Note: Descriptions are shown in the official language in which they were submitted.
lZS~ ~9()
BACKGROUND OF THE INVENTION
SCOPE OF THE INVENTION
This invention relates to the dealkoxyhydroxymethylation of acetals.
More particularly, it relates to a novel process for the
dealkoxyhydroxymethylation of certain dialkyl-, dicycloalkyl-, or diaryl-
formaldehyde acetals by reacting said acetals with syngas, i.e., hydrogen
and carbon monoxide, in the presence of novel ruthenium carbonyl-promoted
cobalt carbonyl catalysts to form the corresponding ethylene glycol
monoethers. Still more particularly, it relates to the catalysts per se
and methods for preparing the same. The methylal described herein may be
added directly or formed in _tu from the corresponding formaldehyde and
alcohol precurors.
The glycol ethers described herein encompass ~nown classes of compounds
having various uses, as for example as jet fuel additives, cleaners,
coatings solvents, intermediates in the production of certain
diphthalates, and the like.
DESCRIPTION OF THE PRIOR ART
One current well-known method of manufacturing ethylene glycol monoethers
such as monoalkyl ethers consists of reacting ethylene oxide with the
alcohol corresponding to the desired alkyl ether, employing various known
catalyst system~.
LS317 -2- ~:e
Alternatively, the cobalt-catalyzed reaction of aldehydes or their
dialkyl acetals with syngas, i.e., a carbon monoxide-hydrogen mixture, to
form the corresponding glycol ether i~ also described in the art. Thus,
for example, a method of making ethylene glycol ethers is described in
U.S. Patent No. 2,525,793 which employs cobalt oxide to catalyze the
reaction of methylal with syngas to provide a reaction mixture which,
after hydrogenation over nickel, gives relatively uneconomical
conversions on the order of 25-33%.
Numerous attempts have been made to obtain more practical yields of
glycol ethers from aldehydes or their dialkylacetals. A number of
promoters have been used in conjunction with variou cobalt catalysts in
an effort to improve reaction rates and product yields. U.S.
Patent 4,062,898, for example, discloses a ruthenium chloride-promoted
cobalt iodide catalyst which hydrocarbonylstes formaldehyde
dimethylacetal (methylal) to ethylene glycol monomethyl ether (EGMME) in
yields of 10% or less. The reaction temperature required is 185~C at
20 atm. or above. A second method, described in J~ Kokai Tokkyo Xoho
81 83,432 (1981) uses substantial quantities of 2,4,6- collidine or
similar aromatic amines to promote the cobalt carbonyl catalyzed
hydrocarbonylation of methylal in benzene as a solvent. The reaction of
methylal with highly pressurized syngas in this process at 190C for 10
hours gave 44% selectivity to EGMME at 98~ conversion. A further patent,
Euro. Pat. Appln. EP 34,374 (1981) uses both iodine and triphenyl or
tricyclohexylphosphine together with RuC13 N20 to promote the
Co(Ac)2 4H20 - catalyzed hydrocarbonylation of methylal using 3000 psig
LS317 _3_
l~Si~t9U
of syngas, and temperatures of between 150 snd 175C to obtain results
nearly comparable to those of the Japanese.
More recently, Knifton has found that cobalt carbonyl promoted with a
Group VIB donor ligand catalyzes the hydrocarbonylation of an aldehyde in
an alcohol to make ethylene glycol monoethers; U.S. 4,308,403. Yields of
ethylene glycol monobutyl ether (EGMB~) as high as 61% were reported in
this patent. A cyclopentadienyl-ligated cobalt catalyst is slso
effective for these reactions giving glycol ethers in up to 54~ yield;
U.S. 4,317,943-
Propylene glycol monoalkyl ethers are formed by contacting high pressuremixtures of carbon monoxide and hydrogen with either an acetal or an
aldehyde and an alcohol using a cobalt catalyst promoted with a tin- or
germanium-containing compound; U.S. 4,356,3~7. Yields of glycol ethers
up to 31% were reported in this patent. Ethylene glycol ethers were also
formed from a formaldehyde acetal or formaldehyde and an alcohol using
tin or germanium promoters for cobalt carbonyl; U.S. 4,357,477. The
highest glycol ether yield (EGMBE) was 53% in this case.
