EP3004045A1 - Procede d'hydroformylation et d'isomerisation controlees d'un nitrile/ester/acide gras omega-insature - Google Patents
Procede d'hydroformylation et d'isomerisation controlees d'un nitrile/ester/acide gras omega-insatureInfo
- Publication number
- EP3004045A1 EP3004045A1 EP14728226.3A EP14728226A EP3004045A1 EP 3004045 A1 EP3004045 A1 EP 3004045A1 EP 14728226 A EP14728226 A EP 14728226A EP 3004045 A1 EP3004045 A1 EP 3004045A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- nitrile
- hydroformylation
- ester
- acid
- fatty acid
- 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- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/32—Separation; Purification; Stabilisation; Use of additives
- C07C253/34—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/373—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in doubly bound form
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
Definitions
- the present invention relates to a new process for synthesizing aldehyde nitrile / ester / fatty acid, such linear aldehydes and therefore corresponds to the formula: OHC- (CH 2) r + 2- may be used in industry , in particular the polymer industry, such as polyamides and polyesters, said process comprising a step of hydroformylation of a nitrile / ester / acide-unsaturated fatty acid.
- nitrile / ester / acide-unsaturated fatty acid is meant any compound of formula:
- CH 2 CH- (CH 2 ) r -R, where R is CN or COORi,
- R 1 being H or an alkyl radical comprising 1 to 4 carbon atoms
- r is an integer such that 1 ⁇ r ⁇ 13, advantageously 2 ⁇ r ⁇ 13 and, preferably, 4 ⁇ r ⁇ 13.
- the polyamide industry uses a variety of monomers formed from diamines and diacids, lactams, and ⁇ -amino acids. These monomers are generally manufactured by chemical synthesis using as raw materials C2-C4 olefins, cycloalkanes or benzene, hydrocarbons from fossil sources. Only a few monomers are manufactured to date from bio-resourced raw materials, such as castor oil, which makes it possible to manufacture the polyamide 1 1 marketed under the trademark Rilsan ® ; the erucic oil which makes it possible to manufacture the 13/13 polyamide, or the lesquerolic oil which makes it possible to manufacture the polyamide 13.
- bio-resourced raw materials such as castor oil, which makes it possible to manufacture the polyamide 1 1 marketed under the trademark Rilsan ® ; the erucic oil which makes it possible to manufacture the 13/13 polyamide, or the lesquerolic oil which makes it possible to manufacture the polyamide 13.
- fatty acid derivatives especially nitriles and fatty acid esters
- Olefin hydroformylation using homogeneous transition metal catalysts is an important industrial process that produces versatile intermediates for pharmaceuticals and fine chemicals.
- US7026473 describes the hydroxycarbonylation or methoxycarbonylation of a pentenenitrile to a 5-cyanovaleric acid or ester (6 C atoms) in the presence of CO (carbon monoxide) and respectively water or alcohol. . Only methoxycarbonylation with methanol is actually exemplified. By reduction, the 5-cyanovaleric acid (ester) forms the 6-aminocaproic acid (ester), which in turn gives ⁇ -caprolactam by ring closure (this is the Nylon-6 monomer).
- the process described in this document has several disadvantages. The methoxycarbonylation step is slow and expensive in the catalyst. The conversion is not complete and requires high reaction times.
- WO97 / 33854 discloses a process for producing linear aldehyde by hydroformylation of an alkene, such as hexene, butadiene, methyl 3-pentenoate or 3-pentenenitrile. This document shows that it is much more difficult to obtain a linear aldehyde (low proportion of linear obtained) from a nitrile (3-pentenenitrile) than from an ester.
- US 6307108 discloses methods of making aldehyde ester by hydroformylation of ⁇ -unsaturated ester.
- the existing hydroformylation processes generally lead to the production of isomers of the starting reagent by isomerization of the double bond.
- these isomers are recycled to the reaction, they could, to a certain extent, restore the starting reagent by isomerization, but they also lead to unwanted co-products such as branched aldehydes by hydroformylation of the internal double bond.
- these isomers are much less reactive than the initial ⁇ -unsaturated compounds. Consequently, if they are recycled in their entirety to the reaction, they accumulate there until they represent most of the reaction medium.
- hydroformylation is generally carried out with very long reaction times of at least 20 hours to promote conversion of the initial reactants and isomerization products. Therefore, the productivity of the process is low.
- the hydroformylation reaction is carried out in a solvent medium, in particular to recover the catalyst (metal and ligands) and recycle it.
- the present invention therefore aims to find a new hydroformylation process simple to implement, and using as much as possible renewable raw materials.
- the present invention aims in particular at increasing the productivity of the hydroformylation reaction for obtaining linear aldehydes, these linear aldehydes being defined as those which are not branched, to improve the quality of the product, the selectivity of the reaction to minimize the production of by-products, and in particular branched or branched aldehyde by-products, using the least possible catalyst, and thus aims at improving the overall economy of the process.
- the purpose of the present invention is in particular to simplify the hydroformylation process applied to a nitrile / ester / acide-unsaturated fatty acid substrate, to reduce the number of stages and ingredients used, while at the same time enabling the catalyst to be recycled at the same time. reaction.
- the Applicant has now found a new process for the hydroformylation of a nitrile / ester / unsaturated fatty acid substrate, under conditions which make it possible to avoid the abovementioned drawbacks, in particular by controlling the parallel isomerization of said substrate leading to the formation of co- products including branched aldehydes, allowing both improved productivity and selectivity and efficient recycling of the hydroformylation catalyst.
- a nitrile / ester / unsaturated fatty acid substrate under conditions which make it possible to avoid the abovementioned drawbacks, in particular by controlling the parallel isomerization of said substrate leading to the formation of co- products including branched aldehydes, allowing both improved productivity and selectivity and efficient recycling of the hydroformylation catalyst.
- the percentages expressed are molar percentages. Unless otherwise stated, the parameters referred to are measured at atmospheric pressure.
