Download Title Syntheses of Antioxidants for Fats and Oils.

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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
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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-