CN1069960A - The preparation method of alcohols - Google Patents
The preparation method of alcohols Download PDFInfo
- Publication number
- CN1069960A CN1069960A CN92109478A CN92109478A CN1069960A CN 1069960 A CN1069960 A CN 1069960A CN 92109478 A CN92109478 A CN 92109478A CN 92109478 A CN92109478 A CN 92109478A CN 1069960 A CN1069960 A CN 1069960A
- Authority
- CN
- China
- Prior art keywords
- group
- acid
- aldehyde
- hydrogenation
- autoclave
- 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.)
- Granted
Links
- 150000001298 alcohols Chemical class 0.000 title claims abstract description 6
- 238000002360 preparation method Methods 0.000 title claims description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 36
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 21
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 17
- 238000007037 hydroformylation reaction Methods 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 150000001728 carbonyl compounds Chemical class 0.000 claims abstract description 7
- 230000003197 catalytic effect Effects 0.000 claims abstract description 4
- 150000002736 metal compounds Chemical class 0.000 claims abstract 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 13
- 150000002576 ketones Chemical class 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 229910052763 palladium Inorganic materials 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000004429 atom Chemical group 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 5
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 150000001450 anions Chemical class 0.000 claims 1
- 150000001923 cyclic compounds Chemical class 0.000 claims 1
- 238000011065 in-situ storage Methods 0.000 claims 1
- 238000002955 isolation Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 44
- -1 carbonic acid gas aldehyde Chemical class 0.000 description 40
- 239000001294 propane Substances 0.000 description 22
- 239000001257 hydrogen Substances 0.000 description 16
- 229910052739 hydrogen Inorganic materials 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 10
- 238000012856 packing Methods 0.000 description 10
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 9
- GYHFUZHODSMOHU-UHFFFAOYSA-N nonanal Chemical compound CCCCCCCCC=O GYHFUZHODSMOHU-UHFFFAOYSA-N 0.000 description 9
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 9
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 8
- 238000013019 agitation Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 125000001118 alkylidene group Chemical group 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000011010 flushing procedure Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 3
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical group CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- 239000007868 Raney catalyst Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- QDHFHIQKOVNCNC-UHFFFAOYSA-N butane-1-sulfonic acid Chemical group CCCCS(O)(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000007172 homogeneous catalysis Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 125000000468 ketone group Chemical group 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 description 2
- 150000002940 palladium Chemical class 0.000 description 2
- REIUXOLGHVXAEO-UHFFFAOYSA-N pentadecan-1-ol Chemical compound CCCCCCCCCCCCCCCO REIUXOLGHVXAEO-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 1
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical class CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 1
- LGYNIFWIKSEESD-UHFFFAOYSA-N 2-ethylhexanal Chemical compound CCCCC(CC)C=O LGYNIFWIKSEESD-UHFFFAOYSA-N 0.000 description 1
- HSXUNHYXJWDLDK-UHFFFAOYSA-N 2-hydroxypropane-1-sulfonic acid Chemical compound CC(O)CS(O)(=O)=O HSXUNHYXJWDLDK-UHFFFAOYSA-N 0.000 description 1
- PNPPVRALIYXJBW-UHFFFAOYSA-N 6-oxohexanoic acid Chemical compound OC(=O)CCCCC=O PNPPVRALIYXJBW-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- 229910019800 NbF 5 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 229910018287 SbF 5 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910004529 TaF 5 Inorganic materials 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002521 alkyl halide group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229940058344 antitrematodals organophosphorous compound Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001500 aryl chlorides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical group OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical class CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- VSSAZBXXNIABDN-UHFFFAOYSA-N cyclohexylmethanol Chemical compound OCC1CCCCC1 VSSAZBXXNIABDN-UHFFFAOYSA-N 0.000 description 1
- TWXWPPKDQOWNSX-UHFFFAOYSA-N dicyclohexylmethanone Chemical compound C1CCCCC1C(=O)C1CCCCC1 TWXWPPKDQOWNSX-UHFFFAOYSA-N 0.000 description 1
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003974 emollient agent Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical group CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- ZODDGFAZWTZOSI-UHFFFAOYSA-N nitric acid;sulfuric acid Chemical compound O[N+]([O-])=O.OS(O)(=O)=O ZODDGFAZWTZOSI-UHFFFAOYSA-N 0.000 description 1
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical group 0.000 description 1
- 229940087291 tridecyl alcohol Drugs 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明涉及一种通过在包括VIII族金属化合物 和二齿膦的均相催化体系存在下，在升高的温度和高 于大气压下，羰基化合物氢化制备醇的方法。已通过 烯属不饱和化合物的氢甲酰化制得的醛被用作原 料。The present invention relates to a kind of by including VIII group metal compound In the presence of a homogeneous catalytic system with bidentate phosphine, at elevated temperature and high At atmospheric pressure, the method of hydrogenation of carbonyl compounds to produce alcohols. passed Aldehydes produced by the hydroformylation of ethylenically unsaturated compounds are used as proto material.
