Methylamine There are basically two routes to Methylamine.

The first involves synthesis of a cetamide, then reaction with hypochlorite in alkaline solution to give off methy lamine gas. The second route involves disproportionation, under acid conditions, of formaldehyde and ammonia into formic acid and methylamine hydrochloride. Acetamide can be prepared by the rapid distillation of ammonium acetate by heating ammonium acetate in a sealed tube and distilling the product, by treating acetic anhydride with anhydrous ammonia, by heating a mixture of ammonium chloride and sodium acetate to 240C, by the action of cold aqueous ammonia on ethyl acetate, or by saturating glacial acetic acid with dry ammonia and then refluxing. Acetamide Procedure #1 In a 5-l. flask is placed 3 kg. (2860 cc., 50.0 moles) of glacial acetic acid and to this is added a weight of ammonium carbonate corresponding to 400g. (23.5 moles) of ammonia (Note 1). The flask is fitted with a one-hole stopper holding an efficient fractionating column 90 cm. long with condenser and receiver. An air condenser 150-200 cm. long may be employed. The mixture in the flask is heated to gentle boiling and the flame so regulated that the rate of distillation does not exceed 180 cc. per hour. The distillation is continued in this way for eight to ten hours, until the temperature at the head of the column reaches 110. The distillate, which is a mixture of water and acetic acid, amounts to 1400-1500 cc. The receiver is changed, the flame under the flask is gradually increased, and the distillation is continued at about the same rate until the temperature at the head of the column rises to 140. The distillate, which amounts to 500-700 cc., is largely acetic acid and may be used in the next run. The contents of the flask are transferred to a 2-L. flask for fractional distillation, having a column 40 50 cm. long, and distilled under atmospheric pressure, using an air condenser. The fraction boiling below 210C, amounting to 250-300 cc., is collected separately. The material remaining in the flask is nearly pure acetamide and may all be distilled, 1150-1200 g. passing over at 210-216C. By redistilling the fraction boiling below 210C, the yield may be increased to 1200-1250 g. (90% yield ). The acetamide thus obtained is pure enough for most purposes, but if a purer product is desired it may be recrystallized from a mixture of benzene and ethyl acetate; 1L of benzene and 300 cc. of ethyl acetate are used per every 1 kg of acetamide. Colorless needles melting at 81C are thus obtained. Crystallization of acetamide , by solution in hot methyl alcohol (0.8 cc. per g.) and dilution with ether (8-10 cc. per g.), has been recommended as the best method of purification. As acetamide is somewha t hygroscopic, it cannot be exposed to the air unless precautions are taken to hav e the air dry. The solvent and the acetamide it contains may be recovered by distillation. Acetamide Procedure #2 44.055 g (0.5 moles) of ethyl acetate is combined at room temperature with 59 grams of concentrated aqueous ammonia (1 mole; conc.=approx 29%) in an Erlenmeyer flask. A stirbar is added, and the flask is stoppered. The flask is stirred at room temperature for three days. At this point the contents of the flask is distilled. At standard pressure, aceamide will distill over between 200-220C. If a vacuum is used (highly recomended), pure acetamide distills at 158C (100 torr), 136C (40 torr), 120C (20 torr), 105C (10 torr), or 92C (5 torr).

