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' 2,684,385
CONTINUOUS ALDOLIZATION
Filed Dec. 16, 1949
CONDENSER
I
5 -> qvnmq
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AQUEOUS
UNREACTED
BUTYRALDEHYDA
-19-
.7
_ :____,..REACTOR AND
PEEHEAIiEP- _ __
I
T .
I6
.SOLVENT
/3:_
lo
___
E753
DIST/LLATIO/V
____
COLUMN
4 __
2:3.
'
'-_'
cg-1T
,4
UTYRALDEHYD; ___
uvoaoaE/VATMN
__
AND
__
IPUR/F/CAT/ON
(g-ETHYL HEXENAL)
_-
QEBO/LER
- /Z
'
"
2/
_/6
I
l5
,18
s-
1.
23
/3\
PRODUCTS
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'HYDROTROP/C sham!
NaOH
SOLUTION
WAWMMPS
By
iA'E'l'ornzg
2,684,385
5 Claims.
1
This invention relates to a novel continuous
(Cl. 260-4501)
2
similar fashion to the formation of aldol from
pot.
The higher molecular weight condensation
products made by this process and particularly
their derivatives such as the C8~Cl2 aliphatic a1
yields.
dibasic organic acids such as phthalic acid is of 45 alpha H compounds other than aldehydes and
ketones. In general, any C-H compound which
particular interest.
will give a sodium derivative, such as malonic
The aldol reaction may be promoted by either
ester, acetoacetic ester, cyanoacetic ester, and
basic or acidic catalysts. For best results, dilute
nitromethane
will condense with aldehydes in
or weak bases are employed to produce the aldol
the presence of a trace of base or acid. As many
condensation in which the double bond of the 50 molecules of aldehyde can react as there are
2,684,385
U
lation.
A wide variety of aldol condensations have
been studied and results of these recorded in the
literature. In the case of acetone such com
invention.
A novel process described herein is an aldoliza
tion in which the aldolizing reaction may be
controlled such that it may proceed in a step
wise manner by which the desired condensation
products are readily obtained.
Employing this novel process, it is preferred to
operate in a continuous manner with the mate
rials to be condensed being fed at an intermediate
point in the column and water or media rich in
Water being fed at an upper point in the column.
The column is provided with conventional re
?uxing and reboiling facilities to provide con
tinuous operation under reboiling and re?uxing
conditions. In the case of reactions between two
dehyde; (S) i-butyraldol from isobutyraldehyde; 40 or more different aldehydes or ketones to pro
duce mixed condensation products the individual
(9) 2,2-dimethyl hexanol-3-al-l and 2-ethyl-4
reactant compounds may be fed at di?erent in
methyl pentanol-3-al-1 from butyraldehyde and
termediate points below the point 01' addition
isobutyraldehyde; and (i0) 2,4-diisopropyl-5,5
of the aqueous re?ux media. Preferably the re
dimethyl-?-hydroxy-1,3-dioxane from three mol
?uxing medium should contain a soluble catalyst
ecules of isobutyraldehyde.
suitable for promoting the aldol condensation
Known conventional aldolization techniques
using merely a caustic catalyst, depend on carry~
ing the reaction out batchwise with some form
of agitation to mix the aqueous alkali catalyst
2,684,385
The
'
2,684,885
The product
consisted primarily of an aqueous hydrotropic 10 of organic product, about 20 vol. percent boils in
the Z-et'hylhexanol range while another 20 vol.
salt-sodium hydroxide solution. A part of this
percent boils at or above the boiling range of
aqueous solution was removed from the system
hydrogenated isobutyraldol. About 22 vol. per
by line 24 and was recycled via lines it and H
cent appears to be iso-butanol, although distilla
back to the reactor and distillation column 4.
The organic phase in phase separator 19 was 15 tion of the hydrogenation feed stock showed
virtually no material in the C4 aldehyde range.
removed by line 2a as mixed Ce condensation
Continuous column aldolization of mixed normal
products of n-butyraldehyde which can be
(co/hr. solvcnt=368+(15)(l4)
0
which is at or slightly above the solubility limit
30
for the aldehyde.
By thus working in a homogeneous system, the
aldolization could proceed smoothly and rapidly
in the presence of very dilute caustic. The high
dilution of the aldehyde in the homogeneous
164.
normal butyral
dehyde.
()
3
411.
0.083.
90.
15/1.
66.5.
17.0.
16.0.
512.
68.5
9.5.
99.8.
percent.
Example II
Example II
Example I
The re?ux
do undergo dehydration.
Vacuum distillation of the product indicated
it to be a mixture of the possible aldols and their
dehydration products. There are a number of
possible reaction products from the condensation H
normal-butyraldol)
2,684,385
10
55
2,489,608
2,516,837