CN112979703B - 一种氢甲酰化反应配体,氢甲酰化催化剂及二元醇的制备方法 - Google Patents
一种氢甲酰化反应配体,氢甲酰化催化剂及二元醇的制备方法 Download PDFInfo
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- CN112979703B CN112979703B CN202110225193.0A CN202110225193A CN112979703B CN 112979703 B CN112979703 B CN 112979703B CN 202110225193 A CN202110225193 A CN 202110225193A CN 112979703 B CN112979703 B CN 112979703B
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- 238000007037 hydroformylation reaction Methods 0.000 title claims abstract description 43
- 239000003446 ligand Substances 0.000 title claims abstract description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000003054 catalyst Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 25
- 125000000168 pyrrolyl group Chemical group 0.000 claims abstract description 5
- 125000001544 thienyl group Chemical group 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims abstract description 3
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 28
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
- JXKQTRCEKQCAGH-UHFFFAOYSA-N 2,6-dibromopyrazine Chemical compound BrC1=CN=CC(Br)=N1 JXKQTRCEKQCAGH-UHFFFAOYSA-N 0.000 claims description 10
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 10
- 238000006555 catalytic reaction Methods 0.000 claims description 10
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 10
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 10
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000010948 rhodium Substances 0.000 claims description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 6
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 claims description 6
- USJRLGNYCQWLPF-UHFFFAOYSA-N chlorophosphane Chemical compound ClP USJRLGNYCQWLPF-UHFFFAOYSA-N 0.000 claims description 6
- 150000003623 transition metal compounds Chemical class 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 5
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 5
- RROBIDXNTUAHFW-UHFFFAOYSA-N benzotriazol-1-yloxy-tris(dimethylamino)phosphanium Chemical compound C1=CC=C2N(O[P+](N(C)C)(N(C)C)N(C)C)N=NC2=C1 RROBIDXNTUAHFW-UHFFFAOYSA-N 0.000 claims description 4
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- ATMPMEZIXCBUHT-UHFFFAOYSA-N cobalt;triphenylphosphane Chemical compound [Co].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 ATMPMEZIXCBUHT-UHFFFAOYSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- NIONDZDPPYHYKY-SNAWJCMRSA-N (2E)-hexenoic acid Chemical compound CCC\C=C\C(O)=O NIONDZDPPYHYKY-SNAWJCMRSA-N 0.000 claims description 2