Description
The present invention relates to a kind of by in the method for preparing alcohols in the presence of the homogeneous catalysis system in the temperature that raises and the hydrogenation that is higher than carbonyl compound under the normal atmosphere.
The catalyst system that is used for this method comprises the metallic compound with solubility VIII family, and for example cobalt or rhodium are the catalyzer on basis.
The precursor of Shi Yonging can obtain by the hydroformylation or the hydroacylation of alefinically unsaturated compounds in the presence of VIII family metal catalyst as aldehydes or ketones in the method.In industrial application, it is also referred to as oxo synthesis to hydroformylation process.Usually, from the reaction mixture that obtains by hydroformylation, separate the aldehyde that the hydroformylation by alkene makes,, subsequently isolated aldehyde is used for hydrogenation to remove catalyzer and by product.
US-A-4263449 discloses a kind of method for preparing alcohols, wherein with hydroformylation reaction contain the aldehyde reaction product itself be used for subsequently by heterogeneous Raney nickel or the catalytic hydrogenation of cobalt catalyst.Add entry and be convenient to separate the two phase reaction product of used catalyzer with generation.Except utilizing multiple catalyzer inherent complicacy, use any alkene value that residues in the hydroformylation product of active Raney catalyst hydrogenation simultaneously.
According to GB-A-1270985, knownly can be used as cobalt-carbonyl that hydroformylation catalyst works and be used under the atmosphere that comprises hydrogen and carbonic acid gas aldehyde hydrogenation is alcohol by the tertiary phosphine modification.Yet this method needs high temperature of reaction and pressure.
US-A-3876672 discloses catalyzer that a kind of use comprises the cationic hydride of the Ni, the Pd that cooperate with 2-4 single phosphine ligand or Pt to carry out hydroformylation to alkene and forms aldehyde and pure method.It is quite low and selectivity this conversion is low to observe the transformation efficiency that forms alcohol.
Other known method for hydrogenation needs pure hydrogenation atmosphere, therefore if want directly to use the hydroformylation product that contains aldehyde, then should remove carbon monoxide.
Therefore, the demand that is used for the wider catalyzer of the improved purposes of carbonyl compound hydrogenant is still existed.
Have now found that, in the presence of the homogeneous catalysis system that comprises VIII family metallic compound source and bidentate phosphine, help realizing that aldehydes or ketones hydrogenation is alcohol.
The used catalyst system of the present invention has the following advantages: have high reactivity under demulcent temperature and/or pressure condition, be suitable for having or do not have under the hydrogenation atmosphere of carbon monoxide, with have significant selectivity, wherein alefinically unsaturated compounds is unaffected basically under carbonyl compound is easy to be hydrogenated into the condition of alcohol.
It should be noted that also the present invention can two-forty make the hydrogenation of steric hindrance ketone, steric hindrance ketone is exactly the ketone with at least one second month in a season that is connected with ketone group or tertiary alkyl.