- linear aldehyde is an aldehyde in which carbon monoxide has been added to the terminal carbon of the olefin during hydroformylation, as opposed to a “branched aldehyde”. also referred to as “branched aldehyde”, in which carbon monoxide has been added to an internal carbon of the olefin.
- a “terminal isomer” is an isomer in which the unsaturation (double bond) is terminal, as opposed to an “internal isomer”, also called “internal unsaturation isomer” and denoted by [1 - / nf] in which the unsaturation is not terminal.
- the subject of the present invention is therefore a process for the preparation of a nitrile / fatty ester aldehyde comprising the following steps:
- CH 2 CH- (CH 2 ) r -R, where R is CN or COORi,
- R 1 being H or an alkyl radical comprising 1 to 4 carbon atoms
- r is an integer such that 1 ⁇ r ⁇ 13, advantageously 2 ⁇ r ⁇ 13 and, preferably, 4 ⁇ r ⁇ 13,
- partial pressure of CO denoted PiCO, less than or equal to 40 bar and, preferably, in the range of 5 to 20 bar
- partial pressure of H2, denoted P1H2, less than or equal to 40 bar preferably included in the range from 5 to 20 bar
- the PiCO / Pihb ratio between the respective partial pressures of CO and H2 is in the range of 0.5: 1 to 3: 1,
- a catalyst comprising at least one Group VI II metal, preferably at least one metal chosen from rhodium, cobalt, ruthenium, iridium and their mixtures, preferably chosen from rhodium, iridium and mixtures thereof; and at least one bidentate or monodentate ligand, preferably at least one chelating diphosphine,
- hydroformylation product comprising at least one nitrile / ester / fatty acid aldehyde of formula: OHC- (CH2) r + 2-, and
- TON number of rotations or turnover number
- Stage 2 of separation and recovery of the nitrile / ester / fatty acid aldehyde and the isomerate makes it possible to stop the displacement of the internal unsaturation of the isomers by isomerization as well as to valorize this isomerate.
- the method of the invention performs here the hydroformylation step with a productivity gain which results in a hydroformylation step which takes place with the shortest possible time, sufficient to obtain a total conversion or almost (preferably> 90% or 100%).
- the method according to the invention makes it possible to avoid recycling, to stop the isomerization of the isomers, to reduce the production of hydrogenation product, and thus to improve the selectivity to linear aldehyde.
- the technical solution of the process of the invention is ultimately to work at high conversion (or total) of the initial reagent, without however seeking to convert the isomerization products of this initial reagent, a high conversion signifying a conversion rate of at least 90%.
- the initial unsaturated omega reagent is:
- ⁇ - ⁇ indicates the position of the first unsaturation from the opposite side to the nitrile R, ester or acid group.
- “Isomerate” within the meaning of the invention means at least one isomer with internal unsaturation ( ⁇ - ⁇ : ⁇ -1, ⁇ -2, ⁇ -3, etc.) of the nitrile / ester / acide-unsaturated fatty acid. , who is terminally unsaturated, said isomerate possibly also containing the unconverted initial substrate, i.e. the nitrile / ester / acide-unsaturated fatty acid.
- the internal isomers of the isomerate can be cis and / or trans.
- nitrile / ester / unsaturated fatty acid must be understood to mean nitrile, or ester, or unsaturated fatty acid, that is to say unsaturated fatty nitrile, or unsaturated fatty ester, or fatty acid. unsaturated.
- nitrile / ester / acide-unsaturated fatty acid substrate is meant a "nitrile / ester / unsaturated fatty acid” of which at least 90% comprises a terminal unsaturation " ⁇ ", said substrate possibly comprising at most 10% of nitrile / unsaturated ester-1 ester / fatty acid, i.e. at most 10% of "nitrile / ester / unsaturated fatty acid” having une-1 internal unsaturation.
- the "nitrile / ester / acide-unsaturated fatty acid substrate” comprises saturated compounds, these compounds, which do not react during the hydroformylation reaction, must be eliminated at the end of this reaction, just as the hydrogenation product of the double bond 4.
- the starting unsaturated fatty nitrile used in the process according to the invention is generally obtained from unsaturated (or hydroxylated) acidic compounds or fatty esters by nitrilation (ammoniation) of at least one acid or ester function of these compounds which may be from raw materials of fossil origin or from renewable sources.
- the unsaturated acidic compounds or fatty esters can be obtained, for example, according to the process described by the patent document US4510331.
- the latter describes in particular the manufacture of 7-octenoic acid, by isomerization of 2,7-octadien-1-ol to 7-octen-1-al, then oxidation of the latter to acid.
- 2,7-octadiene-1-ol is produced industrially by reaction (“telomerization") of butadiene with water in the presence of palladium catalyst according to the process described in patent documents GB2074156A and DE31 12213. This type of process uses raw materials of fossil origin.
- the unsaturated fatty nitriles are made from unsaturated fatty acids or esters of renewable origin, derived from natural oils. These processes developed recently by Arkema are described in particular in patent documents: WO2010055273, FR1 1.55174, FR1 1.56526, and FR1 1 .57542.
- unsaturated fatty nitrile within the meaning of the invention is preferably meant those obtained at least partially from unsaturated natural fatty acids. Such unsaturated fatty nitrile may in particular be obtained from an unsaturated acid (or fatty ester) of natural origin of formula:
- n is an integer in the range of 0 to 5 and preferably 0 to 2
- n is an integer in the range of 2 to 13
- p is an integer index such that 1 ⁇ p ⁇ 3, and
- G is H (a hydrogen), an alkyl radical of 1 to 1 carbon atoms or a radical containing 2 or 3 carbon atoms bearing 1 or 2 hydroxyl function (s),
- said manufacture comprising ammoniation (the action of introducing ammonia into a product) of the carbonyl function of the unsaturated fatty acid (or ester) of natural origin in nitrile function.
