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Патент USA US2108133

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.2,108,133
Patented Feb. 15, 1938
‘UNITED STATES PATENT’ OFFICE
PROCESS FOR PRODUCING HIGH MOLECU
LAB ALCOHOLS FROM THE CORRESPOND
ma xa'rorms
Francis John McCall, Wilmington, Del., assignor
to E. 1. du Pont de N monrs a Company,'Wll
‘mini-ton, Del., a cor ration of Delaware
No Drawing. Application November 25, 1936,
‘
Serial No. 112,709
14 Claims.
(Cl. 260-150)
This invention relates to the process of cata
lytically hydrogenating ketones to produce the
corresponding secondary alcohols and, speci?cally,
to the process of producing straight-chain, sec
5
ondary, aliphatic alcohols by catalytically hy
drogenating the corresponding ketones of the
type
0
CH3(0H|)n_-g-(C H1) ‘CH!
10 where "n” and “m" may be any integers from
zero to fourteen, inclusive, the values of “n” and
“m” being subject to the further limitation that
"11” plus “m” must be equal toten, eleven, twelve,
) thirteen, or fourteen.
The phrase “straight
chain aliphatic ketone having approximately
2
?fteen carbon atoms" is for the present purpose
de?ned as, and will hereinafter be used to refer
to any ketone belonging to the above class, or
any mixture which contains only ketones belong
ing tothe above class. Furthermore, an alcohol
will be said to ‘fcorrespond” to a given 'ketone
when the former differs from the latter only in
having a carbinol group in place of the carbonyl
2
group of the ketone.
the presence of a platinum-black catalyst (Vavon,
Ann. Chim. 1 (9), 144 (1914)). The literature
shows, however, that more vigorous conditions
have had to be used in attempts to hydrogenate
the higher ketones, and that, under these more
vigorous conditions, side reactions such as hydro
.carbon formation and polymerization have pre
vented the successful use of the catalyst proce
dure in preparing alcohols from the straight-chain
ketones of higher molecular weight. Thus, Hal 10
ler and Lassieur (Compt. rend. 150, 1017 (1910))
in attempting to convert undecanone-2 to the cor
responding secondary alcohol by hydrogenation at
300° C. over a nickel catalyst obtained, in addi
tion to unchanged ketone, a hydrocarbon and a 15
condensation product having twenty-two car
bons per molecule-but they obtained no'eleven
carbon alcohol. Other workers have observed the
formation of hydrocarbons and condensation
products during the catalytic hydrogenation of 20
higher ketones, and, as will be pointed out later,
one of the. objects of the present invention is the
avoidance of these side reactions.
This invention has as an object the conversion
of straight-chain aliphatic ketones or mixtures 26
The prior art discloses numerous methods for‘ thereof having approximately 13 to 1''! carbon
atoms into the corresponding straight-chain sec
the synthesis of secondary alcohols. The Grig
ondary alcohols or mixtures thereof. A further
nard method may be used quite generally, but be
object is to accomplish the conversion by means
cause it is such an expensive and laborious pro
cedure it is not practical for the commercial of catalytic hydrogenation. A still further object 80
30
is to accomplish the conversion in such a man
preparation of alcohols.
The most practical and direct method?for/ ner as to avoid side reactions which result in
the production of secondary alcohols involves the the formation of hydrocarbons and condensation
chemical reduction or the hydrogenation of a
products, so that, if desired, the alcohols can
ketone. Thus, pentadecanol-B has been prepared
readily be obtained in nearly theoretical yield, 85
from the ketone by a sodium-alcohol reduction
in a high state of purity, and with a minimum of
(Kipping, Jour. Chem. Soc., 63, 455 (1893)).
The reaction involved may be represented by the
effort and expense. Other objects will appear
hereinafter.
