Resorcinol Derivatives.

m-Hydroxyphenoxyacetic Acid (resorcinolacetic acid), OH•CH•O•CH, CO,H,

is obtained on acidifying the potash washings from the condensation product of disodium resorcinol and 2 mols. of ethyl bromoacetate, and extracting the acid solution with ether. It crystallises from water in small prisms, with H2O, melting at 157-158°, and from boiling toluene in needles melting at 158-159°.

0.1739 gave 0.3528 CO2 and 0.0744 H2O. C-55.2; H=4.8.

CH,OH2O requires C-55-2; H=50 per cent.

8

The silver salt was obtained by adding silver nitrate to the solution of the ammonium salt and crystallises in needles from water.

0.2101 gave 0.0896 Ag. Ag=42.7.

CH,O,Ag requires Ag = 430 per cent.

4

2

The anilide, OH·C ̧H12·O·CH2·CO·NH CH,, melts at 125°, and is obtained by heating the acid with aniline at 180°.

-5/21

Ethyl m-Phenylenedioxydiacetate, CH4(O·CH2 CO2CH)2, is formed both by the condensation of disodium resorcinol with 2 mols. of ethyl bromoacetate and by evaporation of an aqueous solution of disodium resorcinol with 2 mols. of chloroacetic acid dissolved in excess of caustic soda. It is obtained on fractional distillation of the products as a thick, colourless oil, which boils at 228° under 32 mm. pressure, and on standing for several weeks crystallises in needles melting at 42°.

The hydrolysis of the ester was carried out in the same manner as that of the catechol derivative, and o-phenylenedioxydiacetic acid, C ̧H1(O·CH2·CO2H)2, was obtained, crystallising from saturated aqueous or acetic acid solutions in fine needles melting at 195°, and from dilute solutions in prisms having the same melting point.

2

0.2436 gave 0.4700 CO2 and 0·0897 H2O. C=52·7; H=4·1. C10H10O6 requires C=53·1; H= 4.4 per cent.

The silver, copper, and iron salts of this acid are obtained from the ammonium salt as amorphous precipitates, insoluble in water; the barium and calcium salts are crystalline, and are slightly soluble in boiling water.

The ester, on agitation with strong aqueous ammonia, is converted into m-phenylenedioxydiacetamide, CH4(O·CH2 CO·NH2)2, which crystallises from water in needles melting at 167°.

0.0806 gave 8.6 c.c. nitrogen at 17° and 758 mm. N=12.3.

C10H1204N2 requires N = 12.5 per cent.

If the ester is warmed with dilute ammonia solution, a substance crystallising in needles melting at 43° is formed. Possibly it has the constitution NH(CO, CH, O.CH, O CH2 CO2CH)2

0.1234 gave 3 c.c. nitrogen at 21° and 758 mm. N = 2.7.

C24H27O10N requires N = 2.9 per cent.

The aniline salt is obtained by boiling the acid with aniline in benzene solution, and melts at 137°; it may be recrystallised from benzene. On distillation, it is converted into m-phenylenedioxydiacetanilide, CH(O.CH2 CO·NH CH)2, which crystallises in prisms from benzene and melts at 169°; the anilide may more easily be obtained by heating the acid with aniline at 190°.

0.1165 gave 7.5 c.c. of nitrogen at 18° and 756 mm. N=7.4. C22H2004N, requires N=7.5 per cent.

On boiling m-phenylenedioxydiacetic acid with fuming nitric acid diluted with half its volume of water, trinitro-m-phenylenedioxydiacetic acid, (NO2)3CH(O CH2 CO2H), is formed and crystallises from the solution on cooling in pale yellow prisms which may be purified by recrystallisation from water, and melt at 174°.

0.1637 gave 17 c.c. nitrogen at 19° and 751 mm.

C10 H7O12N3 requires N = 11.7 per cent.

N=117.

This nitro-compound is converted by potash at 140° into styphnic acid (2:4: 6-trinitroresorcinol), and is consequently the 2: 4: 6-trinitro-derivative.

Quinol Derivatives.

6

p-Hydroxyphenoxyacetic Acid, OH C ̧H ̧·O·CH2·CO2H, is obtained in the same way as the corresponding resorcinol derivative. It crystallises from water in prisms with H2O, and from toluene or xylene in anhydrous needles, both forms melting at 152°.

0.2738 gave 0.5560 CO, and 0.1247 H2O. C-55·3; H=5·0. CHO,H2O requires C=55·2; H=5·0 per cent.

8 4'

After crystallisation from xylene,

0.3418 gave 0.7132 CO2 and 0·1459 H2O. C=57·1; H=4·7. CHO, requires C-571; H=4.7 per cent.

The aniline salt melts at 119.

The anilide, OH·CH ̧·O·CH2· CO⚫NH CH,, crystallises in prisms from benzene and melts at 101°.

0.1462 gave 7·4 c.c. nitrogen at 22° and 763 mm. N = 5.7.

