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The Art of Perfumery Part 36

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In the pure condition the fats are mostly odorless and tasteless; when they possess an odor, it arises mostly from the presence of small quant.i.ties of volatile fatty acids, as butyric acid, capric acid, &c.; which becomes free through the decomposition of their oxide of glycyl combinations. This ensues by the presence of water and air through a kind of fermentation, and as it appears, by the presence of a nitrogenous substance. The fats are insoluble in water, and, with the exception of castor oil, are taken up by cold alcohol in very small quant.i.ties, however, more in proportion as they contain oleine. In boiling alcohol they are dissolved, but are, for the most part, again separated on cooling, particularly those rich in stearine. All fats are taken up by ether but those containing stearine in the smallest quant.i.ty.

Their specific gravities fluctuate between .91 and .93. When heated, fats a.s.sume a dark color, and boil between 482 and 572 Fahr., but the boiling-point continuously rises, while an uninterrupted decomposition proceeds. From oxide of glycyl ensues acroline; oleic acid affords a fatty acid, and among the decomposition products of fats containing stearine and margarine are found pure margaric acid, and, at the same time, some hydro-carbons are formed. When exposed quickly to a high temperature, fats are completely decomposed. (Oil gas.) In closed vessels the pure fats undergo no change, but, placed in thin layers in the air, the fats containing oleine and oline rapidly absorb oxygen under the strong evolution of heat, which will inflame porous bodies, as cotton wool. The purer the fats are the more quickly their oxidation results. When the fats contain slimy materials, these latter can be destroyed with a little oxide of lead and water. (Preparation for the application of varnishes.) The action of nitric acid, nitrous acid, chlorine, sulphuric acid, &c., on fats is the same as that of these bodies on the fatty acids. The fatty oils dissolve sulphur in the heat which is again partly precipitated on cooling. When sulphur is heated with fatty oils, namely, with linseed oil, it dissolves by degrees, and a thick dark ma.s.s is formed, the so-called balsam of sulphur. By raising the heat, a violent reaction ensues under the evolution of sulphuretted hydrogen, and, at the same time, an oil resembling oil of garlic volatilizes. This oil begins to boil at 160 Fahr., but its boiling-point rises continually.

PERFUMES AS PREVENTIVES OF MOULDINESS.

An interesting paper on this subject has been published by Dr.

Macculloch. We presume our readers are aware that mouldiness is occasioned by the growth of minute vegetables. Ink, paste, leather, and seeds, are the substances that most frequently suffer from it. The effect of cloves in preserving ink is well known; any of the essential oils answer equally well. Leather may be kept free from mould by the same substances. Thus Russian leather, which is perfumed with the tar of birch, never becomes mouldy; indeed it prevents it from occurring in other bodies. A few drops of any essential oil are sufficient also to keep books entirely free from it. For harness, oil of turpentine is recommended. Bookbinders, in general, employ alum for preserving their paste; but mould frequently forms on it. Shoemakers' resin is sometimes also used for the same purpose; but it is less effectual than oil of turpentine. The best preventives, however, are the essential oils, even in small quant.i.ty, as those of peppermint, anise, or ca.s.sia, by which paste may be kept almost any length of time; indeed, it has, in this way, been preserved for years. The paste recommended by Dr. Macculloch is made in the usual way, with flour, some brown sugar, and a little corrosive sublimate; the sugar keeping it flexible when dry, and the sublimate preventing it from fermenting, and from being attacked by insects. After it is made, a few drops of any of the essential oils are added. Paste made in this way dries when exposed to the air, and may be used merely by wetting it. If required to be kept always ready for use, it ought to be put into covered pots. Seeds may also be preserved by the essential oils; and this is of great consequence, when they are to be sent to a distance. Of course moisture must be excluded as much as possible, as the oils or ottos prevent only the bad effects of mould.

FUSEL OIL.

BY W. BASTICK.

This organic compound was first discovered by Scheele, as one of the distillation products of the wort obtained from the fermentation of potatoes. It has been subsequently examined by Pelletier, Dumas, Cahours, and others. It is generally now termed the hydrate of the oxide of amyl, from amyl being supposed to be its base or radical, as cyanogen is regarded to be the radical of another series of compounds.

It pa.s.ses over towards the termination of the distillation process in a white turbid fluid, which consists of a watery and alcoholic solution of the fusel oil. The crude oil, consisting of about one-half of its weight of alcohol and water, may be purified, being shaken with water and redistilled, with the previous addition of chloride of calcium. When the temperature of the contents of retort reaches 296 Fahr., pure fusel oil distils over.