- This scheme applies equally well to natural fatty acids (esters) and acides-unsaturated fatty acids.
- the process may be carried out batchwise in the liquid or gaseous phase or continuously in the gas phase.
- the reaction is carried out at an elevated temperature above 250 ° C and in the presence of a catalyst which is generally a metal oxide and most frequently zinc oxide. Continuous removal of the formed water, further entraining the unreacted ammonia, allows rapid completion of the reaction.
- Liquid phase ammoniation is well suited for long fatty chains (with at least 10 carbon atoms). However, by operating with shorter chain lengths, gas phase ammoniation may become more appropriate. It is also known from GB 641, 955 to carry out the ammoniation using, as an agent, urea or cyanuric acid. Any other source of ammonia can also be used. According to a particular embodiment, the unsaturated fatty nitrile used according to the invention is made from unsaturated long-chain natural fatty acids.
- long chain natural fatty acid means an acid derived from the plant medium or the animal medium, including algae or other microorganisms, and therefore renewable, having from 6 to 24 carbon atoms, with preferably at least 7 (if the final amino acid has at least 8 C) carbon atoms, preferably at least 8 carbon atoms, preferably at least 10 carbon atoms, and preferably at least 14 carbon atoms per molecule.
- These various acids are derived from vegetable oils extracted from various plants such as sunflower, rapeseed, camelina, castor oil, lesquerella, olive, soy, palm, coriander, celery, dill, carrot, fennel, Limnanthes Alba (meadowfoam). They are also derived from the terrestrial or marine animal world, and in the latter case, both in the form of fish, mammals and algae. These are usually fats derived from ruminants, fish such as cod, or marine mammals such as whales or dolphins.
- unsaturated fatty acid that is more particularly suitable for the implementation of the invention, mention may be made of: petroselenic acid (cis-6-octadecenoic acid), its derivative 6-heptenoic acid obtained by ethenolysis (cross metathesis with ethylene), ⁇ -linolenic acid (6-9-12-octadecatrienoic acid), these acids can be obtained from coriander, for example; cis-8-eicosenoic acid, cis-5,8,11,14-eicosatrienoic acid (arachidonic acid), ricinoleic acid which after dehydration gives conjugated 8,10-octadecadienoic acid; caproleic acid (cis-9-decenoic acid), palmitoleic acid (cis-9-hexadecenoic acid), myristoleic acid (cis-9-tetradecenoic acid), oleic acid (cis-9-octadecenoic acid), 9-decenoic acid
- unsaturated fatty acids those which are most abundantly available, and in particular ⁇ -9 or ⁇ -10 unsaturated fatty acids by numbering from the acid group, are preferred.
- nitriles and fatty acids containing from 10 to 24 carbon atoms and preferably those containing 10 carbons or 1 1 carbons with unsaturation at the omega or ⁇ position, that is to say at the end of the chain with respect to the acid group.
- fatty acids mentioned above can be isolated by any of the techniques well known to those skilled in the art: molecular distillation, including short path distillation ("short path distillation” in English), crystallization, liquid-liquid extraction, urea complexation, including supercritical CO2 extraction, and / or any combination of these techniques.
- the unsaturated fatty nitrile is obtained from a fatty acid ester
- the latter may advantageously be chosen from the esters of the aforementioned fatty acids, in particular their methyl esters.
- the routes for obtaining a fatty nitrile from a fatty acid ester are for example described in WO2010089512.
- the unsaturated fatty nitrile is obtained from a fatty hydroxy acid, such as 12HSA and 14HEA. More generally, the hydroxy fatty acid may advantageously be chosen from those described in the patent application filed as FR1 1 .56526.
- the unsaturated fatty nitrile is obtained from a triglyceride, the latter being advantageously chosen from: a vegetable oil comprising a mixture of triglycerides of unsaturated fatty acids, such as sunflower oil, rapeseed, castor oil , lesquerella, camelina, olive, soya, palm, sapindaceae (sapindaceae) especially avocado, sea buckthorn, coriander, celery, dill, carrot, fennel, mango, meadowfoam (meadowfoam) and their mixtures; microalgae; animal fats.
- a vegetable oil comprising a mixture of triglycerides of unsaturated fatty acids, such as sunflower oil, rapeseed, castor oil , lesquerella, camelina, olive, soya, palm, sapindaceae (sapindaceae) especially avocado, sea buckthorn, coriander, celery, dill, carrot,
- the unsaturated fatty nitrile is obtained from a vegetable wax, for example jojoba.
- a ⁇ -unsaturated nitrile of formula obtained by transformation of an unsaturated fatty acid / ester into two successive stages (of indifferent order): ethenolysis (cross metathesis with ethylene) and ammoniation, as described in WO2010055273.
- hydroxylated fatty acids are used as raw material, such as ricinoleic acid and lesquerolic acid, which correspond to the general formula
- the unsaturated fatty nitrile is manufactured as described in FR1 1.55174, by ammoniation of a fatty acid, ester or glyceride compound leading to the corresponding unsaturated nitrile.
- the hydrogenation of unsaturated hydroxylated fatty acids containing at least 18 carbon atoms per molecule, leading to saturated hydroxylated fatty acids is carried out as in the process of document FR1 1.56526. followed by dehydration thereof to monounsaturated fatty acids, with either an intermediate nitrilation step of the acid function of the monounsaturated fatty acid leading to an unsaturated nitrile, or an intermediate nitrilation step of the function saturated hydroxylated fatty acid acid from the hydrogenation step with concomitant dehydration leading to unsaturated fatty nitrile.
- Hydroformylation also known as the oxo process, is a synthetic route for producing aldehydes from alkenes discovered in 1938 by Otto Roelen from Ruhrchemie.
- the basic reaction is as follows:
- R-GH CH 2 + GO - 3 ⁇ 4 R ⁇ C 2 H A ⁇ CHO + R ⁇ CH (CHO) CH a ⁇
- the hydroformylation step according to the process of the invention uses methods and devices well known and already employed by conventional hydroformylation processes. All the usual methods for adding and mixing the reactants and the catalyst components, as well as the usual separation techniques for the conventional hydroformylation reaction, can therefore be used for this step of the process of the invention.
