HUE028778T2 - Metatézis lépést tartalmazó eljárás telített aminosavak vagy telített aminoészterek elõállítására - Google Patents
Metatézis lépést tartalmazó eljárás telített aminosavak vagy telített aminoészterek elõállítására Download PDFInfo
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- HUE028778T2 HUE028778T2 HUE11733990A HUE11733990A HUE028778T2 HU E028778 T2 HUE028778 T2 HU E028778T2 HU E11733990 A HUE11733990 A HU E11733990A HU E11733990 A HUE11733990 A HU E11733990A HU E028778 T2 HUE028778 T2 HU E028778T2
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- C07—ORGANIC CHEMISTRY
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
- C07C229/08—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to hydrogen atoms
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- 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
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/12—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/165—Polymer immobilised coordination complexes, e.g. organometallic complexes
- B01J31/1658—Polymer immobilised coordination complexes, e.g. organometallic complexes immobilised by covalent linkages, i.e. pendant complexes with optional linking groups, e.g. on Wang or Merrifield resins
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2265—Carbenes or carbynes, i.e.(image)
- B01J31/2269—Heterocyclic carbenes
- B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
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Description
ii)r prppscjttg amine selg* or ssîtrrafed autism esters : cnmpnsdsg: si metathesis s:fep: tfeseriptson 8i 4 process. fnr fee sÿÂMlM#fo«g^:lÂ-«ua^ml?)ô»{M«K>le:'âdé? or esters írom 8 nmoounsaturaied fetty acid or ester cmHprhipg aï leas.! one metathesis stage.
The polyanudes industry. whether iu m;nn darn· re symhetic liber; or thermnsettmg resirss: uses a who ίο mop of utonomers coosw-mg of dfernhses, dsactds, end in particular long-chant w-îuïubo ackis Tim: iatior sfe norma! ív referred so as Nylon. defused by she length of’the methylene tpsparifeng: rtvoaSSítde -- CO.....Nil- functional grotfps, λ bus It is that Nylon b. Nylon 6-6, Nylon ci-IO. Nylon 7, Nylon :pi: Nylon 9,
Nylon 11. Nylon 13, and she like, are known.
These monomers are pnës'aiïÿ iinitisuiaithrsd by the ehendesd synthesis room using in pAI«rf an starting materkus, <N to olelrnss oyelosíikanes ofbéngene. ilty^Focarhoßs resulting hvmr fossil sources, but alsói In some specific carcv starting; Troth castor oil (Nylöo I 1 j or: crude oil (Nylon is Ίο! or iesquerohc ml (Nylon lay C’urrem developments in environmental 'natters are lendings in the fields .of energy andiOhOssiistryySo the «s.t£.piii5'tk8tjon:íöFBates#'.sttnÄg'iftiàM origJ»Äi|tb&œ a renewable ww being: invofeti This is the reason why some: studies' have been nndertliken to develop, on the lodustfisd: scale:, processes usihg latsy aetds/essers as starting mittend lor the munmaeture n; feese monomess.
This type of approach has only a few Ihdustrihl: examples. One of the rare examples of an industrial process using a natural fairy acid as starling material is thru of the manufacture, from ricmoleu: acid extracted lkat· castor oil: of I fmmiSBmndseaúölc acid, which it; the base Ibr the synthesis of feilsun I !<». This process is described In the work '!U-s Procédés de fkhrochimie'' [Pclmchcnnca! Processes! hy Λ Chauve! et al. which appeared in Editions Technip fl98b). 1I -AminonndeeanoK: acui is obtained in several stages. The first consists of a njethanolysts of cash«· rdf ttr tt basic ntedtune producittg toethy l ricinofeste, oddChuis stibsCituentiy subjected: to a pyrolysis itv order to obtain, on the one hanti, heptamdbehyde and, on the ölhet hand, methyl oodesylgPittee The fatter is emtverfed to the acid form by tsydfotysis, hnOsequemh. the add: formed· is subjected to a hyiiKlbîXîmitîabon to give ihe orbronitnated add. which is convened by ammo mattem: to: I Natrdnoundecanoic seid.
In Ibis ΊΝίΤ rohte, the main studies rafefed: to the synthesis of P-ammoTtonanoie add, which Is the pmeumor oHNylon 9} atom oleic itesd of monte! origin. A;. regards Ibis speed!·, monomer mention may he made of the work -'n-Nyions. Their Synthesis, Structure: and S-Vopetties”, 1997, publishes- by j. Wtley,and Sons, chapter 2.9 (pages 381 to 389} <>f which is: devoted to Nylon 9. This article summaries the achievements with regard to and the studies eatried out c-n the; subject; :Mention: Is made fecfcite oft page yfef, qfthe process developed by the fermer Sovint: thhon which resulted in tbc coinmerelnbaafion of Peisrgpn®, Mention is also made duudn. on page 389. of a ptoeew developed imjapan which uses oleic acid: bum soybean ml as -ms:!imt mate: ad The corresponding description «IV'·« îo the wofo by fo Rüwï, 1 («gar:··-. Chemistn of MuerosnotevTcf' fiTbfi. Marsei Oekker. inc., part SS of wiuci is devoted::£«::-osîl..2'î9s..iHe:«>;tS:t«rîSg of surfs a pm«SS< ipor iis path *1# . applied:; dttmpapy É8S earned Mt sfttdteS tih this: tieid. Sí has described, in the French: r>at»^H«áM«':pbi|.she4 öhddrhltií» M.2$t|74 i v apec««» for i\m·synthesis of »'«»'f^psílaate" 8cids/(ísí«fS of this typ from a pt|fo$. Umgmhaio sfostv sdklteslcr hy sufejeafog: ike imter to a estelydc rfoss iptätlpds reaction •vífH.l·,· sh «ppoööd comprising:. :a nitrile: ftmrfmmd followed hy
Swdrogeaáíson, irr dw French ptttette ppphptten filed on Ffov. ff :2öi& ander number PR $$$77801 !f also:: described a process ihr the sylppsig· of iiHimittotdksriote adds or their esters from: natural linsahjrhted :i<mg·· sham fatty adds passing: through ah iiitermadktte epmpomKfof dwussrfvimlsid nitrile l>p;;öne-öfih«<WfeWivtr forms of which employs, in the Sün ai phase, a m>s* metathesis of tim o-auisamraied: mrrite with a compound Φ acrylate type. FinaHy, sir the h rendi pstem appitessfon hied on i eb. S, 2 »99 ander number .FR ÍI9SÖ794, in described an aiiernative form of the aisove process in which mho IntettMbiat«: compound;: is: of the unsdturated usnMiç type. Aii: these orocessfes result in a final stage of hydrogénation ofliwidtrite ftmefiotlrf group imdof foe double bond.
