# US 2008/0188686 A1 · Carbonylation Method by Adding Secondary Sterically Hindered Amines

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- Number: US 2008/0188686 A1
- Document ID: US20080188686A1
- Status: Published application
- Kind: A1
- Application number: 12/065,091
- Filed: 2006-06-02
- Published: 2008-08-07
- Earliest claimed: 2005-09-07
- Assignees: Oxeno Olefinchemie GmbH
- Inventors: Dieter Hess; Dagmara Ortmann; Oliver Moeller; Klaus-Diether Wiese; Dirk Fridag; Wilfried Buschken
- Web page: https://patentgrep.com/patent/US20080188686A1

## CPC

- C07C 45/50: by oxo-reactions
- B01J 31/0237: {Amines}
- B01J 31/0247: {Imides, amides or imidates (R-C=NR(OR))}
- 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}
- C07F 9/65744: {condensed with carbocyclic or heterocyclic rings or ring systems}
- B01J 2231/321: Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)

## Abstract

The invention relates to a process for reaction of a carbonylatable compound using a metal complex catalyst comprising a metal of transition group VIII and an organophosphorus ligand and in the presence of a stabilizer based on a sterically hindered secondary amine.

## Claims

### Claim 1

A carbonylation process in which at least one compound which is capable of being carbonylated by a carbon monoxide is reacted with the carbon monoxide in the presence of a metal complex catalyst of a metal of transition group VIII of the Periodic Table of the Elements which has an organophosphorus compound as ligand, wherein the carbonylation is carried out in the presence of a sterically hindered secondary amine having the general structural formula I
where Ra, Rb, Rc, Rd, Re and Rf are identical or different hydrocarbon radicals which may be joined to one another.

### Claim 2 (depends on 1)

The process as claimed in claim 1, wherein an amine having a 2,2,6,6-tetramethylpiperidine unit II
is used as secondary amine.

### Claim 3 (depends on 1)

The process as claimed in claim 1, wherein at least one of the compounds of the structural formulae IIb to IIg
where n=1 to 20
where n=1 to 12
where n=1 to 17
is used as secondary amine.

### Claim 4 (depends on 1)

The process as claimed in claim 1, wherein at least one compound having two or more of the functional groups of the formulae III to VI or at least one compound of one of the formulae III to VI
PR2R3R4 III
PR2R3(TR5) IV
PR2(TR5)(TR6) V
P(TR5)(TR6)(TR7) VI
where T=O, NH or NR8 and R2 to R8 are identical or different organic radicals which have from 1 to 50 carbon atoms and may be joined to one another via a covalent bond, is used as organophosphorus ligand.

### Claim 5 (depends on 4)

The process as claimed in claim 4, wherein at least one compound of the formula VIIc-9, VIIc-10 or VIIc-11
where X and Y are substituted or unsubstituted, aliphatic, alicyclic, aliphatic-alicyclic, heterocyclic, aliphatic-heterocyclic, aromatic-aromatic or aliphatic-aromatic hydrocarbon radicals having from 1 to 50 carbon atoms, with X and Y being identical or different or being covalently bound to one another, and Q is an at least divalent, substituted or unsubstituted aliphatic, alicyclic, aliphatic-alicyclic, heterocyclic, aliphatic-heterocyclic, aromatic, aromatic-aromatic or aliphatic-aromatic hydrocarbon radical preferably having from 1 to 50 carbon atoms, with substituted hydrocarbon radicals having substituents selected from among —N(R20)2, —NHR20, —NH2, fluorine, chlorine, bromine, iodine, —OH, —CN, —C(O)—R20, —C(O)H or —C(O)O—R20, —CF3, —O—R20, —C(O)N—R20, —OC(O)—R20 and/or —Si(R20)3, where R20 is a monovalent hydrocarbon radical which preferably has from 1 to 20 carbon atoms and if a plurality of hydrocarbon radicals R20 are present, these can be identical or different, and R16 to R19 are selected independently from among monovalent substituted or unsubstituted aliphatic, alicyclic, aromatic, heteroaromatic, mixed aliphatic-alicyclic, mixed aliphatic-aromatic, heterocyclic, mixed aliphatic-heterocyclic hydrocarbon radicals having 1 to 50 carbon atoms, H, F, Cl, Br, I, —CF3, —CH2(CF2)jCF3 where j=0-9, —OR21, —COR21, —CO2R21, —CO2M, —SR21, —SO2R21, —SOR21, —SO3R21, —SO3M, —SO2NR21R22, —NR21R22, —N═CR21R22, where R21 and R22 are selected independently from among H, monovalent substituted or unsubstituted aliphatic and aromatic hydrocarbon radicals having from 1 to 25 carbon atoms and M is an alkali metal ion, formally half an alkaline earth metal, ammonium or phosphonium ion, or adjacent radicals R16 to R19 together form a fused substituted or unsubstituted aromatic, heteroaromatic, aliphatic, mixed aromatic-aliphatic or mixed heteroaromatic-aliphatic ring system; with substituted hydrocarbon radicals having substituents selected from among —N(R23)2, —NHR23, —NH2, fluorine, chlorine, bromine, iodine, —OH, —CN, —C(O)—R23, —C(O)H or —C(O)O—R23, —CF3, —O—R23, —C(O)N—R23, —OC(O)—R23 and/or —Si(R23)3, where R18 is a monovalent hydrocarbon radical which preferably has from 1 to 20 carbon atoms and when a plurality of hydrocarbon radicals R23 are present, these can be identical or different, and the radicals R16, R17, R18 and R19 are identical or different, is used as organophosphorus ligand.

