Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
5~ Z Z8
(5137)
BACKGROUND OF THE INVENTION
.
The present invention relates to a novel process
for producing oxygenated organlc compounds.
There are several known methods for producing
oxygenated organic compounds. The acid catalyzed (H2S04,
HBF4, etc.) synthesis Or carboxylic acids or esters by the
reactlon Or an olefinic substrate with CO and water or
alcohol has been known since 1931. (J. Falbe, "Carbon
Monoxide in Organic S~nthesis", S~rlnger-Verlag, New York
(1970)). Althougn this process was used on a commercial
scale it does have serious llmitations due to the reaction
conditions and the lsomeric composition o~ the products.
A more commercially important synthesis of car-
boxylic acid/esters is the direct carbonylation of olefinic
substrates with CO and water/alcohol conducted in the pres-
ence Or transition metals. In general, this carbonylation
reaction, discovered by Repp in 194~ (I. Wender and P. Pino,
"Organic Synthesis Via ~etal Carbonyls", ~Tolume 2, John
Wiley, New York (1977)), involves the addition of carbon
monoxide, carboxyl alkyl or amide group (Y-H where Y equals
-OR or -NHR and R is an alkyl), and an olerln.
~owever, when an unsymmetrical olerln is used as
the substrate at least two lsomeric products are obtained.
No general method has been developed ror the control of the
lsomeric product composition.
The present lnvention overcomes some Or these
problems present ln the prior art. For example, the inven-
tive process results ln h~gher conversions, higher yields
and faster reaction rates than those disclosed in the prior
art. Furthermore, the instant process allows one to obtain
a high yield Or a partlcular isomeric product composition.
~LS~228
~5137)
Thus, extremely high selectivities of particular oxygenated
organic compounds can be obtained by the inventive process.
Finally, the prior art carbonylation reactions
operate under extreme conditions of temperature and pres-
sure. In general, temperatures ln the range of 160C to
300C and pressures ln the range Or 1,500 to 5,000 psi are
requlred. On the other hand, the present reaction may be
carried out under relatively mild conditions Or temperature
and pressure. This ~urther advantage can result in substan-
tial cost savings in the production of oxygenated organlc
compounds.
SUr~ARY O~ THE INvErlTIoN
. _
-~ It has now been discovered that oxygenated organiccompounds can be Produced by contacting an olefinically
; 15 unsaturated compound wlth carbon monoxide and a compound
containin~ a replaceable hydrogen atom in the presence Or a
catalyst comprising cobalt and~or ruthenlum carbonyl and a
promoter ligand selected from the grou~ consistlng of
heterocyclic nitrogen compounds and phosphorus or sulfur
oxides.
In particular, the inventive process results in
high yields Or oxygenated organic compounds when operatlng
at ~uch lower temperatures and pressures than disclosed in
the prlor art. In addition, the product distribution can be
varied signlficantly by chan~ing the CO/H2 ratio, pressure,
ligand, solvent, reaction time and other process variables.
Thus, the present lnvention provides a novel cata-
lyst compr~sing a promoter ligand and at least one Or cobalt
and ruthenium carbonyl. ~urthermore, the instant lnventlon
3~ pro~ides a novel process for the production Or an oxy~enated
- ~L5~;)2~8
(5137)
organic compound compr~sing contacting an olefinically un-
saturated compound with carbon monoxide and a compound
containing a replaceable hydrogen atom in the presence of
the above catalyst. Flnally, the present lnventlon provides
? novel process rOr the productlon of an oxygenated organic
co~pound comprising contactlng an ole~inically unsaturated
compound containlng an alcohol moiety with carbon monoxide
in the presence of the above catalyst.
Specifically, the carbonylation reaction of
acrylonitrile, carbon monoxlde, hydrogen gas, and methanol
to yield methyl-~-cyanopropionate proceeds smoothly using a
catalyst comprislng cobalt carbonyl and a heterocycllc
nitroger. oxide promoter ligand.
