DETERGENT RANGE ALDEHYDE AND ALCOHOL MIXTURES AND DERIVATIVES, AND PROCESS THEREFOR

DETERGENTS A BASE DE MELANGES D'ALDEHYDES ET D'ALCOOLS AINSI QUE DE LEURS DERIVES; METHODE DE PREPARATION

English Abstract

DETERGENT RANGE ALDEHYDE AND ALCOHOL MIXTURES
AND DERIVATIVES, AND PROCESS THEREFOR
Novel, liquid mixtures of isomeric aldehydes and
alcohols and their derivatives are described in the C11
- C16 carbon range, the compounds being characterized by
a main carbon branched at the 2-position and moderate
additional branching in most isomers; the aldehyde
mixtures are prepared by an economic route from lower
cost olefins such as propylene, using oxo and aldol
reaction with the reaction conducted in such a way as to
give a high percentage of aldolable product, and
preferably with a base catalyzed aldol reaction
conducted under conditions to make high conversions
attainable. The mixtures can be exemplified by a
mixture of compounds wherein the compounds are
represented by one of the following structures:
<IMG>
having from 11 to 16 carbon atoms, in which R has 6 to 8
carbon atoms, and R' has from 3 to 6 carbon atoms, with
most of the compounds having additional methyl or ethyl
branches, and in which M is hydrogen or a salt-forming
cation. The aldehyde mixtures can be hydrogenated to
alcohols and converted to novel ethoxylates or sulfate
compositions suitable for use as biodegradable
detergents; or hydrogenated and oxidized to novel
carboxylic acid compositions also suitable for detergent
use.

Claims

The embodiments of the invention in which an exclusive
property or privilege is claimed are defined as follows:
1. A mixture of compounds wherein the
compounds are represented by one of the following
structures:
<IMG>
having from 11 to 16 carbon atoms, in which R is an
alkyl group having from 6 to 8 carbon atoms, and R' is
an alkyl group having from 3 to 6 carbon atoms, with
most of the compounds having additional methyl or ethyl
branches, and in which M is hydrogen or a salt-forming
cation.
2. A mixture of isomeric alcohols having from
11 to 16 carbon atoms and characterized as alkanols of 6
to 10 carbon atoms with an alkyl group containing 2 to 6
carbon atoms substituted on the 2-position thereof, and
with additional branching in most of the isomers, with
most of the additional branches being methyl groups, and
further characterized as being liquid at ambient
temperatures and having hydrocarbon hydrophobe moieties
making the mixture suitable for formation of effective
detergents therefrom, and further characterized by
suitable biodegradability.
3. Ethoxyl derivatives derived from a mixture
of isomeric alcohols having from 11 to 16 carbon atoms
and characterized as alkanols of 6 to 10 carbon atoms
with an alkyl group containing 2 to 6 carbon atoms
substituted on the 2-position thereof, and with
additional branching in most of the isomers, with most
of the additional branches being methyl groups, and
further characterized as being liquid at ambient
temperatures and having hydrocarbon hydrophobe moieties,
said ethoxyl derivatives having an average of about 3 to
12 ethoxyl units per alcohol unit.
4. The mixture of Claim 3 in which the ethoxyl
units are in the range on the average of 6 to 12 units
per alcohol unit.
97

5. Sulfate derivatives derived from a mixture
of isomeric alcohols having from 11 to 16 carbon atoms
and characterized as alkanols of 6 to 10 carbon atoms
with an alkyl group containing 2 to 6 carbon atoms
substituted on the 2-position thereof, and with
additional branching in most of the isomers, with most
of the additional branches being methyl groups, and
further characterized as being liquid at ambient
temperatures and having hydrocarbon hydrophobe moieties.
6. Ethoxysulfate derivatives derived from a
mixture of isomeric alcohols having from 11 to 16 carbon
atoms and characterized as alkanols of 6 to 10 carbon
atoms with an alkyl group containing 2 to 6 carbon atoms
substituted on the 2-position thereof, and with
additional branching most of the isomers, with most of
the additional branches being methyl groups, and further
characterized as being liquid at ambient temperatures
and having hydrocarbon hydrophobe moieties.
7. A mixture of isomeric enals having from 11
to 16 carbon atoms and characterized as 2-alkenals of 6
to 10 carbon atoms with an alkyl group containing 2 to 6
carbon atoms substituted in the 2-position thereof, and
with additional branching in most of the isomers with
most of the additional branches being methyl groups, and
further characterized as being liquid at ambient
temperatures and having hydrocarbon hydrophobe moieties
making the mixture suitable for formation of effective
detergents therefrom, and further characterized by
suitable biodegradability.
8. The mixture of Claim 7 in which the
aldehydes on the average have more than 2 branches in
addition to the 2-branch.
9. The mixture of Claim 7 in which aldehydes
of different carbon numbers are present.
98

10. A mixture of C14 isomeric alcohols, or
their corresponding enals in which the alcohols are
characterized as nine-carbon alkanol with a five-carbon
alkyl group substituted on the 2-position thereof, and
with additional branching in most of the isomers, with
most of the additional branches being methyl groups, and
further characterized as liquid at ambient temperature
and having varying hydrocarbon hydrophobe moieties
making the mixture suitable for formation of effective
detergents therefrom, and further characterized by
suitable biodegradability.
11. The alcohol mixture of Claim 10 in which
the alcohols are characterized by the structure:
<IMG>
in which R is an alkyl group with 7 carbon atoms and R'
is an alkyl group with 5 carbon atoms and in which in at
least about 80% of the alcohols, R' is selected from n-
pentyl, 3-methylbutyl and 1-methylbutyl, and R is
selected from n-heptyl, 3-methylhexyl, 5-methylhexyl, 2-
methylhexyl and 2-ethylpentyl groups.
12. The alcohols of Claim 10 in which about
40 to 60% by weight of the alcohols are 2(3-
methylbutyl)-5-methyloctanol,2-(1-methylbutyl)-5-
methyloctanol and 2-pentyl-5-methyloctanol.
13. The alcohols of Claim 12 in which about
65% to about 80% by weight of the alcohols are comprised
of the alcohols named in Claim 12 along with 2-(3-
methylbutyl)-7-methyloctanol,2-pentylnonanol, 2-pentyl-
7-methyloctanol and 2-(3-methylbutyl)-nonanol.
99

14. The alcohols of Claim 12 further
characterized in that about 20 to about 35% of the
alcohol have adjacent branches in their structure, but
there are substantially no alcohols with gem
substituents and therefore substantially no quaternary
carbon.
15. A mixture of Claim 10 having most of the
compounds of the mixture are represented by the
structure:
<IMG>
wherein:
R = methyl or ethyl;
p, q and r = 0 or 1; but only one of p, q and r can
be 1;
m = 3, when p, q and r = 0;
m = 2, when r = 1 and R = methyl;
m = 1, when r = 1 and R = ethyl;
n = 2, when s and t = 0;
n = 1, when s or t = 1;
s and t = 0 or 1, but only one of s and t can be 1;
and X is -CH2OH or -CHO and
when the latter, there is a
2,3 double band.
16. The mixture of Claim 15, wherein the
compounds are alcohols.
17. The mixture of Claim 15, wherein the
compounds are enals.
100

18. As a new compound, a C14 alcohol suitable
for use in formation of nonionic detergents and in
liquid form, designated as 2-(3-methylbutyl)-5-methyl-
octanol.
19. As a new compound, a C14 alcohol suitable
for use in formation of nonionic detergents and in
liquid form, designated as 2-(1-methylbutyl)-5-
methyloctanol.
20. As a new compound, a C14 alcohol suitable
for use in formation of nonionic detergents and in
liquid form, designated as 2-pentyl-5-methyloctanol.
21. As a new compound, a C14 alcohol suitable
for use in formation of nonionic detergents and in
liquid form, designated as 2-(3-methylbutyl)-7-
methyloctanol.
22. The mixture of claim 10, wherein the
mixture is made up of alcohols, the number of alcohols
comprising up to 28 alcohols.
23. A mixture of C14 isomemric enals which
are characterized as nine-carbon 2-alkenal with a
five-carbon alkyl group substituted on the 2-position
thereof, and with additional branching in most of the
isomers, with most of the additional branches being
methyl groups, and further characterized as liquid at
ambient temperature and having varying hydrocarbon
hydrophobe moieties making the mixture suitable for
formation of effective detergents therefrom, and
further characterized by suitable biodegradaibility.
24. A mixture of enals characterized by the
structure:
<IMG>
in which R is an alkylidine group with 7 carbon atoms
and R' is an alkyl group with 5 carbon atoms and in
which in at least about 80% of the compound, R' is
selected from n-pentyl, 3-methylbutyl and
101

1-methylbutyl, and R is selected from n-pentyl, 3-
methylbutyl and 1-methylbutyl, and R is selected from n-
heptylidine, 3-methylhexylidene, 5 methylhexylidene, 2-
methylhexylidene and 2-ethylpentylidene groups.
25. The product of claim 15, wherein the
mixture is made up of enals.
26. A mixture of isomeric enals in accord
with claim 7 and further characterized as having most of
the aldehydes in the mixture represented by the
structure set forth below, and their saturated aldehyde,
alcohol, ethoxylated alcohol, and ethoxylated alcohol
sulfate derivatives:
<IMG>
Wherein:
R= methyl or ethyl; h and m = 0, 1, 3, 4 and 5;
h and s = 0, 1, 2; p, q, r and t = 0 or 1;
m + h can never = more than 5
q and p = 0 when m + h = 5 or
when m + 1 = 3
1 = 3 and m = 1 when R= methyl and q = 1 and
p=0;
q = 0 and p = 1 when 1 = 2 and m = 2 or
when 1 = 1 and m = 3;
n + s can never = more than 3
r and t = 0 when n + s = 3 or
102

-103-
when n + s = 1;
s = 0 when n, r and t = 1 or
when n = 2 and r = 0 and t = 1;
s = 1 when n = 1 and t and r = 0 or 1 but
only one of t and r can be 1;
s = 2 when t = 1 and n= 0;
h = 2 and m = 1 when R = ethyl and q = 1 and p = 0
27. A mixture of isomeric enals in accord
with Claim 7 and further characterized as having most
of the aldehydes in the mixture represented by the
structure set forth below, and their saturated
aldehyde, alcohol, ethoxylated alcohol, and
ethoxylated alcohol sulfate derivates:
<IMG>
Wherein:
m = 0 or 1
p, q, r, s, t = 0 or 1 but only one of s and t can be
1;
m = 1 when r = 0 and only one of p and q can be 1;
m = 0 when p and q = 1

-104-
28. A mixture of isomeric enals in accord
with Claim 7 and further characterized as having most
of the aldehydes in the mixture represented by the
structure set forth below, and their saturated
aldehyde, alcohol, ethoxylated alcohol, and
ethoxylated alcohol sulfate derivatives:
<IMG>
Wherein:
R = methyl or ethyl; h and n = 0, 1, 2, 3, 4, and 5;
n and s = 0, 1, 2; p, q, r and t = 0 or 1;
q and p = 0 when m + k = 5 or when m + k = 2
n + s can never be greater than 2
m + h can never be greater than 5
h = 3 and m = 1 when R= methyl and q = 1 and p = 0;
h = 2 and m = 1 when R = ethyl and q = 1 and p = 0 or
when q = 0 and p = 1;
h = 1 and m = 3 when p = 1 and q = 0;
r and t = 0 when n + s = 3 or when n + s = 0;
s = 0 when n, r and t = 1 or when n = 2, r=0 and t=1;
s = 1 when n = 1 and t and r = 0 or 1 but only one
of t and r can be 1;
s = 2 when t = 1 and n = 0

-105-
m + h = 5 or 4, when p and q = 0;
m and q = 1 and p = 0 when h= 3, 2 or 1 but
R can only be ethyl when h= 1, 2 and R
can only be methyl when h = 2, 3;
h + m can never be greater than 5;
n + s can never be greater than 2;
q = 0 and p = 1 and h = 2 when m = 1 or 0;
q = 0 and p = 1 and 1 = 1 when m = 3 or 2;
r and t = 0 when n + s = 3 or when n= 0 and s = 2;
t = 1 when n = 0 or 1 and s = 1 or 2;
n and t = 1 when s = 0 and r = 1;
29. A mixture of isomerice enals in accord
with Claim 7 and further characterized as having most
of the aldehydes in the mixture represented by the
structure set forth below, and their saturated
aldehyde, alcohol, ethoxylated alcohol, and
ethoxylated alcohol sulfate derivatives:
<IMG>

-106-
Wherein:
R = methyl or ethyl; h and m = 0, 1, 2, 3, 4 and 5;
n and s = 0, 1, 2; p, q, r and t = -0, 1:
m + h = 5 or 4, when p and q = 0;
m and q = 1 and p = 0 when h= 3, 2 or 1 but
R can only be ethyl when h= 1, 2 and R
can only be methyl when h = 2, 3;
h + m can never be greater than 5;
n + s can never be greater than 2;
q = 0 and p = 1 and h = 2 when m = 1 or 0;
q = 0 and p = 1 and l = 1 when m = 3 or 2;
r and t = 0 when n + s = 3 or when n= 0 and s = 2;
t = 1 when n = 0 or 1 and s = 1 or 2;
n and t = 1 when s = 0 and r = 1;

-107-
30. The enals of Claim 23 in which about 40
to 60% by weight of the enals are 2(3-methylbutyl)-
5-methyl-2-octenal, 2(1-methylbutyl)-5-methyl
-2-octenal and 2-pentyl-5-methyl-2-octenal.
31. As a new compound, a C14 enal suitable
for conversion to compounds for use in detergents, and
in liquid form, designated as 2(3-methylbutyl)-5-
methyl-2-octenal.
32. As a new compound a C14 enal suitable
for conversion to compounds for use in detergents, and
in liquid form, designated as 2(1-methylbutyl)-5-
methyl-2-octenal.
33. A process of preparing detergent range
aldehydes which comprises conducting oxo reactions in
which olefins are reacted with hydrogen and carbon
monoxide to provide aldehydes and conducting an aldol
reaction of such aldehydes comprised of at least 50%
alkanals with no branching at the 2-position and of
carbon number so as to produce aldol product having
mainly carbon numbers in the range of 11 to 16 carbon
atoms, to cause good conversion to aldol product but
with that produced from cross-aldol of 2-substituted
aldehydes constituting no more than 20% of the
product.
34. The process of Claim 33 in which
product is obtained in enal form.
35. The process of Claim 33 in which the
aldol rection is conducted in aqueous alkali and a
cosolvent is present which aids in improving contact
of the aldehydes with the aqueous alkali.
36. The process of Claim 35 in which an
hydroxyl compound is employed as cosolvent.
37. The process of Claim 33 in which the

-108-
aldol product is hydrogenated and oxidized to obtain
corresponding saturated carboxylic acids.
38. The process of Claim 33 in which the
aldol product is hydrogenated to alcohol and therefrom
converted to ethoxyl, sulfate or ethyoxyl sulfate
derivative.
39. The process of Claim 33 in which the oxo
reaction is conducted with cobalt catalyst at
temperatures in the range of 80 to 150°C and pressures
sufficient to maintain catalyst stability but not over
5000 psi (34,475K Pa), and the aldol reaction is
conducted in aqueous alkaline medium at temperatures
of about 90 to about 130°C.
40. The process of Claim 33 in which
aldehyde for the aldol reaction has content of
alkanals with no 2-branching of about 60 to about 80%
and the conversions of aldehyde to aldol product are
in the range of about 75% to about 90%.
41. A process of preparing detergent range
aldehydes which comprises conducting an oxo reaction
with hydrogen, carbon monoxide and olefins selected
from those having 5 to 7 carbon atoms to obtain
aldehydes having from 6 to 8 carbon atoms and
comprised of at least 50% alkanals with no branching
at the 2-position and subjecting the aldehydes to an
aldol reaction to cause good conversion to aldol
product but with that produced from cross-aldol of
2-substituted aldehydes constiting no more than 20% of
the product.
42. The process of Claim 41 in which the
aldol reaction is conducted in aqueous alkali and a
cosolvent is present which aids in improving contact
of the aldehydes with the aqueous alkali.
43. The process of Claim 42 in which an
hydroxyl compound is employed as cosolvent.

-109 -
44. The process of Claim 43 in which the
cosolvent is methanol or an alkane diol.
45. The process of Claim 41 in which a C5 olefin
is reacted.
46. The process of preparing detergent range
aldehydes with a high content of aldehyde in the C11 to C14
range which comprises conducting an aldol reaction of heptanals
obtained from oxo reaction of branched hexenes from propylene
dimerization, with butanal and obtaining an aldol product with
a high content of 2-undecenals.
47. The process of Claim 46 in which aldol
product is hydrogenated to alcohol and ethoxylated to an
ethoxyl containing detergent.
48. The process of Claim 46 in which aldol
product is hydrogenated to alcohol and converted to a sulfate
with detergent properties.
49. The process of preparing aldehydes which
comprises conducting an oxo reaction with hydrogen carbon
monoxide and a hexene mixture comprises mainly of
methylpentenes with internal unsaturation with no more than 30%
linear hexenes so as to obtain C7 aldehydes with less than 30%
2-substituted aldehydes and subjecting the aldehydes to aldol
reaction to obtain aldol product with conversion of at least
70% and hydrogenating the aldol product to alcohols, including
hydrogenation of aldehydes which did not react at the aldehyde
stage, separating the resulting C7 alcohols and dehydrating
same to C7 olefins and cycling the olefins back to the oxo
process to convert such olefins to C8 aldehydes which are then
subjected to the aldol reaction and subsequent hydrogenation
with aldol product, thereby producing an alcohol product
comprised mainly of C15 isomers corresponding to the C14 enals,
but with some C14 and C16 alcohols from participation of C8
aldehyde in the aldol reaction.

