D-, methyl ethers

Alginic acid, 279, 281, 286, 314, 322 esters of, 279, 314 salts of, 275, 279, 280, 286 Allopyranoside, methyl 2-acetamido-2-deoxy-a-D-, 3-methyl ethers, 202 Allose, 2-amino-2-deoxy-D-, methyl ethers of, 202, 214... 

The molecular formula of cancentrine was established as C3eHg4N207 by high-resolution mass spectrometry and confirmed by accurate mass measurement of the molecular ions of the D-methyl ether 2 and the... 

PMR chemical shifts for aristolochic acid-D methyl ether lactam in DMSO-de. ... 

Isoamyl ether [diisopentyl ether, di-(l-butyl-3-methyl) ether] [544-01-4] M 158.3, b 173.4 , d 0.778, n 1.40850. This is a mixture of 2- and 3-methylbutyl ether. It is purified by refluxing with sodium for 5h, then distilled under reduced pressure, to remove alcohols. Isoamyl ether can also be dried with CaCl2 and fractionally distd from P2O5. 

Isopropyl methyl ether [598-53-8] M 74.1, b 32.5°nnmm, d 0.724, n 1.3576. Purified drying with CaS04, passage through a column of alumina (to remove peroxides) and fractional distn. 

The dl-pukateine methyl ether obtained in small yield in the analogous synthesis was isolated as the hydriodide and resolved by the successive use of d- and 1-tartaric acids into the 1-base, m.p. 136°, [a]ff° — 252° (EtOH), identical with the methyl ether of pukateine, and the d-base, m.p. 136°, [a] " -f 256-4° (EtOH). 

Phaeanthine, C3JH42O0N2. (Item 8 list, p. 350.) This alkaloid was isolated by Santos.It has m.p. 210°, [a]u°° — 278° (CHCI3), yields a hydriodide, m.p. 268°, picrate, m.p. 263°, aurichloride, m.p. 170-1°, and a platinichloride, m.p. 280° (dec.), and contains four methoxyl and two methylimino groups. By the Hofmann degradation process it yields an optically inactive methine base A, m.p. 173°, which is oxidised by potassium permanganate in acetone to 2-methoxy-5 4 -dicarboxydiphenyl ether (p. 348). A comparison of the properties of phseanthine and tetrandrine by Kondo and Keimatsu indicates that these two alkaloids are optical antipodes, so that phseanthine will be represented by either (XXXIX) or (XL) as given on p. 348, 1 and of these two formula (R = Me) one must represent oxyacanthine methyl ether and the other berbamine methyl ether (centres of asymmetry d- and 1-) tetrandrine (centres of asymmetry both d-) and phseanthine (centres of asymmetry both 1-). 

Dihydro- -strychnine, C21H24O3N2, m.p. 240-3° (vac.), [a]D38-7/d (CHCI3), forms a methyl ether, m.p. 209° (vac.) and a benzylidene derivative, m.p. 209-215° (Leuehs and Rack, 1940). Unlike -strychnine, the dihydro-derivative can be converted, either by boiling with acetic anhydride or by condensation with malonie acid, into the corresponding 9-acetie acid, in this ease dihydrostrychnine-9-acetie acid, C23H26O4N2, m.p. 300-3° (vac. dec.), 43-0° (H2O) (Leuehs et al., 1942). 

These results the authors consider cannot be aeeounted for on the basis of a 6-membered ring B and the adoption of a 5- or 7-membered ring B introduces a difficulty in explaining the formation of 2 3 4 7-tetramethoxyphenanthraquinone in the oxidation of deaminocolchinol methyl ether. There is, however, a precedent in Weitzenbock s oxidation of 4 5 6 7-dibenzo-d -c /cZoheptatriene-l-aldehyde (X) to phenanthraquinone, for representing the a -unsaturated ketone as 9 12 13 14-tetramethoxy-3 4 5 6-dibenz-d -c /cZoheptatriene-7-one (XI CH2 at —> CO), using the system of numbering adopted by... 

These results indieate that deaminoeolehinol methyl ether is 9 12 13 14-tetramethoxy-3 4 5 6-dibenz-d = -cycloheptatriene (XI j... 

Quaternary salts of the substances represented by tliese formulae have been prepared by Kogl, Veldstra and van der Laan as well as of the next lower homologues, the substituted butyraldehydes, and the methyl ethers of both series. Their pharmacological activities were negligible in comparison with that of muscarine, but as six stereoisomeric forms may be produced in each synthesis, the inactivity may be due to stereoisomerism, just as in the case of threonine (a-amino-)3-hydroxy-butyric acid) where West and Carter found that only the d —) form is... 

Methoxy-D-Homo-estra-l,3,5(10)-trien-17a-one (96)" (/) Acetic acid (6.4 ml) is added to a stirred solution of estrone methyl ether (93 1.1 g) in ethanol (35 ml) containing potassium cyanide (6 g) at 0°. After being stirred for 1 hr at 0° and 2.5 hr at room temperature, the reactants dissolve and potassium acetate preciptates. Water (65 ml) is added to the reaction mixture and the precipitated solid is collected by filtration. The crude product is dissolved in ethyl acetate and the ethyl acetate solution is washed with water, dried over anhydrous magnesium sulfate and evaporated to dryness under reduced pressure. Recrystallization of a portion of the crude product from cyclohexane-acetone gives 3-methoxy-17a-cyano-estra-l, 3,5(10)-trien-17j5-ol (94a) as needles mp 158.5°. 

During 1961-2 four independent groups almost simultaneously reported the first syntheses of D-norsteroids, based on the photolysis of 16-diazo-17-ketones. In a typical procedure. Cava and Moroz ° convert the 16-oximino-17-one (93) derived from estrone methyl ether (92) to the diazoketone (94)... 

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