Finally, propylene glycol monoalkyl ethers were formed by
hydrocarbonylation of acetaldehyde acetals or acetaldehyde and alcohols
using rhodium, ruthenium or nickel compounds to promote either cobalt
carbonyls or cobalt compounds having group V ligand systems attached.
Glycol ether yields up to 28% were realized when these promoters were
used; Knifton, U.S. 4,390,734 (1983).
LS317 ~4~
1~4~90
Thus, the use of various promoters for the cobalt-catalyzed
hydrocarbonylation of aldehydes or acetals has resulted in glycol ether
yields of from 10-61%, depending on the glycol ether produced. The
highest reported yield of EGMME is 44%, of EGMBE is 61% and PGi~EE is 28%.
SUMMARY 0~ THE INVE~TION
In accordance with the present invention, there is provided an improved
process for the reaction of certain dialkyl-, dicycloalkyl-, or
diaryl-formaldehyde acetals or their formaldehyde-alcohol precursors with
syngas in the presence of novel ruthenium carbonyl-promoted cobalt
carbonyl catalysts, to form the corresponding ethylene glycol monoethers.
This reaction, which may best be dcscribe(3 as the
dealkoxyhydroxymethylation of an acetal formed separately or in situ by
the known reaction of formaldehyde with an alcohol, may be depicted by
the following general reaction scheme.
ORl OR1
CH ~ + CO + 2H2 ~ C1~2 + R20H
oR2 \ CH20H
wherein Rl and R2, which may be the same or different, and which together
may be joined by one or more bridging atoms as described below to form a
cyclic compound, comprise any organic moieties which are inert to the
conditions of the reaction, and are selected from the group consisting
of:
LS317 _5_
so
a) a straight or branched chain alkyl group
having from I to about 20 carbon toms, such
as methyl, ethyl, propyl, isopropyl, n-bvtyl,
t-butyl, 2-ethylheYyl, dodecyl, and the like;
b) a substituted or un~ubstituted cycloalkyl
group having ~rom 5 to sbout 20 carbon ~toms,
6uch a~ cyclopentyl, cyclohexyl, cyclobeptyl,
3-methylcyclopentyl, 3-butylcyclohexyl,
cyclooctyl, adamantyl, decalyI,
3-phenylcycloheptyl and the li~e; and
c) a 6ubstituted or unsub6tituted aryl group
having fr~m 6 to about 20 carbon atoms ~uch as
benzyl, phenyl, naphthyl, fluoroanthryl,
tetralyl, tolyl, ethylphenyl, cumyl, anisyl,
chlorophenyl, and the like.
It will be under~tood that when Rl and R2 in the foregoing reaction
scheme are different, the resulting products will actually be mixtures of
the corresponding ethers and alcohols.
This invention i~ also described to the novel ruthenium-promoted cobalt
carbonyl catalysts per se, and to methods for preparing the same.
LS317 -6-
;~1
125~9~
This process, using the novel catalysts of this invention, provides an
improvement over the methods of the prior art in that the instant
catalysts do not require the added presence of the iodide, amines, or
phosphine promoters such as are disclosed in the prior art, and thus are
less costly and easier to prepare and recover. Moreover, these novel
catalysts permit the reaction to be carried out under more mild
conditions of time and temperature than those of the prior art, yet most
surprisingly provide rate and selectivities of de~ired product over
those obtained by the use of cobalt carbonyl alone.
DESCRIPTION OF THE_PREFERRED EMBODIMENTS
The novel homogenous catalysts of this invention which may be prepared in
varying ways, are ruthenium carbonyl-promoted dicobalt octacarbonyls,
more specifically, triruthenium dodecacarbonyl-dicobalt octacarbonyl
mixtures. This catalyst system is readily prepared by simply mixing
dicobalt octacarbonyl (Co2(CO)8) with ruthenium dodecacarbonyl
~Ru3(CO)12) in the reaction medium. The molar ratios of these two
components are optimally in the range of about 10:1 to 1:10, and s9
preferably about 5:1 to 1:5.
It has also been found, in accordance with this invention, that when the
catalyst mixture is allowed to precipitate from the reaction medium
following completion of the hydroxymethylation reaction this material
unexpectedly ha6 been found to have superior catalytic activity over the
initial ruthenium-cobalt carbonyl mixture in terms of rates and
selectivities. This activity has been found to vary somewhat, however,
~5317 -7-
~4~90
depending upon the rate at which the precipitate forms, along with other
factors such as the initial concentrations, ratios, and the like. Thus,
for example, when the ruthenium and cobalt carbonyl catalysts are mixed
into the reaction medium in ~olar ratios of 1:1, and the mixture allowed
to precipitate out of solution, following dealkoxyhydroxymethylation, for
a period of 1-25 days, the re~ultin~ solid, when introduced into a
methylal-syngas reaction, has equal ~r increased activity with respect to
rates and selectivities for ethylene glycol monoether.
