EP1131274A2 - Procede pour la preparation d'aldehydes chiraux - Google Patents
Procede pour la preparation d'aldehydes chirauxInfo
- Publication number
- EP1131274A2 EP1131274A2 EP99968786A EP99968786A EP1131274A2 EP 1131274 A2 EP1131274 A2 EP 1131274A2 EP 99968786 A EP99968786 A EP 99968786A EP 99968786 A EP99968786 A EP 99968786A EP 1131274 A2 EP1131274 A2 EP 1131274A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- bar
- reaction
- chiral
- carbon dioxide
- carried out
- 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- Withdrawn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
- 238000000034 method Methods 0.000 title claims abstract description 35
- 150000001299 aldehydes Chemical class 0.000 title claims abstract 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000003446 ligand Substances 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 23
- 238000007037 hydroformylation reaction Methods 0.000 claims abstract description 19
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 9
- 150000003624 transition metals Chemical class 0.000 claims abstract description 8
- 239000012429 reaction media Substances 0.000 claims abstract description 4
- 125000001424 substituent group Chemical group 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052703 rhodium Inorganic materials 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical group CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 238000010924 continuous production Methods 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 4
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 14
- 239000010948 rhodium Substances 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 4
- -1 diphenylphosphino Chemical group 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WWMQIJFJSHVMDM-UHFFFAOYSA-N 2-ethenoxycarbonylbenzoic acid Chemical class OC(=O)C1=CC=CC=C1C(=O)OC=C WWMQIJFJSHVMDM-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- 125000006519 CCH3 Chemical group 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 description 1
- CMWTZPSULFXXJA-UHFFFAOYSA-N Naproxen Natural products C1=C(C(C)C(O)=O)C=CC2=CC(OC)=CC=C21 CMWTZPSULFXXJA-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- HRJABHWZEQHPFS-UHFFFAOYSA-N [1-[2-(12,14-dioxa-13-phosphapentacyclo[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3,5,7,9,16,18,20,22-decaen-13-yloxy)naphthalen-1-yl]naphthalen-2-yl]-diphenylphosphane Chemical compound O1C=2C=CC3=CC=CC=C3C=2C(C2=CC=CC=C2C=C2)=C2OP1OC1=CC=C2C=CC=CC2=C1C(C1=CC=CC=C1C=C1)=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 HRJABHWZEQHPFS-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001371 alpha-amino acids Chemical class 0.000 description 1
- 235000008206 alpha-amino acids Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000001760 anti-analgesic effect Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000002512 chemotherapy Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229960001680 ibuprofen Drugs 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- WMFOQBRAJBCJND-UHFFFAOYSA-M lithium hydroxide Inorganic materials [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229960002009 naproxen Drugs 0.000 description 1
- CMWTZPSULFXXJA-VIFPVBQESA-N naproxen Chemical compound C1=C([C@H](C)C(O)=O)C=CC2=CC(OC)=CC=C21 CMWTZPSULFXXJA-VIFPVBQESA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 229910006400 μ-Cl Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Definitions
- the present invention relates to processes for the preparation of chiral aldehydes by enantioselective hydroformylation of prochiral substrates with the aid of a catalyst consisting of a transition metal and a chiral phosphorus-containing ligand which contains aromatic rings which are substituted by perfluoroalkyl groups.
- Chiral aldehydes also provide access to ⁇ -amino acids, polyether-based antibiotics and macrocyclic antitumor agents.
- the most efficient catalyst system for enantioselective hydroformylation to date is based on a rhodium catalyst which contains the ligand (R) - 2- (diphenylphosphino) - 1, 1 '-binaphtol-2'-yl (S) - 1, 1' -binaphtol-2, 2'-diyl phosphite (R, S) -Binaphos (Topics in Catalysis 1997, 4, 175; EP 0 614 870 A3) and related ligands (EP 0 684 249 AI, EP 0 647 647 AI).
- the main disadvantages of the processes based on this catalyst system are, on the one hand, the limited regioselectivity for the formation of the desired branched isomer in the hydroformylation of vinyl aromatics (see Scheme 1).
- the regioselectivity with (R, S) -binaphos is, for example, 88%, and the 12% linear aldehyde is a worthless by-product which has to be separated and disposed of in a complex manner.
- these catalyst systems only work with the greatest efficiency if toxicologically and ecologically questionable solvents, such as. B. benzene can be used.
- Scheme 1 Reaction scheme for enantioselective hydroformylation using the example of vinyl aromatics. Table 1. Synthesis of chiral aldehydes by enantioselective hydroformylation.
- Compressed carbon dioxide in the liquid (liqC02) or supercritical state (SCCO2) is an interesting solvent for the implementation of catalytic reactions, because unlike conventional organic solvents it is toxicologically and ecologically harmless.