- the hydroformylation step according to the method of the invention has the advantage of being used directly in the many existing devices. This would not be the case for methoxycarbonylation or hydroxycarbonylation, for example.
- the pressure conditions of the hydroformylation reaction are as follows:
- the partial pressure of CO is less than or equal to 40 bar
- the partial pressure of hb is less than or equal to 40 bar
- the PiCO / Pihb ratio between the respective partial pressures of CO and hb is in the range of 0.5: 1 to 3: 1.
- the hydroformylation is carried out under partial pressure of CO in the range of 5 to 20 bar and advantageously in the range of 10 to 20 bar.
- the hydroformylation is carried out under partial pressure of CO in the range of 5 to 40 bar and, preferably, in the range of 10 to 40 bar.
- the hydroformylation is carried out under a partial pressure of hb in the range of 5 to 20 bar and, preferably, in the range of 10 to 20 bar.
- the PiCO / Pihb ratio between the respective partial pressures of CO and hb is in the range of 1: 1 to 3: 1.
- the hydroformylation is carried out at a temperature in the range of 100 to 130 ° C, preferably 100 to 120 ° C, preferably at a temperature substantially equal to 120 ° C.
- the hydroformylation is carried out for a time in the range of 1 to 12 hours, preferably in the range of 2 to 6 hours, preferably in the range of 3 to 5 hours, preferably in the range of 1 to 12 hours. 4 hours.
- the hydroformylation is preferably conducted up to a nitrile / ester / acide-unsaturated fatty acid conversion ratio in the range of 90 to 100%, preferably in the range of 95 to 100%, preferably in the range of 97 to 100%.
- the hydroformylation is conducted in the presence of a catalyst, this catalyst comprising at least one Group VIII metal and at least one ligand, this ligand may be monodentate or bidentate.
- the catalyst comprises at least one phosphine, a phosphite or a chelating diphosphine chosen from: PP i3, P (OPh) 3, Dppm, Dppe, Dppb, Xantphos and / or BiPhePhos, preferably Xantphos and / or BiPhePhos, preferably BiPhePhos.
- the catalyst ligand is a bidentate ligand, which may in particular be a chelating diphosphine.
- the chelating diphosphine may in particular be chosen from Dppm, Dppe, Dppb, Xantphos and / or BiPhePhos. This chelating diphosphine is preferably selected from Xantphos and / or BiPhePhos, and is more preferably BiPhePhos.
- the metal of the catalyst is provided in the form of a precursor comprising said metal and at least one compound chosen from acetylacetonates, carbonyl compounds, cyclooctadienes, chlorine, and mixtures thereof.
- the hydroformylation catalyst comprises rhodium, preferably provided by a precursor such as Rh (acac) (CO) 2, ruthenium, preferably provided by a precursor such as Ru3 (CO) 12, where acac is a ligand acetylacetonate and CO is a carbonyl ligand, and / or iridium, preferably provided by a precursor such as lr (COD) CI, where COD is a 1,5-cyclooctadiene ligand and Cl is a chlorine ligand, preferably comprises iridium.
- the hydroformylation is catalyzed by a system chosen from: Rh-Xantphos, Rh-BiPhePhos, Ir-Xantphos,
- the catalysts based on rhodium and iridium are preferred, they substantially improve the conversion.
- the rhodium and iridium catalysts have better selectivity for the aldehydes, result in less hydrogenation as a parallel reaction, and offer linear product / branched product ratios in favor of the linear products.
- the hydroformylation catalyst comprises rhodium, preferably provided by a precursor such as Rh (acac) (CO) 2, ruthenium, preferably provided by a precursor such as Ru3 (CO) 12, where acac is a acetylacetonate ligand and CO is a carbonyl ligand, and / or iridium, preferably provided by a precursor such as 1r (COD) CI, where COD is a 1,5-cyclooctadiene ligand and Cl is a chlorine ligand, preferably includes iridium.
- the hydroformylation is advantageously catalyzed by a system chosen from: Rh-Xantphos, Rh-BiPhePhos, Ir-Xantphos, Ir-BiPhePhos and mixtures thereof.
- the molar ratio [substrate] / [metal] is in the range of 5000 to 50,000.
- This embodiment of the process according to the invention is particularly advantageous in the sense that a substantially linear hydroformylation product is obtained while only using a very small amount of metal, which is of course of interest. economically significant on the industrial level.
- the preparation method according to the invention further comprises, and prior to the hydroformylation step, a step of pretreatment of the substrate.
- This pretreatment step aims at eliminating any oxidation products of the nitrile / ester / fatty acid substrate, such as the hydroperoxides and degradation products of these hydroperoxides, which would be capable of attacking the metal of the catalyst used during the reaction. hydroformylation, to the detriment of the reactivity of said catalyst.
- Such pretreatment may be, for example, carried out by a distillation of the substrate followed by purification by adsorption thereof, in particular by means of alumina.
- the [ligand] / [metal] molar ratio is in the range of 20: 1 to 100: 1, preferably 40: 1 to 100: 1.
- the hydroformylation is carried out using a quantity of solvent sufficient to solubilize at least a portion of the catalyst (in particular one of the precursors or the two precursors of the catalyst), preferably in an amount of less than 1%, preferably less than 1/1000, relative to the nitrile / ester / acide-unsaturated fatty acid reagent.
- hydroformylation can be carried out in an organic medium, for example in solution in toluene, but is preferably carried out "without solvent", that is to say in an amount of less than 1%, preferably less than 1/1000. , relative to the nitrile / ester / acide-unsaturated fatty acid reagent
- the hydroformylation step comprises the recycling of the hydroformylation catalyst system, optionally supplemented with a fresh catalyst (or "fresh”) and / or new ligand ( or “fresh”) in a subsequent hydroformylation cycle.