50. A process for preparing detergent range
aldehydes which are liquid and suitable for conversion to
alcohols for use in formation of effective and
biodegradable detergents, from olefin feedstock in an
efficient process with good yields compared to other routes for
producing detergent alcohols from olefins, which comprises
conducting an oxo process with cobalt catalyst with a hexene
mixture obtained by dimerization of propylene and comprised
mainly of methylpentenes to obtain aldehyde product with at
least 75% or so of aldolable aldehyde, and subjecting the
aldehydes to an aldol reaction with basic catalyst to obtain
enals which are liquid at ambient temperature and comprising
C14 enal isomers characterized as nine carbon enals with a five
carbon alkyl substituent on the 2-position thereof and with
additional, mostly methyl branching in most isomers.
51. The process of Claim 49 in which the
hexenes contain a substantial amount of 2-methyl-2-pentene from
which the aldehyde product is composed of more than 85%
aldolable product and the aldolable content of the aldehyde
mixture is better than 75%.
52. The process of Claim 49 in which the hexene
mixture comprises substantially the hexenes mixture from a
dimerization of propylene over a nickel and aluminum alkyl
catalyst.
53. The process of Claim 41 in which the
hexenes include 4-methyl-pentene-1 produced by alkali catalyzed
dimerization of propylene.
54. A process of preparing detergent range
aldehydes which comprises conducting oxo reactions in which
olefins are reacted with hydrogen and carbon
110

monoxide to provide aldehydes and conducting an aldol reaction
of such aldehydes comprised of at least 50% alkanals with no
branching at the 2-position and of carbon number so as to
produce aldol product having mainly carbon numbers in the range
of 11 to 16 carbon atoms, and with the slower reacting 2-
branched aldehyde being recycled to the aldol reaction to
generate a higher yield of the desired unsaturated aldehyde.
55. A member selected from the group consisting
of (a) the ethoxyl derivatives, (b) the sulfate derivatives and
(c) the ethoxysulfate derivatives of a mixture of C14 isomeric
alcohols which are characterized as nine-carbon alkanol with a
five-carbon alkyl group substituted on the 2-position thereof,
and with additional branching in most of the isomers, with most
of the additional branches being methyl groups, and further
characterized as liquid at ambient temperature and having
varying hydrocarbon hydrophobe moieties.
56. The product of Claim 55, wherein the ethoxy,
sulfate or ethoxy sulfate derivatives are derived from said
alcohols in which there is about 20 to about 35% of the alcohol
have adjacent branches in their structure, but there are
substantially no alcohols with gem substituents and therefore
substantially no quaternary carbon.
57. A detergent composition comprising the
product of Claim 55 or 56.
111

Description

~:25~35
-1- 07-21-(183)A
DETERGENT RANGE A$DEHYDE ~D AL~OHOL MIXTURES
AND DERIVATI~ES, AND PROCESS THEREFOR
The present invention is concerned with a
process for preparing detergent hydrophobes from
olefin feedstock-, and with novel detergent range
aldehyde, alcohol and acid hydrophobes.
BACKGROUND OF THE INVENTION
The principal commercial surfactants in use
today are linear alkylbenzene sulfonates and linear
alcohol ethoxylates. The hydrophobic portion of both
surfactants is a linear alkyl chain of between eleven
an~ elghteen carbon atoms. These surfactants had been
preceded by synthetic detergents which contained
highly branched groups as a hydrophobic portion. The
change to the currently employed linear groups, which
occurred in the 1960's, was prompted by concern over
the slow biodegradation characteristics of the
branched hydrophobes. The perceived need for
linearity led to development of particular approaches
to hydrophobe preparation. The linear alkyl benzene
sulfonates are based upon linear olefins derived
from paraffins, which in turn are obtained through
molecular sieve separations from~ paraffin mixtures.
The linear alcohol based detergents are produced by
way of ethylene oligomerization, followed by processes
to manipulate the broad range of olefins obtained into
the desired molecular weight range. The processing
involved in such approaches adds considerably to
energy and facilities usage and consequently to

~2~7~9~
-2- 07-21-(183)A
product cost. When olefins of the requisite carbon
atom number have been obtained, they can be
hydroformylated to produce aldehydes, generally with
one more carbon atom than the olefin, which can be
hydrogenated to an alcohol.
An alternate method for generating longer
chain alcohols from short chain oleflns is via a
sequence involving hydroformylation (or oxo reaction)
ollowed by aldol condensation and hydrogenation.
Thus 2-ethylhexanol is prepared on a very large scale
by (a) hydroformylating propylene to a mixture of
n-butanal and isobutanal, (b) separating the mixtures
of aldehydes (c) aldol reaction of n-butanal to
2-ethylhexenal and (d) hydrogenation of 2-ethylhexenal
to 2-ethylhexanol. While this approach is well-
recognized to be cost effective for generation of
medium chain alcohols, it has not heretofore been
shown to be an economical method for generation of
longer chain alcohols. Among patents teaching
conversion of aldehydes to higher aldehydes by the
well known aldol reaction is U.S. patent 2,852,563.
Medium chain length olefins are usually
derived from dimerization or oligomerization of
ethylene or propylene. Among dimerization processes is
the Dimersol ~ dimerization process ~or dimerizing
olefins using a nickel coordination complex and an
aluminum alkyl as catalyst. The process can convert
propylene to hexenes with selectivity in excess of
85%. The hexenes can be converted by oxo reaction to
aldehydes and then alcohols, producing heptanols.
Processes are also known for dimerizing propylene with
trialkylalumminum metals to 4-methyl-1-pentene, see
Industrial Organic Chemistry, Klaus Weissermel and
Hans-Jur~en Arpe; English translation by Alexander
Muller (Verlag Chemie, Weinheim, ~ew York, 1978), pp

~ 2~3~9~
-3- 07-21-(183)A
75-77. Also oxo reactions of certain branched olefins
have been studied; see M. Johnson, . Chem Soc. 1963,
~859; Piacentl et al, J. Chem. Soc., 1966, 488; and
Vysokinskii et al, J. Applied Chemistry of USSR, 1972,
Vol. ~5, pp. 1352-1355. Also oxo reactions of certain
non-terminal octenes have been reported to give less
than 60~ of the straight chain aldehyde isomers, see
Kummer et al, Homogeneous Catalysis-II, pages 19 to
26, Advances in Chemistry Series 132 (Edited by Denis
Forster and James F. Ro~h), American Chemical Society,
Washington D.C., 1974.
Reactions of the type described
characteristically produce mixtures of products, often
with extensive branching. Therefore, in order to
control the branching, or to eliminate unreactive
components, it has been common practice to employ
distillation at intermediate stages to remove some of
the isomers.
SU~MARY OF T~E IMVENTION
The invention is concerned with a process in
which olefins selected from those with 3 to 7 carbon
atoms are converted to aldehydes with 4 to 8 carbon
atoms, which are then subjected to aldol condensation
to obtain aldol products in relatively high yield.
The aldehydes can be hydrogenated to alcohols having
useful properties and derivative uses, with especial
interest in conversion of hexenes to heptanals and to
C14 alcohols for use in detergents. The aldehydes can
also be converted to other compounds useful as
detergents or for other purposes. The inven~ion is
particularly concerned with the foregoing process in
which the olefins have 5 to 7 carbon atoms and are
converted to aldehydes with 6 to 8 carbon atoms, and
then to enals and saturated aldehydes with 12 to 16
carbon atoms, in the detergent hydrophobe range. Such

.5.`~
-4- 07-21-(183)A
processes and the aldehyde, alcohol and detergent
derivative products thereof are particularly
exemplified herein by processes leading to, and
products mainly composed of, compounds with 14 carbon
atoms. The conditions of the exemplary process are
generally applicable to those employing other
reactants in the stated carbon atom ranges.
The present invention particularly concerns
a hydrophobe aldehyde or alcohol mixture composed
almost entirely of C14 aldehydes or alcohols with a
structure branched at the 2-position, with the
alcohols being generally 2-pentylnonanols, i. e.
having a five-carbon alkyl group substituted on the
2-position of a nlne-carbon alkanol; with most of the
isomers in the mixture having moderate additional
branching, primarily methyl groups. The mixture is
liquid at ambient temperatures and the hydrophobe
groups of the alcohols are such as to make the mixture
- useful for formation of very effective detergents.
The alcohol structures are further characterized by
the absence of quaternary carbon or other structures
strongly resistant to biodegradation, while generally
having vicinal branching within limited ranges, and
are still suitably biodegradable. The invention is
further concerned with other aldehydes and alcohol
mixtures of such 2-branched structure, but with 11 to
15 carbon atoms., e.g. ethyl-nonanol and
hexyldecanols.
The invention is further directed to
processes for converting olefins to described C14
aldehydes and alcohols, involving dimerization, oxo,
aldol and hydrogenation processes based on propylene.
In particular, a process involves conducting an oxo
reaction with a hexene mixture comprised mainly of
methyl pentenes, as produced by dimerization of

~5 o'~
-5- 07-21-(183)A
propylene, and obtaining a heptanal product in which
carbonylation has occurred primarily on terminal
carbon so that upwards of 75~ oE the heptanal isomers
are unbranched at the 2-position and capable of
reacting directly in aldol reactions under basic
conditions; and conducting an aldol reaction of the
heptanal product to obtain C14 aldehydes which are
then hydrogenated to C14 alcohols. The invention
further includes use of cobalt catalyst in the oxo
procedure under conditions to produce high percentages
of desired aldolable product, and utilization of a
co-solvent and suitable aldol conditions to obtain the
C14 product. Fortuitously, it has been found that in
the hydroformylation of isomeric hexenes, the
formylation of the prominent 2-methyl-2-pentene isomer
occurs primarily on a terminal bond, with the
percentage of such terminal formylation being much
higher than that generally characteristic of
hydroformylation of internal olefins; and a high
percentage of aldolable product is obtained from
terminal formylation of isomeric hexenes. The present
invention involves an efficient process for converting
propylene dimers to detergent hydrophobe alcohols in
high overall yields such as 70~ or better, and the
alcohols are suitable for conversion to detergents
having detergent and biodegradation properties
comparable to those of the common commercial
detergents. Moreover, the present process provides a
much more efficient and economical route to detergent
hydrophobes from olefin feedstock than that provided
by the routes prominent in present commercial use.
This route permits detergent alcohols to be built up
from low cost propylene as compared to present
commercial processes based on ethylene~ In the
processes of the invention, the immediate precursor of

~:25~g~
-6- 07-21-(183)A
an alcohol is an aldehyde, and the aldehydes can also
be converted to other useful compounds.
DETAILED DESCRIPTION OF THE INVE~TION
The C14 alcohols of the present invention
can be represented:
R--CHcH2oH
R'
in which R is an alkyl group with seven carbon atoms
and R' is an alkyl group with five carbon atoms. In a
high percentage of the alcohols in the mixture,
generally more than 80-85% or so, R'is selected from
n-pentyl, 3-methylbutyl and l-methy butyl, and R is
selected from n-heptyl, 3-methylhexyl, 5-methylhexyl,
2-methylhexyl and 2-ethylpentyl groups. While there
will be some variance in the alcohol mixture with
variation in preparation conditions, generally close
to 50% or so of the alcohol mixture will be composed
of2-~3-methylbutyl)-5-methyl-octanol,2-(1-methylbutyl)
5-methyloctanol and 2-pentyl-5-methyloctanol.
Considering the type of branching involved, close to
50~ or so by weight of the alcohols will have
branching not only at the 2-position, but with each
branch having an additional methyl branch, i.e. with
R' and R in the above formula being selected from
methylbutyl and methylhexyl groups respectively. The
alcohols are also characterized as generally having a
limited amount of vicinal substitution, i.e.
substitution or branching on ad~acent carbon atoms,
and little or virtually no di substituted carbon chain
atoms, i.e. quaternary carbon atoms. Significant
amounts of alcohols with guaternary carbon atoms have
not been found in product analyses, and the types of

~:~57~
-7- 07-21-(183)A
reactants and reactions used in product preparations
make it very unlikely that significant amounts of such
alcohols would be found in unidentified portions of
products. The lack of quaternary carbon in the
alcohols of the mixture is fortunate in that such
carbon is ordinarily resistant to biodegradation.
The described alcohols are obtained by
hydrogenation of aldehydes of the same structure, and
such aldehydes are similarly useful for their
hydrophobe character and convertability to useful
detergent or other derivatives. Such aldehydes are
represented by the formula:
R - CHCHO
R
or when still in the enal form:
R = IHC~O
where the double bond is to one of the carbons o~ the
R group. In such formulae, R and R' have the same
meanings as described with respect to the alcohols,
except that R in the enal is now alkylidine. For
alcohols, enals and saturated aldehydes of twelve
carbon atoms, R has six carbon atoms, and R' has four;
and for sixteen carbon atoms R has eight carbon atoms
and R' has six. R and R' will similarly vary for
other structures having 11 to 16 carbon atoms, R from
6 to 8 carbon atoms, and R' from 2 to 6 carbon atoms~
As with the C14 alcohols, the Cll, Cl~, 16
aldehydes and alcohols will often have branching not

~ 257~
-8- 07-21-(183)A
only at the 2-position, but with each branch having an
additional methyl or ethyl branch.
A useful group of the unsaturated aldehydes
of the present invention can also be represented:
RCH = C - CHO
R'
in which R plus R' total 8 to 13 carbon atoms and in
which often in a high percentage t75~) of the
unsaturated aldehyde, alkyl branches R and R' can be
branched also with branching being limited to methyl
or ethyl groupS-
With further regard to the particular Calcohol mixture, approximately 40 to 60~ by weight
will generally be the 2(3-methylbuty)-5-methyloctanol,
2-(1-methylbutyl)-5-methyloctanol and 2-pentyl
-5-methyloctanol; and at least about 65~ and possibly
65 to 80~ or so by weight will be comprised of these
- alcohols, along with 2-(3-methylbutyl)-7-
methyloctanol, 2-pentylnonanol,2-pentyl-7-
methyloctanol and 2-(3-methylbuty)-nonanol. In
addition to the indicated ranges of these alcohols,
various other C14 isomers will be present in small
percentages, particularly those other alcohols listed
in Table 4 herein, in amounts by weight usually
approximating those in the Table and generally no more
than 5% each and usually in ranges up to 1 to 2~ or
so, and with the balance of the C14 alcohols being
generally composed of the other alcohols in Table 3
herein, which will generally be present only in small
percentages of each isomer. It will be noted that
those isomers present only in small amount, with no
amount reported in Table ~, but included in ~able 3,
tend to be more highly branched, i.e. multi-branched,

p
-9- 07-21-(183)A
than the other isomers, although most branches are
still methyl, or occasionally ethyl groups. Taking
these isomers into consideration, the amount of
vicinal branched material may range as high as 20 to
35% or so by weight of the Cl4 alcohols. However, the
mlxtures of alcohol isomers are biodegradable as
indicated by tests reported herein. One of the
alcohols which can be present in fairly-good
proportion, such as 10 to 20% or so,
2-(1-methyl-buty)-5-methyloctanal is a vicinal
branched alcohol. The alcohols in the mixture are
characterized by a fair degree of branching, although
the alcohols present in large amount tend to be less
branched than some of the minor components. Thus the
18 or so alcohols constituting about 90-95~ or so by
weight of the alcohols have an average of slightly
more than 2 branches, about 2.2 to 2.4 branches, while
the other 5 to 10~ of the alcohols may have upwards of
above 3.5 branches, such as 3.75-3.8 branches.
In addition to the novelty of the Cl4
alcohol mixtures of the present invention, the
particular alcohols are also new except for the
2-pentylnonanol. Thus the other 27 alcohols named in
Table 3 are new compounds suitable for formation of
nonionic detergents.
The alcohols comprising most of the present
alcohol mixtures produced from branched hexenes can
also be represented by the formula:

~.25~
-10- 07-21-(183)A
CH3-C~ (CH2)~_ CH _ CH CH _ _ CH2CH
I
(CH3)p (CH3)q (R)r CH (CH3)S
(CH2)n
I
CH (CH3)t
CH3
wherein:
R = methyl or ethyl;
p, q and r = 0 or 1; but only one of p,
5 and r can be 1;
m = 3, when p, q and r = o;
m = 2, when p or q = 1;
m = 2, when r =1 and R = methyl;
m = 1, when r = 1 and R = ethyl;
n = 2, when s and t = 0;
n = 1, when s or t = 1;
s and t = 0 or 1, but only one of s and t
can be 1.
The alcohol mixtures, and the individual
components thereof, are liquids at ambient
temperatures. This is advantageous in that the
alcohols can be more readily transferred from one
vessel to another, or moved by pumping through
conduits, etc., than is the case with solid alcohols.
2~ ~lso the liquid form is more convenient for mixing
with reactants and solvents for conversion to
detergent compounds or other useful products as
contemplated. It happens that C14 alcohols with
straight chains, or with considerably less branching
than the present alcohols, are generally solids. Thus

~5~
-11- 07-21-(183)A
detergent alcohols obtained by way of ethylene
oligomerization, such as 75% to 80% normal primary
C12 15 alcohols and 75~ normal C14 primary alcohols,
consisting of the designated percentages of normal
alcohols and the balance of isomeric 2-alkyl~primarily
2-methyl)primary alcohols, are solid materials.
Mixtures of aldehydes can also be represented by the
above formula, with the CH2OH group replaced by CHO.
For the corresponding enal structure, there is
unsaturation at the 2-position:
I
-CH ~C - CHO
(l-r)
The detergent alcohols of the present
invention are particularly suitable for conversion to
nonionic detergents of good detersive and
blodegradation properties. The largest volume use of
detergent alcohols is as nonionic surfactants. The
polyethoxylate surfactants are particularly important,
and can be generated from the present alcohols by base
cataly~ed reaction between ethylene oxide and alcohol:
ROH + n CH2 - CH2 Ro(cH2cH~o)nH
Typical values of n are in the range of 6 to 12, and R
represents the alkyl portion of the alcohol, which for
the present alcohols is generally a 14-carbon alkyl
group. Ethoxylates prepared from the present alcohols
were tested for detergency and found to be comparable
to a leading commercial nonionic detergent under a
variety of washing conditions. The commercial
detergent is that prepared from C12 15 alcohols of

~2~
-12- 07-21-~183)A
75-80% linearity, Neodol ~ 25.
In addition to detersive properties, anothec
concern with surfactants has been biodegradability.
The first major synthetic detergents were so-called
alkylbenzene sulfonates,-with an alkyl hydrophobe
group derived from propylene tetramer. The propylene
tetramer was produced by acid catalyzed polymerization
and hence was highly branched, including extensive
quaternary branching. This gave rise to a peoduct
with rather poor biodegradation properties, which led
to extended life for surfactant properties in rivers
and lakes. Public concern over the asthetic impact
(foam) and possible toxicity of long lasting
surfactants led to a voluntary change over to
predominatly linear hydrophobes. Prominent among
current surfactants are linear alkylbenzene sulfonate
and the linear alcohol ethoxylates discussed above.
The linear alkylbenzene sulfonate (L~S) involves a
linear alkyl group substituted on a benzene ring,
generally at one of the secondary carbon atoms of the
alkyl group. LAS has been found to be a suitably
biodegradable detergent, although being degraded
some~hat more slowly in standard tests than the
substantially linear alcohol ethoxylates. The
ethoxylates produced from the alcohols of the present
invention are comparable in biodegradation to LAS, and
therefore suitable in this regard. It is fortunate to
find that the present alcohols are biodegradable,
despite the presence of multiple branching. The
substantially linear alcohol ethoxylates, such as
Neodol ~ 25, are known to be biodegradable, but those
alcohols include substantial percentages of linear
alcohols, and the branching is ordinarily only a
single methyl or other lower alkyl group. In
contrast, most of the alcohols in the present mixture

` ~L2~,9~;
-13- 07-21-(183)A
have more than two alkyl branches. It is advantageous
to be able to produce the present detergent alcohols,
of properties comparable to Neodol ~ alcohols, in a
more efficient process and from a less expensive
feedstock, i.e. from propylene rather than ~rom
ethylene.
The enals and aldehydes produced in the
present process are also suitable for conversion to
other useful compositions. Thus, in accord with the
discovery of one of the present applicants, olefins
can be converted to useful amine compounds by
reactions involving hydroformylation and aldol
reactions, followed by reaction with amines to obtain
substituted amines. The reaction can be effected at
the enal stage, or with the saturated aldehydes. Thus
tetradec-2-enals or tetradecanals are reacted with a
secondary amine under reductive conditions to obtain
tetradecyl amines, e.g. dimethyl amine gives
N,N-dimethyltetradecylamines. Use of a primary amine
gives di(tetradecylamines), e.g. with mono-methyl
amine, di-(tetradecyl)methylamines are produced. The
amines with one or two long chain hydrophobe groups
have detergent properties, and can be oxidized to
amine oxides which also have detergent properties, or
quaternized to ammonium salts which have interesting
germicidal and other properties. Thus the present
invention provides aldehydes which can be utilized for
production of amines or ammonium compounds with useful
properties. The aldehydes can also be converted to the
corresponding saturated or unsaturated acids in accord
with procedures described herein. While some
branched-chain acids in the detergent range have an
objectionable odor, the Cll to C16 derivatives of the
aldehydes described herein are expected to have
suitably low odor in view of the type of branching