He objeöfc.o&the process of: the: invention is to improve the :pet:%anaoes of pmc«ss#s:#^fo>i«fo;i:8:fhé final phase, successively a cross metathesis: and a hydrogenation·: This- is besmuse it is hnportanf to he «Éje to have available an efficient catalysts: of these:: two successive^reactions white minimizing the inubher of opm&sfoni;, which imdorady has an disci: on tim: Corf cost.
The IsydrogenaPoi! of the abrite tbnetiona! group to give a primary am ins is generally; cart sod out on the iMusttml scale :iï[«hiy·"rédtic^n^;:'heterogeneous catalysts, such as Ratify cobait or nicker The use of other mends known tor their emniyfo ucostty In hydrogenation has also been envisaged «rider heterogeneous conditions, Mention may be miete, for example, of piatlmtm, palladium, ruthenium or iridium, alone or in combination. Mention may be made, by way otilhistration, of patent UK 1 ! ?7 154. widen describes the use ot various catalysts. Raney nickel, palladium or platinum, for the hydrogenation of the nitrite tunes louai group of I Ucyanmmdeeanote acid, and patent UK I 273 874, which describes the use of a rulhemum camlys· deposited μ silica for the same reaction; resulting In tf-aminodtfoeesnoie acht However, nickel deposited cm a,support, such as sihea. is thesatalyst most generally adopted:
The homogeneous ealrfysis of this hydrogenation reaction of nitriles: &> give amines has also been the subject of studies ami is described; in rite literature Mention may he made, for evampte:, of rite hybíOgeimflmvöí heiuomtrite to: give bemytetftte«: wftb .homogeötiöös tateto» catalysts described by M, ffidai or al. in Organonleteihes, 2002, 23, 3897,: an# m the paper by R. H. Moms et: ait m Organottistsloes; 2007, 2fo 594P-$949, and In the paper by M. Beller el al. in ChemSusChem. 2008, i. j006: Chest; Bur, T, 2008. 14. 949! : Tetrahedron Lett., 2009. 50; 3p$4 The addition of a base in order to cury out this type of reaction is described in Simse papers.
The sequence of reactions, metathesis and ihen hydrogenation ni the metathesis psc-doeis. is described; In patent application: OS 3009/(|9|4d9 of Cargill, which describes a methpd; ;for pröducsitg hydröggfigted rnoimbesis products: with sucousslye stage;; ofptetathesisitmd jiydrugenatitm: in which the tiydsogenation stage is: carried out by treat Írig rjsc: rnotuthesis reaction -íTíe:íí:í tt m<. :«5çî·« î at nft í>g.:-:í:hiE?:· rn e-tüthes is stiái^í^ st, using a heterogeneous hv8rogena&>o catalyst ceawisiibg. according s? alSdhe examples, of supported nickel. h may also be çpectfled that therçaelsost carried OiR iß the cMmpies is a homontcfalheds «rstsybesa oil which results, due torihe eompodfiprr of thisr oil: arid: Ida #sciRtí of ahy segafatiori of ilie »tcMaesis reaction: products, itt a complex, mixture ofesters atsdriotin a monomer eáp'^^xáfn^ípgspói^erl^i hí prnnt of tact, the apposant company has discovered thai I? w pens inks in the process.; to carry odfthe metathesis and hydrogenation stages «sing just one Initial catalytic compound thus composing the same active metal as catalyst. The metathesis catalyst:, upgraded at íhe:end ot: the: metathesis reaetlotr, tldlils, during the second stage, the mié ofhydrogenatioti catalyst, A suhlen· maues of the invendue |:Sai:.pr.ôçgssifotrlhe,sysithesiS:itsl a saturated hmg-cham saumtnmo ester lacdd) -eo-rípiisiep; horn: ő to Γ7 cat boti at 000., characterized at that it is Obtained. in a Sum stare, b;· a Cross metathesis reaction between a first acrylic compound, chosen frooMmtvionlírilc, acrylic acid or on acrylic truer, and a second mononnsmuraied cotfipormd comprising at ie«st one nitrile, add -ofester"trivîtI one ofthe.se compounds comprising 0 nhrde functional group and the other .an acid or ester ftwtk»1$ group, in she presence of a metathesis catalyst of rnthemum earbenes type, and, m a: second stage, by ike hrdrogcnatloa of the mtmormsannsted nitrile-ester (acid) obtained in rhopresence of tbemteiaiheBis catalyst horn the praeedspg stagemmg as hydrogenatton catalyst. TStc metatiiesis reaetioi· under consideration is across meiitthbsw tenet ; on between g: m<motmsatorat»d: acid or cs-cr compound, generally resulting front hteochcmistry,: with neiy!bnhdle:, or across metathesis: reaction:. between an urtsaturated nlttute cismpounil generally residting. írom óiéoctssroistyy:. with so acrylie compound:. an add or acrylate, and, in this case, preierahty methyl acrylate.
The process has ken-tisyeiopea lot: the purpose ·ί>Γ:ΐΝ^·^^ϊ*ί<τ»·ΐ^ίΰ>ο::ρ^^^·ΐ»^,ί:««ϊ«ΓΪ&Η:Τ^ from renewable natural sources, However, it can also dearly be gpplkÖ to the analogous: snonounsatarated eompounos obta ined by chem ica I sy.oihtuns.
The mets thesis stage: is carried out oecth'dmgdo Shu following réaction scheme:
Vmvm * ™""*' Ncugdh %/' w R^CH-CHRs
With Rr~'H or (OU. · R!f R .“COOR.·. or CN. R^OORíörCd,
Rf~H or R*. R;—alkyl radical cd' I to 4 earhon atoms. n-2 to 1:3, nr d U) 11. and k; is different from R>.
The f#mm &f-m. final ester iacid}sywihesMsssefttmliy άηρβ&** v^Hch macis with Öté aery he compound.
In tfe compound rssoliinf from eleoehemistry, nr obtained Rom renewt*^ mttumi iimy * acids, E, is d-her H or an alkyl radical ora ttmclmon! alkyl fiscal comprising ä irivUMt fimetid&ä plup fCN. COOH orCOOR). iRv wifi be H when tbc mmmri fatty ester will, feu: example, be snbtected m au etheooiyms nr, m some esses, to a pyrolysis. "Πιο inroads of the «,ιη-attutto estermetd obtained is inert dtrccHy related In toe i( rkl·*..... radical of tbc bitty e^lerkf bos it is thai a will be egad to 7 with oldó acid, to 4 wi th petrmieienic acm. to 8 from tiemoieig acid snbjixmd in a pyrolysis. o> 10 from: iesquerohe acid subjected ίο u pyrolysis and the ike, as is described Ortho French pdeot application published endet murdwr Fii 2 012 :741:
Ry wtlibe ári alkyl rabteat when, m ÍO%kr~R*, Reis Hi Tbls corresponds: ist the use in iheproeesspi ä ittOttiattissttufaied nsurtd tatty acid such as, for cxantpte, oleic adidf paimitdicic acid, petroseienw aem, ieuromie acid, and tbc like,
Rywiiifea a Rt&eilbwd'alkykksáissf whtm*.1« {¢2140,^ --¾ %&i$% radical-represent mg a kV kOOH or COOR bivalent Rfsermua! group which will be identical to R >. The conuxsnnd tv ill then be \n tbc discid:, flieste·· or dittitrite fôrm. It wîiî then he. partie«iarly advantageous for ids formula of the con^emnd io tSiWM· k: symmetry which makes it possible to optimise the yields uf ima! «..m-amino eslerriickl. 1 he product am oi compounds of this type, in particular by metathesis, Is described in the abovemernkmed »pplicimom: I R 2Ri2741. FR 0857780 and FR 09507941
As regards the: acrylic· compound, the: choice of the trivalent functions!: group R* te related to tbs nature; of tbc teivdent Iknetiofial group of: ihe :other eompsnnd, Rj having to be: nitrile: when R;,> is estenaeid and conversely sstef/aelO.svhea R.: is nitrite.
This reaevkm results· in unsaluraied idtrite-acids or nitrlie-esters.
Preièrabiy, tim crass metathesis seaet iter wi th acryhmbrds is carried out: with acompound chosen.from 9-deccuoic acid Of ntsthyi k-deeeamm·. tesulimg fi-om the ethenoiysis of oidc acid or methyl okate. i(k tmdeeegoie seid or methyl iOmrakeenosia, madring: Rom file cracking of ridooicic add ormeihyi tidttolesie, oleic add dr methyl oienie, Rmeiadeeenedide acid or methyl O-octadeccnedioate. resulting from the iiomometaító of oleic add, crude: add and methyl isueaie, or i24ríd&eenoie,acfd or methyl i2mi:deepn&ate,.r£su^
The cross metathesis reaction of the acrylic ester (aeid) Is carried out with * compound: chosen ttonr 9-deoenenltrile, : resuiitng Rom 9-deceneie acid,, i:ó-ttndeeenen:iíriie,: resulting Írom i R-undeeenoie add, .9-. oetadeeenemtrik or oieouttrile, resnlttng Írom olde aefd, R-octadecenedinitrile. rest)!·Ing from 9-oetasieccnedieic acid, efucnnltrile or l2-trid«eervoîîiîrde, i^suitlng iionr iesquefoilOaerdi rbc eross metathesis reaction with a compound: of acry iie type Is cartisd Opt nuder conditions which are fully known,thé metathesis reaclmn is preferably carried out at a reagtl^.tPitprätMfi AÎ&9tW«ip 2b and 120 “C and under a pressure oi between 1 and IP bar. m the pmseaec ofa turnenums-based t.TUaiys?. k Wilkprejcfäbiy bs í'in-kd mst <u 4 mw Ptç,sSU?“ bf between and U) har and more prefix dxy at atmospheric pressure whstr the ^ meuidiC^;i results in. (hr formation of a light compound, fix example ethylene. xi ordre to make possible j>ÄSV r ç· I ϋίϊ íil ô î ííiof ’ Í h s? (Csetlőn Cím f?g carried out without: stdvesx or in. fheprexCdcc of a solvent, soon ·»» totooot gvietses or diofdooSntotbone. bonsene, chkooherzesie or dimethyl carbonate, ; lie catalysis of the metathesis reaction has been (he subject of a great r«an> stsklies: and: die deyeioonîéotxrf bophistiostbif vSiaiyixr svstan^, Mention may be mmíe, for example, bf (N tungsten; complexes: developed ?><·" hchroek et al (h Am Chem, Sue.. HR! {iöS6í, S77i)m: Basset,ei ah. Aogew. €hem„ 1:.(1 (mgr, ,>J ; 1092). 62>9· <;€>rubbv” catalysts have more recently appeared: (CitPhhs ef nt., Angew. (hem.. f.d hngl.. 34 (Abkfb 2()39, and Organic kCiM'S I :(1999:), 953), Ouch are rHtheidnin-benayiidene complexes operating th homogeneous: catalysis;
