EP1515939A2 - Verfahren zur herstellung einer ungesättigten carbonsäure - Google Patents

Verfahren zur herstellung einer ungesättigten carbonsäure

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Publication number
EP1515939A2
EP1515939A2 EP03760736A EP03760736A EP1515939A2 EP 1515939 A2 EP1515939 A2 EP 1515939A2 EP 03760736 A EP03760736 A EP 03760736A EP 03760736 A EP03760736 A EP 03760736A EP 1515939 A2 EP1515939 A2 EP 1515939A2
Authority
EP
European Patent Office
Prior art keywords
bismuth
process according
aldehyde
group
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP03760736A
Other languages
English (en)
French (fr)
Inventor
Roland Jacquot
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Chimie SAS
Original Assignee
Rhodia Chimie SAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rhodia Chimie SAS filed Critical Rhodia Chimie SAS
Publication of EP1515939A2 publication Critical patent/EP1515939A2/de
Withdrawn legal-status Critical Current

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Classifications

    • 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

Definitions

  • the present invention relates to a process for the preparation of an unsaturated carboxylic acid from the corresponding aldehyde.
  • the invention relates more particularly to the preparation of an aliphatic carboxylic acid having at least one unsaturation conjugated with the carbonyl group.
  • It relates in particular to the preparation of geranic acid.
  • the objective of the present invention is to provide a process involving a catalytic system.
  • a process for the preparation of an unsaturated carboxylic acid from the corresponding aldehyde characterized in that it comprises an oxidation step of said aldehyde, in a controlled basic medium and using molecular oxygen or a gas containing it, in the presence of a catalyst based on palladium and / or platinum and an activator based on bismuth, under conditions such that oxidation takes place in diffusion mode.
  • an unsaturated aliphatic carboxylic acid can be obtained by oxidation of a compound comprising one or two double bonds insofar as both the regime of the reaction, which must be a diffusion regime, is controlled and the basicity of the medium.
  • the term "diffusion regime” also known as “physical regime” means a regime which corresponds to the conventional definition known to the skilled person. For this purpose, one can refer to the various works of J.
  • the conditions of diffusion regime are conditions such that the concentration of dissolved oxygen in the medium is close to zero.
  • the process of the invention applies very particularly to the oxidation of all the compounds of aldehyde type which are liable to undergo degradation or isomerization during the oxidation reaction in basic aqueous medium. It is therefore an aliphatic or cycloaliphatic aldehyde having at least one unsaturation, a double bond or a triple bond.
  • the process of the invention is perfectly applicable to an aliphatic aldehyde having two double bonds, at least one of which is conjugated with the carbonyl group.
  • the invention preferably relates to the use of an unsaturated aldehyde of the terpene type.
  • terpene means the oligomers derived from isoprene.
  • Said substrate comprises a number of carbon atoms multiple of 5.
  • total number of carbon atoms is meant the formyl group.
  • - A represents a hydrocarbon group having at least one unsaturation having from 4 to 19 carbon atoms which may be a saturated or unsaturated, linear or branched acyclic aliphatic group; a saturated or unsaturated or aromatic, mpnocyclic or polycyclic carbocyclic group; a chain of a saturated or unsaturated aliphatic group and / or of a saturated, unsaturated or aromatic carbocycle.
  • the unsaturation can be carried by an aliphatic hydrocarbon chain and / or included in a cycle.
  • the substrate involved in the process of the invention more particularly corresponds to formula (I) in which A represents an unsaturated acyclic aliphatic group.
  • A represents a linear or branched acyclic aliphatic group preferably having from 4 to 19 carbon atoms comprising one to several unsaturations on the chain, generally, 1 to 5 unsaturations which may be single or conjugated double bonds or triple bonds: Unsaturation which can be at the end of the chain and / or inside the chain and / or conjugated with the group CO.
  • the hydrocarbon chain may optionally carry one or more substituents insofar as they do not react under the reaction conditions and mention may in particular be made of a halogen atom or a trifluoromethyl group.
  • the preferred unsaturated aliphatic substrates are those which correspond to formula (I) in which A represents a linear or branched alkyl group having from 4 to 19 carbon atoms and comprising at least one double bond, preferably two double bonds of which at least one is conjugated with the group CO.
  • groups comprising 8 carbon atoms having a double bond and carrying two methyl groups, preferably in positions 3 and 7.
  • examples of A there may be mentioned an octen-7-yl group, a 2,6-dimethylheptadie-1,5-nyl group
  • A can represent a cyclic aliphatic group including a double bond in the ring.
  • A represents a carbocycle having 3 to 8 carbon atoms in the ring, preferably 5 or 6 and comprising 1 or 2 unsaturations in the ring, preferably 1 or 2 double bonds. In this case, the double bond is included in the cycle.
  • the preferred unsaturated cycloaliphatic substrates are those which correspond to formula (I) in which A represents a cycloalkyl group having from 3 to 8 carbon atoms, preferably 5 or 6 and comprising a double bond.