These objects are accomplished by bringing a
mixture of hydrogen and ketone or mixture of all)
ketones in intimate contact with a catalyst in
such a temperature range that the carbonyl
group is selectively converted into the carbinol
following general equation:
'
w
4
It has long been known that acetone, methyl
ethyl ketone, and other ketones of low molecular
weight can be catalytically hydrogenated to the
corresponding secondary alcohols in either the
liquid or vapor phase and in the presence of any
of a wide variety of noble or base metal hydro
genation catalysts. For example, acetone has
‘been completely converted into propanol-2 by
5 O hydrogenation in the presence of an‘ Iactive
nickel catalyst at
drogen pressure of
and Adkins, Jour.
(1932)). Similarly
as
23° C., and under a hy
2 to 3 atmospheres (Covert
Am. Chem. Soc. 54, 4117
heptanone-4 has been con
verted into heptanol-4 under mild conditions in
group.
‘
Ketones suitable for use in carrying out this 45
invention may be prepared according to a wide
variety of procedures. For example,- pentadec
anone-8 can be prepared by ketonization of
capryllc acid from coconut oil. Similarly, ke
tonization of the mixture of enanthic, caprylic,
and pelargonic acids obtained from the oxidation
of oleic acid gives a mixture of tridecanone-‘l,
tetradecanone-7, pentadecanone-7, pentadecan
one-8, hexadecanone-S, and heptadecanone-Q.
Likewise, ketonization of coconut oil acids with
so.
2
9,108,188
acetic acid gives a mixture from which tri
‘decanone-2, pentadecanone-2, heptadecanone-2,
tridecanone-6, pentadecanone-6, heptadecanone
6, pentadecanone-8, and heptadecanone-8 may
be separated, etc.
The following examples are instances of the
application of this invention. They are not to be
considered as limitations of the invention since
many modi?cations may be made without de
10 parting from the spirit and scope thereof.
In addition to the above, the following alco
hols have been prepared by hydrogenating the
proper ketone under conditions similar to those
of ,Example I: tridecanol-7, B. P. 130° to 131° C.
at 9 mm. pressure, M. P. 41° C.; heptadecanol-Q,
B. P. 174;’ C. at 9 mm. pressure, M. P. 595° C.;
pentadecanol-‘i, B. P. 155° to 156° C. at 10 mm.,
M. P. 31° C.; and pentadecanol-2, B. P. 166° C.
to 170° C. at 14 mm. pressure, M. P. (crude) 27°
to 28° C.
‘
10
Although in the above examples certain de?
nite conditions of pressure, temperature, catalyst
ratio, etc., have been mentioned, it is to be
Example I
A solution of 141 grams of pentadecanone-8 in
47 grams of 95% ethanol was charged into a understood that these conditions are'by no means
16 pressure tube equipped with a shaking device and
critical except as hereinafter speci?ed.
15
15 grams of ‘unsupported nickel catalyst was
‘In general, the process is operable between
added. Hydrogen was then admitted to the ves ‘the temperature limits of about 75° to about
sel and maintained at a pressure of 2000 to 2400 200° C. Temperatures of about 100° to about
pounds per square inch during the hydrogenation 150° C. are preferred, however, for the reasons
20 which, at 150° 0., required ?fteen minutes.
that the reaction is less rapid at the lower op
The product from this and a similar run were erable temperatures, and at the higher operable 20
combined and ?ltered while still warm. The temperatures side reactions such as hydrocarbon
?ltrate, upon distillation, gave a 97% yield of formation begin to be important.
pentadecanol-8, B. P. 172° to 177° C. at 23 mm.
Hydrogen pressures from about atmospheric
25 pressure, of which 93% boiled at 175° to 177° C.
pressure up to and above 5000 pounds per square
at 23 mm. pressure.
The product was a white,
waxy solid: M. P. 485° C.; hydroxyl number,
found, 241.0, 238.7 (calculated value, 246.0).
Example I!
A 100-gram sample of pentadecanone-8 was
hydrogenated under conditions similar to those
‘of Example I, except that absolute alcohol was
used as solvent and the hydrogenation proceeded
85 at a temperature of 100° to 120° C. A 91 per cent
yield of pentadecanol-8, B. P. 172° to 177° C. at
23 mm. pressure, was isolated.
