EP2729446A1 - Verfahren zur herstellung von verbindungen mit nitrilfunktionen - Google Patents

Verfahren zur herstellung von verbindungen mit nitrilfunktionen

Info

Publication number
EP2729446A1
EP2729446A1 EP12733683.2A EP12733683A EP2729446A1 EP 2729446 A1 EP2729446 A1 EP 2729446A1 EP 12733683 A EP12733683 A EP 12733683A EP 2729446 A1 EP2729446 A1 EP 2729446A1
Authority
EP
European Patent Office
Prior art keywords
carbon atoms
acid
general formula
mixture
nitrile
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Withdrawn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
EP12733683.2A
Other languages
English (en)
French (fr)
Inventor
Philippe Marion
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 Operations SAS
Original Assignee
Rhodia Operations 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 Operations SAS filed Critical Rhodia Operations SAS
Publication of EP2729446A1 publication Critical patent/EP2729446A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/02—Preparation by ring-closure or hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/80—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D211/84—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen directly attached to ring carbon atoms
    • C07D211/86—Oxygen atoms
    • C07D211/88—Oxygen atoms attached in positions 2 and 6, e.g. glutarimide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/24—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals

Definitions

  • the present invention relates to the manufacture of compounds comprising nitrile functions and cyclic imide compounds.
  • nitrile functions from compounds comprising carboxylic functions, preferably of natural and renewable origin, and from an N mixture of dinitriles comprising 2-methylglutaronitrile (MGN), 2-ethylsuccinonitrile (ESN) and adiponitrile (AdN).
  • MGN 2-methylglutaronitrile
  • ESN 2-ethylsuccinonitrile
  • AdN adiponitrile
  • amine compounds comprising nitrile functions are important products for the manufacture of amine compounds.
  • the dinitrile compounds lead to amines which are, for example, monomers which are the origin of polymers such as polyamide, for example.
  • the mononitrile compounds lead to amines or amides which are for example used for the manufacture of cationic surfactants.
  • nitrile synthesis processes including synthetic processes from ammonia and carboxylic acids. These processes mainly use hydrocarbon compounds derived from petroleum refining, and ammonia, which are obtained from hydrogen from steam reforming processes that consume gas and energy, as starting material.
  • renewable resources can be produced from plant material grown or not, such as trees, plants such as sugar cane, maize, cassava, wheat, rapeseed, sunflower, palm, castor oil or the like.
  • This plant material is transformed by methods generally comprising several mechanical, chemical and biological steps.
  • adiponitrile a large chemical intermediate used in particular in the synthesis of hexamethylene diamine and caprolactam (monomers for the manufacture of polyamides), obtained by hydrocyanation of butadiene, generates a stream of dinitrile byproducts comprising predominantly branched dinitrile compounds such as 2-methylglutaronitrile, 2-ethylsuccinonitrile.
  • This mixture of branched dinitrile compounds is obtained by distillation to separate it from adiponitrile. Since the separation is generally not complete, the mixture of branched dinitrile compounds may also comprise a small proportion of adiponitrile.
  • This process requires purification steps of 2-methylglutaronitrile and 2-methylpentamethylenediamine.
  • the invention provides a process for the preparation of at least one nitrile of general formula I
  • y 1 or 2
  • R represents a hydrogen atom or one or more substituents
  • an N mixture of dinitriles comprising 2-methylglutaronitrile (MGN), 2-ethylsuccinonitrile (ESN) and adiponitrile (AdN) is used. At least the cyclic imides 3-methylglutarimide and 3-ethylsuccinimide are obtained.
  • MGN 2-methylglutaronitrile
  • ESN 2-ethylsuccinonitrile
  • AdN adiponitrile
  • the N mixture of dinitriles is a mixture resulting from the process for the manufacture of adiponitrile by double hydrocyanation of butadiene. It preferably corresponds to the distillation fraction making it possible to separate the branched dinitriles (2-methylglutaronitrile, 2-ethylsuccinonitrile) from adiponitrile.
  • This mixture of dinitriles generally has the following composition by weight:
  • 2-methylglutaronitrile between 70% and 95%, preferably between 80 and 85%
  • Adiponitrile between 0% and 10%, preferably between 1 and 5%, the 100% complement corresponding to different impurities
  • the process of the invention uses a carboxylic acid of general formula II as described above.
  • the carboxylic acid of general formula II or IV is derived from a renewable material of vegetable origin.
  • a material or renewable resource is a natural resource, animal or plant, whose stock can be reconstituted over a short period on a human scale. In particular, this stock must be renewed as quickly as it is consumed.
  • renewable raw materials contain a significant proportion of 14 C.
  • the nitriles of the invention consist of organic carbon from renewable raw materials.
  • this preferred characteristic could be certified by determination of the 14 C content according to one of the methods described in the ASTM D6866 standard, in particular according to the mass spectrometry method or the liquid scintillation spectrometry method which are described in this standard. .
  • renewable resources can be produced from plant material grown or not such as trees, plants such as sugar cane, corn, cassava, wheat, rapeseed, sunflower palm, castor or like.
