Synthetic Tannins, Their Synthesis, Industrial Production and Application Part 8

With the introduction of the carboxylic group the tendency of condensation to diphenylmethane derivatives is lessened; by protocatechuic acid the tendency is nil. Nierenstein considers this reaction a.n.a.logous to the formation of cork, to the genetic relation of which with the diphenylmethane formation Drabble and Nierenstein have referred in an earlier publication. [Footnote: _Biochemical Jour._., 1907, 2, 96.] It is hence possible that the plants may employ formaldehyde as a methylation medium, and produce these insoluble condensation products for the purpose of ridding themselves of the poisonous phenols and aromatic hydroxy acids (and tannins), in addition to oxidising processes whereby phlobaphenes, ellagic acid, etc., are formed.

The reaction between phenols and aldehydes has been further studied by Michael, [Footnote: _Amer.Jour_., 5, 338; 9, 130.] who prepared a condensation product from phenol and resorcinol with benzaldehyde, and Russanow, [Footnote: _Ber_.9 1889, 22, 1944.] who also employed benzaldehyde and phenol. Lipp [Footnote: Diss., Bern., 1905.]

investigated the action of benzaldehyde and piperonal on phenols, anisoles, cresols, cresylic ether, resorcinol, and the ether of the latter and phenol, and showed that when free phenols are condensed with benzaldehyde the hydroxyls occupy the same position as by the interaction between benzaldehyde and the corresponding phenolic ethers. The resulting dihydroxytriphenylmethane derivatives form beautiful crystals, which on oxidation are converted into benzaurines, the const.i.tution of the latter probably being--

O= ^=_____ ^ OH | | | | | |== __| | =v v v C | C_6H_5

In alkalies, the hydroxylated triphenylmethanes dissolve without imparting any colour to the solution; by concentrated sulphuric acid they are taken up with intense coloration.

If the hydroxyls occupy the ortho-position to methyl, they may form xanthenes by splitting off water--

O ^ ^ ^ | | | | | | | | CH_3 v v v CH_3 CH | C_6H_5

In the benzene series this reaction is difficult to establish, and has to be induced by distilling the particular dihydroxy-diphenylmethane at ordinary pressure. In the naphthalene series, on the other hand, the ring closes up by, for instance, the condensation of [Greek: b]-naphthol with benzaldehyde or paraldehyde, and yields the following compounds:--

C_10H_6 C_10H_6 C_6H_5-CH{ }O CH_3-CH{ }O C_10H_6 C_10H_6

These xanthenes are white, silk-glossy needles, which are soluble in water and in alkalies. In concentrated sulphuric acid, they are taken up with beautiful fluorescence.

6. Summary

From the qualitative reactions of the different condensation products described it may be seen that their tannoid properties are not dependent on whether they precipitate gelatine or are adsorbed by hide powder or not. Hydroxynaphthylmethanesulphonic acid, for instance, precipitates gelatine but does convert pelt into leather; on the other hand, sodium dicresylmethanesulphonate does not precipitate gelatine, and neither does it tan pelt; nevertheless it is adsorbed by hide powder as "tanning matter". The author discovered that _o_-nitrophenol does not precipitate gelatine, but has some tanning action on both hide powder and pelt.

Relatively to the possibilities of forming condensation products possessing tannoid properties, the following may be stated:--

All mono- and polyhydric phenols may be converted into true tanning matters by either condensing them as such, or after their conversion into the corresponding sulphonic acids, by substances capable of eliminating the elements of water. It makes no difference to the final product whether the condensation is the first step followed by sulphonation and consequent solubilisation of the intermediary insoluble product, or whether, vice versa, the sulphonic acid is subjected to condensation. Alkaline solution of phenols may also be condensed, the reaction products, when condensed, const.i.tuting tanning matters soluble in water.

Among the subst.i.tution products of the phenols, the thio-, chloro-, bromo-, nitro-, and aminophenols as a rule yield tanning matters similar in character.

The quinones are as such--_i.e._, without being condensed--substances possessing tannoid properties.

The aromatic dihydric alcohols are easily condensed with the different sulphonic acids and yield valuable tanning matters.

Of aromatic acids all those which yield water-soluble sulphonation products seem suitable for the industrial production of tanning matters. If the acids themselves do not yield water-soluble sulphonation products, the alkali salts of the latter may be condensed with formaldehyde, and the resulting products then const.i.tute tanning matters provided their solutions can be neutralised or faintly acidified without the solute being thrown out of solution in insoluble form.

The diphenyl derivatives of the above groups often possess tannoid properties.

The same holds good of those compounds with condensed nuclei (naphthalene, anthracene, etc.), and all their derivatives which satisfy the above conditions.

The choice of condensing agent is, as a rule, of little significance. Elimination of the elements of water by the mere application of heat succeeds in few cases only, since the high temperature required to induce reaction in many cases causes decomposition of the substances. This difficulty is overcome by heating _in vacuo_. Condensation with formaldehyde always succeeds, with acetaldehyde and benzaldehyde only partly.

The action on hide powder, pelt, and gelatine by these characteristic substances is tabulated below:-- Relative Behaviour towards Substance. Gelatine. Hide Powder Pelt Formaldehyde ... ... Tanning Phenol Ppte. ... ...

Chlorophenol " ... ...

Surface Tribromophenol Slight ppte Tanning tanning _o_ Nitrophenol No ppte " "

Bromonitrophenol Slight ppte " "

Trinitrophenol Ppte " Tanning Bromotrinitrophenol Slight ppte " "

_p_ Aminophenol Ppte ... ...

_m_ Dihydroxybenzene " ... ...

Orcinol " ... ...