~Z~7~
-14- 07-21-(183)A
involved.
Hexenes, as produced by dimerization of
propylene with transition metal catalysts, as in the
Dimersol ~ dimerization process, are characterized by
being composed mainly of internal oleEins, and a
linear content which has a range from about 20~ up to
32% or so. The main isomer present is a
- 2-methyl-2-pentene, along with other 2- and 4-methyl
pentenes and around 6~ 2,3-dimethyl-2-butene.
As indicated above, the linear content of
propylene dimers is fairly low, being around 20~ to
30% or so. ~t times there may be advantage in
separating the linear components prior to conducting
the present process. Separation can be effected by
use of a molecular sieve or other suitable procedure.
However, it has been found that the entire hexenes
portion of the propylene dimerization product can be
utilized as feedstock for the present oxo-aldol
process. The branched isomers are typified by
2-methyl-2-pentene which, when subjected to oxo
reaction with cobalt catalyst, has been found to be
very selectively converted to 3-methyl and
5-methylhexanals. Fortunately it has been found that
cobalt catalyst, in contrast to rhodium, has the
effect of isomerizing the internal olefins so that the
aldehyde group is predominantly on the end of the
chain. It is very important to the use of propylene
dimer in the present process, that the oxo product is
predominantly a non 2-branched alkanal., i.e. there is
no substituent in the 2-position. Such aldehydes,
which will direc~ly reac~ in base-catalyzed aldol
reactions are sometimes referred to herein as
"aldolable" aldehydes. As discussed herein, aldehydes
with substituents in the 2-position do not readily
undergo base-catalyzed aldol reactions. Thus i~ the

~257~
-15- 07-21-(183)A
internal hexenes were converted largely to such
unreactive aldehydes, it would be very difficult to
effect self-condensation of such aldehydes to a useful
extent, and thç use of propylene dimers in the present
oxo-aldol process would be impractical. However, as
discussed herein, the oxo process with cobalt catalyst
converts the hexenes largely, e.g. 75 to 80~ or so, to
aldehydes which will react in the aldol reaction,
making hexenes, obtained from propylene dimerization
very suitable as a feedstock for producing detergent
range alcohols in accord with the present invention.
This result is surprising in view of the fact that oxo
reactions of certain non-terminal octenes are reported
to give less than 60~ of straight chain aldehyde
isomers. It appears that the methyl substitutent has
some influence in directing the oxo reaction to obtain
a great predominance of aldehydes with no substituent
in the 2-position. There will similarly be advantage
in using branched pentenes and heptenes in the present
process, including those with no more than 20 to 30
linear content, even including those with mainly
internal unsaturation, and obtain similarly good
results in the oxo and aldol reactions taught herein.
Particular branched hexene isomers are
converted to non 2-branched alkanals with very high
selectivity, with 2-methyl-pentene-1 selectivity of
better than 90~ to such aldehydes being obtainable.
The mixture of both branched and linear hexenes from
propylene dimeri2ation can be converted to such
aldolable aldehydes with selectivity such as about 79~
or so. In contrast, the selectivity to such aldehydes
from the linear hexenes may be only 60~ or so. Thus,
surprisingly it is found that higher selectivity to
aldehydes desirable for the aldol reaction can be
obtained by using the crude hexenes mixture for the

" ~ Z S 7 ~ g ~
-16- 07-21-(183)A
oxo reaction, rather than only the linear hexenes.
Depending upon relative value and availability of the
linear and branched hexenes, one might find advantage
in using only the branched hexenes in the present
process because of the high selectivity in the oxo
process to aldehydes with no 2-branching suitable for
aldol reaction.
The linear hexenes can be separated from the
crude dimerization product by use of a molecular sieve
or other suitable procedure, and the linear hexenes
alone then subjected to an oxo reaction to obtain
heptanal products, with the linear content of the
heptanals ran~ing up to 75% or more. Branched isomers
which may be present include 2-methylhexanal, and
2-ethylpentanal. The oxo product mixture can be
reacted in an aldol reaction, employing aldol
conditions as described herein, to produce aldol
products. Under the aldol conditions employed, the
n-heptanal reacts with itself at a rate about 10-15
times faster than it reacts with 2-methyl-he~anal or
other 2-substituted aldehydes. Thus, when the C7
aldehydes are produced from linear hexenes, a product
compound predominantly of product from
self-condensation of n-heptanal can be obtained by
carrying out an aldol reaction of the oxo reaction
product, with some control over the amount of product
from 2-substituted aldehydes by controlling the
amounts of conversion which is permi~ted. It may be
desirable to have better than 50 to 60~ completion for
efficient use of feed stock, and conversion of 80~ or
higher may at times be desirable. The reaction can be
run to achieve 95~ or better conversion of the
n-aldehyde to aldol product, while only about 1/4 to
1/3 or so of the 2-substituted aldehydes are usually
converted to aldol product by a cross-aldol reaction.

~Z57;~
-17- 07-21-(183)A
With use of appropriate control, aldol product with
about 80~ to say 95~ from self-condensation of
n-heptanal can be obtained, for example at least 85
from self-condensation, with no more than 15~ of
cross-aldol product. Depending upon the properties
desired in the product, the degree of branching can be
controlled to a considerable extent by the present
process. It happens that some known detergent range
alcohols have a fair degree of branching and still
have satisfactory biodegradability. Regardless of the
desired degree of branching, there is advantage in
being able to carry out an aldol reaction o~ the oxo
product of the hexenes, without need for separating
branched aldehyde isomers, and obtain a useful
product, particularly considering the low cost nature
of the feed stock and process. With a proper heptanal
mixture, the process can be used to obtain a product
composed of about 85% 2-pentylnonanol and 15%
2-pentyl-4-methyl-octanol.
The oxo process can generally be utilized to
achieve ~0-95% yields of aldehydes. With linear
hexenes as reactant, selectivity to aldehydes without
2-substituents, i. e. ~ -aldehydealkanes, can be as
high as 60 to 65%, but in large scale operation will
possibly range from 50 to 65%.
The present invention employs an oxo
reaction of substantially branched hexenes to obtain a
mixture of aldehydes, which is then subjected to an
aldol reaction. The oxo reaction involves contacting
hexenes with hydrogen and carbon monoxide and
hydroformylation catalyst under hydroformylation
conditions suited to obtaining a high proportion of
terminal formylation of the olefin feed. It is
desirable to have the resulting aldehyde constitute 75
to 80~ or more of the aldehyde product.

~25~29~
-18-
It is important that the hydroformylation of
the mixed hexenes give a relatively hi~h ratio of
aldehydes without 2-branching, as this contributes to
the feasibility of using the aldehyde mixture for an
aldol reaction to obtain a good yield of aldol product.
The use of moderate temperatures in the hydroformylation
contributes to forming aldehydes without 2-branching,
but reaction rate improves with temperature. Thus
temperatures sufficient to produce an appreciable
reaction rate, ranging from 80 to 100C. or so can be
usedr and temperatures on up to 125-140C. can be
employed to obtain better reaction rates. Still higher
temperatures up to 150C. or higher can be used. To
some extent high catalyst concentrations can be employed
to obtain reaction rates, even at relatively low
temperatures. Cobalt catalyst is especially suited to
obtain the desired high proportion of aldehyde with no
2 branches. Unmodified cobalt carbonyl catalyst can
conveniently be used. Such catalyst conventionally
designated as dicobalt octacarbonyl, can be provided or
employed in many forms known to be useful as a
hydroformylation catalyst, although it may be necessary
to exercise some choice to provide catalyst best suited
to obtaining a high proportion of aldehyde with product
suitable for direct base-catalyzed aldol reaction. U.S.
Patent 4,4~6,542 of January 17, ]984 discloses
conditions as above for hydroformylation of mixed linear
butenes, stating that moderate temperatures in
hydroformylation contribute to obtaining about a 3:1
mixture of normal to branched aldehydes. The conditions
can be used for hydroformylation of olefins with 3 to
7, or more narrowly, 5 to 7 carbon atoms. US patent
4,426,542 further described as exemplary a process
in which mixed butenes are

~25~
-19- 07-21-(183)A
converted to a ten-carbon plasticizer alcohol
comprised of at least about 80-90% 2-propylheptanol by
an oxo reaction of the butenes to obtain amyl
aldehydes with at least about 66~ n pentaldehyde
content, followed by an aldol reaction of the
aldehydes under conditions to cause substantially all
of the-n-pentaldehyde to react but with incomplete
conversion of branched aldehydes, and then
hydrogenating to produce alcohols in which the
ten-carbon alcohols are comprised of at least 80-90%
2-propylheptanol. Under the aldol conditions employed
the 2-methylbutanal present does not readily condense
with itself, and condenses at a comparatively slow
rate with the n-pentanal, so that the
2-propyl-4-methylhexanol content (resulting from the
so-called cross aldol of n-pentanal with
2-methyl butanal) in the resulting alcohol is held to
no more than about 15-20%, often 12% or less. Under
the aldol conditions employed , the n-pentanal reacts
with itself to form aldol product at a rate about 15
times greater than it reacts with 2-methylbùtanal.
The aldol reaction is permitted to go to 80% or so
completion so that if about 25% of the aldehyde
supplied is 2-methylbutanal, about 3/4 of it will
remain unreacted, and about 88~ of the aldol product
will be that from self-condensation of n-pentanal.
The conversion of n-pentanal to aldol product will be
very high and desirably nearly complete, such as
upwards of 90 or 95%. There will be some variation
with conditions and isomer content of the aldehydes
utilized, but it was contemplated to obtain aldol
product with about 80% to about 95% being from the
self-condensation of n-pentanal, and preferably at
least 85% from self-condensation with no more than 15%
of 2-propyl-4-meth~lhexanal being produced. In the

-20- 07-21-(183)A
process, the aldol intermediate, 2-propyl-3-
hydroxyl-heptanal, will ordinarily be dehydrated in
the aldol procedure to 2-propylheptenal. under some
conditlons the immediate aldol product can be
isolated, but ordinarily under the temperature
conditions employed the 2-propyl-2-heptenal is
- produced. In such procedure, it was desirable to have
the n-pentanal to branched aldehyde ratio at least
about 2.0:1, representing at least about 66.7~
n-pentanal content. Aldehydes with 70-75~ normal
content, or even higher normal contents are desirable
to the extent available from oxo reactions, possibly
up to 85~, and wlll be useful for the aldol stage.
The oxo stage of the reaction can be
conducted under the usual conditions pertaining to
cobalt catalyzed hydroformylation reactions with
attention to the temperature conditions as described
above. Usual pressure conditions apply, such as
50Q-4000 or up to 5000 psi (3447.5-27,580 on up to
34,475 kilopascals) total pressure, with most of the
pressure being from the carbon monoxide and hydrogen
supplied. The carbon monoxide and hydrogen are
conveniently used in 1:1 ratio and obtained from usual
synthesis gas sources, but other ratios can be
employed in keeping with known hydroformylation
prac~ice. The reaction can be carried to the desired
stage of completion in 1 to 3 hours or so on a batch
basis, temperature, pressure and catalyst
concentration.
The reaction can be conveniently conducted
either without a solvent or with solvents and,
employing concentrations customary for homogeneous
catalyst reactions, such as 2 to 10 molar or greater
concentrations of the hexenes (or butenes or other
olefins) in a solvent, e.g. hydrocarbon solvents such

-21-
as toluene, and 0.1% by weight, based on cobalt, of
catalyst.
The present invention is particularly
concerned with preparing detergent range alcohols and
aldehydes from propylene feedstock. The detergent range
alcohols are somewhat higher in carbon number than
plasticizer alcohols, often having 14 carbon atoms, but
in some cases ranging from about 11 to about 16 or so
carbon atoms. Propylene can be dimerized to hexenes,
and the hexenes can be converted to aldehydes by an o~o
reaction as described herein, and the resulting
heptaldehydes can be reacted in an aldol reaction to
produce aldol products which cn be hydrogenated to C14
alcohols. Using oxo product in which the content of
aldehyde without 2-substitution may range from 60 up to
near 80~ or so, aldol conversions may approach 75 to
90%, even though participation of the 2-substituted
aldehydes is limited, so that it is involved in cross-
aldol producing no more than 20~ of the product.
The aldol reaction is carried out for the most
part utilizing the usual aldol catalysts and temperature
conditions, using elevated temperatures upwards of
60C., particularly temperatures of about 90C. to
130C., or possibly up to 150C. or higher if desired,
the conditions also being those disclosed for n-pentanal
in U.S. Patent 4,426,542. The reaction is operable over
broad pressure ranges including pressures less than
atmospheric as well as elevated pressures, but will
usually be effected at slightly elevated pressures
sufficient to maintain the reactants substantially in
the liquid stata~ The reaction can also conveniently be
conducted at reflux.
The aldol reaction can utilize strongly
alkaline catalyst, such as sodium and potassium

57~9~
-22- 07-21-(183)A
hydroxide, or sodium and potassium cyanide. The
concentratlon of the aqueous alkali can be varied, but
molar or similar concentrations of alkali metal
hydroxides can be used, and concentrations selected
will generally be in the range of about 1 to 10~ by
weight. The amount of aqueous alkali to aldehyde
reactant can also vary, for example from about 15~ by
volume aqueous alkali up to about 75~ by volume
aqueous alkali. The aldol reaction will be run for a
sufficient time to obtain the desired degree of
conversion, which for batch reactions may be in the
range of about 1 to about 3 hours, while in continuous
reaction times of less than five minutes are
achievahle. The reaction is stopped by permi~ting the
reaction mixture to cool and separating the organic
reaction phase from the aqueous alkali phase.
In one major respect it is difficult to
conduct aldol reactions of heptanals in conventional
manner, as in aqueous NaOH, because this procedure
requires appreciable solubility of the organic
aldehyde in the aqueous phase, or vice versa. The
mutual solubility is so low with C7 aldehydes that
little reaction occurs in reasonable time periods.
However, it has been found that use of a co-solvent
overcomes this problem and results in suitable
reaction rates. In principle, any solvent with
miscibility with both the aldehyde and the aqueous
base, or at least some solubility with respect to
each, will act to increase the rate of the reaction.
It is also desirable that the solvent be relatively
inert under the reaction conditions so as not to cause
interfering reactions or to be readily degraded
excessively by the hot basic medium. In general,
polar solvents will tend to have the requisite
solubility characteristics, and hydroxy alkanes, for

~25';~2~
-23- 07-21-(183)A
example, alkane diols, having the appropriate
solubility characteristics can be used. Hexanediol is
very suitable. Methanol is also a suitable cosolvent.
In the aldol reactions involved in the
present invention it is necessary to utilize a high
proportion of aldehydes without 2-branching, also
referred to herein as aldolable aldehydes, in order to
achieve good yields of aldol. The 2-substituted
aldehydes do not undergo self-condensation aldol
reactions with any facility under the usual basic
aldol conditions, although they will serve as acceptor
molecules to some extent in cross-aldol reactions, as
illustrated with the following heptanal isomers:
CH3 ~H3
RCH--CHO RCH--CH
NaOH ¦l
+ H20 RCH 2-C-CHO
R CH2CH2CHO
in which R represents a butyl group~ However, the
2-substituted aldehydes react more slowly than other
aldehydes, and therefore would constitute an
undesirably high residue of unreacted component if
2~ provided to the reaction mixture in high proportion.
In the present process with 75 to 80~ or so of
aldehydes without 2-branching, the aldol reaction can
be conducted to include some cross-aldol of
2-substituted aldehydes so as to have yields of 85~ or
more based on starting aldehydeO In general, the C14

~57~
-24- 07-21-(183)A
aldehydes resulting from such cross-aldol reactions,
and the alcohols produced therefrom, have properties
comparable to those produced from aldol reactions of
aldehydes without 2~substitution, and are suitably
present in alcohol mixtures for detergent preparations
as described herein. The conversion of aldehydes
without 2-branching in such aldol reactions can be in
the range of 95% or better while possibly only about
1/4 to 1/3 of the 2-substituted aldehydes are
converted to aldol product.
The hydrogenation of the enals from the
aldol reaction can be conducted under the usual
catalytic hydrogenation conditions for reducing
olefinic bonds and aldehyde groups. The
carbon-to-carbon bond reduces more rapidly and at a
lower temperature than the aldehyde group, e.g. at
about 90C., with cobalt on Kieselguhr catalyst at
elevated hydrogen pressure. The hydrogenation will
generally be carried out at 100-20000 psi, or greater
hydrogen pressures and temperatures of 100 to 200C.
or higher, although any temperatures which are
effective with a particular catalyst can be used. The
stated conditions will be effective for reducing both
the carbon-to-carbon bond and the aldehyde group to
obtain saturated alcohol. Various other hydrogenation
catalysts can be used including platinum and platinum
on carbon catalysts, copper chromite, activated
nickel, etc., and individual catalysts can be utilized
in conjunction with other catalysts.
The present invention can include an oxo
reaction, followed by an aldol reaction, and then a
hydrogenation to convert enals to alcohols. For large
scale operations, the oxo reaction will be conducted
with usual provisions for separating gaseous reactants
and products, and catalysts, from the aldehyde

-25- 07-21-(183)A
products, with recycle as appropriate. The aldehyde
product mixture will then be subjected to an aldol
reaction, followed by decantation and water washing or
other simple procedures to separate the organic
product-containing phase from the aqueous phase. The
product phase is then hydrogenated, converting both
unreacted heptanals and C14 enals to the corresponding
alcohols when the product phase is from a heptanal
reaction. The hydrogenation is followed by a
distillation to remove light ends, followed by a
distillation to remove C7 alcohols. Both the C7 and
C14 alcohols can then be treated in further
hydrogenation polishing operations to improve the
alcohol quality by insuring complete hydrogenation.
The separation of the C7 from C14 alcohols
is readily effected by distillation in equipment
constructed of inexpensive alloys such as carbon
steel. Separation at this stage is simple, compared
to the difficult separation which would be required to
separate the seven carbon aldehyde isomers prior to
the aldol reaction.
As an alternate to the above procedure, it
is possible to separate the unreacted seven-carbon
aldehydes by distillation from the 14 carbon enals
prior to hydrogenation. For convenience of
separation, distillation of the alcohols is generally
preferred, However, if the aldehydes are desired for
some purpose, separation is appropriate, and this has
the advantage of avoiding unnecessary hydrogen use.
The aldehyde separation can, of course, be effected
with other aldehydes, e.g. to separate five-carbon
aldehydes from 10-carbon enals.
In the present process the oxo product is
used in the aldol reaction without any need for
separation of some of the components. This contrasts