  • groups A mention may in particular be made of cyclopentene, cyclohexene, 1-methylcyclohex-1-ene, 4-methylcyclohex-1-ene, cycloheptene, menthene.
  • A represents a polycyclic carbocyclic group comprising from 3 to 6 carbon atoms in each ring and at least one of the rings of which comprises an unsaturation; the other cycle can be saturated or aromatic.
  • A is preferably bicyclic which means that at least two rings have two carbon atoms in common.
  • A represents a saturated or unsaturated, linear or branched aliphatic group carrying a cyclic substituent.
  • ring is preferably understood to mean a saturated, unsaturated or aromatic carbocyclic ring, preferably cycloaliphatic or aromatic, in particular cycloaliphatic ring comprising 6 carbon atoms in the ring or benzene.
  • the acyclic aliphatic group can be linked to the cycle by a valential link, a heteroatom or a functional group and examples are given above.
  • A represents an aliphatic group carrying a cyclic substituent exhibiting at least one unsaturation on the aliphatic chain and / or in the ring.
  • the invention relates in particular to substrates constituted by an unsaturated aliphatic chain carrying a phenyl group and it may be mentioned in particular that a styrenyl group.
  • substituents are one or more alkyl groups, preferably three methyl groups, a methylene group (corresponding to an exocyclic bond), an alkenyl group, preferably an isopropene-yl group.
  • aldehydes capable of being used, there may be mentioned:
  • safranal the unsaturated monocyclic or polycyclic cycloaliphatic terpene aldehydes such as:
  • campholenic aldehyde campholenic aldehyde
  • the preferred aldehydes are the following:
  • the compound to which the process according to the invention applies more particularly advantageously is the preparation of geranic acid.
  • the catalyst used in the process of the invention must work in physical regime. To this end, the quantity of oxygen dissolved in the medium is limited by controlling different process parameters such as temperature, pressure and stirring. It is important that oxygen is consumed as soon as it arrives in the environment.
  • the catalyst involved in the process of the invention is based on a metal called Mi which is palladium, platinum or their mixtures.
  • a metal called Mi which is palladium, platinum or their mixtures.
  • platinum and / or palladium catalysts taken in all the available forms such as for example: platinum black, palladium black, platinum oxide, palladium oxide or the metal noble itself deposited on various supports such as carbon black, graphite, activated carbon, activated aluminas and silicas or equivalent materials. Carbon based catalytic masses are particularly suitable.
  • the metal is deposited in an amount of 0.5% to 95%, preferably from 1% to 5% of the weight of the catalyst.
  • the amount of this catalyst to be used expressed by weight of metal M-j relative to that of the compound of formula (I) can vary from 0.001 to 10% and, preferably, from 0.002 to 2%.
  • the metal Mi is brought beforehand to the zero oxidation state, by introducing formaldehyde in any form (aqueous formaldehyde, trioxane or polyoxymethylene) in an adequate amount.
  • formaldehyde in any form (aqueous formaldehyde, trioxane or polyoxymethylene) in an adequate amount.
  • the quantity to be used expressed by weight of formalin per gram of metal, can vary from 0.02 g to 0.1 g / g.
  • Bismuth is used as activators.
  • bismuth is used, in the form of free metals or cations.
  • the associated anion is not critical and any derivatives of these metals can be used.
  • metal bismuth or its derivatives are used.
  • the remainder associated with bismuth n ' is not critical from the moment that it satisfies this condition.
  • the activator can be soluble or insoluble in the reaction medium.
  • Illustrative compounds of activators which can be used in the process according to the present invention are: bismuth oxides; bismuth hydroxides; the salts of mineral hydracids such as: chloride, bromide, bismuth iodide; the mineral oxyacid salts such as: sulfite, sulfate, nitrite, nitrate, phosphite, phosphate, pyrophosphate, carbonate, bismuth perchlorate.
  • Suitable compounds are also salts of aliphatic or aromatic organic acids such as: acetate, propionate, benzoate, salicylate, oxalate, tartrate, lactate, bismuth citrate. These salts can also be bismuthyl salts. As specific examples, we can cite:
  • bismuth acetate Bi C 2 H 3 0 2 ) 3 ; bismuthyl propionate (BiO) C 3 H 5 0 2 ; benzoate basic bismuth C 6 H 5 C0 2 Bi (OH) 2 ; bismuthyl salicylate C 6 H 4 C0 2 (BiO) (OH); bismuth oxalate (C 2 0 4 ) 3 Bi 2 ; bismuth tartrate Bi 2 (C 4 H 4 0 6 ) 3 , 6H 2 0; bismuth lactate (C 6 H 9 0 5 ) OBi, 7H 2 0; bismuth citrate C 6 H 5 0 7 Bi.
  • the bismuth derivatives which are preferably used to carry out the process according to the invention are: bismuth oxides; bismuth hydroxides; bismuth or bismuthyl salts of mineral hydracids; bismuth or bismuthyl salts of mineral oxyacids; bismuth or bismuthyl salts of aliphatic or aromatic organic acids.
  • a group of activators which are particularly suitable for carrying out the invention consists of: bismuth oxides Bi 2 0 3 and Bi 2 0 4 ; bismuth hydroxide Bi (OH) 3 ; neutral bismuth sulfate Bi 2 (S0 4 ) 3 ; bismuth chloride BiCI 3 ; bismuth bromide BiBr 3 ; bismuth iodide Bil 3 ; neutral bismuth nitrate Bi (N0 3 ) 3 , 5H 2 0; bismuthyl carbonate (Bi0) 2 C0 3 , 0.5H 2 0; bismuth acetate Bi (C 2 H 3 0 2 ) 3 ; bismuthyl salicylate C 6 H 4 C0 2 (BiO) (OH).
