WO2015096022A1 - Production d'un composé comprenant au moins un groupe fonctionnel acide carboxylique - Google Patents

Production d'un composé comprenant au moins un groupe fonctionnel acide carboxylique Download PDF

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Publication number
WO2015096022A1
WO2015096022A1 PCT/CN2013/090286 CN2013090286W WO2015096022A1 WO 2015096022 A1 WO2015096022 A1 WO 2015096022A1 CN 2013090286 W CN2013090286 W CN 2013090286W WO 2015096022 A1 WO2015096022 A1 WO 2015096022A1
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Prior art keywords
compound
acid
process according
anyone
reaction
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PCT/CN2013/090286
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English (en)
Inventor
Pascal Metivier
Yan Zhao
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Rhodia Operations
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Priority to PCT/CN2013/090286 priority Critical patent/WO2015096022A1/fr
Publication of WO2015096022A1 publication Critical patent/WO2015096022A1/fr

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    • 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
    • C07C51/27—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with oxides of nitrogen or nitrogen-containing mineral acids

Definitions

  • the present invention concerns a process for the production of a compound comprising at least one carboxylic acid functional group, comprising the reaction of a compound comprising at least one nitrile functional group with nitronium ions.
  • carboxylic acids are obtained through a limited number of processes which are well known to those skilled in the art. Hence, carboxylic acids are generally produced through oxidation of saturated or unsaturated hydrocarbon substrates such as fatty acid substrates using either a gaseous component such as air and ozone, a nitric acid/metal catalyst component or a combination of both components. Numerous prior art documents disclose variants of such oxidation processes.
  • Nitriles are readily converted to the corresponding carboxylic acids by a variety of chemical processes, but these processes typically require strongly acidic or basic reaction conditions and high reaction temperatures, and usually produce unwanted byproducts and/or large amounts of inorganic salts as unwanted byproducts.
  • dicarboxylic acids from the conversion of dinitriles by a process consisting in a reaction between nitrile and water in presence of a strong acid such as sulfuric acid and hydrochloric acid.
  • a strong acid such as sulfuric acid and hydrochloric acid.
  • Corresponding carboxylic acids are then produced as well as with 2 equivalent amounts of inorganic salts, such as ammonium salt, ammonium chlorine, ammonium sulfate, and ammonium nitrate.
  • the conversion of the nitrile functional groups to carboxyl functional groups may also be obtained by reaction of the nitrile compounds with a basic hydroxyl compound in solution water, organic solvents, such as ethanol, dioxane, glycol, MeOCH 2 CH 2 OH ormixture thereof.
  • a basic hydroxyl compound in solution water, organic solvents, such as ethanol, dioxane, glycol, MeOCH 2 CH 2 OH ormixture thereof.
  • the ammonia formed is removed and the salt obtained is reacted with an inorganic acid and the diacids formed are isolated and recovered.
  • the basic hydroxyl compound is an alkali metal hydroxide, such as sodium hydroxide, potassium hydroxide or the like.
  • the corresponding carboxylic acids are produced as salt and it is necessary to proceed with a further treatment.
  • Process of this invention is a novel route for recovering in value and converting these nitrile compounds or mixture of chemical compounds which can be recovered in value and which are economically advantageous.
  • An object of the present invention is to provide aprocess for the production of such a substance which is simple, which does not involve critical reacting conditions, which is economical, and which provides large yields.
  • the process further enables the carboxylic acid compound to be produced in a relatively high quantity.
  • the carboxylic acid compounds that are produced can also be relatively easily separated and recovered.
  • the present invention concerns then a process for the production of a compound (A) comprising at least one carboxylic acid functional group, comprising at least the step of mixing at least:
  • the present invention also concerns a process for the production of a compound (A) comprising at least one carboxylic acid functional group, comprising at least the step of reacting at least:
  • the present invention also concerns a compound (A) comprising at least one carboxylic acid functional group susceptible to be obtained by the above identified process.
  • composition comprising at least:
  • salts from 0.001 to 0.8 equivalent of salts, preferably from 0.001 to 0.5 equivalent of salts, for 1 equivalent of compound (A); notablyinorganic salts, such as for instance ammonium salt, ammonium chlorine (NH 4 C1), ammonium sulfate ((NH4) 2 SO 4 ), and ammonium nitrate (NH 4 NO 3 ), ammoniumfluoride (NH 4 F), ammonium bromide( H 4 Br), ammonium iodide (NH 4 I), ammonium acetate (CH 3 COONH 4 ).
  • ammonium salt such as for instance ammonium salt, ammonium chlorine (NH 4 C1), ammonium sulfate ((NH4) 2 SO 4 ), and ammonium nitrate (NH 4 NO 3 ), ammoniumfluoride (NH 4 F), ammonium bromide( H 4 Br), ammonium iodide (NH 4 I), ammonium acetate (CH 3 COONH 4 ).
  • hydrocarbon group refers to a group consisting of carbon atoms and hydrogen atoms, which group may be saturated or unsaturated, linear, branched or cyclic, aliphatic or aromatic. Hydrocarbon groups of the present invention may be alkyl groups, alkenyl groups, alkynyl groups, aryl groups and heterocyclic groups.
