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Патент USA US3073873

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United grates Fatent 151cc
3,073,863
Patented data. 15, 15.053
3.
f3.
EXAMPLE 1
3,073,363
’
PARATEEN GXY-JMIETYLAM
Preparation of p-Nonyl Phenoxyacezyl~p~Amin0phenol
HEY it}
DERlVATlVE§
‘
m't, End, and Cl
grams to tallies
i rporation oi’ in
One hundred and sixty-four (164) g. of 1PAP, 12 g.
of boric acid, and 608 g. of a toluene solution which
contained 423 g. of [3-(p-nonyl)phenoxyacetic acid, were
mixed and heated to re?ux temperature under a nitrogen
Burton,
-..torres, inc,
~
' 3 May 5, 1.950, .3 a.
.1 Claim. ($2.
4
-
atmosphere. After re?uxing had continued for about 3
hours, 36 ml. of Water formed in the reaction had been
w‘
This invention relates generally to derivatives of p-ami 10 removed as an azetrope with toluene. The resulting
reaction mixture was stripped of 112 g. of toluene, and
pounds having the formula:
the remaining mixture treated with 15 g. of char in 88%
nophenols, and more particularly, to a new series of com
isopropanol. Attempts to crystallize the product by di
luting the solvent to 40% with water were unsuccessful,
15 resulting in a black oil. The oil was stripped of solvent
to form a very stilt tar containing the ?nal product.
wherein R is selected from the group consisting of alkyl
EXAMPLE 2
substituted phenoxy radicals. Compounds coming within
this formula have excellent oil solubility, and are useful
Preparation of 2,4-Di-Sec0ndary Bm‘yl Phenoxyacetyl
as antioxidants for rubber and various resinous polymers.
p-Aminophenol
The present compositions are prepared by reacting 20
One hundred and sixty-four (164) g. PAP, 12 g.
boric
acid, and 623 g. of toluene solution containing
“PAP”) with an acid which will provide the desired acyl
395 g. of 2,4-di-secondary butyl phenoxyacetic acid were
radical RCH2CO—, in the presence of boric acid, as rep
mixed and heated to re?ux under nitrogen atmosphere.‘
resented by the following equation:
25 During the ?rst three hours of re?uxing, 32 ml. of water
were separated from the reaction mixture. The reaction
mixture, which solidi?ed when cooled, was stripped of
p - aminophenol
(hereinafter
sometimes
abbreviated
toluene at reduced pressure (about 10 mm. Hg), decolor
ized with 15 g. of activated carbon, and recrystallized
30
from 40% isopropanol. On cooling during recrystalliza
tion, the product tended to oil out, but agitating the re
crystallizing mixture at 5 to 10° C. solidi?ed the oil par
ticles. The crystallized product was ?ltered off, and
washed ?rst with 200 ml. of cold 40% isopropanol, then
wherein R has the meaning ascribed to it above. Prefer
ably the acid reactant is dissolved in a suitable solvent
which will not enter into the reaction but which will 35 with sodium hydrosul?te water, and, ?nally, with tap
water. The product was then recrystallized from 40%
provide a good reaction medium, such as toluene, and the
isopropanol, yielding 287 1g. of a slightly yellow solid;
reaction is carried out under reflux conditions. Prefer
melting point, 1405-1415” C.
ably, also, an inert atmosphere, e.g., carbon dioxide or
nitrogen, is provided in the reaction vessel while the re
EXAMPLE 3
action is taking place. During the re?ux reaction water 40
Preparation
of
p-Secondary
Butyl Phenoxyacetyl
formed in the reaction is removed as an azeotrope with
p-Aminophenol
toluene. After the reaction has been completed, the
toluene is stripped from the reaction mixture, the re
Thirty-nine (39) g. PAP, 3 g. boric acid, and 306 g.
maining material being then preferably decolorized with
of a toluene solution containing 69.5 g. of ?-p-secondary
activated carbon in a suitable solvent such as isopropanol,
butyl phenoxyacetic acid were mixed and maintained
and the decolorized product crystallized from the solvent. 45 at re?ux temperature under nitrogen atmosphere for 61/2
The p-aminophenol and many species of the reactant
hours, during which time 10.4 ml. of water was removed
acid, which are used as starting materials in preparing
therefrom as an azeotrope with toluene. The reaction
the present compositions, are commercially available.
mixture was stripped of 263 g. of toluene, and the re
Those species of the acid which may not be easily pro 50 maining mixture was recrystallized from 40% isopro
cured in the market may be prepared by methods well
panol. Oil which separated initially during the recrystal
known in the art. Representative acids which may be
lization was solidi?ed when the recrystallization medium
reacted satisfactorily with PAP to produce the instant
was cooled to 2° C. The recrystallized product was
novel compounds are those derivatives of acetic acid in
recovered by ?ltration, washed with isopropanol, and
which the R-group, in the above formula, is 2,4-di-second 55 dried to give 67 g. of a product of slight yellow color;
ary butyl phenoxy; p-secondary butyl phenoxy; and
melting point 119-l20.5° C.
What is claimed is:
p-nonylphenoxy. Further operative acids are those de
rivatives of acetic acid in which the R-group is
2,4-di-secondary butyl phenoxyacetyl-p-aminophenol.
References @ited in the ?le of this patent
UNITED STATES PATENTS
60
wherein R’ and R" may be hydrogen or an alkyl group
provided that R’ and R" are not both hydrogen, and
CH3
0
2,423,730
2,653,158
2,711,415
65
2,730,500
2,852,540
2,945,870
wherein x is an integer less than 5.
The following speci?c examples illustrate representa
tive compounds encompassed by our invention, and a
method for their production.
Salminen ____________ __ July 8,
Young et al. _________ __ Sept. 22,
Cottle ______________ __ June 21,
Young et al. _________ __ Jan. 10,
Young et al. _________ .... Sept 16,
Young ______________ __ July 19,
1947
1953
1955
1956
1958
1960
OTHER REFERENCES
Lucas: Organic Chemistry (2nd ed.), pages 508-509,
published by American Book Company, New York
(1953).
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