EP4013735A1

EP4013735A1 - Carbonyl compounds, methods for preparing same and uses thereof

Info

Publication number: EP4013735A1
Application number: EP20753966.9A
Authority: EP
Inventors: Serge Ratton; Marc Lemaire; Luc MATHIS; Estelle METAY
Original assignee: Global Bioenergies SA
Current assignee: Global Bioenergies SA
Priority date: 2019-08-16
Filing date: 2020-08-17
Publication date: 2022-06-22
Also published as: WO2021032673A1; US20220340512A1; FR3099930A1

Abstract

The present application relates to a compound of the following formula (I), in which: - R¹, R², R³ and R⁴ represent, independently of each other, H or a (Ci-C₃₀) alkyl group, the total sum of the number of carbon atoms of R¹, R², R³ and R⁴ being equal to 6+4x, x being a whole number between 1 and 6, provided that: - at most two of the groups R¹, R², R³ and R⁴ are H, - R⁵ represents H, OR, or NR'R" - R, R' and R", identical or different, represent H, a (C1-C10) alkyl group, at least one of the groups R¹, R², R³ or R⁴ comprises or is a tertiobutyl group. (I) the method for preparing same and the uses thereof as a plasticising lubricant, surfactant or in a cosmetic composition.

Description

CARBONYL COMPOUNDS, THEIR PREPARATION METHODS AND THEIR

USES

The present invention relates to new isomers of carbonyl branched alkanes, alone or in mixtures, as well as their preparation processes. It also relates to the use of said compounds alone or in mixtures.

Functionalized branched alkanes comprising a large number of carbon atoms, in particular 8 or more carbon atoms, have various applications. They can in particular be used as surfactants, emollients, solvents or monomers for the preparation of various polymers.

However, these compounds are generally derived from fossil resources, in particular petroleum. In addition to having a negative impact on the environment, the use of fossil resources, and in particular oil, results in alkanes with impurities such as aromatic compounds. In addition, to obtain higher alkanes, in particular with a number of carbon atoms at least equal to 16, it is necessary in particular to go through oligomerization reactions, these reactions leading to mixtures of olefins and then to mixtures. alkanes (after hydrogenation of the olefins) comprising n carbon atoms which exhibit impurities at n-4 and n + 4 carbon atoms when the olefins are accessed by oligomerization. Such impurities are not desired.

The aim of the present invention is to provide new carbonyl compounds which can in particular be used as plasticizers, lubricants, surfactants or for cosmetic applications, said compounds being biobased.

Thus, the present invention relates to a compound of formula (I) below: in which : - R ¹ , R ² , R ³ and R ⁴ represent, independently of each other, H or a (Ci-C3o) alkyl group, the total sum of the number of carbon atoms of R ¹ , R ² , R ³ and R ⁴ being equal to 6 + 4x, x being an integer from 1 to 6, provided that:

- two at most among the groups R ¹ , R ² , R ³ and R ⁴ are H,

- when one of the groups R ¹ or R ² is H or when the groups R ¹ and R ² are H, then the groups R ³ and R ⁴ are (Ci-C3o) alkyl groups, and

- when one of the groups R ³ or R ⁴ is H or when the groups R ³ and R ⁴ are H, then the groups R ¹ and R ² are (Ci-C3o) alkyl groups;

- R ⁵ represents H, OR, NR'R ”

- R, R ’and R”, identical or different, represent H, a (C1 - C10) alkyl group,

Preferably, the main chain comprises at least one tert-butyl group (at least one of the groups R ¹ , R ² , R ³ or R ⁴ comprises or is a tert-butyl group), preferably the tert-butyl group is a terminal group.

Preferably, the total sum of the number of carbon atoms of R ¹ , R ² , R ³ and R ⁴ being equal to 6 + 4x, x represents 1, 4 or 6 or x represents 2, 3, 4, 5, 6 and R ⁵ represents OR, NR'R ”.