  • alkyl groups include saturated hydrocarbons having one or more carbon atoms, including straight-chain alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclic alkyl groups (or "cycloalkyl” or “alicyclic” or “carbocyclic” groups), such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl, branched-chain alkyl groups, such as isopropyl, tert-butyl, sec-butyl, and isobutyl, and alkyl-substituted alkyl groups, such as alkyl- substituted cycloalkyl groups and cycloalkyl-substituted alkyl groups.
  • aliphatic group includes organic moieties characterized by straight or branched-chains, typically having between 1 and 22 carbon atoms. In complex structures, the chains may be branched, bridged, or cross-linked. Aliphatic groups include alkyl groups, alkenyl groups, and alkynyl groups.
  • alkenyl or “alkenyl group” refers to an aliphatic hydrocarbon radical which can be straight or branched, containing at least one carbon-carbon double bond.
  • alkenyl groups include, but are not limited to, ethenyl, propenyl, n-butenyl, i-butenyl, 3-methylbut-2-enyl, n-pentenyl, heptenyl, octenyl, decenyl, and the like.
  • alkynyl refers to straight or branched chain hydrocarbon groups having at least one triple carbon to carbon bond, such as ethynyl.
  • aryl group includes unsaturated and aromatic cyclic hydrocarbons as well as unsaturated and aromatic heterocycles containing one or more rings.
  • Aryl groups may also be fused or bridged with alicyclic or heterocyclic rings that are not aromatic so as to form a polycycle, such as tetralin.
  • An "arylene” group is a divalent analog of an aryl group.
  • Aryl groups can also be fused or bridged with alicyclic or heterocyclic rings which are not aromatic so as to form a polycycle.
  • heterocyclic group includes closed ring structures analogous to carbocyclic groups in which one or more of the carbon atoms in the ring is an element other than carbon, for example, nitrogen, sulfur, or oxygen. Heterocyclic groups may be saturated or unsaturated. Additionally, heterocyclic groups, such as pyrrolyl, pyridyl, isoquinolyl, quinolyl, purinyl, and furyl, may have aromatic character, in which case they may be referred to as “heteroaryl” or “heteroaromatic” groups.
  • Aryl and heterocyclic including heteroaryl groups may also be substituted at one or more constituent atoms.
  • heteroaromatic and heteroalicyclic groups may have 1 to 3 separate or fused rings with 3 to about 8 members per ring and one or more N, O, or S heteroatoms.
  • heteroatom includes atoms of any element other than carbon or hydrogen, preferred examples of which include nitrogen, oxygen, sulfur, and phosphorus. Heterocyclic groups may be saturated or unsaturated or aromatic. Nitronium ions and compound (I)
  • the nitronium ionNO 2 + is a reactive cation created by the removal of an electron from the paramagnetic nitrogen dioxide molecule, or the protonation of nitric acid.
  • the reagents to form nitronium ions are notably concentrated nitric acid, fuming nitric acid, or the mixture of nitric acid with sulfuric acid or nitric acid with dehydration agent, like concentrated sulfuric acid, P2O5, glacial acetic acid, and acetic anhydride.
  • a compound (I) able to produce nitronium ions notably in the conditions of the reaction.
  • a compound (I) is preferably chosen in the group consisting of: nitric acid (HNO 3 ), dinitrogenpentoxide (N 2 0 5 ) or nitronium salt, such as for instanceNO 2 + BF 4 ⁇ , NO 2 + Cl " , NO 2 + SbF 6 + , and N0 2 + PF 6 ⁇
  • the molar ratio of compound (I) to compound (N) is preferably comprised between 15: 1 and 1 :0.5, notably at the start of the reaction, more preferably comprised between 10: land 1 : 1.
  • compound (I) is able to produce a range from 1 to 10 equivalent of nitronium ions, for 1 equivalent of nitrile function, notably in the conditions of the reaction.
  • compound (I) is nitric acid and the process of the invention concerns then a process for the production of a compound (A) comprising at least one carboxylic acid functional group comprising the reaction of a compound (N) comprising at least one nitrile functional group with a range from 1 to 10 equivalent of nitric acid (HNO 3 ) for 1 equivalent of nitrile function.
  • a compound (A) comprising at least one carboxylic acid functional group
  • N comprising at least one nitrile functional group with a range from 1 to 10 equivalent of nitric acid (HNO 3 ) for 1 equivalent of nitrile function.
  • Reaction with nitric acid may be expressed as follows:
  • nitric acid employed may vary fairly widely in strength and purity.
  • nitric acid preferably provides a concentration comprised between 80and 99.9% in water, more preferably comprised between 85and 99%.
  • the state of the art provides different analyzing methods from the field of titration, NIR- spectroscopy, UV spectroscopy/photometry, and chromatography.
  • Another possibility for the determination of the nitric acid by means of titration consists in that, in addition to the titration of the acids with lye, a second titration using a solution of lanthanum salt as titrant is performed for the measurement of the sum of the fluoride containing compounds.
  • the content of nitric acid can be determined by way of netting the results of both titrations.
  • the reaction medium provides at the start of the reaction aH + ions concentration ([H + ]) superior or equal to 11 mol/L, ie per litre of the total reaction medium.
  • Process of the present invention may also comprise a source of water that may be for instance H 2 O, H 2 O 2 or nitric acid.Addition of the source of water to the reaction medium may be carried out at the start of the reaction or during the reaction for instance.
  • a source of water may be for instance H 2 O, H 2 O 2 or nitric acid. Additional of the source of water to the reaction medium may be carried out at the start of the reaction or during the reaction for instance.
  • the molar amount of acid compounds in the reaction medium is superior or equal to the molar amount of water, notably at the start of the reaction.
