United States Patent Office 3,093,691

Patented June 11, 1963

2
3,093,691 Suitable trialkylaluminum compounds include such
PREPARATION OF ALCOHOLS FROM ALUMNUM. compounds wherein the carbon content of the alkyl rad
TRALKYLS icals varies from 1 to 20 or even more. Although theoret
Gifford G. McClaflin and Mark T. Atwood, Ponca City, ically there is no limit to the number of carbons in the
Okla, assignors to Continental Oil Company, Ponca alkyl radical that can be used, we generally prefer to
City, Okla., a corporation of Delaware employ a trialkylaluminum compound wherein the car
NoDrawing. Fied Nov. 5, 1959, Ser. No.851,023 bon content of alkyl radicals varies from 2 to 12. Obvi
2 Claims. (Cl. 260-638). ously the alkyl radicals of the trialkylaluminum com
pound may be the same or different. As a rule a com
This invention relates to a novel method of preparing 10 pound wherein the alkyl radicals are the same is desired
aliphatic alcohols. More particularly the present inven as the use of such a compound produces one alcohol. If
tion relates to a two stage process of preparing such alco on the other hand a compound is used wherein the alkyl
hols which comprises reacting a trialkylaluminum com" radicals are different a mixture of alcohols is formed.
pound in the first stage with an aliphatic aldehyde and A specific compound that we have used very successfully
then in the second stage hydrolyzing the resultant prod 15 in our process is triethylaluminum. Methods for the prep
uct to form the desired alcohol. aration of this particular compound and other trialkyl
Various methods have been proposed for the produc 3 aluminum compounds are described in the literature and
tion of alcohols involving processes other than fermenta forms no part of the present invention. In this regard
tion methods or the destructive distillation of wood. In reference is made to U.S. Patents 2,781,410; 2,787,626;
one proposed method a high molecular weight ketone is 20 2,826,598; 2,835,689; and British Patent. 808,055.
ireacted with sodium or potassium acetylide to form the so Suitable aliphatic aldehydes include the lower molec
'dium or potassium derivatives of a substituted ethinyl car ular weight compounds. We prefer to use formaldehyde
binol which product is then hydrolyzed to the ethinyl car because it is both economical in price. and is available in
binol. In another method an aldehyde is reduced to the large quantities. In addition it is easily handled and can
corresponding alcohol employing a secondary metallic alk 25 be used as the pure compound or as a polymer. Gen
oxide as the reducing agent. In another method it has erally we prefer to employ the polymer as it is the
been proposed that alcohols can be produced by a process easiest to handle and improved yields of the desired alco
involving the reaction of formaldehyde with a metal hol are obtained using that product.
alkyl compound, such as a lithium, magnesium, or so The proportions of the reactants, namely, the trialkyl
dium alkyl compound. None of these proposed methods 30 aluminum compound and the aldehyde may be varied
have been entirely satisfactory. In the process using so over a wide range. Theoretically in our process three
dium or potassium acetylide that compound is prepared moles of the aldehyde and three moles of water are used
by reacting acetylene wtih metallic sodium or potassium, per mole of the trialkylaluminum compound. This may
Since metallic sodium and potassium are very reactive, be illustrated by the equation given below in which tri
they must be handled with extreme care. 35 ethylaluminum is reacted with formaldehyde and then
In the process involving the reduction of an aldehyde hydrolyzed to produce normal propyl alcohol.
the alcohol will have the same number of carbon atoms
as the aldehyde. Furthermore, the reducing agent used
is an alkoxide which can be considered an alcohol pre Although as pointed out above three moles each of
cursor. In the last process described above metal alkyl 40 formaldehyde or other aldehyde and water are required
compounds are employed which are expensive, difficult per mole of the trialkylaluminum compound, we prefer in
to work with, and are not readily available. practice to employ an excess of both the aldehyde and
It is, therefore, a principal object of our invention to water. Any unreacted aldehyde can be easily recovered
provide a process for the production of aliphatic alcohols from the reaction mass, consequently we generally employ
which obviates the disadvantages of the prior art proc 45 an amount of aldehyde which may be two to three times
CSSeS. the theoretical amount required.
