It is a colourless liquid of characteristic fusel-like odour; sp. gr. 832 at 0° and '819 at 16°, and boils at 116°-117°; on oxidation it yields a ketone or propionic and acetic acids.

4. Isobutyl carbinol, or first primary isoamylic alcohol, is the longest known fermentation amylic alcohol. It occurs invariably in fusel oils, especially in that from potato spirit, and is separated from them by fractional distillation as an unpleasant, fusel-like-smelling liquid of sp. gr. 825 at 0°, boiling at 129°-130°. It is scarcely soluble in water, but mixes in every proportion with alcohol and ether. Its vapour, when inhaled, causes coughing and acts as a poison. When quickly fractioned from fusel oil it rotates the plane of polarisation to the left slightly, but loses its optical activity on heating for a long time, or quickly if distilled from caustic alkali, without apparently undergoing any chemical change. The property of optical activity, indeed, appears to belong not to the usual isoamlyic alcohol, but to a small quantity of an isomer (7?) mixed with it. By oxidising agents isoamylic alcohol is converted into isovaleric aldehyde and acid.

5. Methyl-isopropyl carbinol, secondary isoamylic alcohol, also termed amylene hydrate, is obtained from the isoamylene, prepared by heating 4 with zincic chloride, by uniting it with hydriodic acid, and then converting the secondary isoamylic iodide so obtained into the alcohol by means of moist argentic oxide. It boils at 106-108°, and its vapour, on heating to 200°, splits up into isoamylene and water:

It suffers the same decomposition when mixed with sulphuric acid, without the aid of heat. On oxidation it is probably first oxidised to isopropyl-methyl ketone, but that is very readily further oxidised to carbonic and acetic acids.

6. Ethyl-dimethyl carbinol, or tertiary amylic alcohol, is obtained by the action of zinc methyl on propionic chloride :

and decomposition of the product by water. It boils at about 100°, appears not to solidify at -10°, and on oxidation yields carbonic and acetic acids.

7. Second primary isoamylic alcohol is probably the active admixture in fermentation amylic alcohol (4), which, though of nearly the same boiling point (125-129°), still shows some difference from the 'active,' especially in the properties of the respective acid sulphates. 8. Trimethyl-carbin carbinol is not known at present.

Hexylic Alcohols, C6H140 or CH13.OH.

171. Of the (16) possible hexylic alcohols only some are known of still in part doubtful constitution.

1. Amyl carbinol, or normal primary hexylic alcohol:

CH3.CH2.CH2 CH2.CH2.CH2.OH,

is prepared mixed with butyl-methyl carbinol :

CH3.CH2.CH2.CH2.CH(OH).CH3,

by treatment of the mixed first chlor-substitution products of normal hexane with potassic acetate, and saponification of the resulting acetates. The mixture of alcohols so formed, boiling at 149°-152°, yields on oxidation caproic acid, CH3.CH2.CH2.CH2.CH2.CO.OH, and methyl-butyl ketone, CH3.CH,.CH2.CH.CO.CH3.

In the pure state it is obtained from the ethereal oil of Heracleum giganteum, which consists of hexylic butyrate and octylic acetate; by treatment with alcoholic potassic hydrate the alcohols are liberated, and are then separated by fractional distillation; it boils at 157-158°, has sp. gr. ·819 at 23°, and gives normal caproic acid on

oxidation.

2. Methyl-butyl carbinol, or first normal secondary hexylic alcohol, CH3CH2CH2.CH2CH(OH).CH,, is prepared from its iodide (obtained by distilling mannite with hydriodic acid):

CH3.CH2.CH2.CH2.CHI.CH3,

by decomposition with moist argentic oxide, as a colourless liquid insoluble in water, boiling at 137° and of sp. gr. 8327 at 0°. On oxidation it gives, as already mentioned, methyl-butyl ketone.

