The thio-Claisen rearrangement of prenyl phenyl sulfide (γ, γ-dimethyl allyl phenyl sulfide) (1a) gave 2-isopropyl-1-thiacoumaran (2), 2, 2-dimethyl-1-thiachroman (3) and 3-methyl-1-butenyl phenyl sulfide (4). The similar reactions of β, γ-dimethyl allyl phenyl sulfide (7a) and crotyl phenyl sulfide (12) were also studied. From these results, the effect of γ-methyl groups of allylic phenyl sulfides on the rearrangement reactions was discussed.
Tetrafluorophthalonitrile reacted readily with nucleophilic reagents such as methanolic potassium hydroxide, aqueous ammonium hydroxide or dimethylamine. In all cases, the fluorine atom of 4-position was replaced first, and 3, 5, 6-trifluoro-4-methoxy-, 3, 5, 6-trifluoro-4-amino- and 3, 5, 6-trifluoro-4-dimethylamino-phthalonitrile were obtained. Tetramethoxyphthalonitrile was obtained if an excess methanolic potassium hydroxide was used. The structures of these products were determined by 19F and 1H nmr spectra.
An apparatus for simultaneous differencial thermal and evolved gas analysis under high pressure, useful in the field of organic synthesis under various gaseous pressure, was developed. It consists principally of a couple of particular small steel autoclaves, glass sample containers and thermal and pressure detectors. The behavior of potassium phenoxide and mono potassium p-hydroxy benzoate under carbon dioxide pressure was studied by using the apparatus.