Thus, the present invention relates to a compound of formula (I) below: in which :

- R ¹ , R ² , R ³ and R ⁴ represent, independently of each other, H or a (Ci-C3o) alkyl group, the total sum of the number of carbon atoms of R ¹ , R ² , R ³ and R ⁴ being equal to 6 + 4x, x being an integer from 1 to 6, provided that:

- two at most among the groups R ¹ , R ² , R ³ and R ⁴ are H,

- R ⁵ represents H, OR, NR'R ” - R, R 'and R ”, identical or different, represent H, a group (C1 -

C10) alkyl,

Preferably x is equal to 1.

The compounds of formula (I) correspond to isomers of carbonyl branched alkanes, depending on the nature of the above-mentioned ^{group R 5.}

These compounds comprise in total (not counting the group R ⁵ ) 8 + 4x carbon atoms, which corresponds to the total number of carbon atoms of the groups R ¹ , R ² , R ³ and R ⁴ and of the two carbon atoms carrying these groups (the whole is considered hereinafter as the branched hydrocarbon chain comprising 8 + 4x carbon atoms). The compounds of formula (I) according to the invention are therefore branched compounds whose main chain comprises 12, 16, 20, 24, 28 or 32 carbon atoms and carrying a COR ⁵ side chain as defined above. Preferably the number of carbon atoms is equal to 8 + 4x, x represents 1, 4 or 6 or x represents 2, 3, 4, 5, 6 and R ⁵ represents OR, NR'R ”.

Preferably, the main chain comprises at least one tert-butyl group (at least one of the groups R ¹ , R ² , R ³ or R ⁴ comprises a tert-butyl group or represents a tert-butyl group), preferably the tert-butyl group is a group terminal.

In the above-mentioned formula (I), according to one embodiment, one of the groups R ¹ , R ² , R ³ or R ⁴ contains a tert-butyl group. According to one embodiment, in formula (I), one of the groups R1, R2, R3 or R4 is a tert-butyl group.

According to one embodiment, in formula (I), one of the groups R ¹ , R ² , R ³ or R ⁴ contains a tert-butyl group and corresponds to the formula -AC (CH ₃ ) 3, A representing a radical alkylene comprising from 1 to 6 carbon atoms.

The term “alkylene” designates according to the invention a radical comprising from 1 to 6 carbon atoms, and preferably from 1 to 4 carbon atoms. An alkylene radical corresponds to an alkyl radical as defined here from which one atom has been removed. of hydrogen. In the context of the present invention, by C _t -C _z is meant a carbon chain which may have from t to z carbon atoms, for example C1-C3, a carbon chain which may have from 1 to 3 carbon atoms.

According to the invention, an alkyl group denotes a saturated, linear or branched aliphatic hydrocarbon group comprising, unless otherwise specified, from 1 to 30 carbon atoms. Mention may be made, by way of examples, of methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, tertbutyl or pentyl groups, or also undecenyl, lauryl, palmyl, oleyl, linoleyl, erucyl, terpenyl and ricinoleyl groups.

The present invention also relates to a mixture of branched carbonyl alkane isomers, each carbonyl branched alkane comprising a branched hydrocarbon chain and a side chain of formula COR ⁵ , R ⁵ being as defined above, said branched hydrocarbon chain of each branched carbonyl alkane comprising 8 + 4x carbon atoms, x being an integer ranging from 1 to 6. Preferably the number of carbon atoms is equal to 8 + 4x, x represents 1, 4 or 6 or x represents 2, 3, 4, 5, 6 and R5 represents OR, NR'R ”.

Preferably, the main chain comprises at least one ter-butyl group (at least one of the groups R1, R2, R3 or R4 comprises a ter-butyl group or represents a ter-butyl group), preferably the ter-butyl group is a terminal group.

According to one embodiment, the mixture of carbonyl branched alkane isomers according to the invention comprises at least two compounds of formula (I) as defined above.

According to one embodiment, the mixtures of the invention are such that all the compounds of formula (I) as defined above comprise a branched hydrocarbon chain comprising 8 + 4x carbon atoms, x being as defined above and being identical for all compounds of said mixture and comprising a side chain of formula COR ⁵ .