Equally surprising, it has also been found that an even more active
catalyst than the precipitate described above may be obtained by heating
the ruthenium and cobalt mixture for periods of from about 1 to 5 hours
in the presence of an inert organic solvent, preferably a chlorinated
aromatic such as chlorobenzene, o-dichlorobenzene, or the like, under
pressurized syngas. The mixture, on cooling, results in an
orange-colored precipitate, which when used as a catalyst in the
dealkoxylhydroxyme~hylation of methylal, results in significant
improvements in the rates and selectivities for the ethylene glycol ether
over the original catalyst mixture. For example, when ruthenium and
cobalt carbonyl are mixed in molar ratios of 1:1, heated in chlorobenzene
at about 150 C. underrv 3000 psi of syngas for about 3 hours, and then
cooled, the resulting precipitate has increased catalytic activity in a
methylal dealkoxyhydroxymethylation reaction.
The formaldehyde acetsl dealkoxyhydroxymethylation reaction with syngas,
as described above, utilizing the novel ruthenium-cobalt carbonyl
catalyst mixtures of this invention, including the aforedescribed
LS317 -8-
l~S4190
precipitated forms thereof, msy conveniently be conducted in a generally
known manner whereby the desired ~cetal is reacted with syngas under
elevated temperature and pressures for given periods of time, during
which period the reaction mixture is efficiently stirred. In this
reaction, the volume ratio of carbon monoxide to hydrogen in the syngas
desirably is in the range of from about 1:3 to 3:1, and more preferably
1:2 to 2:1. Following rapid cooling, the reaction product i8 then
recovered from the mixture in a routine manner.
In contrast to the prior art reaction conditions described above, the
novel ruthenium-cobalt carbonyl catalysts of this invention
advantageously permit the use of more mild operating conditions. Thus,
temperatures in the range of from about 100 to 200C, and preferably
about 125 to 175C, pressures of from about 500 to 5000 psi, and
preferably about 1000 to 3000 psi, may satisfactorily be employed.
The ratio of the weight of catalyst mixture employed, to the weight of
acetal, is desirably in the range of from about .001:0.1, and preferably
.005:.05 in a batch reaction.
In a further embodiment of this invention, it has been found that highly
advantageous effects may also be obtained in this
dealkoxyhydroxymethylation process by the addition of solvents in
combination with the catalyst system of this invention.
The solvents which may be advantageously used comprise any polar or
non-polar organic solvents which are inert to the conditions of the
LS31~ _9_
l~S4'1~0
reaction. Included amongst these solvents are Cl 12 alcohols, preferably
those corresponding to the alkyl group of the formaldehyde acetal, such
8s methanol, ethanol, butanol, 3-ethyl~2-hexanol and the li~e; ethers
which will not cleave under the conditions of the reaction, such as
glyme, diglyme, diphenyl ether and the like; aromatics and substituted
aromatics ~uch a6 benzene, toluene, xylene, chlorobenzene,
dichlorobenzene, anisole, and the like.
The solvents may constitute anywhere from 0 to 9~ volume percent of the
reaction mixture, and preferably 20 to 80 percent.
The acetal starting materials employed in this invention have the
aforedescribed general formula, namely
~ORl
C~
~ oR2
wherein the R and R2 groups are as defined above. These acetals can be
prepared in a known manner, separately or in situ, as for example as
described in E.V. Dehmlav and J. Schmidt, Tetrahedron Letters, p.95-6
(1976) B.S. Bal and H.W. Pinnick, J. _r~K~ Chem. V44 (21), p. 3727-8(1979)
D.W. Hall, U.S. Patent 3,492,356, Jan. 27 (197~), by the reaction of
formaldehyde with an alcohol, or mixture of alcohols, of the general
formula RlOH or R20H, where again R1 and R2 are as defined above, form
the correspondin~ acetal. Hereinafter, when the acetal is referred to,
it will be understood that the corresponding precursors, formaldehyde and
the desired alcohol, are also intended to be included.
