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Патент USA US2407203

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Patented Sept. 3, 1946
2,407,203
UNITED STATES PATENT OFFICE’
2,407,203
oc-AMINO-"y-ALKOXYBUTYRIC ‘ACIDS
AND
METHOD OF PREPARING THE SAME
Quintin P. Cole and Richard 0. Roblin, Jr., 0141
Greenwich, Conn, assignors to American Cy
anamid Company, New York, N. Y., a corpora
tion of Maine
No Drawing. Application May 29, 1944,
Serial No. 537,968
r
1 Claim. (Cl. 260-534)
2
This invention relates to new organic com
pounds and to a method of preparing the same.
?ned in the appended claim. All parts are by‘
weight unless otherwise stated.
The new compounds of the present invention
may be represented by the following general for
mula:
'
“
Example 1
‘
‘ Fifty-seven (57) parts of sodiophthalimido
malonic ester and 39 parts of ,3-methoxyethyl
bromide were heated under reflux for 62 hours.
The excess ,B-methoxyethyl bromide was removed
In this formula R is an alkyl radical of from 1
by distillation, and the sodium bromide formed
to about 18 carbon atoms. These compounds may 10 in the reaction was removed by trituration of the
be prepared by hydrolyzing l-alkoxy-B-phthal
product with water. The residue of 2-(p-meth
oxyethyl) ‘-2-phthalimidomalonic ester was crys
tallized from alcohol.
amidopropane-3,3-dicarboxylic acids. ‘ The reac
tion may be represented by means of the follow
ing equation:
'
Thirty-one (31) parts of Z-(B-methoxyethyh
15 2-phthalimidomalonic ester, 40 parts of ethyl
alcohol, and 90 parts of 5N aqueous sodium hy
droxide were combined and heated under re?ux .
for 1 hour. Strong acidi?cation with hydro
chloric acid yielded a precipitate of l-methoxy
20
3-phthalamidopropane-3, B-dicarboxylic acid.
Twenty-?ve
(25)
parts
of
1-methoxy-3
phthalamidopropane-3,3-dicarboxylic acid, 400
parts of water, and 48 parts of concentrated hy
drochloric acid were combined and heated on a
g steam bath for 11/2 hours. Two hundred thirty
This reaction will be described in detail herein
(230) parts of concentrated hydrochloric acid
after. The new compounds may also be prepared
' was added, and heating was continued for 45
by other methods which will occur to those
minutes. The cold solution was ?ltered to re
skilled in the art. Obviously, salts of our new
move phthalic acid, and the ?ltrate was evapo
acids may be prepared by simple neutralization 30 rated
to dryness at reduced pressure. The resi
with a suitable alkali, ammonia, or a moderately
due,
consisting
largely of the hydrochloride salt,
strong amine, or by methods of double decompo
was taken up in 150 parts of alcohol and 20 parts
sition. The acid salts are also formed upon treat
of pyridine. a-Amino-v-methoxybutyric acid
ment with equivalent amounts of a suitable min
eral or organic acid.
crystallized from the solution after standing for
a short time.
The new compounds of the present invention
Example 2
Those in
which R is a lower alkyl radical, such as methyl,
Sixty (60) parts of sodiophthalimidomalonic
have antibacterial properties and are useful as
ester and 45 parts of B-butoxyethyl bromide were
germicides and in chemotherapeutic prepara
heated together for 40 'hours at 150° C. The ex
tions. Those in which R is a higher alkyl radical, 40 cess p-butoxyethyl bromide was removed by dis
for example, octyl, possess surface-active proper
tillation at reduced pressure, and the sodium
ties and may be used as such or in the form of ,
bromide formed in the reaction was removed by
their alkali or acid salts in the production of wet
"trituration
with water. The residue of 2-(5
‘
are useful for a variety of purposes.
ting agents, detergents, ?otation reagents, and
butoxyethyl)-2-phthalimidomalonic ester was
the like. Other uses of these new compounds will 45 crystallized from alcohol.
occur to those skilled in the art.
Thirty-four (34) parts of Z-(c-butoxyethyD
Preparation of representative members of this
new class of compounds will now be described
Z-phthalimidomalonic ester, 45 parts of ethyl
alcohol, and 100 parts of 5N sodium hydroxide
in the following examples, in which their syn
were combined and heated under re?ux for 1
thesis from readily obtainable intermediates is 50 hour. The solution was cooled and strongly acid
described. It will be understood, of course, that
i?ed with hydrochloric acid to precipitate the
these examples are intended to be illustrative
l-butoxy-3 - phthalamidopropame-3,3 - dicarbox
only. since various modi?cations in the conditions
ylic acid.
of the various reactions may be made without
Twenty-seven (27) parts of l-butoxy-B
departing from the spirit of the invention as de
phthalamidpropane-3,3 -dicarboxylic acid, 400
2,407,203
3
parts of water, and 55 parts of concentrated hy
drochloric acid were heated together on a steam
bath for 11/2 hours. Two hundred sixty (260)
parts of concentrated hydrochloric acid was
added, and heating was continued for 45 minutes.