It may be noted that people such as Y.Ben-David at J.Am.Chem.Soc.1989,111, described the compound that comprises palladium and the catalyst system of bidentate phosphine among the 8742-4, but only in the carbonylation of aryl chloride, used.
Carbonyl compound as precursor comprises aldehyde and ketone in the present invention.
Be used to carry out the aliphatic aldehyde that hydrogenant aldehyde preferably has 2-20 carbon atom.They can contain 1 or a plurality of aldehyde radical, and are the inert substituting group in addition under reaction conditions, as aryl, hydroxyl, carboxyl, C
1-4Alkoxyl group or have the ester group of 1-7 carbon atom.With the aldehyde particularly suitable with 3-20 carbon atom of oxo synthesis preparation.Suitable example comprises propionic aldehyde, butyraldehyde, 2 methyl propanal, 4-acetaldol, 6-oxo-caproate, octanal, aldehyde C-9, tridecylic aldehyde or 2-ethyl hexanal.
Be used to carry out the aliphatic ketone that hydrogenant ketone preferably has 3-20 carbon atom, they can contain 1 or a plurality of ketone group, and aforesaid inert substituent is arranged, and typical ketone comprises methyl isopropyl Ketone, ethyl nezukone and dicyclohexyl ketone.
Hydrogenation is to carry out in the presence of the catalyst system that comprises VIII family metal, and it is better that VIII family metal is selected from palladium, platinum and rhodium, and palladium is best.
VIII family metallic catalyst constituents can VIII family metal-salt form provide, for example VIII family metal-salt is nitric acid, sulfuric acid, sulfonic acid (for example trifluoromethanesulfonic acid or tosic acid); And the salt of carboxylic acid (for example acetate or trifluoroacetic acid).VIII family metal-salt can title complex form exist, the title complex that forms with phosphine and/or other ligand for example, VIII family metal also can metallic elements or are provided with form that ligands such as phosphine or carbon monoxide form the zeroth order title complexs.If provide with metallic forms, then it just uses with protonic acid so that form a kind of soluble salt or title complex on the spot.
The amount of VIII family metal is not critical, and every mole of aldehyde substrate is with 10
-7-10
-1Grammeatom VIII family metal is better, and 10
-6-10
-2Better.
Second basal component of the used catalyst system of the present invention is bidentate phosphine.In this article, bidentate phosphine is intended to comprise the P atom that has at least two phosphine groups and do not hinder two phosphines and sterically hindered any organo phosphorous compounds of single metal Atomic coordinate.Do not get rid of the existence of coordination in addition or non-coordination phosphine groups.
The used preferred bidentate phosphine of the present invention has the following formula structure:
R wherein
1, R
2, R
3And R
4The alkyl of representing a kind of any replacement respectively, or R
1And R
2Together and/or R
3And R
4The bivalent hydrocarbon radical of representing a kind of any replacement together, R
1, R
2, R
3And R
4At least one is an aliphatic group, and X represents the divalent bridging group of a kind of 2-8 of having bridge atom.Be more preferably R
1, R
2, R
3And R
4Represent aliphatic group independently of one another, for example replace or unsubstituted side chain or cyclic alkyl, be advisable to have 1-20 carbon atom.
Preferred aliphatic group is a unsubstituted alkyl, they can be side chain or cyclic and have the alkyl of 1-10 carbon atom, the alkyl with 1-6 carbon atom is better.The example of suitable alkyl is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, cyclohexyl and n-hexyl.Preferred alkyl has 1 or 2 a-hydrogen atom, preferably has 1 a hydrogen atom, as the situation in secondary alkyl.Most preferred alkyl is ethyl, sec.-propyl, n-propyl, sec-butyl and normal-butyl.If constitute bivalent hydrocarbon radical together, then R
1And R
2Or R
3And R
4Preferably represent aliphatic divalent group, as the alkylidene group of any replacement or ring alkylidene group, hexa-methylene or encircle octylene for example.
