intense blue solution, while the tertiary compound does not act with nitrous acid. The reactions outlined above may be thus represented:—
R·CH2OH→ R·CH2I→ R·CH2·NO2→ R·C⪕NOH
NO2
Primary alcohol.Nitrolic acid.
R
R1
CH·OH →R
R1CH·I→R
R1CH·NO2 →R
R1C 
NO2
NO
Secondary alcohol.Pseudo nitrol.
(R1R2R3)C·OH → (R1R2R3)C·I → (R1R2R3)C·NO2
Tertiary alcohol.
By heating to the boiling point of naphthalene (218°) tertiary alcohols are decomposed, while heating to the boiling point of anthracene (360°) suffices to decompose secondary alcohols, the primary remaining unaffected. These changes can be followed out by determinations of the vapour density, and so provide a method for characterizing alcohols (see Compt. Rend. 1904, 138, p. 984).
Alcohols may be readily prepared from the corresponding alkyl haloid by the action of moist silver oxide (which behaves as silver hydroxide): by the saponification of their esters; or by the reduction of polyhydric alcohols with hydriodic acid, and the subsequent conversion of the resulting alkyl iodide into the alcohol by moist silver oxide. Preparation. Primary alcohols are obtained by decomposing their sulphuric acid esters (from sulphuric acid and the olefines) with boiling water; by the action of nitrous acid on primary amines; or by the reduction of aldehydes, acid chlorides or acid anhydrides. Secondary alcohols result from the reduction of ketones; and from the reaction of zinc alkyls on aldehydes or formic acid esters.
CH3CHO → CH3·CHC2H5
OZnC2H5 → CH3·CHC2H5
OH
Acetaldehyde.Methyl ethyl carbinol.
| HC⪕ | O | → HC⪪ | OZnCH3 | → HC⪪ | OZnCH3 | → HC⪪ | OH |
| OC2H5 | CH3 | CH3 | CH3 | ||||
| OC2H5 | CH3 | CH3 |
Formic ester.Isopropyl alcohol.
Tertiary alcohols may be synthesized by a method devised by A. Butlerow in 1864, who thus discovered the tertiary alcohols. By reacting with a zinc alkyl (methyl or ethyl) on an acid chloride, an addition compound is first formed, which decomposes with water to give a ketone. If, however, a second molecule of a zinc alkyl be allowed to react, a compound is formed which gives a tertiary alcohol when decomposed with water.
| R·C⪕ | O | → R·C⪪ | CH3 | → R·C⪪ | CH3 | → R·C⪪ | CH3 |
| Cl | OZnCH3 | OZnCH3 | OH | ||||
| Cl | CH3 | CH3 |
Acid chloride.Tertiary alcohol.
It is interesting to note that, whereas zinc methyl and ethyl give tertiary alcohols, zinc propyl only gives secondary alcohols. During recent years (1900 onwards) many brilliant syntheses have been effected by the aid of magnesium-alkyl-haloids.
The alcohols are neutral in reaction, and the lower members possess the property of entering into combination with salts, in which the alcohol plays the rôle of water of crystallization. Sodium or potassium dissolves in them with the formation of alcoholates, the hydrogen of the hydroxyl group being replaced by the metal. With strongProperties. acids water is split off and esters are formed. The haloid esters of the paraffin alcohols formed by heating the alcohols with the halogen acids are the monohaloid derivatives of the paraffins, and are more conveniently prepared by the action of the phosphorous haloid on the alcohol. Energetic dehydration gives the olefine hydrocarbons, but under certain conditions ethers (see Ether) are obtained.