3. Ethyl-propyl carbinol, or second normal secondary hexylic alcohol, CH3CH2CH2.CH(OH).CH.CH3, results from the decomposition of bichlor ether with zinc ethyl :

CH.CH,CH3 + 2HI = H‚ ̧O + CH.CH„.CH ̧ + C2H ̧I

O.C2Hs

and decomposition of this latter by moist argentic oxide. 4. Dimethyl-propyl carbinol :

CH2>C(OH)—CH,—CH,—CH2,

is prepared from butyric chloride and zinc methyl; it boils at 115° and yields acetic and propionic acid on oxidation.

K

results from the action of isobutyric chloride (CI.CO.CH CH2

on zinc methyl. It boils at 1120-115°, and solidifies at -40° to a crystalline mass.

6. Diethyl-methyl carbinol:

CH3.CH2C(OH).CH3,
CH3.CH2

is prepared in similar manner from acetic chloride and zinc ethyl. It boils at 120°, and is completely converted into acetic acid by oxidation.

7. Fermentation hexylic alcohol, or caproylic alcohol, is separated from the fusel oil of the marc of grapes by fractional distillation. It is a light unpleasant-smelling_oil, boiling at 148°-150°, and yielding caproic acid on oxidation. Its constitution has not yet been deter

mined.

CH3

CH3
It boils at 120°,

8. Methyl-trimethyl-carbin carbinol, CH3.CH.(OH).C-CH3, is prepared by action of nascent hydrogen on pinacoline. has sp. gr. 834, and at low temperatures solidifies to crystals, melting at 14°; on oxidation it first yields the ketone CH3.CO.C(CH3)3, and finally carbonic and trimethacetic acid.

Heptylic Alcohols, C7H160 or C2H15.OH.

172. A primary heptylic alcohol of unknown constitution, œnanthylic alcohol, is contained in the fusel oil of wine. It boils at 165°, and on oxidation gives œnanthic acid, C-H1402. By the distillation of castor oil with a fixed alkali a primary ananthylic alcohol is formed, which appears to be the normal

CH3.CH2.CH2.CH2.CH2.CH2.CH2.OH,

as it yields the same cnanthic acid on oxidation as the normal primary alcohol from normal heptane. This latter alcohol boils at 170°-172°. At the same time that its chloride is formed from normal heptane, a secondary chloride is also formed, from which a normal secondary heptylic alcohol or methyl-amyl carbinol :

CH3.CH2.CH2.CH2.CH2.CH(OH).CH3,

is obtained as a liquid boiling at 160°-162°.

Dipropyl carbinol, CH3.CH2.CH2.CH(OH).CH2.CH2.CH3, is obtained by the action of nascent hydrogen on dipropyl ketone. It boils at 149° and has sp. gr. 814 at 25°.

Isohexyl carbinol,

CH3

3>CH.CH2.CH2.CH2.CH2.OH, is obtained, together with the next-mentioned body, from the products of the chlorination of ethyl isoamyl, which are converted into acetates and then saponified. It boils at 163°-165°, and yields isocnanthic acid on oxidation.

CH

Isoamyl-methyl carbinol, CHCH.CH.CH.CH(OH).CH2, is prepared by the reduction of methyl-isoamyl ketone by sodium amalgam. It boils at 148°-150°, possesses a fusel-like odour, and has sp. gr. 8185 at 17°.

Isobutyl-dimethyl carbinol, CH3>CH.CH.C(OH)CH3;

is pro

duced by action of zinc methyl on valeryl chloride. It is a colourless liquid, of camphoraceous taste and smell, boils at 129°-131°, and yields acetic and isobutyric acids on oxidation.

Diisopropyl carbinol, CH3CH.CH(OH).CHCH, prepared by

CH

action of nascent hydrogen on diisopropyl ketone, is a liquid of pleasant ethereal odour, boiling at 131°-132° and of sp. gr. 8593 at 0°.

CH3CH2

Propyl-ethyl-methyl carbinol, CH3.CH2.CH, C.OH, prepared by

CH3

the successive actions of zincic methide and ethide and water on normal butyric chloride, boils at 135-138°.