; ! DETAILED DESCRIP.ION
According to the present invention, improved
yields and selectivities of oxygenated or~anic compounds are
obtained by contacting an olefinically unsaturated compound
with carbon monoxide and a compound containing a replaceable
hydrogen atom over a catalyst comprising cobalt and/or
ruthenium carbonyl and a promoter ligand selected from the
~roup consisting of heterocyclic nitrogen compounds and
phosphorus or sulfur oxides. The overall reaction taking
place in this process is represented by the following equation:
~R2 1l
- ~5 RlCH = CHR2 + HY + CO > RlCH2CH - C Y
1 ~
~C~H 2
Rl, R2 and Y are defined below.
~5~2:28
(5137)
Reactants
Olefinlcally unsaturated compounds which can be
employed as reactants ln the inventive process have the
rollowing structure:
RllCH = CHR12
wherein Rll and R12 are each lndependently selected
from:
(1) hydrogen teither Rll or R12 but not both);
(2) Cl_30 alkyl;
(3) -(CH2)p-CN, wherein p is 0-3; and
( 2)z OR13, wherein z is 1-30 and R13 ls
hydrogen or methyl.
Preferably, the olefinically unsaturated compounds
comprise compounds whereln Rll and R12 are each indepen-
dently selected rrom:
(1) hydrogen (either Rll or R12 but not both);
(2) Cl_l0 alkyl;
(3) -(CH2)p-CN, wherein p is 0-2; and
(4) -(CH2)~-OH, wherein q is 1-10.
Most preferably, the olefinically unsaturated
compounds comprise compounds wherein Rl and R2 are each
independently selected from hydrogen (either Rl or R2 but
not both), methyl and -(CH2)p CN, wherein p ls 0-1.
Lhe second component in the inventive reaction
system is a ccmpound containing a replaceable hydrogen atom.
This compound can be represented by the followlng formula:
H - Y
wherein Y ls selected from the group consisting
of:
3o (1) OR14 wherein R14 ls a Cl_30 alkyli
~15~ 28
(5137)
(2) N~ R15 wherein R15 and R16 are each lndepen-
dent~y selected from Cl 10 alkyls; and
(3) H.
Preferably Y ls selected from the group consisting
Or:
(1) OR14 wherein R14 is a Cl_10 alkyl;
(2) N~ 15 wherein R15 and R16 are each lndepen-
dent~y selected from Cl 4 alkyls; and
(3) H.
More preferably Y ls selected rrom the group consistlng of:
(1) OR14 whereln R14 is a Cl 4 alkyl; and
(2) H.
The second component ls most preferably elther methanol or
hydrogen.
.15 In the embodiment Or the lnventlon in which H-Y ls
an alcohol or amlne~ lt ls preferred to add hydrogen gas to
the reactlon system. Preferably the amount Or hydrogen gas
so added comprises less than 1070 by volume of the total
amount Or the hydrogen gas and carbon monoxlde gas in the
reaction system. More preferably the hydrogen ~as comprlses
0.5% to 7.5% by volume Or the hydrogen and carbon monoxide
gas. he addition of hydro~en gas can increase both the
yleld and selectivity to desired products in this mode Or
the invention.
When H2 ls the compound containing a replaceable
hydro~en atom then the reaction system will preferably con-
tain ~070 to 60~o by volume hydrogen gas based on the total
volume Or the carbon monoxlde and hydrogen gas. r'Ore pre-
ferably the reactlon system will contain about 50Z hydrogen
gas.
One way to supply carbon monoxide and hydro~en gas
lnto the reaction system ls in the form Or synthesis gas.
(5137~
The amount of hydrogen in the synthesis gas can be easlly
ad~usted prior to lnsertlon lnto the reactor.
The amount of carbon monoxlde ln the reactlon
system is not crltical. Preferably the carbon monoxlde is
present in at least stolchlometric amcunts and most pref-
erably the carbon monoxlde is present ln amounts greatly in
excess o~ stolchiometric amounts. If desired, a carrler gas
which ls lnert to the reactants, products and catalyst can
be lncluded ln the reactlon system.
The molar ratio of the compound contalnlng a re-
placeable hydrogen atom to the oleflnlcally unsaturated com-
pound can be 0.5-100:1 with a ratio of 1-10:1 being pre-
ferred. This ratlo does not lnclude the hydro~en gas which
may be added to the reaction system when H-Y ls an alcohol
or amlne.
