Synthetic Tannins, Their Synthesis, Industrial Production and ApplicationGrasser, Georg
Science
Synthetic Tannins, Their Synthesis, Industrial Production and Application
Grasser, Georg
Tannins
Amongst other compounds chlorphydroxybenzoic acid is used in the
preparation of the materials employed in the synthesis of depsides; the
free phenolic group, however, exerts a disturbing influence when
aromatic acids are acted upon by phosphorus chloride, and another group,
which can subsequently be easily removed, must therefore be introduced
to cover the disturbing influence referred to. For this purpose, Fischer
[Footnote: _Ber_., 1908, 41, 2860.] chose the carbomethoxy group, and
this investigator succeeded, by the action of chlorocarbonic alkyl
ester and alkali upon hydroxybenzoic acid in cold aqueous solution, in
obtaining substances with the properties required. [Footnote: _Ber._,
1908, 41, 2875.] In such substances (_e.g._, salicylic acid) where the
hydroxyl occupies the ortho-position to the carboxyl, complete
carbomethoxylation does not take place, whereas the _m_- or _p_-
positions offer no hindrance. In the case of the _o_-position, however,
the action of chlorocarbonic alkyl ester is successfully assisted by the
presence of dimethylaniline in an inert solvent, _e.g._,
benzene.[Footnote: U.S. Pat, 1,639,174, 12, xii., 1899.] The difficulty
encountered by the _o_-position is eliminated when the carboxyl is not
directly linked to the benzene nucleus, _e.g._, _o_-cumaric acid. Many
hydroxybenzoic acids require an excess of chlorocarbonic methyl ester,
which then also, to some extent, attacks the carboxyl group; but on
dissolving the product in acetone and treating it with bicarbonate the
carboxyl group as such is again restored without splitting off the
carbomethoxy group.[Footnote: _Ber._, 1913, 46, 2400.] In this way all
hydroxybenzoic acids may be carbomethoxylated. [Footnote: _Ibid._,
1908, 41, 2877, 2881, 2882; 1909, 42, 226, 218, 223, 225; Liebig's
_Ann._, 1912, 391, 357, 366; _Ber._, 1913, 46, 1145, 2390, 2400.] The
carbomethoxy group is easily removed by excess of aqueous alkali in the
cold, and is also partially removed when insufficient alkali is present;
the latter fact is of importance in the synthesis of didepsides.
Chlorides of Carbomethoxyhydroxybenzoic Acids
The chlorides of these compounds are obtained when phosphorus
pentachloride is allowed to act upon the acids, and are as a rule
crystalline. For the purpose of synthesis they may be employed as
follows:
1. They readily form esters with alcohols, which on subsequent
saponification with alkali are converted into the esters of the free
hydroxybenzoic acids.
2. The chlorides interact energetically with esters of amino-acids, and
may be coupled with amino-acids in aqueous alkaline solution. On
subsequently removing the carbo-methoxy group derivatives of
hydroxybenzoic acids are obtained, _e.g._,
CH_3.CO_2.O.C_6H_4.CO.Cl + 2NH_2CH_2.CO.C_2H_5
= NH_2.CH_2.CO_2.C_2H_5 + HCl + CH_3.CO_2.O.C_6H_4 CO.NH.CH_2CO_2C_2H_5.
CH_3.CO_2.O.C_6H_4.CO.NH.CH_2.CO_2.C_2H_5 + 3NaOH
= Na_2CO_3 + C_2H_5OH + CH_3OH + HO.C_6H_4.CO.NH.CH_2.COONa.
Public-domain text, read in full here on John Shaqi.
Reviews
Reviews
No reviews yet
Be the first to share your thoughts on this work.
Join the Discussion
Join the discussion
Sign in to leave a comment or review.
Sign InorCreate an account