definition
Any of a series of univalent radicals of the general formula CnH2n+1 derived from aliphatic hydrocarbons.
If alkyl or aryl-ortho-diamines be used azonium bases are obtained.
They add on alkyl iodides readily, forming alkyl azonium salts.
The hydrogen of the hydroxyl group in phenol can be replaced by metals, by alkyl groups and by acid radicals.
The alkyl derivatives may be obtained by heating phenol with one molecular proportion of a caustic alkali and of an alkyl iodide.
Alkyl compounds of germanium such as germanium tetra-ethyl, Ge(C2H5)4, a liquid boiling at C., have been obtained.
It is a most important synthetic reagent; with sodium or sodium ethylate it forms sodio-malonic ester, which reacts readily with alkyl halides, forming alkyl malonic esters, which are again capable of forming sodium derivatives, that by further treatment with alkyl halides yield the di-alkyl malonic esters.
We may also notice that thio-ethers combine with alkyl iodides to form sulphide or sulphonium compounds, R3; SI.
In fact, the analogy between the alkyl groups and metallic elements forms a convenient basis from which to consider many derivatives.
On the chromophoreauxochrome theory (the nitro group being the chromophore, and the hydroxyl the auxochrome) it is necessary in order to explain the high colour of the metallic salts and the colourless alkyl and aryl derivatives to assume that the auxochromic action of the hydroxyl group is only brought strongly into evidence by salt formation.
The measure of the loss of symmetry associated with the introduction of alkyl groups depends upon the relative magnitudes of the substituent group and the rest of the molecule; and the larger the molecule, the less would be the morphotropic effect of any particular substituent.
Other substituent groups exercise morphotropic effects similar to those exhibited by the alkyl radicles; investigations have been made on halogen-, hydroxy-, and nitro-derivatives of benzene and substituted benzenes.
The N-derivatives are prepared by the action of alkyl halides and acid chlorides on potassium pyrrol.
The thiazoles are somewhat basic in character, and combine with the alkyl iodides to form thiazolium iodides.
These salts are like those of tin; and the resemblance to this metal is clearly enhanced by the study of the alkyl compounds.
Grignard (Comptes Rendus, 1900 et seq.) showed that aldehydes combine with magnesium alkyl iodides (in absolute ether solution) to form addition products, which are decomposed by water with the formation of secondary alcohols, thus from acetaldehyde and magnesium methyl iodide, isopropyl alcohol is obtained.
The nitrate of this base (known as nitron) is so insoluble that nitrates may be gravimetrically estimated with its help. These bases combine with the alkyl iodides to yield quaternary ammonium salts.
They combine readily with the alkyl iodides to form alkyl acridinium iodides, which are readily transformed by the action of alkaline potassium ferricyanide to N-alkyl acridones.
The organic derivatives of silicon resemble the corresponding carbon compounds except in so far that the silicon atom is not capable of combining with itself to form a complex chain in the same manner as the carbon atom, the limit at present being a chain of three silicon atoms. Many of the earlier-known silicon alkyl compounds were isolated by Friedel and Crafts and by Ladenburg, the method adopted consisting in the interaction of the zinc alkyl compounds with silicon halides or esters of silicic acids.
The normal esters may be prepared by the action of silver carbonate on the alkyl iodides, or by the action of alcohols on the chlorcarbonic esters.
By heating with phosphorus pentachloride an alkyl group is eliminated and a chlorcarbonic ester formed.
The replacement of one hydrogen atom by one alkyl or aryl group gives rise to primary amines; of two hydrogen atoms by two groups, to secondary amines; of three hydrogen atoms by three groups, to tertiary amines.
The tertiary amines possess the power of combining with one molecular proportion of an alkyl iodide to form quaternary ammonium salts.
By the action of ammonia on the alkyl iodides a complex mixture of primary, secondary and tertiary amines, along with a quaternary ammonium salt, is obtained, the separation of which is difficult.
When heated with alkyl or aryl iodides, they are converted into secondary and tertiary amines.
