EP4680600A1

EP4680600A1 - Method for producing tetrahydrofuran-2-carboxylic acid

Info

Publication number: EP4680600A1
Application number: EP23926799.0A
Authority: EP
Inventors: Wenjuan ZHOU; Olivier BACK; Stephane Streiff
Original assignee: Specialty Operations France SAS
Current assignee: Specialty Operations France SAS
Priority date: 2023-03-16
Filing date: 2023-03-16
Publication date: 2026-01-21
Also published as: WO2024187444A1; CN120897910A

Abstract

Provided is a method for producing tetrahydrofuran-2-carboxylic acid by an oxidation reaction of tetrahydrofurfuryl alcohol with a peroxide in a liquid phase in the presence of a supported Pt-Bi catalyst.

Description

METHOD FOR PRODUCING TETRAHYDROFURAN-2-CARBOXYLIC ACID

TECHNICAL FIELD

The present invention relates to a method for producing tetrahydrofuran-2-carboxylic acid by an oxidation reaction of tetrahydrofurfuryl alcohol with a peroxide.

BACKGROUND

The following discussion of the prior art is provided to place the invention in an appropriate technical context and enable the advantages of it to be more fully understood. It should be appreciated, however, that any discussion of the prior art throughout the specification should not be considered as an express or implied admission that such prior art is widely known or forms part of common general knowledge in the field.
Utilization of biomass as source of chemicals has received much attention because of the depletion of fossil resources and global warming issue. Furanic compounds are very important because they can be synthesized from inedible lignocellulosic biomass and can be converted into various compounds. For example, tetrahydrofurfuryl alcohol can be obtained directly from furfural, which are industrially manufactured from pentoses.
Tetrahydrofuran-2-carboxylic acid is a useful pharmaceutical intermediate relevant to the production of several drugs and can also be transferred to monomers, solvents and surfactants. It has been reported that tetrahydrofuran-2-carboxylic acid can be obtained from tetrahydrofurfuryl alcohol. For instance, EP 0611762 A1 teaches tetrahydrofuran-2-carboxylic acid can be produced by reacting tetrahydrofurfuryl alcohol with oxygen in the presence of water and a Pt/C catalyst. Disadvantageously, pure oxygen is preferred and more importantly a stoichiometric amount of a base is added during the process resulting to the carboxylate salt. This is disadvantageous in sustainability and costs point of views as a stoichiometric amount of salt is produced in order to convert the carboxylate salt back to the desired carboxylic acid. In Example 7, when a mixture of oxygen with nitrogen gas is used, the yield is only about 73%.
WO 2016/026132 discloses a process of oxidizing an alcohol, wherein the oxidation is performed in a liquid phase using a peroxide as oxidant and in the presence of a base compound and a noble metal catalyst. Again, the process is not environmental-friendly since a salt must be formed in order to convert the carboxylate salt to the desired carboxylic acid. No mention is made of tetrahydrofurfuryl alcohol/tetrahydrofuran-2-carboxylic acid in this document.
As such, there remains a need for an improved method for producing tetrahydrofuran-2-carboxylic acid.