C14H18ON requires N = 5.8 per cent.

p-Phenylenedioxydiacetate,

Ethyl C&H (O-CH2 CO,C,H,), -The ethereal solution from the condensation of 1 mol. of disodium quinol with 2 mols. of ethyl bromoacetate, after washing with potash, begins to crystallise, and on distilling off the ether, a solid cake of ethyl p-phenylenedioxydiacetate is obtained. When recrystallised from dilute alcohol or light petroleum, the ester melts at 72°.

0.1713 gave 0.3747 CO2 and 0.0994 H2O. C-59-6; H=6.4. C14H180 requires C=595; H=6.3 per cent.

The crystalline ester is converted on hydrolysis with alcoholic potash into p-phenylenedioxydiacetic acid, C&H (O.CH, CO2H)2, which melts at 251°, and is very sparingly soluble in all solvents, but may be obtained as a microcrystalline powder from boiling acetic acid.

0.2394 gave 0.4640 CO2 and 0·0996 H2O. C=52·3; H=4·6.

2

C10H100 requires C=53; H=4·4 per cent.

On neutralising the acid with ammonia, the ammonium salt is formed, which crystallises from water in needles; its solution gives amorphous precipitates with silver, copper, and iron salts, and crystalline precipitates with barium and calcium salts. The barium salt was analysed with the following result :

0.3660 lost 0.0011 at 160°, and gave 0·2324 BaSO4. Ba=37·4. C10H8OBа, H2O requires Ba≈ 37.9 per cent.

6

The anilide, CH4(O·CH2 CO NH.CH)2, crystallises in glistening needles from benzene and melts at 210°.

0.1617 gave 10.3 c.c. nitrogen at 18° and 756 mm. C22H2004N2 requires N=7.5 per cent.

N=7.3.

The investigations of Prof. C. A. Bischoff (compare Ber., 1900, 33, 924) having been confined to acids of the type CH1(O.CRR'.CO2H)2, we concluded he had, with intention, omitted the study of the acetic acid derivatives. We communicated with him, however, and in a letter dated May 26th he announced his intention of investigating the acetic acid derivatives of resorcinol and quinol, and, subsequently to the abstract of this paper being communicated to the Society, a notice to this effect has appeared in the Berichte (loc. cit., 1692).

THE OWENS COLLEGE,

MANCHESTER.

CXVII.-Specific Gravities of the Halogens at their Boiling Points, and of Oxygen and Nitrogen.

By JULIEN DRUGMAN, Ph.D., and WILLIAM RAMSAY, F.R.S. THE object of the following experiments was to determine the specific gravities of the halogens in the liquid state under similar conditions. The conditions chosen were the boiling points of the elements under atmospheric pressure, as from Young's experiments (Ramsay and Young, Phil. Mag., 1885, [v], 20, 518; Young, Phil. Mag., 1892, 33, 161; 1894, 37, 4) the benzene halides have molecular volumes at the boiling point under equal pressures which bear constant ratios to one another for all equal pressures, and therefore also for their critical pressures.

If similar halides have these properties, it is reasonable to expect that the halogens would also bear the same ratios to one another, and that the densities at their boiling points would bear the same ratios under the ordinary atmospheric pressure as at their critical pressure.

The specific gravity of iodine was first determined. For this purpose, a small glass bulb with a capillary tube bent twice at right angles was used. Its capacity was accurately determined, and then it was filled with liquid iodine by heating, dipping the end of the capillary in liquid iodine, and afterwards letting it cool. The bulb was then hung up by means of a wire in a wide tube about 18 inches in length containing boiling iodine, and left there long enough to get heated to the same temperature as the vapours from the boiling iodine. It was now quickly drawn out, allowed to cool, and the weight of the iodine left in it determined. following results were obtained:

The

No. 3 was too low owing to a piece of the capillary containing some iodine having cracked off on cooling. The average would then be 3.706 at a temperature of about 184 35°, that is, the boiling point under 760 mm. (Ramsay and Young, Trans., 1886, 49, 461).

In determining the volume of the bulb, the expansion of the glass was taken into account, and in all the following determinations the expansion or contraction of the bulb was allowed for. The coefficient used was 0.000025 for the temperatures above zero, and 0.0000219 for those at lower temperatures (Baly, Phil. Mag., 1900, [v], 49, 518).

The specific gravity of bromine under similar conditions having already been found, that of chlorine was next determined.

The apparatus for chlorine was necessarily more complicated, but the method was the same as that just described, that is, heating a bulb containing the liquid by means of the vapours of the same liquid boiling in an outer jacket at atmospheric pressure, and then determining the weight of the contents of the bulb.

The bulb was in this case an ordinary thermometer bulb with the

stem bent twice at right angles, and graduated for 2 or 3 inches from the bulb upwards. The weight of the chlorine was determined by absorbing the gas in potassium iodide solution and titrating the liberated iodine with thiosulphate solution.

The bulb and jacket were exhausted several times by means of an air-pump. The accompanying diagram shows the apparatus used. A was first connected to a T-tube leading on one side to the vacuum pump, and on the other to the chlorine generator;