# US 2019/0375703 A1 · Process for the preparation of levulinate esters

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- Number: US 2019/0375703 A1
- Document ID: US20190375703A1
- Status: Published application
- Kind: A1
- Application number: 16/472,716
- Filed: 2017-06-30
- Published: 2019-12-12
- Earliest claimed: 2016-12-21
- Assignees: Le Centre National De La Recherche Scientifique; Universite De Poitiers
- Applicants: Le Centre National De La Recherche Scientifique; Universite De Poitiers
- Inventors: Alban CHAPPAZ; Francois JEROME; Karine DE OLIVEIRA VIGIER; Eric MULLER; Jonathan LAI; Matthieu CORBET; Didier MORVAN
- Web page: https://patentgrep.com/patent/US20190375703A1

## CPC

- C07C 67/00: Preparation of carboxylic acid esters
- C07C 67/29: by introduction of oxygen-containing functional groups
- B01J 31/2256: {being perfluorinated, i.e. comprising at least one perfluorinated moiety as substructure in case of polyfunctional ligands}
- C07C 69/716: Esters of keto-carboxylic acids {or aldehydo-carboxylic acids}
- B01J 2231/49: Esterification or transesterification
- B01J 2531/31: Aluminium
- B01J 2531/32: Gallium
- B01J 2531/42: Tin
- B01J 2531/54: Bismuth
- B01J 2531/842: Iron
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS

## Abstract

A process for synthesizing at least one levulinate ester, said process comprising the reaction of furfuryl alcohol with at least one other alcohol in the presence of water and at least one catalyst, said furfuryl alcohol being present in a quantity of at least 5% by weight, based on the total weight of the alcohols, and said catalyst comprising at least one triflate ligand and at least one metal selected from bismuth, gallium, aluminum, tin and iron.

## Claims

### Claim 1

A process for synthesizing at least one levulinate ester, said process comprising the reaction of furfuryl alcohol with at least one other alcohol in the presence of water and at least one catalyst, said furfuryl alcohol being present in a quantity of a least 5% by weight, based on the total weight of the alcohols, and said catalyst comprising at least one triflate ligand and at least one metal selected from bismuth, gallium, aluminum, tin and iron.

### Claim 2 (depends on 1)

The process according to claim 1, wherein the metal of the catalyst is selected from bismuth and gallium.

### Claim 3 (depends on 1)

The process according to claim 1, wherein the catalyst is selected from SnX1X2X3(OTf) and MX1X2(OTf).xH20 wherein:
M represents a metal selected from Bi, Ga and Al,
X1, X2, and X3 represent independently to each other a ligand, selected from triflate, halogen, alkoxy, sulfate, nitrate, carboxylate, —N(SO2CF3)2, alkyl, aryl, metal ligands;
OTf represents a triflate; and
x ranges from 0 to 10.

### Claim 4 (depends on 1)

The process according to claim 1, wherein the catalyst is selected from Bi(OTf)3 and BiCl2OTf.

### Claim 5 (depends on 1)

The process according to claim 1, wherein the catalyst is in an anhydrous form.

### Claim 6 (depends on 1)

The process according to claim 1, wherein furfuryl alcohol is present in a quantity ranging from 5 to 50% by weight, based on the total weight of the alcohols.

### Claim 7 (depends on 1)

The process according to claim 1, wherein the furfuryl alcohol is obtained from the reduction of furfural.

### Claim 8 (depends on 7)

The process according to claim 7, wherein said process is performed in two steps, the first step being the reduction of furfural into furfuryl alcohol and the second step comprising the addition of the other alcohol for the reaction between furfuryl alcohol and the other alcohol.

### Claim 9 (depends on 1)

The process according to claim 1, wherein the catalyst is present in an amount ranging from 0.05 to 20% mol, relative to the molar amount of furfuryl alcohol.

### Claim 10 (depends on 1)

The process according to claim 1, wherein the molar ratio water/metal of the catalyst ranges from 0.1 to 20.

### Claim 11 (depends on 1)

The process according to claim 1, wherein the other alcohol is selected from alcohols of formula ROH wherein R is selected from linear, branched, cyclic, saturated or unsaturated hydrocarbyl radicals.

### Claim 12 (depends on 11)

The process according to claim 11, wherein R comprises from 1 to 30 carbon atoms.

### Claim 13 (depends on 1)

The process according to claim 1, wherein the other alcohol is in the form of a solution comprising only one alcohol or at least two different alcohols.

### Claim 14 (depends on 1)

The process according to claim 1, comprising the following steps:
a) providing a reaction mixture comprising all or part of the catalyst, all or part of the water, and all or part of the other alcohol,
b) introducing all or part of the furfuryl alcohol and optionally the remaining part of the other alcohol into the reaction mixture in order to synthesize the levulinate esters,
c) recovering the levulinate esters.

### Claim 15 (depends on 14)

The process according to claim 14, further comprising a step of heating the reaction mixture obtained at the end of step a) to a temperature ranging from 80° C. to 200° C.