The action of thionyl chloride and of phosphorus pentachloride on the methylene ethers of catechol derivatives / by George Barger.

  • George Barger
Date:
[1908]
Catalogue details

Licence: Attribution 4.0 International (CC BY 4.0)

Credit: The action of thionyl chloride and of phosphorus pentachloride on the methylene ethers of catechol derivatives / by George Barger. Source: Wellcome Collection.

Provider: This material has been provided by The Royal College of Surgeons of England. The original may be consulted at The Royal College of Surgeons of England.

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    tube at the laboratory temperature for two days. On allowing the excess of ammonia to evaporate at the ordinary temperature, a red solid remained, which was completely freed from ammonia in a vacuum over sulphuric acid and then crystallised from water. The crystals were somewhat coloured and melted at 212°. With ferric chloride they gave an intense green coloration : 0*2392 gave 18*7 c.c. moist nitrogen at 5° and 770 mm. N = 9*7. C7H703N requires N = 9*2 per cent. 3 : i-Carbonyldioxybenzanilide, 0!C!02Ci; Hs* CO • NH• G0IL. Two molecular proportions of aniline, dissolved in a little benzene, were added to 0*5 gram of 3 :4-carbonyldioxybenzoyl chloride, dissolved in 10 c.c. of benzene. A precipitate consisting of the anilide and of aniline hydrochloride was formed. On extracting the precipitate with water, the anilide remained behind and was then crystallised from boiling alcohol and subsequently from ethyl acetate. It formed white, hair-like needles melting sharply at 214° : 0-2271 gave 11*0 c.c. moist nitrogen at 14° and 766 mm. N = 5*7. C14H904N requires N = 5*5 per cent. Protocatechucmilide, (OH).2CeH3,CO*NH,C0H5. 3 :4-Carbonyldioxybenzanilide was dissolved in pyridine and an equal volume of water was then added; bubbles of carbon dioxide were given off. After removal of most of the pyridine by distillation, white, glistening plates separated, consisting of protocatechuanilide. The hydrolysis of the carbonate can also be performed by suspending it in boiling water, and adding dilute ammonia, drop by drop, as described for phenyl protocatechuate. The substance retains water at 100° and was dried at 115° until of constant weight: 0T441 gave 0*3591 C02 and 0*0606 H20. C = 6S*0; H = 4*7. 0*3177 ,, 16*6 c.c. moist nitrogen at 14° and 766 mm. N = 6*2. C13Hu03N requires C = 68*l; H = 4*8; N = 6*l per cent. Protocatechuanilide melts at 166—167°. It is sparingly soluble in hot water, but readily so in hot alcohol; its solutions gave the characteristic green coloration with ferric chloride. The substance has been prepared before from protocatechuic acid by Schiff (Ber., 1882, 15, 2589) and by Thibault {Bull. Soc. chim., 1904, [iii], 31, 920). The latter author criticises Schiff’s method of preparation and himself gives the melting point 154—156°. The analytical figures and the melting point given above would, however, appear to refer to a purer specimen, and illustrate the advantage of pre-