### Claim 6 (depends on 4)

The process as claimed in claim 4, wherein a compound of the formula VIIb-1 or VIIb-2
where k=2 and R16, R17, R18, and R19 having the meanings given for the formulae VIIc-9 to VIIc-11, Q is a divalent substituted or unsubstituted aliphatic, alicyclic, mixed aliphatic-alicyclic, heterocyclic, mixed aliphatic-heterocyclic, aromatic, heteroaromatic, mixed aliphatic-aromatic hydrocarbon radical having from 1 to 50 carbon atoms, with aliphatic parts of Q being able to contain oxygen, sulfur and/or nitrogen and substituted hydrocarbon radicals Q being able to have substituents having the same meanings as R16 to R19, is used as organophosphorus ligand.

### Claim 7 (depends on 1)

The process as claimed in claim 1, wherein the organophosphorus ligand is used in a molar ratio to the metal at which the organophosphorus ligand is also present as free ligand in the reaction mixture.

### Claim 8 (depends on 1)

The process as claimed in claim 1, wherein at least one olefinically unsaturated compound selected from the group consisting of substituted or unsubstituted alpha-olefins, internal olefins, cycloolefins, alkenyl alkyl ethers and alkenols is used as starting compound to be carbonylated.

### Claim 9 (depends on 1)

The process as claimed in claim 1, wherein at least one compound selected from the group consisting of among hydrogen, water, amine and alcohol is used as further reactant in addition to the carbon monoxide and the starting compound to be carbonylated.

### Claim 10 (depends on 1)

The process as claimed in claim 1, wherein at least hydrogen is used as further reactant in addition to the carbon monoxide and the starting compound to be carbonylated and a hydroformylation is carried out.

### Claim 11 (depends on 1)

The process as claimed in claim 1, wherein cobalt or rhodium is used as the metal of transition group VIII of the Periodic Table.

### Claim 12 (depends on 1)

The process as claimed in claim 1, wherein the sterically hindered secondary amine is used in a molar ratio to the catalyst metal of from 0.1:1 to 100:1 in the reaction mixture.

### Claim 13

A mixture comprising a metal complex catalyst of a metal of transition group VIII of the Periodic Table of the Elements which has an organophosphorus compound as a ligand and a sterically hindered secondary amine having the formula I,
where Ra, Rb, Rc, Rd, Re and Rf are identical or different hydrocarbon radicals which may be joined to one another.

### Claim 14 (depends on 13)

The mixture as claimed in claim 13, wherein an amine having a 2,2,6,6-tetramethylpiperidine unit II
is present as secondary amine.

### Claim 15 (depends on 13)

The mixture as claimed in claim 13, wherein at least one compound selected from among the compounds of the formulae IIb to IIg
where n=1 to 20
where n=1 to 12
where n=1 to 17
is present as secondary amine.

### Claim 16 (depends on 13)

The mixture as claimed in claim 13, comprising at least one compound having two or more of the functional groups of the formulae III to VI or at least one compound of one of the formulae III to VI
PR2R3R4 III
PR2R3(TR5) IV
PR2(TR5)(TR6) V
P(TR5)(TR6)(TR7) VI
where T=O, NH or NR8 and R2 to R8 are identical or different organic radicals which have from 1 to 50 carbon atoms and are optionally joined to one another via a covalent bond, as an organophosphorus ligand.

