Hexamethylenetetramine, reactions preparation

It is made by the nitration of hexamine (hexamethylenetetramine), itself prepared from formaldehyde and ammonia. Hexamine was originally nitrated with a large excess of concentrated nitric acid at temperatures below 30°C and the product recovered by adding the reaction liquor to an excess of chilled water. Later the yield was improved by adding ammonium nitrate to the reaction as this reacts with the liberated formaldehyde. A much-used process converts the hexamine first to its dinitrate, which is then reacted with ammonium nitrate, nitric acid and acetic anhydride (the last reagent being re-formed from the product by use... 

SOMMELET REACTION. Preparation of aldehydes from aralkyl or alkyl halides by reaction with hexamethylenetetramine followed by mild hydrolysis of the formed quaternary salt,... 

Delepine reaction. Preparation of primary amines by reaction of alkyl halides with hexamethylenetetramine followed by acid hydrolysis of the formed quaternary salts. 

To overcome the objectionable reoxidation of formaldehyde and decomposition at the temperature of the reaction zone in the oxidation of methane, it has been proposed to react the formaldehyde as fast as formed with some substance to give a compound more stable under the conditions of the reaction and thus to increase the yields obtainable. It is claimed 101 that a reaction between the newly formed formaldehyde and annnonia to form a more stable compound, hexamethylene-tetramine, is possible under certain conditions, so that the formaldehyde is saved from destruction and can be obtained in a technically satisfactory yield. The hexamethylenetetramine is prepared by oxidizing methane with air in the presence of ammonia gas. A mixture consisting of six volumes of methane, twelve volumes of oxygen, and four volumes of ammonia gas is passed through a constricted metal tube which is heated at the constriction. The tube is made of such a metal as copper, silver, nickel, steel, iron, or alloys of iron with tin, zinc, aluminum, or silicon or of iron coated with one of these metals. Contact material to act as a catalyst when non-catalytic tubes are used in the form of wire or sheets of silver, copper, tin, or alloys may be introduced in the tube. At atmospheric pressure a tube temperature... 

Hexamethylenetetramine. Pure hexamethylenetetramine [100-97-0] (also called hexamine and HMTA) is a colorless, odorless, crystalline sohd of adamantane-like stmcture (141). It sublimes with decomposition at >200° C but does not melt. Its solubiUty in water varies Htde with temperature, and at 25°C it is 46.5% in the saturated solution. It is a weak monobase aqueous solutions are in the pH 8—8.5 range (142). Hexamethylenetetramine is readily prepared by treating aqueous formaldehyde with ammonia followed by evaporation and crystallisation of the soHd product. The reaction is fast and essentially quantitative (142). 

Primary amines can be prepared from alkyl halides by the use of hexamethylenetetramine followed by cleavage of the resulting salt with ethanolic HCl. The method, called the Delepine reaction, is most successful for active halides such as allylic and benzylic halides and a-halo ketones, and for primary... 

Other electrophilic substitution reactions on aromatic and heteroaromatic systems are summarized in Scheme 6.143. Friedel-Crafts alkylation of N,N-dimethyl-aniline with squaric acid dichloride was accomplished by heating the two components in dichloromethane at 120 °C in the absence of a Lewis acid catalyst to provide a 23% yield of the 2-aryl-l-chlorocydobut-l-ene-3,4-dione product (Scheme 6.143 a) [281]. Hydrolysis of the monochloride provided a 2-aryl-l-hydroxycyclobut-l-ene-3,4-dione, an inhibitor of protein tyrosine phosphatases [281], Formylation of 4-chloro-3-nitrophenol with hexamethylenetetramine and trifluoroacetic acid (TFA) at 115 °C for 5 h furnished the corresponding benzaldehyde in 43% yield, which was further manipulated into a benzofuran derivative (Scheme 6.143b) [282]. 4-Chloro-5-bromo-pyrazolopyrimidine is an important intermediate in the synthesis of pyrazolopyrimi-dine derivatives showing activity against multiple kinase subfamilies (see also Scheme 6.20) and can be rapidly prepared from 4-chloropyrazolopyrimidine and N-bromosuccinimide (NBS) by microwave irradiation in acetonitrile (Scheme... 

Experiment 6. Reaction with Ammonia.—Of the formaldehyde prepared 10 c.c. are mixed with a small excess of ammonia and the mixture is evaporated in a small glass dish on the water bath. The colourless crystals which remain consist of hexamethylenetetramine (CH2)6N4 (urotropine.) This reaction proceeds quantitatively. It should be so carried out and the result compared with that obtained by titration. 

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)... 

Naphthaldehyde has been made from a-naphthonitrile by reduction with stannous chloride, and from naphthalene by the action of aluminum chloride, hydrogen cyanide, and hydrochloric acid. The best preparation is the Sommelet reaction from a-chloro- or a-bromomethylnaphthalene and hexamethylenetetramine in aqueous alcohol is.is. .is.w or glacial acetic acid. This method has been improved in the present procedure by the use of 50% acetic acid as solvent. 

Phenacylamine hydrochloride has been prepared by (1) the hydrolysis of the quaternary salt obtained from phenacyl bromide and hexamethylenetetramine (the Delepine reaction),6-11 (2) the hydrolysis of N-phenacylphthalimide (the Gabriel reaction),12-14... 

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. 

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. 

Aromatic and heteroaromatic aldehydes can alternatively be prepared from the corresponding methyl compound by subjecting the chloromethyl or bromomethyl derivative to the Sommelet reaction. This procedure involves an initial reaction between the halomethyl compound and hexamethylenetetramine (hexamine), and hydrolysing the resulting quaternary hexamine salt (4) with hot aqueous acetic acid. 