  • Molar amount of acid compounds may express for instance the sum of molar amount of nitric acid and the molar amount of acid compound able to increase the acidity of the reaction medium, such as for example sulfuric acid, such as concentrated sulfuric acid, acetic acid or glacial acetic acid, acetic anhydride or hydrochloric acid.
  • the source of water that may be necessary for the hydration reactions of the nitrile functional groups and the hydrolysis of the amide functional groups,may be added at the beginning of the hydration reaction.
  • the amount of water added is advantageously between 1 and 20 mol of water per nitrile functional group to be hydrated, preferably from 1 to lOmol of water per nitrile functional group to be hydrated.
  • Compounds (N) comprising at least one nitrile functional group may notably comprise one, two or three nitrile functional groups.
  • Said compounds (N) may comprise a straight, branched or cyclic hydrocarbon group, that may be for example an alkyl, alkenyl, aryl, cycloalkyl or heterocyclic group, optionally comprising one or several heteroatoms such as O, S, F, and N.
  • compound (N) comprises from 2 to 10 carbon atoms.
  • Compound (N) may be for instance an aliphatic a, ⁇ -dinitrile.
  • 2-methyl-3-butenenitrile and dinitriles such as 2-methylbutyro-nitrile, methylglutaronitrile, ethylsuccinonitrile, succinonitrile, glutaronitrile, adiponitrile or analogous products, or a mixture of at least two of the said compounds.
  • Compounds (N) comprising at least one nitrile functional are either commercially available, may be prepared by known procedures or otherwise may be prepared using conventional chemistry knowledge.
  • the nitrile compounds suitable for the invention are the dinitrile compounds formed in the process for the hydro cyanation of butadiene, more particularly the branched dinitrile compounds, such as methylglutaronitrile and ethyl-succinonitrile, alone or as a mixture; the carboxylic acids recovered are either methylglutaric acid or a mixture of methylglutaric acid, ethylsuccinic acid and adipic acid.
  • Compounds (A) may notably comprise one, two or three carboxylic acid functional groups.
  • Said compounds (A) may comprise a straight, branched or cyclic hydrocarbon group, that may be for example an alkyl, alkenyl, aryl, cycloalkyl or heterocyclic group, optionally comprising one or several heteroatoms such as O, S, F, and N.
  • compound (A) comprises from 2 to 10 carbon atoms.
  • Compound (A) may be for instance an aliphatic a, ⁇ -dicarboxylic acid.
  • compounds (A) chosen in the group consisting of: 2-methyl butyric acid,n-valeric acid,2-methylbut-2-enoic acid,pent-2-enoicacid, pent-3-enoicacid, pent-4-enoicacid,
  • dicarboxylic acids include, but are not limited to, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, malic acid, tartaric acid, aspartic acid, glutaric acid, glutamic acid, glutaconicacid, adipic acid, muconic acid, suberic acid, itaconic acid, and terephthalic acid.
  • tricarboxylic acids include, but are not limited to, citric acid, isocitric acid, aconitic acid, propane- 1,2,3-tricarboxylic acid, and trimesic acid.
  • the process of the present invention comprises at least the step of heating a blend of at least compound (N) and compound (I) as previously defined.
  • Temperature of the reaction may be comprised between 20°C and 120°C, preferably between 30°C and 110°C, more preferably between 50°C and 100°C.
  • Reaction time is preferably comprised between 30 minutes and 20 hours.
  • the exact residence time will generally be chosen so that a satisfactory space/time efficiency is achieved.
  • the process of the invention can be carried out batchwise or continuously.
  • the reaction can be effected in fixed bed reactors, stirred reactors, fluidized bed or transport reactors, gravity flow moving bed reactors or any other conventional mode for reactions.
  • the reaction may be carried out in a single plug-flow reactor or in several stirred reactors arranged in series.
  • the reaction is advantageously carried out in a device comprising two successive and separate reaction regions, a first region operating under stirred conditions and a second final region operating under plug-flow conditions.
  • the presence of these two reaction regions makes it possible to obtain complete conversion of the nitrile functional groups to carboxyl functional groups.
  • This complete conversion makes it possible to facilitate the recovery and separation of the carboxyl compounds, in particular when the nitrile compounds to be converted are dinitrile compounds, and thus to avoid the presence of cyano and/or amide compounds in the final reaction medium.
  • the process can be carried out in a device comprising a stirred reactor, equipped with a condenser in order to obtain reflux and a device which recovers the ammonia formed, and a plug-flow reactor arranged in series with the stirred reactor.
  • the first stirred reactor can advantageously be a loop reactor, comprising an internal circulation loop and an external circulation loop.
  • a heat exchanger is advantageously provided on the external circulation loop.
  • other types of stirred reactors may be used.
  • the temperatures and the pressures in the stirred reactor and the plug-flow reactor can be different.
  • the plug-flow reactor advantageously operates adiabatically.
  • the reaction temperature in the plug-flow reactor is higher than that present in the stirred reactor.
  • the operating conditions of the reactor are determined in order to advantageously obtain a degree of conversion of the nitrile functional groups reaching 100%.
  • NO x compounds relate to nitrogen oxides, nitroso gases or nitrogen oxides, and therefore refers to gaseous oxides of nitrogen. On hand, they are abbreviated by NO x , since several nitrogen-oxygen-compounds exist, such as N 2 O, NO, N 2 O 3 , NO 2 , N 2 O 4 , N 2 O 5 , because of the many oxidation states of nitrogen.
  • the compounds (A) as obtained are advantageously used as such or in the form of a mixture in, for example, the manufacture of polyurethanes, polyesters, polyamides or the like.

