394. Condensation products of phenols and ketones. Part X. The structure of dianin's compounds, a unique inclusion-forming substance

Abstract

A product, " Dianin's compound,'' first prepared in 1914 from phenol and mesityl oxide, is shown to be 4-P-hydroxyphenyl-2 : 2 : 4-trimethylchroman (111). Oxidation yields 2 : 2 : 4-trimethylchroman-4-carboxylic acid, and thermal degradation gives phencl and 2 : 2 : 4-trimethylchromen. The latter compound has been synthesised and yields Dianin's compound by addition of phenol.Dianin's compound forms inclusion compounds with over fifty widely differing organic solvents, some inorganic gases, and with iodine. The large, separate cavities in the crystals are defined by six molecules of Dianin's compound, and the ratio of number of molecules of Dianin's compound to the number of included molecules is generally 6 : 1, though a ratio of 3 : 1, i.e., 2 molecules per hole, is found with a number of small molecules.PREVIOUS papers 1, have described inter al. some derivatives of 2'-hydroxy-2 : 4 : 4-trimethylflavan prepared by condensing simple phenols with acetone, and these flavans formed inclusion compounds with a variety of organic solvents.2* The condensation product of phenol with mesityl oxide was studied by Dianin: and he observed that it formed crystalline adducts with certain organic solvents. We have now reinvestigated this substance, which will be referred to as " Dianin's compound " (see a preliminary note by Baker and McOmie 7.Dianin showed that phenol (2 mol.) reacted with mesityl oxide (1 mol.) in presence of hydrogen chloride to give a monohydric phenol, C18H2002, which formed a benzoate and a *

The crystal structure and thermal expansion of the CCl4 adduct of Dianin's compound

“…This was converted to the unsolvated form of 1 by bubbling COz gas through a basic solution of the ethanol adduct in H20 (2). The resultant white powder was dissolved in carbon tetrachloride to produce the CCl4 adduct of l (2). Single crystals were obtained by slow evaporation; samples for the X-ray powder diffraction were obtained by rapid recrystallization.…”

“…Dianin's compound (1) was prepared from phenol and mesityl oxide according to the method of Baker et al (2), and isolated as the ethanol adduct. This was converted to the unsolvated form of 1 by bubbling COz gas through a basic solution of the ethanol adduct in H20 (2).…”

“…The cage is held together at the roof and floor by the hydrogen-bond network, and at the waist by van der Waals forces between t h~ molecules. The cages are quite large, free volume about 180 A3, and can accommodate even bulky molecules (2). 'Present address: Institut fiir Anorganische Chemie, P.O.…”

Modification of photochemical reactivity through the use of clathrates: the Norrish type I and type II reactions in Dianin's compound

“…All ketones were purified by column chromatography and (or) vacuum distillation prior to use. Dianin's compound (1) was prepared and purified by the method of Baker et al (33). Unsolvated Dianin's compound was obtained by sublimation of the ethanol complex at 140°C and 1 Torr (mp 166 -167°C).…”

“…Subsequent work has shown that Dianin's compound is capable of including a wide variety of organic molecules, including ketones (33). X-ray crystallography (34,35) reveals that six molecules of compound 1 form a cage and that theSages are hourglass shaped with a length of approximately 11 A, a mid-pointowidth of 4.2 A, and a maximum upper and loyer width of 6.3 A.…”