CN107445995B - The method that a kind of novel manganese catalysis ethanol condensation prepares butanol - Google Patents
The method that a kind of novel manganese catalysis ethanol condensation prepares butanol Download PDFInfo
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- CN107445995B CN107445995B CN201710669609.1A CN201710669609A CN107445995B CN 107445995 B CN107445995 B CN 107445995B CN 201710669609 A CN201710669609 A CN 201710669609A CN 107445995 B CN107445995 B CN 107445995B
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- reaction
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- manganese
- butanol
- ethyl alcohol
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 239000011572 manganese Substances 0.000 title claims abstract description 74
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 title claims abstract description 57
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 40
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title abstract description 20
- 238000009833 condensation Methods 0.000 title abstract description 7
- 230000005494 condensation Effects 0.000 title abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 82
- 235000019441 ethanol Nutrition 0.000 claims abstract description 69
- 238000007869 Guerbet synthesis reaction Methods 0.000 claims description 19
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 17
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 8
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 30
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 239000002028 Biomass Substances 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 9
- 239000002551 biofuel Substances 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000005859 coupling reaction Methods 0.000 abstract description 5
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- 238000013461 design Methods 0.000 abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 34
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 34
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 239000007789 gas Substances 0.000 description 25
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 22
- 239000003446 ligand Substances 0.000 description 22
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 19
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 18
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 18
- 229910052786 argon Inorganic materials 0.000 description 17
- -1 alcohol compound Chemical class 0.000 description 16
- 239000000047 product Substances 0.000 description 14
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 12
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 238000004679 31P NMR spectroscopy Methods 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 8
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 7
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 7
- 238000007872 degassing Methods 0.000 description 7
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 6
- 239000004305 biphenyl Substances 0.000 description 6
- 235000010290 biphenyl Nutrition 0.000 description 6
- 229910000085 borane Inorganic materials 0.000 description 6
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 6
- 239000000446 fuel Substances 0.000 description 6
- 238000004896 high resolution mass spectrometry Methods 0.000 description 6
- 239000005457 ice water Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000003502 gasoline Substances 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 150000002696 manganese Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000005311 nuclear magnetism Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- HLKHRWHKYARNDC-UHFFFAOYSA-N [Mn]N Chemical compound [Mn]N HLKHRWHKYARNDC-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000026030 halogenation Effects 0.000 description 3
- 238000005658 halogenation reaction Methods 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 3
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000002574 poison Substances 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- WCASXYBKJHWFMY-NSCUHMNNSA-N 2-Buten-1-ol Chemical compound C\C=C\CO WCASXYBKJHWFMY-NSCUHMNNSA-N 0.000 description 2
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
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- 230000000996 additive effect Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- 125000002541 furyl group Chemical group 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
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- 229910000510 noble metal Inorganic materials 0.000 description 2
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
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- 238000001291 vacuum drying Methods 0.000 description 2
- FGFBEHFJSQBISW-UHFFFAOYSA-N 1h-cyclopenta[b]pyridine Chemical compound C1=CNC2=CC=CC2=C1 FGFBEHFJSQBISW-UHFFFAOYSA-N 0.000 description 1
- ONRREFWJTRBDRA-UHFFFAOYSA-N 2-chloroethanamine;hydron;chloride Chemical compound [Cl-].[NH3+]CCCl ONRREFWJTRBDRA-UHFFFAOYSA-N 0.000 description 1
- FTVIGQGOGIHMBS-UHFFFAOYSA-N 2-di(propan-2-yl)phosphanyl-n-[2-di(propan-2-yl)phosphanylethyl]ethanamine Chemical compound CC(C)P(C(C)C)CCNCCP(C(C)C)C(C)C FTVIGQGOGIHMBS-UHFFFAOYSA-N 0.000 description 1
- MJYKYLNPIGDVEF-UHFFFAOYSA-N 2-ditert-butylphosphanyl-n-(2-ditert-butylphosphanylethyl)ethanamine Chemical compound CC(C)(C)P(C(C)(C)C)CCNCCP(C(C)(C)C)C(C)(C)C MJYKYLNPIGDVEF-UHFFFAOYSA-N 0.000 description 1
- CSDSSGBPEUDDEE-UHFFFAOYSA-N 2-formylpyridine Chemical compound O=CC1=CC=CC=N1 CSDSSGBPEUDDEE-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- AWMHRVHGKOFCNI-UHFFFAOYSA-N C(CCCC)OC(C(C)(C)C)OOCCC(C)C Chemical compound C(CCCC)OC(C(C)(C)C)OOCCC(C)C AWMHRVHGKOFCNI-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910018385 Mn(CO)5 Inorganic materials 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
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- 238000013019 agitation Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
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- 230000004075 alteration Effects 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 229910052796 boron Inorganic materials 0.000 description 1
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- 238000000855 fermentation Methods 0.000 description 1
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- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
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- 239000011261 inert gas Substances 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
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
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- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
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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
- C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
- C07F13/005—Compounds without a metal-carbon linkage
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
The invention discloses a kind of methods that novel manganese catalysis ethanol condensation prepares butanol.The Mn catalyst that the method uses is manganese complex shown in Formulas I, Formula II, formula III or formula IV.Based on manganese complex of the present invention, a kind of method that the ethyl alcohol coupling based on the catalysis of cheap metal manganese prepares butanol is provided, shows very high catalytic activity (TON=114120, wherein the TOF of preceding 12h is 3078h‑1) and 92% butanol selectivity (Fig. 1)；The present invention will efficiently utilize biomass resource, especially to the production of high-quality bio-fuel, the catalytic activation of biomass platform chemicals and conversion and corresponding cheap, effective catalyst design, provide important technical support and theoretical direction.