The secondary amines may be of two types-namely,the purely aromatic amines, and the mixed secondary amines, which contain an aromatic residue and an alkyl group. The purely aromatic amines result upon heating the primary amines with their hydrochlorides, and, in some cases, by heating a phenol with a primary amine and anhydrous zinc chloride.
The mixed secondary amines are prepared by the action of alkyl iodides on the primary amines, or by heating salts of the primary amine with alcohols under pressure.
The mixed tertiary amines are produced by the action of alkyl halides on the primary amines.
On treatment with zinc and alkyl iodides or with zinc alkyls they are converted into esters of hydroxy-dialkyl acetic acids.
Their alkyl derivatives readily oxidize to pyrazine carboxylic acids.
This reaction shows that the alkyl or aryl group is attached to the carbon atom in the nitrile.
This reaction shows that the alkyl or aryl group is linked to the nitrogen atom.
Such a reaction can only take place if the addition of the alkyl group takes place on the nitrogen atom of the isonitrile, from which it follows that the nitrogen atom must be trivalent and consequently the carbon atom divalent.
Grignard (Comptes rendus, 1900 et seq.) observed that magnesium and alkyl or aryl halides combined together in presence of anhydrous ether at ordinary R temperatures (with the appearance of brisk boiling) to form compounds of the type RMgX(R = an alkyl or aryl group and X = halogen).
With unsaturated alkyl halides the products are only slightly soluble in ether, and two molecules of the alkyl compound are brought into the reaction.
A Klages (Ber., 1902, 35, pp. 2633 et seq.) has shown that if one uses an excess of magnesium and of an alkyl halide with a ketone, an ethylene derivative is formed.
Meyer (Ber., 18 94, 2 7, p. 510 et seq.) showed that in benzenoid compounds ortho-substituents exert a great hindering effect on the esterification of alcohols by acids in the presence of hydrochloric acid, this hindering being particularly marked when two substituents are present in the ortho positions to the carboxyl group. In such a case the ester is best prepared by the action of an alkyl halide on the silver salt of the acid, and when once prepared, can only be hydrolysed with great difficulty.
They are readily hydrolysed by water, and combine with bases to form alkyl ureas, and with alcohols to form carbamic esters.
They may be prepared by the action of concentrated sulphuric acid on the alcohols, alkyl sulphuric acids being first formed, which yield ethers on heating with alcohols.
They may also be prepared by heating the alkyl halides with silver oxide.
Phosphorus pentachloride converts them into alkyl chlorides, a similar decomposition taking place when they are heated with the haloid acids.
Wislicenus found that only one hydrogen atom in the -CH 2 - group is directly replaceable by sodium, and that if the sodium be then replaced by an alkyl group, the second hydrogen atom in the group can be replaced in the same manner.
These alkyl substitution products are important, for they lead to the synthesis of many organic compounds, on account of the fact that they can be hydrolysed in two different ways, barium hydroxide or dilute sodium hydroxide solution giving the socalled ketone hydrolysis, whilst concentrated sodium hydroxide gives the acid hydrolysis.
It receives application in synthetic organic chemistry by virtue of its power to remove the halogen atoms from alkyl haloids, and so effect the combination of the two alkyl residues.
It is a tertiary base, and combines readily with the alkyl halides to form pyridinium salts.
Ladenburg that the pyridinium alkyl iodides rearrange themselves when strongly heated and yield a and -y alkyl pyridines (Ber., 1883, 16, p. 1410 seq.; Ann., 1888, 247, p. I).
Alkyl pyridines -CO /COare also obtained by heating aldehyde ?
Just as the amines are derived from ammonia, so from phosphine are derived the primary, secondary and tertiary organic phosphines by the exchange of hydrogen for alkyl groups, and corresponding to the phosphonium salts there exists a series of organic phosphonium bases.
The tertiary phosphines are characterized by their readiness to pass into derivatives containing pentavalent phosphorus, and consequently they form addition compounds with sulphur, carbon bisulphide, chlorine, bromine, the halogen acids and the alkyl halides with great readiness.
It combines readily with the alkyl halides.
The alcohol is first acted upon with phosphorus and iodine, and the resulting alkyl iodide is treated with silver nitrite, which gives the corresponding nitroalkyl.