- CIBMDQOEVWDTDT-UHFFFAOYSA-N 5-methylhex-3-enoic acid Chemical compound CC(C)C=CCC(O)=O CIBMDQOEVWDTDT-UHFFFAOYSA-N 0.000 claims description 2
- MLHOXUWWKVQEJB-UHFFFAOYSA-N Propyleneglycol diacetate Chemical compound CC(=O)OC(C)COC(C)=O MLHOXUWWKVQEJB-UHFFFAOYSA-N 0.000 claims description 2
- NIONDZDPPYHYKY-UHFFFAOYSA-N Z-hexenoic acid Natural products CCCC=CC(O)=O NIONDZDPPYHYKY-UHFFFAOYSA-N 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 238000007112 amidation reaction Methods 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- HWVKIRQMNIWOLT-UHFFFAOYSA-L cobalt(2+);octanoate Chemical compound [Co+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O HWVKIRQMNIWOLT-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- HDKCVDHYIIKWFM-UHFFFAOYSA-K octanoate;rhodium(3+) Chemical compound [Rh+3].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O HDKCVDHYIIKWFM-UHFFFAOYSA-K 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 claims description 2
- BDDWSAASCFBVBK-UHFFFAOYSA-N rhodium;triphenylphosphane Chemical compound [Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 BDDWSAASCFBVBK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 150000002334 glycols Chemical class 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 125000003118 aryl group Chemical group 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 125000002883 imidazolyl group Chemical group 0.000 abstract description 2
- 125000004076 pyridyl group Chemical group 0.000 abstract description 2
- 125000003107 substituted aryl group Chemical group 0.000 abstract description 2
- 125000000335 thiazolyl group Chemical group 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract 1
- 238000005265 energy consumption Methods 0.000 abstract 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 39
- 238000006243 chemical reaction Methods 0.000 description 29
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 6
- YIYBQIKDCADOSF-UHFFFAOYSA-N alpha-Butylen-alpha-carbonsaeure Natural products CCC=CC(O)=O YIYBQIKDCADOSF-UHFFFAOYSA-N 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- YIYBQIKDCADOSF-ONEGZZNKSA-N trans-pent-2-enoic acid Chemical compound CC\C=C\C(O)=O YIYBQIKDCADOSF-ONEGZZNKSA-N 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 3