In the embodlment .of the lnventlon in which the
olefin reactant ls an alcohol ~l.e. wherein Rl or R2 ls
~(CH2)q~0H)~ lt has been found that the terminal hydro&en
atom on the alcohol group will itself serve as a replaceable
hydrogen atom. As a result, the alcohol moeity of the
olefln will react wlth the olefinic double bond of the
olefln thereby producing a lactone. In thls reaction system
no H-Y component need be included slnce the olefln itself
acts both as the olefin and the H-Y component. The reaction
in this particular system is shown by the following equation:
RlCH = CHR2 + C0 Cat.~ Lactone
wherein at least one of Rl and R2 is an alcohol.
Process Conditions
Clenerally, in carrying out the inventive process,
the oleflnically unsaturated compound, carbon monoxide, and
the compound containing a replaceable hydrogen atom are
~1~;;92Z8
t513
contacted wlth one another in the liouid ph~e in the pres-
ence of the catalyst described below. The lmentive reaction
can be accompllshed in the batch mode or continuously.
The reaction temperature is normal~ maintalned
between 50C to 150C. and most preferably at about 100C.
The reaction pressure ls normally maintained at 100 to 2500
psl, preferably at 700 to 1000 psi. When th~ reactlon ls
carried out in a batch mode, the reactants a~ catalysts are
contacted with one another rOr a period of ten minutes
through six hours, and preferably one half h~ur to four
hours. A reaction time of less than ten minutes or more
than six hours can be used if desired although better re-
sults will be obtained lf the reaction time ls maintained
within thls range. When the process is carried out on a
continuous basis, the reaction catalyst contact tlme is
normally 10 seconds.to 10 minutes, preferably 100 seconds to
5 minutes.
Both the rate of reaction and product distribution
can be varled significantly by changing the process para-
meters. ~or example, normally an increase ln pressure in-
creases the rate of reactlon. However, at very hlgh pres-
sures the reaction rate may decrease due to catalyst decom-
posltlon. ~urthermore, the selectivity to a particular
product may be affected by pressure chan~es, e.g. ln the
carbonylation of acrylonitrile there is an increase in the
selectivity to the n-cyanoester (3CF) as the pressure de-
; creases.
A balance exists between temperature and pressure
with respect to catalyst decomposition. C.enerally, as the
temperature increases the rate of reaction increases. How-
ever, an anomolous effect may occur due to partial catal~st
115~228
(5137)
decomposition. mhus, the temperature and pressure must be
carerully adJusted.
Similarly, residence time has a large effect on
homogeneous processes. For example, in the process for the
carbonylation Or acr~lonltrile, the selectlvlty to methyl-~-
cyanopropionate is much higher at short reaction tlmes.
Applicants surmise that the reduction ln selectlvity as a
function of reaction tlme is caused by the reductlon Or the
ligand, e.g. 4-plcoline-N-oxide ls reduced to 4-picoline.
In view Or the above discussion, it ls clear that a par-
ticular reaction rate and product distribution can be
; obtained by a careful ad~ustment Or the process variables.
~atalysts
The catalyst employed in the inventlve process can
be generally described as one of two types. Both types com-
prise cobalt and/or ruthenium carbonyl and a promoter
ligand in an or~anic solvent. The promoter li~and is
either a heterocyclic nitrogen compound or a phosphorus or
sulfur oxide.
The nitrogen heterocyclic promoter ligand has the
following structure:
/x~
R5 - C f _ Rl
R4 - C ~ C - R
2~ C
R3
wherein X is one of N and I~O; and
Rl, R2, R3, R4, and R5 are each indepen-
dently selected from the group consisting of:
(1) H;
(2) Cl_10 alkyls;
llS~ZZ8
(5137)
(3) (CH2)qOH wherein q is 0-10;
(4) (CH2)s-C~ OH wherein s is 0-10; and
(5) O(CH2)tCH3 wherein t is 0-10J
wherein Rl and R2 may comprise a flve to elght membered carbo-
cyclic fused ring optionally substituted with C1 10 alkyls.
