Methyl alcohol cyanide

Into a 1500 ml. round-bottomed flask place 97-5 g. of finely-powdered sodium cyanide (1), 125 ml. of water, and a few chips of porous porcelain. Attach a reflux condenser and warm on a water bath until all the sodium cyanide dissolves. Introduce a solution of 250 g. (196 ml.) of n-butyl bromide (Sections 111,35 and 111,37) in 290 ml. of pure methyl alcohol, and reflux gently on a water bath for 28-30 hours. Cool to room temperature and remove the sodium bromide which has separated by filtration through a sintered glass funnel at the pump wash the crystals with about 100 ml. of methyl alcohol. Transfer the filtrate and washings to From n caproamide by SOClj method. 

P-Phenylethylamine is conveniently prepared by the hydrogenation under pressure of benzyl cyanide with Raney nickel catalyst (see Section VI,5) in the presence of either a saturated solution of dry ammonia in anhydrous methyl alcohol or of liquid ammonia the latter are added to suppress the formation of the secondary amine, di- P phenylethylamine ... 

When heated in air the cyanide burns with a pale blue flame. It is soluble to a slight extent in chloroform and carbon tetrachloride. It is also soluble in cold methyl alcohol without change, but when the solution... 

Over 25% of the elements, ineluding carbon, have been identified, as well as molecules of water, carbon monoxide, carbon dioxide, ammonia, ethane, methane, acetylene, formaldehyde, formic acid, methyl alcohol, hydrogen cyanide, and acetonitrile. When applied to the planets only, the science is called chemical planetology,... 

The reaction mixture is stirred for one hour alter all the cyanide has been added and then is allowed to stand overnight. The ether layer is separated and the ac iieotis li< iioi is e lmeted with six 300-cc. portions of ether. The clliei cxliacls me combined and the ether is distilled. The residue, vvliic li 1 cmsisls mainly of acetone cyanohydrin, is diluted with Soo ci. of methyl alcohol. The solution is cooled and salinated with ammonia gns (Note 3). Pile reaction mixture is allowed to stand lor two or three clays... 

Methyl alcohol of very high purity can be obtained by fractional distillation using a column of 1-3 metres effective length and then refluxing with aluminium amalgam. It is then refluxed under a column packed with dehydrated copper sulphate, to remove ammonia. A sensitive test for acetone and formaldehyde is the addition of cone, mercuric cyanide solution, in 6N-sodium hydroxide. A white precipitate indicates ketone if it darkens on standing aldehyde is also present. (J. C. S., 127, 2552.)... 

By passing the vapor of methyl alcohol and hydrogen cyanide over catalysts at high temperatures. Smith and Smith, can. pat. 274,065 (1927). 

The W. A. Noyes method of preparation [J. Am. Chem. Soc. 26, 1545 (1904)] from ethyl chloroacetate and potassium cyanide in methyl alcoholic solution gives a mixture of methyl and ethyl esters. Urushebana, Bull. Chem. Soc. Japan 2, 143 (1927) C. A. 21, 2879 (1927)]. 

A mixture consisting of 200 ml methyl alcohol, 1680 ml 40% aqueous dimethy-lamine solution, dimethyl ami nc HCl (303 g), and 200 g potassium cyanide (200 g) was added to l,4-dioxaspiro[4.5]decan-8-one (200 g), then stirred 65hours. A white suspension that formed was extracted four times with 800 ml diethyl ether, then concentrated, and the residue dissolved in 500 ml CH2C12. The organic phase was isolated, dried using Na2S04, then concentrated, and 265 g product isolated as a white solid. 

A solution of 50 g. (1 mole) of sodium cyanide (98 per cent purity) in 100 cc. of water is placed in a 2-1. round-bottomed flask (Note 1) fitted with a ground-glass stopper. A solution of 58.9 g. (1.1 moles) of ammonium chloride in 140 cc. of lukewarm water is added, followed by 67 cc. (1 mole) of concentrated ammonium hydroxide (sp. gr. 0.9). This mixture is stirred mechanically and is cooled by a stream of water while a solution of 86.1 g. (1 mole) of diethyl ketone in 160 cc. of methyl alcohol (Note 2) is added. The flask is then stoppered (Note 3) and half immersed for five hours in a water bath, the temperature of which is kept at 55-60°. The reaction mixture is then cooled in an ice bath and poured (with precautions, Le., under a properly ventilated hood) into 800 cc. of concentrated hydrochloric acid (sp. gr. 1.18) contained in a 5-1. round-bottomed flask which is surrounded up to the neck by ice and water. The reaction flask is rinsed with two... 

To a solution of 100 g. (2.0 moles) of 98 per cent sodium cyanide in 400 cc. of water, contained in a 3-1. round-bottomed llask fitted with a Hershberg stirrer (Org. Syn. 17, 31), is added IIX g. (2.2 moles) of ammonium chloride. The mixture is stirred at room temperature under a properly ventilated hood. When the ammonium chloride has dissolved, a solution of 212 g. (2.0 moles) of benzaldehyde in 400 cc. methyl alcohol is added in one portion. The reaction begins rapidly, the temperature rising to about 45°. Stirring is continued for two hours. The heterogeneous mixture, after dilution with 1 1. of water, is extracted with 1 1. of benzene, and the aqueous layer is discarded. The benzene layer is washed with three 50-cc. portions of water, and I lie aminonitrile is extracted, in the form of its hydrochloride, by shaking the benzene solution with 6 N hydrochloric acid, first with one 600-ce. portion and then with two 300-cc. portions. 

A) 2-Nitro-6-methoxybenzonitrile.—Five hundred grams (2.97 moles) of technical m-dinitrobenzene (m.p. 88-89°) is dissolved in 7.5 1. of absolute methyl alcohol in a 12-1. round-bottomed flask fitted with an efficient mechanical stirrer. The temperature is raised to 40° by means of a water bath and maintained there while a solution of 230 g. of potassium cyanide in 400 cc. of water is added with stirring. The dark purple mixture is stirred for two hours and then is allowed to stand at room temperature for two to three days. The black precipitate is collected with suction on a Buchner funnel, pressed as dry as possible, and then spread out in the air to dry. It weighs about 185-188 g. 

Sodium (23 g) was dissolved in 400 ml methyl alcohol, ethylene glycol, dimethyl ether and (9.3 g), 50 ml dimethyl carbonate added, and 300 ml methyl alcohol collected during distillation. Thereafter, copper cyanide (915 g) and 2,3,6-tribromo-4-methylphenol (34.4 g) dissolved in 100 ml ethylene glycol and dimethyl ether were added over 3 hours at 80 °C. The mixture was stirred 5 hours, 800 ml water added, cooled to 50 °C, and 100 ml methyl sulfate added. The mixture was stirred 2 hours at ambient temperature, concentrated, 250 ml NH4OH added, and the product extracted with methyl chloride. The organic phase was washed with dilute HCl, water, dried, concentrated, and 20 g product isolated, bp = 100°C at 0.1 mmHg. 

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