SUMMARY OF THE INVENTION

The aim of the present invention is then to provide a method for producing tetrahydrofuran-2-carboxylic acid, which features high selectivity and/or conversion and can be performed in an environmental-friendly system.
The present invention is directed to a method for producing tetrahydrofuran-2-carboxylic acid by an oxidation reaction of tetrahydrofurfuryl alcohol with a peroxide in a liquid phase in the presence of a supported Pt-Bi catalyst.
The Applicant has namely found that the combined use of a peroxide and a supported Pt-Bi catalyst allows working without the addition of a base, namely at a pH value of the liquid phase at the beginning of the oxidation reaction, which is below 9.
With the method according to the present invention, it is possible to achieve high conversion of tetrahydrofurfuryl alcohol and/or high selectivity towards tetrahydrofuran-2-carboxylic acid.
In some preferred embodiments, the base compound is present in trace amount or even not present in the liquid phase. Thus, this method is more simple and environmental-friendly.
The present invention also provides a composition comprising:
(i) tetrahydrofurfuryl alcohol,
(ii) a peroxide,
(iii) a supported Pt-Bi catalyst, and
(iv) optionally a solvent,
Other subjects and characteristics, aspects and advantages of the present invention will emerge even more clearly on reading the detailed description and the examples that follow.
DEFINITIONS
Throughout the description, including the claims, the term "comprising one" should be understood as being synonymous with the term "comprising at least one" , unless otherwise specified, and "between" should be understood as being inclusive of the limits.
As used herein, the terminology " (C_n-C_m) " in reference to an organic group, wherein n and m are both integers, indicates that the group may contain from n carbon atoms to m carbon atoms per group.
The articles “a” , “an” and “the” are used to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article.
The term “and/or” includes the meanings “and” , “or” and also all the other possible combinations of the elements connected to this term.
It is specified that, in the continuation of the description, unless otherwise indicated, the values at the limits are included in the ranges of values which are given.
Ratios, concentrations, amounts, and other numerical data may be presented herein in a range format. It is to be understood that such a range format is used merely for convenience and brevity and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also all the individual numerical values or sub-ranges encompassed within that range as if each numerical value or sub-range is explicitly recited.
DETAILS OF THE INVENTION
The present invention provides a method for producing tetrahydrofuran-2-carboxylic acid by an oxidation reaction of tetrahydrofurfuryl alcohol with a peroxide in a liquid phase in the presence of a supported Pt-Bi catalyst.
The source of tetrahydrofurfurfuryl alcohol is not particularly limited. Preferably, tetrahydrofurfurfuryl alcohol is produced from furfural, which is obtained directly from bio-based materials.
The peroxide used in the process of the present invention is not particularly limited, and may be selected from a group consisting of: hydroperoxides, such as hydrogen peroxide, tert-butyl hydroperoxide, and cumene hydroperoxide; peracids, such as performic acid, peracetic acid, peroxybenzoic acid, meta-chloroperoxybenzoic acid; diacyl peroxides, such as benzoyl peroxide, lauroyl peroxide, and the like; ketone peroxides, such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, and the like; and inorganic peroxides such as peroxodisulfate salts (S₂O₈M_n where M is an alkali (in that case n=2) or an alkaline earth metal (in that case n=1) ) or perborate salts such as for example sodium or potassium perborate. Particular preference is given to hydrogen peroxide and tert-butyl hydroperoxide, of which hydrogen peroxide is further preferred.
As hydrogen peroxide, hydrogen peroxide aqueous solution may be used. Typically, the concentration of the hydrogen peroxide solution used is 5 to 60wt%, preferably 8 to 45 wt%and more preferably 30 to 40 wt%.
The upper amount of peroxide in the method of the invention is not particularly limited. A typical amount of peroxide is 0.1 mol to 15 mol equivalent, preferably 0.5 mol to 10 mol equivalent, more preferably 2 mol to 8 mol equivalent of tetrahydrofurfuryl alcohol.