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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)

Abstract

28 ABRÉGÉ 5 PRODUCTION D'UN COMPOSÉ COMPRENANT AU MOINS UN GROUPE FONCTIONNEL ACIDE CARBOXYLIQUE 10 La présente invention concerne un procédé pour la production d'un composé comprenant au moins un groupe fonctionnel acide carboxylique, lequel procédé comprend la réaction d'un composé comprenant au moins un groupe fonctionnel nitrile 15 avec des ions nitronium.
PCT/CN2013/090286 2013-12-24 2013-12-24 Production d'un composé comprenant au moins un groupe fonctionnel acide carboxylique WO2015096022A1 (fr)

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Application Number Priority Date Filing Date Title
PCT/CN2013/090286 WO2015096022A1 (fr) 2013-12-24 2013-12-24 Production d'un composé comprenant au moins un groupe fonctionnel acide carboxylique

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PCT/CN2013/090286 WO2015096022A1 (fr) 2013-12-24 2013-12-24 Production d'un composé comprenant au moins un groupe fonctionnel acide carboxylique

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62106042A (ja) * 1985-10-31 1987-05-16 Mitsui Toatsu Chem Inc カルボン酸の製法
WO2007141404A1 (fr) * 2006-06-09 2007-12-13 Rhodia Operations Procede de transformation de composes nitriles en acides carboxyliques et esters correspondants.
US20100145091A1 (en) * 2006-11-24 2010-06-10 Olivier Buisine Conversion of nitrile compounds into corresponding carboxylic acids and esters
CN103539655A (zh) * 2012-07-12 2014-01-29 上海万香日化有限公司 一种2-甲基-2-戊烯酸的合成方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62106042A (ja) * 1985-10-31 1987-05-16 Mitsui Toatsu Chem Inc カルボン酸の製法
WO2007141404A1 (fr) * 2006-06-09 2007-12-13 Rhodia Operations Procede de transformation de composes nitriles en acides carboxyliques et esters correspondants.
US20100145091A1 (en) * 2006-11-24 2010-06-10 Olivier Buisine Conversion of nitrile compounds into corresponding carboxylic acids and esters
CN103539655A (zh) * 2012-07-12 2014-01-29 上海万香日化有限公司 一种2-甲基-2-戊烯酸的合成方法

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