The present invention also relates to a process for preparing a compound as defined above, corresponding in particular to formula (I), or mixture as defined above, comprising a carbonylation step, in particular hydro-, hydroxy-, alkoxy-, amido-carbonylation, of at least one isomer of branched olefins or mixture of isomer of branched olefins, each olefin branched being formed of a hydrocarbon chain comprising 8 + 4x carbon atoms, x being as defined above.

The carbonylation step corresponds to a step of addition of a CO compound to which has been added H ₂ for the hydrocarbonylation, H ₂ 0 for the hydroxycarbonylation, R ⁵ -OH for the alkoxycarbonylation and R'R ”- NH for amidocarbonylation.

Preferably, the carbonylation step is carried out by organometallic catalysis, in particular using a catalyst based on Rh or Co, for example.

The carbonylation step is carried out at a temperature between 40 ° C and 150 ° C, preferably between 70 ° C and 120 ° C.

According to one embodiment of the process of the invention, the branched olefin isomers have the following formula (II): in which R ¹ , R ² , R ³ and R ⁴ are as defined above in formula (I).

As mentioned above, in formula (II):

- two at most among the groups R ¹ , R ² , R ³ and R ⁴ are H,

- When one of the groups R ³ and R ⁴ or H or when the groups R ³ and R ⁴ are H, then the groups R ¹ and R ² are (Ci-C3o) alkyl groups.

According to one embodiment of the process of the invention, the branched olefin isomers have the following formula (II): in which R ¹ , R ² , R ³ and R ⁴ are as defined above in formula (I). As mentioned above, in formula (II):

- at most two of the groups R ¹ , R ² , R ³ and R ⁴ are H, R ¹ , R ² , R ³ or R ⁴ comprises or is a tert-butyl group), preferably the tert-butyl group is a terminal group.

The process of the invention can use a branched olefin of formula (II) or a mixture of branched olefins of formula (II) comprising the same number of carbon atoms or a different number of carbon atoms, from preferably the same number of carbon atoms.

According to one embodiment of the process of the invention, the mixture of branched olefin isomers comprises at least two branched olefin isomers of formula (II).

The olefins of formula (II) therefore correspond to one of the following formulas: in which R'i, R'2, R ' ₃ and R'4 are (Ci-C ₃ o) alkyl groups. preferably According to one embodiment, the olefins of formula (II) may comprise two hydrogen atoms, one corresponding to the group R'i or R ' ₂ and the other to the group R' ₃ or R'4.

As mentioned above, the compounds of formula (II) are branched compounds comprising in total 8 + 4x carbon atoms with x ranging between 1 and 6. The compounds of formula (II) are therefore branched compounds whose main chain contains 12, 16, 20, 24, 28 or 32 carbon atoms. Preferably the number of carbon atoms is equal to 8 + 4x, x represents 1, 4 or 6 or x represents

2, 3, 4, 5, 6 and R ⁵ represents OR, NR'R ”.

The mixture of branched olefin isomers according to the invention is a mixture comprising at least two olefins of formula (II). Preferably, the mixtures of the invention are such that all the compounds of formula (II) as defined above comprise 8 + 4x carbon atoms, x being as defined above and being identical for all the compounds of said mixed. Preferably the number of carbon atoms is equal to 8 + 4x, x represents 1, 4 or 6 or x represents 2, 3, 4, 5, 6 and R ⁵ represents OR, NR'R ”.

The branched olefins or mixture of branched olefin isomers according to the invention, in particular when n represents 16, 24 or 32, can be obtained by dimerization of a mixture of branched olefin isomers comprising n / 2 carbon atoms . Thus, the branched olefins or the mixture of branched olefin isomers as defined above is obtained by dimerization of a mixture of branched olefin isomers comprising 4 + 2x carbon atoms, with x a defined even number. above, preferably obtained from bioresources. Thus, branched olefins comprising 16 carbon atoms can be obtained by dimerization of branched olefins comprising 8 carbon atoms. Branched olefins comprising 24 carbon atoms can be obtained by dimerization of branched olefins comprising 12 carbon atoms. Olefins branched comprising 32 carbon atoms can be obtained by dimerization of branched olefins comprising 16 carbon atoms.