LS317 -10-
1~S'~3S?
As also mentioned above, the organic substituents of the resulting acetal
may be joined by one or more bridBin8 atoms to form such cyclic compounds
as
0--fH2C ~ ~CH C ~ CH2--CH2
O - CH~ O - CH ~ ~ - CH2 - CH2
O - CH ~ O - CX2~
2 ~--CX2~'
and the like, wherein X is selected from the group consisting of alkyl,
aralkyl, aryl and cycloalkyl groups having from 1 to about 20 carbon
atoms.
It is essential t in selecting the acetal starting material, that it not
contain any substituents which are reactive under the conditions of the
dealkoxyhydroxymethylation process of this invention. In other words,
the R1 and R2 groups should not, for example, contain or comprise such
reactive moie~ies as phosphine, arsine, amino, sulfido or carbonyl
groups, acetal moieties, or olefins or acetylenic double bonds. Other
like groups will be recognized or readily determined by those skilled in
the art as resulting in products other than the desired monoethers.
When these acetals are dealkoxyhydroxymethylated with ~yngas in
accordance with the process of this invention, there is obtained the
corresponding ethylene glycol monoether in which the ether moiety will
correspond to the organic moieties of the acetal starting material. Also
formed in lesser amounts is the trialkoxyethane of the general formula
LS317 -Il-
12S4~9~
~O
RlOCH2CH
\ORl,
together with the alcohol R20H, which may be recycled to form additional
acetal starting material. Again, as above, if the R groups of the acetal
are different, a mixture of corresponding R-substituted compounds will
result.
As shown below, the selectivitie6 for ehe desired monoether over the
trialkoxy by-product are in the ratio of from about 3:1 to as much as
10:1 or more.
In a preferred embodiment of this invention, the starting materials are
preferably symmetrical acetals where the R groups are lower alkyl groups
of 1 to 4 carbon àtoms, thereby forming the corresponding ethylene glycol
mono-lower alkyl ether~ such as the monomethyl ether, the monoethyl
ether, and the like.
Alternatively, the acetal may contain such Rl and R2 groups as naphthyl
and phenyl. In the case of naphthyl, the reaction of the resulting
formaldehyde acetal with syngas will provide 2-(2-naphthyloxy) ethanol, d
known ~edative, which in turn may be oxidized ~o the corresponding
2-naphthyloxyacetic acid, a plant growth hormone.
LS317 -12-
.lZ~4~90
Likewise, the dealkoxyhydroxymethylation of the acetal, wherein Rl and
R are phenyl, will produce 2-phenoxy-ethanol, a topical antiseptic,
which when oxidized, results in phenoxyacetic acid, a fungicide.
Similarly, the formaldehyde acetal wherein R1 and R are 2, 4,
5-trichlorophenyl wiil yield, in accordance with this process, 2, 4,
5-trichlorophenoxyacetic acid, an herbicide. In a like manner, when
R and R2 are p-nonylphenyl, p-nonylphenoxyacetic acid, a corrosion
inhibitor and antifoaming sgent in gasoline and cutting oils will be formed.
Each of these aforedescribed products may be recovered routinely by
methods well known in the art.
The invention will now be illustrated by, but is not intended to be
limited to, the following examples.
EXAMPLES
Examples 1-21
A series of runs was carried out in which the following general procedure
was employed, using as the catalyst a mixture of Co2(CO)8 and Ru3(CO)12,
or Co2(C0~8 alone (for comparative purposes). In the table below, it
should be noted that wheress addition of Ru3(CO)12 caused an increase in
production of the glycolether, B, over that obtained with C02(CO)8 alone,
other metal carbonyls had no such effect.
LS317 -13-
12S~90
To a 300 ml stainless steel autoclave equipped with a magnedrive stirrer
was charged: methylal, solvent (if any), and catalyst. Carbon monoxide,
S00 psig, and hydrogen, 1600 psig, were admitted and the reaction mixture
was rapidly heated to the desired temperature. The mixture was stirred
for the designated time at reaction temperature after which the reactor
was cooled by immersion in an ice bath. When the contents reached 25C
the final pressure was recorded. After venting the gas the liquid was
analyzed by GLPC.
The results are reported in Table I below. Reaction conditions, amounts,
and the use of solvents were varied in accordance with the data set forth
in this table.