- 229940035437 1,3-propanediol Drugs 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- -1 and similarly Chemical compound 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229940043375 1,5-pentanediol Drugs 0.000 description 2
- YURNCBVQZBJDAJ-UHFFFAOYSA-N 2-heptenoic acid Chemical compound CCCCC=CC(O)=O YURNCBVQZBJDAJ-UHFFFAOYSA-N 0.000 description 2
- MWCBGWLCXSUTHK-UHFFFAOYSA-N 2-methylbutane-1,4-diol Chemical compound OCC(C)CCO MWCBGWLCXSUTHK-UHFFFAOYSA-N 0.000 description 2
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- JSRLURSZEMLAFO-UHFFFAOYSA-N 1,3-dibromobenzene Chemical compound BrC1=CC=CC(Br)=C1 JSRLURSZEMLAFO-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- VLPBEKHOQWMYTR-UHFFFAOYSA-N 2,3-dibromopyrazine Chemical compound BrC1=NC=CN=C1Br VLPBEKHOQWMYTR-UHFFFAOYSA-N 0.000 description 1
- HYFFNAVAMIJUIP-UHFFFAOYSA-N 2-ethylpropane-1,3-diol Chemical compound CCC(CO)CO HYFFNAVAMIJUIP-UHFFFAOYSA-N 0.000 description 1
- DYHGIZFXHVQIEA-UHFFFAOYSA-N 2-methylhexane-1,6-diol Chemical compound OCC(C)CCCCO DYHGIZFXHVQIEA-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- MUALRAIOVNYAIW-UHFFFAOYSA-N binap Chemical compound C1=CC=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 MUALRAIOVNYAIW-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IDYWQONQVXWFQP-UHFFFAOYSA-N butan-1-ol;octan-1-ol Chemical compound CCCCO.CCCCCCCCO IDYWQONQVXWFQP-UHFFFAOYSA-N 0.000 description 1
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006606 decarbonylation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002192 fatty aldehydes Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- SXCBDZAEHILGLM-UHFFFAOYSA-N heptane-1,7-diol Chemical compound OCCCCCCCO SXCBDZAEHILGLM-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
- C07F9/6509—Six-membered rings
- C07F9/6512—Six-membered rings having the nitrogen atoms in positions 1 and 3
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6558—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system
- C07F9/65583—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system each of the hetero rings containing nitrogen as ring hetero atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6558—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system
- C07F9/65586—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system at least one of the hetero rings does not contain nitrogen as ring hetero 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