When alkyl or alkylidene group are expressed as any replacement, it can by 1 or a plurality of substituting group of the catalytic activity forfeiture of catalyst system that can not make replace.Suitable substituting group comprises halogen atom, alkoxyl group, alkylhalide group, halogen alkoxyl group, acyl group, acyloxy, amino, hydroxyl, itrile group, amido and aryl.
The bridged group of being represented by X is preferably hydrocarbon, ether or thioether residue.For example, bridged group can be by 1 or the alkylidene chain of any replacement of separating arbitrarily of a plurality of oxygen and/or sulphur atom, as-CH
2CH
2-,-CH
2CH
2CH
2-;-CH
2CH
2CH
2CH
2-; Or-CH
2CH
2OCH
2CH
2-.
It is better that bridged group contains 2-6 bridge atom, and 3-5 bridge atom is better.For example, when bridged group was propane or neopentane residue, bridge contained 3 atoms.Preferred bridged group X comprises trimethylene, tetramethylene and 3-oxa-pentamethylene.
Can be used for the phosphine example shown in the formula I of the inventive method is:
1, two (di-n-butyl phosphino-) ethane of 2-,
1, two (dimethyl phosphino-) propane of 3-,
1, two (diethyl phosphino-) propane of 3-,
1, two (di-isopropyl phosphino-) propane of 3-,
1, two (di phosphino-) propane of 3-,
1, two (diisobutyl phosphino-) propane of 3-,
1, two (di-n-butyl phosphino-) propane of 3-,
1, two (the di-secondary butyl phosphino-) propane of 3-,
1, two (di-t-butyl phosphino-) propane of 3-,
1, two (di-n-hexyl phosphino-) ethane of 3-,
1, two (dicyclohexyl phosphino-) propane of 3-,
1, two (the normal-butyl methyl phosphino-) propane of 3-,
1, two (the normal-butyl ethyl phosphino-) propane of 3-,
1, two (the encircling octylene phosphino-) propane of 3-,
1, two (di-isopropyl phosphino-) butane of 4-,
1, two (dimethyl the phosphino-)-3-oxa-pentanes of 5-,
1, two (the di-n-butyl phosphino-s)-3 of 8-, 6-two oxa-octanes and
1, two (the di-n-butyl phosphino-s)-2,2,3 of 4-, 3-4-methyl-butane.
When the hydrogenation unsymmetrical ketone, particularly during steric hindrance ketone,, then can use the chirality phosphine ligand if seek out chiral alcohol.
Better, 0.9-5 is better in the scope of 0.5-10 for the mole number proportion of phosphine shown in the every grammeatom VIII family metal Chinese style I, and 1-3 is best.
Be preferably, the catalyst system that is used for method of the present invention comprises the VIII family metal that exists with cationic form.Required negatively charged ion can generate on the spot, perhaps better is that the component as catalyst system provides.The preferred protonic acid in anionic source.Yet it also can be the salt of VIII family metal, for example palladium salt.It can also be another kind of metal, and for example the salt of vanadium, chromium, nickel, copper or silver perhaps passes through to add alkali, as the resulting salt of aromatics N-heterocycle, for example pyridinium salt.
Be preferably, negatively charged ion is right coordination or weak coordination negatively charged ion: promptly not with or only faintly with palladium positively charged ion coordinate negatively charged ion, it preferably is derived from strong acid, the pKa of strong acid＜2 are better, pKa＜-1 better (recording in 18 ℃ of aqueous solution).Because halid negatively charged ion, particularly muriatic negatively charged ion tends to cooperate with palladium quite doughtily, so negatively charged ion preferably is derived from the strong acid except that haloid acid.
For example, negatively charged ion can be derived from nitric acid; Sulfuric acid; Sulfonic acid such as fluosulfonic acid, chlorsulfonic acid, methylsulfonic acid, 2-hydroxy-propanesulfonic acid, tertiary butyl sulfonic acid, tosic acid, Phenylsulfonic acid, trifluoromethanesulfonic acid or sulfonation ion exchange resin; High hydracid such as perchloric acid; Or by Lewis acid, as BF
3, PF
3, AsF
5, SbF
5, TaF
5, or NbF
5, with bronsted acid, as HF(silicofluoric acid for example, HBF
4, HPF
6, HSbF
6) interact and the acid of deriving and obtaining.
