Ether-Soluble Compounds

From the ether-soluble fraction, Takahashi etal. 134, 135) isolated sitosterol-P-D-glucoside, sitosterol, p-elemene (96), eremophilene (97) and a new polyacetylenic alcohol named panaxynol (98), the structure of which was elucidated as heptadeca-l,9(Z)-diene-4,6-diyn-3-ol by degradative and synthetic procedures. It is identical with carotatoxin from carrots 136) and falcarinol from Falcaria vulgaris 137). Recently two other polyacetylenic alcohols, 9,10-epoxy-3-hydroxyheptadeca-l-en-4,6-diyne [(99), panaxydol] 138) and heptadeca-l-en-4,6-diyn-3,9-diol (100) 139) were isolated from Ginseng roots by Wrobel et al. 

Campesterol, stigmasterol and sitosterol have been identified in Ginseng roots by GLC 140) and an analysis of the fatty acids has been reported 141). 

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Very little information exists on the phenolic protein-conplexing resins, except for that on creosote bush and sane arctic plants. In contrast to condensed tannins and hydrolyzable tannins, these are typically ether-soluble compounds this may allow their entry into the body across cell membranes, and thios give them the potential for action outside the gut lumen. Reports for animals consuming seaweed indicate that astringent protein-precipitating substances (presumably phlorotannins), are potentially important in marine plant-herbivore interactions. 

Dolomedes scriptus E Courtship by males elicited by ether soluble compounds from females Kaston, 1936... 

A number of peroxychromate derivatives have been made, the most familiar being the blue, ether-soluble compound, Cr05, resulting from treatment of acidified dichromate solutions with HjO . These have peroxide bridges —that is, three-membered rings formed by a chromium... 

XL Other Constituents of Ginseng Roots 1. Ether Soluble Compounds... 

Hydrolysis of a substituted amide. A. With 10 per cent, sulphuric acid. Reflux 1 g. of the compound (e.g., acetanilide) with 20 ml. of 10 per cent, sulphuric acid for 1-2 hours. Distil the reaction mixture and collect 10 ml. of distillate this will contain any volatile organic acids which may be present. Cool the residue, render it alkaline with 20 per cent, sodium hydroxide solution, cool, and extract with ether. Distil off the ether and examine the ether-soluble residue for an amine. 

Amino-2-hydroxybenZOiC acid. This derivative (18) more commonly known as 4-aminosa1icy1ic acid, forms white crystals from ethanol, melts with effervescence and darkens on exposure to light and air. A reddish-brown crystalline powder is obtained on recrystallization from ethanol —diethyl ether. The compound is soluble ia dilute solutioas of nitric acid and sodium hydroxide, ethanol, and acetone slightly soluble in water and diethyl ether and virtually insoluble in benzene, chloroform or carbon tetrachloride. It is unstable in aqueous solution and decarboxylates to form 3-amiaophenol. Because of the instabihty of the free acid, it is usually prepared as the hydrochloride salt, mp 224 °C (dec), dissociation constant p 3.25. 

Pyridine, and its monomethyl and 3,5-dimethyl derivatives " combine exothermically with dimethyl acetylenedicarboxylate in ether yielding some ether soluble materials, including trimethyl pyrrocoline-1,2,3-tricarboxylate (Section III,F,3) and deep red ether-insoluble gums. A number of crystalline compounds have been isolated from these gums by fractional crystallizations and will now be considered in detail. In the case of pyridine, Diels et al. ° isolated a red labile 1 2 molar adduct, which they formulated as (75), which isomerized rapidly on standing to a yellow stable adduct (76). These formulations are no longer accepted. Diels and Alder also suggested that the acetylenic ester first dimerized to the diradical (74) which then combined with the pyridine. 

Thiamin (vitamin B-l, 177) when photolysed, gives preparations having a characteristic odour. Photolysis of an aqueous solution with a high-pressure mercury lamp is reported to give the pyrimidine (178) [ 113]. Other work used irradiation at 254 nm and concentrated on the approximately 0.1% yield of ether-soluble odoriferous products. As many as nine compounds have been identified (179), (180), (181), 2-methyl-3-formyl-4,5-dihydrofuran, 3-acetyl-4,5-dihydrofuran, 4-oxopentyl formate, 3-formyl-5-hydroxypentan-2-one, 3-mercapto-2-methyl-4,5-dihydrofuran and bis(4,5-dihydro-2-methylfuran-3-yl)disulphide [114, 115]. 

The nitrosophenol is precipitated from the cooled aqueous solution by acidification with dilute sulphuric acid and is extracted with ether in a separating funnel. After brief drying over calcium chloride the brownish-green solution is concentrated on the water bath. The sparingly soluble compound crystallises from the ether on cooling. Melting point 120°-130° (decomp.). Complete purification of nitrosophenol is difficult. 

Scammonin VII (62), as a minor ether-soluble resin glycoside, was isolated by reversed-phase HPLC from Convulvulus scammonia L. (47). Under basic hydrolysis, it gave orizabic acid A as weU as 2-methyIbutyric and tiglic acids. Compound 62 exhibits lactonization at C-3 of the rhamnose unit and is acylated by a (25)-methylbutanoyl residue at C-2 of the rhairmose unit and a tigloyl residue at C-4 of the terminal quinovose. 

These compounds have only been studied on the trace scale. An ether soluble polonium dibenzyl is reported (80, 118) to be formed by the action of dimethylphenylbenzy 1-ammonium chloride on sodium polonide/telluride mixtures in water saturated with hydrogen. The dimethyl was prepared in the same way, but with dimethyl sulfate (118) and may also be formed in... 

If, as a criterion of value to the study of lignin depolymerization by alkaline hydrolysis, the maximum yield of oxygen-bearing, phenylpropanoid derivatives is chosen, then the conditions of such a study have been optimized here at a treatment severity corresponding to a reaction temperature of 300°C for 1 hour. Under these conditions, 20% of the lignin is recovered as ether-solubles of which 55% is identifiable as monomeric derivatives. The rest of this material probably consists of dimeric-type compounds not identified by capillary gas chromatography. 

While aromatic nitro and azoxy compounds have been reduced to azo compounds with lithium aluminum hydride, aliphatic nitro compounds produced only the corresponding aliphatic amines [65]. The usual technique involves dropwise addition of 1 mole of nitro compound in ether to 1.05-1.15 moles of lithium aluminum hydride in ether solution at Dry Ice temperatures followed by warming to room temperature. If the resulting product is only slightly soluble in ether, hydrolysis should be carried out with dilute sulfuric acid. Then the azo compound simply needs to be filtered off, washed with water, and dried. If the product is ether-soluble, the ether layer is separated, evaporated, and the residue is recrystallized [65, 66]. 

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