Prererably, X is ~O, and Rl, R2, R3, R4, and R5
are selected from H, Cl 4 alXyls, CH2OH, OH, C~ OH, and
OCH3. Most preferably~ Rl, R2, R3, k4, and R~ are selected
from H, CH3, and OCH3.
The phosphorus or sulfur oxlde promoter ligands
have the rO 1 1 owl n~ formulae:
~ ~ R10~ ,~
_ R7 - I = o and ~ S( ~
R6 R9 )n
in R6, R7~ R8, Ra~ and Rlo are each indepen_
dently selected from:
(1) Cl_10 alkyls;
(2) polynuclear aryls contalning u~ to 12 carbon
atoms, optionally substituted with Cl 10
alkyls; and
(3) O(CH2)tCH3, wherein t is 0-10; and
wherein n is 0 or 1.
Preferably, R6, R7, R8, R9, and Rlo
independently selected rrom Cl 4 alkyls and most preferably
R6' R7~ R8, R9, and Rlo are C~3.
! The lnventive catalyst can be prepared by mixing
the cobalt and/or ruthenium carbonyl wlth at least one pro-
moter li~and in a solvent. The cobalt and/or ruthenium
carbonyl and the promoter ligand may be added simultaneously
or separately to the solvent. The exact relationship in the
solvent between the cobalt and/or ruthenium carbonyl and the
promoter ligand is not known.
10 .
5~228
(5137)
Any solvent ln which the catalyst is soluble may
be used ln the present inventlon. Preferably, the solvent
is an alcohol, aromatlc, ester, nitrile and/or dinitrile.
The olvent is most pre~erably an alcohol or ester. In
fact, the alcohol can be both a compound containlng a re-
placeable hydrogen atom descrlbed above and the solvent. ~he
preferred catalyst concentration in the solvent ls normally
between 0. lZ to 5% by weight.
The cobalt and/or ruthenium carbonyl can be added
to the solvent in any form from whlch cobalt and/or ruthenlum
carbonyl could be formed. ~or exampleg lt is well known in
the art that carbonyls can be formed from naphthalates,
salts and nitrates and thus suitable naphthalates, salts
and nitrates can be added to the solvent to form a carbonyl
compound in situ. Preferably, the catalyst contains cobalt
carbonyl.
In general, the promoter ligand to cobalt and/or
ruthenium carbonyl molar ratlo is 0.1-50:1, preferably about
0.5-4, and most preferably about 2:1. ,his ratio will vary
depending on the promoter ligand chosen. At high ligand to
carbonyl ratlos (i.e. 4:1) the rate Or reaction substan-
tially decreases even though selectivlty to the deslred
product may be lncreased. Thus, in the carbonylation Or
acrylonitrile, at high ligand/carbonyl ratlos the reactlon
rate decreases but the selectivity to methyl~ -cyanopropionate
; increases.
The catalyst of this invention is dissolved in the
reaction medium as a homo~eneous catalyst. These homo-
geneous catalysts are prepared by known techniques. SDecific
preparations Or these catalysts are shown in the working
examples of this specification. Broadly, however, the
/
.,
11 .
~15~;~Z8
(5137)
catalysts Or this lnvention can be prepared by any of the
techniques known in the art.
Recovery
The reactlon product obtalned upon completion of
the reaction ls normally in the form of a liquid and composed
primarlly of unreacted reactants, catalyst and oxygenated
organic compounds. Thls reaction product can be sub~ected
to suitable known separation technlques, l.e. solvent ex-
tractlon and fractional dlstlllation, to yleld the desired
end products.
A partlcularly good method for separating the
catalyst from the products obtalned in the present process
- is by the use of con~u~ate phase extraction. In thls sepa-
ration scheme, the reaction effluent is treated with a C5 to
C8 hydrocarbon wh~ich is miscible with the reaction solvent
but which ls a very poor solvent for the catalyst. Examples
of such hydrocarbons are pentane, hexane and octane. Enough
of thls hydrocarbon is added to the reactor effluent to
separate almost all of the catalyst lnto one phase and a
significant amount of products into the other phase. ~.en-
_ erally, this is between l to 4 volumes of hydrocarbon per
volume of reactor effluent.