- the products are evaporated from the reaction medium, so that the isomerate is recovered on the one hand, and the hydroformylation products on the other hand.
- the isomers of the initial reagent - as well as the initial reagent which has not reacted - are recovered in a first fraction and in a second fraction the aldehyde-nitriles (esters) resulting from the hydroformylation reaction.
- the evaporation of the reaction medium is not complete, in order to be able to recycle the catalyst and the ligands to the reaction.
- the hydroformylation process according to the invention easily and quickly consumes compounds having a terminal double bond. Therefore, the method makes it possible to separate the internal double bond compounds from the terminal double bond compounds. Since these isomers usually have very close physicochemical properties, they are not easily separable. However, under the operating conditions implemented by the process according to the invention, the terminal double bond isomer has been converted to linear aldehyde, so that the problem of separation of the internal and terminal isomers hardly arises. The separation of the internal isomers is thus facilitated.
- the isomerate or isomers thus isolated find applications in the field of aromas and perfumes.
- Givaudan has claimed (EP 1 1741 17) the use of such a mixture of isomers in formulations.
- the isomerate production process according to the invention is also much simpler than the processes of the prior art, as shown for example in the aforementioned patent document Givaudan, in the prior art and in the synthesis examples 1).
- the methyl esters obtained according to the process of the invention can also be used for these applications.
- the esters obtained can be further converted into acids, aldehydes and alcohols, which also have applications as flavors and fragrances.
- the method of the invention further comprising a step:
- the process of the invention further comprises the recovery of the isomerate or at least one of its isomers, or of their derivatives, said upgrading being chosen from: use, especially as aroma or perfume, in a perfumery composition, especially functional perfumery, in a cosmetic or pharmaceutical product composition, in the textile industry, in the metal processing industry, as a monomer in the polymer industry, especially as an odorless or perfumed specialty monomer; the use as lubricant, emulsifier, surfactant, defoaming agent, superfatting agent, spreading agent, antistatic agent, ink solubilizer, in particular printing inks, cooling fluid and / or anticorrosion agent, these products can be scented or odorless.
- the subject of the present invention is also an isomerate that can be obtained according to the process of the invention, characterized in that it comprises at least one nitrile / ester / fatty acid isomer with internal unsaturation, and at least 80% of which is internal isomer (s) of the isomerate are composed of the unsaturated is-1 isomer of formula
- the subject of the present invention is also the use of an isomerate according to the invention, or at least one of its isomers, or of their derivatives obtained in particular according to the process of the invention, in particular as aroma or perfume, in a perfumery composition, in particular a functional perfumery, in a cosmetic or pharmaceutical composition, in the textile industry, in the metal processing industry, as a monomer in the polymer industry, especially as an odorless or perfume specialty monomer; product used as lubricant, emulsifier, surfactant, defoaming agent, superfatting agent, leveling agent, antistatic agent, ink solubilizer, in particular printing ink, cooling fluid and / or anticorrosion agent, these products being able to be perfumed or odorless.
- the present invention also relates to a perfume composition
- a perfume composition comprising an isomer according to the invention, at least one of its isomers, and / or their derivatives obtained in particular according to the process of the invention.
- the present invention also relates to a consumer product comprising a perfume composition according to the invention.
- the method of the invention further comprises a step:
- step 1 in which the aldehyde nitrile / ester / acid obtained in step 1) is converted to the acid nitrile / ester / fatty acid of formula HOOC- (CH 2 ) r + 2-R, or
- the aldehyde-nitrile / ester / acid obtained has the advantage of being oxidized very easily in contact with oxygen.
- the oxidation step is carried out by dispersing dioxygen or a gaseous mixture containing dioxygen in the product resulting from the hydroformylation.
- the oxidation step is carried out without the addition of a solvent and / or without the addition of a dioxygen activation catalyst.
- the oxidation step is carried out under a partial pressure of oxygen ranging from 0.2 bar to 50 bar, in particular from 1 bar to 20 bar, preferably from 1 to 5 bar.
- the oxygen is injected continuously into the reaction medium, preferably in the form of a flow of air or oxygen, preferably injected in excess relative to the stoichiometry of the oxidation reaction.
- the molar ratio of oxygen relative to the product from the hydroformylation step is in the range of 3: 2 to 100: 2.
- the oxidation is carried out at a temperature in the range from 0 ° C to 100 ° C, preferably from 20 ° C to 100 ° C, in particular from 30 ° C to 90 ° C, preferably from 40 ° C to 80 ° C, possibly in two consecutive stages of increasing temperatures.
- the process of the invention also comprises a reduction step 3 ') in which the acid-nitrile obtained in step) is converted to the ⁇ -amino acid of formula HOOC- (CH 2) r + 3 -NH2 in the case of the acid-nitrile; or
- the process of the invention further comprises a polymer synthesis step, in particular polyamide, by polymerization using ⁇ -amino acid or the diacid obtained in step 3 '); or polyester, by polymerization using the alcohol ester obtained in step 2 ").
- a polymer synthesis step in particular polyamide, by polymerization using ⁇ -amino acid or the diacid obtained in step 3 '); or polyester, by polymerization using the alcohol ester obtained in step 2 ").
- the step of synthesizing ⁇ -aminoesters or ⁇ -amino fatty acids from, respectively, nitrile-esters or nitrile-fatty acids consists of a conventional reduction or hydrogenation.
- the reduction of nitrile function to primary amine is well known to those skilled in the art.
- the hydrogenation is carried out for example in the presence of precious metals (Pt, Pd, Rh, Ru ...) at a temperature of between 20 and 100 ° C. under a pressure of 1 to 100 bar, and preferably of from 1 to 50 bar. It can also be conducted in the presence of catalysts based on iron, nickel or cobalt, which can cause more severe conditions with temperatures of the order of 150 ° C and high pressures of several tens of bar.