~25~g ~
-26- 07-21-(183)A
with the usual commercial procedure, for example, for
preparing 2-ethylhexanol as a plasticizer alcohol,
wherein it is the practice to remove isobutanal before
conducting an aldol reaction with n-butanal. The
separation is effected by distillation and, since
isomeric aldehydes have similar boiling points,
separation on a commercial scale involves high capital
cost equipment with consequent expense, and a
substantial energy cost. There is a definite
advantage in avoiding such a distillation step in the
present process.
The C7 branched aldehydes which do not react
in the aldol reaction can be separated from the
reaction ~ixture for various purposes, or hydrogenated
with the mixture and utilized as a C7 branched
alcohol. If desired, the branched C7 alcohol can be
dehydrated, and then subjected to an oxo reaction to
produce an aldehyde with an additional carbon atom.
Thus 2-meth~l-hexanol can be converted to
- 20 2-methylhexene-1, which can be recycled to the oxo
stage of the reaction process and hydroformylated to
predominantly 3-methyl-beptanal. This
3-methylheptanal, not having any substituent in the
2-position, reacts at a good rate in the aldol
reaction. Other unreacted aldehydes, such as
2,4-dimethylpentanal and 2-ethyl-pentanal, can
similarly be hydrogenated and dehydrated and recycled
to be converted in the oxo stage to C8 aldehydes with
no substituent in the 2-position, which will take part
in the aldol reaction when recycled through that
stage. This procedure to use the unreacted C7
aldehyde results in greater conversion of the original
reactants to the desired final product, rather than to
a concomitant product such as C7 alcohols. Use of
this recycle feature in the oxo-aldol process changes

~:257~9
-27- 07-21-(183)A
the components of the product from mixed hexenes to
some extent, but the properties will be similar as the
main dlfference in the additional components will be
an additional methyl substituent as in 2~1-methylbuty)
-5-methylnonanol, 2-(3-methylbuty)-5-methylnonanol
and ~-pentyl-5-methylnonanol, for example.
The Dimersol ~ dimerization process has been
referred to in various publications, e.g. see "How
First Dimersol is Working" by Benedek et al,
Hydrocarbon Processing, May 1980, page 143; also
Chauvin et al, "The IFP Dimersol ~Process for the
Dimerization of C3 and C4 Olefinic Cuts", Advances in
Petrochemical Technology, presented at American
Institute of Chemical Engineers, April 13, 1976,
Kansas Clty, Missouri.
The combination of the Dimersol ~
dimerization process, oxo process, aldol and
hydrogenation provides a very efficient route from
propylene to detergent range alcohols. Qne of the
known routes to such alcohols relies upon
oligomerization of ethylene to obtain higher molecular
weight materials which are then subjected to an oxo
reaction. The presently proposed route is in many
respects more efficient and economical than those
involving ethylene oligomerization, as propylene costs
less than ethylene, and the reactions involved using
dimerization, oxo and aldol are more straight forward
than an oligomerization which can produce a broad
mixture of products and require extensive equipment
and procedures to direct it to suitable product. As
discussed hereinabove, the mixture of isomers obtained
from a dimerization can be carried through the oxo,
aldol and hydrogenation reactions to obtain high
overall conversions and yields, despite the presence
of extensive branching in the materials~ It is

~:~5~
-28- 07-21-(183)A
fortunate to find that a high proportion of the
materials are capable of taking part sequentially in
all of the required reactions, and in particular that
the aldehyde failing to react to a significant degree
in the aldol reaction, because of 2-substitution, is
at a comparatively low level.
In the oxo stage of the present process it
will be noted that cobalt catalyst is employed with
the hexenes in order to promote migration of the
olefinic bond and high selectivity to desired aldehyde
isomers, such catalysts being for example Co2tCO)8
which may be equivalent to HCo(CO)4 under reaction
conditions.
The processes of the present invention can
utilize mixtures with olefins of dlfferent carbon
numbers, along with isomeric mixtures of olefins of
particular carbon number. The oxo product of such
mixtures can be subiected to aldol reactions as tau~ht
herein to give aldol product. Such procedures can,
for example, use butenes in conjunction with Dimate R
hexenes. Also, Dimate ~ hexenes may at times have
various amounts of C5, C7 and Cg olefins, and still be
usefully employed in the present invention. Such
processes will still have the advantage of production
of high amounts of aldolable aldehydes in the oxo
process, and result in aldol product with carbon
numbers in the detergent range and with branched
structure suitable for detergent use. Also, in the
Dimersol ~ process, butene can also be dimerized or
codimerized with propylene, and this provides
additional ways to modify the present process by
variation o~ the olefin feed stoc~ while still
producing aldol product in the detergent range. In
the procedures which use mixed olefins, it is also
possible to conduct the oxo reaction with olefins of

-29- 07-21-~183)A
dlfferent carbon number, and to combine the resulting
oxo products for an aldol reaction. Another olefin of
particular interest for use in the present process is
4-methyl-1-pentene, which can be produced by ~a catalyst
dimerization of propylene, as reported in Industrial
Organic Chemistry, cited hereinabove. The reaction is
conducted at approximately 150C and 40 bar, using
Na/K2CO3. The 4-methyl-1-pentene in an oxo process
will give very high aldolable product as shown by the
results for 4-methyl-pentene-2 in Example ~, and is
therefore well suited for use in the present process
to prepare C14 enals and detergent derivatives
thereof.
The C14 or other detergent range alcohols
produced by the present process can be readily
converted to detergents by known procedures. Thus
non-ionic detergents are prepared by reaction with
ethylene oxide to have a desired number of ethoxyl
groups, e.g. 6 to 10 or 12 or so. These, or other
ethoxylated alcohols, possibly with 2 to 3 ethoxyl
groups can be reacted to form an alcohol ether
sulfate, having a sulfate anionic end group with a
sodium or other cation. The alcohols can also be
reacted to prepared sulfate derivatives. The
detergents thus prepared will have the requisite
hydrophobic groups for detergent properties.
Moreover, the structures are such as to provide
biodegradability, in that the structures a;e acyclic
alkyl groups which are essentially free of any
quaternary carbon groups. There is some branching on
adjacent carbon atoms, but that and the common
2-branching characteristic of aldol product, with or
without various additional methyl or other lower alkyl
branches in non-adjacent positions, do not have any
important effect on the biodegradable nature of the

~25~g`~
-30- ~7-21-~183)A
compounds. An alcohol ether sulfate prepared from
2-pentylnonanol has been described as biodegradable by
Crawland et al, Surfactant Congress No. 4, Vol. 1,
page 93 (1967). Also Kravetz et al, Proceedings of
the American Oil Chemists' Society, 69th annual
meeting, May, 1978, St. Louis, MO., concluded that
variation of branching from 45% to 75% linear had no
appreciable effect on biodegradation rates of primary
alcohol ethoxylates, and make reference to 58
branching giving biodegradation at rates not
appreciably different from ~ero branching. The
branching involved in both of these prior studies was
a single branch, and this can be contrasted with the
materials described herein which contain at least two
branches in almost all cases.
A quantity of Dimate ~ hexenes from a
refinery stream was distilled to have a C6 cut,
approximately 73% of the total material. Analysis is
given in Table 1. The Dimate ~hexenes had been
produced by dimerization of propylene over a catalyst
by the Dimersol ~ process.

~Z57~
-31- 07-21-(183)A
TABLE 1
Dimersol ~ Hexene Distribution
~ (100% basis)
2,3-dimethyl-2-butene 4.5
2-methyl-2-pentene 35.6
5 trans-4-methyl-2-pentene 18.4
cis-4-methyl-2-pentene 3.7
2-methyl l-pentene s~]
2,3-dimethyl-1-butene +
4-methyl-pentene-1 1.7
10 trans-2-hexene 17.8
trans-3-hexene 6.3 f31.0~
cis-3 + cis-2 hexene 6.8 ¦linear
l-hexene 0.1 J
The distillation serves to remove some C5,
C7 and Cg hydrocarbons resulting from oligomerization
involving some ethylene present in the original olefin
feed, or trimerizations. It also removes C6
chlorides, along with the Cg hydrocarbons; these
chlorides, resulting from the dimerization catalyst,
could contaminate the oxo catalyst if not removed.
It is fortunate that the hexenes mixture is
amenable to reaction at a good rate in the oxo
reaction. It is sufficiently reactive to permit use
of moderate conditions and equipment therefor, with
suitable reaction rates and times. This is in
contrast to an octenes Dimate ~mixture which is
characterized by more relatively unreactive dibranched
olefin isomers and much slower reaction rates. Such
material requires more severe reaction conditions in
more expensive equipment, and additional reactor
capacity.

~2~ 9~
-32- 07-21-(183)A
Since the oxo product is tc be reacted in an
aldol reaction, it is to be conducted under cond1tions
which favor production of aldehydes as contrasted with
alcohol or other products.
EXAMPLE 1
Hydroformylation of a Dimate hexenes
mixture, of composition reported in Table 1, was
carried out in an autoclave with agitation. The
autoclave was charged with 0.52 g dicobalt
octacarbonyl, 74.06 Dimate hexenes and 3000 psi. gauge
(20,786 KPa) of 1:1 C0 and H2. The autoclave was
heated to 130C. and held for four hours. Liquid
samples were taken every hour. The autoclave was
cooled rapidly and the product removed under nitrogen.
Analysis indicated 92~ conversion of the olefins. The
product was analyzed chromatographically, with results
as reported in Table 2 (along with other examples). It
will be noted that 77.9% of the aldehyde product was
unbranched at the 2-position and therefore aldolable.
This result was obained, even though the hexene
reactants were more than 90% composed of internal
olefins, including some linear hexenes which give
product little more than 50% aldolable. A similar run
employing a 110C. temperature with cobalt catalyst
for 23 hours is also reported.
EXAMPLE 2
The autoclave of Example 1 was charged with
0.49 g. of dicobalt octacarbonyl, 69.84 g.
2-methylpentene-2 and 3000 psi gauge (20,786 KPa) of
CO and H2 in 1 to 1 ratio. The autoclave was heated
to 130C. and held at this temperature for three
hours. The autoclave was cooled and the product
removed under a blanket of argon, and analyzed.
Conversion of the olefin was 83~. The procedure was
repeated substantially, but e~ploying a temperature of

~3
-33- 07-21-(183)A
116 C. for a 4~% conversion. Results of the analysis
are reported in Table 2. It is notable that better
than 90% of aldehydes unbranched at the 2-position,
i.e. aldolable aldehydes, were obtained.
Approximately ~he same results were shown from samples
taken during the reactions, with the 116 reaction at
1 hour giving 17% conversion and 35.4~ 5-methylhexanal
and 55.5% 3-methylhexanal; and the 130 reaction
temperature ~5~ conversion at 1 hour with 32.5%0 5-methylhexanal and 57.6% 3-methylhexanal,
EXAMPLE 3
Hydroformylation was Garried out on
2-methyl-1-pentene with cobalt catalyst in accord with
the procedure of Example 2 at 116C. for a three-hour
perlod. A 41~ conversion was obtained, with 95~ of
aldolable aldehyde unbranched at the 2-position being
obtained, Results are reported In Table 2.
EXAMPLE 4
Hydro~ormylation was effected with
4-methyl-2-pentene in accord with the Example 2
procedure, employing a 130C. temperature. Results
are reported in Table 2.

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1257;~9~-~
-35- 07-21-(183)A
EXAMPLE S
Hydroformylation was effected with
2,3-dimethyl-2-butene at 130C, employing the
procedure of Example 2. At 1, 2 and 3 hours
conversions were respectively 18, 43 and 71~, and in
each case the aldehyde product was analyzed as 100%
3,4-dimethylpentanal, an aldolable aldehyde.
EX~PLE 6
This example was a simulation of two oxo
reactors operating at different temperatures. The
autoclave was charged with 0.~4 g. dicobalt
octacarbonyl, and 73~94 9. Dimate hexenes. The
autoclave was sealed, pressure checked and run under
3000 psigt20,786 KPa) of 1/1 CO to H2 at 130aC for 1
hour then heated to 140 C for an additional 4 hours.
The autoclave and contents were rapidly cooled and the
product removed under nitrogen. Analysis of the final
product yielded that the olefin was 97~ converted with
83% as the aldehydes, 11% as alcohols, and 3~ high
boilers. The unreacted olefln consists of
2-methylpentene-2, 2,3-dimethylbutene-2 and
trans-hexene-2. The aldehydes after normalization are
39~ 3-methylhexanal, 20% 5-~ethylhexanal, 16~
heptanal, 9~ 2-methylhexanal, 6% 2,4-dimethylpentanal,
5% 2-ethylpentanal, 4~ 3,4-dimethylpentanal, 1%
2-ethyl-3-methylbutanal, 1% 2,2-dimethylpentanal. The
aldehydes were distilled from the catalyst, unreacted
starting material and other products at 20 mmHg from
41 to 45C.
The percentage of aldehydes unbranched at
the 2-position produced was 79%.
The results in Example 6 lndicate that the
percentage of aldehydes unbranched at the 2-position
from branched hexenes (69~ of hexenes) was 88.7~,

~25~9~3
-36- 07-21-(183)A
compared to only 53.3% of such aldehydes from the
linear hexenes (31~ of hexenes). Considering only the
methylpentenes (62.8~, ignoring the small amount with
2,4-dimethylbutene in Table 1), the aldolable aldehyde
unbranched at the 2-position content of the aldehyde
product was 86.6%;.
EXAMPLE 7
An aldehyde mixture representative of that
from the oxo reaction of Dimate ~ hexenes, as
described in Example 16, was reacted in an aldol
reaction. An autoclave was charged with 50 ml of 0.8
M NaOH, 100 ml of 2,5-hexanediol ~nder 20 psi gauge
argon. Then 36.2 g., 50 ml, of the aldehydes were
pressured into the autoclave with argon after the
autoclave had been heated to 100C. and agitation set
at 1500 rpm. The reaction was run for an additional
hour and the system rapidly cooled. The product was
removed and the upper and lower phases were separated.
The upper phase contained 16.8% unreacted aldehydes,
2.4% heptanols, 72.9% tetradecenals and 4.1~
2,5-hexanediol. The conversion of the aldehydes
approximated 79~.
EXAMP~E 8
Unsaturated aldehydes representative of
- 25 product from oxo and aldol reactions of Dimate ~
hexenes as produced in Example 7, were subjected to
hydrogenation. An autoclave was charged with 130.95 g
of 45% + 5% cobalt on Rieselguhr, 1336.1 grams of the
aldol condensation product and hydrogen to 1500 psi
gauge (10,644 RPa). The autoclave was carefully heated
; to 160C., with gas uptake starting at 100C. The
pressure and temperature were maintained for 4 1/2
hours. The catalyst was filtered off and washed with
methanol to remove any residual alcohols. The
material was then distilled using a 30 cm. *VIGREUX
* Trade Mark
, ,

9~
-37- 07-21-(183)A
column at S mm Hg. The C14 alcohols were collected
from 119 to 122C. From analysis of the aldehydes
prior to the aldol reaction, and analysis of
derivatives of some of the alcohol components,
together with gas chromatographic and other
identiflcation as included and described hereinbelow,
lt was concluded that the product includes some 28
alcohols in amounts and as named and illustrated by
skeletal structure in Table 3 where the
hydroxyl-bearing group is designated by an asterisk.

~25~9~
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~Z57 ~s9;.3
-40-
Chromatographic retention times Eor
particular alcohols, both as components of a mixture and
from individual synthesis, are set forth in Table 4,
together with the aldehyde pair involved in the
synthesis.
Each of the individual alcohols in Tables 3
and 4, as well as the total mixture, can be converted to
ethoxyl derivatives, sulfates, or ethoxyl sulfate
derivatives. This is also the case with other alcohols
described herein. Similarly, the individual enals and
enal mixtures can be readily converted to saturated
aldehydes, alcohols and acids.
In the subsequent description, reference
will be made to the drawings, in which: ~
Figure 1 is a schematic illustration of a chemical
compound; and
Figure 2 is a chromatograph of the acetate
derivative of the mixture of alcohols of Table 3.
~ ,

~ZS7~9~g
-~1- 07-21- ( 183 )A
u3
.
~ ~3
~ ~ @ @~ ~ @ @
.~
C ~ o r~ 0 ~ o
+ C~ OD +
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--~2- 07-21- ~183 )A
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b
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~57~9~-~
_I -43-07-21- ( 183 )A
g3 O` ~ ~ + oa~
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~57~9~
-44- 07-21-(183)A
The identification and reported percentage
composition of the product alcohols were accomplished
by utili~ing gas-liquid chromatography ~G.C.) coupled
with synthesis of the isomers. The individual
alcohols were synthesized by aldol condensation of
pure heptanal aldehyde isomers followed by
hydrogenation to the alcohol. The heptanal pairs can
be reacted together with the procedure of Example 7
above. The elution time of the individual derivatized
isomers were then matched with peak-elution times in
the product mixture to identify the compounds in the
mixture. Verification of the structures was
accomplished by several methods. Gas chromatography
combined with mass spectrometry (G.C. - MS) was used
to show that the mixture contained only tetradecanol
isomers The logic by which we synthesized the
various alcohol isomers, discussed above, was
confirmed in three cases by 13C nuclear magnetic
resonance (nmr) and also in one case by a single
crystal X-ray structural determination of a solid
derivative. Thus, the structures of 2-pentylnonanol,
2-(1-methybutyl-5-methyl-octanol and 2-(3-methylbutyl)
7-methyloctanol were unambiguously identified using
two dimensional double quantum coherence 13C nmr
techniques (G. Bodenhause, "Progress in NMR
Spectrocscopy," 14 , 137 (1981). In addition, the
-napthyl sulfonate ester of 2-(3-methylbutyl-7-methyl
octanol was prepared (m. pt 47) and a single crystal
suitable for X-ray crystallographic investigation was
grown. A single crystal study was performed using
copper K radiation with a Syntex P21 diffractometer.
The space group was found to be P21~N. Cell constants
were = 8.186(1), b = 290958 (7), c = 10.316(2) A; a
= 107.49(2) ; Z = 4; M = 404.62. The structure was

~2~i7~J9'~
-45- 07-21-(183)A
solved by direct methods and refined to a final ~
value of 0.091 uslng 2586 observed reflections. The
structure is shown in the accompanying Figure 1. The
bond lengths and bond angles are given in Table 5.
This X-ray determination unequivocably
confirms the backbone structure of the alcohol as
2-(3-methylbutyl)7-methyl octanol.
TABLE 5
Bond Lengths and Bond Angles in the -Naphthyl
Sulfonate Ester of 2- (3-methylbutyl-7-methyl Octanol
(Numbering system used here i5 shown in Fig 1)
Bond Lengths
Sl - 02 1.565 A
Sl - 011 1.427
Sl - 012 1.427
02 - C3 1.493
C3 - C4 1.543
C4 - C5 1.526
C4 - C23 1.538
C5 - C6 1.534
C6 - C7 1.542
C7 - C8 1.544
C8 - C9 1.573
C9 - C10 1.574
Sl - C14 1.747
C13 - C14 1.392
C13 - C18 1.399
C14 - C15 1.421
C15 - C16 1.347
C16- - C17 1.416
C17 - C22 1.417
C18 - Cl9 1.442

