (Figure 1). Its molecular size is too small to exhibit the bitter taste proposed by the theory presented in Figure 1. Cyclohexamine, similarly, is tasteless. When both solutions are mixed together, a bitter flavor is exhibited. Interestingly, the bitter flavor of the mixed components is changed to sweet when acetic acid is adde (5), a fact consistent with the competitive theory. 

A hexahydro-l,3,5-triacyl-5-triazine was first prepared by Duden and Scharff from ammonium chloride, formalin, and benzoyl chloride or from hexamethylenetetramine and benzoyl chloride. A procedure similar to the one described also has been used for the preparation of hexahydro-1,3,5-triacetyl-, tri(/8-chloropropionyl)-, triacrylyl-, trimethacrylyl-, and tribenzoyl-5-triazine. Several of these compounds also have been prepared by Wegler and Ballauf from the corresponding nitriles and paraformaldehyde in the presence of acetic anhydride and sulfuric acid. 

Compound Name Ammonium Hydroxide Hexamethylenetetramine Ammonium Acetate Ammonium Bifluoride Ammonium Sulfamate Ammonium Sulfamate Ammonium Benzoate Ammonium Bicarbonate Ammonium Dichromate Ammonium Bifluoride Ammonium Carbonate Ammonium Chloride Ammonium Citrate Ammonium Citrate Ammonium Pentaborate Ammonium Dichromate Nickel Ammonium Sulfate Ferric Ammonium Citrate Ferric Ammonium Oxalate Ferrous Ammonium Sulfate Ammonium Fluoride Ammonium Silicofluoride Ammonium Formate Ammonium Gluconate Ammonium Bicarbonate Ammonium Bifluoride Ammonium Sulfide Ammonium Hydroxide Ammonium Thiosulfate Ammonium Thiosulfate Ammonium Iodide Ferrous Ammonium Sulfate Ammonium Lactate Ammonium Lactate Ammonium Lauryl Sulfate Ammonium Molybdate Ammonium Chloride Nickel Ammonium Sulfate Ammonium Nitrate Ammonium Nitrate-Urea Solution Ammonium Oleate... 

The same compound was prepared by Leulier [89] by the action of hydrogen peroxide on hexamethylenetetramine in the presence of nitric acid, but in a lower yield than that in the Girsewald method. Leulier ascribed an incorrect formula to the substance as pointed out by Girsewald and Siegens [85]. 

The chemistry of the preparation of RDX is highly complex. When hexamethylenetetramine is reacted with nitric acid, hexamethylenetetramine dinitrate is formed which is then nitrated to form an intermediate Compound I as shown in Reaction 7.10. 

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