- the step of reducing nitrile-fatty acids to ⁇ -amino fatty acids consists of a hydrogenation using any conventional catalyst and preferably Raney nickel and cobalt, in particular Raney nickel deposited or not on a support such as than silica.
- the polymers which can be manufactured from the nitrile / ester / fatty acid aldehydes of the present invention are specialty products, for example in the case of polyamides, technical polyamides, ie polyamides of high performance, or even very high performance, manufactured from precursors or monomers comprising at least 8 carbon atoms, preferably at least 10 carbon atoms; as opposed to polyamides known as "convenience", such as "nylon 6", the quantities (volumes) marketed are much higher and the costs much lower than those of technical polyamides.
- the process according to the invention consists of a process for synthesizing an ⁇ -amino acid compound of formula
- the method according to the invention further comprises a polyamide synthesis step by polymerization using ⁇ -amino acid obtained in step 3).
- CH 2 CH- (CH 2 ) 8-COOCH 3 which can be hydrolyzed to undecylenic acid
- R being a glyceric radical corresponding to the formula -CH 2 -CHOX-CH 2 OY, X and Y being, independently of one another, H, another fatty chain of the triglyceride (oil) or oleic radicals,
- oleic acid can be converted to oleic nitrile and then ethenolysis (or other cross-metathesis with an alpha-olefin) to obtain the 10 carbon nitrile.
- Rh (acac) (CO) 2 (marketed by STREM) is used as a hydroformylation catalyst precursor.
- Phosphines (marketed by STREM) are used as received or synthesized.
- the isomerate (1 - / ' nf) comprises a mixture of isomers with internal unsaturation ( ⁇ - ⁇ : ⁇ -1, ⁇ -2, ⁇ -3 ...) of the substrate (1) with terminal unsaturation ( ⁇ - unsaturated):
- the hydroformylation reactions were carried out in 100 ml stainless steel autoclaves. Under typical conditions, a solution in toluene (0.5 to 5 ml) of metal precursor (from 0.001 to 0.0001 mmol), phosphine (from 0.002 to 0.02 mmol) and substrate (5 to 25 mmol) is mixed in a Schlenk tube under an argon inert atmosphere to form a homogeneous solution. After stirring at room temperature for 1 hour, this solution is cannulated inside the autoclave previously conditioned under an inert atmosphere.
- metal precursor from 0.001 to 0.0001 mmol
- phosphine from 0.002 to 0.02 mmol
- substrate 5 to 25 mmol
- the reactor is sealed, purged several times with a CO / H 2 (1: 1) mixture, then pressurized to 20 bar of this CO / H 2 mixture at room temperature and then heated to the desired temperature using a water bath. or an oil bath. During the reaction, the pressure is kept constant and several samples are taken to follow the conversion. After a suitable reaction time, the autoclave is brought back to ambient temperature and then to atmospheric pressure. The mixture is collected and analyzed by NMR.
- a solution of Rh (acac) (CO) 2 in toluene (0.65 mg, 0.00025 mmol), Biphephos (4 mg, 0.005 mmol) and undecenitrile (826 mg, 5.0 mmol) is prepared in a Schlenk tube under Inert atmosphere of argon to form a homogeneous solution which is stirred at room temperature for 1 h.
- the molar ratio Biphephos / rhodium is 20: 1 and the molar ratio of substrate / rhodium is 20,000: 1.
- the solution is cannulated inside a 100 ml autoclave previously conditioned under an inert atmosphere.
- the reactor is sealed, purged several times with a CO / H 2 gas mixture (1: 1), then pressurized with 20 bar CO / H 2 (1: 1) at room temperature and then heated to 120 ° C. After 5 h, 100% of the undecenitrile was consumed. After 5 hours, the medium is brought back to ambient temperature and to pressure atmospheric. The mixture is collected and analyzed by NMR. The analysis shows that the reaction is complete and that there remains an internal olefin content of 19%, a proportion of hydrogenation product (4) of 5% and that 86% of products formed correspond to the branched aldehydes (1). %) and linear (99%).
- a solution of Rh (acac) (CO) 2 in toluene (0.65 mg, 0.00025 mmol), Biphephos (20 mg, 0.025 mmol) and undecenitrile (826 mg, 5.0 mmol) is prepared in a Schlenk tube under Inert atmosphere of argon to form a homogeneous solution which is stirred at room temperature for 1 h.
- the molar ratio Biphephos / rhodium is 100: 1 and the molar ratio of substrate / rhodium is 20,000: 1.
- the solution is cannulated inside a 100 ml autoclave previously conditioned under an inert atmosphere.
- the reactor is sealed, purged several times with a CO / H 2 gas mixture (1: 1), then pressurized with 20 bar CO / H 2 (1: 1) at room temperature and then heated to 120 ° C. After 4 h, the medium is brought to room temperature and atmospheric pressure. The mixture is collected and analyzed by NMR. The analysis shows that the reaction is complete and that there remains an internal olefin proportion of 21%, a proportion of hydrogenation product of 5% and that 84% of products formed correspond to the branched aldehydes (1%) and linear (99%).
- Biphephos (0.5 ml), Biphephos (8 mg, 0.01 mmol) and undecenitrile (4.12 g, 25.0 mmol) are prepared in a Schlenk tube under an inert atmosphere of argon to form a homogeneous solution which is stirred at room temperature. ambient for 1 hour.
- the molar ratio Biphephos / rhodium is 20: 1 and the molar ratio of substrate / rhodium is 50,000: 1.
- the solution is cannulated inside a 100 ml autoclave previously conditioned under an inert atmosphere.
- the reactor is sealed, purged several times with a CO / H 2 gas mixture (1: 1), then pressurized with 20 bar CO / H 2 (1: 1) at room temperature and then heated to 120 ° C. After 4 h, 100% of the undecenitrile was consumed.
- the reaction then runs for 48 hours to consume a maximum of internal olefins.