~25~g`~
-46- 07-21-(183)A ~.
C20 - C21 1.449
C21 - C22 1.372
C23 - C24 1.545
C24 - C25 1.564
C25 - C26 1.540
C25 - C27 1.393
Bond Angles
02 - Sl - 011 104.1
02 - Sl - 012 109.8
02 - Sl - C14 103.3
011 - Sl - 012 119.9
011 - Sl - C14 108.9
012 - Sl - C14 109.5
Sl - 02 - C3 117.9
02 - C3 - C4 106.0
C3 - C4 - C5 111.4
C3 - C4 - C23 113.2
C5 - C4 - C23 109.4
C4 - C5 - C6 115.8
C5 - C6 - C7 110.1
C6 - C7 - C8 110.6
C7 - C8 - C9 111.7
C8 - C9 - C10 112.5
C8 - C9 - C28 106.8
C10 - C9 - C28 112.4
C14 - C13 - C18 118.6
Sl - C14 - C13 119.9
Sl - C14 - C15 118.6
C13 - C14 - C15 121.6
C14 - C15 - C16 119~6
C15 - C16 - C17 121.5

~L2X~
-47- 07-21-(183)A
C16 - C17 - C18 118.4
C16 - C17 - C22 122.5
C18 - C17 - C22 119.1
C13 - C18 - C17 120.3
C13 - C18 - Cl9 120.0
C17 - C18 - Cl9 119.6
C18 - Cl9 - C20 119.8
Cl9 - C20 - C21 120.2
C20 - C21 - C22 120.6
C17 - C22 - C21 120.6
C4 - C23 - C24 113.6
C23 - C24 - C25 112.1
C24 - C25 - C26 108.2
C24 - C25 - C27 119.2
C26 - C25 - C27 114.3
In Fig. 1, the ~ napthylsulfonate ester of
2-~3-methylbutyl)-7-methyl octanol is shown. the
sulfur and oxygen atoms are identified by as S and 0
respectlvely, while all other atoms are carbonO The
portion of the structure below the oxygen atom 2 is
the carbon structure of the alcohol, while that above
2 is the naphthylsulfonate portion of the derivative.
The gas chromatography for the retention
procedures discussed was done with acetate ester
derivatives. The acetate esters were prepared by
utilizing 0.1 cc of alcohol sample, 0.3 cc acetic
anhydride, 1 drop of pyridine, and heating in a sealed
vial for 10 minutes at 100C. The product was
injected directly into a gas chromatogram~ which was a
Varian 3700 with splitter for glass capillary columns,
Flame loni~ation detector and Hewlett-Packard 3352

~$~;~g~-o
-48- 07-21-(183)A
computer. Details of the column and procedure were:
SP-2100 ~lass capillary column 60 meter
length x 0.25 mm internal diameter, 27.1 cm/sec
helium;
Injection/splitter 280 C.
Detector 280 C.
Column oven Progress from 120C to
150C at 2C/minu~e, and held
at 150C
Detector Sensiti-
vity Range 10 11 amps/millimole
Injection Size 0.06 ul/spllt 60:1
A typical chromatograph of the acetate derivative of
the mixture of alcohols of Table 3, obtained by the
foregoing procedure, is shown in Figure 2 in which
retention time is meas~red on the horizontal axis in
minutes. The chromatograph was made at a chart speed
of 5 mm/minute and covers from time zero to over 50
minutes. The designations of several peaks by
combinations of two letters indicate the aldehydes
combined in the aldol stage of the product formation,
with the letters symbolizing:
A = n-heptanal
B = 2-methylhexanal
C = 3-methylhexanal
D = ~-methylhexanal
E = 2-ethylpentanal
F = 2,3-dimethylpentanal
EXA~PLE 9
This example demonstrates an aldol condensation of

~ 25~
-49- 07-21-(183)A
heptanal ln glassware under conventional aldol
conditions. The reaction flask was charged with 116
ml of 0.8 M NaOH and the heptanal, 371.03 g., placed
into the addition funnel~ The system was kept under a
nltrogen blanket and the agitation was set at 500 rpm.
The reaction flask was heated to reflux, and the
heptanal added at a constant rate such that the
addition was completed after 230 minutes. A sample
was removed to compare with conventional aldol results
and only 33.5% of the upper phase of the sample was
C14 unsaturated aldehyde and 61~ was unreacted
heptanal. The system was held at reflux for an
additional 10 hours after which the system was cooled.
The lower phase was removed, 135.74 g, and the upper
phase, 336.06 g., was found to contain 66.5%
2-pentylnon-2-enal, 26.4% unreacted heptan~l and 2.5
heptanol.
EXAMPLE 10
This example demonstrates the efficacy of using a
co-solvent with the water to enhance the aldol
reaction of heptanal. The reaction flask was charged
with 31 ml of 0.9 M ~aOH and 100 ml methanol. The
addltion funnel was charged with 115 g. of heptanal
under a nitrogen blanket. The aqueous-methanol
mixture was heated to reflux with agitation of 450
rpm. The heptanal was added over a 40 minute period
and refluxed for an additional 90 minutes. The system
was cooled and the lower phase removed. The upper
phase contains 10.1% methanol, 84.0~
2-pentylnon-2-enal, 2.0% unreacted heptanal and 1.2%
heptanol. This represents 94% conversion with 98%
selectivity. The tetradecenals were hydrogenated as
in Example 8 and the resulting saturated alcohols were
treated as in example 8 including filtration and
dlstillation.

~L~5~
-S0- 07-21-(183)A
The use of methanol in this procedure was
effect1ve as a cosolvent, as compared to Example 9
where a cosolvent was not used.
- EXAMPLE 11
Dimerizatlon of propylene over transition metal
catalysts produces a mixuture of hexenes.
The linear hexenes in the mlxture can be separated
and such linear hexenes are for the most part
2-hexenes. The folloing procedure illustrates the
reaction of linear 2-hexenes in an oxo reaction,
~ollowed by an aldol reactlon of the product. A
sample of refinery 2-hexenes was passed through basic
alumina particles for removal of oxides and 802 grams
of the hexenes was placed in a 1 gallon stainless
steel autoclave wlth 4.75 grams Co2(CO)8 catalyst.
The autoclave was pressured to 2400 psi gauge with 1:1
carbon monoxide and hydrogen, and heated to 110 C.
The temperature was kept at about 110C for 1 hour and
then rose to about 130 as the procedure was continued
for about 5 hours. A 916.5 gram product was obtained,
with conversion about 94% with about 78% selectivity
to C7 compounds, and 71.5~ to C7 aldehydes.
Chromatography indicated the aldehydes were in ratio
of about 29.4 n-heptanal to 16.7 2-methylhexanal to
8.5 2-ethylpentanal. A 907 gram amount of the product
was distilled, with a final pot temperature of 120C.
and vacuum of 3 mm Hg. to obtain a 608 gram
distillation fraction and 278 gram residue.
Chromatography indicated the fraction included C7
aldehydes in ratio 33.4 n-heptanal to 26.8
2-methylhexanal to 17.2 2-ethylpentanal, and minor
amounts of other components. Evidently there was more
loss of the normal aldehyde than the branched ones in
the distillation.
It is feasible to achieve a higher percentage of

~ 25~ ,D
-51- 07-21-(183)A
n-aldehyde than present ln the above distillation
fract1on, such as 60~ or better, and therefore
n-heptanal was added to the above fraction to have a
more typ1cal aldehyde for aldol reaction about 600
grams of the above fraction being used with 500 grams
n-heptanal. A 300 ml amount of 0.8 molar sodium
hydroxlde was placed ln a reaction flask with 955 ml
methanol, and the aldehydes were placed in an addition
funnel. The reaction medium was heated to about
71 C., and addition was slowly started and completed
in about 13 hours. Chromatography indicated about S0
completion of the reaction, with C14 aldehydes in
ratio of about 23.4% 2-pentylnon-2-enal to 8.72
2-penthyl-4-methyloct-2-enal to 1.4%
2-pentyl-4-ethylhept-2-enal. Several C7 aldehydes
were also present in the ratio of 22.0 heptanal to 8.5
2-methylhexanal to 5.3 2-ethylpentanal.
The aldol condensation product was hydrogenated
over a cobalt on Kieselguhr catalyst, using 131 grams
catalyst with 1336 grams of the condensation product.
The materials were maintained at about 160C. and 1500
psi gauge (10,645 KPa) of hydrogen for about two hours
when reaction appeared complete. Reaction conditions
were maintained for an addltional 4.5 hours. Analysis
indicated about 99% completion of the hydrogenation.
The product contained 2-pentyl-nonanol in abcut 18.4
to 7.2 ratio to a mixture of 2-pentyl-5-methyl-octanol
and 2-pentyl-4-ethyl-heptanol and large amounts of C7
alcohols from the unreacted aldehyde, being heptanol
in a 27.5 to 16.3 ratio to a mixture of
2-methylhexanol and 2-ethylpentanol. The product was
fractionated by distillation, with a 280 gram fraction
being obtained at 110-115C. at 2 mm Hg from 1180
grams of hydrogenation product. The fraction was in
large predominance composed oE C14 alcohols.

9~.
-52- 07-21-(183)A
EXAMPLE 12
A mixture of hexenes produced by the Dimersol ~
dlmerization process was utilized as olefin reactant.
The crude hexene cut from the dimerization was used,
and had the dlstribution of linear and branched
hexenes typical of such material. A 1029 gram amount
of the hexenes was used in a 1 gallon autoclave with
6.04 grams catalyst, Co2(CO)8, 0.02 weight ~.
Peroxlde~ had been removed from the hexenes by
treatment on a basic alumina column. The autoclave
was taken to reaction conditions with 1:1 CO/H2 and
maintained at 110C. and 2500 psi gauge (18028 KPa)
for 9 hours, with 80% of theoretical gas uptake, and
then continued overnlght. Chromatography indicated
high conversion to C7 aldehydes, with minor amounts of
residual hexenes. A 1360 gram amount of the product
was subjected to distillation, with a 797 gram
fractlon belng obtained at pot temperatures of 60 to
97 C. as the vacuum dropped from 90 mm Hg to 5 mm Hg.
Chromatography indicated a high portion of C7
aldehydes with a very small amount of C6 olefins.
A 792 gram amount of the above aldehyde fraction
was utili2ed in an aldol reaction, adding the aldehyde
material Erom an addition funnel to a reaction flask
containin~ 564 grams methanol and 250.9 grams 0.8
molar sodium hydroxide. The addition took 6 hours,
with stirring at about 500 rpm and temperature at
72-73C. The reaction mixture was then refluxed for
1.5 hours. Analysis of a sample indicated only about
1 part aldol product to 3 parts aldehyder on a mole
basis. The reaction was continued at reflux
overnight, givlng 1 part aldol product to about 2.6
parts aldehyde reactant. During the reaction it was
observed that the reaction mixture had a large upper
phase and a smaller lower phase, indicating that

~i
-53- 07-21-(183)A
methanol was not very effective in promoting
miscibility and reaction, possibly because of the
relatlvely long chain length of C7 aldehydes.
Chromatography showed a fair amount of the C14 aldol
product, including 2-pentylnonenal, and a large amount
of unreacted C7 aldehydes. (Results were better in
Example 10 above in which a hlgher proportion of
methanol was employed).
The above aldol product was subjected to further
aldol reactlon, after removing ~the methanol to employ
different conditions. A 552 gram amount of the aldol
condensate, 55.6 area percent C7 aldehydes and 31.5
area percent C14 enals, was placed in an addition
funnel and added to a reaction flask containing 163
grams 0.8M NaOH and 389 grams 2,5-hexanediol.
Addition was complete after 45 minutes, with
temperat~re maintained at 100C. with agitation of the
reaction mixture. The reaction mixture was then
refluxed at 100C for 1.75 hours. The reaction
mixture separated into upper and lower phases of about
equal weight. The conversion had been improved in that
the ratio of C14 enals to C7 aldehydes in the product
(upper phase) was now about 1.7 to 1.
A 515 gram amount of the product was subjected to
hydrogenation, employing 51.65 grams cobalt on
Kieselguhr catalyst and 160C., about 1580 psi gauge
(10,995 KPa) hydrogen. Approximately 549 grams of
product was recovered. The conversion of C14
- saturated alcohols was about 90%, with about 10% found
as unsaturated alcohols. The product was filtered to
remove catalyst, and the filtrate was distilled. The
process produced several C14 alcohols in very
substantial amounts, with a number of others in very
small amounts. Several C7 alcohols from unreacted
aldehyde were also present in substantial amount.

~s~
-54- 07-21-(183)A
EXAMPLE 13
A freshly distilled sample of 2-pentene was
hydroformylated ln a 300 ml autoclave, employing 0.41
gram Co(CO)8 catalyst with 65.84 grams pentene. A 1:1
mixture of CO/H2 was used, with initial charge to 1500
psi gauge and heating to 120 C. and 3000 psi. with
agitation at 1000 rpm. Gas-uptake was observed, as
the pressure was increased to 3000 psi (20,684 KPa)
After about 2 hours, an 83 gram product was obtained.
Chromatography showed a small residual amount of
pentene and C6 aldehydes in the ratio of 61.1 hexanal
to 28.9 2-methylpentanal to 10.0 2-ethylbutanal. An
aldehyde sample was provided to have aldehydes in the
same ratio, using 189.1 grams hexanal, 89.9 grams
2-methyl-pentanal, and 31 grams 2-ethylbutanal, and
placed in an addit1on funnel for additlon to 110 ml of
0.8 M NaOH in a round bottom flask equipped with a
mechanical stirrer. Heating was begun and addition
was started after about 15 minutes and continued as
reflux started around 91C. Addition was completed in
about 40 minutes. Stirring was continued for an hour,
but without further heating, and a sample was taken.
Analysis indicated partial reaction. The reaction
mlxture was heated to 95 C. for an additional 1 1/2
hours. Upper and lower phases of the reaction mixture
were separated, and the upper phase was analyzed. The
analysis indicated better than 25~ conversion to C12
enal, nearly all being 2-butyloctanal, and large
amounts of unreacted C6 aldehydes, the major part of
which was branched aldehydes. The aldehyde mixture
can readily be hydrogenated to the corresponding
alcohols.
EXAMPLE 14
An aldol procedure was carrled out as in Example
13 except that the amount of water was increased ten

~2S~g.~'9
-55- 07-21-(183)A
fold. The same amount of NaOH was present, although
now in much more dilute solution. Because of the
large volume, less effective stirring was achieved.
After a two hour reaction, analysis indicated
substantial conversion to C12 enals, although somewhat
lower than in Example 12.
EXAMPLE 15
An aldol reaction was carried out as in Example
13, employing 6.1 to 2.9 to 1 ratio of hexanal to
2-methylpentanal to 2-ethylbutanal, the total amount
being 310 grams. The branched aldehydes were placed
in a flask with 110 ml of ~.8 M NaOH, and
tetrabutylammonium chlorlde in an amount molecularly
equivalent to the NaOH. The tetrabutyl-ammonium
chloride serves as a phase transfer catalyst. The
reaction flask was heated to reflux and addition was
started. The addition continued for about 6 hours
with reflux temperatures (pot) from 90-95C. The
mixture was cooled and separated into two phases.
Analysis of the upper phase showed better than 75%
conversion to C12 enals, about half of which was
2-butyloctenal, and the remainder mainly a mixture of
2-butyl-4-ethyl-heptenal and 2-butyl-4-ethylhexenal.
In the unreacted C6 aldehydes present, the branched
aldehydes were in greater amount the hexanal. The
reaction can be directed to produce a higher
percentage of product from the n-hexanal by adding the
aldehydes together, rather than adding the n-aldehyde
to the branched aldehydes in the reaction mixture as
in the foregoing procedure. The phase transfer
catalyst was effective in improving conversion in this
procedure, but use of co-solvents, such as methanol or
diols, may be more practical for large scale
continuous operations. The use of hexanediol has been
shown effective for aldol reaction of heptanals

9~
-56- 07-21-(183)A
herein, and can similarly be used with hexanals.
It will be noted that the alcohols produced from
both the pentenes and hexenes feedstocks are intended
~or use as detergent ~ange alcohols. The
conslderatlons herein as to reaction conditions and
various parameters of the oxo and aldol reactions as
decribed for the hexenes and resulting C7 aldehydes
also are in general applicable to the pentenes and
resulting C6 aldehydes. The Cl2 alcohols produced
from the reactions starting with pentenes will have
the hydrophobic groups such alcohols provide in
detergents, and the groups will have a degree of
branching similar to that of C14 alcohols from
hexenes. It is feaslble to substantially avoid
presence of branches on adjacent carbon atoms. In one
particular aspect the present invention is directed to
a process of preparing alcohols from an oxo reaction
with olefins selected from those having 5 to 6 carbon
atoms, or mixtures thereof, to obtain aldehydes having
6 to 7 carbon atoms, comprislng high amounts of
aldehydes without 2-substitution and effecting aldol
conversion with limited participation of 2-substituted
aldehyde to obtain aldol product, which is then
hydrogenated to Cl2 or Cl4 alcohols having properties
24 valuable for use in detergents.
EXAMPLE 16
An aldol reaction was-conducted in a l liter round
bottom flask equipped with stirrer, addition funnel,
reflux condenser and adaptors for nitrogen flow. A
100 ml. amount of aqueous l molar potassium hydroxide
solutlon was placed in the flask and heated to about
85C. n-Pentanal and 2-methylbutanal were admixed in
about 3:1 ratio, after each had been purifled by
distillation, and used for gradual addi~ion to the
reaction flask with stirring. Over about one hour,

~57~g~-~
-57- 07-21-(183)A
about 300 ml was added containing 187.7 grams
n-pentanal and 60.8 grams 2-methylbutanal. The
reactlon mlxture was placed ln a separatory funnel;
and the lower aqueous phase (87 grams) was separated.
The organic layer was washed four times with water and
amounted to 213.3 grams. Gas chromatographic analysis
for the starting aldehydes indlcated about a 3:1 ratio
of 2-methylbutanal to n-pentanal, showing that
the n-pentanal had been consumed at a much higher rate
in the reaction. The product contained about 70.5% of
alkenal condensation product and 25.3% of the starting
aldehydes. The product had 2-propyl-heptanal in about
9:1 ratio to 2-propyl-4-methyl-hexanal.
A 110.89 gram amount of the product was utilized
for hydrogenation, employing 11 grams of cobalt on
Kleselguhr catalyst with 4.4 ml H2O as promoter r in a
300 ml stirred autoclave. The autoclave was pressured
to 1000 psi with hydrogen and gradually heated, with
hydrogen uptake starting at about 40C. After one
hour, the pressure had fallen to 480 psi, and the
autoclave was again pressured to 1000 psi. After two
hours, with further addition of hydrogen, the pressure
was lS10 psi and temperature 160C. The run was
continued for a total of sixteen hours. The measured
gas uptake was in very sllght excess of theory for
hydrogenation of both the olefin and aldehyde groups
in the compounds present.
The product was flltered through a Celite filter
mat to remove catalyst, and the mat was washed with
n-hexane. The n-hexane was removed under vacuum,
leaving 88 grams of product for distillation.
Distlllation was carried out at 10 mm Hg., with 18.1
gram being collected at 30-100C., which gas
chromatography indicated to be 66.4% 2-methylbutanol,
27.5% pentanol, and 4.1% 2-propylheptanol. An
*Trade Mark
. , .