It ls desirable to exclude oxygen from this sepa-
ratlon system so that catalyst decomposition will not occur.
It is also desirable to minimlze the amounts of unreacted
substrates ln the reactor effluent prior to treatment with
the hydrocarbon. ~his can be accomplished by simple dlstil-
lation or vacuum stripping. Finally, it is desirable to
separate the products and reactants as qu~ckly as ~ossible
to reduce the possibility of unwanted side reactions, e.~.
methyl~B-cyanopropionate reacts with acrylonitrile to pro-
duce a dicyano ester.
12.
1~5~228
The catalyst containing hydrocarbon phase can be
diluted and recycled back to the reactor. The product phase
is then subjected to known separation techniques such as
distillation or extraction.
The oxygenated organic compounds produced by this
process are useful as precursors to polymers. The esters
are also useful in perfumes, flavorings and pharmaceuticals.
The aldehydes are useful as plasticizers and as intermediates
for alcohols.
Thus, in accordance with present teachings, there is
provided a catalyst composition comprising a phosphorus or
sulfur oxide promoter ligand and at least one of cobalt
carbonyl and ruthenium carbonyl wherein the promoter ligand
has one of the following structures:
Rl~ R ~ ~ O
R7 P=== O and / ~' ~
R6 Rg )n
wherein R6, R7, R8, Rg and Rlo are each independently
selected from:
(1) Cl_10 alkyls;
(2) polynuclear aryls containing up to 12 carbon
atoms, optionally substituted with Cl 10 alkyls;
and
(3) O(CH2)tCH3, wherein t is 0-10; and
wherein n is 0 or 1.
In accordance with a further embodiment of the
present teachings there is provided a process for the production
of an oxygenated organic compound which comprises contacting an
olefinically unsaturated compound with carbon monoxide and a
compound containing replaceable hydrogen atom in the presence
of a catalyst comprising at least one cobalt carbonyl and
B
~ . ~ . . . . - - `
~5~228
ruthenium carbonyl and a promoter ligand which has one of the
above structures previously outlined.
SPECIFIC EMBODIMENTS
; In order to more thoroughly illustrate the present
invention, the following working examples are presented. In
these examples, the following definitions are used:
moles carbon in reactant
% Conv = converted to product
moles carbon in reactant fed X 100
moles carbon of olefinically unsatu-
% Yield = rated compound converted to product
moles carbon of olefinically unsatu- X 100
rated compound fed
The results have all been adjusted to a 100% carbon balance.
In general, the experimental method consists of
placing a pre-washed solution of olefinically unsaturated
compound, promoter ligand, compound containing a replaceable
hydrogen atom and solvent into a glasslined autoclave.
Next, cobalt carbonyl, Co2(CO)8, is added and the autoclave
sealed.
The autoclave is flushed two times with synthesis
gas and then charged with the synthesis gas to the desired
pressure. The temperature is then increased and the reac-
~ tion proceeds for 1 to 4 hours. Occasionally, samples are
; withdrawn during the course of the reaction through the vent
-13a-
~B
l~ZZ8
(5137)
tube and sub~ected to gas chromatography analysls. After
the runs, the glasslined autoclave is brought to room temp-
erature by cooling with cold water, depressurized and opened
for product analysis.
The results of the experiments are shown ln Table
I. A glossery of terms follows Table I and specifies the
meanings Or the abbreviatlons used in Table I.
Example 1
13.5 gms. of acrylonltrile, o.88 gms. Or 4-picoline-
N-oxide, 9.78 gms. of methanol and 100 mls. of adiponitrile
`~ were placed in a glasslined autoclave. Next, 1.37 gms. of
Co2(C0)8 were added and the autoclave sealed.
_ The autoclave was charged with synthesis gas con-
taining 5Z H2 until a pressure Or 1,000 psi was reached.
The temperature was set at 97.5C and the reactlon proceeded
for 90 minutes. The autoclave was then brought to room
temperature by cooling with cold water, depressurized and
opened for product analysis. The product analysis is shown
in Table I.
