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Патент USA US2119899

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Patented June 7, 1938
" . ‘ 2,119,899
‘UNITED ' STATES
PATENT‘ OFFICE
2,119,899‘
raonuolnc ALIPHATIC ALCOHOLS 0F
men MOLECULAR WEIGHT
-
Hermann Zorn, Lnd'wigshafen - on - the - Rhine,
Friedrich Vogel, Mannheim, and Heinrich Wol
ter, Amsdorf, Germany, assignors to I. G. Far
, benindustrie Aktiengesellschaft, Frankfort-on
the-Main, Germany
No Drawing. Application August 13, ‘1934, Se
rial No. 139,634. In Germany August 1'1, 1933
13 Claims. (Cl. 260-156)
This invention relates to the production of ali
simultaneous employment of metal oxides of the
phatic alcohols of high molecular weight ‘prefera
said kind, the alcohols of high molecular weight
bly those having at least 6 or at least 12 carbon at
oms from low molecular aliphatic aldehydes or
are obtained in a preponderating amount.
The catalysts having a condensing action are
_ ‘5 mixtures containing the said alcohols.
We have found that aliphatic alcohols of high
molecular weight can be obtained in a very ad
generally speaking employed in amounts of up to
about 5 per cent, advantageously from 0.5 to 1
per cent, calculated with reference to the alde
vantageous manner by condensing saturated or ‘ 'hyde. The condensation is carried out at ordinary
‘unsaturated aldehydes of low molecular weight or slightly elevatedtemperature, as for example
10 by means of organic substances having a condens
at from 20° to 40° C. and as a rule not'above‘ 80°
C. The addition of the hydrogenation catalysts
drogenation catalysts and in the presence of con
is preferably eifected directly before the hydro
densing agents being e?ected simultaneously or 4 genation. In many cases it is advantageous to
carry out the condensation and also the hydro
As initial materials may be mentioned for ex
15
genation in the presence of inert solvents, as for
ing action, hydrogenation while employing hy
subsequently.
'
'
,
ample acetaldehyde, propionaldehyde, butyralde
hyde, . stearic aldehyde, and crotonaldehyde as
well as substitution products of the said aldehydes,
as for example aldehydes containing halogen. Ac
20 cording to this invention, probably a kind of aldol
condensation ?rst takes place between the alde
example cylohexane. The hydrogenation may be '
effected at atmospheric or_ increased pressure,
preferably at temperatures between 100° and 200°
C. and while employing the usual hydrogenation
catalysts, as for example nickel, cobalt or copper
catalysts. The catalysts may also be employed
hydes, two, three'or more molecules of aldehyde ,
taking part to form a straight or branched chain ’ precipitated on carrier substances, such as ‘active
v which then yields alcohols 'of high molecular carbon, kieselguhr or silica gel, or also on the
25- weight by hydrogenation, in some cases‘ after metal oxides employed having an activatingac
tion. The condensation of aldehydes of low
splitting oii water.
Catalysts‘ having a condensing action which ' molecular weight and the hydrogenation of the
are suitable for the purposes of this invention are condensation. products may be carried out in
especially organic nitrogenous compounds, as for
30- example secondary amines, such as vdiethylamine
or dibutylamine, piperidine, hydrogenated quino
line compounds, such as decahydroquinoline or
hydrogenated naphthoquinoline, piperazine, mor
pholines, and pyrroles, as for example proline, and
35 pyrrolidines or mixtures of these substances. The
said organic basic‘ substances are employed in the
hydrogenation step‘ in the free state, i,-e, not in
the form of their salts. These condensing agents,
one operation or in two stages.
’
_
_
The alcohols obtained ‘are suitable as solvents
and as initial materials for the preparation of
arti?cial compositions, assistants for the textile
industry and pharmaceutical products.
The following examples will further illustrate
the nature of this invention but‘ the invention is
not restricted to these examples. The parts are
by weight.
.
_
,
'
Example 1
especially when employing'crotonaldehyde, yield '
40- valuable alcohols of high molecular weight by ‘ _ 12' parts of calcium hydroxide and 5 parts of
hydrogenated beta-naphthoquinoline are added
hydrogenation. The said catalysts having a con
densing action may be activated for example by to 500 parts'of crotonaldehyde. The mixture, at
oxides and hydroxides of metals of the second and - ter being allowed to stand for six days, is sub
third groups of the periodic system, as for example iected to hydrogenation in the presence of a co- ~
45 calcium, strontium, magnesium or aluminium hy _ bait catalyst. at 150° C. under'a pressure of 200
droxide, or salts having a basic reaction,',as for atmospheres. A good yield of a product'is ob
example disodium phosphate, sodium carbonate _
or sodium acetate. By suitable selection of cata
lysts or special mixtures it is possible to in?uence
50 the reaction as regards the ?nal products ‘formed;
thus for example by employing only organic cata
lysts, products are obtained in which alcohols cor
responding to the aldehydes , employed as initial
. materials preponderate as compared with the al
55 cohols or high molecular weight, whereas by the
tained which contains butyl and octyl alcohols and.
also about 55 per cent of a mixture of monohy
title and polyhydric alcohols of high molecular‘ '
>weight.
