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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    01687 gave 0-3289 C02 and 0-0365 H20. C = 53-2 ; H = 2-4. CsH4Q5 requires C = 53-3 ; H = 2-2 per cent. 3 : i-Carbonyldioxybenzoic acid melts at 228° with effervescence. It is insoluble in water, and somewhat sparingly soluble in most organic solvents in the cold. Its alcoholic solution is not coloured by ferric chloride. On boiling the acid with water or with salt solution, it is quantitatively converted into protocatechuic acid, which separates in white crystals melting at 197—198°. Methyl 3 : 4-C arbonyldioxybenzoate, O!C!O2!C0H3*CO2,CH3. This substance was prepared by dissolving the acid chloride in methyl alcohol without rise of temper-ature. On the addition of water, ci’ystals separated melting at 90° : 0-1752 gave 0 3549 C02 and 0 0495 H20. C = 55-4 • H = 3'l. C4lH605 requires C = 55-7 ; IT = 32 per cent. Methyl 3 : 4-carbonyldioxybenzoate is very soluble in most organic solvents, and does not give a reaction with ferric chloride. By boiling with water or making alkaline with ammonia, it is changed to methyl protocatechuate, which could, however, not be obtained quite pure owing to further decomposition, resulting in the formation of protocatechuic acid. Phenyl-3 : i-carbomjldioxybenzoate, 0!C!02!C6H3*C02*C6H5. Equimolecular proportions of phenol and of 3 :4-carbonyldioxy- benzoyl chloride were heated together, until the evolution of hydrogen chloride ceased. A little benzene was then added to the hot liquid and, on cooling, phenyl 3 : 4-carbonyldioxybenzoate crystallised in stout crystals, melting at 126°: 0 1433 gave 0-3458 C02 and 0-0405 H20. C = 65-S ; 11 = 3-1. 0UH806 requires 0 = 65-6 ; II = 31 percent. Phenyl Protocatechuate, (0II)2CGII:j-C02-C6lI-. The substance just described was suspended iu boiling water, and dilute ammonia was added drop by drop until all was dissolved. If an excess is avoided, the solution scarcely darkens at all. After filtra- tion, dilute hydrochloric acid was added drop by drop to the hot solution, so that crystals of phenyl protocatechuate separated out. The substance was recrystallised from very dilute alcohol and then melted at 189°. It is readily soluble in cold alcohol, but almost