- the mixture is collected and analyzed by NMR after 48 hours. The analysis shows that the reaction is complete and that there remains a proportion of internal olefin of 6%, of hydrogenation product of 7% whereas 87% of formed products correspond to branched aldehydes (1%) and linear ( 99%).
- a solution of [1 R (COD) (Cl)] 2 (0.83 mg, 0.00025 mmol) in toluene (5 mL), Biphephos (4 mg, 0.005 mmol) and undecenitrile (5.0 mmol) is prepared in a Schlenk tube under argon inert atmosphere to form a homogeneous solution which is stirred at room temperature for 1 h.
- the molar ratio Biphephos / iridium is 20: 1 and the molar ratio of substrate / iridium is 20,000: 1.
- the solution is cannulated inside a 100 ml autoclave previously conditioned under an inert atmosphere.
- the reactor is sealed, purged several times with a CO / H 2 gas mixture (1: 1), then pressurized with 20 bar CO / H 2 (1: 1) at room temperature and then heated to 120 ° C. After 18 h, 100% of the undecenenitrile was consumed.
- the mixture is sealed, purged several times with a CO / H 2 gas mixture (1: 1), then pressurized with 20 bar CO / H 2 (1: 1) at room temperature and then heated to 120 ° C. After 18 h, 100% of the undecenenitrile was consumed.
- Rh (acac) (CO) 2 (0.13 mg, 0.0005 mmol) in toluene (0.5 ml), Biphephos (8 mg, 0.01 mmol) and methyl-10-undecenoate (25.0 mmol) is prepared in a Schlenk tube under argon inert atmosphere to form a homogeneous solution which is stirred at room temperature for 1 h.
- the molar ratio Biphephos / rhodium is 20: 1 and the molar ratio of substrate / rhodium is 50,000: 1.
- the solution is cannulated inside a 100 mL autoclave previously conditioned under an inert atmosphere.
- the reactor is sealed, purged several times with a CO / H 2 gas mixture (1: 1), then pressurized with 20 bar CO / H 2 (1: 1) at room temperature and then heated to 120 ° C. After 5 h, 100% of the undecenoate was consumed.
- the reaction then runs for 48 hours to consume a maximum of internal olefins.
- the mixture is collected and analyzed by NMR after 48 hours. The analysis shows that the reaction is complete and that there remains an internal olefin content of 6%, hydrogenation product of 9% while 85% of products formed correspond to branched (1%) and linear aldehydes. (99%).
- a solution of Ni / Raney (40 mg) in a mixture of water / ethanol (2 ml / 2 ml), amoniaque (3 mmol, 1 M in methanol) and nitrile acid (360 mg, 2 mmol) is prepared in a Schlenk tube at room temperature.
- the solution is cannulated inside a 100 ml autoclave previously conditioned under inert atmosphere.
- the reactor is sealed, purged several times with H2 gas, then pressurized with 40 bar H 2 at room temperature and then heated to 130 ° C. After 12 h, 100% of the acidic nitrile was hydrogenated. Depressurized at room temperature and then added 5 mL of acetic acid.
- the catalyst is then filtered off and the filtrate is evaporated. A white precipitate is obtained after washing with ether (15 mL).
- NMR5 and IR analysis show that the zwitterionic product was obtained.
- Example 15 hydroformylation reaction of 1/1 - / nf in the presence of Rh-biphephos:
- the total pressure is a means which makes it possible to control the isomerization, by acting on the displacement of the double bond, as well as the ratio between the isomers with cis and trans internal unsaturation.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1301301A FR3006685B1 (fr) | 2013-06-06 | 2013-06-06 | Procede d'hydroformylation et d'isomerisation controlees d'un nitril/ester/acide gras omega-insature. |
PCT/EP2014/061899 WO2014195493A1 (fr) | 2013-06-06 | 2014-06-06 | Procede d'hydroformylation et d'isomerisation controlees d'un nitrile/ester/acide gras omega-insature |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3004045A1 true EP3004045A1 (fr) | 2016-04-13 |
Family
ID=49274694
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP14728226.3A Withdrawn EP3004045A1 (fr) | 2013-06-06 | 2014-06-06 | Procede d'hydroformylation et d'isomerisation controlees d'un nitrile/ester/acide gras omega-insature |
Country Status (5)
Country | Link |
---|---|
US (1) | US20160115120A1 (fr) |
EP (1) | EP3004045A1 (fr) |
CN (1) | CN105263897B (fr) |
FR (1) | FR3006685B1 (fr) |
WO (1) | WO2014195493A1 (fr) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109280004B (zh) * | 2018-11-30 | 2023-08-22 | 黄冈师范学院 | 氧化氮催化空气氧化乙二醛制乙醛酸的方法、装置及应用 |
CN114426662B (zh) * | 2020-09-30 | 2024-09-20 | 中国石油化工股份有限公司 | 利用植物油制备聚合酯的方法、聚合酯和聚酯型润滑油 |
IT202100022328A1 (it) | 2021-08-25 | 2023-02-25 | Versalis Spa | Metodo per la preparazione di acidi ω-ammino-carbossilici e loro derivati. |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013079888A1 (fr) * | 2011-12-01 | 2013-06-06 | Arkema France | Procede de preparation d'aminoacide comprenant une etape d'hydroformylation d'un nitrile gras insature |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2729385B1 (fr) * | 1995-01-17 | 1997-04-04 | Centre Nat Rech Scient | Procede d'hydroformylation d'une olefine en milieu biphasique |