-
- 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
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
-
- 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
- B01J2531/822—Rhodium
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
技术领域
本发明涉及催化领域,具体涉及用于氢甲酰化反应的单膦配体和氢甲酰化催化剂;本发明还涉及二元醇的制备。
背景技术
氢甲酰化,又称羰基合成反应,是化工上常用的制备比所用烯烃多一个碳原子的脂肪醛的方法。氢甲酰化反应已经成为工业生产中规模最大的均相催化反应。
二元醇,常用于做聚酯或改性聚酯原料,如1,3-丙二醇、1,4-丁二醇、乙二醇、丁辛醇、1,6-己二醇等,目前这些二元醇价格高,已工业化的方法少,且有较高的利润。
利用价格较低的不饱和酸氢甲酰化、加氢、水解制备相应的二元醇是一种新兴的有工业化前景的路线,专利CN105523891A提出了以混合金属为催化剂、SiO2/Al2O3为载体催化醋酸烯丙酯氢甲酰化、后经水解制备1,3-丙二醇的方法;专利US4072709用均相铑为催化剂将乙酸乙烯酯氢甲酰化制备1,3-丙二醇,同样经氢甲酰化、水解两步制备1,3-丙二醇。
目前,以不饱和酸氢甲酰化制备二元醇都需要经过相应的醛加氢、然后将羧基官能团水解的工艺流程,这就大大的提高了生产成本,降低了技术优势。
发明内容
为克服现有技术中存在的上述缺陷,本发明的目的是提供一种用于氢甲酰化反应的配体,所述配体具有高反应活性和线型选择性。
本发明的另一目的是提供一种所述配体在不饱和酸氢甲酰化制备二元醇中的应用。
一种氢甲酰化反应配体,其结构通式如式I:
通式中:R1、R2为H、芳基或取代芳基、噻吩基、吡咯基、噻唑基、咪唑基、吡啶基中的一种;R2与R1相同或不同;优选为噻吩基、吡咯基。
噻吩基及吡咯基团小,易旋转空间位阻小,易在氢甲酰化反应中被不饱和酸进攻。
本发明所述的配体的制备方法,包括以下步骤:
(1)将2,6-二溴吡嗪与氯代膦R1R2PCl发生偶联反应生成中间体IV;
(2)中间体IV与二氧化碳反应生成中间体V;
(3)中间体V与胍进行酰胺化反应得到配体I。
反应式示意如下:
本发明所述步骤(1)中,2,6-二溴吡嗪与氯代膦的摩尔比为1:(1.0-3.0),优选为1:(1.0-1.5)。
优选的,本发明所述步骤(1)在正丁基锂的催化下进行,所述正丁基锂与2,6-二溴吡嗪的摩尔比为(1.0-3.0):1,优选为(1.0-1.5):1。
优选的,本发明所述步骤(1)在溶剂存在下进行,所述溶剂为二氯甲烷、甲苯、三氯甲烷、丙酮中的一种或多种,优选为二氯甲烷和/或三氯甲烷。
本发明所述步骤(1)的反应温度为-78℃至-196℃,优选为-78℃至-90℃。
优选的,本发明所述步骤(2)在正丁基锂的催化下进行,所述中间体IV与正丁基锂的摩尔比为1:(1.0-3.0),优选的为1:(1.0-1.5)。
本发明所述步骤(2)中,二氧化碳的通入量为中间体VI摩尔量的1.0-5.0倍;优选的为1.5-2.0倍。
优选的,本发明所述步骤(2)在溶剂存在下进行,所述溶剂为正己烷、氯苯、二氯甲烷中的一种或多种,优选的为正己烷。
本发明所述步骤(2)的反应温度为-78℃至-196℃,优选的为-78℃至-90℃。
本发明所述步骤(3)中,中间体V与胍的摩尔比为1:(1.0-3.0),优选的为1:(1.0-1.5)。
优选的,本发明所述步骤(3)在缩合剂的存在下进行,所述缩合剂优选苯并三氮唑-1-基氧基三(二甲基氨基)磷鎓六氟磷酸盐和三乙胺,其中苯并三氮唑-1-基氧基三(二甲基氨基)磷鎓六氟磷酸盐的加入量为中间体V摩尔量的(1.0-3.0)倍,优选的为(1.0-1.5)倍;三乙胺的加入量为中间体V摩尔量的(1.0-3.0)倍,优选的为(1.0-1.5)倍。
优选的,本发明所述步骤(3)在溶剂的存在下进行,所述溶剂为正己烷、氯苯、二氯甲烷中的一种或多种,优选的为二氯甲烷。
本发明所述步骤(3)的反应温度为室温。
本发明所述的配体能够用于不饱和脂肪酸氢甲酰化制备二元醇。
一种氢甲酰化催化剂,包括:本发明所述的配体和过渡金属化合物。
本发明所述的过渡金属化合物可以是Fe、Mn、Pt、Pd、Rh、Ru、Ir、Co等过渡金属中心原子的盐中的一种或多种,优选Co、Rh的盐中的一种或多种。
作为一个优选的方案,本发明所述的过渡金属化合物包括醋酸铑、辛酸铑、乙酰丙酮铑、乙酰丙酮羰基铑、二羰基乙酰丙酮铑、三苯基膦乙酰丙酮铑、醋酸钴、辛酸钴、乙酰丙酮钴、乙酰丙酮钴、三苯基膦乙酰丙酮钴中的一种或多种,更优选二羰基乙酰丙酮铑、三苯基膦乙酰丙酮钴、乙酰丙酮钴。
一种二元醇的制备方法,包括以下步骤:在本发明所述的氢甲酰化催化剂的存在下,不饱和脂肪酸氢甲酰化反应制备二元醇。
本发明所述不饱和脂肪酸为C3-C10直链或支链单烯不饱和酸,优选为乙酸乙烯、乙酸丙烯、丙烯酸、丁烯酸、丁酸乙烯、2-己烯酸、5-甲基己-3-烯酸中的一种或多种。
本发明所述的二元醇的制备方法中,氢甲酰化催化剂的用量为不饱和脂肪酸质量的0.02-0.2倍,优选0.02-0.05倍。
本发明所述的二元醇的制备方法中,反应温度为40℃-80℃,优选45-60℃。
本发明所述的二元醇的制备方法中,反应压力为0.5-3.0MPaG,优选0.9-1.5MpaG。