The dimerization step can be carried out in the presence of a catalyst chosen from Bronsted acids in solution, for example H2SO4, H3PO4, HF; solid Bronsted acids, for example organic resins, clays, zeolites, H3PO4 on silica; Lewis acids, for example ZnCh, AICI3; organometallic compounds, for example Ni complexes, mixtures of Ni and Al complexes; ionic liquids, for example [BMIm] [N (CF ₃ S02) 2] / HN (CF ₃ SC> 2) 2; clays with lamellar structures such as Montmorillonite; organic resins such as Amberlysts, sulfonic resin; organometallic compounds such as for example [LNiCH ₂ FÎ ⁹ ] [AICl4] in which L = PR ¹⁰ , R ⁹ represents an alkyl, linear or branched, comprising 9 carbon atoms and R ¹⁰ represents a group - CH2-R ⁹ .

The dimerization step is preferably carried out at a temperature between 30 and 250 ° C.

Particularly advantageously, the branched olefins comprising 8 and 12 carbon atoms are obtained from isobutene. Preferably, said isobutene is obtained from bioresources, in particular as described in application WO2012052427, WO2017085167 and WO2018206262, for example from polysaccharides (sugars, starches, celluloses, etc.).

Particularly advantageously, the production of branched olefins by dimerization makes it possible to obtain branched olefins or a mixture of branched olefins free of n-4 and n + 4 olefins.

The branched olefins or mixture of branched olefin isomers according to the invention can also be obtained by co-dimerization of at least two mixtures of branched olefins comprising respectively m and p carbon atoms so as to have m + p = n.

Preferably, at least one of the starting olefins (olefin comprising m or p carbon atoms) comprises at least one tert-butyl (C (CH ₃ ) 3) group, preferably comprises a tert-butyl group in the terminal position. The co-dimerization step can also be followed by one or more purification steps, for example by distillation, for example to remove the olefins in n-4 and n + 4.

The branched olefins or mixture of branched olefin isomers according to the invention can also be obtained by metathesis of at least two mixtures of branched olefins comprising respectively m and p carbon atoms so as to have m + p is greater than to n. The metathesis step can also be followed by one or more purification steps, for example by distillation, for example to remove the olefins in n-4 and n + 4.

Preferably, the branched olefins comprising m + p carbon atoms are obtained from bioresources and in particular from isobutene obtained according to the process described in application WO2012052427, WO2017085167 and

WO2018206262, for example from polysaccharides (sugars, starches, celluloses, etc.).

In the case of processes by codimerization or metathesis, one of the olefins comprising m or p carbon atoms are obtained from bioresources and in particular from isobutene obtained according to the process described in application WO2012052427, WO2017085167 and WO2018206262 , for example from polysaccharides (sugars, starches, celluloses, etc.).

The co-dimerization step can be carried out in the presence of a catalyst chosen from Bronsted acids in solution, for example H2SO4, H3PO4, HF, methanesulfonic acid, triflic acid (CF3SO3H); solid Bronsted acids, for example organic resins, clays, zeolites, FI3PO4 on silica; Lewis acids, for example ZnCl2, AICI3; organometallic compounds, for example Ni complexes, mixtures of Ni and Al complexes; ionic liquids, for example [BMIm] [N (CF3S02) 2] / HN (CF3S02) 2; clays with lamellar structures such as Montmorillonite; organic resins such as amberlysts, sulphonic resins; organometallic compounds such as, for example [LNiCF12R ²¹ ] [AICI4] in which L = PR ²² , R ²¹ represents an alkyl, linear or branched, comprising 9 carbon atoms and R ²² represents a group -CH ₂ -R ²¹ .

Preferably, the amount of catalyst used in the codimerization is between 1000 ppm and 10% by weight, preferably between 1000 ppm and 5% by weight, relative to the weight of olefin. The co-dimerization step is preferably carried out at a temperature between 30 and 250 ° C, preferably between 100 and 200 ° C.

Particularly advantageously, the olefins can be obtained from isobutene. Preferably, said isobutene is obtained from bioresources, in particular as described in application WO2012052427, for example from polysaccharides (sugars, starches, celluloses, etc.).