`` LS317 -14-
i2S4t9V
~ o o
~ <1 ~ ,,
~e
Z ~ ~ ~ ~
~ O CO L~l 1~ U'l _ ~ I` O O O 0~ O ~CI N r~
o o ~ ~ ~ ~ ~ ~ r_ co ~ X ~ ~ ~ ~ ~ 1~ ~
3~
:~:
~ o~ o o o o o o o c~ o o o o o o o o o o o o o o
~ t ~ ~
o X
~ ~ ~ ~ ~1
c~ =<~ ol 0~ 0~ 0 0 0 O O O O O O O O o U~ o
~ o
~; X
g g g g ~ g g g g g ~ ~ g g g ~ ~ ~ o ~3 ~
~ ~ U~ Z Z Z Z Z Z Z ~ Z Z Z Z Z Z ~ Z ~ ~ ~ ~ Z
20 !~_ ~ o c~l
+ ~ O ô~ O O ô~ O ~, , , , ,
C~ ~~ ~ ~ ~ U
~ X 0'' O ~
~ :c ô~'l
t~ O ~ o ~ o ~ ~I o ~1 o o o o o o o o ~`J o o ~ ~
~ ~ ~ a
:I E
O o
, co~
o .a 1~ _
Il 1
X ~ ~ ~ ~ U ~ ~o 1~ oo o~ o _ C~l ~ ~ ~ ~o r~ ~ ~ o ~- _
i~S'~l~O
Examples 22-25
In addition to the above runs, another series of runs was carried out in
accordsnce with the following general procedure, using varying condi-
tions 9 etc., in which the catalyst employed was precipitated from solu-
tions of Co-Ru catalyzed methylal dealkoxyhydroxymethylation, with or
without a solvent being present.
The catalyst system and methylal were charged to a 300 ml autoclave and
the system flushed thoroughly with C0 and H2. A 1:1 CO~H2 mixture was
added to a pressure of 2400 psig and the temperature rapidly raised to
150~C. The reaction mixture was stirred for the designated time period
and then rapidly cooled, the pressure released, gases collected and
analyzed by gcms and the liquid removed and analyzed by standardized
glpc .
The results of these runs are reported in Table II below.
LS317 16
1~54t90
I` `D ~
~ o ~~o ~ .~
~ ,U ,,,
~,
o o oo ,~ ~ ~ U o o~
C
o .
~,
a ~
~O-- ~ A d ;~
~ ~ ,~ Oo ~
o ~~ 00 ~ ~ ~ a
~3 ~ ~ 2 o~
i ;
~ . ,~
E-- cn l o o o o ~ o
O
~ ~ ~1 o ox~ a
~:1 ~"~ v " 30 ~C o
H 0 ~3 ~IJ EiC ~
V~ C~10 .1~ .
~ c ~ ~ ~ c~ ~ a
~-:1 O 1~ _~ N O N ~ --
;~ t~ ~ ~ ~ ~~ o ~ ~J
~ ~ ~ ~~ ~ S~
H ~ ~ ~ ~ 0
H ~ ~ U ~ U p4 ~ Ua~ a
~,~ ~ ~~ ~ o c~ o
o 0 ~ ~~ J 4~ .o o
o ~ o ~ c~ u
~ ~ ~. ^ o
~ V ; O C~ O 111 OD
~; ~ O
~ ~ ~~ ~ ~ ~ S od ~ od C ) ~ Iq
,~ ,~ ~ ',. C~ 0~ ,~
0~ ~o 0~ ~0
)3 E u o
~i , + ~ o ~a o~
!~ ~4 . o ~o ~ ~ ~ a~ ~ O a
~ ~ ¦ ~ ~ o ~ ~ ~ X
X n~ ~ O
~ O , U ~~ O ~ '~ ~
H ~ ~ P~ Vd ~ J d
f~ ~ ~ ~ u ~ u tn ~ ~ :~
5~ , O ~ P
I_1~ _~ 4~ ~ ~ ~ h ~ t~l 11)
~ 8 0 o x ~ 0 ~ 0
-- E~ o 0 ~ p ,~ p ~1 p u~ ~J 0
~ I ~I ~ O .C ~ ~ p
~3 0 al ~ ~a ~ o ~ ~
o ~ o ~ p~ u
O ~ ~ 0 a~ 0 ~ ~ o c~
c, 0 .- Il r, 0 ~1 ~ ~o u~ .
