Ether, dimethyl potassium salts

Dimethyl sulfate, reaction with di-methylformamide, 47, 52 Dimethyl sulfoxide, in synthesis of phenyl f-butyl ether, 45, 89 potassium salt, preparation, 48, 109, 110... 

Its Potassium salt, deliquescent crysts Mercury salt, pltlts, dec >240°and Silver salt, voluminous ppt, explodes violently when heated have been prepd in addn to many other derivs (Ref 1) l,l-Dimethyl-2-propyn-l-nitrite 3,3-Dimethyl-l-propyn-3-ol (called Nitrite Ester of 2-Methyl-3-hutyn-2-ol in CA), HCiC.C(CH3)2.ONO mw 113.11, N 12.38% liq, hp 80-82° at 750mm press nD 1.3926 at 20° was prepd when NOCl ether were added to a stirred soln of 3 methyl-l-butyn-3-oI (parent compd)... 

Various approaches to the synthesis of menaquinones have been made, in which the aromatic component is activated to encourage nucleophilic attack upon a receptive prenyl fragment. Thus alkylation of the potassium salt of 2-methyl-1,4-naphthoquinol (236) or 4-methoxy-3-methyl-l-naphthol (237) with geranyl bromide (244) gave menaqui none-2 (246) in 20 and 45% yield, respectively, after oxidation. Hydrogenolysis of the dimethyl ether (238) of 1 -oxymenaquinol-2 [from... 

A synthetic route to ( )-0,f>-dimethyltubocurarine iodide (CXXV), via the racemate of 0,0-dimethylbebeerine (CXXIII), was announced in 1959 by Tolkachev and his collaborators (94). It started by the condensation of 3-methoxy-4-hydroxyphenethylamine with 4-benzyloxy-phenylacetic acid to give the amide CXXVI. Reaction of the potassium salt of the latter with the methyl ester of 3-bromo-4-methoxyphenyl-acetic acid in the presence of copper powder gave compound CXXVII. This on condensation with 3-methoxy-4-hydroxy-5-bromophenethyl-amine afforded compound CXXVIII, which was methylated to CXXIX. The latter compound was cyclized with phosphorous oxychloride to the dihydroisoquinoline derivative CXXX. Debenzylation of CXXX followed by intramolecular Ullmann condensation yielded compound CXXXI. The latter was converted to racemic dimethylbebeerine (CXXIII) by reduction with zinc dust in acetic acid followed by methyla-tion. Finally, treatment of ( + )-CXXIII with methyl iodide furnished the dimethyl ether of ( + )-tubocurarine iodide, identified by comparison of its UV-spectrum with that of the dimethyl ether of natural tubo-curarine iodide and by melting-point determination of a mixture of the two specimens. 

Potassium salt, soly (mg/ml) water (1.0) DMSO (8/1.5) 1 1 DMSO-H20 (3.0) also readily sol in DMF. dimethyl-acetamide, pyridine. Sparingly sol in ethyl acetate, acetoni -trile, methanol, chloroform. Insol iu hexanes, benzene, acetone, ether-... 

Isomerization has been effected under a range of alkaline conditions including potassium hydroxide in ethanediol at 170-180 °C, potassium r-butoxide in r-butanol at 70 °C or in diethyl ether at 25 °C, the potassium salt of the methyl ether of triethylene glycol at 25 or 60 °C, dimsyl sodium or dimsyl potassium in dimethyl sulphoxide and/or tetra-hydrofuran at 25 °C, the potassium salt of 1,3-diaminopropane at 50 °C and tetramethylammonium hydroxide. 

Methylisourea hydrochloride has been prepared by the action of hydrogen chloride on a suspension of silver cyanamide 2 or a solution of cyanamide3-4 in methanol,3 and by the action of dimethyl sulfate on urea at 112°.6 The free base is obtained by treating the salt with powdered potassium hydroxide in a water-ether mixture 3 or with sodium methoxide in methanol.0... 

A one-pot procedure was developed by Otera et al. from p-cyclogeranylsulfone [32]. Its lithium salt reacted with 3,7-dimethyl-8-oxo-2,6-octadienyl acetate to the sulfone-alcohol. The hydroxyl group was protected to the MOM ether with MeOC Cl. Double elimination could be achieved with potassium MeOK to provide vitamin A in 50% yield, Fig. (12). 

Nitro-4-methoxyaniline has been prepared by heating nitro-hydroquinone dimethyl ether with aqueous ammonia 2 by heating the tetramethylammonium salt of 3-nitro-4-aminophenol 3 by the hydrolysis of 2-nitro-4-methoxyacetanilide la with alcoholic potassium hydroxide 11 lc or hydrochloric acid ld and by the hydrolysis of the />-toluenesul fonamide,4 the 3-nitrobenzenesul-fonamide,5 the 3-nitro-/>-toIuenesulfonamide,3 and the acetyl derivative of the />-toluenesulfonamide6 of 2-nitro-4-methoxyani-line with concentrated sulfuric acid. 

In order to introduce a second hydroxyl group al C-l 1 of the ester (99) its sodium salt was treated with p-nitrobenzene diazonium chloride in methanol. The resulting product on methylation and then reduction with potassium dithionate afforded the amino ester (100). Diazotization and methanolysis produced ethyl ( )-camosate dimethyl ether (101), which on saponification produced camosic acid dimethyl ether (102). Wenkert [22] accomplished demethylation of dextrorotatory camosic dimethyl ether with boron tribromide. Thus the work of Meyer lacks only the... 

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