The pH value of the liquid phase at the beginning of the oxidation reaction determined from pH meter is preferably below 9. The pH value is preferably set between 6 and 8 and more preferably between 6.2 and 7.5. The pH value can be equal for example to 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, or any range between these values. In a particular embodiment, the pH value is between 6.5 and 7.0.
In some embodiments, a base may be present in trace amount in the liquid phase. Said trace amount is an amount that the molar ratio of the base to tetrahydrofurfuryl alcohol is less than 0.01: 1, preferably less than 0.005: 1, more preferably less than 0.001: 1, most preferably less than 0.0005: 1.
The term “base” is used to refer to one or more than one base, which can promote the oxidation reaction of tetrahydrofurfuryl alcohol with the peroxide. Non-limiting examples of base are inorganic bases, such as alkali metal hydroxides and alkali earth metal hydroxides. The base is particularly sodium hydroxide or potassium hydroxide.
In some embodiments, the base is completely not present in the liquid phase.
Advantageously, the molar ratio of the peroxide to tetrahydrofurfuryl alcohol is from 3: 1 to 9: 1, perferably from 4: 1 to 8: 1, more perferably 5: 1 to 7: 1.
The support to Pt-Bi is not particularly limited. It can be a metal oxide selected from the group consisting of aluminum oxide (Al₂O₃) , silicon dioxide (SiO₂) , titanium oxide (TiO₂) , zirconium dioxide (ZrO₂) , calcium oxide (CaO) , magnesium oxide (MgO) , lanthanum oxide (La₂O₃) , niobium dioxide (NbO₂) , cerium oxide (CeO₂) and mixtures thereof.
The support can also be a zeolite. Zeolites are substances having a crystalline structure and a unique ability to change ions. People skilled in the art can easily understand how to obtain those zeolites by preparation method reported, such as zeolite L is described in US 4503023 or commercial purchase, such as ZSM available from ZEOLYST.
The support can even be Kieselguhr, clay or carbon.
Preferably, the support is carbon.
The loading of Pt ranges from 1 to 10 wt. %and preferably from 3 to 5 wt. %, based on total weight of the supported Pt-Bi catalyst.
The weight ratio of Bi to Pt in the supported catalyst preferably ranges from 0.03: 1 to 1: 1 and more preferably from 0.2: 1 to 0.3: 1.
The molar ratio of tetrahydrofurfuryl alcohol to Pt is from 50: 1 to 1000: 1, preferably from 60: 1 to 800: 1 and more preferably from 70: 1 to 400: 1.
The supported Pt-Bi can be commercially available or home-made. Examples of commercially available supported Pt-Bi are from Johnson Matthey.
The method of the invention can be optionally carried out in a solvent. The solvent is not particularly limited as long as its presence does not prevent the oxidation reaction of tetrahydrofurfuryl alcohol with the peroxide or interact with at least one of the reactants. Excellent result is obtained when the reaction is carried out in water.
Said liquid phase may consist of the reactant (s) and the optional solvent.
According to the method of the present invention, the reaction temperature generally depends on the reaction conditions, such as the reactant (s) and the solvent. For example, when water and hydrogen peroxide are used, the reaction temperature can be lower than 110 ℃, preferably lower than 100 ℃, more preferably lower than 90 ℃ and most preferably lower than 80 ℃. Advantageously, the reaction temperature can be from 30℃ to 80℃ and preferably from of 40℃ to 70℃.
According to the method of the present invention, the reaction time is not particularly limited and generally depends on the temperature, the catalyst loading, the reactants concentration and the nature of the reactants. The preferred reaction time can be from 2 to 20 hours, preferably from 3 to 15 hours and more preferably from 4 to 10 hours.
The method of the present invention may comprise following steps:
a) preparing a mixture (M1) comprising tetrahydrofurfuryl alcohol, the supported Pt-Bi catalyst and optionally the solvent,
b) heating M1 to a proper temperature,
c) adding the peroxide to M1 to form a mixture (M2) , and
d) reacting tetrahydrofurfuryl alcohol and the peroxide in M2 to produce tetrahydrofuran-2-carboxylic acid.
The proper temperature in step b) is preferably same as the reaction temperature above defined.