~25~
-58- 07-21-(183)A
additional 38.9 grams was collected at 103.5-105C.,
11.3~ 2-propyl-4-methylhexanol and 87.7~
2-propylheptanol. It can be seen that the above
described procedure provides 2-propylheptanol with
only very minor adulteration by the aldol alcohols
product of branched aldehydes. Also the
2-propylheptanol from the 2-methylbutanol produced by
hydrogenation of the 2-methylbutanal which did not
undergo the aldol condensation.
Another sample of hexenes product from a Dimersol
dimerization refinery product was analyzed and found
to have the following distribution:
Hexene Distribution
lS ~ (100% Basis)
2,3-dimethyl-2-butene 6.4
2-methyl-2-pentene 39.2
trans-4-methyl-2-pentene15.9
cis-4-methyl-2-pentene 2.9
2 methyl-l-pentene 5.0
2,3-dimethyl-1-butene +
4-methyl pentene-l 1.7~
trans-2-2hexene 16.5¦
trans-3-hexene 5.8~ 28.9
cis 3 + cis 2-hexene5.6¦
l-hexene 1. oJ
The hexenes are suitable for conversion to
detergent alcohol in accord with the present
invention.
EXAMPLE 17
An aldehyde mixture representative of that from
the oxo reaction of Dimate ~ hexenes, as described in
Example 1, was reacted in an aldol condensation. A

5~9~-~
-5~- 07-21-(183)A
stirred autoclave was charged with 735 ml 0.8M NaOH,
1470 ml methanol and 20 psig argon ( KPa) .The
autoclave was heated to 100C and 735 ml (551.0g) of
the aldehydes were pressurized into the autoclave with
argon. The reaction was run for an
additional hour and the system was rapidly cooled.
The product was removed and the upper and lower phases
were separated. The upper phase contained 14.4%
unreacted aldehydes, 2.1% heptanols, 4.4% methanol,
1.6% high boilers and 77.5% tetradecenals. The
tetradecenals product consists of some 28 isomers in
amounts as named and lllustrated in Table 5 where the
aldehydic function is designated by an asterisk.

- 5 9a- ~L25~;~
w
x ~ ~ x ~ ~ ~ x
N ~ ~ E S 7 1 I W
z
= ~ ~ X X ~ X X
80 .~
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X u~ ~ ~ u~ . ~ ~n ~ ~D
o .r o o _I ~ ~ ~
W C ~ .r .r N
~0
u
., O, . ..
~ # U--y_~ Y_u O--u ~- y 4 ~ Y~
U y_U o o U ~ O--O U 1) o ~Y~ U

~ 25~
Z
~ ~ ~ Z ~ ~ H
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V: N ~r~: N
~S ~
W ~ ~ ~ X ~ H
h
,~ ~ N .-1 0 0 0 0 0 Z
Z ~ Z ~ ~I
O ~ H
z m P- z ,., W I m ~ u~
- Z E~
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P a a P P ~ P D ~ a
~ O m :: a
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+ + + + * + + + ~
Y ' Y
~ V V y y y y
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U ~U--~ V ~ t~--~ U
U--U y ,~ $ ~--Y * Y * Y ~--~ Y * ~--Y *
y ~--~ y ~ y ~--U C~
y--U, y U--~J y y y y y--y y y
y u--y v y O u y u y y y C~ly--u
u u - u u u u ~ u u u ~J - u
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-59C~ 5~;~5~
z~ ~ ~ z~
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C ~ 8
.
X ~ ~ Z Z D Z D ~
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~2S~9~'i
-60- 07-21-t183)~
EXAMPLE 18
This experiment and Example 19 illustrates the
utility of the invention for mixtures of olefins.
Hydroformylation of Dimate ~ hexenes and butenes was
--- 5 carried out in an autoclave with agitation. The
autoclave was charged with 2.61 g of dicobalt
octacarbonyl(catalyst pcecursor), 270.2 g of Dimate ~
hexenes and 180.9 g butenes and 3000 psi gauge (20.786
KPa) of 1:1 CO and H2. The autoclave was heated to
120 C and held for two hours. The autoclave and
contents were cooled rapidly and the product removed
under argon. The product was analyzed
chromatographically as reported in Table 6.
TABLE 6
Dimate ~ hexene, butene-2 Hydroformylation Products
Compound
- Area %
Butene-2 1.5
Dimate hexenes 9.6
20 2,2-dimethylpentanal 0.5
2,4-dimethylpentanal ^ 2.1
2-methylbutanal 10.0
Pentanal 23.6
2 ethyl-3-methylbutanal 0.4
2S 2-ethylpentanal 3~3
3,4-dimethylpenntanal 0.5
2-methylhexanal 3.2
3-methylhexanal 18.5
5-methylhexanal 12.5

~2~;d;~,g~:~
-61- 07-21-(183)A
Heptanal 9 3
High Boilers (including heptyl
alcohols and Formates) 5.0
The percent of aldehyde production without
2-substitution was over 76%.
EXAMPLE 19
An aldehyde mixture representative of that
from the oxo reaction of Dimate ~ hexenes and butene
as described in Example 18 was reacted in an aldol
condensation. A stirred autoclave was charged with
313 ml methanol, 0.8M NaOH, and 110 psi (758.4 KPa)
gauge argon. The system was heated to 100C and the
mixture of aldehydes, 313 ml, was pressured into the
autoclave with argon. The reaction was run an
additional one hour and thirty minutes and the system
rapidly cooled. The product was removed and the upper
phase and lower phases were separated. The upper
phase contained 0.5% unreacted pentanals, 31.7
unreacted heptanals, 25.6% decenals, 27.1~
2-dodecenals, 6.3% 2-tetradecenals, 1.7~ pentanals,
6.3% heptanals and 0.8~ high boilers. The skeletal
structures of the 2-decenals and the 2-dodecenals are
glven in TABLE 7. The enals can readily be converted
to alcohols and ethoxyl, sulfate or ethoxylsulfate
derivatives.

~257~
-62- 07-21~ 3)
TABLE 7
2-DECENALS AND 2-DODECENALS F~OM ALEOL OF
PENTANAL AND DIMATE HEXENES HEPTANALS
COMPOUND
STRUCTURE NAME
C-C-C-C-C=C-C-C-C (E+z)-2-PROPYL-2-HEPTENAL
1,
2-DODECENALS
C-C-C-C-C-C-C=C-C-C-C (E+z)-2-PROPYL-2-NoNENAL
C*
C-f-C-C-C=f-C-C-C ~ E+Z)-2-PRoPYL-7-METHYL-2-oCTENAL
C C*
C-C-C-C-C-C=f-C-C-C ~ E-~Z)-2-PRoPYL-5-METHYL-2-oCTENAL
C C*
C C C C C=C l C C C ~E+Z)-2-~1-METHYLBUTYL)-2-HEPTENAL
C*
C-C-C-C-C=f-C-C-C-C (E+Z)-2-(3-METHYLBUTYL)-2-HEPTENAL
C* C
C-C-C-C-C=C-C-C-C-C-C ~E+Z)-2-PENTYL-2-HEPTENAL
C*C
C C C C C=C l C C ~E+Z~-2-~1,2-DIMETHYLPRoPYL)-2-HEPTENAL
l l
C* C
C-f-C-C-C=f-C-C-C (E+Z)-2-PROPYL-4,5-DIMETHYL-2-HEPTENAL
C C*
C-C-C-C-C-C=C-C-C-C ~E+Z)-2-PRoPYL-4-METHYL-2-oCTENAL
C C*
C-C-C-f-C=f-C-C-C ( E+Z)-2-PROPYL-4-ETHYL-2-OCTENAL
C-C, C*
. .

~;~S7~35
-63- 07-21-(183)A
The structure of most of the product is
represented by the following formula:
Structure of C to C Enals from Aldol of Pentanal
- - 10 14- - -
with heptanals from Oxo of Dimate_Hexenes.
3 ~1 (2-p))h (CH(2-q)~m- CH = C - CHO
(CH3)p (R)q (CH(2_r))n (CH3~r
( CE~2 ) S
I
Cu~2-t) (CH3)t
Wherein:
R= methyl or ethyl; h and m = 0, 1, 3, 4 and 5;
h and s = 0, 1, 2; p, q, r and t = 0 or 1;
m + h can never = more than 5
q and p = 0 when m + h = 5 or
when m + 1 = 3
1 = 3 and m = 1 when R= methyl and q = 1 and
p=O;
q = 0 and p = 1 when 1 = 2 and m = 2 or
when 1 = 1 and m = 3;
n + s can never = more than 3
r and t = 0 wh~n n + s = 3 or
when n + s = l;
s = 0 when n, r and t = 1 or
when n = 2 and r = 0 and t = 1;
s = 1 when n = 1 and t and r = 0 or 1 but
only one of t and r can be l;
s = 2 when t = 1 and n= 0;
h = 2 and m = 1 when R = ethyl and q = 1 and p = 0

~25~5~-9
-64- 07-21-(183)A
EXAMPLE 20
The autoclave of Example 1 was charged with
0.25 g carbonylbis (triphenylphosphine) rhodium (I)
chloride, 11.78 g triphenylphosphine, 46.20 g
3-methylbutene-1 and 300 psi (2068.~ KPa) gauge 1:1 CO
and ~2. The autoclave was heated to 130C and held at
this temperature for one hour and 35 minutes. The
autoclave was cooled and the product removed under a
blanket of argon and analyzed. The product is 83
4-methylpentanal with 7% 3-methylpentanal and 7
unreacted 3-methylbutene-1 starting material.
EXAMPLE 21
Hydroformylation was carried out on
2-methylbutene-1 with rhodium catalyst in accord with
15 the procedure of Exammple 20 at 100C for an eight
hour fifteen minute period. A 49~ conversion was
obtained with 98% selectivity to 3-methylpentanal.
EX~P~E 22
An aldehyde mixture repeSentative of that
from the oxo reactions as described above in Examples
20 and 21 was reacted in an aldol condensation. An
autoclave was charged with 50 ml 0.8M NaO~, 50 ml
methanol, and 10 psig (68.9 KPa) argon. The autoclave
was heated to 100C with agitation set at 1500 rpm and
25 the mixture of 23.08 g 3-methylpentanal and 23.11 g
4-methylpentanal, 50 ml total, were pressured into the
- autoclave with argon. The reaction was run for an
additional hour and the system rapidly cooled. The
product was removed and the upper and lower phases
were separated. The upper phase contained 2%
methanol, 4.0~ unreacted 3-methylpentanal, 2.6~ -
unreacted 4-methylpentanal, 0.4~ hexanols, 0.6% high
boilers with 92.4~ as dodecenals. The skeletal
structures of the dodecenals are the same as the first
four structures of dodecenals listed in Table 8 which

~2~ 95
-65- 07-21-(1~3)A
details skeletal structures of a mixed pentene stream with
Dimate ~ hexenes, if hydroformylated with cobalt catalyst and
aldol condensed as in Examples 17 and 18.
TABLE 8
2-WDECENALS AND 2-TRIDECENALS F~ M OXO AND ALDOL OF
PENTENES AND DIMATE HEXENES
COMPOUND
STRUCTURE NAME
C-f-C-C-C=f-C-f-C ( E+Z)-2-~2-METHYLPROPYL)-6-METHYL-2-HEPTENAL
C C* C
C-C-C-C-C=C-C-C-C (E+Z)-2-(2-METHYLPRoPYL)-5-METHYL-2-HEPTBNAL
c . 1~ c
C
C-f-C-C-C=f-C-C-C ( E+Z)-2-(1-METHYLPROPYL)-6-METHYL-2-HEPTENAL
C C~
C-C-f-C-C=f-C-C-C ( E+Z)-2-(I-METHYLPROPYL)-5-METHYL-2-HEPTENAL
C C*
C-C-C-C-C-C=C-C-c-c-c (E+z)-2-BuTyL-2-ocTENAL
C-C-C-C-C=f-C-C-C-C ( E+Z)-2-BUTYL-6-METHYL-2-HEPTENAL
C C~
C-C-f-C-C=f-C-C-C-C (E+Z)-2-BUTYL-5-METHYL-2-HEPTENAL
C C*
C
C-f-C-C=f-C-C-C-C (E+Z )-2-~UTYL-~,5-DIMETHYL-2-HEXENAL
C C* C
C-C-C-C-C-C=f-C-C-C (E+Z)-2-(1-METHYLPROPYL)-2-OCTENAL
C*
C-C-C-C-C-C=C-C-f-C (E+Z)-2-(2-METHYLPROPYL)-2-OCTENAL
', C~ C
f f'
C-C-C-C=f-C-C-C (E+z)-2-(l-METHyLpRopyL)-4~5-DIMETHyL-2-HExENAL
C C~

~S~g~9
-66- 07-21- ( 183 )A
C-C-C-C-C=C-C-C-C-C tE+Z)-2-BUTYL-4-METHYL-2-HEPTENAL
C C~
C-C-C-C=C-C-C-C-C (E~Z)-2-3UTYL-4-ETHYL-2-HEPTENAL
C-C C~
C
C-C-C-C~C-C-C-C-C ~E+Z)-2-BUTYL-4,5-DIMETHYL-2-HEXENAL
C-C-C-C-C-C-C=C;C-C-C-C ~E+Z)-2-BUTYL-2-NONENAL
C-C-C-C-C-C=C-C-C-C-C-C (E+Z)-2-PENTYL-2-HEPTENAL
C-C-C-C-C-C-C=C-C-C-C (E+Z)-2-(2-METHYLPROPYL)-2-NONENAL
C~ C
C-C-C-C-C=C-C-C-C-C-C ~EtZ)-2-PENTYL-4-METHYL-2-HEPTENAL
C C~
C-C-C-C-C-C;C-C-C-C-C (E+Z)-2-PENTYL-5-METHYL-2-HEPTENAL
C-C-C-C-C=C-C-C-C-C-C (EtZ)-2-PENTYL-6-METHYL-2-HEPTEilAL
C C~ '
1 0 C-C-C-C-C-C=C-C-C-C-C (E+Z)-2-BUTYL-7-METHYL-2-oCTENAL
C C~

~5~9~1
-67- 07-21-~183)
C-C-C-C-C=C-C-C-C-C (E+Z)-2-BUTYL-5,6-DIMETHYL-2-HEPTENAL
C C*
C-C-C-C=C-C-C-C-C-C (E+Z)-2-PENTYL-4,5-DIMETHYL-2-HEXENAL
C* `
,
c-c-c-c-c-c-c=7-c-c-c ( E+Z)-2-tl-METHYLPROPYL)-2-NONENAL
C*
C
C_C_C_C_C_C=7_C_C-C (E+Z)-2-(1,2-DIMETHYLPROPYL)-2-OCTENAL
C* C
C-C-C-C-C=C-C-C-C-C (E+Z)-2-~UTYL-4-ETHYL-2-HEPTENAL
C-C C*
C-C-C-C=C-C-C-C-C-C tE+Z)-2-PENTYL-4-ETHYL-2-HEXENAL
l l
C-C C*
C-C-C-C-C=C-C-C-C tE+z)-2-(2-METHyLpRopyL)-2-METHyL-2-HEpTENAL
C C~ C
C
C-C-C-C=C-C-C-C (E~Z)-2-(2-METHYLPROPYL)-4,5-DIMETHYL-2-HEXENAL
l l l
C C* C
C-C-C-C-C-C=C-C-C-C (E+Z~-2-(2-METHYLPROPYL)-5-METHYL-2-OCTENAL
l l
C C* C
C
C-C-C-C-C=C-C-C-C-C (E+Z)-2-(1-METHYLBUTYL)5-METHYL-2-HEPTENAL
C C~
C-C-C-C-C=C-C-C-C-C (E+Z)-2-(3-METHYLBUTYL)-6-METHYL-2-HEPTENAL
C C* C
.i,

~25~
-68- 07-21-~183)
C-f-l-C=C-C-C-f-C (E+Z)-2-(3-METHYLBUTYL)-4,5-DIMETHYL-2-HEPTENALC C* C
C C
C-C-C-C-C=C-C-C-C tE+Z)-2-$1-METHYLPROPYL)-4,5-DIMETHYL-2-HEPTENAL
C C*
C-C-C-C-C-C=f-C-C-C (E~Z)-2-(1-METHYLPROPYL)-7-METHYL-2-OCTENAL
C
C-f-C-C-C=C-C-C-C-C (E+Z)-2-(1-METl1YLBUTYL)-6-METHYL-2-HEPTENAL
C C*
C-C-C-C-C=C-C-C-C-C (E+Z)-2-(3-METHYL~UTYL)-4-METHYL-2-HEPTENAL
C C* C
C-C-f-C=C-l-C-C-C (E+Z)-2-(1-METHYLBUTYL)-4-ETHYL-2-HEXENAL
C-C C*
c c c c c=c l c c (E+Z~-2-(1-METHYLPROPYL)-4-ETHYL-2-HEPTENAL
C-C C*
C-C-C-C-C=f-C-C-C-C (E+Z)-2-(1-METllYL8UTYL)-4-METHYL-2-HEPTENAL
C C*
C-C-f-C=f-C-C-f-C (E+Z)-2-(3-METHYL8UTYL)~4-ETHYL-2-HEXENAL
C-C C* C
C-C-C-f-C=f-C-f-C (E+Z)-2-(2-METHYLPROPYL)-4-ETHYL-2-HEPTENAL
C-C C* C

g~
-69- 07-21-(183)
C-C-C-C-C=C-C-C-C tE+Z1-2-(1,2-DIMET13YLPROPYL)-7-METI3YL-2-13EXENAL
l l
C C* C
C-c-f -C-C=C-C-f-C (E+Z~-2-(1,2-DIMETHYLPROPYL)-5-METHYL-2-HEXEN~L
C C* C
C-C-C-C-C=C-C-C-C (E+Z)-2-(1,2-DIMETHYLPROPYL)-4-METHYL-2-HEPTENAL
C C* C
C-C-f-C=C-l-f-C (E+Z)-2-(1,2-DIMETHYLPROPYL)-2-ETHYL-2-HEXENAL
C-C C* C
C-C-C-C-C-C=C-C-C-C (E-~Z)-2-(2-METHYLPROPYL)-6-METHYL-2-OCTENAL
1*
C-C-C-f-C=C-l C-C-C (E+Z)-2-(1-METHYLBUTYL)-4,6-DIMETIIYL-2-HEPTENAL
C C*
C-C-C-C-C=C-C-C-C (E+Z)-2-(1,2-DIMETHYLPROPYL)-5-METHYL-2-HEPTEN~L
l* l
C-C-C-C-C-C=f-C-C-f-C ( E+Z)-2-(3-METHYLBUTYL)-2-OCTENAL
C* C
: C-C-C-f-C-C=C-C-C-C-C (E+Z )-2-BUTYL-S-METHYL-2-OCTENAL
C C*
C C C C C C=C l c c c (E-~Z)-2-(1-METT3YLBUTYL)-2-OCTENA~
C*