  • the amount of activator used expressed by the amount of metal contained in the activator relative to the weight of the metal M 1 engaged, can vary within wide limits. For example, this quantity can be as small as 1% and can reach 200% of the weight of metal M- engaged and even exceed it without inconvenience. Advantageously, it is around 100%.
  • the oxidation reaction carried out in accordance with the invention is carried out in basic medium.
  • hydroxides such as sodium, potassium or lithium hydroxide.
  • sodium or potassium hydroxide is used.
  • the concentration of the basic starting solution is not critical.
  • the alkali metal hydroxide solution used has a concentration generally between 2 and 25%, preferably between 2 and 10% by weight.
  • the amount of base introduced into the reaction medium is such that the ratio between the number of moles of OH- and the number of moles of aldehyde varies between 0.9 and 1.1, preferably equal to approximately 1. If said compound has salifiable functions other than the carboxylic group formed, the quantity of base necessary to salify all the salifiable functions is introduced.
  • the concentration by weight of the compound of formula (I) in the liquid phase is usually between 1% and 40%, preferably between 2% and 30%.
  • Water can be supplied by the basic solution.
  • the oxidation temperature is preferably chosen, in a temperature range from 20 ° C to 60 ° C, preferably between 30 ° C and 40 ° C.
  • the stirring conditions advantageously vary between 500 and 700 revolutions / min .
  • reaction mixture kept under sweeping of inert gas for example nitrogen
  • oxygen or a gas containing it (air) is introduced.
  • the mixture is then stirred at the desired temperature until an amount of oxygen corresponding to that necessary to transform the formyl group into a carboxylic group is consumed.
  • the catalytic mass is separated from the reaction medium, for example by filtration.
  • the resulting medium is acidified by adding a protonic acid of mineral origin, preferably hydrochloric acid or sulfuric acid or an organic acid such as, for example, methanesulfonic acid up to obtaining a pH lower than the pKa of the acid obtained.
  • a protonic acid of mineral origin preferably hydrochloric acid or sulfuric acid or an organic acid such as, for example, methanesulfonic acid
  • the concentration of the acid is indifferent and preference is given to commercial forms. Acidification is generally done between room temperature (most often between 15 ° C and 25 ° C).
  • the acid is then recovered in a conventional manner according to conventional separation techniques, for example by distillation.
  • the organic phase can be extracted with a solvent, for example an aromatic hydrocarbon, preferably toluene then the organic phase is distilled to recover first the solvent, optionally the starting aldehyde and then the carboxylic acid formed and optionally formed products.
  • a solvent for example an aromatic hydrocarbon, preferably toluene
  • the process of the invention is particularly applicable to the preparation of unsaturated carboxylic acids of terpene type and more preferably to geranic acid.
  • the reaction can be carried out in any type of reactor provided that the process parameters enabling work in physical mode with respect to oxygen are chosen.
  • the transformation rate (TT) corresponds to the ratio between the number of transformed substrates and the number of moles of substrate engaged.
  • the yield (RR) corresponds to the ratio between the number of moles of product formed (carboxylic acid) and the number of moles of substrate used.
  • the stirring is carried out using a stirrer of the 4 inclined blades type, the position of the propeller relative to the height of the liquid in the reactor is one third relative to the bottom of the reactor.
  • the mixture is stirred for 30 min at room temperature under a nitrogen sweep. 20 g of citrus are then introduced and air is introduced at a flow rate of 35 ml / minute and the medium is heated to 45 ° C. under a stirring speed of 600 rpm.
  • the reaction is carried out under atmospheric pressure.
  • the reaction must be carried out in diffusion mode.
  • the mixture is stirred for 30 min at room temperature under a nitrogen sweep.
  • the mixture is stirred for 30 min at room temperature under a nitrogen sweep. 20 g of citrus are then introduced and air is introduced at a flow rate of 35 ml / minute and the medium is heated to 35 ° C.
  • the mixture is stirred for 30 min at room temperature under a nitrogen sweep.
  • the mixture is stirred for 30 min at room temperature under a nitrogen sweep. 20 g of citrus are then introduced and air is introduced at a rate of
  • the mixture is stirred for 30 min at room temperature under a nitrogen sweep. 20 g of citrai are then introduced and air is introduced at a flow rate of 35 ml / min and the medium is heated to 45 ° C.
  • citrai In a single-phase medium, citrai degrades to 6-methyl-5-hepten-2-one.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
EP03760736A 2002-06-21 2003-06-18 Verfahren zur herstellung einer ungesättigten carbonsäure Withdrawn EP1515939A2 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0207731 2002-06-21
FR0207731A FR2841242B1 (fr) 2002-06-21 2002-06-21 Procede de preparation d'un acide carboxylique insature
PCT/FR2003/001856 WO2004000763A2 (fr) 2002-06-21 2003-06-18 Procede de preparation d'un acide carboxylique insature