Advantageously, the exothemy of the oxidation reaction is controlled when adding the peroxide in step c) . For example, the skilled person will set the proper flow rate of hydrogen peroxide based on specific reaction conditions to avoid the accumulation of peroxide in M2 and to limit its unproductive decomposition to oxygen.
Good results can be obtained if M1 is placed to a preheated reactor in step b) . For example, the reactor can be preheated by an oil bath to the proper temperature above defined.
An aspect of the present invention also provides a composition comprising:
(i) tetrahydrofurfuryl alcohol,
(i) a peroxide,
(ii) a supported Pt-Bi catalyst, and
(iii) optionally a solvent.
It can be understood by the skilled person that the composition is used for producing tetrahydrofuran-2-carboxylic acid. At the beginning of the oxidation reaction of tetrahydrofurfuryl alcohol with the peroxide, the composition preferably comprises a liquid phase having a pH value below 9. The pH value is preferably set between 6 and 8 and more preferably between 6.2 and 7.5. The pH value can be equal for example to 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, or any range between these values. In a particular embodiment, the pH value is between 6.5 and 7.0.
In some embodiments, the composition comprises a liquid phase in which a base is present in trace amount. Said trace amount is an amount that the molar ratio of the base to tetrahydrofurfuryl alcohol is less than 0.01: 1, preferably less than 0.005: 1, more preferably less than 0.001: 1, most preferably less than 0.0005: 1.
In some embodiments, the base is completely not present in the liquid phase.
Tetrahydrofurfuryl alcohol, the peroxide, the supported Pt-Bi catalyst and the solvent have the same meaning above defined.
The composition may further comprise tetrahydrofuran-2-carboxylic acid.
The following examples are included to illustrate embodiments of the invention. Needless to say, the invention is not limited to describe examples.
EXPERIMENTAL PART
Materials
- Tetrahydrofurfuryl alcohol (CAS Number: 97-99-4) , Merck;
- Hydrogen peroxide (H₂O₂, 30.0%, CAS number: 7722-84-1) , Sinopharm;
- H₂O, deionized water;
- 5%Pt-1.5%Bi/C, 5%Pt-1.0%Bi/C, Johnson Matthey.
Example 1: Preparation of tetrahydrofuran-2-carboxylic acid (THF COOH) by reacting tetrahydrofurfuryl alcohol (THFA) with hydrogen peroxide without using a base compound
0.7827 g of THFA and 15 ml of water with an initial pH value at 6.8 were mixed with 0.5781 g of 5%Pt-1.5%Bi/C (Johnson Matthey, moisture 52.5 wt. %) catalyst in a three-necked flask equipped with a magnetic stirrer, a cooling condenser and a double-rowed pipe, respectively. The mixture was heated to 60℃ for 5 min and then 5.1556 g of H₂O₂ (30 wt. %) was pumped into the mixed solution during 4 hours. The reaction was carried out for 4 hours further. After the reaction, the liquid was analyzed by NMR.
Example 2: Preparation of tetrahydrofuran-2-carboxylic acid (THF COOH) by reacting tetrahydrofurfuryl alcohol (THFA) with hydrogen peroxide in the presence of a base compound
0.7820 g of THFA and 15 ml of water with an initial pH value of 11.5 were mixed with 0.3065 g of NaOH and 0.5783 g of 5%Pt-1.5%Bi/C (Johnson Matthey, moisture 52.5 wt. %) catalyst in a three-necked flask equipped with a magnetic stirrer, a cooling condenser and a double-rowed pipe, respectively. The mixture was heated to 60℃ for 5 min and then 5.1562 g of H₂O₂ (30 wt. %) was pumped into the mixed solution during 4 hours. The reaction was carried out for 4 hours further. After the reaction, the liquid was analyzed by NMR.
Example 3: Preparation of tetrahydrofuran-2-carboxylic acid (THF COOH) by reacting tetrahydrofurfuryl alcohol (THFA) with hydrogen peroxide without using a base compound
0.7827 g of THFA and 15 ml of water with an initial pH value at 6.8 were mixed with 0.5354 g of 5%Pt-1.0%Bi/C (Johnson Matthey, moisture 55.1 wt. %) catalyst in a three-necked flask equipped with a magnetic stirrer, a cooling condenser and a double-rowed pipe, respectively. The mixture was heated to 60℃ for 5 min and then 5.1556 g of H₂O₂ (30 wt. %) was pumped into the mixed solution during 4 hours. The reaction was carried out for 4 hours further. After the reaction, the liquid was analyzed by NMR.
Table 1
Conditions: 5%Pt-1.5%Bi/C or 5%Pt-1.0%Bi/C, 7.5 mmol reactant in 15 ml of H₂O, THFA: metal molar ratio 80: 1, 60℃, H₂O₂ flow rate 0.02 ml/min.
As shown in Table 1, same yields were obtained when tetrahydrofurfuryl alcohol was oxidized by hydrogen peroxide in the presence or in the absence of a base compound.