~25~9~-~
-70- 07-21-(183)A
C-C-C-C-C=f~C-C-C-C (E+Z)-2-(3-METHYLBUTYL)-5-METHYL-HEPTENAL
C C* C
C
C-C-C-C-C=f-C-C-C (E+Z~-2-(1,2-DIMETHYLPROPYL)-4-METHYL-2-HEPTENAL
C C*, C
C C
C-C-f-C=C-C-C-C-C (E-~Z)-2-(1-METHYLDUTYL)-4,5-DIMETHYL-2-HEXEN~L
C C
C Cl
C-C-C-C=C-C-C-C (E+z)-2-(lr2-DIMETJlyLpRopyL)-4l5-DIMET~yL-2-HExENAL
C C C*
Cl
C-C-C-C-C-C=f-C-C-C (E+Z)-2-(2-METHYLPRoPYL)-4-METHYL-2-OCTENAL
C C*
C
C-C-C-C-C-C=C-C-C-C (E+Z)-2-(1-METHYLPROPYL)-4-METHYL-2-OCTENAL
C C*
C-C-C-C-C-C=C-C-C-C-C (E+Z)-2-B~TYL-4-METHYL-2-oCTENAL
C C*
Cl
c-c-7-c=c-c-c-c (E+Z)-2-(1,2-DIMETHYI,PROPYL)-4-ET~YL-2-OCTENAL
C-C C* C

~Z5~9~
-71- 07-21-(183)A
C-C-C-C-C-C=f-C-f-C t E+Z)-2-(2-METHYLPROPYL)-2-OCTENAL
C* C
C-C-C-C=f-C-C-C-C tE-~Z)- 2-BUTYL-4,5-DIMETHYL-2-HEXENAL
C C* C
C-C-C-C-C-C=C-C-C-C (E+Z)-2-(1-METHYLPROPYL)-2-OCTENAL
C*

~25~;~9~
-72- 07-21-(183)A
Similarly, such oxo-aldol reactions of a
predominant component of isoamylene streams,
2-methyl-butene-2, would produce an enal mixture with
most components represented by the structure:
Structures of Dodec-2-enals from Oxo-Aldol of
2-~c~vlb~'e~e ~
3 1 (2-p) IH(2-q) (cH(2-r))m- CH = C-CHO
(CH3)p (CH3)q (CH3)r CH('i_s)(cH3)s
CH ( 2- t ) ~ CH 3 ) t
Wherein:
m = 0 or 1
p, q, r, s, t = 0 or 1 but only one of s and t can be
l;
m = 1 when r = o and only one of p and q can be 1;
m = 0 when p and q = 1
-___________
At the oxo stage of the reaction the main aldehydes
produced are 3-methylpentanal-1 and 4-methylpentanal-1
with possi~ly up to 10~ 2,3-dimethylbutanal-1.
The aldol products are mainly 5-methyl-2-
20 (1-methylpropyl)hept-2-enal-1, 6-methyl-2-
(2-methylpropyl)-hept-2-enal-1,6-methyl-
2(1-methylpropyl)hept-2-enal-1 and 5-methyl-2
(2-methylpropylhept-2-enal-1, and two C10 aldehydes
in very small amounts.
EXAMPLE 23
The unsaturated aldehydes representative of

~Z5~7~5~
-73- 07-21-(183)A
product from oxo and aldol reactions of
2-methylbutene-1 and 3-methylbutene-1 as produced in
Example 22 were subjected to hydrogenation. An
autoclave was charged with 3.74 9 of 45% + 5% cobalt
on Kieselghur, 37.27 g of the aldol condensation
product, 23.16 g methanol and hydrogen to 1500 psi
(10,644 RPa) gauge. The autoclave was heated to
160C. The pressure and temperature were maintained
for seventeen hours. The catalyst was filtered off
and washed with methanol to remove any residual
alcoholsO The dodecanols were distilled at 25 mm Hg
and collected from 137 to 139C.
EXAMPLE 24
This example illustrates the utility of the
invention for synthesis of Cll and Cl4 unsaturated
aldehydes.
An aldehyde mixture representative of that
from the oxo reaction of Dimate ~ hexenes, as
described above in Example 1 was reacted in an aldol
condensation along with normal butanal. A stirred
autoclave was charged with 600 ml 0.8M NaOH, 1160 ml
methanol and 20 psig (137.8 KPa) argon. The autoclave
was heated to 100C and a mixture of 323.2 g heptanals
from oxo of Dimate ~ hexenes and 212.9 g butanal,
total volume 600 ml was pressured into the autoclave
with argon. The reaction was run for an additional
hour and the system rapidly cooled. The product was
removed and the upper and lower phases were separated.
The upper phase contained 2.7~ methanol, 5.1%
unreacted heptanals, 13.7~ (Z+E)-2-ethyl-hexenal,
56.0% 2-undecenals, 18.4% 2-tetradecenals, 0~5%
heptanols and 3.5~ high boilers. The mole ratio of
the butanal to heptanals is 1.04:1, the mole ratio of
the product aldehydes, 2-ethyl-hexenal, 2-undecenals
and 2-tetradecenals is 0.84 to 2.51 to 0.65

- ~25i~5~
-74- 07-21-(183)A
respectively. The 2-undecenals were separated from
the other products by reduced pressure distillation at
40 mm Hg. The 2-undecenals were collected in the
temperature range of 119 to 132C. The skeletal
5 structures of the undecenals are given in Table 9.

`- ~2~
-7 5 - 0 7--21--( 1 8 3 ) A
TABLE 9
2-UNDECENALS FROM ALDOL OF HEPTANI~LS AND BUTANAL
COMPOUND
STR UC TURE NAME
C-C-C-C-C-C-C=C-C-C (E+Z ~-2-ETHYL-2-NONENAL
C*
C-f-C-C-C=f-C-C ( E+Z ) -2 -ETHYL-7 -METHYL -2 -OC TENAL
C C*
C-C-C-f -C-C=C-C-C t E-~Z ) - 2 -ETHYL -5 -METHYL-2 -OC TENAL
C C*
C-C-C-C=C--C--C-C-C ( E+z )--2--( 1 -METHYLBUTYL )--2 -llEXENAL
C*
C-C-C-C=f-C-C-f-C (E+Z)-2- ( 3-METHYLBUTYL )-2-HEXENAL
C* C
C-C-C-C=f-C-C-C-C-C ( E+Z ) - 2 - PENTYL - 2 -HEXENAL
C*
f
C-C-C-C=f-C-f-C - ( E-~Z ) -2- ( 1, 2-DIMETHYLPROPYL ) -2-HEXENAL
C* C
f
C-C~C-C-C=C-C-C (E+Z )-2-ETHYL-4, 5-DIMETHYL-2-HEPTENAL
1*
C-C-C-C-f-C=f-C-C ( E+Z ) - 2 -ETHYL - 4 -METHYL - 2 -OC TENAL
C C*
C-C-C-f-C=f-C-C ( E+Z ) - 2 -ETHYL - 4 -ETIIYL- 2 -HEPTENAL
C-C C*

2~ g
-76- 07-21-(183)A
The 2-undecenals and 2-tetradecenals in the product
which are sultable for preparing detergent
hydrophobes, can be represented by the following
formula:
Structure of C8, Cll 14 Enals from Aldol of
Butanal
and Mixed Heptanals
CH3 - (CH(2_p))h - (CH(2-q))m C
(CH3)p (R)q (CH(2_r))n(CH3)r
( ~CH2) S
~ (2-t~--(CH3)t
Wherein: CH3
R = methyl or ethyl; h and n = 0, 1, 2, 3, 4, and 5;
n and s = 0, 1, 2; p, q, r and t = 0 or 1;
q and p = 0 when m + k = 5 or when m + k = 2
n + s can never be greater than 2
m + h can never be greater than 5
h = 3 and m = 1 when R= methyl and q = 1 and p = 0;
h = 2 and m = 1 when R = ethyl and q = 1 and p = 0 or
when q =-0 and p = 1;
h = 1 and m = 3 when p = 1 and q = 0;
r and t = 0 when n + s = 3 or when n + s = 0;
s = 0 when n, r and t = 1 or when n = 2, r=0 and t=l;
s = 1 when n = 1 and t and r = 0 or 1 but only one
of t and r can be l;
s = 2 when t = 1 and n = 0

` ~2~9~i
-77- 07-21-(183)A
EXAMPLE 25
This example illustrates the utility of the
lnvention for a single hexene isomer, ~-methylpen-
tene-l. The hydroformylation was performed in a 300
ml autoclave with agitation. The autoclave was
charged with 0.29 g carbonyltris(triphenylphosphine)-
rhodium hydride, 33.0 g triphenylphosphine, 100.0 g
4-methylpentene-1 and 200 psi t200 KPa) gauge pressure
with 9 parts hydrogen to 1 part CO. The autoclave was
heated to 100C. and the pressure brought to 300 psi
(2068.4 KPa) gauge using feed gas in 1 to 1 ratio
hydrogen to CO. The temperature and pressure were
maintained for 2 hours and ~5 minutes after which the
autoclave and contents were cooled rapidly. The
product was removed and analyzed chromatographically.
The product consists of 5.65~ hexenes (5.57%
4-methylpentene-1), 10.64~ 2,4-dimethylpentanal,
68.84% 5-methylhexanal, and approx. 15
triphenylphosphine, by area percent.
An aldehyde mixture representative of the
oxo reaction of 4-methylpentene-1, as described above
was reacted in an aldol condensation. The reaction
vessel was a 100 ml 3 neck round bottom flask equipped
with pressure e~uilizing funnel, thermometer, spiral
condensor, a mechanica- stirrer and a nitrogen
blanket, maintained by using a slow bleed of nitrogen
and a mineral oil bubbler. The reactor was charged
with 12 ml 0.8M NaOH, and 12 ml 2,5-hexanediol, as
co-solvent. The system was heated to 80C and the
aldehydes, 12 ml, were added over a six minute period.
The system was heated to 89-90C and held at
temperature for an additional 30 minutes. The system
was cooled and the upper and lower phases were
separated. The upper phase was analyzed
chromatographically and contained 2.0~

~,9--9
-78- 07-21-(183)A
2,4-dlmethylpentanal, 1.5% 5-methylhexanal, 5%
tetradecenal isomers, 85% 7-methyl-2-
(3-methylbutyl)-2-octenal, 2.5% 2,5-hexanediol and a
balance of high boilers.
EXAMPLE 26
The unsaturated aldehydes representative of
product from oxo and aldol reactions of 4
methylpentene-l as in example 25 were subject to
hydrogenation. The reaction was performed in a 300 ml
10 autoclave which was charged with 0.90 g 45 + 5% cobalt
on Kieselghur, 7.92 g unsaturated aldehydes, 50.02 g
methanol (used to ensure proper mixing) and 1500 psi
(10644 RPa) gauge hydrogen. The autoclave was heated
to 150C. The pressure and temperature were
maintained for one hour. The catalyst was filtered
off and washed with methanol to remove any residual
alcohols. The 7-methyl-2-(3-methylbuty)-2-octenal was
dlstllled at 20 mm Hg and was collected from 158 to
159C. This example comblned with Example 28
illustrates the conversion of the unsaturated
aldehydes to saturated carboxylic acids.
EXAMPLE 27
Hydrogenation to a saturated aldehyde from
an unsaturated aldehyde mixture representative of that
from the oxo and aldol of Dimate R hexenes as
described in Examples 1 and 17, was carried out in a
300 ml autoclave with agitation. The autoclave was
charged with 2.60 g 5% palladium on carbon, 44.81 g
methanol (used to ensure proper agitation), 8.24 g
tetrade-2-enals and 200 psig (1379 KPa) H2. The
autoclave was heated to 85C and held for one hour.
The autoclave ~as then heated to 125C and held for 2
hours. The autoclave was cooled and an infrared
spectrometric analysis confirmed the reduction of the
olefinic bond and the presence of a strong carbonyl

~5~
-79- 07-21-(183)A
band at 1740 cm 1. The untreated 2-tetradecenals
have bands at 1698 cm 1, strong, and 1643 cm 1
moderate, which are characteristic of unsaturated
aldehydes,
EXAMPLE 28
This example, combined with Example 27
illustrates the conversion of the unsaturated
aldehydes to saturated carboxylic acids.
Oxidation of a saturated aldehyde mixture
representative of that from the hydrogenation of the
unsaturated aldehydes as described in Example 27 was
carried out in a Fisher-Porter aerosol bomb, with
agitation. The bomb was charged with 60 ml heptene,
8.2 g tetradecanals, and 100 psi (689,4 KPa) gauge
oxygen. Agitation was started and pressure was
allowed to drop to 60 psi 1413.7 XPa) gauge when the
bomb would be re-pressured to 100 psi gauge. The
reaction continued for 3 1/4 hours and the temperature
varied from 23 to 30C. The pressure was released
and system heated to 80C and held for 2 hours. The
product was analyzed chromatographically and by gas
liquid chromatography - mass spectrometry to confirm
that saturated acid was formed, and 98~ of the
aldehydes were converted.
EXAMPLE 29
Oxidation of an unsaturated aldehyde mixture
representative of that from the oxo and aldol
reactions described in Examples 1 and 17, was carried
out in a Fisher-Porter aerosol bomb with agitation.
The bomb was charged with 60 ml heptane, 8.2 g
tetradec-2-enal and 100 psi (68g.~ KPa) gauge oxygen
in a darkened area. Agitation was started and the
pressure in the bomb was allowed to drop to 70 psi
(482.63 KPa) gauge at which time the bomb was
repressurized to 100 psi (689.4 KPa) gauge. The

-80- 07-21-(183)A
reaction continued in this manner for four hours and
the temperature varied from 20C to 25C. The
pressure was released and the system heated to 80C
for 2 hours. The product was analyzed
chromatographically and by mass spectrometry and
contained unsaturated tetradecanoic acids and 97~ of
the aldehydes were converted.
A mixture of amylenes and Dimate ~ hexenes
can be subjected to oxo and aldol processes in accord
with the present invention. Thus, pentenes containing
n-pentene-l, n-pentene-2, 3-methylbutene-1,
2-methylbutene-2, and 2-methylbutene-1 in admixture
with Dimate ~ hexenes can be reacted in an oxo
reaction, with the product treated in an aldol
reaction, in accord with procedures in Examples 18
and 19, and the resulting enals (see Table 8) can be
represented by the following structure:
Structure of Dodec-2-enals and Tridec-2-enals
from the, Oxo-Aldol of mixed pentenes
and Dimate Hexenes
3 (1CH(2-p))h (lcH(2-q))m~cH=c-cHo
(CH3)p (R)q (CH(2_r))n (CH3)r
(ICH2)S
CH(2 t) (CH3)t
CH3
Wherein:
R = methyl or ethyl; h and m = 0, 1, 2, 3, 4 and 5;
n and s = 0, 1, 2; p, q, r and t = -0, 1;

~ 2~
-81- 07-21-(183)~
m ~ h = 5 or 4, when p and q = 0;
m and q = 1 and p = 0 when h= 3, 2 or 1 but
R can only be ethyl when h= 1, 2 and R
can only be methyl when h = 2, 3;
h + m can never be greater than 5;
n + s can never be greater than 2;
q = 0 and p = 1 and h = 2 when m = 1 or 0;
q = 0 and p = 1 and 1 = 1 when m = 3 or 2;
r and t = 0 when n + s = 3 or when n= 0 and s = 2;
t = 1 when n = 0 or 1 and s = 1 or 2;
n and t = 1 when s = 0 and r = 1;
The aldehydes which are branched at the
2-position which react at a much slower rate in the
aldol reaction can be recycled to generate Cll-C16
enals in several different ways. Thus these aldehydes
can be simply recycled to the aldol reaction until
their concentration is high enough that they are being
reacted in cross-aldol reactions at a rate essentially
the same as they are being generated in the
hydroformylation reaction. Another approach is to
allow these relatively unreactive aldehydes to proceed
through hydrogenation to give branched chain alcohols.
These alcohols can then be readily dehydrated to a
mixture of branched olefins. If these olefins are
recycled to the hydroformylation reaction they are
hydroformylated primarily to aldehydes without a
branch at the 2-position and hence they will undergo
the alcohol reaction and generate aldol products in
the desired Cll to C16 range. This can be illustrated
by considering the mixture of aldehydes generated by
the hydroformylation of Dimate R hexenes (see Table
2). The 2-methylhexanal, 2-ethylpentanal and
2,4-dimethylpentanal isomers pass through the aldol
reaction stage largely unreacted. On hydrogenation
they are converted to 2-methylhexanol, 2-ethylpentanol

~2~
-82- 07-21-(183)A
and 2,4-dimethylpentanol. These alcohols can be
dehydrated by passage over heterogeneous catalysts at
temperatures of 120-500C. Catalysts should be chosen
such that alcohol dehydration occurs readily but
minlmal skeletal rearrangement occurs. suitable
catalysts are various types of aluminas, thorias and
metal phosphates (e. g. AlPO4, BPO4, Ca3(PO4)2. (For-
further catalyst information see Journal of the
American chemical Society, 85, 2180 (1963) and Topics
in Phosphorus Chemistry Vol. 10. page 285). As an
example we can consider the recycle of 2-methylhexano.
Over a dehydration catalyst it would give primarily
2-methylhexene-1 and 2-methylhexene 2. These olefins
when charged to the hydroformylation reaction would
give rise to primarily 3-methylheptanal with lesser
amounts of 6-methylheptanal and minor amounts of other
isomers. The 3-methylheptanal and 6-methylheptanal
readily undergo aldol condensation and in coniunction
with the C7 aldehydes resulting directly from the
hydroformylation of the Dimate R hexenes will give
rise to predominantly C15 unsaturated aldehydes with
minor amounts of C16 unsaturated aldehydes. See Table
10 for specific names of the unsaturated aldehyde
products. The described recycle involving dehydration
and formation of aldolable aldehydes, permits handling
smaller volumes of materials in the aldol reaction
than is the case when the concentration of 2-branched
aldehyde reactant is permitted to build up.