Fusel oil is a colorless oily fluid, which possesses at first not an unagreeable odor, but at last is very disgusting, producing oppression at the chest and exciting cough. It has a sharp hot taste, and burns with a white blue flame. It boils at 296 Fahr., and at temperature of -4 Fahr. it becomes solid, and forms crystals. Its specific gravity at 59 Fahr. is 0.8124, and its formula C_{10}H_{12}O_{2}. On paper it produces a greasy stain, which disappears by heat, and when exposed to the action of the air it acquires an acid reaction. Fusel oil is slightly soluble in water, to which it imparts its odor; and soluble in all proportions in alcohol, ether, volatile and fixed oils, and acetic acid. It dissolves phosphorus, sulphur, and iodine without any noticeable change, and also mixes with caustic soda and potash. It rapidly absorbs hydrochloric acid, with the disengagement of heat. When mixed with concentrated sulphuric acid, the mixture becomes of a violet-red color, and bisulphate of amyloxide is formed. Nitric acid and chlorine decompose it. By its distillation with anhydrous phosphoric acid, a fluid, oily combination of hydrogen and carbon results. By oxidation with bichromate of potash and sulphuric acid, fusel oil yields valerianic acid, which is used in medicine, and apple-oil, employed as a flavoring ingredient in confectionery.

ESSENCE OF PINE-APPLE.

BY W. BASTICK.

The above essence is, as already known, butyric ether more or less diluted with alcohol; to obtain which pure, on the large scale and economically, the following process is recommended:--

Dissolve 6 lbs. of sugar and half an ounce of tartaric acid, in 26 lbs.

of boiling water. Let the solution stand for several days; then add 8 ounces of putrid cheese broken up with 3 lbs. of skimmed and curdled sour milk and 3 lbs. of levigated chalk. The mixture should be kept and stirred daily in a warm place, at the temperature of about 92 Fahr., as long as gas is evolved, which is generally the case for five or six weeks.

The liquid thus obtained, is mixed with an equal volume of cold water, and 8 lbs. of crystallized carbonate of soda, previously dissolved in water, added. It is then filtered from the precipitated carbonate of lime; the filtrate is to be evaporated down to 10 lbs., when 5-1/2 lbs.

of sulphuric acid, previously diluted with an equal weight of water, are to be carefully added. The butyric acid, which separates on the surface of the liquid as a dark-colored oil, is to be removed, and the rest of the liquid distilled; the distillate is now neutralized with carbonate of soda, and the butyric acid separated as before, with sulphuric acid.

The whole of the crude acid is to be rectified with the addition of an ounce of sulphuric acid to every pound. The distillate is then saturated with fused chloride of calcium, and redistilled. The product will be about 28 ounces of pure butyric acid. To prepare the butyric acid or essence of pine-apple, from this acid proceed as follows:--Mix, by weight, three parts of butyric acid with six parts of alcohol, and two parts of sulphuric acid in a retort, and submit the whole, with a sufficient heat, to a gentle distillation, until the fluid which pa.s.ses over ceases to emit a fruity odor. By treating the distillate with chloride of calcium, and by its redistillation, the pure ether may be obtained.

The boiling-point of butyric ether is 238 Fahr. Its specific gravity, 0.904, and its formula,

C_{12}H_{12}O_{4}, or C_{4}H_{5}O + C_{8}H_{7}O_{3}.

Bensch's process, above described, for the production of butyric acid, affords a remarkable exemplification of the extraordinary transformations that organic bodies undergo in contact with ferment, or by catalytic action. When cane sugar is treated with tartaric acid, especially under the influence of heat, it is converted into grape sugar. This grape sugar, in the presence of decomposing nitrogenous substances, such as cheese, is transformed in the first instance into lactic acid, which combines with the lime of the chalk. The acid of the lactate of lime, thus produced, is by the further influence of the ferment changed into butyric acid. Hence, butyrate of lime is the final result of the catalytic action in the process we have here recommended.

PREPARATION OF CRUDE PELARGONATE OF ETHYL-OXIDE (ESSENCE OF QUINCE.)

BY DR. R. WAGNER.

It has been believed, until the most recent period, that the peel of quinces contains oenanthylate of ethyl-oxide. New researches, however, have led to the supposition that the odorous principle of quinces is derived from the ether of pelargonic acid. In my last research on the action of nitric acid on oil of rue, I found that besides the fatty acids, which Gerhardt had already discovered, pelargonic acid is formed.

This process may be advantageously employed for the preparation of crude pelargonate of ethyl-oxide, which, on account of its extremely agreeable odor, may be applied as a fruit essence equally with those prepared by Dobereiner, Hofmann, and Fehling. For the preparation of the liquid, which can be named the essence of quince, oil of rue is treated with double its quant.i.ty of very diluted nitric acid, and the mixture heated until it begins to boil. After some time two layers are to be observed in the liquid: the upper one is brownish, and the lower one consists of the products of the oxidation of oil of rue and the excess of nitric acid. The lower layer is freed from the greater part of its nitric acid by evaporation in a chloride of zinc bath. The white flocks frequently found in the acid liquid, which are probably fatty acids, are separated by filtration. The filtrate is mixed with spirit, and long digested in a gentle heat, by which a fluid is formed, which has the agreeable odor of quince in the highest degree, and may be purified by distillation. The spirituous solution of pelargonic ether may also be profitably prepared from oleic acid, according to Gottlieb's method.--_Journal fur Praktische Chemie._

PREPARATION OF RUM-ETHER.

Take of black oxide of manganese, of sulphuric acid, each twelve pounds; of alcohol, twenty-six pounds; of strong acetic acid, ten pounds. Mix, and distil twelve pints. The ether, as above prepared, is an article of commerce in Austria, being the body to which rum owes its peculiar flavor.--_Austrian Journal of Pharmacy._

ARTIFICIAL FRUIT ESSENCES.

