Alcoholic Hydrogen Chloride Research Articles

194. Factors in the formation of isomerically and optically pure alkyl halides. Part I. Alcohol–hydrogen chloride or –thionyl chloride systems

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Solubility of hydrogen halides in organic compounds containing oxygen. II. Assessment of contributions of groups in alcohols

AbstractContinuation of the study of saturation solubility of hydrogen chloride in alcohols at 0–50° has led to the assessment of the contribution to the solubility of each part of a molecule, according to its polar character and distance from the oxygen atom. Correlation of solubility with electron density on the oxygen atom is in excellent agreement with the correlation of the basic strength of alcohols, esters and ethers, and certain physical and chemical properties.

Solubility of hydrogen halides in organic compounds containing oxygen. III. Solubility of hydrogen chloride in alcohols and certain esters at low temperatures

AbstractSolubility of hydrogen chloride in organic compounds containing oxygen depends primarily on the electron density on the oxygen atom, which in turn is governed by the structure of the solvent molecule. Values of the solubility are given for a number of solvents. Remarkably large values were observed at low temperatures. A linear relationship is found to exist for some compounds between the molar fraction of hydrogen chloride and the logarithm of the absolute temperature.

The Thermodynamics of Hydrogen Chloride in Ethyl Alcohol from Eleatromotive Force Measurements

The Thermodynamics of Hydrogen Chloride in Ethyl Alcohol from Eleatromotive Force Measurements

Quinquevalent compounds of uranium—I Alkoxides and complex chlorides

The new complex, (C 5H 6N) 2UOCl 5(I), was obtained from reactions involving UCl 5, SOCl 2, alcoholic hydrogen chloride, and pyridine. Reaction of (I) with alcohol and ammonia afforded a novel method of preparing uranium penta-alkoxides U(OR) 5 by disproportionation of the oxide-alkoxides initially formed. The new compound, UOCl 3, EtOH(II), was isolated from the reaction involving UCl 5,SOCl 2 and very dry ethyl alcohol, and this explains the formation of (I).

Solubility of hydrogen halides in organic compounds containing oxygen. I. Solubility of hydrogen chloride in alcohols, carboxylic acids and esters

AbstractThe solubility of hydrogen chloride, as moles per mole of compound, in series of alcohols, carboxylic acids and their esters appears to be determined mainly by electron density (basic strength) of the significant oxygen atom. Change in solubility with change in substituents follows the expected change in basic strength. Alkyl substituents increase solubility, whereas substitution by chlorine causes a more pronounced decrease. The solubility in a carboxylic acid is much lower than in the corresponding alcohol; but compensation is gained by replacing the acidic hydrogen atom to form an ester.Values for different temperatures are given and from these, linear plots of solubility‐reciprocal of the absolute temperature are obtained.

Absorption spectra and molecular structure

1. The absorption spectra of solutions of mono-, di-, tri-, and tetra-chloro derivatives of the phenylhydrazone of 9-acridinecarboxaldehyde hydrochloride in alcoholic hydrogen chloride were investigated. 2. It was shown that with respect to the hypsochromic effects of their halogen atoms, the monochloro derivatives fall into the sequence corresponding to the demands of the inductive effect of the substituent. 3. The presence of the substituents has little effect on the general shape of the curve and the positions of the short-wave absorption maxima. As the number of substituents increases, there is a regular displacement of the principal absorption maximum in the direction of the short waves. The effects of the substituents are approximately additive. 4. It can be inferred from the behavior of the chlorine derivatives of the phenylhydrazone of 9-acridine-carboxaldehyde hydrochloride that complete additivity of the effects of substituents is practically never observed. This fact is to be attributed to the mutual effects of atoms. 5. Nine new chloro derivatives of 9-acridinecarboxaldehyde phenylhydrasome were prepared.

Interaction of alcohols with hydrogen halides

AbstractPrevious and submitted evidence on the mechanism of interaction between an alcohol and a hydrogen halide points to the conclusion that the formation of an alkyl halide entails two steps: the rapid formation of an oxonium halide, ROH2+ X−, and the rate‐determining dehydration of it. Results from the studies of kinetics and optical rotatory power are as yet inconclusive on the mechanism of the second step, but they point to the concurrence of several modes.The maximum amount of hydrogen halide absorbed by an alcohol depends on the nature of the alcohol and on the temperature. This amount is of great significance because it determines the maximum concentration of the oxonium halide, and also can control the extent to which the water produced reduces the rate of formation of alkyl halide. Because of these points, and because the concentration of halide ion can be increased, certain added substances, such as pyridine, dioxan and even water, can increase the rate of formation and final yield of alkyl halide.Results of experiments on the solubility of hydrogen chloride in different alcohols, and on the extraction of the halide by water, are discussed.