What should understand is, when using weak acid, during as the palladium salt of acetate, the affiliation that adds of strong acid such as sulfonic acid generates a kind of palladium and salt and weak acid than strong acid.
The phosphine of formula I itself is a compound known, the general method preparation described in their available documents, and for example at Houben-Weyl, Vol. X II/I, the P.21 middle method of describing.
Catalyst system of the present invention can constitute in liquid phase, and this catalyst system is preferably in the homogeneous mixture that forms with the liquid phase of reacting and uses.Also can use the catalyst system that exists with false heterogenize form, for example a kind of at the lip-deep adsorptive liquid of porous support.A kind of independent solvent of also nonessential in the method for the invention use.Initial aldehydes or ketones and pure product usually can form a kind of suitable liquid phase.Yet, in some cases, may need to use a kind of independent solvent.Any inert solvent all can be used for this purpose, and representational suitable solvent comprises hydro carbons, sulfoxide, sulfone, ether, ester, ketone, alcohol and acid amides.This reaction can be carried out in gas phase.
Aldehyde can for example be able to hydrogenation in hydroformylation in the reaction mixture that can obtain them.
Therefore, same catalyzer both can be used for by preparing aldehyde by hydroformylation, can be used for being hydrogenated to subsequently corresponding alcohol again.Under quick hydroformylation and slow hydrogenant reaction conditions, in reaction mixture, can obtain high density aldehyde, necessary, can therefrom separate it.By making reaction conditions be suitable for rapid hydrogenation, for example, intermediate aldehydes is further reacted generate alcohol by improving temperature or increasing hydrogen partial pressure.
By the reaction conditions of suitable selection rapid hydrogenation, can directly prepare alcohol as raw material with aldehyde precursor alefinically unsaturated compounds.The aldehyde of Xing Chenging is consumed in hydrogenation then at once at the beginning, forms alcohol.
Method of the present invention is convenient at 20 ℃-200 ℃, particularly carries out under 50 ℃-150 ℃.
Method of the present invention is preferably under the total pressure of 1-80 crust carries out.Can use the pressure that is higher than 100 crust, but because of the special equipment of needs, so not attractive economically usually.Available pure hydrogen atmosphere is carried out hydrogenation, or hydrogen atmosphere can comprise inert gas diluent.For example, can use the atmosphere that comprises hydrogenation and carbon monoxide.
Method of the present invention can be carried out in batches, but industrial, preferably carries out continuously.
The alcohol of producing with the inventive method can be used as chemical solvents or as the precursor of various chemical.
Now by the following example explanation the present invention.
Embodiment 1
20ml propionic aldehyde, 40ml diglyme (2,5,8 one trioxa nonane), 0.25mmol acid chloride, 0.3mmol1, two (di-isopropyl phosphino-) propane of 3-and the 1mmol tosic acid 25ml magnetic agitation autoclave of packing into.After the flushing autoclave, pressurize with 60 crust hydrogen.Autoclave is sealed, is heated to 90 ℃, and under this temperature, kept 15 minutes, analyze the sample of material in the autoclave by vapor-phase chromatography (GLC).From analytical results as can be seen, propionic aldehyde changes the 1-propyl alcohol fully into, and its selectivity is near 100%.Per hour observe every grammeatom palladium and on average transform 3900 moles of propionic aldehyde.
Embodiment 2-4
Except that phosphine and negative ion source consumption and reaction times are described in table 1 below, repeat embodiment 1.Observed propionic aldehyde transformation efficiency (%), conversion rate (moles per gram atom palladium/hour) and the selectivity (%) that generates the 1-propyl alcohol are listed in the table.
