Methylamine acidity

Pyrolysis of the methylamine salt (produced by neutralising mucic acid with aqueous methylamlne) in the presence of glycerol yields JV-methylpyrrole ... 

An alternative method of preparation involves the interaction of methylamine hydrochloride with urea to give methylurea, followed by interaction with nitrous acid as above ... 

Determine the methylamine content of the commercial solution by titration with standard acid using methyl orange as indicator. Adjust the quantity of methyl-amine solution in accordance with the methylamine content for some commercial samples, the figure may be 33-40 per cent. 

Occasionally the liquid may not become acidic after the first or second addition, even through the sulphonyl chloride has reacted completely. (This is due to a smaller loss of methylamine than is expected.) If such is the case, no more than 5 minutes should be allowed between successive additions of sulphonyl cliloride and alkali. The whole procedure occupies about 30 minutes. 

Dimethylaminomethylindole (gramine). Cool 42 5 ml. of aqueous methylamine solution (5 2N ca. 25 per cent, w/v) contained in an 100 ml. flask in an ice bath, add 30 g. of cold acetic acid, followed by 17 -2 g. of cold, 37 per cent, aqueous formaldehyde solution. Pour the solution on to 23 -4 g. of indole use 10 ml. of water to rinse out the flask. Allow the mixture to warm up to room temperature, with occasional shaking as the indole dissolves. Keep the solution at 30-40° overnight and then pour it, with vigorous stirring, into a solution of 40 g. of potassium hydroxide in 300 ml. of water crystals separate. Cool in an ice bath for 2 hours, collect the crystalline solid by suction flltration, wash with three 50 ml. portions of cold water, and dry to constant weight at 50°. The yield of gramine is 34 g. this is quite suitable for conversion into 3-indoleacetic acid. The pure compound may be obtained by recrystaUisation from acetone-hexane m.p. 133-134°. 

At the end of this time, allow to cool then add enough 25% Sodium Hydroxide solution to to get the pH above 11. Heat on a water bath or with gentle electric heat to drive the Methylamine off as a gas into the same beaker of Hydrochloric acid used as a trap during the reaction. 

Hexamine, more formally known as Hexamethylenetetramine, is easily and conveniently produced from Formaldehyde and Ammonia solutions. Formaldehyde may be easily produced by depolym-erizing, with heat, Paraformaldehyde (the only ingredient in OTC MildewCide). Hexamine is then reacted with Hydrochloric Acid and heated to yield Methylamine HCI in near quantitative yield. 

For example, the action of a-thiocyanatoacetone on ammonia in ether solution gives 4-methyl-2-aminothiazole but in very low yield (137). Methylamine in ether at 0°C gives in a first step S-acetonyl N-methylisothiourea (196) in 80% yield (Scheme 102) (137). The cycliza-tion of this intermediate occurs either after a prolonged rest at room temperature, either by fusion or by heating with dilute hydrochloric acid to afford the 4-methyl-2-methylaminothiazole (197). 

Chloroacetic acid can be esterified and aminated to provide useful chemical intermediates. Amphoteric agents suitable as shampoos have been synthesized by reaction of sodium chloroacetate with fatty amines (4,5). Reactions with amines (6) such as ammonia, methylamine, and trimethylamine yield glycine [66-40-6J, sarcosine [107-97-17, and carhoxymethyltrimethylammonium chloride, respectively. Reaction with aniline forms /V-phenylglycine [103-01 -5] a starting point for the synthesis of indigo (7). 

Methylamines are formed by heating formaldehyde with primary or secondary amines or their salts under acid conditions (61) ... 

Methylamines are produced from the vapor reaction of methanol with ammonia over a siUca—alumiaa catalyst. Methyl esters result from the reaction of methanol with the corresponding organic or inorganic acid as shown, eg, for methyl methacrylate. 

Naphthol is mainly used in the manufacture of the insecticide carbaryl (59), l-naphthyl A/-methyicarbamate/ iJ-2j5 - (Sevin) (22), which is produced by the reaction of 1-naphthol with methyl isocyanate. Methyl isocyanate is usually prepared by treating methylamine with phosgene. Methyl isocyanate is a very toxic Hquid, boiling at 38°C, and should not be stored for long periods of time (Bhopal accident, India). India has developed a process for the preparation of aryl esters of A/-alkyl carbamic acids. Thus l-naphthyl methylcarbamate is prepared by refluxing 1-naphthol with ethyl methylcarbamate and POCl in toluene (60). In 1992, carbaryl production totaled > 11.4 x 10 t(35). Rhc ne-Poulenc, at its Institute, W. Va., facihty is the only carbaryl producer in United States. 

Pigment Red 179 [5521-31-3] 71130 Perylene imidation of perylene 1,6,7,12-tetra-carboxyhc acid dianhydride with methylamine... 

Other preparative routes iaclude hydrogenation of succinonitdle in the presence of methylamine and hydrogenation of solutions of maleic or succinic acid and methylamine (82,83). Properties are Hsted in Table 3. l-Meth5i-2-pyrrohdinone is completely miscible with water, lower alcohols, lower ketones, ether, ethyl acetate, chloroform, and benzene. It is moderately soluble in aUphatic hydrocarbons and dissolves many organic and inorganic compounds. 

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. 

Hydrogen cyanide, as the nitrile of formic acid [64-18-6] CH2O2, undergoes many of the typical nitrile reactions. For example, it can be hydrolyzed to formic acid by aqueous sulfuric acid (4) it can be hydrogenated to methylamine [74-89-5], CH N (5) and it can be converted to phenylformamidine [618-39-3], CyHgN2, using aniline and hydrogen chloride (6). 

The original commercial source of E was extraction from bovine adrenal glands (5). This was replaced by a synthetic route for E and NE (Eig. 1) similar to the original pubHshed route of synthesis (6). Eriedel-Crafts acylation of catechol [120-80-9] with chloroacetyl chloride yields chloroacetocatechol [99-40-1]. Displacement of the chlorine by methylamine yields the methylamine derivative, adrenalone [99-45-6] which on catalytic reduction yields (+)-epinephrine [329-65-7]. Substitution of ammonia for methylamine in the sequence yields the amino derivative noradrenalone [499-61-6] which on reduction yields (+)-norepinephrine [138-65-8]. The racemic compounds were resolved with (+)-tartaric acid to give the physiologically active (—)-enantiomers. The commercial synthesis of E and related compounds has been reviewed (27). The synthetic route for L-3,4-dihydroxyphenylalanine [59-92-7] (l-DOPA) has been described (28). 

The alkylthio group is replaceable by nucleophiles. The positions 7 and 4 react under mild conditions in that order the 2-alkylthio functions require more drastic treatment. Conversion of l-methyl-4-methylthiopteridin-2-one (157) into the 4-methylamino derivative (158) can be achieved by stirring with methylamine at room temperature (equation 48). The reactivity of an alkylthio group can often be further enhanced by oxidation to the corresponding sulfoxide and sulfone. Thus, reaction of l,3-dimethyl-7-methylthiolumazine (160) with m-chloroperbenzoic acid yields 7-methylsulfinyl- (161) and 7-methylsulfonyl-l,3-dimethyllumazine (162 equation 49) (82UP21601). 4-Amino-2-methylthio-7-... 

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