Publications (1)

Publication Number Publication Date
EP1515939A2 true EP1515939A2 (de) 2005-03-23

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EP03760736A Withdrawn EP1515939A2 (de) 2002-06-21 2003-06-18 Verfahren zur herstellung einer ungesättigten carbonsäure

Country Status (5)

Country Link
US (1) US20060100459A1 (de)
EP (1) EP1515939A2 (de)
AU (1) AU2003258810A1 (de)
FR (1) FR2841242B1 (de)
WO (1) WO2004000763A2 (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114405499B (zh) * 2022-02-14 2023-09-26 辽宁石油化工大学 一种铋氧化物及其制备方法和应用

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5210233A (en) * 1975-07-16 1977-01-26 Mitsui Toatsu Chem Inc Process for oxidation of aromatic alcohols
FR2734565B1 (fr) * 1995-05-24 1997-07-04 Rhone Poulenc Chimie Procede de preparation de 3-carboxy-4-hydroxybenzaldehydes et derives
JPH09255626A (ja) * 1996-03-25 1997-09-30 Mitsubishi Rayon Co Ltd 芳香族カルボン酸エステルの製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2004000763A2 *

Also Published As

Publication number Publication date
WO2004000763A2 (fr) 2003-12-31
FR2841242B1 (fr) 2004-09-24
AU2003258810A1 (en) 2004-01-06
FR2841242A1 (fr) 2003-12-26
AU2003258810A8 (en) 2004-01-06
WO2004000763A3 (fr) 2004-04-08
US20060100459A1 (en) 2006-05-11

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