Finally, studies have been carried »«· for the preparation of immobil)«:·:! catalysts, that ss to say, catalysts having an active principle which is that of the hixoogenPhus cataiyst, in particular riiiheninm-aubenc complexes, hot which is immdhdiaixPixran inactive support. The dies* .Stôdfès is to increase the selectivity of the cross metathesis reaction with regard to side reactions,: síiéit as Mtomometatheass" between lise reactants brought together Äy relate pot only to the structure of the catalysis |uf also to She effect of the reaction::medium:and the additives whileh may be introduced: the rnthebtuín catalysts dtc ipreterably ctmsen ilaxtv ehatgecl or uncharged catalysis of general lorm-da (X ! M:X2 uRuicarbcnc ¢11(1.11,(1..2 (,1(1.3¾ in \vh ich ; o abb,: c, d and teas« Identical :©t different integers, with a and b espial to (), 1 or 2¾¾ d and e equal to Cf i, 1:, 3 ,·»· 4; ο XI ähd X2. winch are identical or ddlereuf each represent a charged or uncharged ansi momieholatmg or poiyehelaring ligand; mention may he made, by way of exatnpleSi of bandes, -utbase, carbonate, earhoxyiates, alkoaides, ghenolafes, amides, tosyisitc, iiexanuorophosphaic. tetrad uiiroborafe:, bis(trfflyl}amide. an, alkyl, Kdraphenylhoraie and derivative;,. Xi or >;;; ciiÎÎ be bunded to tU or (.,2} ;x to ?ho icarbene (,'} so a,x to form a bukmtate c-r chelate ligand on the ruthenium; and A ig t. 13 ami (. y which are Identical or dinerem, arc eissitrorwdotritfipg ppnds^sneh as phosphine, phosphite, phosphonite. ph:osphmite,: arsine, rallbene. an olefin: or an aromatic compound, a carbonyl compoitnd, an ether, an alcohol, an amine, a pyridine or derivative, an ionra:, a ttnoctnev c.-r n hetciao'ychc carbone; si 1.1, 1.2 or (.a gmt he bonded to the (caibcaa Π so as to farm a. bkiemase or chelate ligand, or a tridenmte ligand: i&: the icarbrne C) boat?, represented by the general fortnula: ; R1} (1(2), lor which R ! and R2 are identical or different groups, such as hydrogen or any other saturated or tmsaiarated gtid cyclic, branched or linear Hydmesrboo group or aromatic hydrocarbon group. 'Mention may be made, by way of examples. of rnthetnusn alkylldcnc, benzyíitfeúe or cuiMlsae complexes, such as vinyikfene-s RtwAmCHR or alteOyiktcncx Rue<>m2-~CR1R2 or nmebyiiofenss. Λ fmmdemal group which msk«s: ü possible lo improve the retention of she ruthenium ç.ôsïtpfek îo an Ionic: liquid cats bo gpa&ed: to· at leas; one of the ligands XJ, X2, Id os· 1..2 or to- the earbehe C, This functional group can be charged or utteh&rged, such as, preferably, an ester, an ether, a thiol, an acids an alcohol, an amine, a nlftogenorss heterboyde, a sulfonate, o carboxylate, a quaternary ammonium, a guSnkhniorn, à quaternary phosphonium.,.a pyridtmum, an rmidazokum, a rmrplmtlnkm'r or a sulionkun.
The- mutafeems· eufs-lysi. can optionally be rendered heierogenebns on a 'support in: order to racibtate the tarn ο V e ty/r e e y ç H hg thereo f
Tite cross metathesis· catalysts of dse process of the invention· .as preferably ruthénium Carbones: described, tor example, la Aidrichimica Actio Vol, 4(5, bio. 2, 2087, pn. 45-52. The preferred: catalysts are the catalyst; Umicore MSI (sold by Unocore) of ioromia (A) below, and the 2nd generation Hövéydn-Grnbbs catalyst, also known as Hoveyda H (sold by SignUt-Aidrich), of formula SB} below:.
The reaction tinte is Chosen as a fenctioft of the reactants and operating conditions employed and in order to reánk the end of She reaction.
As the metathesis is ait Equilibrium· reaction, it is advisable to shift this equilibrium in order to proceed towards tetalconvers km. in order to do tins in the case where the Co-produet of the reaction ss a light: olefin, such as ethytCoCi u is easy to "degas” the reactor from time to time in order to force the removal of the light products and Sims to proceed towards total conversion, In the ease where the co-product is a heavier olefin, optionally a: fttnetional one, the extraction operation is more problematic Insofar as it is necessary to keep the two reactants and She catalyst ns the reaction medium, furthermore, if it is necessary to separate, at least in part, the tmsaittrafed: nitrile-ester (acid} by distillation and to remove the light products before the hydrogenation, thé· operation has to be carried out so that the metathesis catalyst .remains in dm heavy fraction with the nitrile-ester (acid) In; order ίο use it in its foie of hydrogenation catalyst. fp this operation, during the separation, the very heavy compounds pp; removed: from the medium, which compounds would: thus be hydrogenated with the heavy fraction, the it separation: oeeurrfag élni ing asahsequem purification of the final: amino aeidfester.
The other way of shifting the equilibrium is to use. an excess of reactant, typically in this atstance an excess of acrylonitrile or alky l acrylate (generally methyl acrylate). From a processing viewpoint, the IIrsf stage would be carried out to completion with the exhausting of the metathesis catalyst, the excess acrylate or would be distilled ídr recycling, and íhen, is a second Magé, fog unssfuratcd íian-ídsrile^íiiíísvaisd: •'Omooumi présen) in the reaction medium would be hydrogenated m the presence oí the mtfoß «i the: catalyst of ids Isi stage in its hydrogénation rohr Î he amount of ruthenium metathesis catalyst mtroduced dot ing the first: stage is chosstt so that it Sisnm ail the possible conversion of the nonacrytic reactant present in the change. H observed that: said catalyst, under the oosratmg cohdbiMs o f the metathesis siagg, |s; converted alter the rettcifom tf is er dene-ivated and loses its catalytic activity stier metathesis - It will be o-bseque-oh os'ooteu by foe term degraded" tor saul reactiots lo the batch process, the amoünt of catalyst can east!y be «41utled t« order to give: foe destted convennot; at eompiete degradation of the catalyst.
Altar: lise romathess map, the: reaction tncdittm comprising the tniheníiom is ttes s»fo|8ol:e«l IP A hydrepnatlou, The. ruthenium metathesis catalyst is degraded on epropfCriooof the nteiidhesis stage dm tbs: metal Is sitii preseni in the reaction medium iß «".form apptOpriate ldi· the hydropnmhm stage.
The hydrogenrmon feactldh is thus directly carried otü oti the reactant mixtnre: scsniUng from thst arietatlîcsis stage add nr the preadnee of the residual metathesis: catalyst acting as bydropnationeutaiyst, mtoer a hydrogen pressuré -mé ré tfejlrérérété Pf a base, the pressure is between 5 anti 1110 bam prêterais iy between id: and 30 bar. The temperature in between s0 and 150 '"C. preferably between 80 and 100 T'. I be base can lse, tor e cample. smiimn hydroxide, potassium hydroxide, potassium teftfontoxide or ammonm. I be nase is generally used at a content pf 10 to 80 mol % with respem to the nnsaoaated mtriíe-ester substrate.
The hydrbg&tmtion reaction can be earrigd ónt with or withotn solvent, in the: case ot a reaction to a solvent medium, the preferred solvents used for the metathesis and hydfpgenatimr stages are aromatic solvents, such ns toluene or xylenes, or « chlorinated solvent, such a.s dwhlosomethane or ehíorobctmeme, or dimethyl carbonate.
Dp emtclusipn of this h$dro#&«t.k>S, hläge. pám^á fan without a specific hydrogsttatstm catalyst, the degree of conver.'non of the nitrile fonctional group to give a primary annne is particularly high, even Without addition of Nf 1;, attd also, of cossrae, the redaction of the oieilmc tmsatnranon, without the carboxyl functional group having been affected.
It is fom shown, unexpectedly, tl-at the tlegraded metathesis camiysi exhfoued ac-ivi;y anti selectivity for the hydrogenation of the unsatnrateçt mtoiemcids or nitrile-esters to give sstnfaied amino amds o; amino esters.
The degraded metathesis catalysa can optionally he employed with, in addition, a commotion;-)! hydrogenation catalyst tot the hydrogenation stage. Mention ok-λ be made, among the oictah; cc-nvcntionaily used (or the hydrogenation, of nickel, palladium, pialmom, rhodium or indram Preien-biy. -he degraded netadtesia catalyst might be suppiemenfofohy Raney nTM or pgliadinni-oibcbarcoal
Thus, so a spéciik embodiment, the hydrogenation reaction is earricil out In the presence ot she degraded metathesis eaiaiysl resulting 1rom; the first stage supplemented by a eonventionni hydrogenation: cats if si. U can »fs«? be empipygd ib tbc presence of a solid support (charcoal, SIC, and tbc like} \n order to simplify its recovery.
Tbc amino acids or amino esters obtained according to tbc process of the invention oats be used as monomers itt tbc synthesis of ptbyamides.
Tbc process of the invention is iSiasSotäeäby the following examples.
Cross metathesis of methyl andecenwyte with acrylomtrile,. Ibliowed by hydrogenation, with the Hovevda-Orobfes ! i catalyst;
IÖ0 mg of methyl: I Omndecenoale (0.5 rnmol), S3 no· of acrylonitrile (I mmol) and 10 ml of toluene: distilled over sodium banrophersooe ate charged to a SO mi Schienk tobe purged with nitrogen, 9T mg of 2nd generation· Hoveydir-Cb'nhbs calaiys· t1.5··: |0 : mmol. supplier Signra-Aidrich): are added: and: the mixture is heated a! 5 (10 ;>C for 4 hours:.
The gas chromatography analysis shews that the conversion of the methyl ΙΟ-täodeceaoate Is 100 moi % 196 mol %} and: Shat the yield of unsaturaied nitrile-ether Is 95 mol %.
The reaction minîore is then transferred into a SO ml bam bomb (22 nd). I? mg of potassium hydroxide tCI.3 mmol): are added and'the bomb Is pressurized ander ;?.i) bar of hydrogen, if is heated at 80 '€ lor 48 h with magnetic stirring.
The gas: chromatography analysis shows that the conversion of the onsaturaied rsitrilc-ester Is 100 mol ff and that the yield of methyl I Omminododeeaunate is 00 mol 3%.
Bdimmkl
Cross metathesis of methyl tmdeeenoase with acrylonitrile, foi loosed by hydrogenation:, with .Umicore M5Ï catalyst:
The procedttrc ts thé same as lb example 1, the Hoveyda-Gfubbs 11 catalyst bemg replaced with: 10 mg of Umicore M5 I catalyst ; 1.5- Iff ·'· mmol, supplier Umicore), and the notassmm hydroxide being replaced with 8.5 mg Of potassitsm ierUbsnoXide (0,075 rmrmi).
The gas. chromatography analysis shows that the yield of methyl I T-ammedodecancmts is 88 mol H, bsiurtple g
Unbeceneminisônethyt acrylate w§s fallowed by ibydrogengtiün, with the Hoveyds-
Gmhhs U catalyst:
S3 mg of iOmobèéehetWile (0 5 mmol), 86 mg <4 methyl aeryIaïe 0 mmol) and 10 nil of toluene distilled over sodium heogephenone are charged to a 56 oil Sebből; tőbe pörgeti with nitrogen. 9.5 ing of 2nd genes anon ikweyda-Grubbs e;4:ai;ysi (1 ,Sx 10 ;: mmol) are added and the tnlxtw'e is heated at 1()0 ' for 1 hour.
The gás dtfOmätogfaphy analysis shoves that the conversion of the lO-untieccoeolulie is 100% nod tirât the yield ofumaSonUed mtrlie-ester is 03%. lire reactioo mixture is then transferred into a :K? nd parr bomb (22 mi), i? mg of potassium tert-bittoside (δ. 13 mmol) are added and the bomb ts pressurized under 20 bar of hydrogen, the bomb is heated at 80 *C for 40 h with magnetic stirring;. I'he gas chromatography analysis shores that the conversion of the unset orated nitrile-ester is 100 root % and that the yield of methyl U-aisdtBSdtbccanoate is 90 mol %.
Telpopie 4
Methyl oodecenoiste/aeryionitnie cross metathesis with Hoveyda-Grubbs 11 catalyst, followed by hydrogenation, with supplementary addition of ITU. catalyst; 100 tog of methyl lO-ondecenoate (0 S mmol}, S3 ing of aCrylOSrdrile (t vntuol) and it) mi of toluene distilled over sodium benzophenone are cbarged: to a SO ml Scblestk tube purged with nitrogen, 3 mg of 2nd generation i loveyda-Grubbs cahdy-a (SxlO'Gnptoi) are added ahd the trti store is heated at ; 00 ( ' lord boors.
The gas ebremmiography attalysls shows: that the conversion of the methyl lO-uodeoenoate is 98% msd that the yield of mssfurated nltrile-estcr is 93¾¾.
The reaction mixture is then: transferred into a 36 mi .Pair bomb (22 mj > 10 mg of Í34 Pd/C catalyst, and i 7 mg-of potassium terbhuKsidde (Ο-1 § mmol) are added and the bomb is pressumed tinder 20 bar of hydrogen,. The bomb is heated at 80 >. for 48 It oath magnetic stirring,
The gas chromatography analysis shows that the conversion of the uosaHsntted moile-ester is 90% and that the yield of methyl 12-ammododeeanoale Is 34%
Claims (8)
- 'S.-ühíul a ! m s i gé t ; y po n t o k . Glg-ms d-í? szénatomö; tartalmazó, .íelííett. hosszé lánc:) íímwmrinoészíer (sav) smtézisém, azzal ietieniezve, hogy egyszereséi? tdjitstt mtril-ásxtet (savai 5 aUipmk dó egy dsö lépésben ai: gktffftitt'sl, .sktli&ay. és ük: ftsSft-v! k&züi választott ebo :akri ívegy utct és egy második, -legalább egy niai!. sav vagy észter trivslerts esöportai .tartalmazó egyszeresen telken vagyaiét közötti keresguttbiátéads reakcióval, ezen -vegyütetök egyike nini!-. a másik sav- vagy észter mnkcios csoportot tanalnsaz, irutdoium-'kadsd« típusú metstéás .k»t#iixá$ö>· jdeídeiéhea. és egy második lépésben a telnett, hosszú láncé uzo-aroinoeszier? («avat) kapjak az egyszeres«« telített ails il -észter (sav) lödregéncxesévci a megelőző íépésbeo nlkftiptazpit. hídrogéttezö katalizátorkén· viselkedő metatézis kaíailaétor jeleniétében.
- 2. Át !. igénypont szerinti eljárás, azé«! jellemezve, hogy a inptatdzis lépési a kővetkező reftkeiováziat szerint vd-ezzük:i'FyCti-'CHR,;: ahol Rí Π vagy (CH2),;- kW, R; - COOR- vagy GM;, R;í -- CÖÖR.;. vagy CR. Rí " H vagy R R< - 1-4 szenatöraos aiki lesöpöri, rt “ 2Ί 3, m 1-1 G és R;· jelentése IG-töi eltérő. a Az 1. vagy 2, igénypont szerinti eljárás, azzal jellemezve, hogy az akrilmírille! történő Imresztmetzíozi:; reakciót a kővetkezők kozni s'áiítóztott vegyi; leiek kei végezzük; 9~decénsay, nteíi Ml-deeetteáL iO-gndeeén&av. ntetll-ló-undeeénoát öiftjsav, méíiholeát y-oklsöeeéndísav, mGoG-oktadeeéndloái, erekasav, meri kenj kát 12-á ídecénsav és metil- ; 2-trideeériöát
- 4, AZ. 1, vagy 3, jgéóyppni szerinti eljárás, azzal jellemezve, hogy az akriiészterrel (savval) Uaiénő kerosztmetatézis reakciót a következők közöl választón vegyöletekkd végezzük: ö-decésniürs!, lő-undeeénnitrik 9-oiüadeeénÍíÍíS'il vagy oleonitrd. ö-oktadeeéndirüírih mtkattgril vagy 12-irideeéoührik
- 5. Az 1-4, jgénypomok Mrmdyike szerint; eljárás, azzal jel lemez ve, hogy a metatézis makeio: 3DVC és :2(G€ közötti kőmérsékieten és 1-3P hat, előnyösen 1-10 bar nyomásótl végezzük, 1Î 8-895 LG/Ho
- 6, Az S -5. igénypontok bármelyik« szerimi âijâxé%> azzal jellemezve. bogy a ínemsé.zis reakciót « köve; kezö általános képleté töltéssel rendelkező vagy töltéssel nem rendelkező katalizátorok közöl választót-rőtén! üm kimtlíxáíorleletdétébea végezzük: ; XíigX2)s,löXkarbéö C)iLi íXl.ét:: lőy amelyben; ♦ a, h, e, ti és e jelentése azemos vagy altéré étáékú égésé szám, ahol a ős b értéke ö, I vagy 2; e, d és a értéke 0. I, '2.1 vagy 4; » XI es X2 jelentése, azonosén vagy díarik-o. tőkéssel rendelkező vagy tőkéssé! tsem rendelkező ta’yfogii vagy íöbbfogu iíg-anclum, elémyösen a következők körül váláséivá; halogének, szulfát, karbonát, kstlmzilátok, alkoxidok, tcnoiáíök, amldok, f oviié·, hevaíluoHősxíöt, ícíraflnőr-borál, bisziínílil)amid, ietrahmibhorát és származékaik, XI vagy X2 kapcsolódhat Yi-hez vagy Ytöhöz (Ll -kéz vagy t2-höz) vagy a {karóén C)~hez, .