- the ligand (R, S) -binaphos cannot be used efficiently in compressed carbon dioxide, since the enantioselectivity drops drastically in the presence of compressed carbon dioxide (S. Kainz, W. Leitner, Catal. Lett., In press).
- the chiral ligand is a compound of the general formula 1
- the synthesis route for such a ligand is shown using the example of the ligand (R, S) -la (Scheme 2).
- the catalysts for the enantioselective hydroformylation can either be used in the form of isolated complex compounds which already contain the chiral ligands of the formula 1, or they are formed in situ from a ligand of the formula 1 and suitable metal-containing precursors.
- suitable metal-containing precursors A detailed description of possible catalyst systems can be found, for example, in Chem. Rev. 1995, 95, 2485.
- Compounds or salts of transition metals can be used as metal components in the present process. Catalysts based on the metals Fe, Co, Ir, Ru, Pt, Rh, particularly preferably Pt and Rh are preferred.
- the optimal molar ligand / metal ratio depends on the particular system, but should generally be between 1: 1 and 10: 1, preferably between 1: 1 and 4: 1 lie.
- Examples of such compounds can be found in the following group, without the choice of the compounds implying a limitation in the range of use: vinylaromatics (e.g. styrene and substituted styrene derivatives such as chlorobenzene, para- (isobutyl) sytrol or vinylnaphtol and its derivatives) , Vinylpyridine, acrylic acid and its derivatives (e.g.
- ⁇ -acetamidoacrylic acid esters vinyl acetate, vinyl phthalates, allyl acetate, indene, dihydro-2-pyridones, norbornene etc.
- the complete solubility of the substrates and the products during the entire reaction time is not necessary when carried out in compressed CO2 Prerequisite for an effective reaction process.
- the molar ratio of substrate to catalyst is mainly determined by economic considerations and represents one Compromise of catalyst costs and practically acceptable reaction rate. The optimal value can therefore vary widely depending on the substrate and catalyst. With the catalyst la / Rh substrate / catalyst ratios between 100: 1 and 100000: 1 are possible, preferably a ratio between 500: 1 and 10000: 1 is used.
- the gases H2 and CO can either be added separately or as a mixture to the reactor.
- the partial print /? the individual gases are in the range between 1 and 100 bar, preferably in the range between 5 and 50 bar.
- the reaction gases can be introduced before, after, or together with the CO2.
- the amount of CO2 is chosen so that the total pressure at the reaction temperature,? ° g e s. > In the range between 20 and 500 bar, preferably in the range between 50 and 350 bar.
- the reaction temperature can be varied within a wide range and is between -20 ° C and 100 ° C, preferably between 20 ° C and 60 ° C.
- Preferred solvents are, for example, pentane, hexane, toluene, benzene, diethyl ether, tetrahydrofuran, chloroform, methylene chloride, perfluorinated hydrocarbons or pefluorinated polyethers.
- the product When carried out in compressed carbon dioxide, the product can pass through the catalyst as described in DE 197 02 025 after the reaction Extraction are separated with CO2, the catalyst remaining in the reactor in active and selective form.
- the combination of reaction and extraction can be realized in batch, semi-batch or in continuous processes.
- CO2 (approx. 5-8 g) was filled in with a compressor and heated to the desired reaction temperature T, a pressure p ° ⁇ being established. After the reaction time t, the reactor was cooled to 0 ° C. and slowly let down. To isolate the reaction products, the contents of the reactor were either extracted using SCCO2 or the contents of the reactor were taken up in hexane or toluene, filtered through a little silica gel and the solvent was removed by distillation or in vacuo.
- Sales, regioselectivity in favor of Branched aldehyde and enantiomeric excess (ee) were determined by gas chromatography (HP 5890 with FID, column: Ivadex 7, injector temp .: 240 ° C, column temp .: 60-200 ° C; detector temp .: 300 ° C, carrier gas: H2).