パラ・アミノベンゼンスルフォンー<i>N</i><sup>1</sup>-3,4-ヂメチルベンゾイルアミドの合成 (第1報)

A new method for the preparation of p-aminobenzenesulfone-N1-3, 4-dimethylbenzoylamide in good yield is described. 3, 4-Dimethylbenzimido ethyl ether, prepared from 3, 4-dimethylbenzonitrile by means of alcoholic hydrogen chloride, was converted into the corresponding amidine by treating with alcoholic ammonia, which was then condensed with acetosulfanil chloride, giving p-acetaminobenzenesulfone-N1-3, 4-dimethylbenzamidine. The latter gave p-aminobenzenesulfone-N1-3, 4-dimethylbenzoylamide on being treated with 15% hydrochloric acid.

Deacylation of aromatic acetylamino compounds in acid alcoholic medium

AbstractAromatic acetylamino compounds are converted into the corresponding amino compounds by heating with absolute alcoholic hydrogen chloride; the acetyl group is split off in the form of an ester. This acid deacylation has been studied more closely and compared with the (pseudo) catalytic deacylation in alkaline medium.Contrary to what was found in the latter process, the mesomeric effect (‐M‐effect) of substituents present in the nucleus plays no significant role; acid deacylation is not, like alkaline deacylation, dominated by quinonoid structures. Consequently steric inhibition of the mesomerism in this case has no appreciable influence on the rate of deacylation.Derivatives of acetanilide with two ortho‐substituents are deacylated strikingly slowly. There is no doubt that here we are dealing with cases of classical steric hindrance; on the contrary, this phenomenon does not occur in alkaline deacylation.Acid deacylation is frequently very useful for preparative purposes, particularly in the presence of alkoxycarbonyl groups, carbonamido groups, cyano groups and the like. These substituents remain Intact during the reaction, which is not the case in the classical methods for hydrolysing acetylamino compounds.

Structure and colour in the 1:2-dihydroquininolo (3':2':3:4) quinolines.

THE preparation of 4-keto-1-phenyl-1 : 2 : 3 : 4-tetrahydroquinoline (I) has recently been described by Cookson and Mann1, who showed that the phenyl-hydrazone of this ketone, when boiled with alcoholic hydrogen chloride, underwent indolization and de-hydrogenation to give 1-phenyl-ψ-indolo(3' : 2' : 3 : 4)-quinoline. This yellow base gives colourless salts with acids, and further work has now confirmed the structures suggested by the above workers for the base and its salts.

Structure of Alginic Acid

ALGINIC acid, the industrial importance of which is increasing, constitutes a large proportion of the dry weight of certain seaweeds. It is noteworthy among polysaccharides in that it appears to be built up entirely of d-mannuronic acid residues, although its resistance to hydrolysis is so great that no quantitative transformation to d-mannuronic acid has been achieved1. The results we have recently obtained from a study of the action of methyl alcoholic hydrogen chloride on the polysaccharide show that high yields of d-mannuronic acid are obtainable from alginic acid.

Constitution of coumarinopyrones deriver from 7-hydroxy-coumarins

When umbelliferon condenses with malic acid two isomeric compounds are formed. The angular coumarino-7: 8-α-pyrone is the major product (95%) and its constitution is established from its preparation from umbelliferon-8-aldehyde by the Perkin's reaction. The second compound which should be the linear coumarino-7: 6-α-pyrone is formed in a very small yield only (5%). Under the same conditions 4-methylumbelliferon produces only one compound whose constitution as 4-methylcoumarino-7: 8-α-pyrone is arrived at from its independent synthesis from 4-methylumbelliferon-8-aldehyde. The constitution of this aldehyde is deduced not only from analogy but also from its reduction to 4: 8-dimethyl-7-hydroxycoumarin which has been prepared from 2-methylresorcinol and ethylacetoacetate. 4-Methylumbelliferon and ethylacetoacetate also give only one compound which is given the constitution 4: 4′-dimethylcoumarino-7: 8-α-pyrone. This compound has been found to be produced in good yield from resorcinol and ethylacetoacetate in the presence of alcoholic hydrogen chloride.

STUDIES ON LIGNIN AND RELATED COMPOUNDS: XXI. INSOLUBLE METHANOL LIGNIN

When spruce wood meal is extracted with anhydrous methyl alcoholic hydrogen chloride, about 30% of the lignin can be removed in soluble form. The insoluble lignin in the residual wood can be isolated as a fully methylated derivative by a prior complete methylation with dimethyl sulphate followed by hydrolysis with methyl alcoholic hydrogen chloride. The fully methylated insoluble methanol lignin is insoluble in organic solvents.Demethylation experiments followed by subsequent treatment with methylating and acetylating agents, alone or combined, have established a very close relation between the insoluble and the soluble form. The formation of the insoluble form from the native lignin is accompanied by loss of one hydroxyl group as indicated in the two formulas: soluble methanol lignin, C42H32O6(OCH3)6(OH)4, and insoluble methanol lignin (fully methylated), C42H32O6OCH3)9. The new evidence obtained indicates that of the five methoxyl groups present in the original native lignin, at least three are phenolic or enolic in character.