EP1174117B1 (fr) * | 2000-07-21 | 2004-11-10 | Givaudan SA | Composition parfumante contenant un mélange de nitriles |
JP2003137758A (ja) * | 2001-10-29 | 2003-05-14 | Kiyomitsu Kawasaki | 頭髪化粧料用のマスキング組成物及び該マスキング組成物を含有する頭髪化粧料並びに頭髪化粧料のマスキング方法。 |
DE10313319A1 (de) * | 2003-03-25 | 2004-10-07 | Basf Ag | Verfahren zur Hydroformylierung |
-
2013
- 2013-06-06 FR FR1301301A patent/FR3006685B1/fr active Active
-
2014
- 2014-06-06 CN CN201480032335.XA patent/CN105263897B/zh active Active
- 2014-06-06 US US14/896,247 patent/US20160115120A1/en not_active Abandoned
- 2014-06-06 EP EP14728226.3A patent/EP3004045A1/fr not_active Withdrawn
- 2014-06-06 WO PCT/EP2014/061899 patent/WO2014195493A1/fr active Application Filing
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013079888A1 (fr) * | 2011-12-01 | 2013-06-06 | Arkema France | Procede de preparation d'aminoacide comprenant une etape d'hydroformylation d'un nitrile gras insature |
Non-Patent Citations (6)
Title |
---|
ELENA PETRICCI ET AL: "Microwaves Make Hydroformylation a Rapid and Easy Process- supporting information", ORGANIC LETTERS, 17 August 2006 (2006-08-17), United States, pages 3725 - 3727, XP055700794, Retrieved from the Internet <URL:https://epo.summon.serialssolutions.com/2.0.0/link/0/eLvHCXMwjV07T8MwELZaGGDhLSiPygIGFovEdp14rKI-hpahlIEpcmxHIKpSESjqv-ecpIFKRbAm58jxnf3d-V4IXUuhrO-FnFCmNeGhbBGVcEZcTqMGQLaJcPnOjxEf94JRjw9q6OoXDz71b18nDnJ8Oq-jTRoI6cS4dzeoXAUAQDIvikoZcaVgluWDfg510KOzFeipP7nAxxVVMoeU7u6_JrOHdkqNEbcLFu-jmp0eoK1o2ajtEMm> [retrieved on 20200603], DOI: 10.1021/ol061312v * |
ELENA PETRICCI ET AL: "Microwaves Make Hydroformylation a Rapid and Easy Process", ORGANIC LETTERS, vol. 8, no. 17, 1 August 2006 (2006-08-01), pages 3725 - 3727, XP055700795, ISSN: 1523-7060, DOI: 10.1021/ol061312v * |
J?R?MY TERNEL ET AL: "Rhodium-Catalyzed Tandem Isomerization/Hydroformylation of the Bio-Sourced 10-Undecenenitrile: Selective and Productive Catalysts for Production of Polyamide-12 Precursor", ADVANCED SYNTHESIS & CATALYSIS, vol. 355, no. 16, 11 November 2013 (2013-11-11), pages 3191 - 3204, XP055099257, ISSN: 1615-4150, DOI: 10.1002/adsc.201300492 * |
LAMBERS-VERSTAPPEN M M H ET AL: "RHODIUM-CATALYSED ASYMMETRIC HYDROFORMYLATION OF UNSATURATED NITRILES", ADVANCED SYNTHESIS AND CATAL, WILEY, WEINHEIM, DE, vol. 345, no. 4, 1 January 2003 (2003-01-01), pages 478 - 482, XP009059163, ISSN: 1615-4169, DOI: 10.1002/ADSC.200390053 * |
See also references of WO2014195493A1 * |
TOM?S SMEJKAL ET AL: "Transition-State Stabilization by a Secondary Substrate-Ligand Interaction: A New Design Principle for Highly Efficient Transition-Metal Catalysis", CHEMISTRY - A EUROPEAN JOURNAL, vol. 16, no. 8, 22 February 2010 (2010-02-22), DE, pages 2470 - 2478, XP055430153, ISSN: 0947-6539, DOI: 10.1002/chem.200902553 * |
Also Published As
Publication number | Publication date |
---|---|
US20160115120A1 (en) | 2016-04-28 |
WO2014195493A1 (fr) | 2014-12-11 |
FR3006685A1 (fr) | 2014-12-12 |
CN105263897A (zh) | 2016-01-20 |
CN105263897B (zh) | 2017-12-29 |
FR3006685B1 (fr) | 2016-07-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR101331741B1 (ko) | 단일불포화 지방산 또는 에스테르로부터의 오메가-아미노산 또는 에스테르의 합성 방법 | |
JP5389943B2 (ja) | モノ不飽和脂肪酸またはエステルを出発物質とするオメガアミノ酸またはエステルの合成方法 | |
JP5568470B2 (ja) | 天然脂肪酸および/またはエステルからの二酸またはジエステルの合成方法 | |
EP2785682B1 (fr) | Procede de preparation d'aminoacide comprenant une etape d'hydroformylation d'un nitrile gras insature | |
EP2307353B1 (fr) | Procede de synthese de l'acide amino-9-nonanoïque ou de ses esters a partir d'acides gras naturels insatures | |
EP2566842A1 (fr) | Procede de preparation d'amino-acides ou esters satures comprenant une etape de metathese | |
EP2953923B1 (fr) | Synthese conjuguee d'un nitrile- ester/acide et d'un diester/diacide | |
JP5389912B2 (ja) | ω−アミノ−アルカン酸またはこのエステルを天然脂肪酸から合成する方法 | |
JP5372935B2 (ja) | ω−不飽和脂肪酸の合成方法 | |
EP3004045A1 (fr) | Procede d'hydroformylation et d'isomerisation controlees d'un nitrile/ester/acide gras omega-insature | |
EP0937039B1 (fr) | Preparation de caprolactame | |
FR2922208A1 (fr) | Procede de synthese d'un compose hydrocarbone alpha-omega-difonctionnel symetrique a partir d'un aldehyde omega-octenoique |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20151209 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: TERNEL, JEREMY Inventor name: DUBOIS, JEAN-LUC Inventor name: CARPENTIER, JEAN-FRANCOIS Inventor name: COUTURIER, JEAN-LUC |
|
DAX | Request for extension of the european patent (deleted) | ||
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
17Q | First examination report despatched |
Effective date: 20180914 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 20201222 |