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Патент USA US2412209

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Patented Dec.’ 10, 1946
UNITED STATES PATENT OFFICE
2,412,209
I PREPARATION OF ALIPHATIC AIMINES
Joseph B. Dickey and James G. McNally, Roches
. ter, N. Y., assignors to Eastman Kodak Com
pany, Rochester, N. Y., a corporation of New ~
Jersey
No Drawing. Application Apr-i122, 1943,
Serial No. 484,078
-
4Claims. (01. 260-584)
1
2
This invention relates to aliphatic hydroXy
amines and to the preparation thereof.
dihydric alcohol is led over the catalyst, e. g.
nickel on kieselguhr, in a glass or metal tube
It is known that aliphatic monoamines can be
heated to the desired temperature.
The following examples will serve .to illustrate
prepared by condensing monohydric alcohols
with ammonia, in the presence of a metallic hy-. 5 the manner of practicing our invention.
drogenation
catalyst.
When
dihydric
alcohols,
_ _
such as tetramethylene glycol and pentamethyl-
_
_
_
,
Example 1' 2 EZeEZJZLZZQZZWthQW) anon]
ene glycol, are condensed with ammonia in the
v
'
presence of a hydrogenation catalyst, however, a
400 g. of methylene 8137001 ‘
considerable amount of cyclization occurs with 10 (HMMHPW
the formation of compounds such as pyrrol and
,
CH2_()_CH2___CH,_OH)
pyridine, so that tetramethylene diamine and
_
I
pentamethylene diamine cannot be commercialwere cmirged mto an autoclave‘ with 20 g- of
h, prepared by thiS method_ For this season 8p.
Raney nickel catalyst. The glycol was then sat
parently tetra- and pentamethylene diamines, as 15 mjated with ammoma from 9‘ cyhnder of ammo‘
well as high,3r molecular weight diamines, are
mm. The autoclave was closed and the mixture
prepared by reducing the appropriate dinitri1es_ I
heated with shaking at 205° C. for 31 hours. The
We have now found that dihydnc ether a1co_
autoclave was then cooled and the contents made
hols,' such as diethylene glycol and triethylene
acid with hydrochlonc acid- The non-Mic m9‘
glycol, can he condensed with ammonia, in the 20 terials were then removed from the mixture by
presence of hydrogenation catalysts to give good
distillation under reduced pressure. The residue
yields of hydroxy amines. Some cyclization oc-.
Wa§ treated Wlth an excess of 50 Percent aqueous
curs and some formation of diamines occur, but
Sodlum hydroxide t0 free the M91110, bodies fmm
the hydroxy amines can be readily separated
their hydrochlorides. The amines which sepa
from the cyclic compounds and the dmminea 25 rated were removed from the aqueous liquors and
We have also found that aliphatic diamines can
dlsmled under redilced pl‘essure-
be prepared in good yields from hexa- to decameth lane
1 cols b
condensin
the
l cols with‘
1
ammgnia, igny the piesence of ga hygrsggenation
catalyst
I
'
'
boiling at 95° to 105° C. at 5 mm. of mercury pres
so sure and 40 g. of
It is accordingly, an object of our inventioi; to
provide new hydroxy amines.
2° 8- 0f
H,N_.CtH4_/Q_CQH4_O_CZH4__NH,
HO-—CzH4,—O‘—CzH4—O—-CzH4-—NH:
A further ob ect
.
is to provide a process for prepmng such hy_
'
o
c
boiling at 120 .to 1.30 C. at 4 mm. of‘ mercury
droxy amines and a. process for, preparing di-
pressure, were obtained. The residue from the
di tin ti
6 t i d m h. b m
ec nd
hereinafter.
and tertiary amines.
amines.
Other objects will become apparent at
In accordance with our invention, we condense
ammonia with a dihydric alcohol characterized
by one of the following general formulas:
s
a on
on a ne.
0 n8 8
0
My
Example. 2.——2-(2-hydro:ryethoxy)-eth1/lamine
424 g’ of diethylene glycol
/
Heme
g er
*0 an
'
g.o nceon
H2-—CH2—-O
eseg
rwerepace
Ho"CH"*"CH2_O(O”CH’_CH-’)‘_oH
an autoclave. The mixture was saturated with
wherein n represents a positive integer of from‘6
ammonia from a cylinder of ammonia. _ The au
to 10 and :1: represents a positive integer of from
toclave was then closed and the mixture was
1 to 2, at a temperature of from about 160° C. to 45 heated at 205° C. with shaking for 37 hours. At
about 400° C., in the presence of a hydrogenation
the end of this time, the autoclave was cooled and
catalyst. When diethylene glycol is employed as
a starting material, the temperature employed is
advantageously from 200° to 250° C. Exemplary
the contents made acid with hydrochloric acid.
The monobasic materials were then removed
from the mixture by distillation under reduced
of hydrogenation catalysts which we have em- 50 pressure. To the residue was added an excess of
ployed are Raney nickel, copper chromite, copper nickel chromite, iron, cobalt, titanium, cop-
50 percent aqueous sodium hydroxide to free the
amino bodies from their hydrochlorides. The
per, etc. The condensations can be carried out
amines which separated were removed from the
in the‘ liquid or gaseous phase. If the condensa-
aqueous liquors and fractionally distilled, ?rst at
tions are carried out in the gaseous phase, the no ordinary pressures and then under reduced pres
2,412,209
4
with a dihydric alcohol 0! the following formula:
HO—CH2-——CH2—-O-—CH2-—
CH2-—O—CH:-—-CH2—-OH
sures. Morpholine boiling at 182° to 184° C. at
745 mm. of mercury pressure, and a good yield
of 2-(2-hydroxyethoxy)-ethylamine boiling at
123° C. at '1 mm. of mercury pressure, were ob
tained. In addition there was obtained a small
amount of some amines boiling between 135° C.
and 180° C. at '7 mm. of mercury pressure.
Example 3.-—1,10-'didmino decane
at a temperature of from about 200° to about
250° C., in the presence of a hydrogenation
catalyst.
~
.
2. A process for preparing an aliphatic hy
droxyamine comprising condensing ammonia
10 with a dihydric alcohol of the following formula:
82 g. of decamethylene glycol were placed in an
autoclave with 10 g. of Raney nickel. To the
mixture were added 180 g. of ammonia by passing
ammonia into the mixture __from a cylinder of
at a temperature of from about 200° to about
ammonia; The autoclave was then closed and
250° C.,in the presence of a metallic hydrogena
the mixture heated with shaking at 220° to 260° 15 tion catalyst.
3. A process for preparing a hydroxyamlne
C. for 40 hours. The autoclave was then cooled
and the contents steam distilled to obtain the de
comprising condensing ammonia with a dihydric
camethylene diamine. A 25 percent yield of dia
alcohol of the following formula:
mine melting at 61° to 62° C. was obtained.
In a similar manner octamethylene glycol can >
be condensed with ammonia to give 1,8-diamino
‘octane and‘ hexamethylene glycol can be con
densed with ammonia to give 1,6-diamino hexane.
What we claim as our invention and desire to
be secured by Letters Patent of the United States
is:
1. A process for preparing an aliphatic hy
droxyamine comprising condensing ammonia
CH:-—O-—CHz-—CH2-—OH
at a temperature of from about 200° to about 250°
C., in the presence of a nickel hydrogenation
catalyst.
\
'
4. 2- [2 - (Z-hydroxyethoxy) - ethoxyl-ethyla
mine.
JOSEPH B. DICKEY.
JAMES G. McNALLY.
I
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