STUDIES ON LIGNIN AND RELATED COMPOUNDS: XVIII. LIGNIN SULPHONIC ACID—A PRELIMINARY INVESTIGATION ON ITS ISOLATION AND STRUCTURE

Several methods for the isolation of a pure lignin sulphonic acid have been studied. A satisfactory method, employing dialysis in the presence of an excess of sulphurous acid, followed by precipitation with quinoline and subsequent decomposition with sodium hydroxide, has been developed. The free acid is unstable, becoming insoluble on standing or when heated above 50 °C., particularly in the presence of mineral acids. Treatment with pyridine and acetic anhydride also yields an insoluble material. The salts of lignin sulphonic acid are stable towards heat and methylation reagents at room temperature, and therefore are more suitable for investigations on its structure. The methyl and benzyl esters have been prepared but in low yield only,—a result, presumably, of the well-known abnormally reactive character of esters of sulphonic acids. The permutoid character of its salts makes it difficult to prepare the neutral salts in a pure state. The pure sodium salt, however, was prepared by the use of electrometric titration to indicate the neutral point. The salts (Na, Tl, Ag) are soluble in alcohol containing a trace of water, but are precipitated by inorganic salts such as sodium or thallium acetate. The acid on methylation with methyl alcohol-hydrogen chloride yields a product which is soluble in organic solvents and in water, and which contains an additional methoxyl group. Methylation of the free acid with diazomethane gives a water-insoluble product (OCH3, 18.4%), while a similar methylation of the sodium salt yields a water-soluble product (OCH3, 19.4%, ash-free basis). The acid therefore contains at least one free phenolic or enolic hydroxyl group. It can be methylated at room temperature with dimethyl sulphate and sodium hydroxide (5% excess) to a maximum methoxyl content of 27.7% (ash-free basis), no structural change, other than the loss of some loosely bound sulphurous acid, apparently taking place. The analytical data provide additional support for the empirical formula for lignin proposed by Brauns and Hibbert.

TWO-COMPONENT SYSTEMS INVOLVING COMPOUND FORMATION

The two-component systems ethyl ether-hydrogen chloride and methyl alcohol-hydrogen chloride have been examined in the gaseous state, and from the pressure-volume-temperature relationship of the binary mixture evidence is adduced of the existence of compound formation. The heats of reaction appear to be constant in the temperature range investigated, and are 5400 calories for the ether hydrochloride, and 9200 calories for the alcohol hydrochloride. The pressure-volume-temperature data for ethyl ether, methyl alcohol and ethyl alcohol are given over the temperature range 50–200 °C., and over the pressure range below one atmosphere.

The behaviour of electrolytes in mixed solvents. Part. III.–The molecular refractivities and partial molar volumes of lithium chloride in water-ethyl alcohol solutions

It is well known that the molecular refractivity of most salts, as calculated by the Lorentz-Lorenz formula, is nearly independent of the concentration in moderately dilute aqueous solutions. Walden determined the refractivities of tetra-ethyl-ammonium iodide and other similar salts in a variety of solvents and found that, while the molecular refractivity was approximately independent of the concentration in each solvent, it varied from one solvent to another, the greatest variation from the value in water, amounting to about 2 per cent., being obtained in nitro-methane, Schreiner has recently determined the molecular refractivity of hydrogen chloride and lithium chloride in methyl and ethyl alcohols, and found that in the case of lithium chloride the value is independent of the concentration up to a concentration of about 3 M. His values for R 18 D for lithium chloride are: 8.73 in water, 8.55 in methyl alcohol and 8.38 in ethyl alcohol. The difference between the values in water and ethyl alcohol appeared to make it just possible to determine the variation of the refractivity with the composition of the solvent in mixtures of water and the alcohol. It is possible that a solvent might he found, miscible in water in all proportions, in which the value of It is further removed from that in water. Such a substance would he more suitable than alcohol for the investigation of this effect, but in order to correlate the results with the measurements recorded in Part II of the activities of alcohol and water in water-alcohol-lithium chloride solutions, it seemed desirable to investigate this case in the first instance. The variation of the refractivity of a salt with the composition of a mixed solvent may be expected to give some indication of the composition of the solvent in the immediate vicinity of the ions. For the refractivity of a salt is determined by (1) the polarisability of the ions themselves and (2) the change in the polarisability of the solvent produced by their presence. The molecular refractivity of a salt in a solution containing m grams of a salt in w grams of the solvent is taken as R = M/ m ( n 2 -1/ n 2 + 2 . w + m / d - n 2 0 -1/ n 2 0 + 2 . w / d 0 (1) where n , and d and n 0 , d 0 are the refractive index and density of the solution and of the solvent, respectively, and M the molecular weight of the salt.

XVII.The transport numbers of hydrogen chloride in ethyl alcohol

Summary Measurements have been made of the E.M.F.s of cells containing hydrogen chloride in ethyl alcohol, with and without liqllid junctions, and the most probable value for the transport number of the hydrogen ion at infinite dilution has been found to be 0·71±0·01.

CXVIII.The activity coefficients of hydrogen chloride in ethyl alcohol

CXVIII.<i>The activity coefficients of hydrogen chloride in ethyl alcohol</i>

LXXIX.The activity coefficients and transport number of solutions of hydrogen chloride in methyl alcohol

LXXIX.<i>The activity coefficients and transport number of solutions of hydrogen chloride in methyl alcohol</i>