.
Example HI
About one-third of a commercial sample of
coconut oil acids was distilled to give a dis
tillate consisting mainly of caproic, caprylic, and
capric acids. Ketonization of the distillate gave
a mixture which consisted of thirteen, ?fteen,
45 and seventeen carbon straight-chain ketones.
Hydrogenation of this crude ketone mixture,
according to the procedure described in Ex
ample I, gave a corresponding mixture of sec
ondary alcohols, a white waxy solid having a
50. slight fatty odor: B. P. 135° to 208° C. at 15 mm.
pressure, freezing point 39° to 41° C. The run
required 425 hours at a pressure of about 2000
pounds per square inch and a temperature of
150° C.
55
6.0
65
70
75
‘
_
Example IV
A mixture of ketones similar to that described
in Example III was hydrogenated at 125° C.,
inch may be used. It is preferable to use pres
sures of about 100 to about 3000 pounds per
square inch, because at lower pressures there is
25
a tendency toward polymerization and higher
pressures necessitate the use of more expensive 80
equipment.
'
It is preferable to use a solvent such as ethanol,
methanol, dioxane, or any other solvent which
does not react with the ketone, alcohol, or cat
alyst. The use of a solvent appears to accelerate 86
the hydrogenation somewhat and, since the
higher alcohols are usually solids, a solvent'as
sists in the removal of the catalyst from the ‘
product.
However, it has been shown that the reaction
proceeds readily in the absence of a solvent; 40
under certain circumstances, therefore, (for ex
ample, when the product is to _be used directly
without puri?cation) the use of a solvent may
be quite undesirable.
The ketone to be hydrogenated does not need 45
to be pure. It is only necessary that it contain
no large amount of materials which poison the
catalyst (for example, acids, organic sulfur, etc.).
Since the product is usually white or colorless
and corresponds in purity to that of the ke 60
tone hydrogenated it is unnecessary, for most
purposes, that the product be puri?ed. When a
puri?cation is desired it may be accomplished by
distillation, recrystallization, or by other known
methods.
4
In the practice of this invention any hydro
in the absence of a solvent and in the presence genating catalysts, such as platinum, palladium,
of 5 per cent of a nickel-on-kieselguhr catalyst. copper (or oxide), iron (or oxide), or mixtures
This run required ?ve hours at a pressure range - of the above may be used, but nickel is pre 60
of 300 to 500 pounds per square inch and gave ferred because of its high degree of activity,
low cost, and ease with which it is prepared in
a product similar to that described under Ex
very active form.
_
ample III.
It'is preferred to allow the reaction to pro
Emample V
ceed until no more hydrogen is being absorbed
A sample of mixed enanthic, caprylic, and in order that the product may be of the highest
pelargonic acids was obtained by the oxidation purity. However, since the last 0-20 per cent of
of oleic acid. Ketonization of these acids gave hydrogen absorption usually takes place at a
a mixture which consisted of the thirteen, four
lower rate than that of the initial absorption,
teen, ?fteen, sixteen, and seventeen carbon ke
it is sometimes economical from the time stand
tones. Hydrogenation of the mixture of ketones, point to interrupt the hydrogenation before it 70
according to the procedure of Example I, gave is complete.
a mixture of the corresponding secondary al
Those skilled in the chemical art will recog
cohols: B. P. 152° to 185° C. at 14 mm. pressure, nlre the importance of alcohols as one of the
freezing point 48° to 50° C.
most fundamental intermediates in the prepara 76
3
tion of a wide variety of organic chemicals. It
characterized in that the reaction is carried out
at a temperature of about 100° to about 150° C.
and under a pressure of about 100 to about 1000
pared by direct sultation of the alcohols, and _ pounds per square inch.
