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Патент USA US2128887

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Patented Aug. 30, 1938
2,128,887
UNITED STATE"-S are TENT Bowl-cs
2,128,887
"PRODUCTION »OF SATURATED‘ MORPHO
'
:LINE ALKANOL-ALKYL ETHERS
‘Alexander L. Wilson, .PittsburghaPanr assignonlby
mesne assignments, to UnionOarbide and Car
‘bon’Cjorporation, a corporation of‘New'Yoi‘k
No Drawing. Original application December 4,
“1934, Serial No. 755,9 12. . ‘Divided and thisap
‘ V plication ,May 5, 1937, Serial No. 140,837
5 Claims. (Cl. 260-247)
This invention relates to ‘the production of and each R represents either hydrogen or \the
morpholine'ethanolsand certain of their ethers. same or- a di?erent alkyl group:
‘One modi?cation of the invention concerns the
production of the said compounds by a process
I. (a) 2XCHR—OHR—O—CHR—CHRX+4NH: :aqua or alcohol
a B5’ dihalogeuated dialkyl other
,5 thatinvolves reacting a. '13s’ dihalogenated dialkyl
ether'with ammonia in aqueous or alcoholic solu
tion, or-With morpholine or a substituted mor
pholine in an alkaline vmedium. The resultant
reaction pro-ducts .are heated and reacted with a
N H alkaline
A
o/
‘_ o+nHx
‘\onn-onn/zéonnfona/
an’ excess of morpholine with or without diluent
ride or intermediateproduct, azstrong base such
410
‘CHE-"OER
a ,dimorpholinium halide
'15 ‘or, as in the reactionroftmorpholine with di
‘as- sodium-hydroxide isrrequired.
.
‘ solution
‘;1.0 ?xed alkalisuch as caustic soda, preferably in
‘excess. The reaction mixture must be maintained
alkaline-during the ?rst step of the process either
:by the use .of an excess .of ammoniacal solution,
chlordiisopropyl ‘tether, why caustic ‘alkali. For
‘the decompositionlof ‘the dimorpholinium chlo
———-—>
GHR—Q HR
II.
OHR-—OHR
21:15
can-‘one
0. (+Na0H hot)
\
—————)
'
When in the ‘process, p5’ dichlordiisopropyl
ether is reactedwith-morpholine, there is pro
duced as at'?nal :product, dimethyl morpholine
ethanol, which is a stronglyrbasic water-soluble
amine boilingat 230?’ C. ‘under. atmospheric pres
z25 sure.
i :25
‘According ‘to zanother ‘modi?cation of the .in
'vention, a vinyl ether of 1a morpholine ‘ethanol,
‘which may be produced in a manner described
; $30
above vin the process of producing ~morpholine
~~ethanol, or in other ‘suitable manner, is hydro
lyzed and converted‘ to 'a'morpholine ethanol by
acidifying the said ether inaqueous solution fol
lowed "by a treatment of the resultant product
9,5 with a‘strong ‘base, such as sodium hydroxide.
Thus itis possible to securev Very high yields ,of
morpholine ethanol from (the dihalogenated di
alkyl ether used as starting material.
The morpholine 'alkanol-vinyl ethers produced
H4“ in the ?rst step of the process further may be
convertedvto saturated morpholine alkyl ethers
by ‘the catalytic vapor phase hydrogenation
‘thereof‘at temperatures somewhat above the boil
ingipoint of the morpholine alkanol alkyl ether
' being‘produced.
The liquid condensate from the
‘ hydrogenation is then boiled with aqueous min
eral acid or the equivalent’to decompose any un
reacted morpholine alkanol vinyl ether, follow
ing' which an excess of sodiumphydroxide is added
7:50 and the amine layer which then separates is
fractionally distilled. The type of reactions in
volved in the various steps of this invention is
illustrated by the following equations, in which
X stands, for any halogen, n=either 42 or 4,
7-30
>N——CHR—CHRO OHzGHz
one-011R
- a morpholine alkanol ethyl ether
The followingvexamples. serve .to ‘illustrate ‘the
invention:
‘
'
_
‘ Example ‘1
A mixture of 83 pounds 5,6’ dichlordiethyl
ether, 176 pounds of water and 98 pounds of 40
ammonia was reacted to completion .in an .agi
tated closed vessel during a period of four to
?ve ‘hours at a‘temperature within the range
from 65° to 80° C., and under a pressure rang
ing vfrom 45 to 75 pounds per square inch gauge. 45
The reaction product was cooled to around
40° C., and was then treated ‘with a- slight excess
of sodium :hydroxide. ‘The ammonia,tfree low
boiling amines, and water vwere then distilled
from the mixture, leaving‘ behind a residue 'rof
sodium chloride containing ‘the ‘less volatile
amines. These latteramines :wereextractedfrom
the sodium chloridewith-benzeneandiwere added
to the distillate. Refractionation of, this :faug
pmented distillate -then yielded ,successive time
2,128,887
sodium hydroxide was ‘then added whereupon the
ture of water and morpholine ethanol vinyl liquid strati?ed, forming an amine layer which
ether, morpholine, and morpholine ethanol. The was separated and was fractionally distilled.
