Bibliography #6408

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Landrieu 1924	P. Landrieu and M. Blatt, Bull. Soc. Chim. Fr. 35, 14241236 (1924) Thermochemical Study of Diphenylphenylethinylcarbinol and Its Derivatives Abstract: With a bomb and a calorimeter to be described later, capable of great precision, heats of combustion were determined and heats of formation calculated from the values C + O2 = CO2 + 94.3 Cals.; H2 + O = H2O + 69 Cals. Cv-Cp = 2 Cals. (In the following, the figures after the compound represent m. p., heat of combustion in small cals. per g. as determined, mol. heat of combustion in large Cals., molar heat of formation in large Cals., resp.) Diphenylphenylethinylcarbinol (I), 82°, 9047, 2569, -37. Phenylbenzalacetophenone (II), prepared by treating 10 g. of I with AcOH and H2SO4, and recrystallizing twice from a mixture of Et2O and petroleum ether, and 3 times from ligroin, m. 87-8°; or by treating 10 g. of I with 100 cc. of EtOH and 10 cc. of H2SO4, and recrystallizing 3 times from EtOH, rn. 88.5°,-, 8962, 2542, -10. Me ether (III) of I, prepared by treating I with MeOH and H2SO4 and recrystallizing 3 times from MeOH, 123-4°, 9181, 2735, -39. Et ether (IV) of I, 51°, 9255, 2887, -28. Pr ether (V) of I, 42.5°, 9335, 3042, -20. beta,beta-Diphenyl-beta-hydroxypropiophenone (VI) prepared from CH2Bz2 and PhMgBr (yield 35-40%) and purified by 3 recrystallizations from EtOH, 117°, 8994, 2584, + 67. Benzophenone (VII) (com. product recrystallized from EtOH, Et2O and twice more from EtOH), 48.5-9°, 8536, 1553, +18. Since the difference in heat of combustion between an alc. and a higher homolog is 155 Cals. while the difference between that of an alc. and its ether is 166-7 Cals., the compound designated as the Me ether of I is thus seen to fall in line with the rule. The 2 heats of combustion of I and III differ by 166 Cals. while III and IV differ by 152 Cals. and IV and V by 155 Cals. The transformation of I to II liberates 27 Cals. and hence II is a much more stable form than I. II can be considered as arising from the union of VII and Me: Ph2CO (solid) + MeCOPh (liquid) = Ph2C:CHCOPh (liquid) + H2O, (18 Cals.) + (39.5 Cals.) = (-10 Cals.) + (69 Cals.) + Q. By using the value -10 Cals. for the heat of formation of II, a value of Q of 1.5 Cals. is obtained, which is very near to that for the hypothetical reaction of the same nature: PhCHO (liquid) + MePh (liquid) = PhCH:CHPh (solid) + H2O (liquid), (23.5 Cals.) + (2,3 Cals.) = (-43.1 Cals.) + (69 Cals.) + Q; where Q = 0.3 Cals., and where the same kind of a double bond is formed by elimination of water between a C:O and a Me group. Hence the structure assigned to II is deemed correct. I has a heat of hydration to VI; Ph2C(OH)C CPh (solid) + H2O (liquid) = Ph2C(OH)CH2COPh (solid), (-37 Cals.) + (69 Cals.) = (67 Cals.) + Q; whence Q = 35 Cals. which is in good agreement with the value of -36 Cals. given by Moureu and Andre for the hydration of PhC CN to BzMe. Again, comparing II with VI, its hydration compound: Ph2C:CHCOPh + H2O = Ph2C(OH)CH2COPh, (-10 Cals.) + (69 Cals.) = (67 Cals.) + Q; Q = 8 Cals., which agrees well with value for propylene of 8.9 Cals. and amylene of 8.5 Cals. and is a further proof of the correctness of the structures assigned to these compounds.

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Landrieu 1924

P. Landrieu and M. Blatt, Bull. Soc. Chim. Fr. 35, 14241236 (1924)
Thermochemical Study of Diphenylphenylethinylcarbinol and Its Derivatives
Abstract: With a bomb and a calorimeter to be described later, capable of great precision, heats of combustion were determined and heats of formation calculated from the values C + O2 = CO2 + 94.3 Cals.; H2 + O = H2O + 69 Cals. Cv-Cp = 2 Cals. (In the following, the figures after the compound represent m. p., heat of combustion in small cals. per g. as determined, mol. heat of combustion in large Cals., molar heat of formation in large Cals., resp.) Diphenylphenylethinylcarbinol (I), 82°, 9047, 2569, -37. Phenylbenzalacetophenone (II), prepared by treating 10 g. of I with AcOH and H2SO4, and recrystallizing twice from a mixture of Et2O and petroleum ether, and 3 times from ligroin, m. 87-8°; or by treating 10 g. of I with 100 cc. of EtOH and 10 cc. of H2SO4, and recrystallizing 3 times from EtOH, rn. 88.5°,-, 8962, 2542, -10. Me ether (III) of I, prepared by treating I with MeOH and H2SO4 and recrystallizing 3 times from MeOH, 123-4°, 9181, 2735, -39. Et ether (IV) of I, 51°, 9255, 2887, -28. Pr ether (V) of I, 42.5°, 9335, 3042, -20. beta,beta-Diphenyl-beta-hydroxypropiophenone (VI) prepared from CH2Bz2 and PhMgBr (yield 35-40%) and purified by 3 recrystallizations from EtOH, 117°, 8994, 2584, + 67. Benzophenone (VII) (com. product recrystallized from EtOH, Et2O and twice more from EtOH), 48.5-9°, 8536, 1553, +18. Since the difference in heat of combustion between an alc. and a higher homolog is 155 Cals. while the difference between that of an alc. and its ether is 166-7 Cals., the compound designated as the Me ether of I is thus seen to fall in line with the rule. The 2 heats of combustion of I and III differ by 166 Cals. while III and IV differ by 152 Cals. and IV and V by 155 Cals. The transformation of I to II liberates 27 Cals. and hence II is a much more stable form than I. II can be considered as arising from the union of VII and Me: Ph2CO (solid) + MeCOPh (liquid) = Ph2C:CHCOPh (liquid) + H2O, (18 Cals.) + (39.5 Cals.) = (-10 Cals.) + (69 Cals.) + Q. By using the value -10 Cals. for the heat of formation of II, a value of Q of 1.5 Cals. is obtained, which is very near to that for the hypothetical reaction of the same nature: PhCHO (liquid) + MePh (liquid) = PhCH:CHPh (solid) + H2O (liquid), (23.5 Cals.) + (2,3 Cals.) = (-43.1 Cals.) + (69 Cals.) + Q; where Q = 0.3 Cals., and where the same kind of a double bond is formed by elimination of water between a C:O and a Me group. Hence the structure assigned to II is deemed correct. I has a heat of hydration to VI; Ph2C(OH)C CPh (solid) + H2O (liquid) = Ph2C(OH)CH2COPh (solid), (-37 Cals.) + (69 Cals.) = (67 Cals.) + Q; whence Q = 35 Cals. which is in good agreement with the value of -36 Cals. given by Moureu and Andre for the hydration of PhC CN to BzMe. Again, comparing II with VI, its hydration compound: Ph2C:CHCOPh + H2O = Ph2C(OH)CH2COPh, (-10 Cals.) + (69 Cals.) = (67 Cals.) + Q; Q = 8 Cals., which agrees well with value for propylene of 8.9 Cals. and amylene of 8.5 Cals. and is a further proof of the correctness of the structures assigned to these compounds.