### Claim 17 (depends on 13)

The mixture as claimed in claim 13 which comprises at least one compound of the formula VIIc-9, VIIe-10 or VIIc-11
where X and Y are substituted or unsubstituted, aliphatic, alicyclic, aliphatic-alicyclic, heterocyclic, aliphatic-heterocyclic, aromatic-aromatic or aliphatic-aromatic hydrocarbon radicals having from 1 to 50 carbon atoms, with X and Y being identical or different or being covalently bound to one another, and Q is an at least divalent, substituted or unsubstituted aliphatic, alicyclic, aliphatic-alicyclic, heterocyclic, aliphatic-heterocyclic, aromatic, aromatic-aromatic or aliphatic-aromatic hydrocarbon radical preferably having from 1 to 50 carbon atoms, with substituted hydrocarbon radicals having substituents selected from among —N(R10)2, —NHR20, —NH2, fluorine, chlorine, bromine, iodine, —OH, —CN, —C(O)—R10, —C(O)H or —C(O)O—R20, —CF3, —O—R20, —C(O)N—R20, —OC(O)—R20 and/or —Si(R20)3, where R20 is a monovalent hydrocarbon radical which preferably has from 1 to 20 carbon atoms and if a plurality of hydrocarbon radicals R20 are present, these can be identical or different, and R16 to R19 are selected independently from among monovalent substituted or unsubstituted aliphatic, alicyclic, aromatic, heteroaromatic, mixed aliphatic-alicyclic, mixed aliphatic-aromatic, heterocyclic, mixed aliphatic-heterocyclic hydrocarbon radicals having 1 to 50 carbon atoms, H, F, Cl, Br, I, —CF3, —CH2(CF2)jCF3 where j=0-9, —OR21, —COR21, —CO2R21, —CO2M, —SR21, —SO2R21, —SOR21, —SO3R21, —SO3M, —SO2NR21R22, —NR21R22, —N═CR21R22, where R21 and R22 are selected independently from among H, monovalent substituted or unsubstituted aliphatic and aromatic hydrocarbon radicals having from 1 to 25 carbon atoms and M is an alkali metal ion, formally half an alkaline earth metal, ammonium or phosphonium ion, or adjacent radicals R16 to R19 together form a fused substituted or unsubstituted aromatic, heteroaromatic, aliphatic, mixed aromatic-aliphatic or mixed heteroaromatic-aliphatic ring system; with substituted hydrocarbon radicals having substituents selected from among —N(R23)2, —NHR23, —NH2, fluorine, chlorine, bromine, iodine, —OH, —CN, —C(O)—R23, —C(O)H or —C(O)O—R23, —CF3, —O—R23, —C(O)N—R23, —OC(O)—R23 and/or —Si(R23)3, where R18 is a monovalent hydrocarbon radical which preferably has from 1 to 20 carbon atoms and when a plurality of hydrocarbon radicals R23 are present, these can be identical or different, and the radicals R16, R17, R18 and R19 are identical or different, as an organophosphorus ligand.

### Claim 18 (depends on 13)

The mixture as claimed in claim 13 which comprises a compound of the formula VIIb-1 or VIIb-2
where k=2 and R16, R17, R18, and R19 having the meanings given for the formulae VIIc-9 to VIIc-11, Q is a divalent substituted or unsubstituted aliphatic, alicyclic, mixed aliphatic-alicyclic, heterocyclic, mixed aliphatic-heterocyclic, aromatic, heteroaromatic, mixed aliphatic-aromatic hydrocarbon radical having from 1 to 50 carbon atoms, with aliphatic parts of Q being able to contain oxygen, sulfur and/or nitrogen and substituted hydrocarbon radicals Q being able to have substituents having the same meanings as R16 to R19, as an organophosphorus ligand.

### Claim 19 (depends on 13)

The mixture as claimed in claim 13, wherein the organophosphorus ligand is present in a molar ratio to the metal of from 0.1:1 to 100:1.

### Claim 20 (depends on 13)

The mixture as claimed in claim 13, wherein cobalt or rhodium is present as the metal of transition group VIII of the Periodic Table.

### Claim 21 (depends on 13)

The mixture as claimed in claim 13, wherein the stabilizer is present in a molar ratio to the catalyst metal of from 0.1:1 to 100:1.