Example 2
13.5 gms. of acrylonitrile, o.88 gms. Or 4-picollne-
.~-oxide and 100 mls. of methanol were placed in a glasslined
autoclave. Next, 1.37 gms. Or Co2(C0)8 were added and the
autoclave sealed.
The autoclave was charged with synthesis gas con-
taining 5% H2 to a pressure of 1,000 psi. The temperature
was set at 97.5C and the reaction proceeded for 150 minutes.
The autoclave was then brought to room temperature by
cooling with cold water, depressurized and opened ror pro-
duct analysis. The product analysis is shown in Table I.
14.
- ~ ~ S~ 2 Z~
(5137)
Examples 3 thru 80
The procedure outlined ln Example 1 was followed
with the molar ratio Or cobalt carbonyl/ligand, temperature,
pressure, solvent and reaction tlme being varied. These
varlables are specified ln Table I for each example. ~able
I also shows the product analysis for Examples 3 thru 80.
Example 81
13.5 gms. of acrylonitrlle, 0.75 gms. of pyridine-
N-oxlde and 100 mls. Or methanol were placed into a glass-
lined autoclave. Next, 1.37 ~ms. Or Co2(C0)8 were added and
the autoclave sealed.
The autoclave was charged wlth synthesis gas con-
taining 5~ H2 to a pressure of 800 psi. The temperature was
set at 95C and the reactlon proceeded for 60 minutes. The
~ 15 glasslined autoclave was then brought to room temperature by
- cooling with cold water, depressurized and opened for pro-
duct analysis. The product analysis is shown ln Table I.
Exa~ple 82
Thls example followed the same procedure outlined
in Example 81 except that the temperature and reaction time
were varied as set forth in Table I. The results are shown
in Table I.
Example 83
13.5 gms. Or acrylonitrile, o.88 gms. of 2-picoline-
N-oxlde and 100 mls. Or methanol were placed in a glasslined
autoclave. Next, 1.37 gms. of Co2(C0)8 were added and the
autoclave sealed.
The autoclave was charged with synthesis gas con-
tainlng 5% H2 to a pressure of 800 psi. The temperature was
3~ set at 95C and the reaction proceeded for 120 mlnutes. The
glasslined autoclave was then brought to room temperature by
15.
115~)228
(5137~
cooling with cold water, depressurized and opened for pro-
duct analysls. The product analysis ls shown in Table I.
Examples 84 thru 97
The procedure outlined ln Example 83 was rollowed
except that the molar ratio Or cobalt carbonyl/ligand,
solvent, llgand, temperature, pressure and reaction time
were varied. These variables are speciried in Table I for
each example. Table I also shows the product analysis for
Examples 84 thru 97.
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(5137)
COMPOUND NAME A~B~EYIATIONS
Abbreviation Compound Name
~, ADN adlponitrlle
BlPy-Nox blpyrldyl-dl-N-oxlde
2 CE mcthyl-~-cyanopropionate
3 CE methyl-~-cyanoproplonate
3 CPA 3-cyano-proplonaldehyde
3 C~AA 3-cyano-propionaldehyde
~: dlmethyl acetal
.
DIAPLO dlazablcyclo (2.2.2) octane
,` 10
DMP dlmethylphthalate
D~SO dlmethyl sul~oxlde
3-MPN 3-methoxy propionltrlle
4-MPyNox 4-methoxy-pyrldlne-N-oxlde
4-NPy~Jox 4-nltro-pyrldlne-N-oxlde
Pc cld plcollnlc acid-N-oxlde
2-FcNox 2-plcollne-N-oxlde
4-Pc~ox 4-Plcollne-N-oxide
PN proplonltrlIe
P~PYRL polyvinylpyrrolidone
3-Py Carb 3-pyridylcarblnol-N-oxlde
Py'lox pyrldlne-N-oxlde
QuNox qulnoline-N-oxlde, dihydrate
$AD tetraazadecane
t-but PyNox 4-t-butyl-pyrldlne-N-oxide
: ~ 25
~EPO triethYl phos~hate oxlde
~
~PPO trlphenylphosphlne oxide
'' .
