EP0314759A4 - Hydroformylations asymetriques d'olefines prochirales en aldehydes chiraux en grandes quantites excedentaires enantiomeres. - Google Patents

Hydroformylations asymetriques d'olefines prochirales en aldehydes chiraux en grandes quantites excedentaires enantiomeres.

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Publication number
EP0314759A4
EP0314759A4 EP19880904854 EP88904854A EP0314759A4 EP 0314759 A4 EP0314759 A4 EP 0314759A4 EP 19880904854 EP19880904854 EP 19880904854 EP 88904854 A EP88904854 A EP 88904854A EP 0314759 A4 EP0314759 A4 EP 0314759A4
Authority
EP
European Patent Office
Prior art keywords
diphenylphosphino
hydroformylation
methyl
platinum
pyrrolidine
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Withdrawn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
EP19880904854
Other languages
German (de)
English (en)
Other versions
EP0314759A1 (fr
Inventor
John K Stille
Giovanni Parrinello
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.)
Colorado State University Research Foundation
Original Assignee
Colorado State University Research Foundation
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Filing date
Publication date
Application filed by Colorado State University Research Foundation filed Critical Colorado State University Research Foundation
Publication of EP0314759A1 publication Critical patent/EP0314759A1/fr
Publication of EP0314759A4 publication Critical patent/EP0314759A4/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
    • C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • B01J31/2414—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/48—Preparation of compounds having groups
    • C07C41/50—Preparation of compounds having groups by reactions producing groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C07C45/505—Asymmetric hydroformylation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
    • C07C51/14—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on a carbon-to-carbon unsaturated bond in organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0213—Complexes without C-metal linkages
    • B01J2531/0219—Bimetallic complexes, i.e. comprising one or more units of two metals, with metal-metal bonds but no all-metal (M)n rings, e.g. Cr2(OAc)4
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/42—Tin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/828—Platinum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/07—Optical isomers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
    • C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms

Definitions

  • This patent disclosure teaches improved processes for the hydroformylation of prochiral olefins to chiral aldehydes.
  • these improved processes comprise contacting, under hydroformylation conditions, an olefin containing a prochiral center with hydrogen and carbon monoxide in the presence of a catalyst comprising a complex of platinum II and N-(t-butoxycarbonyl)-(2S,4S)-4-(diphenylphosphino)-2- [(diphenylphosphino)methyl pyrrolidine and stannous chloride, and removing the resulting chiral aldehyde from the reaction system as it is formed.
  • the reaction goes slower than it does in benzene, but the reaction gives a chiral acetal of particularly high enantiomeric purity which does not undergo racemization under hydroformylation conditions. Moreover, no solvent effect is observed in the product distribution (98.6% selectively and 0.5 b/n ratio).
  • the triethyl orthoformate trapping agent is also particularly effective in hydroformylation reactions of vinyl acetate, p-isobutylstyrene, 2-vinylnapthalene, 2-ethenyl-6-methoxynaphthalene, 4- (2-thienylcarbonyl) styrene, methyl methacrylate, and norborene.
  • the polymer containing the chiral phosphine ligand was then converted to the platinum catalysts by reaction with bis (benzonitrile) dischloroplatinum(II).
  • the hydroformylation of styrene with this polymer-supported complex was carried out in the presence of stannous chloride to generate the active catalyst.
  • This particular polymer would not swell in triethyl orthoformate, and therefore this solvent could not be used as a hydroformylation catalyst in this instance.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Des hydroformylations asymétriques d'oléfines chirales peuvent être obtenues en mettant en contact, dans des conditions d'hydroformylation, une oléfine contenant un centre prochiral avec de l'hydrogène et de l'oxyde de carbone en présence d'un catalyseur comprenant un complexe de platine II et de N-(t-butoxycarbonyl)-2S,4S)-4-(diphénylphosphino)-2-[(diphénylphosphino)méthyl] pyrrolidine et du chlorure stanneux, et en extrayant l'aldéhyde chiral résultant à mesure qu'il se forme. Un procédé préféré d'extraction de l'aldéhyde chiral résultant consiste à utiliser un agent d'emprisonnement tel qu'un orthoformate de triéthyle, un orthoformate de triméthyle, un orthoacétate de triéthyle, un orthoacétate de triméthyle, un diéthyl-cétal d'acétone et un diméthyl-acétal d'acétone utilisé en présence d'un support catalyseur à l'état solide tel qu'un polystyrène réticulé.
EP19880904854 1987-05-14 1988-05-05 Hydroformylations asymetriques d'olefines prochirales en aldehydes chiraux en grandes quantites excedentaires enantiomeres. Withdrawn EP0314759A4 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US5051287A 1987-05-14 1987-05-14
US50512 2005-02-03

Publications (2)

Publication Number Publication Date
EP0314759A1 EP0314759A1 (fr) 1989-05-10
EP0314759A4 true EP0314759A4 (fr) 1990-01-29

Family

ID=21965668

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19880904854 Withdrawn EP0314759A4 (fr) 1987-05-14 1988-05-05 Hydroformylations asymetriques d'olefines prochirales en aldehydes chiraux en grandes quantites excedentaires enantiomeres.