Claims

A method for producing tetrahydrofuran-2-carboxylic acid by an oxidation reaction of tetrahydrofurfuryl alcohol with a peroxide in a liquid phase in the presence of a supported Pt-Bi catalyst.
The method of claim 1, wherein the pH value of the liquid phase at the beginning of the oxidation reaction is below 9.
The method according to claim 2, wherein the pH value of the liquid phase at the beginning of the oxidation reaction is set between 6 and 8 and preferably between 6.2 and 7.5.
The method according to any one of the preceding claims, wherein the pH value of the liquid phase at the beginning of the oxidation reaction is set between 6.5 and 7.0.
The method according to any one of the preceding claims, wherein the oxidation reaction is carried out in water.
The method according to any one of the preceding claims, wherein the support of the supported Pt-Bi catalyst is selected from the group consisting of metal oxide, zeolite, Kieselguhr, clay and carbon and preferably carbon.
The method according to any one of the preceding claims, wherein the loading of Pt ranges from 1 to 10 wt. %based on total weight of catalyst and preferably from 3 to 5 wt. %.
The method according to any one of the preceding claims, wherein the weight ratio of Bi to Pt in the supported catalyst preferably ranges from 0.03: 1 to 1: 1 and more preferably from 0.2: 1 to 0.3: 1.
The method according to any one of the preceding claims, wherein the peroxide is selected from a group consisting of: hydroperoxides, such as hydrogen peroxide, tert-butyl hydroperoxide, and cumene hydroperoxide; peracids, such as performic acid, peracetic acid, peroxybenzoic acid, meta-chloroperoxybenzoic acid; diacyl peroxides, such as benzoyl peroxide, lauroyl peroxide, and the like; ketone peroxides, such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, and inorganic peroxides such as peroxodisulfate salts (S₂O₈M_n where M is an alkali (in that case n=2) or an alkaline earth metal (in that case n=1) ) or perborate salts such as for example sodium or potassium perborate, preferably hydrogen peroxide and tert-butyl hydroperoxide, and more preferably hydrogen peroxide.
The method according to any one of the preceding claims, wherein the amount of the peroxide is 0.1 mol to 15 mol equivalent, preferably 0.5 mol to 10 mol equivalent, more preferably 2 mol to 8 mol equivalent of tetrahydrofurfuryl alcohol.
The method according to any one of the preceding claims, wherein a base is present in trace amount in the liquid phase, said trace amount is an amount that the molar ratio of the base to tetrahydrofurfuryl alcohol is less than 0.01: 1, preferably less than 0.005: 1, more preferably less than 0.001: 1, most preferably less than 0.0005: 1.
The method according to any one of the preceding claims, wherein the base is completely not present in the liquid phase.
The method according to any one of the preceding claims, comprising the following steps:

a) preparing a mixture (M1) comprising tetrahydrofurfuryl alcohol, the supported Pt-Bi catalyst and optionally the solvent,

b) heating M1 to a proper temperature,

c) adding the peroxide to M1 to form a mixture (M2) , and

d) reacting tetrahydrofurfuryl alcohol and the peroxide in M2 to produce tetrahydrofuran-2-carboxylic acid.
A composition comprising:

(i) tetrahydrofurfuryl alcohol,

(ii) a peroxide,

(iii) a supported Pt-Bi catalyst, and

(iv) optionally a solvent.
The composition according to claim 14, wherein the composition further comprises tetrahydrofuran-2-carboxylic acid.