It is another object of the present invention to provide Instead of using water as such we have found it pref
improved process for the production of aliphatic alco erable to employ an aqueous solution of a mineral acid
OS. such as 25 percent hydrochloric acid. Other aqueous
Another object of this invention is to provide an eco 50
solutions of mineral acids and of different concentra
nomical and direct process for the manufacture of ali tions may, of course, be used.
phatic alcohols involving a minimum of process steps and In view of the fact that the particular reactants used
using moderate reaction conditions. may be selected from a large list and since the best op
Further objects and advantages will become apparent erating temperature depends largely upon the specific
from the following description. 55
reactants used, the temperature employed may vary
To the accomplishment of the foregoing and related from -50 to about 150° C. Generally, we prefer to
ends, this invention then comprises the features here operate within a temperature range of 30 to 100° C.
inafter fully described and particularly pointed out in the Somewhat more specifically as a rule we prefer to op
claims, the following description setting forth in detail erate at the reflux temperature of the mixture. It is to
certain illustrative embodiments of the invention, these 60 be understood, however, that higher or lower tempera
being indicative, however, of but a few of the various tures may be used with a resultant increase or decrease
ways in which the principle of the invention may be em in the reaction rate in accordance with the general law
ployed. of chemical reactions.
Broadly stated, the present invention may be described In order to disclose the nature of the present invention
as a process for preparing an aliphatic alcohol by react still more clearly, the following illustrative examples
ing a trialkylaluminum compound with an aliphatic 65 will be given in which "parts by weight' bear the same
aldehyde and then hydrolyzing the resultant product to relation to "parts by volume' as do grams to cubic cen
form the desired alcohol. timeters.
Before proceeding with specific examples illustrating Example l
our invention, it may be well to indicate in general the 70
nature and amounts of the materials required in the 32 parts by weight of paraformaldehyde was added to
process. a reaction vessel which was equipped with an agitator.
 3,093,691.
3 4.A.
The vessel was then flushed with nitrogen and then 50 1. A process for the manufacture of a primary aliphatic
parts of anhydrous ether added. While the contents of alcohol which comprises reacting trioxane with a trial
the flask were stirred 40 parts of triethylaluminum was kylaluminum compound of the type (R-CH2)Al in
slowly added to the vessel. The mixture was heated for which R is selected from the group consisting of primary
a period of two hours at reflux temperature after which Saturated aliphatic hydrocarbon radicals having from 1
period the reaction product was hydrolyzed with an to 19 carbon atoms and hydrogen at a temperature of
aqueous 25 percent hydrochloric acid solution. The nor 30 to 100° C., to yield a reaction product, hydrolyzing
mal propyl alcohol formed was recovered by distillation of said reaction product and recovering from the hy
in a fair yield based on the triethylaluminum. drolysis product the corresponding alcohol of the type
Example 2 0 R-CH-CH-OH.
2. The process according to claim 1 in which the tri
The procedure of Example 1 was repeated with the alkylaluminum compound is triethylaluminum.
exception that 32 parts of trioxane was substituted for the
paraformaldehyde used in Example 1. A yield of nor References Cited in the file of this patent
mal propyl alcohol was obtained. 5 UNITED STATES PATENTS
Example 3 1,410,223 Schumann et al. --------- Mar. 21, 1922
The procedure of Example 2 was repeated with the 2,699,457 Ziegler et al. ----------- Jan. 11, 1955
exception that 25 parts of trimethylaluminum was sub FOREIGN PATENTS
stituted for the 40 parts of triethylaluminum used in Ex 20
ample 2. A yield of ethyl alcohol was obtained. 803,178 Great Britain ----------- Oct. 22, 1958
While particular embodiments of the invention have OTHER REFERENCES
been described, it will be understood, of course, that the Meerwein et al.: Chemical Abstracts, (1937), 31,
invention is not limited thereto since many modifications 655-6.
may be made, and it is, therefore, contemplated to cover 25 Meerwein et al.: J. Prakt. Chem., 147, pp. 226-50
by the appended claims any such modifications as fall (1936).
within the true spirit and scope of the invention. Rochow et al.: The Chemistry of Organometallic Com
The invention having thus been described, what is pounds, pp. 278, 288-291 (1957). (Copies of refer
claimed and desired to be secured by Letters Patent is: ences available in Sci. Lib.)