Process for the preparation of 3-pentenoic acid from allylic butenyl alcohols or esters using a nickel catalyst

Process for making 3-pentenoic acid acid by reacting an allylic butenyl alcohol or its corresponding ester with carbon monoxide in the presence of nickel, and a source of iodide. ##STR1##

BACKGROUND OF THE INVENTION 
3-Pentenoic acid is a well-known intermediate which can be used to make 
both caprolactam for nylon 6, and adipic acid for nylon 6,6. 
EP-A-428979 describes a process for the preparation of 3-pentenoic acid by 
carbonylation of allylic butenols and butenol esters in the presence of a 
rhodium catalyst and a promoter selected from hydrogen bromide and 
hydrogen iodide. 
U.S. Pat. No. 4,140,865 describes a process for the manufacture of vinyl 
acetic acid by reacting allyl alcohol with carbon monoxide in the presence 
of a cobalt, nickel, rhodium, or palladium catalyst and an iodide source 
chosen from methyl iodide and palladium iodide. 
EP-A-338730 describes the carbonylation of allyl alcohol and allyl acetate 
in a two-phase system containing a nickel cyanide catalyst and a phase 
transfer catalyst. 
U. S. Pat. No. 5,334,755 describes the carbonylation of methanol in the 
presence of a Group VIII metal and a pyridine promoter. See U.S. Pat. No. 
5,334,755 for example. 
BRIEF SUMMARY OF THE INVENTION 
The present invention is a process for preparing 3-pentenoic acid by 
reacting an allylic butenyl alcohol or ester with carbon monoxide in a 
solvent containing a carboxylic acid in the presence of a source of 
nickel, a source of iodide, optionally water, and optionally a promoter at 
a temperature between about 60.degree. C. and about 140.degree. C. and a 
pressure between about 200 psig and about 4000 psig. 
DETAILED DESCRIPTION 
In the process of the present invention, an allylic butenyl alcohol or its 
corresponding ester is reacted with carbon monoxide in the presence of a 
source of nickel and HI or selected metal iodides in a carboxylic 
acid-containing solvent. The reaction can be carried out at temperatures 
in the range of about 60.degree. C. to about 140.degree. C. and pressures 
in the range of about 200 psig to about 4000 psig. The nickel and iodide 
combination is believed to act as a catalyst for the reaction. The process 
may be carried out in the presence of water or hydrogen and/or in the 
presence of a promoter. 
The expression "allylic butenyl alcohol" means cis or trans crotyl alcohol 
or 3-butene-2-ol. 
The allylic butenyl alcohol or ester used in the invention is crotyl 
alcohol, 3-butene-2-ol or their corresponding carboxylic acid esters. 
The nickel portion of the catalyst may be finely divided nickel metal 
(alone or on a support such as carbon or alumina) or a nickel compound 
which is or becomes soluble in the reaction medium. Suitable nickel 
compounds include nickel(II) salts such as nickel acetate or nickel 
iodide, nickel(O) compounds such as Ni(COD).sub.2 [COD=cyclooctadiene] or 
Ni(CO).sub.2 ((PC.sub.6 H.sub.5).sub.3).sub.2. The nickel catalyst should 
be used at a concentration between about 20 and about 200 mmoles/liter of 
reaction medium. The allylic butenyl alcohol or ester conversion rate 
becomes too slow at lower concentrations of nickel. Higher concentrations 
of nickel are limited by solubility. 
The iodide portion of the catalyst may be HI or any metallic iodide that is 
capable of generating HI under the reaction conditions. Iodides of the 
following metals are suitable: B, Al, Ga, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, 
Gd, Tb, Dy, Ho, Er, Yb, Lu, Ge, Sn, Ti, Zr, Cr, Mo, W, Mn, Fe, Co, Ni and 
Zn. Highly ionic iodides such as NaI and LiI are not suitable. 