Embodiment 5
20mla-octene, 40ml diglyme (2,5,8-trioxa nonane), 0.25mmol acid chloride, 0.6mmol1, two (di-isopropyl phosphino-) propane of 3-and the 1mmol tertiary butyl sulfonic acid 25ml magnetic agitation autoclave of packing into.After the flushing autoclave, the usefulness dividing potential drop separately carbon monoxide and the hydrogen of 30 crust is at the most pressurizeed.Autoclave is sealed, is heated to 70 ℃, and kept under this temperature 7 hours, the α-octene of the GLC analysis revealed 80% of material sample has been converted into nonyl aldehyde in the autoclave, and wherein 88% is linear chain aldehyde, and the 12%th, branched chain aldehyde.
After the cooling, the flushing autoclave pressurizes with 60 crust hydrogen then and heated 5 hours down at 90 ℃.GLC analysis revealed nonyl aldehyde 100% changes into corresponding nonyl alcohol, its initial conversion speed surpass 300 moles per gram atom palladiums/hour.Octene remaining after the hydroformylation step remains unchanged in hydrogenation process basically, has only 6% to be hydrogenated.
Embodiment 6
A.20ml α-octene, 40ml diglyme, 0.25mmol acid chloride, 0.6mmol1, two (di-isopropyl phosphino-) propane of 3-and the 1mmol tosic acid 25ml magnetic agitation autoclave of packing into.After the flushing autoclave, the usefulness dividing potential drop separately carbon monoxide and the hydrogen of 30 crust is at the most pressurizeed.Autoclave is sealed, is heated to 90 ℃, and kept under this temperature 5 hours, the α-octene of the GLC analysis revealed 67% of material sample transforms in the autoclave, and the selectivity that generates nonyl aldehyde is 94%, and the selectivity that generates nonyl alcohol is 5%.
B.15mla-octene and same solvent and the catalyst system autoclave of packing into repeats the program of this example a, pressurizes to autoclave with 20 crust carbon monoxide and 40 crust hydrogen, and 125 ℃ of heating 5 hours down.α-the octene of GLC analysis revealed 63% transforms, and the selectivity that generates nonyl alcohol is 88%, and the selectivity that generates nonyl aldehyde is 9%.
Can see and utilize same catalyst system, the aldehyde of generation is the primary product of a, and alcohol is the primary product of b under higher hydrogen-pressure and higher temperature.Obviously, aldehyde all is to generate in first reactions steps in two experiments, is consumed as the second step hydrogenant raw material subsequently, is helping under hydrogenant temperature and the density of hydrogen condition, and the speed of reaction of a is lower, and the speed of reaction of b is higher.
Embodiment 7
General program according to embodiment 6b, 20ml α-dodecylene, 40ml diglyme, 0.25mmol acid chloride, 0.6mmol1, two (1,5-the encircles octylene phosphino-) propane of 3-, 1mmol tosic acid and 1mmol trifluoroacetic acid 250ml magnetic agitation autoclave of packing into.Pressurize to autoclave with 20 crust carbon monoxide and 40 crust hydrogen, and heated 5 hours down at 125 ℃.Find that α-dodecylene of 62% transforms, the selectivity that generates tridecyl alcohol is 98%, also has the corresponding aldehyde of trace.
Embodiment 8
As previously described in the embodiment, the inner undersaturated C of 30ml
14Alkene, 40ml diglyme, 0.5mmol acid chloride, 1.2mmol1, two (di-isopropyl phosphino-) propane of 3-, 2mmol tosic acid and the 1mmol trifluoroacetic acid 250ml magnetic agitation autoclave of packing into.Pressurize to autoclave with 20 crust carbon monoxide and 40 crust hydrogen, and heated 10 hours down at 155 ℃.Find 71% C
14Alkene transforms, and the selectivity that generates pentadecyl alcohol is 98%.
Embodiment 9
As previously described in the embodiment, 20ml tetrahydrobenzene, 50ml diglyme, 0.25mmol acid chloride, 0.6mmol1,3 a pair ofs (dimethyl phosphino-) propane, 1mmol trifluoroacetic acid and the 1mmol tosic acid 250ml magnetic agitation autoclave of packing into.Pressurize to autoclave with 20 crust carbon monoxide and 40 crust hydrogen, and heated 5 hours down at 130 ℃.Find that 6% tetrahydrobenzene transforms, the selectivity that generates hexahydrobenzyl alcohol is 99%.