_~ ~ ~ p O ~ ~ d ~ g 11
o--~ ~ I I I
c.
U ~ -~ 3
~3 ~ ~ o
~` x 3 ~ ~ ~ ~E-I
C ~ ~ ~ U~
~ i C~
l~S~90
The catalysts for Examples 23, 24 and 25 of Table II were prepared as
follows:
Example 23 Catalyst
The catalyst for Example 23 was prepared by allowing the liguid recovered
from two runs identical to Example 18, Table l to stand for several
weeks, after which an or~nge solid precipitated. Filtration of the
orange solid followed by drying in vacuo ~ave a material which exhibited
characteristic metal carbonyl bands in the infrared but was neither
Co2(C0)8 nor Ru3(C0)12. The ir bands in the isolated solid were at 4.83,
4.92 and 4.98u. The brid8ing carbonyl of the startinB Co2(C0)8 (5.37u)
had totally disappeared in forming the new active complex. The solid,
2.5 grams, was used as a catalyst for Example 23.
Example 24 Catalyst
The catalyst for Example 24 was prepared by all.owing the liquid recovered
from two runs identical to Example 4, Table I to stand for several weeks
after which an orange solid precipitated. This solid, 2.0 grams, after
filtration and drying in vacuo, was used as the catalyst for Example 24.
The solid which was isolated had characteristic metal carbonyl bands at
4.83, 4.92 and 4.98u. The bridging carbonyl of the starting Co2(C0)8 had
completely disappeared.
LS317 18
lZ~t9~
Example 25 Catalyst
The catalyst for Example 25 was prepared as indicated in footnote (c) of
Table Il. The isolated orange solid had infrared bands at 4.83u, 4.92u
an 4.97u indicative of a metal carbonyl complex in which there was no
bridging carbonyl band at 5.37u.
In the following examples, Examples 26-32, experiments were csrried out
in a manner similar to Examples 1-25, except that dibutoxymethane was
substituted for methylal, and solvents and temperatures were varied as
shown in Tables III and IV, to produce ethylene glycol monobutyl ether.
LS317 19
12S~
Examples 26-29
In Examples 26-2~ formaldehyde dibutylacetal, (CH2(0Bu)2), was
dealkoxylhydroxymethylated to ethylene glycol monobutyl ether, EGMBE,
using a 1:1 mixture of Co2~C0)8 and Ru3(C0)12 as the catalyst~ It can be
seen from the tsbulated results of Table III that running the reaction in
a solvent such as n-butyl alcohol or o-dichlorobenzene gives generally
superior yields to running the reaction in neat CH2(0Bu)2.
In Table III, the examples were conducted in accordance with the
following general procedure:
Dicobalt octacarbonyl, 4 mmoles, triruthenium dodecacarbonyl, 4 mmoles,
CH2(0Bu)2 in the amount listed in the table and solvent in the amount
listed in the table were charged to a 300 ml stirred autoclave to which
3200 psi of a 1:1 mixture of C0 and H2 were added and then heated to
150C for 3-4 hrs. The autoclave was cooled, drained and the product
weighed and subjected to standardized gas chromatographic analysis.
~S317 20
~ ~ - ~
m ~ o ~ c~
o ~ ~ C~l
o
C~
P ~ ~ ~ C~l
C~
^
o :~
m u
j ~ o ~ ~ o~ o~
C ~ o~
O 1: A A A
C
D C ~ p
r~ ~ ~ C~
~ a~2 ~
C~ q I~ _ ~') O
Z ~ ~
E~'~: IJ
. ~_ ~ ~ O ~
o
~ ~C P C~
Hp~: C t~l 00 1- 00 0
~ ~ ~
~ ~ ~ O
C.~ ~
~u
_l C~ O
U~ ~ :~ :~
. m
h~
5 1~ t~
O ~ _1 ~ ~ O ~ --
V~ P~ Cr~
E~ ~ ~
O o U~
L~l ~ ~ C ~ d
c o C a~
~1 ~ A o a,
m~ o ~ o o
o ~ X O ~ ~ ~ ~ U P~
_ ~ o~ ~ ~ ~ ~ P. ~ o
:c~ e ~ o ~ ~ A
C ~ U
:~: o ~ ~O ~ C C
~ ~ 'p, O 1`
~ A ~ N
~ ~ ~ U
C ~ ~ ~ O
P ~ 0~ 0~ ~ ~ I O D.
c m m ~ x m ~ ,,
O O ~ I I C~ i 3 C ~
v~ z c a o ~ ~ m~ _ ~, o
`D 1` 0~ O~ _~
X C~ l C`l ~ .o U ~ ~ ~
lZ5~19V
Examples 30-32
In Examples 30-32, the results of which are ~u~marized in Table IV, it
can be seen that as the reaction temperature is raised from 125 to 175C
the EGMBE yield increases from 12 to 34.