The reaction may be promoted further with the use of various promoters. The 
reaction is strongly promoted by organic nitrogen bases and their iodide 
salts, for example lutidinium iodide, tetrabutylammonium iodide, 
methyltriphenylphosphonium iodide. The base strength (pKa) of the base is 
not critical provided there is an excess of HI over base under the 
reaction conditions. Bases varying in strength from simple alkylamines and 
imidazoles to alkyl-substituted ureas and thioureas promote the reaction. 
Suitable organic nitrogen bases include pyridine, optionally substituted 
with C.sub.1 -C.sub.5 alkyl or C.sub.6 -C.sub.20 aryl groups. Substituted 
pyridines such as the isomeric lutidines and even the highly hindered 
2,6-di-t-butylpyridine are particularly effective. Polymeric pyridines 
such as poly(vinylpyridine) may also be used. 
Other suitable organic nitrogen bases include quinoline, optionally 
substituted with alkyl or aryl groups; isoquinoline, optionally 
substituted with alkyl or aryl groups; imidazole, optionally substituted 
with alkyl or aryl groups; thiazole, optionally substituted with alkyl or 
aryl groups; and oxazole, optionally substituted with alkyl or aryl 
groups. In the above compounds, preferred alkyl substitutents are C.sub.1 
-C.sub.5 alkyl groups and preferred aryl substitutents are C.sub.6 
-C.sub.20 aryl groups, such as phenyl, substituted phenyl, naphthyl, and 
phenanthryl. 
The promoter may also be the hydrogen iodide salt or a quaternary iodide 
salt of the above organic nitrogen bases. For example, 2,6-lutidinium 
iodide and 1,3-dimethylimidazolium iodide are effective promoters in the 
presence of excess hydrogen iodide. 
Other suitable organic nitrogen base promoters are alkyl-substituted ureas 
and thioureas, and aliphatic amides such as N,N-dimethylacetamide. 
The promoter may also be an alkyl, aryl or arylalkyl phosphine. The term 
"aryl" denotes phenyl, substituted phenyls (especially C.sub.1 -C.sub.5 
alkyl substituted phenyls), and condensed aromatics such as naphthyl and 
phenanthryl. The phosphines may be monodentate or bidentate. If a 
bidentate phosphine is used, it is preferred that it be of the formula 
R.sup.3.sub.2 P-Q-PR.sup.4.sub.2 in which Q is a 3 to 6 carbon atom 
bridging group and R.sup.3 and R.sup.4 are the same or different C.sub.1 
-C.sub.10 alkyl or C.sub.6 -C.sub.20 aryl groups. Examples of suitable 
bidentate phosphines may be found in U.S. Pat. No. 5,618,983, the 
disclosure of which is incorporated herein by reference. 
Molybdenum compounds may also be used as promoters. Compounds of Group VI 
and Group VII metals (Cr, Mo, W, Mn, Re) may also be used as promoters. 
Suitable promoters include molybdenum hexacarbonyl, molybdenum(II) acetate 
dimer, and molybdenum (III) halide, where the halide is chlorine, bromide, 
or iodide. Preferred is Mo(CO).sub.6, which strongly promotes butadiene 
carbonylation with Ni/HI, Ni/AlI.sub.3 and Ni/CrI.sub.3 catalysts. 
Preferred reaction conditions are those in which the ratio of iodide to 
nickel is in the range of 2/1 to 20/1, the ratio of organic nitrogen base 
or phosphine to nickel is in the range 2/1 to 20/1. The preferred ratio of 
iodide to promoter depends on the base strength of the promoter. For 
pyridine bases and for phosphines, this ratio should be greater than one; 
for weaker organic nitrogen bases such as tetramethylurea, the ratio of 
iodide to promoter is preferably less than one. 
It is preferred to carry out the reaction in the presence of water, which 
speeds up the reaction and gives a higher yield of 3-pentenoic acid. It is 
important, however, to limit the amount of water, because too high 
concentrations can slow the reaction down. Preferred water concentration 
is in the range of about 1.5% to about 8.0% by weight. The most preferred 
concentration is about 4.5%. 