Embodiment 10
As previously described in the embodiment, 20ml vinylbenzene, 50ml diglyme, 0.25mmol acid chloride, 0.6mmol1,3 a pair ofs (di-isopropyl phosphino-) propane and the 1mmol tosic acid 250ml magnetic agitation autoclave of packing into.Pressurize to autoclave with 20 crust carbon monoxide and 40 crust hydrogen, and heated 5 hours down at 125 ℃.Find that 90% vinylbenzene transforms, the selectivity that generates 3-phenyl-1-propyl alcohol is 85%, and the selectivity that generates 2-phenyl-1-propyl alcohol is 15%.
Embodiment 11
As previously described in the embodiment, 10ml ethyl nezukone, 30ml2-butanols (as solvent), 0.25mmol acid chloride, 0.3mmol1,3 a pair ofs (di-isopropyl phosphino-) propane and the 2mmol trifluoromethanesulfonic acid autoclave of packing into.Pressurize to autoclave with 50 crust hydrogen, and heated 6 hours down at 70 ℃.Find that 100% ethyl nezukone transforms, the selectivity that generates 2-methylpropanol-3 is 98%.
Embodiment 12
Remove outside pack into 20ml methyl ethyl ketone rather than ethyl nezukone and 20ml rather than the 30ml2-butanols solvent and repeat embodiment 11 fully.After 70 ℃ are reacted 2 hours down, observe 90% methyl ethyl ketone conversion, the selectivity that generates the 2-butanols is about 98%.
Embodiment 13
As previously described in the embodiment, 10ml methyl isopropyl Ketone, 25ml2-butanols, 0.25mmol acid chloride, 0.3mmol1,3 a pair ofs (di-isopropyl phosphino-) propane and the 2mmol tosic acid autoclave of packing into.Heated 6 hours down to the autoclave pressurization and at 70 ℃ with 50 crust hydrogen.Find that 60% methyl isopropyl Ketone transforms, the selectivity that generates 3-methyl butanol-2 is 98%.
Claims (10)
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB919118603A GB9118603D0 (en) | 1991-08-30 | 1991-08-30 | Process for the preparation of alcohols |
| GB9118603.1 | 1991-08-30 | ||
| EP92202087.0 | 1992-07-08 | ||
| EP92202087A EP0529698B1 (en) | 1991-08-30 | 1992-07-08 | Process for the preparation of alcohols |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1069960A true CN1069960A (en) | 1993-03-17 |
| CN1042128C CN1042128C (en) | 1999-02-17 |
Family
ID=26131545
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92109478A Expired - Fee Related CN1042128C (en) | 1991-08-30 | 1992-08-27 | Process for preparation of alcohols |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP3410120B2 (en) |
| CN (1) | CN1042128C (en) |
| CA (1) | CA2077007C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1071731C (en) * | 1995-08-25 | 2001-09-26 | 纳幕尔杜邦公司 | Hydroformylation process |
| CN105001046A (en) * | 2015-07-09 | 2015-10-28 | 武汉工程大学 | Nonyl alcohol synthesis process |
| CN111333492A (en) * | 2018-12-18 | 2020-06-26 | 捷恩智株式会社 | Process for preparing saturated homopolyethers from unsaturated carbonyl compounds |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3928315B2 (en) * | 1998-12-14 | 2007-06-13 | 三菱化学株式会社 | Method for producing aldehyde |
| JP5487537B2 (en) * | 2007-07-24 | 2014-05-07 | 三菱化学株式会社 | Method for producing alcohol |
| JP5478510B2 (en) * | 2008-12-11 | 2014-04-23 | 高砂香料工業株式会社 | Method for producing alcohol compound |
| US8680302B2 (en) | 2008-12-11 | 2014-03-25 | Takasago International Corporation | Method for producing alcohol compound |
| CN102395427B (en) * | 2009-03-17 | 2016-03-16 | 约翰森·马瑟公开有限公司 | Process for the hydrogenation of ketones in the presence of Ru(II) catalysts |
-
1992