így a ndétfiumoa kétíogá vagy keiár %andntnot kialakítva; és * i, !, 1.2 és L3 jelentése, azonosan vagy eltérően, «iektton-donor ligahdtsm, mint például ioszj'in, toszfit, iosvibnm Ktsznnip arzin, sztUbésr, öleim vagy aromás vegyüiet, karbon!! vegyüiet, éter, alkohol, amin. pirldln vagy származéka, hrmvboéier vagy heterociklusos karbém 1,.1. 1.2 vagy L3 esetén lehetséges a rkarbén CYhez történő kapcsolódás. Így kétfógá vagy kelét kgandnmot vagy hammfbgtt ligandtmsöt kialakítva. a (kerben C) a következe áháláaös képlet-ei jellentzett: € (Rt) 022), amelyben RÍ és R2 azonos vagy különböző csoport, előnyösen hidrogén vagy bármely más teiltest vagy telítetlen és ciklusos, elágazó vagy egyenes láncú szénhidrogén csoport vagy aromás szénhidrögéo csoport. ?.. A. 6. igénypont szerinti eljárás, azzal jellemezve, hogy a metatézis katalizátor megieleí vagy az alábbi (A) kénPandí vssöv fföVkíö-siíünek-(A) <8)
- 8. Az í~7. igénypontok bármelyike szerimi eljárás, azzal jellemezve, hogy a h-drogénezesi reakciót a metatézis lépés által eredményezett reakeióelegyen végéxzhk ei a hidrogénező katalizátorként viselkedő, maradék metatézis katalizátor iclenlétéhen, hidrogén nyomás alatt és bázis jelenlétében.
- 9. Az 1-8. igénypontok bármelyike szerimr eljárás, azzal jellemezve, hogy a hldrogénezési reakciót 5-100 bar, eidóyösen 20<·3.0 bar nyomóson, és Scb'C és ÍS(A€ közötti, előnyösen 80°C és HXFC közötti hőmérsékleten végezzük. J.Ö. Λ;·: 1-9. igénypontok bámsélyiks szgnnil eljárás, azzal jcilciítezve, hogy a hiötyyé-nvés; rsakeisit ti következők közűi választó·? bázis jelenlétében végezzük a íebnstle» iiitsibészíer szabsz? ?uir;s S'öeätkoztätöH: Hb 80 sk>í% mrtaiomnál: nátrlum-hsdrósMi. Hálmm-hidmkids-káSi'ürtv^erc-'bíStöxíd vagy ajzüüébia,
- 11, Az MO, igenypösüok hármejyiKe tzeAnti e^áras, azzal jefléinezee, hogy « fozlrögénezési reakeiöt az első lépés által eredményezeit degradál? iaennsZls katalizáló?' jélenléíében végezzük, ;,u?n:Ke· kiegészítünk szok;tsös klílrogénezö katalizátorral.
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| FR1053595A FR2959742B1 (fr) | 2010-05-07 | 2010-05-07 | Procede de preparation d'amino-acides ou esters satures comprenant une etape de metathese |
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| EP (1) | EP2566842B1 (hu) |
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| FR2826924B1 (fr) | 2001-07-06 | 2003-10-10 | Rodolphe Brichet | Systeme de commande, systeme directionnel pour vehicule leger et tricycle equipe d'un tel systeme |
| FR2978764B1 (fr) * | 2011-08-01 | 2013-08-16 | Arkema France | Procede de synthese d'un omega-aminoacide ou ester a partir d'un acide ou ester gras mono-insature |
| WO2013056463A1 (en) * | 2011-10-21 | 2013-04-25 | Lanxess Deutschland Gmbh | Catalyst compositions and their use for hydrogenation of nitrile rubber |
| FR2984309B1 (fr) * | 2011-12-16 | 2014-01-10 | Arkema France | Procede de synthese de nitrile-acide/ester omega insature dans lequel on alterne de maniere consecutive deux types de metathese croisee procede swing |
| CN103635508A (zh) * | 2012-03-13 | 2014-03-12 | 因温斯特技术公司 | 尼龙聚合物和方法 |
| WO2014005197A1 (en) * | 2012-07-06 | 2014-01-09 | Monash University | Amino acid analogues and methods for their synthesis |
| WO2014005196A1 (en) * | 2012-07-06 | 2014-01-09 | Monash University | Processes for producing amine compounds |
| US20150336879A1 (en) | 2013-01-07 | 2015-11-26 | Arkema France | Process for the synthesis of omega-unsaturated nitrile-acid/ester in which two types of cross metathesis are alternated consecutively, swing process |
| FR3000743B1 (fr) | 2013-01-07 | 2016-02-05 | Arkema France | Procede de metathese croisee |
| FR3000744B1 (fr) | 2013-01-07 | 2014-12-26 | Arkema France | Procede de metathese croisee |
| FR3001964B1 (fr) | 2013-02-08 | 2015-02-20 | Arkema France | Synthese de compose insature ramifie par metathese croisee |
| FR3013356B1 (fr) * | 2013-11-15 | 2018-03-16 | Arkema France | Procede de synthese de polyamide |
| US10266483B2 (en) | 2013-11-18 | 2019-04-23 | Rhodia Operations | Process for the manufacture of an amino ester |
| US10087137B2 (en) * | 2014-06-23 | 2018-10-02 | The University Of Toledo | Cross metathesis approach to C11-C13 fatty-chain amino esters from oleic acid derivatives |