_p_ Dihydroxybenzene " Tanning Tanning Monochloro _p_ dihydroxybenzene " ... ...

_o_ Dihydroxybenzene " ... ...

Pyrogallic acid " ... ...

Surface Tribromopyrogallic acid " Tanning Tanning Gallic acid No ppte Not tanning Not tanning Bromophloroglucinol Ppte Tanning "

Gallotannic acid " " Tanning Galloflavine Slight ppte " Not tanning Quinone " " Tanning Bromosalicylic acid " " Not tanning Dinaphthylmethanedisulphonic acid Ppte " Tanning Diphenylmethanedisulphonic acid " " "

Dicresylmethanedisulphonic acid " " "

Sodium dicresylmethanedisulphonate acid No ppte " Not tanning Dixylylmethanedisulphonic acid Ppte " Tanning Naphtholdisulphonic acid " Not tanning Not tanning Methylenedinaphthol " Tanning Tanning Hydroxyphenylmethanesulphonic " " "

acid Not tanning Hydroxynaphthylmethanesulphonic Slight ppte " "

acid Diaminonaphthylmethanedisulphonic Ppte Tanning Not tanning acid Dihydroxynaphthylmethanedisulphonic acid " " "

Dichloronaphthylmethanedisulphonic acid " " Surface tanning Dinitronaphthylmethanedisulphonic acid " " "

Dithionaphthylmethanedisulphonic acid " " Tanning Bromo _[Greek: b]_ naphthol [1] Slight ppte " "

Rosolic acid_ [1] Ppte " "

[Footnote 1: In alcoholic solution.]

SECTION III

TANNING EFFECTS OF MIXTURES AND NATURAL PRODUCTS

1. Mixture of Phenolsulphonic Acid and Formaldehyde

The most important invention relatively to the search for new tanning materials was that of Weinschenk,[Footnote: Ger. Pat., 184,449.] who first showed that pelt may be converted into leather by the action upon it of mixtures of naphthols and formaldehyde. This process consists of two steps: the pelt is first immersed in a 0.25-0.50 per cent, formaldehyde solution, and secondly in an aqueous solution of -[Greek: a] or -[Greek: b] naphthol; this order may be reversed. If, on the other hand, a pasty mixture is made of formaldehyde and naphthol, and this is allowed to act upon the pelt, the latter is rapidly converted into leather, but the mixture must be administered very gradually or otherwise the insoluble methylenedinaphthol is formed outside the pelt and hinders any tanning effect.

Leather obtained through the action of [Greek: a]-naphthol is, when freshly tanned, pure white and sufficiently soft and firm, but quickly a.s.sumes a brown colour on storing; if, however, [Greek: b]-naphthol is employed, a cream-coloured leather results, the colour of which turns only slightly more yellowish even when exposed to the direct rays of the sun.

A similar process has recently (25, xii., 1915) been protected by Ger. Pat, 305,516, granted to the Deutsch-Koloniale Gerb--und Farbstofif Gesellschaft, in Karlsruhe. According to this patent, pelt is treated in separate solutions, one of which is formaldehyde, the other being that of such aromatic compounds or their salts which yield water-soluble condensation products with formaldehyde; for example, pelt is immersed in 2-5 per cent, solution of formaldehyde for a few days, and is subsequently treated with 1-2 per cent neutral or faintly acidified solutions of [Greek: a]-naphthylamine hydrochloride, resorcinol or sodium phenate or cresylate, for several days. The resultant leather is claimed to be soft and full and to possess good tensile strength.

The tanning properties of mixtures of phenolsulphonic acid and formaldehyde have been examined by the author with the following results:--

I. II. III.

Grammes formaldehyde 10 20 40 " phenolsulphonic acid 20 50 100 " caustic soda (sol, 40 per cent.) 10 20 40 " water 500 500 500

The above solutions were made up and allowed to act upon pelt pieces weighing 15 gm.; whereas Solution I. remained clear throughout the experiment, Solution II. became somewhat clouded, and Solution III. a.s.sumed a milky appearance. The pelts were tanned through in seven days and yielded leathers which, after drying and finishing, possessed yellow colour, long fibre, and good tensile strength, but a rather empty feel.

To prevent separation of insoluble matter during tannage, another experiment was carried out, in which the pelts were first submitted to the action of formaldehyde (10, 20, and 40 gm. in 500 c.c. water) for three days, being subsequently removed to fresh solutions of partly neutralised phenolsulphonic acid (_cf_. above). Similar results were obtained, but the leather felt even more empty than those obtained by the former experiment.

Attempts at converting pelt into leather by first immersing the pelt in a partly neutralised solution of phenolsulphonic acid, and subsequently transferring it to fresh solutions of formaldehyde, gave merely negative results; the phenolsulphonic acid effected pickling action upon the pelt, but was subsequently quickly replaced by the formaldehyde, before the latter had penetrated the pelt in sufficient quant.i.ty to induce condensation, thereby exerting tanning action.

To explain the tanning effects of these mixtures, the author a.n.a.lysed the leathers resulting from the effects of the latter, and was able to show, that in these cases also, condensation of phenolsulphonic acid and formaldehyde takes place _inside_ the pelt, since on the one hand the a.n.a.lyses left no doubt but that true tannage had been effected, and on the other hand an ammoniacal extract of the leathers gave the typical reaction for condensation products of phenolsulphonic acid, with aniline hydrochloride. [Footnote: _Collegium_ 1913, 516, 142.]

The leather a.n.a.lyses gave the following figures:--

Moisture - - - 18.30 per cent.

Fats - - - - 0.47 "

_ Ash - - - - 0.98 "