Alcohol of sulphur

The word kohl referred to above as denoting stibnite in a finely powdered state came gradually to mean any fine powder. Thus reduced iron was known as alcohol of Mars, and as late as 1812 Davy referred to flowers of sulphur as alcohol of sulphur. In the theatrical profession pigments used for darkening the eyes are still known as kohl. Francis Bacon in his Sylva Sylvarum or a Naturall Historic , 1626, p. 739, says The Turkes have a black powder made of a mineral called alcohole. ... 

Marcet and Berzelius (working in Marcet s private laboratory) showed that alcohol of sulphur is a compound of sulphur and carbon (carbon disulphide), a result which was anticipated in publication by Vauquelin. Marcet froze mercury by the rapid evaporation of ether under an air pump later he used carbon disulphide. He described an alcohol-oxygen blowpipe flame the oxy-hydrogen blowpipe had been described by Hare. Marcet s paper on the analysis of sea and lake waters contains a great number of results. In a later paper he showed that sea water does not contain mercury, as Rouelle had stated (see p. 77) he noticed the crystallisation from the residual brine of the double salts carnallite (KMgCls, 6H2O) and schonite (K2Mg(S04)2, fiHjO), but did not determine the quantitative compositions. 

CH3COOH + HOC2H5 - CH3GOOC2H3 + H2O If, however, concentrated sulphuric acid is present, the water is absorbed, the back reaction prevented, and a high yield of ethyl acetate is obtained. In practice the reaction is not so simple. It was formerly supposed that, since the sulphuric acid is usually added to the alcohol, ethyl hydrogen sulphate and water are formed, the latter being absorbed by the excess of sulphuric acid, A mixture of ethanol and acetic acid is then added to the ethyl hydrogen sulphate,... 

In the following experiment, salicylic acid is reduced to o-hydroxybenzyl alcohol (or saligenin), which being crystalline is readily isolated the excess of hydride is destroyed by the addition of undried ether, and the aluminium hydroxide then brought into solution by the addition of sulphuric acid. 

I. Action of sulphuric add. To 0 5 ml. of the alcohol, add 0 5 ml. of cone. H2SO4 and shake the mixture. Heat is evolved and a white gelatinous polymer gradually separates. The reaction is hastened by warming and the product darkens. 

By treatment of the alcohol with a mixture of constant boiling point hydrobromic acid and concentrated sulphuric acid the presence of sulphuric acid results, as a rule, in more rapid reaction and improved 3delds. A typical example is ... 

Diethyl ether may be prepared from ethyl alcohol by the sulphuric acid process. A mixture of alcohol and sulphuric acid in equimolecular proportions is heated to about 140° and alcohol is run in at the rate at which the ether produced distils from the reaction mixture. Ethyl hydrogen sulphate (or ethyl sulphuric acid) is first formed and this yields ether either by reacting directly with a molecule of alcohol or by the formation and alcoholysis of diethyl sulphate (I) ... 

The above simple process cannot be applied to the preparation of the homo-logues a higher temperature is requir (di-n-amyl ether, for example, boils at 169°) and, under these conditions, alkene formation predominates, leading ultimately to carbonisation and the production of sulphur dioxide. If, however, the water is largely removed by means of a special device (see Fig. Ill, 57,1) as soon as it is formed, good 300 of ethers may be obtained from primary alcohols, for example ... 

It is marketed as a 35-40 per cent, solution in water (formalin). The rpactions of formaldehyde are partly typical of aldehydes and partly peculiar to itself. By evaporating an aqueous solution paraformaldehyde or paraform (CHjO), an amorphous white solid is produced it is insoluble in most solvents. When formaldehyde is distilled from a 60 per cent, solution containing 2 per cent, of sulphuric acid, it pol5unerises to a crystalline trimeride, trioxane, which can be extracted with methylene chloride this is crystalline (m.p. 62°, b.p. 115°), readily soluble in water, alcohol and ether, and devoid of aldehydic properties ... 

The oxidation with excess of dichromate and dilute sulphuric acid is not always satisfactory for alcohols higher than n propyl because of the attendant production of appreciable amounts of esters indeed by using a fairly high concentration of sulphuric add, good yields of esters are obtained since esterification takes place at once, even in the cold, as long as an excess of alcohol is present, for example ... 

In some instances the use of sulphuric acid leads to unsatisfactory results. Thus with formic acid carbon monoxide would be evolved. Esters of formic acid are most simply prepared from the alcohol and excess of formic acid, for example ... 

