by treatment with PCl_5, and the chloride thus obtained further condensed with sodium phenolsulphonate, saponified, and the solution acidified, the pure tridepside
HO.C_6H_4.SO_2.O.C_6H_4.SO_2.O.C_6H_4.SO_3Na
is precipitated as white crystalline needles which not only precipitate gelatine, but are capable of converting animal hide into leather.[Footnote: Chem. Ztg., 1919, 43, 318.]
Of the class of hydroxy-cymenes thymol,
C_6H_3.CH_3.C_3H_7OH,
was converted into the water-soluble sulphonic acid by warming with concentrated sulphuric acid at 50° C., the sulphonic acid being subsequently easily condensed with formaldehyde by slightly heating the mixture. The condensation product thus obtained is a viscous brown mass which is easily soluble in water, precipitates gelatine completely, gives a bluish-black coloration with iron salts, and gives a precipitate with aniline hydrochloride. To investigate its tannoid properties, the mixture was brought to the acidity 1 gm = 10 c.c. N/10 NaOH and a piece of bated calf skin was then introduced into a solution measuring about 2° Bé. After eighteen hours the pelt was nearly tanned through, and a further twenty-four hours completed the tanning process, after which a light fat-liquor was given. The dried leather was brownish-grey in colour, possessed soft and full feel and good tensile strength.
On account of their importance, the three dihydroxybenzenes were examined with a view to test their suitability for conversion into tannoid substances.
o-Dihydroxybenzene, catechol, yields a sulphonic acid easily soluble in water, which on the careful addition of formaldehyde assumes a blue colour. The compound thus obtained may be heated to 100° C., without depositing insolubles. A further addition of formaldehyde, however, results in the formation of a considerable quantity of insolubles whilst the liquid assumes a brown coloration. If, on the other hand, the sulphonic acid is diluted with twice its volume of water, formaldehyde added and the mixture heated on the water bath, the liquid immediately turns brown, the formaldehyde is completely fixed, and a condensation product soluble in water results. The latter gives a brownish-black coloration with ferric chloride, completely precipitates gelatine, but gives no opalescence with aniline hydrochloride. Tanning experiments with the partly neutralised (1 gm.= 10 c.c. N/10 NaOH) substance resulted in both grain and flesh being tanned with a black colour, whereas the interior of the pelt was pickled (white colour). After a further forty-eight hours, however, the black colour penetrated the pelt, and tannage was complete. The washed and lightly fat-liquored leather was soft, of full feel and good tensile strength, and was greyish coloured throughout.
With regard to the black colour possessed by leathers tanned with synthetic tannins the following should be noted. When sulphonating and especially when condensing substances, black dyestuffs or very finely divided carbon in the colloidal state are often formed. Such a substance does not deposit the black particles, even when filtered through kaolin, and hence convert pelt into leather possessing black colour on the surface. The hide in this case acts as a perfect filtration medium, whereby the surface layers retaining the coloured particles assume their colour; thus only the pure tanning matter enters into the interior, which then, according to the composition of the former, imparts a colour varying from white to light brown to the inner layers.
m-Dihydroxybenzene, resorcinol, is also easily sulphonated by concentrated sulphuric acid, the brownish-coloured sulphonic acid being easily soluble in water. If the sulphonic acid is diluted with three times its volume of water, cooled down, a few drops of formaldehyde added and the mixture heated on the water bath to completely fix the formaldehyde, and this process repeated till no more formaldehyde is taken up, a brown water-soluble condensation product results, the aqueous solution of which precipitates gelatine completely, aniline hydrochloride only partly and which gives a deep blue colour with ferric chloride.