  • the carboxylic acid of general formula II or IV may be derived from renewable resources such as natural polysaccharides such as starch or cellulose, the starch being able to be extracted, for example, from maize, wheat or potato. It can in particular come from various transformation processes, including conventional chemical processes, enzymatic transformation processes or by fermentation.
  • 2,5-Furannedicarboxylic acid can for example be obtained from mucic acid or from hydroxymethylfurfural.
  • R is chosen from:
  • linear or branched alkyl groups preferably having from 1 to 6 carbon atoms and even more preferentially from 1 to 4 carbon atoms,
  • linear or branched mono, poly or perhalogenated alkyl groups preferably having from 1 to 6 carbon atoms and from 1 to 13 halogen atoms and even more preferably from 1 to 4 carbon atoms and from 1 to 9 carbon atoms; halogen atoms,
  • R 2 represents a linear or branched alkyl group having from 1 to 6 carbon atoms and even more preferably from 1 to 4 carbon atoms or the phenyl group ,
  • halogen atom preferably a fluorine atom.
  • y is 1 and R represents -CO-O-R 3 with R 3 which represents an alkyl group having 1 to 4 carbon atoms in the general formula II or IV
  • the compound of formula II or IV is selected from 2,5-furannedicarboxylic acid, 2,5-tetrahydrofurannedicarboxylic acid, 2-furoic acid, 2,5-furannedicarboxylic acid monomethyl ester or 2,5-tetrahydrofuranyl dicarboxylic acid monomethyl ester.
  • the compound of formula IV when the compound of formula IV is 2,5-tetrahydrofurannedicarboxylic acid, it can be used in the form of the trans isomer, the cis isomer or a mixture of the isomer cis and trans isomer.
  • the process of the invention is advantageously carried out at a temperature of between 150 and 350 ° C.
  • the pressure used is generally between atmospheric pressure and a few bars.
  • Catalysts can be implemented in the context of the process of the invention.
  • catalysts mention may be made of phosphoric acid, phosphates, borophosphates, sulfuric acid, sulphonic acid, benzene sulphonic acid, toluene sulphonic acid, such as para toluene sulphonic acid, naphthalene sulfonic acids, silica, alumina, clay, silica / alumina.
  • a quantity of 2-methylglutaronitrile (MGN) or of mixture N is used such that at least one molecule of 2-methylglutaronitrile (MGN) or 2-ethylsuccinonitrile ( ESN) is introduced into the reaction medium, by acid function of the carboxylic acid of general formula II or IV to be converted into a nitrile function.
  • imides are formed, in particular 3-methylglutarimide from MGN and 3-ethylsuccinimide from the ESN.
  • the process of the invention also comprises a step of recovering at least the nitrile of formula (I) or (III) on the one hand, and at least the cyclic imide on the other hand from the reaction medium.
  • This recovery can be carried out by separation of the compounds of the reaction medium, according to any known method such as distillation.
  • the compounds can be obtained by reactive distillation.
  • the nitrile of formula (I) or (III) that it is desired to obtain has a boiling point lower than that of the reaction temperature (which is particularly the case for nitriles having a low number of carbons)
  • this nitrile can be distilled as it is formed, displacing the equilibrium of the reaction in favor of the formation of this nitrile; this is therefore particularly advantageous.
  • This reactive distillation method may for example be used when the nitrile of formula (I) or (III) is 2,5-dicyanotetrahydrofuran or a mononitrile.
  • the compounds can be separated by extraction with hot water.
  • the imides are generally soluble in water, unlike nitriles, which allows a good separation by an easy way to implement.
  • This route is preferred especially when the nitriles and imides to be separated have boiling temperatures that are close and they are therefore difficult to separate by conventional distillation, for example.
  • the temperature of the water during this extraction is generally greater than or equal to 50 ° C.
  • the nitrile of formula (I) or (III) thus recovered is hydrogenated to form the corresponding amine, according to a method known to those skilled in the art.
  • a nitrile of formula (I) is recovered, its hydrogenation can lead to the amine corresponding to the compound of formula (III), by hydrogenation not only of the nitrile function, but also by hydrogenation of the double bonds of the furan ring.
  • an amine in which all the carbons are biobased (because derived from a biosourced carboxylic acid, that is to say a carboxylic acid derived from a renewable raw material), and whose nitrogen atoms are recycled ( as derived from by-products usually burned which generates carbon dioxide and oxides of nitrogen, greenhouse gases that must be treated to meet the legislation in force).
  • the diamines can be used as raw materials for the manufacture of polyamides, which will thus be partially or completely biobased depending on the acids used for the polymerization.
  • Amines can also be used to prepare surfactants.
  • the cyclic imide recovered according to the process of the invention can be reacted with an alcohol to form the corresponding diester.
  • an alcohol such as WO2008 / 009792 and WO 2009/056477.
  • the diesters can be used as solvents.
  • THFDCA cis 2,5-tetrahydrofuran dicarboxylic acid
  • reaction medium is then analyzed by GPC and the following results are obtained:
  • reaction medium is then analyzed by GPC and the following results are obtained:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Furan Compounds (AREA)
  • Hydrogenated Pyridines (AREA)
EP12733683.2A 2011-07-08 2012-07-05 Verfahren zur herstellung von verbindungen mit nitrilfunktionen Withdrawn EP2729446A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1156222A FR2977586B1 (fr) 2011-07-08 2011-07-08 Procede de fabrication de composes comprenant des fonctions nitriles
PCT/EP2012/063093 WO2013007586A1 (fr) 2011-07-08 2012-07-05 Procede de fabrication de composes comprenant des fonctions nitriles