The cold solution was ?ltered to remove phthalic
acid and the ?ltrate evaporated to dryness at
4
moved by distillation at reduced pressure, and
the sodium bromide formed in the reaction was
removed by trituration with water. The residue
of 2- (c-dodecyloxyethyl) ~3-phthalimidomalonic
ester was crystallized from alcohol.
Twenty-four (24) parts of Z-(B-dodecyloxy
ethyl) -2-phthalimidomalonic ester, 35 parts of
ethyl alcohol, and 7 5 parts of 5N sodium hydrox
The residue was taken up in
ide were combined and heated under reflux for
150 parts of alcohol and 20 parts of pyridine and
yielded d-amino-v-butoxybutyric acid on stand 10 1 hour. The solution was cooled and strongly
acidi?ed with hydrochloric acid to precipitate
ing.
the 1-dodecyloxy-3-phthalamidopropane-3,3-di
Example 3
carboxylic acid.
Eighteen (18) parts of l-dodecyloxy-3
Fifty-?ve (55) parts of sodiophthalimido
malonic ester and 45 parts of p-octyloxyethyl 15 phthalamidopropane-3,3-dicarboxylic acid, 300
parts of water, and 40 parts of concentrated hy
bromide were heated together for 20 hours at
reduced pressure.
USO-170° C. The excess o-octyloxyethyl bromide
was removed by distillation at reduced pressure.
and the sodium bromide formed in the reaction
was removed by trituration with water. The res
idue of Z-(p-ootyloxyethyl) -2-phthalimidomalo
nic ester was crystallized from alcohol.
Thirty (30) parts of 2-(p-octyloxyethyl) -2
phthalimidomalonic ester, 40 parts of ethyl alco
drochloric acid were heated together on a, steam
bath for 11/2 hours. Two hundred (200) parts
of concentrated hydrochloric acid was added, and
heating was continued for 45 minutes. The cold
solution was ?ltered to remove phthalic acid and
the ?ltrate evaporated to dryness at reduced
pressure. The residue was taken up in 250 parts
of water and 15 parts of pyridine to yield a-ami
hol, and 90 parts of 5N sodium hydroxide were 25 no-“/—dodecy1oxybutyric acid.
While hydrochloric acid was employed as the
combined and heated under reflux for 1 hour.
hydrolyzing agent in the foregoing examples,
The solution was coo-led and strongly acidi?ed
it will be understood that any other moderately
with hydrochloric acid to precipitate the l-octyl
strong acid, such as sulfuric, may be used in lieu
oxy-3-phthalamidopropane-3,S-dicarboxylic acid.
Twenty-three (23) parts of 1-octyloxy-3 30 thereof. The temperature of the hydrolysis may
also vary from room temperature up to about
phthalamidopropane - 3,3 - dicarboxylic acid, 350
125° C. Of course, at lower temperatures more
parts of water, and 50 parts of concentrated hy
time is required for the hydrolysis. These fac
drochloric acid were heated together on a steam
tors are within the skill of those in the art, and
bath for 11/2 hours. Two hundred fifty (250)
a detailed discussion thereof is not believed to
parts of concentrated hydrochloric acid was
be necessary.
added, and heating was continued for 45 minutes.
The compounds of the present invention are
The cold solution was ?ltered to remove phthalic
generally characterized as being white crystalline
acid and the ?ltrate evaporated to dryness at re
solids with high melting points. The compounds
duced pressure. The residue, which was taken
up in 150 parts of water and 20 parts of pyridine, 40 are very soluble in water, particularly when R
is a short chain alkyl group. They are slightly
yielded a-amino-Y-octyloxybutyric acid.
soluble in alcohol and for the most part insoluble
Example 4
in hydrocarbon and non-polar solvents.
Fifty (50) parts of sodiophthalimidomalonic
We claim:
a-Amino—y-methoxybutyric acid.
ester and 40 parts of B-dodecyloxyethyl bromide 45
QUINTIN P. COLE.
were heated together for 20 hours at 160-170° C.
RICHARD O. ROBLIN, JR.
The excess B-dodecyloxyethyl bromide was re
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