EP0314759A4 - ASYMMETRIC HYDROFORMYLATIONS OF PROCHIRAL OLEFINS IN CHIRAL ALDEHYDES IN LARGE ENANTIOMER EXCESS QUANTITIES. - Google Patents
ASYMMETRIC HYDROFORMYLATIONS OF PROCHIRAL OLEFINS IN CHIRAL ALDEHYDES IN LARGE ENANTIOMER EXCESS QUANTITIES.Info
- 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- Withdrawn
Links
Classifications
-
- 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.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (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)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US5051287A | 1987-05-14 | 1987-05-14 | |
US50512 | 1987-05-14 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0314759A1 EP0314759A1 (en) | 1989-05-10 |
EP0314759A4 true EP0314759A4 (en) | 1990-01-29 |
Family
ID=21965668
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19880904854 Withdrawn EP0314759A4 (en) | 1987-05-14 | 1988-05-05 | ASYMMETRIC HYDROFORMYLATIONS OF PROCHIRAL OLEFINS IN CHIRAL ALDEHYDES IN LARGE ENANTIOMER EXCESS QUANTITIES. |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0314759A4 (ja) |
JP (1) | JPH02501068A (ja) |
WO (1) | WO1988008835A1 (ja) |
Families Citing this family (22)
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 |
BR112013011810B1 (pt) | 2010-11-12 | 2021-02-02 | Basf Se | processo de extração para remover sais metálicos de um fluido de reação de hidroformilação orgânico |
US9174907B2 (en) | 2012-06-04 | 2015-11-03 | Dow Technology Investments Llc | Hydroformylation process |
RU2639156C2 (ru) | 2012-09-25 | 2017-12-20 | Дау Текнолоджи Инвестментс Ллс | Способ стабилизации фосфитного лиганда против деградации |
EP2740535A1 (en) | 2012-12-04 | 2014-06-11 | Dow Technology Investments LLC | Bidentate ligands for hydroformylation of ethylene |
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 |
EP3126319B1 (en) | 2014-03-31 | 2019-07-17 | Dow Technology Investments LLC | Hydroformylation process |
ES2901236T3 (es) | 2016-02-11 | 2022-03-21 | Dow Technology Investments Llc | Procesos para convertir olefinas en alcoholes, éteres o combinaciones de los mismos |
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 (en) | 2017-10-25 | 2019-05-02 | Dow Technology Investments Llc | PROCESS FOR REDUCING THE FORMATION OF HEAVY MINERALS IN A SOLUTION COMPRISING ALDEHYDE COMPOUNDS FORMED DURING A HYDROFORMYLATION PROCESS |
JP7269238B2 (ja) | 2017-11-13 | 2023-05-08 | 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 | ヒドロホルミル化プロセスからロジウムを回収するためのプロセス |
CN112055614A (zh) | 2018-05-30 | 2020-12-08 | 陶氏技术投资有限责任公司 | 包括单膦、四膦配位体的组合的催化剂组合物和使用其的加氢甲酰化过程 |
US11130725B2 (en) | 2018-05-30 | 2021-09-28 | Dow Technology Investments Llc | Methods for slowing deactivation of a catalyst and/or slowing tetraphosphine ligand usage in hydroformylation processes |
CN112088153A (zh) | 2018-05-30 | 2020-12-15 | 陶氏技术投资有限责任公司 | 控制加氢甲酰化过程的方法 |
TW202126385A (zh) | 2019-11-05 | 2021-07-16 | 美商陶氏科技投資有限公司 | 自氫甲醯化製程回收銠之方法 |
WO2021126421A1 (en) | 2019-12-19 | 2021-06-24 | 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 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4482748A (en) * | 1967-05-29 | 1984-11-13 | Celanese Corporation | Hydrocarbonylation |
-
1988
- 1988-05-05 JP JP63504573A patent/JPH02501068A/ja active Pending
- 1988-05-05 WO PCT/US1988/001513 patent/WO1988008835A1/en not_active Application Discontinuation
- 1988-05-05 EP EP19880904854 patent/EP0314759A4/en not_active Withdrawn
Non-Patent Citations (4)
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 |
---|---|
WO1988008835A1 (en) | 1988-11-17 |
EP0314759A1 (en) | 1989-05-10 |
JPH02501068A (ja) | 1990-04-12 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19890207 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE FR GB IT LI LU NL SE |
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A4 | Supplementary search report drawn up and despatched |
Effective date: 19900129 |
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18W | Application withdrawn |
Withdrawal date: 19900306 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN |
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R18W | Application withdrawn (corrected) |
Effective date: 19900306 |