Publications (1)

Publication Number Publication Date
EP2729446A1 true EP2729446A1 (de) 2014-05-14

Family

ID=46506365

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12733683.2A Withdrawn EP2729446A1 (de) 2011-07-08 2012-07-05 Verfahren zur herstellung von verbindungen mit nitrilfunktionen

Country Status (7)

Country Link
US (1) US8981128B2 (de)
EP (1) EP2729446A1 (de)
JP (1) JP2014523893A (de)
CN (1) CN103649050A (de)
BR (1) BR112014000397A2 (de)
FR (1) FR2977586B1 (de)
WO (1) WO2013007586A1 (de)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2982858B1 (fr) * 2011-11-18 2013-11-29 Rhodia Operations Procede de fabrication de composes comprenant des fonctions nitriles
HUE029038T2 (en) 2012-05-25 2017-01-30 Janssen Sciences Ireland Uc Uracil spirooxetan nucleosides
GEP201706757B (en) 2012-12-21 2017-10-25 Alios Biopharma Inc Substituted nucleosides, nucleotides and analogs thereof
EP3786234B1 (de) * 2018-04-26 2025-04-16 Zeon Corporation Polymerzusammensetzung, herstellungsverfahren für cyanogruppenhaltiges polymer und cyanogruppenhaltige polymerzusammensetzung
TWI874791B (zh) 2020-02-18 2025-03-01 美商基利科學股份有限公司 抗病毒化合物
TWI794742B (zh) 2020-02-18 2023-03-01 美商基利科學股份有限公司 抗病毒化合物
AU2021224588B2 (en) 2020-02-18 2024-07-18 Gilead Sciences, Inc. Antiviral compounds
JP7688152B2 (ja) 2021-04-16 2025-06-03 ギリアード サイエンシーズ， インコーポレイテッド アミドを使用してカルバヌクレオシドを調製する方法
US12345003B2 (en) 2021-05-04 2025-07-01 Schwarze Industries Llc Automatic side broom strike pattern positioning system for a street sweeping machine
JP7719954B2 (ja) 2021-08-18 2025-08-06 ギリアード サイエンシーズ， インコーポレイテッド リン脂質化合物並びにその製造方法及び使用方法
CN118724850A (zh) * 2024-06-18 2024-10-01 上海巽田科技股份有限公司 一种连续制备2,5-呋喃二甲腈和2,5-四氢呋喃二甲腈的方法

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GB722843A (en) * 1952-06-19 1955-02-02 Distillers Co Yeast Ltd Manufacture of nitriles
FR1525498A (fr) * 1966-06-02 1968-05-17 Basf Ag Procédé pour la production de nitriles
JPS5419963A (en) * 1977-07-13 1979-02-15 Noguchi Kenkyusho Production of 2*55 furandicarbonitrile
JPS5687549A (en) * 1979-12-19 1981-07-16 Mitsubishi Petrochem Co Ltd 2-formyl-2-methylglutaronitrile
FR2902095B1 (fr) * 2006-06-09 2008-12-05 Rhodia Recherches & Tech Procede de transformation de composes nitriles en acides carboxyliques et esters correspondants
FR2903983B1 (fr) 2006-07-18 2010-07-30 Rhodia Recherches & Tech Procede de fabrication de diesters.
FR2922887B1 (fr) 2007-10-31 2010-01-01 Rhodia Operations Procede ameliore de fabrication de diesters.
FR2960236B1 (fr) * 2010-05-21 2012-05-11 Rhodia Operations Procede de fabrication de composes comprenant des fonctions nitriles

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2013007586A1 *

Also Published As

Publication number Publication date
FR2977586B1 (fr) 2013-07-12
WO2013007586A1 (fr) 2013-01-17
BR112014000397A2 (pt) 2016-08-23
US20140171663A1 (en) 2014-06-19
FR2977586A1 (fr) 2013-01-11
JP2014523893A (ja) 2014-09-18
US8981128B2 (en) 2015-03-17
CN103649050A (zh) 2014-03-19

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