- Enantioselective hydroformylation in other solvents (Ex. 1-2): The desired amount was added to a mixture of [ ⁇ (R, S) -la ⁇ Rh (acac)], (R, S) -la and styrene prepared as described above Given solvent. Synthesis gas was then injected to the pressure p m _ co and the solution was heated to the desired reaction temperature T while stirring. After the reaction time t, the reactor was cooled and let down. The reaction solutions were filtered through a little silica gel and the solvent removed in vacuo or by distillation. The analysis was carried out as described above.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
La présente invention concerne des procédés pour la préparation d'aldéhyde chiraux par hydroformylation éniantosélective de substrats prochiraux à l'aide d'un catalyseur constitué d'un métal de transition et d'un ligand chiral. Ces procédés sont caractérisés en ce que le ligand chiral est un composé de la formule générale (1), les cycles R7-R10 représentés en pointillés pouvant ne pas toujours être présents et un ou plusieurs des cycles R1-R6 ou R7-R10 étant substitués avec un ou plusieurs substituants, pouvant être choisis indépendamment les uns des autres, de la formule générale(CH2)x(CF2)yF (x = 0-5; y = 1-12), ou leurs isomères ramifiés. L'invention concerne notamment la réalisation desdits procédés dans du dioxyde de carbone comprimé (liquide ou surcritique) comme milieu de réaction.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19853748 | 1998-11-21 | ||
DE19853748A DE19853748A1 (de) | 1998-11-21 | 1998-11-21 | Verfahren zur Herstellungh chiraler Aldehyde |
PCT/EP1999/008661 WO2000031010A2 (fr) | 1998-11-21 | 1999-11-11 | Procede pour la preparation d'aldehydes chiraux |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1131274A2 true EP1131274A2 (fr) | 2001-09-12 |
Family
ID=7888553
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99968786A Withdrawn EP1131274A2 (fr) | 1998-11-21 | 1999-11-11 | Procede pour la preparation d'aldehydes chiraux |
Country Status (6)
Country | Link |
---|---|
US (1) | US6399834B1 (fr) |
EP (1) | EP1131274A2 (fr) |
JP (1) | JP2002530360A (fr) |
CA (1) | CA2351397A1 (fr) |
DE (1) | DE19853748A1 (fr) |
WO (1) | WO2000031010A2 (fr) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10049228A1 (de) * | 2000-09-28 | 2002-04-11 | Studiengesellschaft Kohle Mbh | Verfahren zur Trennung verzweigter und linearer Aldenyde durch selektive Extraktion mit komprimiertem Kohlendioxid |
DE10355066A1 (de) * | 2003-11-25 | 2005-06-23 | Basf Ag | Verfahren zur asymmetrischen Synthese |
DE102014209532A1 (de) * | 2014-05-20 | 2015-11-26 | Evonik Degussa Gmbh | Neue Monophosphitliganden mit einer tert-Butyloxycarbonyl-Gruppe |
PL3145940T4 (pl) * | 2014-05-20 | 2019-05-31 | Evonik Degussa Gmbh | Sposób redukcji zawartości chloru w organomonofosfitach przy zastosowaniu dwóch roztworów |
DE102014209534A1 (de) * | 2014-05-20 | 2015-11-26 | Evonik Degussa Gmbh | Neue Monophosphitliganden mit einer Carbonat-Gruppe |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5530150A (en) * | 1993-03-12 | 1996-06-25 | Takasago International Corporation | Phosphine compound, complex containing the phosphine compound as ligand, process for producing optically active aldehyde using the phosphine compound or the complex, and 4-[(R)-1'-formylethyl]azetidin-2-one derivatives |
DE69425917T2 (de) | 1993-03-12 | 2001-01-18 | Takasago International Corp., Tokio/Tokyo | Verfahren zur Herstellung von optisch-aktiven Aldehyden unter Verwendung von Übergangsmetall-Phosphin-Komplexen, und Verfahren zur Herstellung eines Zwischenprodukts bei der Herstellung von Carbapenemantibiotika unter Verwendung dieser Komplexe |
DE19702025A1 (de) * | 1997-01-23 | 1998-07-30 | Studiengesellschaft Kohle Mbh | Verwendung perfluoralkylsubstituierter Phosphorverbindungen als Liganden für die homogene Katalyse in überkritischem Kohlendioxid |
-
1998
- 1998-11-21 DE DE19853748A patent/DE19853748A1/de not_active Withdrawn
-
1999
- 1999-11-11 CA CA002351397A patent/CA2351397A1/fr not_active Abandoned
- 1999-11-11 WO PCT/EP1999/008661 patent/WO2000031010A2/fr not_active Application Discontinuation
- 1999-11-11 US US09/831,925 patent/US6399834B1/en not_active Expired - Fee Related
- 1999-11-11 JP JP2000583839A patent/JP2002530360A/ja active Pending
- 1999-11-11 EP EP99968786A patent/EP1131274A2/fr not_active Withdrawn
Non-Patent Citations (1)
Title |
---|
See references of WO0031010A2 * |
Also Published As
Publication number | Publication date |
---|---|
DE19853748A1 (de) | 2000-05-25 |
US6399834B1 (en) | 2002-06-04 |
JP2002530360A (ja) | 2002-09-17 |
WO2000031010A3 (fr) | 2000-11-02 |
WO2000031010A2 (fr) | 2000-06-02 |
CA2351397A1 (fr) | 2000-06-02 |
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