It is preferred that the reaction is carried out in a solvent that contains 
a carboxylic acid. When the starting material is an ester (e.g., crotyl 
acetate) the carboxylic acid solvent is preferred but not necessary. When 
the starting material is an alcohol, a carboxylic acid solvent is 
necessary for suitable reactivity. Preferred solvents are carboxylic acids 
such as acetic acid, propionic acid, glutaric acid or a mixture of these 
acids. Mixtures of a carboxylic acid and a non-acidic solvent such as 
toluene, n-butyronitrile or dimethylacetamide may also be used. To 
facilitate product separation, a carboxylic acid solvent which has a 
higher boiling point than that of 3-pentenoic acid is preferred. 
The reaction of the present invention may be carried out in a batch or 
continuous type process by heating under Co pressure a mixture of 
nickel(II) salt, hydrogen iodide, allylic butenyl alcohol or ester, and, 
preferably, water and a nitrogen base, phosphine or molybdenum carbonyl 
promoter in a carboxylic acid solvent. 
The following are preferred operating conditions: 
______________________________________ 
Temperature 90.degree. C.-120.degree. C. 
CO pressure 700 to 2000 psig 
Solvent Carboxylic Acid 
Ni concentration 0.5 to 1.0% by weight 
Water concentration 
1.5 to 8.0% by weight 
I/Ni 5/1 to 10/1 
Promoter/Ni 4/1 to 12/1 
______________________________________ 
The invention is illustrated by the following examples, which are not 
intended to limit the scope of the invention.

EXAMPLES 
Example 1 
Carbonylation of 3-Acetoxybutene-1 in Acetic Acid at 90.degree. C. and 900 
psig with Triphenylphosphine TPP Promoter 
A 120 mL mechanically stirred Hastelloy-C autoclave was charged with 1.0 g 
(4 mmole) of nickel acetate, 4.19 g (16 mmole) of triphenylphosphine, 4.49 
g 57% aqueous HI (20 mmoles HI+107 mmoles water), 1.7 g (93 mmoles) water 
and 34 g acetic acid solvent. The solution was heated to a temperature of 
90.degree. C. under an initial pressure of 500 psig carbon monoxide. 
Reaction was initiated by injecting a solution of 11.4 g (100 mmole) of 
3-acetoxybutene-1 and 0.5 g 1,2,4-trichlorobenzene (TCB), a gas 
chromatography (GC) internal standard, and adjusting the total pressure 
with CO to 900 psig. The total solution volume at room temperature was 
approximately 50 mL. Carbon monoxide was continuously fed to the autoclave 
from a reservoir so as to maintain the total pressure constant at 900 
psig. Samples were removed at intervals for GC analysis on a 30 M J&W 
Scientific DBFFAP capillary GC column. The reaction was allowed to run for 
a total of 3 hours. 
The product was a clear yellow homogeneous solution from which some 
crotyltriphenylphosphonium iodide separated on standing. 
The GC analysis of the solutions indicated about 46% of the allylic butenyl 
acetate (crotyl acetate and its isomer 3-acetoxybutene-1) was consumed in 
30 minutes, 59% in 60 minutes, 91% in 180 minutes and 99% in 300 minutes. 
The major product was 3-pentenoic acid. 
Following is a summary of the results of the GC analyses: 
______________________________________ 
Moles per mole 3AcB1 Charged 
Time(Min.) 
BD + Butenes CrX 3PA 2M3BA VL 
______________________________________ 
30 1.7 53.8 23.3 0.7 0.0 
60 5.1 40.7 41.6 1.3 0.4 
180 1.6 8.8 74.8 2.4 2.8 
300 2.4 1.0 84.6 2.8 7.2 
______________________________________ 
BD=butadiene 
3AcB1=3-acetoxybutene-1 
2M3BA=2-Methyl-3-butenoic acid 
CrX=Mixture of Crotyl acetate, 3-Acetoxybutene-1, 3-Iodobutene-1, cis- and 
trans-crotyl iodides 
3PA=cis+trans-3-pentenoic acid 
VL=gamma-valerolactone 
The butenyl acetate and iodide conversion after 6 hours was 99%, the yield 
of 3-pentenoic acid was 85.5% and the yield of valerolactone was 7.3%. The 
first order rate constant for the conversion of all C4 precursors (butenyl 
esters butenyl iodides and butadiene) was 0.72 Hr.sup.-1, corresponding to 
a turnover frequency of 13 moles 3AcB1 converted to 3PA per g-atom of 
Nickel per hour. The space-time yield over the first hour was 730 mmoles 
3PA/L/Hr. 
Example 2 
Carbonylation of 3-Acetoxybutene-1 in Acetic Acid at 100.degree. C. and 900 
psi without Promoter 
The experiment in Example 1 was repeated, except that the phosphine 
promoter was omitted, the nickel and iodide concentrations were increased 
by a factor of 2 (16 mmole Ni and 80 mmole HI per 100 mL solution), and 
the temperature was increased to 100.degree. C. After 3 hours the total 
conversion of allylic acetates and iodides was 24.7% and the 3PA yield was 
71.2%. The first order rate constant was 0.072 Hr.sup.-1, corresponding to 
a turnover frequency of 0.65 moles 3AcB1 converted per g-atom of Ni per 
hour. The space-time yield (STY) was 228 mmole 3PA/L/Hr. The result show 
that the carbonylation of the allylic acetate to 3PA takes place in good 
yield in the absence of promoter but the reaction rate is much slower than 
when a promoter is present. 
Example 3 
Carbonylation of 3-Acetoxybutene-1 in Anhydrous Acetic Acid at 90.degree. 
C. and 900 psi with Ni/AlI.sub.3 /TPP catalyst 
The experiment in example 1 was repeated, except that the water was 
omitted, the aqueous HI was replaced with anhydrous aluminum iodide (4 
mmoles/100 mL) and the nickel acetate was replaced with anhydrous nickel 
iodide (4 mmoles/100 mL). The Ni/Iodide/TPP ratio was maintained at 
1/5/4). 
The butenyl acetate conversion after 6 hours was 41%, the yield of 
3-pentenoic acid was 74% and the yield of valerolactone was 1.9%. This 
sample also showed the presence of significant amounts of acetic anhydride 
(15.4 moles per mole 3AcB1 charged) and smaller amounts (ca 0.5 Mole %) of 
the mixed anhydride of 3-pentenoic and acetic acids. 
The first order rate constant for the conversion of all C4 precursors 
(butenyl esters and butadiene) was 0.11 Hr.sup.-1, corresponding to a 
turnover frequency of 2.0 moles 3AcB1 converted per g-atom of Nickel per 
hour. 
Example 4 
Carbonylation of 3-Acetoxybutene-1 in Acetic Acid at 110.degree. C. and 900 
psi with 2,6-Lutidine Promoter 
The experiment in Example 1 was repeated, except that the temperature was 
110.degree. C., the iodide source was NiI.sub.2 (2.5 g; 8 mmoles/100 mL), 
the HI/Ni mole ratio was 8 (Total I/Ni=10), and the promoter was 
2,6-lutidine (3.4 g; 32 mmoles). After 5 hours the conversion was 66%, and 
the yield of 3PA was 93%. 
Example 5 
Carbonylation of 3-Acetoxybutene-1 using a Nickel catalyst, an Iodide 
Promoter and Triphenylphosphine Ligand 
A 25 mL glass-lined pressure vessel was charged with 5 mL of a solution 
containing 11.4 g (100 mmol) 3-acetoxybutene-1 (3AcB1), 1.00 g (4.0 mmol) 
of nickel acetate tetrahydrate and 1.00 g 1,2,4-trichlorobenzene (internal 
GC standard) in 100 mL acetic acid. To the 5 mL aliquot was added 0.225 g 
of 57% aqueous HI (5 equivalents of HI per equivalent of Ni) and 0.21 g 
triphenylphosphine (4 equivalents per equivalent of Ni). The pressure 
vessel was freed from air by purging first with nitrogen (twice) and then 
with CO (twice). The vessel was then pressurized to 900 psig CO and heated 
to 90.degree. C. with agitation for 4 hours. The heat was shut off, the 
pressure vessel was allowed to cool to room temperature and the excess 
pressure was vented. The product was a clear yellow homogeneous solution. 
It was analyzed directly by GC on a 30 M J&W Scientific DBFFAP capillary 
GC column. The results are summarized below: 
______________________________________ 
mmoles 
Product (per 100 mmoles 3AcB1 charged) 
______________________________________ 
Butadiene + Butenes 
1.4 
3-Acetoxybutene-1 
17.5 
Crotyl Acetate 8.1 
cis + trans 3-pentenoic acid 
61.1 
2-Methyl-3-butenoic acid 
2.2 
Valerolactone 0.8 
______________________________________ 
Conversion of the allylic acetates (3-acetoxybutene-1 and crotyl acetate) 
to all products was 74%, 3-pentenoic acid yield was 85% and product 
accounting was 95%. 
Small amounts of crotyl pentenoates, vinylcyclohexene, sec-butyl acetate, 
valeric acid and methylglutaric acid (analyzed as its dimethyl ester after 
esterification with methanol) were also present. 
Example 6 
Carbonylation of Crotyl Acetate using a Nickel catalyst and Hydrogen Iodide 
Promoter 
The experiment in Example 5 was repeated, except that the 3-acetoxybutene-1 
was replaced with an equivalent amount of crotyl acetate 
(1-acetoxybutene-2). The results are shown in Table 1. 
Example 7 
Carbonylation of Crotyl Alcohol using a Nickel catalyst and Hydrogen Iodide 
Promoter 
The experiment in Example 5 was repeated, except that the 3-acetoxybutene-1 
was replaced with an equivalent amount of crotyl alcohol (2-butene-1-ol). 
The results are shown in Table 1. 
Example 8 
Carbonylation of 3-Butene-2-ol 
The experiment in Example 5 was repeated, except that the 3-acetoxybutene-1 
was replaced with an equivalent amount of 3-butene-2-ol. The results are 
shown in Table 1. 
Example 9 
Carbonylation of Crotyl Acetate using a Nickel catalyst and Hydrogen Iodide 
Promoter 
The experiment in Example 5 was repeated, except that the 3-acetoxybutene-1 
was replaced with an equivalent amount of crotyl acetate 
(1-acetoxybutene-2), the temperature was reduced to 70.degree. C., and the 
CO pressure was reduced to 500 psig. The results are shown in Table 1. 
Example 10 
Carbonylation of Crotyl Acetate using a Nickel catalyst and Hydrogen Iodide 
Promoter 
The experiment in Example 5 was repeated, except that the 3-acetoxybutene-1 
was replaced with an equivalent amount of crotyl acetate 
(1-acetoxybutene-2), the temperature was reduced to 50.degree. C. and the 
CO pressure was reduced to 300 psig. The results are shown in Table 1. 
TABLE 1 
______________________________________ 
Ex Substrate Temp Pressure 
Conversion 
3PA Yield 
______________________________________ 
5 3AcB1 90 900 73.8 84.7 
6 CrOAc 90 900 67.9 89.0 
7 CrOH 99 900 73.1 73.3 
8 3B2OL 90 900 73.3 70.8 
9 CrOAc 70 500 42.9 74.7 
10 CrOAc 50 300 29.9 57.8 
______________________________________ 
3AcB1 = 3Acetoxybutene-1 
CrOAc = Crotyl acetate 
CrOH = Crotyl alcohol 
3B2OL = 3Butene-2-ol 
Examples 11-17 
Carbonylation of 3-Acetoxybutene-1 using a Nickel catalyst and Various 
Iodide Promoters 
The experiment in Example 5 was repeated, except that the hydrogen iodide 
was replaced with an equivalent iodide amount various metal iodides, and 
the temperature was varied. The results are shown in Table 2. 
TABLE 2 
______________________________________ 
Ex Iodide Temp Conversion 
3PA Yield 
______________________________________ 
11 BI.sub.3 
90 44 63.6 
12 ZnI.sub.2 
90 13 20.8 
13 SnI.sub.4 
90 25 28.0 
14 AlI.sub.3 
110 85 81.7 
15 CrI.sub.3 
110 88 86.3 
16 CoI.sub.2 
110 31 65.8 
17 SnI.sub.4 
110 35 70.1 
______________________________________ 
Examples 18-27 
Carbonylation of 3-Acetoxybutene-l using a Nickel catalyst and Various 
Iodide Promoters 
The experiment in Example 5 was repeated, except that the 
triphenylphosphine was replaced with an equivalent amount of various 
phosphines, and the ratios of HI to Nickel and Phosphorus to Nickel were 
varied. The results are shown in Table 3. 
TABLE 3 
______________________________________ 
Ex Ligand HI/Ni P/Ni Conv 3PA Yield 
______________________________________ 
18 (n-C.sub.4 H.sub.9).sub.3 P 
5 4 61 78.5 
19 C.sub.2 H.sub.5 PPh.sub.2 
5 4 58 78.8 
20 (p-MeOC.sub.6 H.sub.4).sub.3 P 
5 4 54 74.3 
21 (p-C1C.sub.6 H.sub.4).sub.3 P 
5 4 57 66.0 
22 DPPE-O 5 4 67 75.2 
23 DPPE-S 5 4 61 80.6 
24 (1-Naph).sub.3 P 
5 4 26 48.4 
25 DPPE 10 2 25 17.9 
26 DPPP 10 4 43.4 53.3 
25 DPPB 10 4 84.5 82.3 
27 DPPPent 10 8 93.7 71.5 
______________________________________ 
DPPE-O = Diphenylphosphinoethane monoxide 
DPPES = Diphenylphosphinoethane monosulfide 
DPPE = Diphenylphosphinoethane 
DPPP = Diphenylphosphinopropane 
DPPB = Diphenylphosphinobutane 
DPPPent = Diphenylphosphinopentane 
Ph = phenyl 
Naph = naphthyl 
Examples 28-29 
Carbonylation of 3-Acetoxybutene-1 using a Heterogeneous Nickel catalyst 
The experiment in Example 5 was repeated, except that the nickel acetate 
was replaced with an equivalent amount of finely divided nickel on 
Kieselguhr, and the HI/Ni ratio was increased to 10. The results are shown 
in Table 4. 
TABLE 4 
______________________________________ 
Ex Nickel Source 
Hi/Ni TPP/Ni Conv 3PA Yield 
______________________________________ 
28 Ni/Kiesselguhr 
10 4 90 84.2 
29 Ni(OAc).sub.2.4H.sub.2 O 
10 4 89 86.0 
______________________________________ 
OAc = acetate 
Examples 30-33 
Carbonylation of 3-Acetoxybutene-1 using a Nickel catalyst and Isoquinoline 
The experiment in Example 4 was repeated, except that the 
triphenylphosphine was replaced with isoquinoline, the iodide was AlI3 and 
the ratios of Iodide to Nickel, Isoquinoline to Nickel and water 
concentration were varied. The results are shown in Table 5. 
TABLE 5 
______________________________________ 
Ex Temp Isoq/Ni I/Ni H.sub.2 O/Substrates 
Conversion 
3PA Yield 
______________________________________ 
30 120 4 10 2 39 50.9 
31 120 4 20 2 51 24.9 
32 100 4 20 1.5 50 50.7 
33 100 8 20 1.5 27 21.5 
______________________________________ 
Isoq = isoquinoline 
Examples 34-38 
Carbonylation of 3-Acetoxybutene-1 using a Nickel catalyst and an Iodide 
Promoter in the absence of water 
The experiment in Example 4 was repeated, except that the Nickel compound 
was Ni(CO).sub.2 (PPh3)2(Ph=phenyl) (Strem Chemical), the total Ph3P/Ni 
ratio (including the Ph.sub.3 P in the Ni complex) was maintained at 4/1, 
the water was omitted and the iodide was varied. The results are shown in 
Table 6. 
TABLE 6 
______________________________________ 
Ex Ni Source Iodide I/Ni Conv 3PA Yield 
______________________________________ 
34 Ni(CO).sub.2 (PPh.sub.3).sub.2 
HI 5 57 71.2 
(Anh) 
35 Ni(CO).sub.2 (PPh.sub.3).sub.2 
AlI.sub.3 
5 34 50.3 
36 Ni(CO).sub.2 (PPh.sub.3).sub.2 
TiI.sub.4 
5 51 66.0 
37 Ni(CO).sub.2 (PPh.sub.3).sub.2 
CeI.sub.3 
5 28 57.9 
38 Ni(CO).sub.2 (PPh.sub.3).sub.2 
CeI.sub.3 
5 37 41.5 
______________________________________ 
Anh = Anhydrous 
Examples 39-42 
Carbonylation of 3-Acetoxybutene-1 at High Pressures using a Nickel/HI 
catalyst and 2,6-Lutidine Promoter 
The experiment in Example 5 was repeated, except that the temperature was 
100.degree. C., nickel compound was NiI.sub.2, the Iodide/Ni ratio was 10, 
the promoter was 2,6-lutidine, the water concentration was 4.5% (2.5/1 
H.sub.2 O/Substrate), and the pressure was varied over the range 1500 to 
3000 psig. The results are shown in Table 7. 
TABLE 7 
______________________________________ 
Pressure 3PA 3PA 2M3BA VL 
Ex (Total) Conv. (mole/100) 
Yield 
Yield Yield 
Acctg 
______________________________________ 
39 1500 97.9 82.5 86.6 3.4 9.5 101 
40 2000 76.1 70.5 95.0 3.2 1.6 99 
41 2500 52.7 48.6 94.5 3.3 0.7 99 
42 3000 42.1 36.9 90.0 3.2 0.4 97 
______________________________________ 
Acctg = Product Accounting (100 .times. X total moles recovered/moles 
charged) 
Examples 43-48 
Carbonylation of 3-Acetoxybutene-1 with 2,6-Lutidine Promoter in Different 
Solvent Systems 
The experiment in Example 5 was repeated except that the temperature was 
100.degree. C., the nickel compound was nickel 2-ethylhexanoate (4 
mmole/100 ml), the Iodide/Ni ratio was 10, the promoter was 2,6-lutidine 
(0.6/1 Promoter/HI mole ratio), the water concentration was 4.5%, and the 
solvent was varied. The results are shown in Table 8. 
TABLE 8 
______________________________________ 
mmoles 
Ex Solvent Conv 3PA Yield 
______________________________________ 
43 Acetic Acid 78.1 65.6 87.5 
44 Pivalic acid 55.4 31.8 59.8 
45 n-Butyronitrile 
39.7 15.2 39.8 
46 Acetonitrile 46.4 21.6 48.4 
47 N-Methylpyrrolidone 
67.7 6.9 10.6 
48 Toluene 17.1 1.2 2.9 
______________________________________ 
Examples 49-65 
Carbonylation of 3-Acetoxybutene-1 using a Nickel catalyst and Various 
Nitrogen Base Promoters 
The experiment in Example 5 was repeated, except that the temperature was 
110.degree. C., the nickel acetate concentration was 8 mmoles/100 mL, the 
HI/Ni ratio was 10, the promoter/Ni ratio was 4, the water concentration 
was 7.7%. and the promoter was varied. The results are shown in Table 9. 
