Methyl alcohol iodide

Dimethyl ethyl carbinol (2-methy 1-2-butanol or amyl alcohol), CH3CHjCOH(CH3).2. From ethyl propionate and methyl magnesium iodide. Collect the tertiary alcohol at 100-102°. 

Methyl Iodide. Use 38 g. (48 ml.) of methyl alcohol, 8-27 g. of purified red phosphorus and 127 g. of io ne. Cover the iodine completely with the hot methyl alcohol before running the alcoholic solution into the boiling alcohol - phosphorus mixture. B.p. 42-42-5°. 

The present procedure was developed from those of Wallach and Freylon, based upon the general method discovered by Leuckart. a-Phenylethylamine also can be prepared satisfactorily by the reduction of acetophenone oxime with sodium and absolute alcohol or sodium amalgam, but the reagents are more expensive and the processes less convenient. The amine has been obtained by reducing acetophenone oxime electro-lytically, by reducing acetophenone phenylhydrazone with sodium amalgam and acetic acid, from a-phenylethyl bromide and hexamethylenetetramine, and by the action of methyl-magnesium iodide upon hydrobenzamide, as well as by other methods of no preparative value. 

The base boiled in methyl alcoholic solution with methyl iodide and potassium hydroxide, forms a gelatinous methiodide, which was converted by silver chloride into the methochloride. The latter when boiled with 20 per cent, solution of sodium hydroxide, produced a mixture of methine bases, which were separated as the methiodides into 0-methylbebeerine-methine methiodide B, m.p. 237° (cf. p. 375), and a lasvorotatory form, m.p. 190°, which proved to be the lasvo-enantiomorph of d-O-methyl-bebeerinemethine methiodide (form C, p. 375). Chondrofoline therefore belongs to the bebeerine type represented by formula (III). In it R = H, the single phenolic hydroxyl is at ORj or OR4 and the remaining groups, OR2, OR 3, OR or alternatively ORj, OR2, OR 3 are methoxyl groups (King,i 1940). 

When treated with aleoholie alkalis the y-methoxyl group in skimmianine is replaced by the alkyloxy group of the alcohol used. The ethoxy-analogue, C1JH15O4N, has m.p. 138°, yields a picrate, m.p. 194°, is re-converted to skimmianine by boiling with methyl alcohol, with methyl iodide yields woskimmianine, and is oxidised to the ethoxy-analogues of skimmianal, m.p. 212°, and skimmianic acid, m.p. 225° (I EtO in 4). 

Ewins has synthesised both substances from m-methoxybenzoic acid, which on nitration gave 2-nitro-3-methoxybenzoic acid, and this, on reduction and treatment with methyl iodide, yielded damasceninic acid, which, by esterification with methyl alcohol, furnished damascenine. Kaufmann and Rothlen found that the additive product of 8-methoxy-quinoline and methyl sulphate, on oxidation with permanganate, yields formyldamasceninic acid, MeO. CgH3(NMe. CHO). COOH, which can be transformed into damasceninic acid by warming with dilute hydrochloric acid. ... 

Veratramine, C27H3g02N, occurs naturally in V. viride and V. grandi-florum and is also formed by the hydrolysis of veratrosine. It has m.p. 209-210-5°, fa] — 68° (MeOH), and yields a dihydro-derivative, m.p. 198-200°, and a triacetyl-derivative, m.p. 204-6°, which on controlled hydrolysis leaves a. V-acetyl derivative, m.p. 177-180°. Aceording to Saito, veratramine on treatment with methyl iodide in methyl alcohol in presence of sodium carbonate, yields A-methylveratramine methiodide, m.p. 268° (dec.), from whieh the methoehloride, m.p. 277°, ean be prepared. 

The methyl alcohol is poured into a round flask (250 c.c.) connected with an upright condenser. The sodium, cut into small pieces, is then added, the flask being detached from the condenser for a moment and replaced. When the sodium has dissolved, the phenol and methyl iodide are added. The mixture IS heated on the water-bath until the solution has no longer an alkaline reaction (two to three hours). As much as possible of the methyl alcohol is distilled off on the water-bath and water added to the amber-coloured residue. A colourless oil separates out, which is e.xtracted with ether. The ethereal solution is dehydrated over calcium chloride and distilled, first on the water-bath until the ether has been driven off, and then over the flame. Almost the whole of the residue distils at 150—155. Yield, nearly theoretical. 

An ester of alanine with an arylaliphatic alcohol has shown promise as a non-tricyclic antidepressant. It may be speculated that the hindered milieu of the ester linkage protects the compound from hydrolysis by endogenous esterases. The preparation starts by reaction of pheny-lacctate 83 with methyl magnesium iodide to give tertiary carbinol 84. Acylation with 2-bromo-]>ropionyl bromide leads to ester 85 displacement of halogen with ammonia leads to alaproclate ( 6) [211. 

It can be prepared by digesting y3-naphthol-sodium with the calculated quantity of methyl iodide in methyl alcohol solution or by heating 1 part of y3-naphthol, 3 parts of methyl alcohol, and 1 part of hy ochloric acid in an autoclave to 150°. 

The final step is the reaction hetween acetyl iodide and methyl alcohol, yielding acetic acid and the promotor ... 

One of the first examples of this type of reaction, using a chiral alcohol as an auxiliary, was the asymmetric synthesis of 2-hydroxy-2-phenylpropanoic acid (atrolactic acid, 3, R1 =C6H5 R3 = CH3) by diastereoselective addition of methyl magnesium iodide to the men-thyl ester of phcnylglyoxylie acid4,5 (Table 22). 

A methyl group can be placed on cobalt in dicyano[cobyrinic acid heptamethyl ester] when it is treated with excess methyl magnesium iodide (the ester side chains being converted into tertiary alcohol groups). The alkylation could also be achieved using lithium alkyls (176). Presumably this reaction would be successful with any corrinoid which is soluble in solvents compatible with Grignard reagents. 

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