CH3.CH2

Triethyl carbinol, CH3CH2C(OH).CH2.CH 3, is obtained by the action of propionic chloride, (CH3.CH2.CO.Cl), upon zinc ethyl. It boils at 140°-142°, and is viscid at

20°.

Isopropyl-ethyl-methyl carbinol, CH3>CH.C(OH)<CH,CH,
CH3

obtained by the successive actions of zincic ethide and methide and of water on isobutyric chloride. It boils at 124°-127°.

CH3
CH

CH3 is ob

Trimethyl-carbin-dimethyl carbinol, CH3C.C(OH)CH3

tained by the successive actions of zincic methide and water on trimethacetic chloride. It forms long needles, melting at 17°, and boils at 123°-132°.

Octylic Alcohols, C ̧H180 or CH17.OH.

173. The ethereal oil of Heracleum spondylium consists mainly of the acetate (boiling at 206°-208°) of primary normal octylic alcohol, CH3CH2CH2.CH2.CH2.CH2.CH2.CH2.OH. The same body is contained, along with hexylic butyrate, in the oil of Heracleum giganteum. The alcohol obtained by saponification with potash boils at 1900-1920, has sp. gr. 83 at 16° and a peculiar penetrating odour.

Methyl-hexyl carbinol, or a normal secondary octylic alcohol:

CH3.CH2.CH2.CH2.CH2.CH2.CH(OH).CH3,

is obtained from the distillation of castor oil with potassic hydrate, and from the first chlor-substitution products of normal octane. It is an oily liquid, boiling at 181°, and yields by oxidation first methylhexyl ketone and later acetic and caproic acids.

Ethyl-isoamyl carbinol, CH3.CH2.CH(OH).CH2.CH2.CH<

boils at 182°-186°.

CH

CH3'

Diethyl-propyl carbinol :

CH2CH3

CH3.CH2.CH2.C(OH)CH2CH3'

is a tertiary alcohol prepared by the action of zinc ethyl upon butyric chloride. It is not yet known quite pure, but boils between 145° and 155°.

Nonylic Alcohol, C,H20O or C,H19.OH.

174. At present there is only a single body of this formula known; it is prepared from petroleum nonane, boils at about 200°, and is probably methyl-heptyl carbinol.

Decatylic Alcohol, C10H22O = C10H21.OH.

175. The only alcohol of this formula known with any certainty is that obtained by action of zinc ethyl upon bromacetic bromide, and has probably the constitutional formula:

Its boiling point is very low-namely, 155°-157°.

176. Alcohols of the formulæ

C11H24O, C12H26O, C13H28O, C14H30O, and C15H32O

have not yet been prepared, but there are some higher, naturally occurring members of the series known; about whose constitution nothing is ascertained.

177. Cetylic alcohol, or ethal, C16H340 C16H33.OH, is prepared from spermaceti (cetylic palmitate) by long boiling with alcoholic potassic hydrate:

C16H33.O.C16H310 + KOH = C16H33OH + KO.C16H31.O.

After the action is finished, the cetylic alcohol is precipitated by addition of water (in which potassic palmitate is soluble) and purified by crystallisation from alcohol.

It

Ethal so obtained crystallises in leaves, fuses at 49°-50°, and by careful heating, best in a stream of gas, can be slowly volatilised. is completely insoluble in water.

178. Cerylic alcohol, C27H560 = C27H55.OH, forms as its cerotate the chief constituent of Chinese wax, from which it can be prepared in manner similar to that of cetylic alcohol from spermaceti. It is more usual to fuse the Chinese wax with potassic hydrate containing a little water:

C27H55.O.C27H530+ KOH = C27H55.OH + C27H51O.OK,

and to then extract the potassic cerotate from the cooled mass with water. The undissolved cerylic alcohol is then purified by crystallisation from ether. It fuses at 79° and solidifies on cooling to a waxlike mass.