: 23.
.,
. j,~, .
(5137)
Example 101
In each of the above example, methanol was used as
the compound containing a replaceable hydrogen atom. In the
following examples, either t-butyl alcohol or n-amyl alcohol
were used in place of methanol.
13.5 gms. Or acrylonitrile, o.88 gms. Or 4-picoline-
N-oxide and 100 mls. of t-butyl alcohol were placed lnto a
giassllned autoclave. Next, 1.37 gms. of Co2(C0)8 were
added and the autoclave sealed.
The autoclave was charged wlth synthesis gas con-
tainlng 5% H2 to a pressure Or 800 psl. The temperature was
set at 97.5C and the reactlon proceeded for 180 mlnutes.
The glasslined autoclave was then brought to room tempera-
ture by coollng with cold water, depressurlzed and opened
for product analysis. The product analysis is shown ln
Table II.
Exam~les 102 and 103
-
These examples follow the same procedure outlined
ln Example 101 except that the solvent, alcohol and reaction
tlme were varled. These variables and the product analysis
are shown ln Table II.
ExamPles 104
In each of the above examples the unsaturated
olefln ~eed was acrylonitrile. In the following two examples,
other olefins were fed to the lnventive reaction system.
5.26 gms. of propylene, C.88 gms. of 4-plcoline-N-
oxide, 8.15 gms. of methanol and 100 mls. of orthoxylene
were placed into a glasslined autoclave. Mext, 1.37 gms. of
Co2(CG)8 were added and the autoclave sealed~
The autoclave was charged with synthesls gas con-
taining 5,0 H2 to a pressure of 800 psi. The temperature was
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(5137)
set at 97.5C and the reactlon proceeded for 180 minutes.
The glasslined autoclave was then brought to room temoera-
ture by coollng with cold water, depressurized and opened
for product analysis. An 80% conversion of propylene was
obtalned wlth a 56% yleld Or N-methylbutyrate and a 20%
yield of methyl lso-butyrate.
Example 105
14.8 gms. of allyl alcohol, 1.45 gms. Or quinoline-
N-oxlde and 100 mls. of t-butyl alcohol were placed into a
glasslined autoclave. Next, 1.37 gms. of Co2(CO)8 were
added and the autoclave sealed.
- The autoclave was charged wlth synthesls gas con-
talning 5~ H2 to a pressure of 800 psl. The temperature was
set at 97.5C and the reactlon proceeded for 180 mlnutes.
15 . The glasslined autoclave was then brought to room tempera-
ture by cooling with cold water, depressurized and opened
for product analysls. A 1007~ converslon of allyl alcohol
was obtained with a 50~ yield Or propionaldehyde and a 50
yleld Or butyrolactone.
_ Example 106
Each of the above examples used a heterocyclic
nltrogen llgand. The rollowlng examples use phosohorus or
sul~ur oxlde ligands.
13.5 gms. of acrylonltrile, 1.46 gms. of triethyl-
phosphateoxlde and 100 mls. of methanol were placed lnto a
glasslined autoclave. ~ext, 1.37 gms. of Co2(C0)8 were
added and the autoclave sealed.
The autoclave- was charged with synthesis gas con-
taining 5~O H2 to a pressure Or 8~o psi. The temperature was
set at 95C and the reaction proceeded for 180 minutes. The
glassllned autoclave was then brought to room temperature by
228
(51~7)
cooling with cold water, depressurized and opened for pro-
duct analysis. The product analysis is shown in Table III.
Examples 107 thru 109
The procedure outlined in Exam~le 106 was followed
wlth the temperature, reaction tlme and llgand being varled.
ese varlables and the product analysls are shown in Table
III.
.
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~15~228
(5137)
Although only a few embodlments of the present
inventlon have been speclflcally descrlbed above, lt should
be appreclated that many additions and modifications can be
made wlthout departing from the spirit and scope of the in-
vention. These and all other modifications are intended to
be lncluded withln the scope of the present lnvention, which
ls to be llmited only by the followlng claims:
