# US 5,352,813 A · Carbonylation of methanol using a novel transition metal catalyst

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- Number: US 5,352,813 A
- Document ID: US5352813A
- Status: Granted
- Kind: A
- Application number: 07/752,348
- Filed: 1991-09-03
- Granted: 1994-10-04
- Earliest claimed: 1990-08-31
- Assignees: University of Alberta
- Inventors: Ronald G. Cavell; Kattesh V. Katti
- Web page: https://patentgrep.com/patent/US5352813A

## CPC

- B01J 31/1805: {the ligands containing nitrogen}
- B01J 31/18: containing nitrogen, phosphorus, arsenic or antimony {as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms (double metal cyanides B01J27/26; N-heterocyclic carbenes B01J31/2265)}
- B01J 31/189: {containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand}
- B01J 31/1895: {the ligands containing arsenic or antimony}
- B01J 31/226: {Sulfur, e.g. thiocarbamates}
- B01J 31/2291: {Olefins}
- B01J 31/24: Phosphines {, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands}
- B01J 31/2495: {Ligands comprising a phosphine-P atom and one or more further complexing phosphorus atoms covered by groups B01J31/1845 - B01J31/1885, e.g. phosphine/phosphinate or phospholyl/phosphonate ligands}
- C07C 51/12: on an oxygen-containing group in organic compounds, e.g. alcohols
- C07C 67/36: by reaction with carbon monoxide or formates (C07C67/02, C07C67/03, C07C67/10 take precedence)
- B01J 2531/80: Complexes comprising metals of Group VIII as the central metal
- B01J 2531/822: Rhodium
- B01J 2531/845: Cobalt
- B01J 2531/847: Nickel
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS

## Abstract

An improved process is provided for the carbonylation of methanol to acetic acid and/or its derivatives, especially methyl acetate, under mild reaction conditions using a novel catalyst precursor. The precursor is a transition metal complex having a heterodifunctional bidentate phosphorus--nitrogen ligand attached to the metal. The carbonylation reaction can now typically be carried out at 80.degree. C. and CO pressure of 40 p.s.i.g.

## Claims

### Claim 1

In a catalytic process for the carbonylation of methanol to one or more of acetic acid and its esters, the improvement comprising:
reacting methanol and carbon monoxide using a transition metal catalyst precursor having a phosphorus-nitrogen chelated ligand attached to the metal as a catalyst the catalyst precursor having the general formula: ##STR22## wherein M is a Group VIII B transition metal
Y, Y' are same or different, selected from CO, Cl.sup.-, phosphines and olefinic hydrocarbons
R.sub.1-4, R.sub.6-12 are same or different substituted or unsubstituted aryl groups
Q is selected from a benzene ring connected to P and X in the o-positions, an olefin connected to P and X across the double bond, or (CH.sub.3)CH
X is P or As
R=a substituted aromatic ring ##STR23## where A, B, C or D are selected from F, H, NO.sub.2, CN and alkyl and E is endocyclic nitrogen, a C--NO.sub.2 group of a C--CN group, or isomers thereof, or R=SiMe.sub.3 or TiCl.sub.2 Cp, where Me is methyl, and Cp is cyclopentadienyl, or P(O)(OPh).sub.2, where Ph is a phenyl ring,
R.sub.5 is aryl or alkyl, and
S.sup.* is S, Se, O or N--R, R being as defined hereinabove.

### Claim 2 (depends on 1)

The improved process of claim 1, wherein M is selected from Rh, Co or Ni.

### Claim 3 (depends on 1)

The improved process of claim 1, wherein the catalyst precursor has the formula I wherein M is selected from Rh, Co and Ni, R.sub.1-4 are phenyl groups, and Q is a benzene ring, an olefin or (CH.sub.3)CH, as defined in claim 1.

### Claim 4 (depends on 3)

The improved process of claim 3 wherein, the catalyst has the formula I in which X is P; R is the substituted aromatic ring wherein A, B, C and D are selected from F and NO.sub.2 ; and, if Q is an olefin, it has the formula R'C=CR"(R',R"=H, CH.sub.3, or other alkyl).

### Claim 5 (depends on 1)

The improved process of claim 1, wherein:
(a) the catalyst precursor has the formula II, wherein R.sub.5 is phenyl or methyl and S.sup.* is S, Se or N--R and R is as defined in claim 1, or
(b) the catalyst precursor has the formula III, wherein R.sub.10-12 are phenyl.

### Claim 6 (depends on 1)

The process of claim 1, wherein a promoter is used selected from lithium acetate, sodium tetraphenyl borate, Ph.sub.4 AsCl, LiCl, LiI, KPF.sub.6, Et.sub.3 N, pyridine, quinoline, morpholine or a Bezman salt.

### Claim 7 (depends on 3)

The process of claim 3, wherein a promoter is used selected from lithium acetate, sodium tetraphenyl borate, Ph.sub.4 AsCl, LiCl, LiI, KPF.sub.6, Et.sub.3 N, pyridine, quinoline, morpholine or a Bezman salt.

### Claim 8 (depends on 5)

The process of claim 5, wherein a promoter is used selected from lithium acetate, sodium tetraphenyl borate, Ph.sub.4 AsCl, LiCl, LiI, KPF.sub.6, Et.sub.3 N, pyridine, quinoline, morpholine or a Bezman salt.

### Claim 9 (depends on 1)

The improved process of claim 1, wherein the catalyst precursor is of formula II or III.

### Claim 10

A transition metal complex catalyst precursor having a phosphorus-nitrogen chelated ligand attached to the metal and having the general formula ##STR24## wherein M is a Group VIII B transition metal
Y, Y' are same or different, selected from CO, Cl.sup.-, phosphines and olefinic hydrocarbons
R.sub.1-4, R.sub.6-12 are same or different substituted or unsubstituted aryl groups
Q is selected from a benzene ring connected to P and X in the o-positions, an olefin connected to P and X across the double bond, or (CH.sub.3)CH
X is P or As
R is a substituted aromatic ring, ##STR25## where A, B, C, or D are selected for F, H, NO.sub.2, CN and alkyl and E is endocyclic nitrogen, a C--NO.sub.2 group of a C--CN group, or isomers thereof, or R=SiMe.sub.3 or TiCl.sub.2 Cp, where Me is methyl, and Cp is cyclopentadienyl, or P(O)(OPh).sub.2, where Ph is a phenyl ring,
R.sub.5 is aryl or alkyl, and
S.sup.* is S, Se, O or N--R, R being as defined hereinabove.

### Claim 11 (depends on 10)

A catalyst precursor of claim 10, wherein M is selected from Rh, Co or Ni.

### Claim 12 (depends on 10)

A catalyst precursor of claim 10 which has the formula I, wherein M is selected from Rh, Co or Ni, R.sub.1-4 are phenyl groups and Q is a benzene ring, an olefin or (CH.sub.3)CH, as defined in claim 10.

### Claim 13 (depends on 10, 12)

A catalyst precursor of claim 12, which is of the formula I and in which X is P; R is a substituted aromatic ring, ##STR26## A--E being defined as in claim 10, and if Q is an olefin, it has the formula R'C=CR"(R',R"=H, CH.sub.3, or other alkyl).

### Claim 14 (depends on 10)

A catalyst precursor of claim 10;
(a) which is of the formula II, wherein R.sub.5, is phenyl or methyl R.sub.6-9 are phenyl and S.sup.* is S, Se or NR, where R is a substituted aromatic ring ##STR27## A--E being defined in claim 10, or (b) which is of the formula III, wherein R.sub.10-12 are selected from hydrogen, phenyl or substituted phenyl.

### Claim 15 (depends on 10)

A catalyst precursor as claimed in claim 10, which is of the general formula II or III.

### Claim 16

A phosphorus-nitrogen chelating ligand having the general formula ##STR28## wherein R.sub.1-4, R.sub.6-12 are same or different substituted or unsubstituted aryl groups
Q is selected from a benzene ring connected to P and X in the o-positions, an olefin connected to P and X across the double bond, or (CH.sub.3)CH
X is P or As
R is a substituted aromatic ring ##STR29## where A, B, C or D are selected for F, H, NO.sub.2, CN and alkyl and E is endocyclic nitrogen, a C--NO.sub.2 group of a C--CN group, or isomers thereof, or R=SiMe.sub.3 or TiCl.sub.2 Cp, where Me is methyl, Cp is cyclopentadienyl, or P(O)(OPh).sub.2, where Ph is a phenyl ring,
R.sub.5 is aryl or alkyl, and
S.sup.* is S, Se, O or N--R, R being as defined hereinabove.

### Claim 17 (depends on 16)

A ligand as claimed in claim 16, which is of the general formula II or III.

### Claim 18

A ligand having the general formulae: ##STR30##

### Claim 19 (depends on 18)

A ligand as claimed in claim 18, which is of the general formula IIa-IIc or IIIa-IIIc.