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Title Author(s) Citation Issue Date URL Syntheses of Antioxidants for Fats and Oils. (I) Sisido, Keiiti; Kuyama, Hirosi 京都大学化学研究所報告 (1951), 25: 73-74 1951-09-10 http://hdl.handle.net/2433/74263 Right Type Textversion Departmental Bulletin Paper publisher Kyoto University 28. Alkylaton of Dioxybenzenes by p-Toluenesulionic Acid Ester. (II) Shinsaburo Oka (Nodzu Laboratory) In the previous pyrocatechin, paper resorcin, prepared 70-80% the corresponding it was reported hydroquinone about the alkylation by p-toluenesu1fonic as in the monoalkyl ether cases of the lower esters. from the dialkyl was attained from methanol, in which the dialkyl ether or petroleum tion from ether ether, if it is crystalline. of methanol The yields of monalkyl 29. by fractional we was performed is nearly by means or fractional as of the of aq. NaOH. recrystallisation insoluble. or recrystallisation Dialkyl ether was purified from benzene by recrystallisa- and benzene. and dialkly ethers using 0.2 mol dioxybenzene Syntheses esters enable distillation was refined by redistillation a mixture respectively, Now But in these cases, separation ether was not The separation Monoalkyl acid ester. in yield p-toluenesulfonic acid ester (C8, C103C121C14, C16) from alcohols and p-toluenesulfonyl chloride by using picolin (B.P. 1300-150°) as the condensation reagent. The alkylation of the dioxybenzene by these higher easily (C1, C2s C4, C6) of were about 50-60% and 0.1 mol sodium of Antioxidants for Fats and 20-.25%, for 0.1 mol ester. and Oils. (I) Keiiti Sisido and Hirosi Kuyama (Sisido Laboratory) In view acid of the or NDGA, synthesized. recent several The product Hydroquinone methyl which was then methylated of its hydrobromide, devefopment dinuclear indicated allyl • of an antioxidant, phenols with the with an asterisk ether analogous bis-(2, 5-dimethoxyphenyl)-2, was rearranged were to 2-allyl-4-methoxyphenol to 2, 5-dimethoxyallylbenzene and the Grignard (yellow reagent (yellow oil, b.p. 142- with iodine, giving a meso and racemic 3-dimethylbutane* structure (*) is a new compound. 1-(2, 5-dimethoxypheny1)-2-bromopropane* 152°/5-7 mm.) was treated nordihydroguaiaretic oil, b.p. mixture 240-25075-6 of 1, 4mm., yield 27%). On demethylation by hydrobromic acid and recrystallizations from benzene a mixture of meso and racemic free phenols, 1, 4-bis-(2, 6-dihydroxypheny1)2, 3-dimethylbutane,* 144-145°. was obtained in white ( 73 ) powder. meso-Tetraacetate,* m.p. 2,5-Dimethoxyallylbenzene was isomerizedto 2,5-dimethoxypropenylbenzene by potassiumhyroxide and the hyrobromideaddition compound was condensedby reducediron powder to 3,4-bis-(2, 5-dimethoxyphenyl)-hexane* (yellowoil, b.p. 2152£0°/5mm.) The meso compound*whichcrystallized(yield 11%) melted at 118119°. The demethylationgave 3, 4-bis-(2, 5-dihydroxypheny1)-hexane,*m.p . 219-220°; tetraacetate,*m.p.149-150°. a-Diisosafrolewas treated with phosphoruspentachloridein refluxing toluene and decomposedwith iced aqueoussodiumcarbonate solution yieldingwhite crystals of carbonyldioxyderivativeof diisosafrole,*m.p. 152.5-153°,yield, 37%. Demethylationof metanetholewith methylmagnesiumiodidegave 1-ethy1-1-(phydroxypheny1)-2-methyl-6-indanol* in colorlessneedles,m.p. 158-159°. The antioxidativeproperty and the toxicityof these compoundstogether with 3, 4-bis-(m,p-dihydroxypheny1)-hexane* and 3, 4-bis-(m,p-caraonyldioxypheny1)hexane* (Sisido,Nozakiand Kuyama,J. Org. Chem.,14, 1124(1949))were tested in the laboratory of Prof. Takata. The results will be publishedelsewhere. 30. The Study on the Reaction of Acetylene High Pressure. (III) Synthesis Junji of N-Vinyl Furukawa under Phthalimide and Akira Onishi (Oda Laboratory) N-vinyl phthalimide is now prepared by pyrolysis of 8-acetoxyethylphthalimide (over-all yield 50%) and the polymer is a new source of polyvinylamine. in one patent that the compound was also obtained by the reaction It is claimed of C2H2 and phthalimide at high pressure and temperature with Hg salt as catalyst. (C.A. 35, 32667 (1941)). But our repetition of this methodidisclosed that no vinyl phthalimide could be obtained and metallic-Hg was liberated. Attempts were then made to accomplish this reaction by means of various catalysts, including (CH3C00)2Zn, Zinc stearate and (CH3C00)2Cd. (CH3C00)2Cd has proved successful. The others were less effective. also used, but without success. Catalyst (g) Zn Stearate 3 (CH3C00)2Cd 5 HgC12 6 The results Reactn. Temp. Phthalimide potassium are shown in the following Reactn. time vinyl P.I. Resin 220°C 9 hrs. 0.5g (10%) 5.3g 200 190 2 3 3.0g (50%) 0 6.0 2. 0 phthalimide. P.I. 20g and xylene 40g are used in all cases. ing for recovered P.I. ( 74 ) was table. Yields are calculated allow-