TABLE 9 
______________________________________ 
Yield Yield Yield 
Ex Promoter Conv 3PA 2M3BA VL 
______________________________________ 
49 None (10HI/Ni) 39.9 15.3 0.0 0.0 
50 Pyridine 82.5 64.1 3.1 4.1 
51 2,6-Di-t-Butyl- 
77.9 70.4 3.9 7.9 
Pyridine 
52 2,6-Diphenylpyridine 
92.3 59.6 3.5 12.8 
53 3,4-Lutidine 80.9 61.6 3.4 4.6 
54 4-Picoline 79.6 62.2 3.3 4.1 
55 2-Ethylpyridine 
77.4 62.1 3.2 3.7 
56 3-Benzoylpyridine 
75.3 41.5 2.3 3.2 
57 Isoquinoline 83.2 57.2 3.3 4.7 
58 Tributylamine 78.7 61.3 3.4 3.1 
59 N,N,N',N'- 54.6 48.4 3.1 0.0 
Tetramethyl- 
ethylenediamine 
60 Triphenylamine 70.2 57.5 2.9 2.3 
61 Diphenylethylamine 
84.5 63.1 3.3 10.4 
62 N,N-Di Methylaniline 
62.5 11.2 0.0 0.0 
63 4-methylimidazole 
90.0 61.4 3.3 10.4 
64 N,N'-Dibutylthiourea 
57.5 57.4 3.2 6.0 
65 Polyvinylpyridine 
46.6 61.8 4.2 -- 
(2% cross-linked, 
8 eq/Ni) 
______________________________________ 
Examples 66-76 
Carbonylation of 3-Acetoxybutene-1 using a Nickel catalyst and Various 
Iodide Salt Promoters 
The experiment in Example 5 was repeated, except that the temperature was 
115.degree. C., the nickel acetate concentration was 4 mmoles/100 mL, the 
HI/Ni ratio and the promoter/Ni ratio were varied, the water concentration 
was 4.5%, and the promoter was varied. The results are shown in Table 10. 
TABLE 10 
______________________________________ 
Yield 
Ex Promoter Prom/Ni HI/Ni 
Conv 3PA 
______________________________________ 
66 None (4HI/Ni) 0 4 29.2 53.7 
67 None (4HI/Ni) 0 10 36.8 62.8 
68 1,3-Dimethylimidazolium iodide 
6 4 45.1 66.3 
69 1,3-Dimethylimidazolium iodide 
6 10 76.6 81.9 
70 Ethylquinaldinium Iodide 
6 4 43.6 71.9 
71 1,4-dimethylpyridinium iodide 
6 4 47.3 76.3 
72 Methyltriphenylphosphonium 
4 5 33.5 68.3 
iodide* 
73 3-Ethyl-2-methyl-2-thiazolium 
6 4 43.6 58.8 
iodide 
74 Tetrabutylammonium iodide 
6 4 80.1 87.9 
75 Tetrabutylammonium iodide 
10 5 81.5 85.6 
76 2,6-Lutidinium iodide 
6 4 73.9 88.4 
______________________________________ 
*Run at 100 C. 
Examples 77-83 
Carbonylation of 3-Acetoxybutene-1 using a Nickel catalyst and an Mo, W or 
Re Promoter. 
The experiment in Example 5 was repeated, except that the temperature was 
100.degree. C., nickel acetate concentration was 8 mmoles/100 mL, the 
iodide and promoter were varied, the I/Ni ratio was 5, the promoter/Ni 
ratio and water concentration were varied, The results are shown in Table 
11. 
TABLE 11 
______________________________________ 
Yield 
Ex % H.sub.2 O 
Iodide Promoter 
Metal/Ni 
Conv 3PA 
______________________________________ 
77 1.8 AlI.sub.3 
Mo(CO).sub.6 
4 94.5 73.1 
78 1.8 AlI.sub.3 
Mo(CO).sub.6 
12 94.2 90.4 
79 3.9 HI None 0 40.2 47.4 
80 3.9 HI Mo(CO).sub.6 
8 79.9 76.7 
81 3.9 HI [Mo(OAc).sub.2 ].sub.2 
8 62.2 69.5 
82 3.9 HI W(CO).sub.6 
8 34.3 60.7 
83 3.9 HI Re.sub.2 (CO).sub.10 
8 38.4 58.3 
______________________________________