Methylamine form Acetamide, using Bromine 20g dry acetamide is mixed with 54g Bromine in a 500ml flask. A solution of 20g KOH in 200ml H2O is added dropwise with the flask resting in an ice bath. (Look for a red-brown->yellow color change) Disolve 60g KOH in 100ml water, cool, and add to a 1L round bottom flask. Add the acetbromide dropwise to the flask with a thermometer checking that the temp doesn't exceed 75C. Once addition is complete, and when the rxn mix begins cooling, maintain a temperature of 65C on a water bath for 30 minutes. Set the flask up for distillation, in the receiving flask place 100ml of dilute HCL (probably; calc. 2x mol's needed to form salt of a 60/40 CH3NH2/NH 3 mix). Distill the CH3NH2/NH3 out of the flask and stop when the distillate comin g over is no longer alkaline. Evaporate the water out of the HCl+distillate on a water bath (75C). Dissolve the colorless residue in hot anhydrous ethanol (which does not contain any water) NH4Cl will be insoluble. Filter off what should only be a few grams of NH4Cl. Pour the EtOH into a beaker and cool. Later filter out the Methylamine and dry i t in a dessicator. Sodium bromide reacts with acidified hydrogen peroxide to form bromine in the so lution, this bromine can dissolve into a layer of hydrocarbon solvent, ketone so lvents should not be used. Methylamine form Acetamide using Bleach When reacted with hypochlorite bleach, Acetamide reacts to give off methylamine gas. "Preparation of Methylamine Hydrochloride from Acetamide by Means of Calcium Hyp ochlorite" C.R. Hauser, W.B. Renfrow, J. Chem. Education 1937, 14 (11), p 542 Methylamine Hydrochloride from Ammonium Chloride and Formaldehyde In a 5 liter round-bottomed flask, fitted with a stopper holding a condenser set for downward distillation and a thermomether which will extend well into the li quid, are placed 4 kg (3711 ml, 47-53 moles) of technical formaldehyde (35-40 pe rcent; d 1.078 at 20C) and 2 kg (37 moles) of technical ammonium chloride. The mi xture is heated on the steam bath until no more distillate comes over and then o ver a flame until the temperature of the solution reaches 104C. The temperature i s held at this point until no more distillate comes over (four to six hours). Th e distillate, which consists of methylal (bp 42-43C), methylformate and water may be treated with NaOH solution to recover methylal and sodium formate. The conte nts of the reaction flask are cooled too room temp and the ammonium chloride whi ch separates is filtered off. The mother liquor is concentrated on the steam bat h under reduced pressure to 2500 ml, and again cooled to room temp, whereupon a second crop of ammonium chloride separates. The total recovery of ammonium chlor ide up to this point amounts to 780-815 grams. The mother liquor is again concen trated under reduced pressure until crystals begin to form on the surface of the solution (1400-1500 ml). It is then cooled to room temperature, and a first cro p of methylamine hydrochloride, containing some ammonium chloride is obtained by filtering the cold solution. At this point 625-660 grams of crude product is ob tained. The mother liquor is now concentrated under reduced pressure to about 10 00 ml, and cooled, and a second crop of methylamine hydrochloride (170-190 grams ) is then filtered off. This crop of crystals is washed with 250 cc of cold chlo roform, and filtered to remove most of the dimethylamine hydrochloride which is present. After the washing, the product weighs 140-150 grams. The original mothe r liquor is then evaporated under reduced pressure, as far as possible, by heati

ng on a steam bath, and the thick syrupy solution (about 350 ml) which remains i s poured into a beaker and allowed to cool, with occasional stirring, in order t o prevent the formation of a solid cake, and the crystals obtained are washed wi th 250 ml of cold chloroform, the solution is filtered yielding 55-65 grams of p roduct. There is no advantage in further concentrating the mother liquor, which contains mostly tetramethylmethylenediamine hydrochloride, but no trimethylamine hydrochloride. The total yield of methylamine hydrochloride is 830-850 grams. T he product contains water, ammonium chloride and some dimethylamine hydrochlorid e. In order to obtain a pure product, the impure methylamine hydrochloride is re crystallized from absolute ethanol (solubility 0.6g/100ml at 15C), or preferably butyl alcohol (even less soluble). The recovery of ammonium chloride amounts to 100-150 grams, making the total recovery 850-950 grams. The yield of recrystalli zed methylamine hydrochloride is 600-750 grams (45-51 percent of theory, based o n the used up ammonium chloride). A standard run, from 250 grams ammonium chloride and 500g 37% formaldehyde (cont aining 15% methanol), gives 100-134 grams methylamine hydrochloride, 27 grams di methylamine hydrochloride and 81 grams of recovered ammonium chloride. The disti llate contains methylal (formaldehyde dimethyl acetal) and methyl formate, which after treatment with NaOH can yield 25g of sodium formate and 30 grams of methy lal, as the compound cannot be separated by fractional distillation, neutralizat ion is the way to go. Ammonium chloride is very sparingly soluble in a concentra ted solution of methylammonium chloride, making the separation of the compounds pretty sharp. Similarly, Hexamine and HCl may be used as the reactants instead, illustrating t hat the order of reaction of CH2O, NH3, and acid does not matter.