本发明所述的配体,其催化反应实质是配体与金属中心原子形成络合物后,其酰胺基中的N原子与不饱和脂肪酸中的羧基H形成氢键,而配体中与酰胺基相连的NH2中的H与羧基中的双键氧形成氢键,捕获了羧基发生脱羰反应形成醇;而过渡金属原子由于整体的空间位阻的原因只能与端双键配位发生氢甲酰化生成羟基,这样就得到了线性二元醇。吡嗪的作用是利用其双氮原子的亲核性更易捕获不饱和酸。
使用该配体一步法得到线性二元醇,大大降低了设备投资,催化活性高、线性选择性好,与金属有较强的鳌合能力,反应活性高、适用于工业化大规模生产。
具体实施方式
以下结合具体实施例对本发明的技术方案做进一步详细说明。
本发明实施例和对比例中使用的试剂原料来源如下:
正丁基锂、2,6-二溴吡嗪、氯代膦配体购自百灵威试剂公司;二氯甲烷、正己烷、购自上海国药试剂有限公司。
其余试剂原料如无特别说明,均为市售产品。
本发明实施例和对比例中使用的测试方法如下:
元素分析,仪器为德国Elementar公司Vario EL cube分析仪。
核磁分析,仪器为美国Varian Mercury 400MHz分析仪。
以下结合具体实施例,对本发明作进一步说明。应理解,以下实施例仅用于说明本发明而非用于限定本发明的范围。
实施例1
(1)配体的制备
在氩气氛围下,在-78℃条件下向2,6-二溴吡嗪(100.4g,0.422mol)的CH2Cl2(1.5L)溶液中缓慢添加n-BuLi(29.75g,0.4645mol)。将混合物搅拌30分钟,然后加入Ph2PCl(109.54g,0.4965mol),在-78℃下继续反应1.5小时后升温至室温,并在该温度下再搅拌2小时。随后于-78℃下向反应液逐滴添加n-BuLi(29.75g,0.4645mol)并将混合物在相同温度下反应75min。
然后在-78℃下向溶液中以10ml/min的速率通入二氧化碳30分钟,当溶液颜色变为红色后用氮气将体系内的二氧化碳置换干净,随后在1.5小时内升温至-30℃。然后将反应混合物再次冷却至-78℃并以10ml/min的速率通二氧化碳15分钟,随后缓慢升温至0℃,升温过程为2小时,浓缩,冷却结晶得到粗产品,用乙醇重结晶得到浅黄色固体,即为中间体V(123.3g,0.4mol)。
随后在室温下将中间体V(123.3g,0.4mol)溶解到400mL二氯甲烷溶液中,随后加入缩合剂苯并三氮唑-1-基氧基三(二甲基氨基)磷鎓六氟磷酸盐(177g,0.4mol);三乙胺(40.47g,0.4mol),搅拌120min,浓缩、冷却结晶得到粗产品,用乙醇重结晶得到黄色固体,即为所需配体M1(132.7g,0.38mol),结构如下式
元素分析:C:61.89;H:4.62;N:20.05;O:4.58;P:8.87
1H NMR(500MHz,Chloroform):δ9.34(s,1H);9.12–9.08(m,1H);7.93–7.21(m,14H)。
(2)丙烯酸氢甲酰化制备1,3-丙二醇
用72.06g(1mol)丙烯酸配置0.2M的二氯甲烷溶液,按质量比Rh(acac)(CO)2:配体M1:丙烯酸=1:5:200加入到反应釜中,在CO/H2质量比为5:20,压力为1.5MPa,温度60℃,反应6小时,由气相色谱分析得转化率为97.9%,线性产物1,3-丙二醇选择性为97.06%,2-甲基-1,2-乙二醇的选择性为1.32%。
实施例2
(1)配体的制备
制备步骤与实施例1相同,不同之处在于将实施例1中的Ph2PCl(109.54g,0.4965mol)改为C8H8S2PCl(98.2g,0.422mol)。得到配体M2 144.56g(0.4mol),结构如下式。
元素分析:C:46.25;N:19.31;H:3.84;S:17.62;O:4.43;P:8.55。
1H NMR(500MHz,Chloroform):δ9.29(d,1H),9.08(d,1H),7.36–7.27(m,6H),7.13(dd,2H),6.90(dt,2H)。
(2)丁烯酸氢甲酰化制备1,4-丁二醇
用86.1g(1mol)丁烯酸配置0.2M的二氯甲烷溶液,按质量比Rh(acac)(CO)2:配体M2:丁烯酸=1:5:200加入到反应釜中,在CO/H2质量比为3:15,压力为1.2MPa,温度55℃,反应5小时,由气相色谱分析得转化率为99.3%,线性产物1,4-丁二醇选择性为98.7%,2-甲基-1,3-丙二醇的选择性为0.5%。
实施例3
(1)配体的制备
制备步骤与实施例1相同,不同之处在于将实施例1中的Ph2PCl(109.54g,0.4965mol)改为C8H8N2PCl(125.7g,0.633mol)。得到配体M3 157.15g(0.48mol)。
元素分析:C:51.38;N:29.96;H:4.31;O:4.89;P:9.46。
1H NMR(500MHz,Chloroform):δ9.32(d,1H),9.18(dd,1H),8.19(s,2H),7.56(s,4H),6.88(dd,2H),6.80(dt,2H),6.25(dt,2H)。
(2)戊烯酸氢甲酰化制备1,5-戊二醇
用100.1g(1mol)戊烯酸配置0.2M的二氯甲烷溶液,按质量比乙酰丙酮钴:配体M3:戊烯酸=1:3:150加入到反应釜中,在CO/H2质量比为2:18,压力为1.0MPa,温度50℃,反应7小时,由气相色谱分析得转化率为99.9%,线性产物1,5-戊二醇,选择性为99.1%,2-甲基-1,4-丁二醇的选择性为0.3%。
实施例4
