§ 137. После предлога by дополнение часто выражается инговой формой (герундий, см. § 103).

Например:

The hydrochloride of the di-iodo-compound is very sparingly soluble in boiling 2N-hydro-chloric acid, and traces of 3'-iodo-L-thyronine are easily removed from 3',5'-di-iodo-L-thyronine by treatment with hydrochloric acid. З'-iodo-L-thyronine was conven-tiently prepared by treating thyronine with an excess of iodine and removing the di-ido-thyronine as its hydrochloride.

Slow linear sweep of the field for phase-sensitive detection was obtained by feeding the output from a Miller sweep generator into the control amplifier of the power unit. The purity of the stable isotopes was established by analysing the solutions of the dissolved metal beads, but only limited quantities could be spared for the analysis and the limits of impurity given in Table 2 reflect this. After the solution had been kept for 17 hr., the acid was removed by stirring in barium carbonate, and the precipitate was removed in a centrifuge. Identification of this material was confirmed by comparing its infrared spectrum with that of authentic material.

Potassium hydrogen di-iodate (bi-iodate) was obtained by crystallising equimolar quantities of the constituents from hot water, and deuteroiodic acid from a solution of iodine pentoxide (dried for several days at 200—210") in deuterium oxide.

Anhydrous nickel iodate was prepared by heating together nickel nitrate and iodic acid in 8N-nitric acid, and ferric iodate by adding ferric nitrate in 4N-nitric acid to boiling aqueous iodic acid.

Potassium hexaiodatomanganate (IV) was obtained by boiling together freshly precipitated manganese dioxide, iodic acid, and potassium iodate, according to Berg's method.

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The alkaloids, recovered by extraction with chloroform (4x 300 с. с.), were converted into their hydrochlorides by dissolving them in methanol (150 с. с.), adding concentrated hydrochloric acid (20 с. с.), and precipitating the salts with ether.

§ 138. Когда процессы выражаются не существительными, а глаголами в личной форме страдательного залога [например, is (are, was, were) oxidised, а не oxidation, oxidising; is (are, was, were) treated, а не treatment, treating, вещества, которые исполь-зуются для осуществления этих процессов, часто вводятся предлогом with.

Например:

When 3-nitropurin or 2-hydroxy-3-nitroanthra-l,4,9,10—di-quinone is oxidised in methanol with lead dioxide or potassium permanganate 2-hydroxy-3-nitroacetyl-l,4-naphthaquinone (III) is formed directly.

After being stored overnight, the solutions were neutralized with acetic acid and evaporated. The products were only partly soluble in water, so the deacetylation was repeated to give material completely soluble in water. This was treated with Biodeminrolit resin and evaporated to a syrup.

(a) 3-Nitroalizarin. When 3-nitroalizarin was oxidised in methanol with lead dioxide the first relatively stable product was a methyl ether (I) of 3-nitropurpurin, which on hydrolysis with aqueous hydrobromic acid was converted into 3-nitropurpurin (I). Solvent was removed and the polymer was precipitated with 1 : 1 ether-cyc-lohexane (3 с. с.), then dissolved in water and neutralised with tri-butylamme. The trisaccharide (10 mg.) was reduced with sodium bo-rohydride (20 mg.) for 24 hr. When it was hydrolysed with 1,5 N — sulphuric acid for 6 hr. the glucose liberated amounted to 65% of that from an equivalent weight of unreduced trisaccharide. The acetates were extracted with chloroform (3 X 100 ml), and the combined extracts were washed with sodium hydrogen carbonate solution and water and then dried (Na₂S0₄). In a trial experiment the dextran was hydrolysed with dilute sulphuric acid to degrees of conversion into glucose ranging from 20 to 51 %.

Optical spectra were measured with a Gary recording spectropho-tometer. The column was eluted with water to remove glucose.

§ 139. Встречается также употребление предлогов with и by в тождественных контекстах, что, по-видимому, указывает на отсутствие сознательной дифференциации между орудием действия и непосредственным деятелем.

Например:

The acid polysaccharide (3g.) was hydrolysed by N-sulphuric acid (50 ml.) at 100° for 4 hr. Since chromatography showed several oligosaccharides, both neutral and acidic, the mixture was

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rehydrolysed with N-sulphuric acid (30 ml.) at 100° for 2 hr. In a similar reaction but with decomposition by water and ice, sulphur (0,7 g.) was obtained from the ethereal and thiolbenzoic acid from the aqueous layer. In a similar reaction decomposition with water afforded an unidentified oil from the ethereal layer and benzoic acid from the aqueous layer.

