The carboxyl group constitutes another convenient startingpoint for the orientation of many types of organic compounds.
A third hydroxyl group may be introduced into the - CH: 0 residue with the formation of the radical - C(OH) :0; this is known as the carboxyl group, and characterizes the organic acids.
Hence the positions occupied by the nitro groups in the two different nitrobrombenzoic acids must be symmetrical with respect to the carboxyl group. In 1879, Hubner (Ann., 1 95, p. 4) proved the equivalence of the second pair, viz.
P. Griess (Ber., 1872, 5, p. 192; 18 74, 7, p. 1223) orientated the three diaminobenzenes or phenylene diamines by considering their preparation by the elimination of the carboxyl group in the six diaminobenzoic acids.
The average value for the carboxyl group is 119.75 calories, i.e.
This theory explains the fluorescence of anthranilic acid (o-aminobenzoic acid), by regarding the aniline residue as the luminophore, and the carboxyl group as the fluorogen, since, apparently, the introduction of the latter into the non-fluorescent aniline molecule involves the production of a fluorescent substance.
Piperic acid differs from piperonylic acid by the group C4H 4, and it was apparent that these carbon atoms must be attached to the carbon atom which appears in the carboxyl group of piperonylic acid, for if they were directly attached to the benzene ring polycarboxylic acids would result in oxidation.
OH, termed the carboxyl group, in which the hydrogen atom is replaceable by metals with the formation of salts, and by alkyl radicals with the formation of esters.
The basicity of an organic acid, as above defined, is determined by the number of carboxyl groups present.
The simplest syntheses are undoubtedly those in which a carboxyl group is obtained directly from the oxides of carbon, carbon dioxide and carbon monoxide.
Other reactions which introduce carboxyl groups into aromatic groups are: the action of carbonyl chloride on aromatic hydrocarbons in the presence of aluminium chloride, acid-chlorides being formed which are readily decomposed by water to give the acid; the action of urea chloride Clï¿½COï¿½NH 2, cyanuric acid (CONH) 3, nascent cyanic acid, or carbanile on hydrocarbons in the presence of aluminium chloride, acid-amides being obtained which are readily decomposed to give the acid.
In the preceding instances the carboxyl group has been synthesized or introduced into a molecule; we have now to consider syntheses from substances already containing carboxyl groups.
Phosphorus chlorides give acid chlorides, Rï¿½COï¿½C1, the hydroxyl group being replaced by chlorine, and acid anhydrides, (Rï¿½CO) 2 0, a molecule of water being split off between two carboxyl groups.
ESTERS, in organic chemistry, compounds formed by the condensation of an alcohol and an acid, with elimination of water; they may also be considered as derivatives of alcohols, in which the hydroxylic hydrogen has been replaced by an acid radical, or as acids in which the hydrogen of the carboxyl group has been replaced by an alkyl or aryl group. In the case of the polybasic acids, all the hydrogen atoms can be replaced in this way, and the compounds formed are known as "neutral esters."
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.
With a methyl group, the chief product is an ortho-semidine, whilst with a carboxyl group, the diphenyl derivative is the chief product.
CH2 CHz?CU; CO CH 3 CO CH2 from sodio-malonic ester and 0-unsaturated ketones or ketonic esters: /CH, CO (R02C)2CH2+ Ph CH :CH /CH:>; CH(C02R) C07 from aceto-acetic ester and esters of a$-unsaturated acids, followed by elimination of the carboxyl group: CH2 CR', CH 3 CO CH 2.
It is a colourless liquid having a faint smell resembling that of benzene and boiling at 84° C. In its chief properties it very much resembles benzene, being readily brominated, sulphonated, and nitrated; also, the side chains in the alkyl thiophens are readily oxidized to carboxyl groups.