BY FEHLING.

_Pine-apple Oil_ is a solution of one part of butyric ether, in eight or ten parts of alcohol. For the preparation of this ether, pure butyric acid must be first obtained by the fermentation of sugar, according to the method of Bensch. One pound of this acid is dissolved in one pound of strong alcohol, and mixed with from a quarter to half an ounce of sulphuric acid; the mixture is heated for some minutes, whereby the butyric ether separates as a light stratum. The whole is mixed with half its volume of water, and the upper stratum then removed; the heavy fluid is distilled, by which more butyric ether is obtained. The distillate and the removed oily liquid are shaken with a little water, the lighter portion of the liquid removed, which at last, by being shaken with water and a little soda, is freed from adhering acid.

For the preparation of the essence of pine-apple, one pound of this ether is dissolved in 8 or 10 pounds of alcohol. 20 or 25 drops of this solution is sufficient to give to one pound of sugar a strong taste of pine-apple, if a little citric or tartaric acid has been added.

_Pear-oil._--This is an alcoholic solution of acetate of amyloxide, and acetate of ethyloxide. For its preparation, one pound of glacial acetic acid is added to an equal weight of fusel-oil (which has been prepared by being washed with soda and water, and then distilled at a temperature between 254 and 284 Fahr.), and mixed with half a pound of sulphuric acid. The mixture is digested for some hours at a temperature of 254, by which means acetate of amyloxide separates, particularly on the addition of some water. The crude acetate of amyloxide obtained by separation, and by the distillation of the liquid to which the water has been added, is finally purified by being washed with soda and water.

Fifteen parts of acetate of amyloxide are dissolved with half a part of acetic ether in 100 or 120 parts of alcohol; this is the essence of pear, which, when employed to flavor sugar or syrup, to which a little citric or tartaric acid has been added, affords the flavor of bergamot pears, and a fruity, refreshing taste.

_Apple-oil_ is an alcoholic solution of valerianate of amyloxide. It is obtained impure, as a by product, when for the preparation of valerianic acid, fusel-oil is distilled with bichromate of potash and sulphuric acid. It is better prepared in the following manner:--For the preparation of valerianic acid, 1 part of fusel-oil is mixed gradually with 3 parts of sulphuric acid, and 2 parts of water added. A solution of 2-1/4 parts of bichromate of potash, with 4-1/2 parts of water, is heated in a tubulated retort, and into this fluid the former mixture is gradually poured, so that the ebullition is not too rapid. The distillate is saturated with carbonate of soda, and warmed, when a solution of 3 parts of crystallized carbonate of soda, 2 parts of strong sulphuric acid, diluted with an equal quant.i.ty of water, are added. The valerianic acid separates as an oily stratum.

One part, by weight, of pure fusel-oil is carefully mixed with an equal weight of sulphuric acid. The cold solution is added to 1-1/4 parts of the above valerianic acid; the mixture is warmed for some minutes (not too long or too much) in a water-bath, and then mixed with a little water, by which means the impure valerianate of amyloxide separates, which is washed with water and carbonate of soda. For use as an essence of apples, one part of this valerianate of amyloxide is dissolved in 6 or 8 parts of alcohol.

VOLATILE OIL OF GAULTHERIA PROc.u.mBENS.

BY W. BASTICK.

The chemical history of this oil is one of great importance and interest, affording, as it does, one of the examples where the progress of modern chemistry has succeeded in producing artificially a complex organic body, previously only known as the result of vital force.

This volatile oil is obtained from the winter-green, an American shrub of the heath family, by distillation. When this plant is distilled, at first an oil pa.s.ses over which consists of C_{10}H_{8}, but when the temperature reaches 464 Fahr., a pure oil distils into the receiver.

Therefore the essential oil of this plant, like many others, consists of two portions--one a hydro-carbon, and the other an oxygenated compound; this latter is the chief const.i.tuent of the oil, and that which is of so much chemical interest, from the fact that it has been artificially prepared.

It is termed, when thus prepared, the spiroylate of the oxide of methyl, and is obtained when two parts of wood spirit, one and a half parts of spiroylic acid, and one part of sulphuric acid are distilled together.

It is a colorless liquid, of an agreeable aromatic odor and taste; it dissolves slightly in water, but in all proportions in ether and alcohol; it boils between 411 and 435 Fahr., and has a specific gravity of 1.173. This compound expels carbonic acid from its combinations, and forms a series of salts, which contain one atom of base and one atom of spiroylate of the oxide of methyl. It behaves therefore as a conjugate acid. Its formula is C_{14}H_{5}O_{5} + C_{2}H_{3}O.

The spiroylic acid may be separated from the natural oil by treating it with a concentrated solution of caustic potash at a temperature of 113 Fahr., when wood spirit is formed and evaporates, and the solution contains the spiroylate of potash, from which, when decomposed with sulphuric acid, the spiroylic acid separates and subsides in the fluid.

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The Art of Perfumery Part 36 summary

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