| WO2016042045A1 (fr) * | 2014-09-17 | 2016-03-24 | Rhodia Operations | Procede de synthese d'aminoesters et de polyamides |
| FR3029203B1 (fr) | 2014-11-27 | 2016-12-30 | Arkema France | Compositions elastomeres contenant au moins un plastifiant forme par un ester de diacide gras insature, de preference mono-insature |
| WO2017200792A1 (en) * | 2016-05-20 | 2017-11-23 | Garnett Mckeen Lab, Inc. | Ruthenium-sphingomyelin complexes and methods for their use in the treatment of tumors |
| PL241085B1 (pl) * | 2016-11-10 | 2022-08-01 | Apeiron Synthesis Spolka Akcyjna | Zastosowanie kompleksów rutenu w reakcji metatezy olefin |
| KR102488849B1 (ko) * | 2020-12-21 | 2023-01-17 | 한국화학연구원 | 환원적 아민화와 가수분해 반응의 동시 진행에 의한 오메가 아미노알칸산 제조용 촉매 및 이를 이용한 오메가 아미노알칸산 제조 방법 |
| IT202100022328A1 (it) | 2021-08-25 | 2023-02-25 | Versalis Spa | Metodo per la preparazione di acidi ω-ammino-carbossilici e loro derivati. |
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| FR744739A (hu) * | 1933-04-26 | |||
| FR857780A (fr) | 1939-04-06 | 1940-09-28 | Procédé et dispositif pour la propulsion | |
| FR950704A (fr) | 1947-07-31 | 1949-10-05 | Cotelle & Foucher Ets | Procédé pour le collage des étiquettes sur des récipients tels que bouteilles et installations pour la mise en oeuvre de ce procédé |
| US3372195A (en) * | 1964-05-04 | 1968-03-05 | Dow Chemical Co | Reduction of nitriles to primary amines |
| GB1177154A (en) | 1967-07-18 | 1970-01-07 | Bp Chem Int Ltd | Production of 12-Aminododecanoic Acid or Alkali Metal Salts thereof |
| GB1273874A (en) | 1970-03-16 | 1972-05-10 | Bp Chemicals Internat Ltd | 0,2-aminododecanoic acid |
| JPH04117348A (ja) * | 1990-09-06 | 1992-04-17 | New Japan Chem Co Ltd | 脂肪族第一級アミンの製造方法 |
| DE19547213A1 (de) * | 1995-12-18 | 1997-06-19 | Basf Ag | Verfahren zur Herstellung von 1,6-Hexandiol aus Epoxibutadien |
| JPH1076160A (ja) * | 1996-09-04 | 1998-03-24 | Showa Denko Kk | 水添触媒とそれを利用するアミノメチル化合物の製法 |
| DE10064750A1 (de) * | 2000-12-22 | 2002-06-27 | Bayer Ag | Verfahren zur Herstellung von 1,6-Hexandiolen |
| JP2003089689A (ja) * | 2001-09-20 | 2003-03-28 | Nippon Zeon Co Ltd | ルテニウム錯体化合物、その製造方法、メタセシス反応用触媒及び水素化反応用触媒 |
| CN1768944A (zh) * | 2004-11-01 | 2006-05-10 | 中国科学院大连化学物理研究所 | 一种以膦－亚磷酰胺酯为配体的催化剂及制法和应用 |
| WO2007081987A2 (en) | 2006-01-10 | 2007-07-19 | Elevance Renewable Sciences, Inc. | Method of making hydrogenated metathesis products |
| EP2046719B1 (en) * | 2006-07-12 | 2013-09-04 | Elevance Renewable Sciences, Inc. | Ring opening cross-metathesis reaction of cyclic olefins with seed oils and the like |
| EP2074079B1 (en) * | 2006-10-13 | 2011-08-10 | Elevance Renewable Sciences, Inc. | Metathesis methods involving hydrogenation and compositions relating to same |
| FR2912741B1 (fr) * | 2007-02-15 | 2012-09-21 | Arkema France | Procede de synthese d'acides omega-amino-alcanoiques |
| FR2938533B1 (fr) | 2008-11-17 | 2010-11-19 | Arkema France | Procede de synthese d'un omega-aminoacide ou ester a partir d'un acide ou ester gras mono-insature |
| FR2941694B1 (fr) * | 2009-02-05 | 2011-02-11 | Arkema France | Procede de synthese d'un omega-aminoacide ou ester a partir d'un acide ou ester gras mono-insature. |
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2010
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- 2011-05-09 US US13/696,712 patent/US9096490B2/en not_active Expired - Fee Related
- 2011-05-09 ES ES11733990.3T patent/ES2580004T3/es active Active
- 2011-05-09 HU HUE11733990A patent/HUE028778T2/hu unknown
- 2011-05-09 BR BR112012028369A patent/BR112012028369A2/pt not_active Application Discontinuation
- 2011-05-09 JP JP2013509465A patent/JP5973993B2/ja not_active Expired - Fee Related
- 2011-05-09 CN CN201180022798.4A patent/CN103140471B/zh not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| US20130116458A1 (en) | 2013-05-09 |
| JP2013527855A (ja) | 2013-07-04 |
| EP2566842B1 (fr) | 2016-05-04 |
| FR2959742A1 (fr) | 2011-11-11 |
| MY160415A (en) | 2017-03-15 |
| FR2959742B1 (fr) | 2012-08-24 |
| BR112012028369A2 (pt) | 2017-03-21 |
| WO2011138051A1 (fr) | 2011-11-10 |
| US9096490B2 (en) | 2015-08-04 |
| AR081362A1 (es) | 2012-08-29 |
| JP5973993B2 (ja) | 2016-08-23 |
| PL2566842T3 (pl) | 2016-12-30 |
| CN103140471B (zh) | 2016-03-09 |
| EP2566842A1 (fr) | 2013-03-13 |
| CN103140471A (zh) | 2013-06-05 |
| ES2580004T3 (es) | 2016-08-18 |
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