~L25~
-83- 07-21-(183)A
TABLE 10
2-PENTADE ~NALS AND 2-HEXADECENALS FROM OXO AND ALDOL OF
DIMATE HEXENES AND RECYCLED UNREACTIVE llEPTANALS
COMPO~ND NAME
(E+Z)-2-(1-METHYLPENTYL)-2-NONENAL
~E+Z)-2-(1-METHYLPENTYL)-7-METHYL-2-OCTENAL
(E+Z)-2-~1-METHYLPENTYL)-5-METHYL-2-OCTENAL
(E+Z)-2-(1-METHYLPENTYL)-5,6-DIMETHYL-2-HEPTENAL
(E+Z)-2-PENTYL-5-METHYL~2-NONENAL
(E+Z)-2-(1-METHYLPUTYL)-5-METHYL-2-NONENAL
(E+Z)-2-(3-MEHTYLBUTYL)-5-METHYL-2-NONENAL
(E+Z)-2-(1,2-DIMETHYLPROPYL)-5-METHYL-2-NONENAL
(E+Z)-2-(1-METHYLPENTYL)-4-METHYL-2-OCTENAL
(E+Z)-2-(1-METHYLPENTYL)4-ETHYL-2-HEPTENAL
(E+Z)-2-(4-METHYLPENTYL)~2-NONENAL
(E+Z)-2-(4-METHYLPENTYL)-7-METHYL-2-OCTENAL
(E+Z)-2-(~-METHYLPENTYL)-5-METHYL-2-OCTENAL
(E+Z)-2-(4-METHYLPEN~YL)-5,6-DIMETHYL-2-llEPTENAL
(E+Z)-2-PENTYL-8-METHYL-2-NONENAL
(E+Z)-2-(1-METEIYLBUTYL)-8-METHYL-2-NONENAL
(E+Z)-2-(3-METHYLBUTYL)-8-METHYL-2-NONENAL
(E+Z)-2-(1,2-DIMETHYLPROPYL)-8-METHYL-2-NONENAL
(E+Z)-2-(4-METHYLPENTYL)-4-METHYL-2-OCTENAL
(E+Z)-2-(4-METHYLPENTYL)4-ETHYL-2-HEPTENAL
(E+Z)-2-(1-ETHYLBUTYL)-2-NONENAL
(E+Z)-2-(1-ETHYLBUTYL)-7-METHYL-2-OCTENAL
(E+Z)-2-(1-ETHYLBUTYL)-5-METHYL-2-OCTENAL
(E+Z)-2-(1-ETHYLBUTYL)-5,6-DIMETHYL-2-HEPTENAL
(E+Z)-2-PENTYL-5-ETHYL-2-OCTENAL
(E+Z)-2-(1-METHYLBUTYL)-5-ETHYL-2-OCTENAL
~E+Z)-2-(3-METHYLBUTYL)-5-ETHYL-2-OCTENAL
(E+Z)-2-(1,2-DIMETHYLPROPYL)-5-ETHYL-2-OCTENAL
(E+Z)-2-(1-ETHYLBUTYL)-4-METHYL-2-OCTENAL
~E+Z)-2-(1-ETHYLBUTYL)4-ETHYL-2-HEPTENAL
(E+Z)-2-PENTYL-4-ETHYL-6-METHYL-2-HEP'rENAL
(E~Z)-2-(1-METHYLBUTYL)-4-ETHYL-6-METHYL-2-E~EPTENAL
(E+Z)-2-(3-METHYLBUTYL)-4-ETHYL-6-METHYL-2-HEPTENAL
(E+Z)-2-(1,2-DIMETHYLPROPYL)-4-ETHYL-6-METHYL-2-HEPTENAL
(E+Z)-2-PENTYL-4,7-DIMETHYL-2-OCTENAL
(E+Z)-2-(1-METHYLBUTYL)-4,7-DIMETHYL-2-OCTENAL
(E+Z)-2-(3-METHYLBUTYL)-4,7-DIMETHYL-2-OCTENAL
(E+Z)-2-(1,2-DIMETHYLPROPYL)-4,7-DIMETHYL-2-OCTENAL
(E+Z)-2-PENTYL-4-ETHYL-5-METHYL-2-HEXENAL
(E+Z)-2-(1-METHYLBUTYL)-4-ETHYL-5-METHYL-2-HEXENAL
(E+Z)-2-(3-METHYLBUTYL)-4-ETHYL-5-METHYL-2-HEXENAL
~E+Z)-2-(1,2-DIMETHYLPROPYL)-4-ETHYL-5-METHYL-2-HEXENA~
, ~

~ 25~
-84- 07-21-(183)A
2-HEXADECENALS
(E+Z)-2-(4-METHYLPENTYL)-7-METHYL-2-NONENAL
(E+Z)-2-(1-METHYLPENTYL)-7-METHYL~2-NONENAL
(E+Z)-2-(l~ETHYLBUTYL)-7-METHYL-2-NONENAL
(E+Z)-2-(4-METHYLPENTYL)-4,7-DIMETHYL-2-OCTENAL
(E+Z)-2-(1-METHYLPENTYL)-4,7-DIMETHYL-2-OCTENAL
(E+Z)-2-(1-ETHYLBUTYL)-4,7-DIMETHYL-2-OCTENAL
(E~Z)-2~(4-METHYLPENTYL)-4-ETHYL-6-METHYL-2-HEPTENAL
(E~Z)-2 (1-METHYLPENTYL)-4-ETHYL-6-METHYL-2-HEPTENAL
~E~Z)-2-(1-ETHYLBUTYL)-4-ETHYL-6-METHYL-2-HEPTENAL
(E+Z)-2-(4-METHYLPENTYL)-4-ETHYL-5-METHYL-2-HEPTENAL
(E+Z)-2-~1-METHYLPENTYL)-4-ETHYL-5-METHYL-2-HEPTENAL
(E~Z)-2-(1-ETHYLBUTYL)-4-ETHYL-5-METHYL-2-HEPTENAL
(E~Z)-2-~4-METHYLPENTYL)-4-METHYL-2-NoNENAL
(E~Z)-2-(1-METHYLPENTYL)-4-METHYL-2-NONENAL
(E+Z)-2-~1-ETHYLBUTYL)-4-METHYL-2-NONENAL
(E+Z)-2-(4-METHYLPENTYL)-4-ETHYL-2-oCTENAL
(E+Z)-2-(1-METHYLPENTYL)-4-ETHYL-2-OCTENAL
(E+Z)-2-(1-ETHYLBUTYL)-4-ETHYL-2-OCTENAL
i .

''''`' ~Z~g.'i
-85- 97-21-(183)A
Nonionic detergents prepared from the
present alcohols by ethoxylation were tested for
detersive efficiency in comparison with reference
compounds which were subbstantially normal alcohol
ethoxylates, being Neodol @~ ethoxylates marketed by
Shell Chemical Company. The reference compound
alcohols, produced by ethylene oligomerization, are
composed of designated percentages of normal alcohols,
generally in the range of 70 to 80%, and the remainder
f isomeric 2-alkyl (predominantly 2-methyl) primary
alcohols. The tests employed are recognized tests in
which a fabric soiled with synthetic sebum/airborne
particulate is washed and the results measured by
Rd, change in reflectance by Gardner XL-23 Co~or
Difference meter. Tests were conducted with a
polyester-cotton blend fabric containing 65~
polyester, and with a cotton broadcloth fabric. Three
different ethoxylates of the C14 alcohol mixture of
the present invention (designated C14 Aldol) were
used, having 6.0, 8.7 and 10.5 ethoxylate groups on
the average. The reference compounds for coomparison
were Neodol 45 ethoxylates having 7 and 13 ethoxyl
groups, and Neodol 25 ethoxylates having 7 and 12.5
ethoxyl groups. An individual oxo-aldol C14 alcohol
f the present invention was also tested
~-tl-methylbutyl)-5-methyloctanol. It was prepared by
aldol of 3-methyl-heptanol, and is designated as C14
High Vicinal, because of presence of adjacent branches
in its structure. The results are reported in Tables
ll-a, ll-b, ll-c, ll-d, and ll-e. The tables include
results with the detergent including sodium
tripolyphosphate (STP) builder, sodium carbonate
builder, or no builder, and a washing temperature of
120F in most instances, but 75F in Table ll-d.

~2~7~9.~
-86- 07-21-(183)A
Tests were reported at different amounts of water
hardness as set forth. The sodium tripolyphosphate
built detergent, for example, had a composition of 10
of the nonionic (surfactant), 24% sodium
tripolyphosphate, 12~ R.~. Sebacate (as is), 53~
sodium sulfate, and 1~ sodium carboxyethyl cellulose,
while the one with no builder was similar, with the
STP replaced by additional sodium sulfate. The
detergent was used in concentration 0.15%, for anionic
concentration of 150 ppm. Water hardness was from a
3/2 atom ratio of calcium and magnesium ions, with
concentration calculated as parts per million by
weight of calcium carbonate.
Table lla
Synthetic Sebum Detergency
120F, Cotton ~ Rd
30~ Na2 CO3 Builder System
Water
Sample Hardness 0 50 ppm 100 ppm 200 ppm
Neodol 45-7 32.5 31.5 29.6 27.2
n 45-13 32.3 31.1 29.2 23.3
25 Neodol 25-7 31.8 29.9 28.8 23.9
" 25-12.5 33.1 30.7 27.6 20.2
C14 Aldol 6.0 32.7 29.4 26.0 19.8
n 8.7 32.6 30.8 27.0 24.0
" 10.5 31.5 31.1 28.0 26.2
30 C14 Hi9h
Vicinal 5.5 20.8 20.6 18.8 11.4
9.5 19.5 18.9 19.4 14.8
13.3 15.5 17.0 15.8 11.1

~2~,5~
-87- 07-21-(183)A
Table llb
Synthetic Sebum Detergency
120 F, cotton, ~ Rd
- 0% Builder System _ _
Water
SampleHardness 0 50 ppm 100 ppm 200 ppm
Neodol 31.5 29.5 26.1 24.0
" 31.4 31.3 29.5 27.8
Neodol 25-7 31.7 29.4 26.1 24.8
n 25-12.5 30.1 31.1 29.7 25.9
C14 Aldol- 6.0 30.4 26.0 20.7 16.8
n 8.7 30.2 30.6 24.5 22.4
n 10.5 30.4 30.9 26.3 24.7
C14 High
15Vicinal 5.5 32.7 18.9 21.0 13.9
9.5 32.1 20.1 20.3 17.4
13.3 32.6 17.5 16.1 14.3

~25~
-88- 07-21-(183)A
Table ll-c
-
Synthetic Sebum Detergency
- 120 F, Cotton, ~ Rd
24~ STP Builder System
Water
Sample Hardness 0 50 ~pm 100 p~m 200 ppm
Neodol 45-7 32.2 34.2 35.2 26.9
n45-13 31.5 34.0 35.0 28.9
Neodol 25-7 . 32.2 34.4 34.5 26.1
10 n 25-12.5 31.7 33.5 34.5 27.4
C14 Aldol 6.0 31.4 34.4 34.5 20.5
n 8.7 30.8 33.5 35.7 23.5 .
n 10.5 31.4 34.3 34.8 25.2
C14 High
15 Vicinal 5.5 32.8 35.3 36.6 22.4
9.5 32.8 33.5 35.8 25.3
13.3 32.7 3S.1 34.5 24.9
Table ll-d
Synthetic Sebum Detergency
75F, PE/cotton, ~ Rd
24~ STP Builder System
Water
Sampl_ ~ardness 0 50 ppm 100 ppm 200 ppm
Neodol 45-7 18.3 17.7 15.7 14.0 .

~25~9~-~
-89- 07-21-(183)~
" 45-13 16.7 16.1 15.1 11.9
Neodol 25-7 18.8 19.8 18.0 14.3
" 25-1.25 16.5 17.2 14.5 13.7
C14 Aldol- 6.0 19.8 17.7 19.3 9.4
" 8.7 19.3 18.2 20.0 15.0
n 10.5 17.5 18.1 16.6 14.0
C14 High
Vicinal 5.5 20.8 20.6 18.8 11.4
9.5 19.5 18.9 19.4 14.8
13.3 15.5 17.0 15.8 11.1
Table ll-e
Synthetic Sebum Detergency
120 F, PE/cotton,~ Rd
24% STP Builder System
Water
Sample Hardness 0 50 pm 100 ppm 200 ppm
Neodol 45-7 19.8 19.7 18.7 16.2
" 45-13 18.6 17.8 16.8 12.8
Neodol 25-7 19.9 19.6 20.4 16.7
.. 25-12.5 18.1 17.8 16.6 13.4
C14 Aldol 6.0 19.8 lg.0 18.6 7.9
" 8.7 19.9 21.7 21.1 18.9
" 10.5 20.1 18.8 19.6 17.6
C14 High
25Vicinal 5.5 21.2 18.9 21.0 13.9
9.5 19.4 20.1 20.3 17.4

-9- 07-21-(183)A
13.3 18.4 17.5 1~.1 14
It can be seen that the ethoxylates of ~he
present alcohol mixture are in general comparable in
the tests of detersive eff1ciency to the established
reference ethoxylates. It can be noted that in some
respects the present compounds give better results, as
for example with the 8.7 ethoxylate in Tables 11 d and
5-e involving tests with polyester/cotton.
The C14 mixed alcohol product of the present
1nvention, in ethoxylate form, was tested for
blodegradabillty, in comparison to commercial
detergents. The test procedure used was the
semi-continuous activated sludge test which determines
dissolved organic carbon as the measure of
biodegradation. The results are reported in Table 12
below. The aldol-alcohol (C14) was the alcohol
mixture as described in Table 4 above, which has been
ethoxylated to have an average of 10.5 ethoxyl groups.
It was compared to a Neodol 25-12, which is an
ethoxylate of an approximately linear alcohol in the
12 to 15 carbon range, with an average of 12 ethoxyl
groups. The two LAS reference compounds are linear
alkyl benzene sulfonates of a type utilized
commercially. The test-measuresthe removal of
dissolved organic carbon (DOC), and is a measure of
complete degradation of the compounds.

g~
-91- 07-21-~183)~ ~
, ~,? ~ ~ 1
1~'~ ~ ~ u~
. ~- C) ~
, ~ S
~ ~ S 7
~ 1~o+~+~ ~D
~ ~, ~
. '~ ~ i
;3 C 3 ~ ~ ~

~25~
-92- 07-21-(183)A
While the degradation of the aldol product was not as
fast as that of the linear alcohol product (Neodol
25-12), it was still comparable ~o the L~S compounds
which are suitable for commercial use. Also, the
essentially complete removal in the 72-hour cycles
indicates there are no resistant fragments.
Further biodegradation tests were carried
out utilizing the semi-continuous activated sludge
test, and comparing a C14 aldol isomeric mixture
ethoxylate with an ethoxylate of a high vicinal
alcohol,i~e,3-(1-methyl~butyl)-5-methylheptanol. The
24-hour cycle results for weeks 4, 5 and 6 are
reported in Table 7, While the high vicinal alcohol
degrades somewhat more slowly, its rate is still
fairly close to that of the isomeric mixture which was
shown to be comparable to commercial materials in
Table 6. Moreover, results with the isomeric mixture
indicate that good biodegradation can be obtained even
with a substantial amount of the high vicinal alcohol
present. The results in Table 7 provide a comparison
of the materials tested, but may not be directly
comparable to other tests, because of the low ethoxyl
content which may have affected solubility, or
possibly unexplained test variations.

~L25~9~
-93- 07-21-(183)~
Table 1~
Semi-Continuous Activated Sludge Test
~ DOC. Removal - 24 hr)
Week 4 Week 5 Week 6
5 1. Neodol R 25-7
Reference compound 88 38 97 13 96 8
2. C ~ 6.0 Ethylene
O~de (Dimersol Hexene) 61 13 65 31 72 6
3. High Vicinal Alcohol +
6.3 Ethylene Oxide 66 44 51 39 63 12
~from 3-methylhexanal)

`` ~L25~9~-~
-94- 0?-21-(183)~
EXAMPLE 30
The C14 ethoxylate derivatives described
above and evaluated were prepared by known
ethoxylation procedures. A 100 ml glass reactor was
employed with thermometer, stirrer, and provision for
ethylene oxide addition. A mercury-filled U-tube
manometer was employed, and about 700 mm pressure was
maintained during the reaction. Ethylene oxide was
charged from a small bomb, with the amount charged
determined by weight difference. The weight of the
lo detergent alcohol charge was calculated to have the
desired mole ratio to ethylene oxide. The reaction
temperature was maintained at 165C by a controlled
heating mantle. As catalyst, solid ~OH was charged at
1~ by weight of alcohol used. Thus C14 aldol alcohol
product, like that of Table 3, was reacted in separate
reactions with ethylene oxide in mole ratio of 5.3/1
and 8.9/1 EO/alcohol by weight. The ethylene oxide
addition rate was controlled by a valve and required
about 2 to 2.5 hours for complete addition as
determined by the manométer. The temperature was
reduced to 125C. and the catalyst was neutralized by
addition of H3P04 by syringe through a rubber septum.
The amount of the acid in ml of 85~ H3P04 was 0.7
times the KOH weight in grams. The product was held
for 15 minutes at 125C following the acid addition,
and was then filtered while hot through a layer of
Celite R filter aid on a fritted filter to remove
phosphate salts. NMR analysis showed ethylene oxide
content similar to that charged in the reactions,
being 5.6 ethoxyl units and 8.7 ethoxyl units
respectively. A similar procedure but with a higher
EO/alcohol charge was used to prepare an ethoxylate of
the same alcohol mixture, but with 1~.5 ethoxyl units

~2~g~'~
-95- 07-21-(183)A
per alcohol molecule. The procedure was also used to
prepare the C14 high vicinal alcohol evaluated herein,
using weight charges of EO/alcohol of 5.9, 8.8 and
12.1 to obtain products with 5.5, 9.5 and 13.3 ethoxyl
units as shown by NMR.
EXAMPLE 31
Sulfate derivatives of the alcohols or
ethoxylates were prepared by sulfation with
chlorosulfonic acid. Both an alcohol mixture, and an
ethoxylated alcohol mixture were sulfated in this
manner. The alcohol mixture was from oxo, aldol and
hydrogenation reactions starting with Dimate R
hexenes, as described hereinabove. The ethoxylate was
prepared in accord with the above procedure with an
ethylene oxide charge calculated to provide three
ethoxylate units. The chlorosulfonic acid was
provided on a 1.05 to 1 mole ratio to alcohol or
ethoxylate. In separation reactions, the alcohol and
ethoxylate were placed in flasks and cooled in an ice
bath while acid was added dropwise. HCl vapors were
then drawn off by intermittent vacuum. When HCl
evolution stopped, the sulfated products were
transferred to beakers containing solutions o~ 90%
isopropanol and 10% water, by weight. The sulfate
derivatives were 20% by weight of their respective
solutions. A 50% by weight solution of NaOH in water
was added with agitation to pH 8Ø Salts solids were
removed by filtration. The solutions of sulfate
derivatives were then evaporated to dryness on a
rotary evaporator. The products were then in the form
of a sodium sulfate of the C14 alcohol mixture, and a
sodium sulfate of the ethoxylated C14 alcohol mixture
containing a nominal 3.0 ethoxyl units. Ethanol was
added to the products to form concentrated solutions,
along with water to aid solubility, forming a 55.5%

~;~5~9.^-~
-96- 07-21-(183)A
solution of the alcohol sulfate, and a 50.2~ solution
of the sulfate of the ethoxylated alcohol. The
solutions are a convenient form for preparing samples
for evaluation of detergency, biodegradation and
similar properties. In view of the results reported
herein for ethoxyl derivatives, the sulfate
derivatives are expected to be similarly good.
The detergent hydrophobes of the present
invention are also of interest in the form of
synthetic fatty acids. The long chain aldehydes as
produced herein, can readily be converted to acids by
simple oxidation of the aldehyde group, as in an air
oxidation. The acids retain the branched structure of
the aldehyde, and can have the unsaturation at the
2-position as in the enals, or such unsaturation can
be hydrogenated, or otherwise reduced, to provide
saturated acids. Such acids can be converted to
sodium, potassium or other alkali metal soaps or other
detergents having anionic or hydrophilic groups
attached to the acid, and are expected to have
suitable lathering and other detergent properties. It
will be noted that the acids, which can be termed as
synthetic fatty acids, have the same structure as the
alcohols. Since the alcohols are suitable as
detergent hydrophobes, having suitable detergent and
biodegradation properties, the corresponding acids are
expected to have suitable detergent and biodegradation
properties.