Country Status (3)

Country Link
EP (1) EP0314759A4 (fr)
JP (1) JPH02501068A (fr)
WO (1) WO1988008835A1 (fr)

Families Citing this family (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5360938A (en) * 1991-08-21 1994-11-01 Union Carbide Chemicals & Plastics Technology Corporation Asymmetric syntheses
BE1007410A3 (nl) * 1993-08-23 1995-06-06 Dsm Nv Werkwijze voor de bereiding van een acetaal.
US5430194A (en) * 1994-06-24 1995-07-04 Union Carbide Chemicals & Plastics Technology Corporation Process for improving enantiomeric purity of aldehydes
KR101890961B1 (ko) 2010-11-12 2018-08-22 바스프 에스이 물 첨가에 의한 히드로포르밀화 방법에서의 오손의 완화
CN104379258B (zh) 2012-06-04 2017-05-03 陶氏技术投资有限责任公司 加氢甲酰化方法
IN2015DN02639A (fr) 2012-09-25 2015-09-18 Dow Technology Investments Llc
EP2740535A1 (fr) 2012-12-04 2014-06-11 Dow Technology Investments LLC Ligands bidentates pour hydroformylation d'éthylène
JP6174711B2 (ja) 2012-12-06 2017-08-02 ダウ テクノロジー インベストメンツ リミティド ライアビリティー カンパニー ヒドロホルミル化方法
CN104045532B (zh) 2013-03-15 2018-05-25 陶氏技术投资有限责任公司 加氢甲酰化方法
BR112016021934B1 (pt) 2014-03-31 2021-10-13 Dow Technology Investments Llc Processo de hidroformilação
CA3014177C (fr) 2016-02-11 2023-12-12 Dow Technology Investments Llc Procedes de conversion d'olefines en alcools, ethers ou combinaisons de ces derniers
TWI758353B (zh) 2016-11-08 2022-03-21 美商陶氏科技投資有限公司 使去活化的氫甲醯化催化劑溶液再生的方法
TW201840362A (zh) 2016-11-08 2018-11-16 美商陶氏科技投資有限公司 使去活化的氫甲醯化催化劑溶液再生的方法
TW201840363A (zh) 2016-11-08 2018-11-16 美商陶氏科技投資有限公司 處理氫甲醯化催化劑溶液之方法
WO2019083700A1 (fr) 2017-10-25 2019-05-02 Dow Technology Investments Llc Procédé permettant de réduire la formation de minéraux lourds dans une solution comprenant des composés d'aldéhyde formés au cours d'un procédé d'hydroformylation
WO2019094290A1 (fr) 2017-11-13 2019-05-16 Dow Technology Investments Llc Procédés de récupération de rhodium à partir d'un procédé d'hydroformylation
MY207749A (en) 2018-05-30 2025-03-16 Dow Technology Investments Llc Catalyst composition comprising the combination of a monophopsphine, a tetraphosphine ligand and a hydroformylation process using it
CA3100779A1 (fr) 2018-05-30 2019-12-05 Dow Technology Investments Llc Procedes de commande de processus d'hydroformylation
EP3801899A1 (fr) 2018-05-30 2021-04-14 Dow Technology Investments LLC Procédés de ralentissement de la désactivation d'un catalyseur et/ou de ralentissement de l'utilisation d'un ligand tétraphosphine dans des processus d'hydroformylation
TWI874467B (zh) 2019-11-05 2025-03-01 美商陶氏科技投資有限公司 用於自ｃ６或更高碳數烯烴氫甲醯化製程之催化劑淨化流回收銠之方法
US11976017B2 (en) 2019-12-19 2024-05-07 Dow Technology Investments Llc Processes for preparing isoprene and mono-olefins comprising at least six carbon atoms
CN118103532A (zh) 2021-11-11 2024-05-28 陶氏技术投资有限责任公司 用于从加氢甲酰化过程中回收铑的方法
EP4634148A1 (fr) 2022-12-13 2025-10-22 Dow Technology Investments LLC Procédé pour réduire au minimum l'utilisation de polyphosphine en utilisant des produits de dégradation
CN121194957A (zh) 2023-06-26 2025-12-23 陶氏技术投资有限责任公司 控制加氢甲酰化工艺的方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4482748A (en) * 1967-05-29 1984-11-13 Celanese Corporation Hydrocarbonylation

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
DISSERTATION ABSTRACTS INTERNATIONAL, vol. 47, no. 11, May 1987, order no. DA8705475; G. PARRINELLO: "Asymmetric hydroformylation catalyzed by homogeneous and polymer-supported chiral platinum complexes" *
J. AM. CHEM. SOC., vol. 109, no. 23, 1987, pages 7122-7127, American Chemical Society; G. PARRINELLO et al.: "Asymmetric hydroformylation catalyzed by homogeneous and polymer-supported platinum complexes containing chiral phosphine ligands" *
POLYM. PREPRINT (AM. CHEM. SOC., DIV. POLYM. CHEM.), vol. 27, no. 2, 1986, pages 9-10; G. PARRINELLO et al.: "Asymmetric hydroformylation by polymer-supported chiral catalysis" *
See also references of WO8808835A1 *

Also Published As

Publication number Publication date
JPH02501068A (ja) 1990-04-12
WO1988008835A1 (fr) 1988-11-17
EP0314759A1 (fr) 1989-05-10

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