Thus 1 mol. of dibenzoyl disulphide with 3 mols. of phenylmag-nesium bromide or phenyl-lithium afforded triphenylrnethyl thi-olbenzoate after decomposition by acid. Decomposition with ammonium chloride in case of the magnesium compounds and with water in case of lithium compounds gave, as expected, the triarylmethanols.

2-Phenylethanol has been found to be oxidised by ammonium metavandate to benzaldehyde, benzoic acid, and formic acid under conditions in which (a) dehydration to styrene did not occur and (b) phenylacetic acid was not oxidised, whilst (c) benzyl alcohol was rapidly oxidised. This olefin is only slowly oxidisedby vanadium (V), a:id it cannot be the immediate precursor. Mild oxidation of either y-oxo-y-2-xanthenylbutyric acid (I) or its methyl ester by potassium permanganate in aqueous acetone yielded y-oxo-y-2-xanthonylbutyric acid (II; R=H) or its methyl ester respectively.

Oxidation of the sugar with periodate gave 0,06 mol. of formaldehyde. Reduction of the sugar with potassium borohydride followed by oxidation with periodate gave 0.87 mol. of formaldehyde.

It may be emphasised that in dioxan solution no significant phosphorylation of 5'-hydroxyl groups by diphenyl phosphorochlo-ridate occurred under the conditions employed. The present paper deals with the chemical oxidation of 3-nitro-alizarin and -purpurin by lead dioxide and potassium permanganate in methanol containing some acetic acid; in the following paper we compare the course of this oxidation with the photochemical degradation. Oxidation of the sugar with sodium metaperiodate in the presence of sodium hydrogen carbonate gave 0.04 mol. of formaldehyde. Hydrolysis of the diketo-ester (II; R = Me) with 5% alcoholic potassium hydroxide gave the diketo-acid (II; R = H), but treatment with 10% aqueous sodium hydroxide led to a phenolic acid. When this procedure failed to provide crystalline sulphone, the mixture was decomposed by ice and dilute hydrochloric acid, and the ethylene dichloride layer was separated and dried after being washed successively with water, dilute sodium hydroxide solution, and water again.

In control experiment, treatment of e-galactan with N-sulphuric acid at room temperature for 30 min. afforded no detectable reducing sugars. However, Kulkarni and co-workers obtained mixtures of cis- and trans-3, 4-diols on reduction of dihydrofisetin and dihydro 4'-methoxy-6-methylflavonol by lithium aluminium hydride. Bognar and Rakosi found that the reduction of dihydroflavonol by hydrogen over a supported palladium catalyst gives the trans-3,4-diol in

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both solvents. Reduction of the derived methyl ester methyl glyco-sides with potassium horohydride, followed by hydrolysis, gave galactose only. Oxidation of the disaccharide with periodate gave only traces of formaldehyde, whereas oxidation of the acidic disaccharide alcohol (from reduction by borohydride) gave 0,85 mol. of formaldehyde, a result consistent only with the presence of a 1,5- or 1,6-linkage. Conversion into the methyl ester methyl glycosides, reduction with potassium borohydride, and hydrolysis gave arabirio-se and galactose (chromatography). Similar treatment of the disaccharide alcohol (from reduction by potassium borohydride) gave only arabinose. Aliquot (arabinose) were withdrawn at intervals, excess of periodate was destroyed by ethylene and the liberated acid was titrated with 0,015 N-sodium hydroxide. The ether was removed and replaced by xylene, and the solution heated at 90° overnight. In contrast to the rapid reaction of these anilides, the quinoxalines (VI a-d) and the pyrazine (VII) were all unchanged by concentrated sulphuric acid at room temperature. In pyridine solution the 5'-hydroxyl group was phosphorylated by P¹P²-dibenzyl P¹P²-diphenyl pyrophosphate, tetra-allyl pyrophosphate, and tetrabenzyl pyrophosphate in that order of reactivity. The normal wave-guide connected to the heat-break was warmed by a small heater, to prevent condensation of moisture.