The fraction thereof distilling within the range
morpholine ethanol vinyl ether fraction, boil
of from 204° to 206° C. and containing mor
ing at 209° to_211° C., and the fraction con
taining morpholine ethanol and boiling within pholine ethanol ethyl ether, was separately re
the range 'from'2l5° to 235° C., were separately‘ covered, and represented a yield of 61% based
recovered. In this example ammonia and di-, upon the original morpholine ethanol vinyl ether
.
chlordiethyl ether were employed in the molar reacted.
It will be understood that although reference 10
10 ratio of 10 : 1. '
The molar ratio of ammonia to dihalogenated is made herein to distillations of the various re
dialkyl ether may vary between rather wide action mixtures under atmospheric pressure, it
is readily possible, and under some conditions
limits, ranging from around 2 : 1 to a ratio of
desirable, to conduct these distillations under
20 or more to 1. In general, the yield of mor
subatmospheric
pressures, in order to secure the
pholine alkanol vinyl ether increases as. the am
usual
advantages
of reduced distillation tempera
monia to dihalogenated dialkyl ether decreases,
tions containing ammonia, a constant boiling mix- '
tures and protection against heat decomposition
of the compounds present.
and the maximum obtainable yield of morpho- 7
line ethanol increases similarly.
.
As shown in the various examples, the free
Other Be’ dihalogenated dialkyl ethers may be
20 substituted for that speci?cally named in the
foregoing example. Moreover, it is possible to
substitute morpholine for the ammonia in the
?rst stage of the process, as indicated by the
following example:
v
amines may be obtained from solutions of their 20
hydrochlorides by treatment with less volatile
bases.
In the case of sodium hydroxide, this may
‘be added in the combining proportion, Volatile
amines distilled off, the higher-boiling amines
'
~ extracted from the residue with alcohols, such as
isopropanol, and the amines recovered.
Y Example 2
on the
other hand, an excess of sodium hydroxide may
A mixture containing 1/2 mol each of 55’ di
chlordiisopropyl ether, morpholine, sodium hy
' be used, volatile amines distilled'off, and the
droxide and water was charged into a ?ask under
P30 reflux and was reacted at the boiling point for
?fteen hours with the addition of suf?cient water
to keep in solution the sodium chloride produced.
The reaction product then'was distilled, and un
reacted ether and morpholine thus removed.
1135 The residue, containing salt and amine hydro
higher-boiling amines,’ or both the latter and-the
volatile amines present prior to the distillation,
may be decanted or extracted from the caustic
layer with a volatile solvent such as benzene.
Other means than those speci?cally described
may be used for recovery of the desired amines. v_
Thus, the reaction mixture from the ammonia
" 35
dichlorethyl ether reaction maybe concentrated
chlorides, was evaporated to dryness and ex
and unreacted materials‘ removed,‘ followed by a
tracted with isopropanol, thus throwing out the fractional crystallization 'of the amine hydro
sodium chloride. The extract, upon evaporation ' chlorides, and a treatment with caustic alkali of
yielded dimethyl dimorpholinium chloride in the the appropriate crystalline fraction; or the said
form of a stable white salt of high~melting point, reaction mixture may be concentrated, and then
soluble in water and in alcohols. This salt was heated with'an excess of alkali, thus forming a
heated to 150° C. with a strong hot aqueous solu
layer of mixed amines. This amine mixture then
tion of sodium hydroxide, yielding an _oil layer may be- fractionally ‘distilled, and the various
insoluble in the sodium hydroxide but soluble in amines recovered.
45
.
45 benzene. A benzene extract of this layer wasi
Although the reaction between the dihalogen
distilled, and an amine fraction boiling at 220°
ated ethers and ammonia may be conducted at
to 225° C. under atmospheric pressure was sep
pressures around atmospheric, it is preferable to
arately recovered. This corresponds to di
use low superatmospheric pressures in order to
methyl morpholine ethanol vinyl ‘ether, and was 'eifect the most eflicient operation; and pressures
a strong base, soluble in benzene and alcohols, up to 100 pounds per square inch gauge are par
and less than 1% soluble in water.
ticularly satisfactory.
