# US 2023/0271920 A1 · Improved process to produce specific alpha,beta-unsaturated carboxylates

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- Number: US 2023/0271920 A1
- Document ID: US20230271920A1
- Status: Published application
- Kind: A1
- Application number: 18/010,403
- Filed: 2021-06-08
- Published: 2023-08-31
- Earliest claimed: 2020-06-19
- Assignees: Dsm IP Assets B.V.
- Applicants: Dsm IP Assets B.V.
- Inventors: Werner BONRATH; Estel CANET-MARTINEZ; Roman GOY; Ulrich HINTERMAIR; Jonathan Alan MEDLOCK; Asad SAIB
- Web page: https://patentgrep.com/patent/US20230271920A1

## CPC

- C07C 403/20: having side-chains substituted by carboxyl groups {or halides, anhydrides, or (thio)esters thereof}
- B01J 31/2208: {Oxygen, e.g. acetylacetonates}
- B01J 31/2226: {Anionic ligands, i.e. the overall ligand carries at least one formal negative charge}
- B01J 31/2239: {Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands}
- B01J 31/2409: {with more than one complexing phosphine-P atom}
- C07C 403/12: by esterified hydroxy groups
- C07F 15/0053: {without a metal-carbon linkage}
- B01J 2231/32: Addition reactions to C=C or C-C triple bonds
- B01J 2231/321: Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
- B01J 2531/0216: Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
- B01J 2531/821: Ruthenium
- C07C 2601/16: the ring being unsaturated
- 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 present invention relates to a process for producing specific α,β-unsaturated carboxylates.

## Claims

### Claim 1

Process for the production of a compound of formula (I)
wherein
R1 is a C1-C4-alkyl moiety, preferably —CH3 or —CH2CH3, and
R2 is
(the * is showing where the bond is localized), and wherein a compound of formula (II)
is reacted with a compound of formula (III)
wherein the R1 and R2 have the same meanings as defined above for the compound of formula (I) in the presence of at least one catalyst of formula (IV)
wherein
R3, R4, R5 and R6 signify independently from each other —CH3, —OCH3, —NO2 or halogen, and
W, X, Y and Z signify independently from each other a neutral or ionic ligand, wherein W, X, Y and Z can be monodentate or bidentate with the proviso that the Ru is always six times coordinated, and
m, n, o and p signify an integer 0, 1, 2 or 3
q signifies an integer 1, 2, 3 or 4.

### Claim 2 (depends on 1)

Process according to claim 1, wherein
R1 is —CH3 or —CH2CH3.

### Claim 3 (depends on 1)

Process according to claim 1, wherein R2 is

### Claim 4 (depends on 1)

Process according to claim 1, wherein the compounds of formula (Ia) and (Ib)
are produced.

### Claim 5 (depends on 1)

Process according to claim 1, wherein the catalyst of formula (IVa)
is used.

### Claim 6 (depends on 1)

Process according to claim 1,
wherein
the catalyst of formula (IVb)
is used.

### Claim 7 (depends on 1)

Process according to claim 1,
wherein
the catalyst of formula (IVc)
wherein R7 is H or CH3 is used.

### Claim 8 (depends on 1)

Process according to claim 1, wherein the substrate (starting material) to catalyst ratio (mol-based) is 5000:1 to 10:1.

### Claim 9 (depends on 1)

Process according to claim 1, wherein the process is carried out without any solvent.

### Claim 10 (depends on 1)

Process according to claim 1, wherein the process is carried out in at least one apolar aprotic organic solvent.

### Claim 11 (depends on 10)

Process according to claim 10, wherein the apolar aprotic organic solvent is chosen from the group consisting of aliphatic hydrocarbons, cyclic hydrocarbons aromatic hydrocarbons and carboxylate esters.

### Claim 12 (depends on 1)

Process according to claim 1, wherein the process is carried out at a temperature of between −5° C. and 60° C.

### Claim 13 (depends on 1)

Process according to claim 1, wherein the compound of formula (V)
is added to the reaction mixture.

### Claim 14 (depends on 13)

Process according to claim 13, wherein the compound of formula (V) is added in amount of 0.01-0.75 mol equivalent (in regard of compound of formula (II)).

### Claim 15

Compounds of formulae (IV′), (IV″) and (IV′″)
wherein
R3, R4, R5 and R6 signify independently from each other —CH3, —OCH3, —NO2 or halogen, and
W, X, Y and Z signify independently from each other a neutral or ionic ligand, wherein W, X, Y and Z can be monodentate or bidentate with the proviso that the Ru is always six times coordinated, and
m, n, o and p signify an integer 0, 1, 2 or 3
q signifies an integer 1, 2, 3 or 4.

### Claim 16

Compounds of formulae (IVa), (IVb), (IVc′) and (IVc″)