Sodium methylate

Salts composed of an anion, RO—, and a cation, usually a metal, can be named by citing first the cation and then the RO anion (with its ending changed to -yl oxide), e.g., sodium benzyl oxide for CgH5CH20Na. However, when the radical has an abbreviated name, such as methoxy, the ending -oxy is changed to -oxide. For example, CHjONa is named sodium methoxide (not sodium methylate). 

Manufacture is either by reaction of molten sodium with methyl alcohol or by the reaction of methyl alcohol with sodium amalgam obtained from the electrolysis of brine in a Castner mercury cell (78). Both these methods produce a solution of sodium methylate in methanol and the product is offered in two forms a 30% solution in methanol, and a soHd, which is a dry, free-flowing white powder obtained by evaporating the methanol. The direct production of dry sodium methylate has been carried out by the introduction of methanol vapors to molten sodium in a heavy duty agitating reactor. The sohd is supphed in polyethylene bags contained in airtight dmms filled in a nitrogen atmosphere. 

Typical specifications of the powder are as follows sodium methylate, 97.5% sodium hydroxide, 0.5% sodium carbonate, 0.4% sodium formate, 0.3% and free methanol, 0.5%. 

The solution of sodium methyl sulfide in absolute alcohol is transferred to a 3-I. three-necked flask, which is placed on a steam bath and fitted with a dropping funnel, a reflux condenser, and a mechanical stirrer. The solution is heated until the alcohol begins to boil. Heating is then discontinued and 302 g. (3.7s moles) of ethylene chlorohydrin (Note 5) is added dropwise with efficient stirring over a period of about two hours (Note 6). The reaction mixture is concentrated by distilling as much of the alcohol as possible on the steam bath. The mixture is then allowed to cool and the sodium chloride removed by filtration. The flask is rinsed, and the sodium chloride washed with three loo-cc. portions of 95 per cent alcohol. The combined filtrate and washings are concentrated on the steam bath under reduced pressure until no further distillate passes over. The residue is then transferred to a modified Claisen flask (Org. Syn. Coll. Vol. i, 125) and fractionally distilled under reduced pressure. The yield is 238-265 g. (74-82 per cent of the theoretical amount based on the sodium used) of a product boiling at 68-7o°/20 mm. 

Cellobiose was prepared first by Skraup and Konig by the saponification of the octaacetate with alcoholic potassium hydroxide, and the method was improved by Pringsheim and Merkatz.3 Aqueous barium hydroxide also has been employed for the purpose, and methyl alcoholic ammonia has been used extensively for the hydrolysis of carbohydrate acetates. The method of catalytic hydrolysis with a small quantity of sodium methylate was introduced by Zemplen,i who considered the action to be due to the addition of the reagent to the ester-carbonyl groups of the sugar acetate and the decomposition of the addition compound by reaction with alcohol. The present procedure, reported by Zemplen, Gerecs, and Hadacsy, is a considerable improvement over the original method (see Note 2). 

SODIUM METHYLATE SODIUM MONOXIDE SODIUM NITRATE SODIUM NITRITE... 

Apply sample solution, dry, blow on hydrochloric [75] acid vapor methylate with 2 mol/1 sodium methylate solution. 

Phenols Apply sample solution and spray with saturated sodium methylate solution and then treat with 4% 2,4-dinitrofluorobenzene in acetone and heat to 190°C for 40 min. Chromatograph the dinitro-phenyl ethers so produced. [79]... 

Methylation of the Alkaloids. When cephaeline is treated with methyl sulphate or sodium methyl sulphate under various condition, there is formed in addition to emetine (which was first shown to be the methyl ether of cephaeline and partially synthesised in this way by Carr and Pyman in 1913), more or less N-mcthylcephaeline (wedge-shaped plates, m.p. 194 5°), and N-methylemetine. The latter is also obtained by direct methylation of emetine it is amorphous, [a]n — 52-6° (CHCI3), but yields a hydrobromide, C33H42O4N2.2HBr. 3H2O, m.p. 210-30°, [ajp + 5-6° (H2O). 

After the apparatus has been fitted together the caustic soda solution is run in slowly and the flask shaken. The liquid is no more ammonia is evolved be ascertained by testing a drop litmus paper. If the operation is titrated with half-normal sodium methyl orange as indicator. 

Ethyl Acetoacetate. -The e. planation of the manner in which this substance is produced has been given in the account of the preparation. The result was anived at, not by the iscila-tion of the intermediate compound formed by the union of ethyl acetate with sodium ethylate, but by analogy with the behaviour of benzoic methyl ester with sodium benzylate, which gave the same additive product as that obtained by combining benzoic benzyl ester with sodium methylate, showing that such combinations could occur,... 

Nitro-compounds yield a series of reduction products accordmgto the nature of the reducing agent. Alkaline reducing agents sodium methylate, zinc dust and caustic soda, stannous chloride and caustic soda, produce azoxy, azo- and hydiazo-compounds. 

The sodium methylate acts as a 1 educing agent by taking up oxygen and forming sodium formate. 

Pivorarenko and Khilya investigated a series of organic bases including tribenzyl amine, sodium methylate, sodium terf-butylate, n-methylmorpholine,... 

Sodium methyl mercaptide in xylene was reported to react (25°, 2 hr) in a stepwise fashion with 3,5-dichloro-as-triazine to yield the 3-methylthio-5-chloro and then (70°, 2 hr) the 3,5-bis-methylthio derivatives. However, the structure of the former is very likely to be 307. With dimethylamine in benzene (25°, 5 min), ethyleneimine in ether (25°, 3 min), and alcoholic ammonia (25°, few min), this dichloro derivative was assumed to form 3-amino derivatives. The high reactivity of as-triazines is demonstrated by the facile ethoxylation... 

Complexes 79 show several types of chemical reactions (87CCR229). Nucleophilic addition may proceed at the C2 and S atoms. In excess potassium cyanide, 79 (R = R = R" = R = H) forms mainly the allyl sulfide complex 82 (R = H, Nu = CN) (84JA2901). The reaction of sodium methylate, phenyl-, and 2-thienyllithium with 79 (R = R = r" = R = H) follows the same route. The fragment consisting of three coplanar carbon atoms is described as the allyl system over which the Tr-electron density is delocalized. The sulfur atom may participate in delocalization to some extent. Complex 82 (R = H, Nu = CN) may be proto-nated by hydrochloric acid to yield the product where the 2-cyanothiophene has been converted into 2,3-dihydro-2-cyanothiophene. The initial thiophene complex 79 (R = R = r" = R = H) reacts reversibly with tri-n-butylphosphine followed by the formation of 82 [R = H, Nu = P(n-Bu)3]. Less basic phosphines, such as methyldiphenylphosphine, add with much greater difficulty. The reaction of 79 (r2 = r3 = r4 = r5 = h) with the hydride anion [BH4, HFe(CO)4, HW(CO)J] followed by the formation of 82 (R = Nu, H) has also been studied in detail. When the hydride anion originates from HFe(CO)4, the process is complicated by the formation of side products 83 and 84. The 2-methylthiophene complex 79... 

Imidazole with [(T -C Hg)RuCl2]2 in the presence of sodium methylate gives most probably the tetrameric [(T) -C Hg)RuCl(p-im)]4 where the imidazolate anion performs the N, A -bridging function (93ICA(206)15). 

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