Methyl, alcohol zinc iodide

Under the above-described conditions, esters are nnaffected and aliphatic ketones are barely rednced. In the presence of zinc iodide, however, aliphatic ketones, as well as aldehydes and aromatic ketones, are converted into methyl ethers in high yields. If alcohols other than methanol are nsed, the corresponding alkyl ethers are obtained. 

Benzalacetone has been obtained in small yield by dry distillation of a mixture of calcium acetate and calcium cinnamate 1 by heating the sodium derivative of cinnamaldehyde with methyl iodide 2 by heating cinnamaldehyde and methyl alcohol with zinc chloride 2 by heating acetone and benzaldehyde with acetic... 

Methylamine occurs in herring brine 2 in crude methyl alcohol from wood distillation,3 and in the products obtained by the dry distillation of beet molasses residues.4 It has been prepared synthetically by the action of alkali on methyl cyanate or iso-cyanurate 5 by the action of ammonia on methyl iodide,6 methyl chloride,7 methyl nitrate,8 or dimethyl sulfate 9 by the action of methyl alcohol on ammonium chloride,10 on the addition compound between zinc chloride and ammonia,11 or on phos-pham 12 by the action of bromine and alkali on acetamide 13 by the action of sodamide on methyl iodide 14 by the reduction of chloropicrin,15 of hydrocyanic or of ferrocyanic acid,16 of hexamethylenetetramine,17 of nitromethane,18 or of methyl nitrite 19 by the action of formaldehyde on ammonium chloride.20... 

It is reported that trimethylamine in combination occurs in large amounts in beet-root residues 2 and can be obtained from them by the action of caustic soda it occurs also in herring brine.3 From both of these sources, however, the substance is obtained in an impure state and can be purified only by rather tedious methods. This is indicated by the fact that trimethylamine has always been an expensive substance. Synthetic methods for its production are by the action of methyl iodide on ammonia 4 by the distillation of tetramethylammo-nium hydroxide 6 by the action of magnesium nitride upon methyl alcohol 6 by the action of zinc upon trimethyloxy-ammonium halides 7 by the action of formaldehyde upon ammonium chloride under pressure 8 by the action of ammonium chloride upon paraformaldehyde.9 Of these syn-... 

H. M. Dawson and J. McCrae, D. P. Konowaloff, and W. Gaus also used soln. of various salts of the alkali metals, and of potassium, sodium, cupric, or barium hydroxide in place of water and also copper sulphate, copper chloride, zinc sulphate, and cadmium iodide while M. 8. Sherrill and D. E. Russ examined the effect of ammonium chromate. W. Herz and A. Kurzer examined the distribution of ammonia between water and a mixture of amyl alcohol and chloroform. Observations on the distribution of ammonia between water and chloroform were made by T. S. Moore and T. F. Winmill, G. A. Abbott and W. C. Bray, and J. M. Bell. J. H. Hildebrand gave for the molar fraction N X104 of ammonia at 1 atm. press., and 25°, dissolved by ethyl alcohol, 2300 methyl alcohol, 2730 and water, 3300. 

Denmark et al. studied the effect of zinc iodide on the catalytic, enantioselective cyclopropanation of allylic alcohols with bis(iodomethyl)-zinc as the reagent and a bismethanesulfonamide as the catalyst 17]. They found significant rate enhancement and an increased enantiomeric excess of the product cyclopropane upon addition of 1 equivalent zinc iodide. Their studies and spectroscopic investigations showed that the Schlenk equilibrium appears to lie far on the left (IZnCHjI). Charette et al. used low temperature - C-NMR spectroscopy to differentiate several zinc-carbenoid species [18]. They also found evidence that in the presence of zinc iodide, bis(iodomethyl)zinc is rapidly converted to (io-domethyOzinc iodide. Solid-state structures of (halomethyl)zinc species have been described by Denmark for a bis(iodomethyl)zinc ether complex (6a) [19] and Charette for an (iodo-methyl)zinc iodide as a complex with 18-crown-6 (6b) [20] (Fig. 2). 

Zinc methyl methylate, CH3.Zn.OCH3, is obtained by dissolving zinc dimethyl in methyl iodide and passing air through the mixture or by treating zinc dimethyl with a little methyl alcohol. It forms a camphor-like, crystalline mass, usually containing some zinc dimethylate, Zn(OCH3)2, and is decomposed by w ater into methane, methyl alcohol, and zinc hydroxide. 

Benzalacetone has been obtained in small yield by drv distillation of a mixture of calcium acetate and calcium cinnamate (1) by heating the sodium derivative of cinnamaldehyde with methyl iodide (2) by heating cinnamaldehyde and methyl alcohol with zinc chloride (2) by heating acetone and benzaldehyde with acetic anhydride or zinc chloride (3). It is also formed when styrene and acetyl chloride are condensed by means of stannic chloride and the product is treated with diethylaniline (4) and when the vapors of cinnamic acid and acetic acid are passed together over ferric oxide at 470-490° (5). The only practical method, however, consists in condensing benzaldehyde and acetone by means of dilute aqueous alkali (6). 

The keto ether (187) on treatment with diethyl carbonate in presence of sodium hydride in 1,2-dimethoxyethane afforded the keto ether (188), which was made to react with methyl-lithium in ether, to obtain the tertiary alcohol (189). This on being refluxed with methanolic hydrochloric acid yielded the phenol (190). It was methylated to yield(191) and heated with zinc, zinc iodide and acetic acid to produce pisiferol (192). Its methyl derivative (193) on oxidation with Jones reagent at room temperature, followed by esterification, furnished the keto ester (194). Reduction of (194) with metal hydride produced an alcohol whose tosyl derivative on heating with sodium iodide and zinc dust furnished the ester (195). Its identity was confirmed by comparing its spectral data and melting point with an authentic specimen [77]. The transformation of the ester (195) to pisiferic acid (196) was achieved by treatment with aluminium bromide and ethanethiol. The identity of the resulting pisiferic acid (196) was confirmed by comparison of its spectroscopic properties (IR and NMR) with an authentic specimen [77]. 

Fig. (16). The alcohol (171) was converted to the keto ether (185) applying the standard organic reactions and this on subjection to Robinson annelation. The resulting adduct on treatment with sodium methoxide in methanol afforded the tricyclic ketone (187) which is converted to another keto ether (188). It is converted to tertiary alcohol (189) by treatment with methyllithium. Acid treatment of the alcohol produced the phenol (190). Its methyl derivative (191) is converted to pisiferol (192) by treatment with zinc and zinc iodide. Its methyl derivative (193) was converted to ester (195) via oxidation, reduction, tosylation and detosylation. The reagents mentioned accomplished its conversion to pisiferic acid (196).

N-Methylethylamine has been prepared by heating ethyl-amine with methyl iodide in alcohol at 100° 3 by the hydrolysis of N-methyl-N-ethylarenesulfonamides,4-5 -nitroso-N-methyl-N-ethylaniline,6 or methylethylbenzhydrylidene ammonium iodide 7 by catalytic hydrogenation of ethyl isocyanate or ethyl isocyanide 8 and by the reduction of ethyl isocyanate by lithium aluminum hydride,9 of N-methylacetisoaldoxime by sodium amalgam and acetic acid,10 or of a nitromethane/ethylmagnesium bromide adduct by zinc and hydrochloric acid.11... 

Deoxygenation of alcohols and ethers. Treatment of alcohols and methyl or trlmethylsilyl ethers in acetonitrile with this iodoirimethylsilane equivalent and then zinc (previously activated with aqueous hydrochloric acid) and a little acetic acid results in deoxygenation to alkanes, usually in 60-90% yield. Presumably an alkyl iodide is an intermediate. 

Metal hydride reduction of methyl dehydroabietate (64b) afforded alcohol (65) whose tosyl derivative on heating with sodium iodide and zinc in dimethylformamide yielded (66). The use of hexamethylphosphoramide gave an inferior yield of (66). Regio and stereoselective acetoxylation with Pb(OAc)4 in acetic acid at 100°C gave only 30% yield of (67) but the same experiment realized with Pb(OAc)4 using a Hg medium-pressure lamp at room temperature yielded (67) in 74%. The H NMR spectrum of (67) showed that the OAc group was introduced in 7a-position. This on subjection to acid-catalyzed 13-elimination (EtOH/10% HC1) produced (68) in quantitative yield. 

C-Dihydrotoxiferine I chloride, C-tolKsN +Cl, [a]D —600° (1 1 aqueous alcohol), has two N-methyl groups attached at the quaternary Nb nitrogen atoms (39). Molecular distillation of the alkaloid chloride gives nordihydrotoxiferine with loss of methyl chloride this ditertiary base can be converted back into the bisquatemary alkaloid, as the diiodide, by methylation with methyl iodide (39). Dehydrogenation of C-dihydrotoxiferine I with sulfur or with zinc dust gives isoquinoline... 

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