CA1150228A - Carbonylation of olefinically unsaturated compounds - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Oxygenated organic compounds, e.g. esters, alde-hydes, and amides, are prepared by reacting an olefinically unsaturated compound with carbon monoxide and a compound containing a replaceable hydrogen atom in the presence of a catalyst comprising cobalt or ruthenium carbonyl and a pro-moter ligand. The promoter ligand is selected from the group consisting of heterocyclic nitrogen compounds and phosphorus or sulfur oxides. These reactions are carried out under relatively mild conditions of temperature and pressure.

Description

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

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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;~ O~ 0 _ _ _ ~L~5~228 (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 '' .

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(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 ~ c ~ Z28 o ~ ~

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~ ~- ~ O o ~0 ~lS~)ZZ8 (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 (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:

Claims (13)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A catalyst composition comprising a phosphorus or sulfur oxide promoter ligand and at least one of cobalt carbonyl and ruthenium carbonyl wherein said promoter ligand has one of the following structures:

and wherein R6, R7, R8, R9, and R10 are each indepen-dently selected from:
(1) C1-10 alkyls;
(2) polynuclear aryls containing up to 12 carbon atoms, optionally substituted with C1-10 alkyls, and (3) O(CH2)tCH3, wherein t is 0-10; and wherein n is 0 or 1.

2. The catalyst composition of claim 1 wherein R6, R7, R8, R9 and R10 are each independently selected from:
(1) C1-4 alkyls;
(2) aryls, optionally substituted with C1-4 alkyls; and (3) OCH3.

3. The catalyst composition of claim 1 wherein R6, R7, R8, R9 and R10 are CH3.

4. The catalyst composition of claim 1 wherein the ligand is a phosphorus oxide.

5. The catalyst composition of claim 1 wherein the ligand is a sulfur oxide.

6. The catalyst composition of claim 1 wherein the ligand and the cobalt or ruthenium carbonyl are mixed with an inert organic solvent.

7. A process for the production of an oxygenated organic compound comprising contacting an olefinically unsaturated compound with carbon monoxide and a compound contain-ing a replaceable hydrogen atom in the presence of a catalyst comprising at least one of cobalt carbonyl and ruthenium carbonyl and a promoter ligand with one of the following structures:

and wherein n R6, R7, R8, R9, and R10 are each indepen-d ently selected from:
(1) C1-10 alkyls;
(2) polynuclear aryls containing up to 12 carbon atoms, optionally substituted with C1-10 alkyls; and (3) O(CH2)tCH3, wherein t is 0-10; and wherein n is 0 or 1.

8. The process of claim 7 wherein the olefin-ically unsaturated compound has the following structure:

R11CH = CHR12 wherein R11 and R12 are each independently selected from:

(1) hydrogen (either R11 or R12 but not both);
(2) C1-30 alkyl;
(3) -(CH2)p-CN, wherein p is 0-3; and (4) -(CH2)z-OR3, wherein z is 1-30 and R3 is hydrogen or methyl.

9. The process of claim 7 wherein the compound containing a replaceable hydrogen atom is represented by the following formula:
H - Y
wherein Y is selected from the group consisting of:
(1) OR14 wherein R14 is a C1-30 alkyl;
(2) wherein R15 and P16 are each indepen-dently selected from C1-10 alkyls; and (3) H.

10. The process of claim 7 wherein the compound containing a replaceable hydrogen atom is H2.

11. The process of claim 7 wherein the process is conducted in the presence Or an inert organic solvent.

12. A process for the production of an oxygenated organic compound comprising contacting an olefinically unsaturated compound containing an alcohol moiety with carbon monoxide in the presence of a catalyst comprising at least one of cobalt carbonyl and ruthenium carbonyl and a promoter ligand with one of the following structures:

and wherein R6, R7, R8, R9, and R10 are each indepen-dently selected from:
(1) C1-10 alkyls;
(2) polynuclear aryls containing up to 12 carbon atoms, optionally substituted with C1-10 alkyls; and (3) O(CH2)tCH3, wherein t is 0-10; and wherein n is 0 or 1.

13. The process of claim 12 wherein the olefin-ically unsaturated compound has the following structure:

R11CH = CHR12 wherein R11 and R12 are each independently selected from:
(1) hydrogen;
(2) C1-30 alkyl;
(3) -(CH2)p-CN, wherein p is 0-3; and (4) -(CH2)q-OH, wherein q is 1-30;
with the proviso that at least one of R11 and R12 is an alcohol moiety.