5. The process which comprises bringing a
which are valuable as textile assistants, wetting,
penetrating, emulsifying,‘ and cleansing agents. mixture of hydrogen and a saturated straight
The higher secondary alcohols, as such, may be chaln aliphatic ketone having from 13 to 17 car
used as wax-modifying agents, lubricants, etc. bon atoms dissolved in ethanol in contact with a
~ The present invention furnishes a simple, di
highly active nickel catalyst at a temperature of '
about 100° to about 150° C. and under a pres—; 10
10 rect, economical synthesis for certain of the
higher secondary alcohols.
sure of about 100 to about 3000 pounds per square
By the use of the present invention certain inch.
,
advantages are obtained. These may be enu
6. A process which comprises bringing a mix
merated as follows:
ture of hydrogen and a saturated straight-chain
1. The invention enables one to proceed from, aliphatic ketone having 15 carbon atoms in con 15
15
an abundant naturally-occurring raw material
tact with a highly active nickel catalyst at a tem
is su?icient to mention here the higher second
ary alkyl sulfates, which are advantageously pre
(fatty acid) to the higher secondary alcohols
perature between 75° and 200° C.
by a procedure which consists of only two stages.
7. The process in accordance with claim 6
characterized in that the reaction is carried out
at a temperature of about 100° to about 150° C. 20
2. ‘The process of the present invention is
superior to the purely chemical reductions of the
prior art in that it employs hydrogen, obviously
the most economical of reducing agentsand one
8. The process in accordance with claim 6
characterized in that the reaction is carried out
under a pressure between 100 and 3000 pounds
20
which gives rise to no by-products. As a result
of the latter feature,‘ the product may be used
~without puri?cation or after only a very simple
puri?cation.
I
_3. The process of the present invention makes
30 it possible to convert the higher straight-chain
ketones into the corresponding secondary alco
hols in practically quantitative (97 per 'cent)
yields. As a result the process entails no appre
ciable weight loss, and puri?cation of the prod
uct becomes unnecessary or, where desired, be
comes a relatively simple procedure.v
It is apparent that many widely different em
bodiments of this invention may be made with
out departing from the spirit and scope thereof
40 and therefore it is not intended to be limited ex
cept as indicated in the appended claims.
I claim:
1. The process which comp-rises bringing a
mixture of. hydrogen and a saturated straight
45 chain aliphatic ketone having from 13 to 17 car
bon atoms in contact with a highly active nickel
catalyst at a temperature between ‘75° and 200° C".
2. The, process in accordance with claim 1
characterized in that the reaction is carried out
50 at a temperature of about 100° to about 150° C.
3. The process in accordance with claim 1
characterized in that the reaction is carried out
per square inch.
v
.
'
9. The process in accordance with claim 6 25
characterized in that the reaction is carried out
at a temperature of about 100° to about 150° C.
and under a pressure of about 100 to about 1000
pounds per-square inch.
10. The process which comprises bringing a 30
mixture of hydrogen and a saturated straight
chain aliphatic ketone having 15 _carbon atoms
dissolved in ethanol in contact with a highly ac
tive nickel catalyst at a temperature of about
100° to about 150° C. and under a pressure of
about 100 to about 3000 pounds per square inch.
11. The process which comprises bringing a
mixture of hydrogen and pentadecanone-B in
contact with a nickel catalyst at a temperature
40
between 75° and 200° C.
12. A process which comprises bringing a mix
ture of hydrogen and pentadecanone-8 dissolved
in ethanol in contact with a nickel catalyst at a
temperature of about 150° C. and at a pressure
of about 2000 to about 2400 pounds per square‘
inch.
-
under a pressure between 100 and 3000 pounds
13. A process which comprises bringing a mix
ture of hydrogen and pentadecanone-4 in con
tact with a nickel catalyst at a temperature be
60
tween 75° and 200° C.
14. A process which comprises bringing a mix
ture of hydrogen and pentadecanone-2 in con
tact with a nickel catalyst at a temperature be
per square inch.
tween 75° and 200° C.
.
4. The process in accordance with- claim 1
‘
FRANCIS JOHN McCALL.
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