The metathesis step is carried out by reacting the two olefins in the presence of a metathesis catalyst, in particular a catalyst chosen from catalysts known to those skilled in the art for metathesis, in particular ruthenium catalysts, in particular Grubbs catalysts. ^2nd generation ,, for example Benzylidene 1, 3-bis (2,4,6-trimethylphenyl) -2-imidazolidinylidene dichloro (tricyclohexyl- phosphine) ruthenium or (1, 3-dimesitylimidazolidine- 2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride. The amount of catalyst is preferably between 50 ppm and 5% by weight of element Ru, preferably between 200 ppm and 1%, relative to the weight of olefin. The reaction is preferably carried out at a temperature between 0 and 150 ° C, for example between 20 and 100 ° C. The medium then undergoes a purification step, for example the reaction medium is dissolved in a solvent, for example toluene, then the mixture obtained is filtered, for example on neutral alumina.

The present invention also relates to the use of a compound as defined above, corresponding to the above formula (I), or of the mixture as defined above, as a plasticizer, lubricant, surfactant or in a cosmetic composition.

The present invention also relates to the use of a compound of formula (I) for which R ⁵ = H, to obtain:

- the corresponding acid compound by oxidation; or

- the corresponding alcohol compound by reduction; or

- a compound of ester type obtained by disproportionation (Tishenko reaction) of two compounds of formula (I).

The oxidation reaction can in particular be an oxidation in air or in the presence of C> 2. The reaction can be catalyzed by a metal catalyst in particular based on Mn, Co or Cu. The reaction can be carried out at a temperature between 20 and 200 ° C, preferably between 50 and 150 ° C.

The reduction reaction can in particular be a hydrogenation reaction catalyzed by a metal catalyst in solution or deposited on a support, for example Ni Raney, Pd / C, Pd / SiC> 2, Pt / Al ₂ C> 3. The reaction can be carried out at a temperature between 20 and 150 ° C, preferably between 50 and 100 ° C.

The disproportionation reaction can be carried out in the presence of a catalyst chosen in particular from CaO, BaO, MgO, preferably CaO. Preferably, the reaction is carried out at a temperature between 50 and 150 ° C, preferably between 70 and 120 ° C. The disproportionation reaction can last from 5 to 15 h, preferably from 7 to 12 h.

The present invention also relates to the products obtained from these oxidation, reduction and disproportionation reactions.

The present application will now be described with the aid of non-limiting examples.

Examples

Example 1 Preparation of the compounds of formula (I) according to the invention

After having solubilized 40 mg (0.156 mmol) of Rh (CO) 2 (acac) and 466 mg (0.82 mmol) of TPP (triphenyl phosphine) in toluene (150 ml_), isododecene (22 mmol) is then added. After transferring the solution to a stainless steel reactor, the system is purged 3 times with argon. The reaction medium is then heated to 80 ° C. and then placed under a pressure of 50 bar of Syngas (CO / H2 = 1: 1). The reaction medium is then stirred at a speed of 800 rpm. After 6 hours of heating, the reactor is cooled to ambient temperature and degassed, then the crude medium is then hydrolyzed with 75 mL of water. After extraction with ethyl acetate (3x 50 mL), the organic phase is dried. on Na2SC> 4 then concentrated under reduced pressure. The aldehydes are obtained as a mixture in a ratio 43/56 (Branched / Linear) with a yield of 75%.

Example 2: Oxidation of the compounds resulting from example 1

15 g of a mixture of 43/56 aldehydes (B / L = 5,5-dimethyl-3-neopentylhexanal) 6% mol of RU / Al2O3 (5w%) are introduced into a PARR instrument 300 mL reactor (5w%) as well as 40 mL of dodecane and 200 mL of water. After having purged the system under argon, the reactor is charged to 4 bar of oxygen, stirred. After heating for 2 hours at 150 ° C., the reactor is cooled to 25 ° C. then the reaction medium is filtered. 50 mL of water are added then the two phases are separated. The aqueous phase is extracted with 2x 40mL ethyl acetate. Then the combined organic phases are concentrated under reduced pressure leading to the corresponding acids with a good yield of 81%.