Cognate preparations. p-Nitrobenzaldehyde. This preparation is an example of the Sommelet reaction in which the hexaminium salt is isolated. Dissolve llg (0.13mol) of hexamethylenetetramine in 70ml of chloroform (CAUTION) and add 11.4 g (0.067 mol) of p-nitrobenzyl chloride or 14.4 g of p-nitrobenzyl bromide (Expt 6.28). Heat the mixture under reflux on a steam bath for 4 hours a precipitate gradually separates. Replace the reflux condenser by a condenser set for distillation and distil off about 35 ml of solvent. Add 35 ml of acetone, cool in ice, collect the precipitate by suction filtration and dry it in the air. Heat the hexaminium salt thus obtained under reflux for 1 hour with 100 ml of 50 per cent acetic acid then add 100 ml of water and 25 ml of concentrated hydrochloric acid and continue the refluxing for 5-10 minutes. Cool the solution in ice, collect the crystals of p-nitrobenzaldehyde and dry them in a vacuum desiccator. The yield is 6.4 g (63%), m.p. 106 °C. The p.m.r. spectrum is noted in Expt 6.117. 

A solution of 272 g. (261 ml., 2.00 moles) of a.a -diamino-w-xylene (Note 1), 1.00 kg. (7.1 moles) of hexamethylenetetramine, 480 ml. of concentrated hydrochloric acid, and 3.2 1. of 50% aqueous acetic acid in a 12-1. flask is stirred and heated at the reflux temperature for 2.5 hours. The hot amber reaction mixture is then poured into a large battery jar in a well-ventilated hood, and a solution prepared from 298 g. of sodium hydroxide and 3.85 1. of water is added slowly with stirring (Note 2). The... 

Phenylethylamine has been made by a number of reactions, many of which are unsuitable for preparative purposes. Only the most important methods, from a preparative point of view, are given here. The present method is adapted from that of Adkins,1 which in turn was based upon those of Mignonac,2 von Braun and coworkers,3 and Mailhe.4 Benzyl cyanide has been converted to the amine by catalytic reduction with palladium on charcoal,5 with palladium on barium sulfate,6 and with Adams catalyst 7 by chemical reduction with sodium and alcohol,8 and with zinc dust and mineral acids.9 Hydrocinnamic acid has been converted to the azide and thence by the Curtius rearrangement to /3-phenyl-ethylamine 10 also the Hofmann degradation of hydrocinnamide has been used successfully.11 /3-Nitrostyrene,12 phenylthioaceta-mide,13 and the benzoyl derivative of mandelonitrile 14 all yield /3-phenylethylamine upon reduction. The amine has also been prepared by cleavage of N- (/3-phenylethyl) -phthalimide 15 with hydrazine by the Delepine synthesis from /3-phenylethyl iodide and hexamethylenetetramine 16 by the hydrolysis of the corre-... 

While the neutralization is in progress, a solution of hexamethylenetetramine (Note 8) is prepared by the cautious addition of 520 cc. of formalin (sp. gr. 1.08 approximately 7 moles) to 500 cc. of ammonium hydroxide (sp. gr. 0.90 approximately 7.5 moles). The temperature must be maintained below 20° by external cooling with ice water. The solution is finally chilled to 0° and added dropwise to the cold ammoniacal solution of tartaric acid dinitrate the temperature should not exceed 2°. The addition requires half an hour. Stirring is then discontinued, and the mixture is allowed to stand overnight. During this period the cooling bath and the reaction mixture come to room temperature. 

The final series of five procedures presents optimized preparations of a variety of useful organic compounds. The first procedure in this group describes the preparation of 3-BROMO-2(H)-PYRAN-2-ONE, a heterodiene useful for (4+2] cycloaddition reactions. An optimized large scale preparation of 1,3,5-CYCLOOCTATRIENE, another diene useful for [4+2] cycloaddition, is detailed from the readily available 1,5-cyclooctadiene. Previously, the availability of this material has depended on the commercial availability of cyclooctatetraene at reasonable cost. A simple large scale procedure for the preparation of 3-PYRROLINE is then presented via initial alkylation of hexamethylenetetramine with (Z)-1,4-dichloro-2-butene. This material serves as an intermediate for the preparation of 2,5-disubstituted pyrroles and pyrrolidines via heteroatom-directed metalation and alkylation of suitable derivatives. The preparation of extremely acid- and base-sensitive materials by use of the retro Diels-Alder reaction is illustrated in the preparation of 2-CYCLOHEXENE-1.4-DIONE, a useful reactive dienophile and substrate for photochemical [2+2] cycloadditions. Functionalized ferrocene derivatives... 

The first "Mannich reaction took place accidentally in 1912, when Carl Mannich, at that time a young professor in the pharmaceutical laboratory at Gottingen University, was treating with acid the solution of a pharmaceutical preparation based on salicyl antipyrine and urotropinc (hexamethylenetetramine). He obtained a crystalline precipitate, which was later identified, in collaboration with W. Krogen Kroshe, as having the structure shown in Fig. 1. ... 

Al-sol can be prepared using various aluminum precursors, such as pseudo-boehmite, A10(0H) xH20, and aluminum alkoxide [48-50,55,60]. Xu et al. [55] described several possibilities. Additives, e.g., urea, or organic amines, e.g., hexamethylenetetramine (HMT), can be added to the sol in order to improve the quality of alumina obtained. The decomposition of these additives in heat treatment (calcination) may lead to a better porosity of the alumina. The reaction for urea decornposition is as follows ... 

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