50
By working ~without an'addition of calcium '
oxide but under otherwise similar conditions, a
reaction product is obtained containing about 39
per cent ‘of a-mixture'of alcohols of high'molec- '
' ular'weight.
2
2,119,899
Example 2_
7. The process of producing mixtures of all
.
phatic alcohols containing high molecular alco
hols which comprises condensing crotonaldehyde
15 parts of a nickel catalyst, precipitated‘on
silica gel, containing about 10 per cent of metallic _
by means of a free nitrogenous organic base and .
nickel and 4 parts of decahydroquinollne are in
troduced into 200‘ parts of ' acetaldehyde.
simultaneously hydrogenating the condensation C1
product in the presence of the said condensingv
agent with the simultaneous addition of a hydroq
The
mixture is hydrogenated at 150° C. under a pres
sure of 200 atmospheres of hydrogen. A reaction
product is obtained in good yields which by irac-_
genation catalyst.
‘
-
_8. The process of producing mixtures of _ali
10 alcohol, 21 parts of butylene glycol and 30 parts of ' phatic alcohols containing high molecular alco
tional distillation in vacuo yields 49 parts of ethyl
hols which comprises condensing acetaldehyde
a mixture of higher alcohols.
What we claim is:— '
_
10
by means of free decahydroquinoline and simul
-
taneously'hydrogenating the condensation prod
1. The process of producing mixtures'of ali
phatic alcohols containing highmolecularalcohols uct ‘in ‘the presence of the said condensing
agent while employing a nickel catalyst.
9. The process of producing mixtures of all
phatic alcohols containing high molecular alco
hols which comprises condensing crotonaldehyde
by means of free hydrogenated beta-naphtho
15 which comprises condensing an aliphatic alde
hyde by means of a free nitrogenous organic base
and then hydrogenating the condensation prod
uct in the presence of the said condensing agent
with the simultaneous addition of a hydrogena
tion catalyst.
quinoline and then hydrogenating the conden
_
sation product in the presence of the said con
densing agent while employing a cobalt catalyst. '
2. The process of producing mixtures of aliphatic
alcohol. containing high molecular alcohols
which comprises condensing a low molecular
aliphatic aldehyde by means of a free nitrogenous
10. High molecular aliphatic alcohols obtain
able by condensation of a low molecular aliphatic
aldehyde by means of a free nitrogenous organic 25
base and hydrogenation of the condensation
product in the presence of the said condensing
organic base and simultaneously hydrogenating
the condensation product in the presence of
the said condensing agent and a hydrogenation
catalyst.
>
. agent with simultaneous addition of a hydro
v
genation catalyst, the said alcohols containing-a
3. The process of producing mixtures of ali
higher number than twice the carbon atoms of 30
30 phatic alcohols containing high~molecular al
the said aldehyde.
11. Mixtures of aliphatic alcohols obtainable
by condensation of a low molecular aliphatic
cohols which comprises condensing a low molec
ular aliphatic aldehyde by means _of a mixture
of a free nitrogenous organic base and an in
organic compound having a basic reaction and aldehyde by means of a nitrogenous organic base
35 then hydrogenating the condensation product in » and hydrogenation of the condensation product
in the presence of the said condensing agent
the presence of the said condensing agent with
with simultaneous addition of a hydrogenation
the ‘simultaneous-addition of a hydrogenation
‘catalyst.
‘
'
4. The process of producing mixtures of ali
40 phatic alcohols containing high molecular alco- '
hols which comprises condensing a low molec—
ular aliphatic aldehyde by means of tree nitro
genous organic base and then hydrogenating the
_ condensation product in the presence of the said
condensing agent with the simultaneous addition
of a hydrogenation catalyst.
5. The process of producing mixtures of all
phatic alcohols containing high molecular alco
- hols which comprises condensing an unsaturated
low molecular aliphatic aldehyde by means of
a free nitrogenous organic base and then hydro
genating the condensation product inthe presence
of_ the said condensing agent with the simul
taneous addition of a hydrogenation catalyst.
6. The process of producing mixtures oi.’ ali
phatic alcohols containing high molecular alco
hols which comprises condensing acetaldehyde
by means of a'iree nitrogenous organic base and
60
»
catalyst, the said mixture containing high
molecular aliphatic alcohols with a higher num—
ber than twice the carbon atoms of thesaid alde
hydes.
1
12. Mixtures of aliphatic alcohols obtainable
by condensation of acetaldehyde by means of a
nitrogenous organic base and hydrogenation of
the condensation product in the presenceof the
said condensing agent with simultaneous addi
tion of a hydrogenation catalyst, they said .'mix
ture containing high molecular aliphatic alco
hols with at least 6 carbon atoms. '
13. Mixtures of aliphatic alcohols obtainable '
by condensation of crotonaldehyde by means of
a nitrogenous organic base and hydrogenation of
the condensation product in the presence of the ,
said condensing agent with simultaneous addi
tion of a hydrogenation catalyst, the said mixture‘ 55
containing high molecular aliphatic alcohols with
‘ at least 12 carbon atoms.
>
='ZORN.
simultaneously hydrogenating the condensation
product in the presence of the said condensing
FRIEDRICH VOGEL.
agent with the simultaneous addition of a hydro
HEINRICH WOL'IJER.
genation catalyst, -
»
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