- 1992-08-27 CN CN92109478A patent/CN1042128C/en not_active Expired - Fee Related
- 1992-08-27 CA CA002077007A patent/CA2077007C/en not_active Expired - Fee Related
- 1992-08-27 JP JP25043392A patent/JP3410120B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1071731C (en) * | 1995-08-25 | 2001-09-26 | 纳幕尔杜邦公司 | Hydroformylation process |
| CN105001046A (en) * | 2015-07-09 | 2015-10-28 | 武汉工程大学 | Nonyl alcohol synthesis process |
| CN111333492A (en) * | 2018-12-18 | 2020-06-26 | 捷恩智株式会社 | Process for preparing saturated homopolyethers from unsaturated carbonyl compounds |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1042128C (en) | 1999-02-17 |
| CA2077007C (en) | 2003-02-11 |
| JP3410120B2 (en) | 2003-05-26 |
| CA2077007A1 (en) | 1993-03-01 |
| JPH05246916A (en) | 1993-09-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sakai et al. | Highly enantioselective hydroformylation of olefins catalyzed by new phosphine phosphite-rhodium (I) complexes | |
| NL1015655C2 (en) | Catalyst for asymmetric hydrogenation. | |
| JPH0512355B2 (en) | ||
| CN1678557A (en) | Method for hydroformylation of olefinically unsaturated compounds, in particular the hydroformylation of olefin in the presence of cyclic carbonic acid esters | |
| CN1185784A (en) | Synthesis of Fluorine-Substituted Bidentate Phosphine Ligands and Its Hydroformylation | |
| JP2001261667A (en) | Method for producing allylfuran compound | |
| CN1642646A (en) | Process for the carbonylation of an ethylenically unsaturated compound and catalyst therefore | |
| EP2678304B1 (en) | Hydrogenation of dienals with rhodium complexes under carbon monoxide free atmosphere | |
| JPH09124534A (en) | Method for hydroformylation of olefinic unsaturated compound | |
| FR2485518A1 (en) | PROCESS FOR THE PRODUCTION OF ETHYLENE GLYCOL AND ITS CARBOXYL ESTERS BY CATALYTIC HYDROGENATION OF GLYCOLALDEHYDE | |
| BRPI1010643B1 (en) | “PROCESS FOR ALLYL ALCOHOL HYDROPHORMILATION TO PRODUCE 4-HYDROXYBUTYLDEIDE” | |
| CN109651115B (en) | Method for preparing L-menthone | |
| JP2005126433A (en) | Reduction method for binaphthyl derivative and use of catalyst for the reduction | |
| CN1069960A (en) | The preparation method of alcohols | |
| CN1116265C (en) | Catalysts for hydroformylation and phosphorous compounds as ligands suitable for this purpose | |
| US9260367B2 (en) | Methods of converting polyols | |
| CN108349862A (en) | Olefin hydroformylation method for obtaining branched chain aldehyde | |
| CN111004102A (en) | Method for preparing optical activity citronellal and catalyst used in method | |
| JPH0667947B2 (en) | Ruthenium-phosphine complex | |
| JP4028625B2 (en) | Phosphine compounds and rhodium complexes using them as ligands | |
| US4194051A (en) | Asymmetric catalysis | |
| CN105728047A (en) | Hydroformylation catalyst as well as preparation method and application thereof | |
| CN113583046B (en) | Bidentate phosphine ligand, preparation method and application thereof | |
| JP3919268B2 (en) | Ruthenium-optically active phosphine complex, process for producing the same, and process for producing optically active 4-methyl-2-oxetanone using the same | |
| EP1060793B1 (en) | Stereospecific isomerisation of allylamines with the aid of immobilised phosphorated chiral ligands |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C15 | Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993) | ||
| OR01 | Other related matters | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 19990217 Termination date: 20100827 |