'
The intermediate product or morpholine al
The morpholine alkanol alkyl ethers prepared
kanol vinyl ether formed in the ?rst stages of the in accordance with the invention are excellent
process, is readily convertible to the correspond
high-boiling solvents for gums; resins, such as 55
vinyl resins; and cellulose derivatives. They also
ing saturated morpholine ether, such as, for ex
ample, morpholine ethanol ethyl ether, by a are useful as reaction solvents in Grignard syn—
theses andv reactions involving the liberation of
vapor phase catalytic hydrogenation, as illus
acid, in acetylations with acetyl chloride, and in
trated below.
'
'
dehydrohalogenations. They may be used in
>
Example 3
(El) preparing volatile emulsifying agents and mer
A reaction tube of a well known heat-resistant cerizing penetrants, and in dyeingoperations.
glass was ?lled with chips of a porous arti?cial
The term “a morpholine ethanol alkyl ether”
?lter stone essentially consisting of silica that and similar terms appearing in the speci?cation
had been impregnated with a mixture of nickel and claims are intended to ‘designate not only 65
andthorium oxides which then were reduced morpholine ethanol alkyl ether per se but also
with hydrogen. Through this catalyst cham
substituted morpholine ethanol alkyl ethers, such
as dimethyl morpholine ethanol ethyl ether.
This application is a division of my copending
of‘ hydrogen and morpholine ethanol vinyl ether
vapor in the ratio of '4 to 5 mols of hydrogen application, Serial No. 755,912 for U. S. patent, 70
per ‘mol. of the ether. The resultant vaporsrwere ?led December a, 1934, entitled “Production of
condensed at 20° C., yielding a liquid, which then . morpholine ethanols and certain ethers thereof.”
It will be understood that the invention is not
was boiledwith an excess of dilute aqueous hy
ber heated at 200° to 250° C. was passed a stream
drochloric acid, thereby decomposing unreacted
morpholine’ ethanol vinyl ether.
An excess of
limited by the speci?c disclosure appearing in
the examples, but that on the contrary it is sus
75
3
2,128,887
ceptible of modi?cation within the scope of the
sure containing the morpholine ethanol ethyl
appended claims.
ether.
'
I claim:
1. The process of making a morpholine ethanol
ethyl‘ ether, which comprises hydrogenating a
morpholine ethanol vinyl ether in the vapor phase
in the presence of a hydrogenating catalyst.
2. The process of making a morpholine ethanol
ethyl ether, which comprises hydrogenating a
10 morpholine ethanol vinyl ether in the vapor phase
in the presence of a hydrogenation catalyst, treat
ing the resultant reaction mixture near the boil
ing temperature with aqueous acid solution, re
acting this mixture with an excess of strong
15 alkali, thereby effecting strati?cation of the mix
ture into a plurality of layers including an amine
layer, separating the amine layer from the re
‘
4. The process of making a morpholine ethanol
ethyl ether, which comprises hydrogenating a
corresponding morpholine ethanol vinyl ether in
the vapor phase, heating the reaction mixture
with a dilute mineral acid, thereby decomposing
unreacted morpholine ethanol vinyl ether, react
ing the resultant mixture with an excess of a
strong base, thereby stratifying the mixture into 10
a plurality of layers including an amine layer,
i’ractionally distilling the said amine layer, and
separately recovering the fraction containing the
morpholine ethanol ethyl ether.
5. The process of converting a pp’ dihalogen 15
ated dialkyl ether to a morpholine alkanol ethyl
ether, which comprises reacting a 13;?’ dihalogen
mainder of the mixture, fractionally distilling the
said layer, and separately recovering the fraction
20 containing the morpholine ethanol ethyl ether.
3. The process of making morpholine ethanol
ethyl ether, which comprises hydrogenating mor
pholine ethanol vinyl ether in the vapor phase
caustic alkali, thereby producing a morpholine
alkanol vinyl ether, hydrogenating the latter in
in the presence of a hydrogenation catalyst, treat
25 ing the resultant reaction mixture near the boil
tion catalyst, heating the resultant reaction mix
ing temperature with aqueous acid solution, re
acting the mixture with an excess of strong
alkali, thereby effecting strati?cation of the mix
ture into a plurality of layers including an amine
30 layer, separating the amine layer from the re
mainder of the mixture, fractionally distilling the
said layer, and recovering the fraction boiling
around 204° to 206° C. under atmospheric pres
ated dialkyl ether with an aqueous solution of
a compound selected from the group consisting
of ammonia and a morpholine, treating the re 20
sultant reaction mixture with an excess of a
the vapor phase in the presence of a hydrogena
ture with an aqueous solution of an inorganic
25
acid, treating the acidi?ed mixture with an excess
of a strong alkali thereby stratifying the mixture
into a plurality of layers including an amine
layer, fractionally distilling the latter, and sepa 30
rately recovering therefrom the fraction contain
ing the saturated morpholine alkanol ethyl ether.
ALEXANDER L. WILSON.
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