Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/44—Preparation of carboxylic acid esters by oxidation-reduction of aldehydes, e.g. Tishchenko reaction
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
  • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
  • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
  • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
  • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
  • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
  • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
  • C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
  • C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
  • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
  • C10M129/24—Aldehydes; Ketones
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/08—Aldehydes; Ketones

Definitions

• 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.
• alkanes with impurities such as aromatic compounds.
• 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.
• 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.
• 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:
• R 5 represents H, OR, NR'R ”
• R ’and R identical or different, represent H, a (C1 - C10) alkyl group,
• 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.
• 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 ”.
• 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:
• R 5 represents H, OR, NR'R ” - R, R 'and R ”, identical or different, represent H, a group (C1 -
• 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.
• 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.
• 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 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.
• one of the groups R 1 , R 2 , R 3 or R 4 contains a tert-butyl group.
• one of the groups R1, R2, R3 or R4 is a tert-butyl group.
• 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.
• 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.
• 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.
• 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.
• 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 ”.
• 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.
• the mixture of carbonyl branched alkane isomers according to the invention comprises at least two compounds of formula (I) as defined above.
• the mixture of carbonyl branched alkane isomers according to the invention comprises at least two compounds of formula (I) as defined above.
• 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.
• 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.
• 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).
• the groups R 1 and R 2 are (Ci-C3o) alkyl groups.
• 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.
• 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):
• 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.
• 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.
• 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
• the mixture of branched olefin isomers according to the invention is a mixture comprising at least two olefins of formula (II).
• 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.
• 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 .
• 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.
• 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.
• a catalyst chosen from Bronsted acids in
• the dimerization step is preferably carried out at a temperature between 30 and 250 ° C.
• the branched olefins comprising 8 and 12 carbon atoms are obtained from isobutene.
• said isobutene is obtained from bioresources, in particular as described in application WO2012052427, WO2017085167 and WO2018206262, for example from polysaccharides (sugars, starches, celluloses, etc.).
• 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.
• At least one of the starting olefins 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.
• 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.).
• 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 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.
• the olefins can be obtained from isobutene.
• 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.
• 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 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.
• a catalyst chosen in particular from CaO, BaO, MgO, preferably CaO.
• 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 reactor 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
• Example 3 Reduction of the compounds resulting from example 1

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• 2019
  • 2019-08-16 FR FR1909244A patent/FR3099930A1/fr not_active Withdrawn
• 2020
  • 2020-08-17 EP EP20753966.9A patent/EP4013735A1/de active Pending
  • 2020-08-17 US US17/635,545 patent/US20220340512A1/en active Pending
  • 2020-08-17 WO PCT/EP2020/072990 patent/WO2021032673A1/fr unknown

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