In Table IV, the examples were conducted in accordance with the following
general procedure:
Dicobalt octacarbonyl, 4 mmoles, triruthenium dodecacarbonyl, 4 mmoles,
and CH2(0Bu)2, 90 ml, were charged to a 300 ml autoclave. Then 3200 p6i
of a 1:1 C0/H2 mixture was added and the reaction mixture heated for 3~4
hours at the temperature listed in the Table. The autoclave was cooled,
drained and the product weighed and subjected to standardized gas
chromatographic analysis.
LS317 22
~ ~ 12S~'30
C~ o
X o ,.
x
o
U ,~ ~ ~
.- ~ ~ ,_ ~ .n
,. ~ o ,,
P ~ X
V~ ~
o ~
.,
P ~ o~
a o o
~7
a
~r1 p O r_
Z .-
E~ ~ r~ ~ ~ `D O
i~ h ~ O ~ C~ X
X ~ ~ 00 0~
O ~ r~
~I ~
~i ~Y; ~ ~ O
<1 ~ U~ O O ~
Z P ::q ~
~ ~ O r-~ ~ O a~
~ . ~ o ~
~ ~, ~ ~ ~ ~ fi
~C~ ~ aJ ~
X ~ , o , ~ ~
~ ~ , C~ oo ,,
~, . , ,. ~
~ 5~ ~ cl4
o ~
U~ ~ ~ P
~ ~ c~ o ,1 a a a
~ X ~ ~ ~o ~ ~
o
~_
o ~ ~ o o o ~P` ~ ~
:c o~ oc p a
:~: ~ a~
~ U~o ~ ~ P~
c~
E~ .~ ~ -
_~ ~ ~d I O
O
~_, ~ ~ m
~ o ~ ~ ~ ~ ~ ~ ~
o~
-
X o
P
izs~ o
Example 33
In a manner similar to Example 31, except that formaldehyde dicyrlohexyl
acetal is used instead of formaldehyde dibutyl acetal, ethylene glycol
monocyclohexyl ether is prepared in good yield.
Example 34
In a manner similar to Example 31, except that formaldehyde diphenyl
acetal is used instead of formaldehyde dibutyl acetal, ethylene glycol
monophenyl ether is formed as a reaction product.
Example 35
In a manner similar to Example 31, except that dioxolane is used instead
of formaldehyde dibutyl acetal, diethylene glycol is produced afi a
reaction product.
Example 36-43
Approximately 6 grams of paraformaldehyde and the catalyst package in 90
moles of butanol and 10 ml of toluene were heated at the temperatures
given in Table V at the pressures of hydrogen and CO indicated for two
hours. After this time the reaction mixtures were analyzed by gas
chromatography showing the major product to be ethylene glycol monobutyl
ether. Results are tabulated in Table V.
LS317 24
12.~ 90
TABLE V
REACTIONS OF FORMALDEHYDE, SYNGAS AND BVTANOL
TO GIVE ETHYLENEGLYCOL MONOBUTYL ETHER, EGMBE
EXAMPLE CATALYST COMPONENTS INITIAL PRESSURES REACTION REACTlON PRODUCTS (GC Area ~)
Co2(CO)g RU3(C)12 H CO T. ~CCH30C5Hg ECNBE C~2~DC4H9~2
36 4 4 1600 800 150 2.0 9.4 tr
37 4 4 1600 800 150 2.0 9.7 0.3
38 2 4 1600 800 150 1.7 9.6 0.5
39 2 4 1600 800 150 1.4 9.1 1.5
4 4 1600 1600 150 1.2 10.7 0.5
41 4 4 1600 1600 150 0.7 9.2 1.8
42 2 4 1600 1600 150 0.7 9.2 1.8
43 4 4 1600 800 175 2.3 9.6
a) EGMB = Ethylene glycol ~onobutyl ether
LS317 25