The physical properties of the alcohols exhibit a gradation with the increase of molecular weight. The lower members are colourless mobile liquids, readily soluble in water and exhibiting a characteristic odour and taste. The solubility decreases as the carbon content rises. The normal alcohols containing 1 to 16 carbon atoms are liquids at the ordinary temperatures; the higher members are crystalline, odourless and tasteless solids, closely resembling the fats in appearance. The boiling points of the normal alcohols increase regularly about 10° for each CH2 increment; this is characteristic of all homologous series of organic compounds. Of the primary, secondary and tertiary alcohols having the same empirical formula, the primary have the highest, and the tertiary the lowest boiling point; this is in accordance with the fairly general rule that a gain in symmetry is attended by a fall in the boiling point.
The following monatomic alcohols receive special treatment under their own headings:—Alcohol (Ethyl), Allyl Alcohol, Amyl Alcohols, Benzyl Alcohol, Butyl Alcohols, Methyl Alcohol, and Propyl Alcohols.
ALCOTT, AMOS BRONSON (1799–1888), American educationalist and writer, born on Spindle Hill, in the town of Wolcott, New Haven county, Connecticut, on the 29th of November 1799. His father, Joseph Chatfield Alcox, was a farmer and mechanic whose ancestors, then bearing the name of Alcocke, had settled in eastern Massachusetts in colonial days. The son adopted the spelling “Alcott” in his early youth. Self-educated and early thrown upon his own resources, he began in 1814 to earn his living by working in a clock factory in Plymouth, Conn., and for many years after 1815 he peddled books and merchandise, chiefly in the southern states. He began teaching in Bristol, Conn., in 1823, and subsequently conducted schools in Cheshire, Conn., in 1825–1827, again in Bristol in 1827–1828, in Boston in 1828–1830, in Germantown, now part of Philadelphia, in 1831–1833, and in Philadelphia in 1833. In 1830 he had married Abby May, the sister of Samuel J. May (1797–1871), the reformer and abolitionist. In 1834 he opened in Boston a school which became famous because of his original methods; his plan being to develop self-instruction on the basis of self-analysis, with an ever-present desire on his own part to stimulate the child’s personality. The feature of his school which attracted most attention, perhaps, was his scheme for the teacher’s receiving punishment, in certain circumstances, at the hands of an offending pupil, whereby the sense of shame might be quickened in the mind of the errant child. The school was denounced in the press, was not pecuniarily successful, and in 1839 was given up, although Alcott had won the affection of his pupils, and his educational experiments had challenged the attention of students of pedagogy. The school is perhaps best described in Miss E. P. Peabody’s A Record of Mr Alcott’s School (1835). In 1840 Alcott removed to Concord, Massachusetts. After a visit to England, in 1842, he started with two English associates, Charles Lane and Henry C. Wright, at “Fruitlands,” in the town of Harvard, Massachusetts, a communistic experiment at farm-living and nature-meditation as tending to develop the best powers of body and soul. This speedily came to naught, and Alcott returned (1844) to his home near that of Emerson in Concord, removing to Boston four years, later, and again living in Concord after 1857. He spoke, as opportunity offered, before the “lyceums” then common in various parts of the United States, or addressed groups of hearers as they invited him. These “conversations,” as he called them, were more or less informal talks on a great range of topics, spiritual, aesthetic and practical, in which he emphasized the ideas of the school of American Transcendentalists led by Emerson, who was always his supporter and discreet admirer. He dwelt upon the illumination of the mind and soul by direct communion with the Creative Spirit; upon the spiritual and poetic monitions of external nature; and upon the benefit to man of a serene mood and a simple way of life. As regards the trend and results of Alcott’s philosophic teaching, it must be said that, like Emerson, he was sometimes inconsistent, hazy or abrupt. But though he formulated no system of philosophy, and seemed to show the influence now of Plato, now of Kant, or of German thought as filtered through the brain of Coleridge, he was, like his American master, associate and friend, steadily optimistic, idealistic, individualistic. The teachings of William Ellery Channing a little before, as to the sacred inviolability of the human conscience—anticipating the later conclusions of Martineau—really lay at the basis of the work of most of the Concord transcendentalists and contributors to The Dial, of whom Alcott was one. In his last years, living in a serene and