Example 3: Reduction of the compounds resulting from example 1

In a 300 mL autoclave of the PARR instrument type are introduced 10 g of a mixture of 43/56 aldehydes (B / L = 5,5-dimethyl-3-neopentylhexanal) in 120 mL of cyclohexane as well as 200 mg of Nickel from Raney. After purging the system with argon, a pressure of 10 bar of hydrogen is set and then the autoclave is heated to 80 ° C., mechanical stirring is set at 800 rpm. After 4 hours of reaction, the system is cooled to 25 ° C. then the reaction medium is filtered to remove the catalyst and then concentrated under reduced pressure to lead to a mixture of alcohols with a yield of 92%.

To 100 g of a mixture of 43/56 aldehydes (B / L = 5,5-dimethyl-3-neopentylhexanal) placed in a perfectly stirred reactor are added 5 g of calcium oxide then the whole is heated to 80 ° C for 8 hours. After returning the reactor to 25 ° C, 200 ml of diisopropyl ester or isooctane are added and the reaction medium is then filtered in order to separate the catalyst. The filtrate is then concentrated under reduced pressure to lead to the statistical mixture of the expected esters with a yield of 76%.

Claims

1. Compound of formula (I) below: in which :

- two at most among the groups R ¹ , R ² , R ³ and R ⁴ are H,

- R ⁵ represents H, OR, or NR'R ”

- R, R 'and R ", identical or different, represent H, a (C1 - C10) alkyl group, at least one of the groups R ¹ , R ² , R ³ or R ⁴ comprises or is a tert-butyl group.

2. A compound according to claim 1 in which R ⁵ represents H or OH, preferably H.

3. A compound according to claim 1 or 2, wherein the total sum of the number of carbon atoms of R ¹ , R ² , R ³ and R ⁴ being equal to 6 + 4x, x represents 1, 4 or 6 or x represents 2, 3, 4, 5, 6 and R5 represents OR, NR'R ”.

4. Mixture of branched alkane isomers functionalized by a C = OR ^{5 function} , comprising at least two compounds of formula (I) according to one of claims 1 to 3.

5. Mixture according to claim 4, in which all the compounds of formula (I) comprise, in addition to the group C (0) R ⁵ , 8 + 4x carbon atoms, x being as defined in claim 1 or 3 and being identical for all the compounds of said mixture.

6. Process for preparing a compound according to one of claims 1 to 3 or the mixture according to claim 4 or 5, comprising a carbonylation step of at least one branched olefin isomer, each branched olefin being formed. of a hydrocarbon chain comprising 8 + 4x carbon atoms, x being as defined in claim 1 or 3.

7. The preparation process according to claim 6, wherein the carbonylation step is performed by organometallic catalysis.

8. Preparation process according to claim 6 or 7, in which the mixture of branched olefin isomers comprises at least two branched olefin isomers of the following formula (II): wherein Ri, R ₂ , R ₃ and R ₄ are as defined in claim 1.

9. A method according to any one of claims 6 to 8, wherein the mixture of branched olefin isomers is obtained by dimerization of a mixture of branched olefin isomers comprising 4 + 2x carbon atoms, with x representing an even number, preferably obtained from bioresources.

10. A method according to any one of claims 6 to 8, wherein the mixture of branched olefin isomers is obtained by oligomerization of at least two mixtures of branched olefin isomers comprising respectively m and p carbon atoms. , m and p, different, being whole numbers equal to 4, 8, 12 or 16, and being such that m + p = 8 + 4x.

11. Use of a compound according to one of claims 1 to 3 or of the mixture according to claim 4 or 5, as a plasticizer, lubricant, surfactant or in a cosmetic composition.

12. Use of a compound according to any one of claims 1 to 3 with R ⁵ represents H to obtain:

- the corresponding acid compound by oxidation; or

- the corresponding alcohol compound by reduction; or

- a compound of ester type obtained by disproportionation of two compounds of formula (I).

13. Isomers of branched olefins have the following formula (II):

at most two of the groups R ¹ , R ² , R ³ and R ⁴ are H, at least one of the groups R1, R2, R3 or R4 contains or is a tert-butyl group.