86.1g(1mol)反-2-戊烯酸配置0.2M的二氯甲烷溶液,按质量比Rh(acac)(CO)2:配体M1:反-2-戊烯酸=1:3:150加入到反应釜中,在CO/H2质量比为3:15,压力为1.2MPa,反应温度60℃,反应5小时,由气相色谱分析得转化率为99.1%;线性产物2-甲基-1,4-丁二醇选择性为96.9%,2-乙基-1,3-丙二醇的选择性为2.7%。
实施例5
用128.17g(1mol)庚烯酸配置0.2M的二氯甲烷溶液,按质量比Rh(acac)(CO)2:配体M2:庚烯酸=1:3:150加入到反应釜中,在CO/H2质量比为3:15,压力为1.2MPa,温度45℃,反应5小时,由气相色谱分析得转化率为98.8%;线性产物1,7-庚二醇选择性为97.0%,2-甲基-1,6-已二醇的选择性为1.2%。
对比例1
(1)配体的制备
制备步骤与实施例1相同,不同之处在于将实施例1中的二溴吡嗪改为间二溴苯(99.55g,0.422mol)。得到配体M4 138.94g(0.4mol)。
元素分析:C:69.14;N:12.12;H:5.24;O:4.60;P:8.90。
1H NMR(500MHz,Chloroform)δ8.14(dd,1H),7.86–7.69(m,6H),7.59–6.97(m,11H)。
(2)丁烯酸氢甲酰化制备1,4-丁二醇
用86.1g(1mol)丁烯酸配置0.2M的二氯甲烷溶液,按质量比Rh(acac)(CO)2:配体M4:丁烯酸=1:5:200加入到反应釜中,在CO/H2质量比为3:15,压力为1.2MPa,反应温度55℃,反应5小时,转化率为84.2%;由气相色谱分析得到线性产物1,4-丁二醇选择性为86.8%,2-甲基-1,3-丙二醇的选择性为5.4%。
对比例2
按摩尔比将烯丙醇:二膦配体BINAP:Rh(acac)(CO)2=1:5:2.5加入到反应釜中,在CO/H2质量比为6:13,在压力为1.2MPaG,温度为65℃,反应5小时,由气相色谱分析得转化率为95.68%;线性产物1,4-丁二醇选择性为84.36%;随后在雷尼催化剂催化下,反应温度130℃,氢气压力4MpaG,反应4小时,由气相色谱分析得转化率为98.2%,线性产物1,4-丁二醇,选择性为96.8%。
最后应当说明的是,以上实施例仅用以本发明的优选实施方式进行描述,而非对本发明保护范围的限制,尽管参照较佳实施例对本发明作了详细说明,本领域的普通技术人员应当理解,对本发明的技术方案进行修改或者等同替换作出的各种变型和改进,均应落入本发明的权利要求书确定的保护范围内。
Claims (18)
4.根据权利要求3所述的方法,其特征在于,所述步骤(1)中,2,6-二溴吡嗪与氯代膦的摩尔比为1:(1.0-3.0);和/或,所述步骤(1)在正丁基锂的催化下进行,所述正丁基锂与2,6-二溴吡嗪的摩尔比为(1.0-3.0):1。
5.根据权利要求3所述的方法,其特征在于,所述步骤(1)中,2,6-二溴吡嗪与氯代膦的摩尔比为1:(1.0-1.5);和/或,所述步骤(1)在正丁基锂的催化下进行,所述正丁基锂与2,6-二溴吡嗪的摩尔比为(1.0-1.5):1。
6.根据权利要求3所述的方法,其特征在于,所述步骤(2)在正丁基锂的催化下进行,所述中间体IV与正丁基锂的摩尔比为1:(1.0-3.0)。
7.根据权利要求3所述的方法,其特征在于,所述步骤(2)在正丁基锂的催化下进行,所述中间体IV与正丁基锂的摩尔比为1:(1.0-1.5)。
8.根据权利要求3所述的方法,其特征在于,所述步骤(3)中,中间体V与胍的摩尔比为1:(1.0-3.0)。
9.根据权利要求3所述的方法,其特征在于,所述步骤(3)中,中间体V与胍的摩尔比为1:(1.0-1.5)。
10.根据权利要求3所述的方法,其特征在于,所述步骤(3)在缩合剂的存在下进行,所述缩合剂为苯并三氮唑-1-基氧基三(二甲基氨基)磷鎓六氟磷酸盐和三乙胺,其中苯并三氮唑-1-基氧基三(二甲基氨基)磷鎓六氟磷酸盐的加入量为中间体V摩尔量的(1.0-3.0)倍;三乙胺的加入量为中间体V摩尔量的(1.0-3.0)倍。
11.根据权利要求10所述的方法,其特征在于,所述苯并三氮唑-1-基氧基三(二甲基氨基)磷鎓六氟磷酸盐的加入量为中间体V摩尔量的(1.0-1.5)倍;三乙胺的加入量为中间体V摩尔量的(1.0-1.5)倍。
12.一种氢甲酰化催化剂,包括权利要求1或2所述的氢甲酰化反应配体或权利要求3-11任一项所述的方法制备的氢甲酰化反应配体和过渡金属化合物;所述过渡金属化合物选自Fe、Mn、Pt、Pd、Rh、Ru、Ir、Co的盐中的一种或多种。
13.根据权利要求12所述的氢甲酰化催化剂,其特征在于,所述过渡金属化合物选自醋酸铑、辛酸铑、乙酰丙酮铑、乙酰丙酮羰基铑、二羰基乙酰丙酮铑、三苯基膦乙酰丙酮铑、醋酸钴、辛酸钴、乙酰丙酮钴、三苯基膦乙酰丙酮钴中的一种或多种。
14.一种二元醇的制备方法,包括以下步骤:在权利要求12所述的氢甲酰化催化剂的存在下,不饱和脂肪酸氢甲酰化反应制备二元醇。
15.根据权利要求14所述的方法,其特征在于,所述不饱和脂肪酸为C3-C10直链或支链单烯不饱和酸。
16.根据权利要求14所述的方法,其特征在于,所述不饱和脂肪酸为乙酸乙烯、乙酸丙烯、丙烯酸、丁烯酸、丁酸乙烯、2-己烯酸、5-甲基己-3-烯酸中的一种或多种。
17.根据权利要求14所述的方法,其特征在于,所述氢甲酰化催化剂的用量为不饱和脂肪酸质量的0.02-0.2倍。
18.根据权利要求14所述的方法,其特征在于,所述氢甲酰化催化剂的用量为不饱和脂肪酸质量的0.02-0.05倍。
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