Esterification with cycloaliphatic alcohols is comparatively easy when the alcohol is saturated with hydrogen chloride and treated with excess of the acid, but a very impure ester results from the use of sulphuric acid as a catalyst, for example ... 

CHjClCOONa + KCN —> CHj(CN)COONa + KCl Upon warming the crude sodium cyanoacetate with ethyl alcohol and sulphuric acid, ethyl malonate is produced. Two mechanisms of the reaction have been proposed —... 

Esters of sulphuric acid. These compounds are generally water insoluble liquids and are saponified by boiling with water or dilute alkali to the corresponding alcohols and sulphuric acid ... 

In a typical process 140 parts of fully hydrolysed poly(vinyl alcohol) are suspended in 800 parts of ethanol 80 parts of butyraldehyde and 8 parts of sulphuric acid are added and the reaction is carried out at about 80 C for 5-6 hours. 

Fit up the apparatus as shown in Fig. 43. The distilling -flask should have a capacity of not less than i litre, and is attached to a long condenser. An adapter is fixed to the end"of the condenser, dipping into a conical flask (250 c.c.), which serves as receiver. The alcohol and sulphuric acid are mixed in the distilling flask and cooled to the ordinary tempeiatuie under the tap. The potassium biomide, coarsely pou dered, is then added. The flask, which is closed with a cork, is fixed to the condenser and heated on the sand-bath. A sufficient quantity of water is poured into the receiver to close the end of the adapter. After a short tune the liquid in the flask begins to boil and froth up, and the ethyl bromide, in the form of heavy... 

Anisole.—The prepaiation of anisole fiom phenol is analogous to Williamson s synthesis of the ethers (see p. 236), luit the etheis of phenol cannot be obtained by the action of tire alcohol on the phenol in presence of sulphuric acid. This reaction c.an, howet er, be effected In the case of the naphthdls (see p 316). 

The naphthols differ from the phenols of the henzene senes in foiming ethers after the manner of aliphatic alcohols, viz, by the action of sulphuric acid on a mixture of the naphthol and the alcohol, which the other phenols do not,... 

The identification of camphene is best carried out by its conversion into isobomeol under the influence of acetic acid in the presence of sulphuric acid. In order to effect this conversion, 100 grams of the fraction containing the terpene in substantial quantity are mixed with 250 grains of glacial acetic acid and 10 grams of 50 per cent, sulphuric acid. Tne mixture is heated for two to three hours on a water-bath to a temperature of 50° to 60°. At first the liquid separates into two layers, bat soon becomes homogeneous and takes on a pale red colour. Excess of water is added, and the oil which is precipitated, and which contains the isobomeol in the form of its acetate, is well washed with water repeatedly. It is then saponified by heating with alcoholic potash solution on a water-bath. The liquid is then evaporated and extracted with water, and the residue recrystallised from petroleum ether. 

The best method for producing it artificially is to condense salicylic acid and methyl alcohol by means of sulphuric acid. It is a colourless oil, optically inactive, and possessing an intense wintergreen odour. It has the following characters —... 

Amyl Acetate.—This is, with the exception of amyl formate, which is not of practical importance, the simplest possible ester of amyl alcohol, and has the formula CHj. COO. CsHjj. It is a fruity oil, with a strong odour resembling that of the pear, and is known as art ficial oil of pear. It is prepared on a very large scale by, for example, treating 100 parts of dry sodium acetate, 100 parts of amyl alcohol, and 130 parts of sulphuric acid for twelve hours at ordinary temperature, and then distilling off the ester. It has a specific gravity 0-876, and boils at 138°. The alcohol in this ester is not normal amyl alcohol, but isoamyl alcohol. 

Linalyl Propionate.—This ester is also produced by condensing the free alcohol and the free acid by means of sulphuric acid. It has a somewhat fruity odour recalling that of bergamot, and is especially suitable for perfumes of the lily of the valley type. It is a colourless oil, boiling at 115° at 10 mm. pressure. 

Linalyl Butyrate.—The butyric ester of linalol has the formula, CiflHjjOOC, CH2. CHjCHj. It resembles geranyl butyrate in odour, but is somewhat heavier. It is most useful for imparting fruity odours to flower perfumes. It is prepared by condensing the alcohol and the acid by means of sulphuric acid. 

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