Description
Technical field
The present invention relates to the methods that a kind of novel manganese catalysis ethanol condensation prepares butanol, belong to Catalytic processes technology neck
Domain.
Background technique
The energy is the important material base of human survival and development of civilization, while providing energy and power for us,
It is also the most important source of numerous basic chemicals.Chemicals and fuel required for production and living mainly utilize fossil to provide at present
Source is transformed, and the increasingly consumption of this nonrenewable resources promotes people to develop other alternative renewable carbon sources to fire
The production of material and chemicals.And by the bio-fuel that bioconversion obtains be renewable energy development and utilization important side
To with good storing properties and rodability, it is possible to provide substitute the liquid fuel of petroleum.The whole world produces height altogether within 2015
Up to the biomass fuel for being equivalent to 74,900,000 tons of crude oil energy, wherein be more than 70% bio-fuel being by biomass ferment work
Skill and the bio-ethanol obtained.
The mainly purposes of bio-ethanol is to mix to be directly used in not modified internal combustion engine with gasoline at present, to have
Effect reduces the consumption of petroleum resources.There are many disadvantages as bio-fuel for ethyl alcohol, are primarily due to ethyl alcohol water solubility and are easy moisture absorption, vapour
Oil must closed on using the preceding mixing for carrying out ethyl alcohol and gasoline, to cause the problem of storage and transportational process complexity.Secondly,
Ethyl alcohol can generate acetic acid in combustion, to metal parts especially copper have corrosivity, in addition the energy density of ethyl alcohol compared with
It is low, when using a high proportion of the problem of will cause fuel value and dynamic property decline containing ethanol petrol, the above disadvantage can all be limited
Ethyl alcohol processed is as additive package using in the oil.And higher alcohol is used, for example, the alcohol of butanol and more long-chain, due to fourth
The long-chain alcohols such as alcohol are with higher energy density and have lower vapour pressure, can mix at high proportion with gasoline with more even independent
Fuel as gasoline engine uses.Although the long-chain alcohols such as butanol are more good fuel, still lack at present efficient
Method pass through the direct synthetic long chain alcohol of biomass resource.The method of known best biosynthesis, i.e., so-called ABE fermentation
Method, can obtain acetone only with low yield, the mixture of butanol and ethyl alcohol, since separation is difficult, and higher cost, therefore by with
Propylene is replaced the chemical synthesis process of raw material.
Based on the large-scale production of global range endogenous substance ethyl alcohol, develops one kind and ethyl alcohol is effectively converted into length
The production technology of chain alcohol is produced the important technology of the high-quality bio-fuel of long-chain alcohols by becoming by biomass resource.From certain meaning
Upper theory, Guerbet reaction is a kind of ideal method that butanol or long-chain alcohol are synthesized by ethyl alcohol, because anti-for such
Its by-product is only water for answering.And it is challenging with use ethanol as the substrate of Guerbet reaction.It is first
First, the dehydrogenation reaction of ethyl alcohol is the very unfavorable reaction process of thermodynamics, Δ G0=12.87kcal/mol；Secondly, reaction is intermediate
The aldol condensation reaction of body acetaldehyde also faces the problem of poor selectivity often.Currently, only a smaller number of example reports
Guerbet reaction, wherein heterogeneous catalysis usually requires more harsh reaction condition or has to low butanol selection
Property.In contrast, although using homogeneous catalyst be catalyzed the reaction it is usual under available higher activity, better choice
Property.But the report up to the present in relation to homogeneous catalysis Guerbet reaction is all concentrated mainly on the noble metals such as Ru and Rh (figure
1)。
It is one of catalytic science research field in recent years important using cheap metal catalyst substitution noble metal catalyst
Developing direction.However, the C-C coupling reaction of the low-carbon alcohols micromolecular such as ethyl alcohol that up to the present homogeneous cheap metal is catalyzed
Long-chain alcohol compound is prepared to have not been reported.Therefore, the corresponding efficiently homogeneous cheap metal catalyst of development realizes (biology)
The C-C coupling reaction of the low-carbon alcohols micromolecular such as ethyl alcohol prepares a key technology of high-quality bio-fuel by becoming.
Summary of the invention
The present invention provides the reaction that a kind of novel manganese catalysis ethanol coupling prepares butanol, used manganese complex is
A kind of NNP PNP complex compound based on cheap metal manganese, the reaction show very high catalytic activity (TON=
114120, wherein the TOF of preceding 12h is 3078h-1) and 92% butanol selectivity, therefore, new method provided by the invention will be right
Biomass resource efficiently utilizes, especially to the production of high-quality bio-fuel, the catalytic activation of biomass platform chemicals and conversion
And corresponding cheap, effective catalyst design, important technical support and theoretical direction are provided.
Present invention firstly provides manganese complex, structural formula is as shown in Formulas I, Formula II, formula III or formula IV:
In Formulas I, Formula II and formula III,Indicate NNP ligand or PNP ligand；
Wherein, X2It is methyl, ethyl, isopropyl, tert-butyl, cyclopenta, cyclohexyl, phenyl or 2- pyridine for N or P, R
Base；R1For H, methyl, ethyl, benzyl or 2- picolyl；
In Formulas I, X and X1Independently selected from H, Cl, Br, I, CO (carbonyl), OAc (acetate), OEt (ethyoxyl), OMe
(methoxyl group), OBn (benzyloxy), OH and OTf (trifyl), and X and X1It is not simultaneously CO.
The structural formula of the NNP ligand is as shown in Formula V or Formula IV:
In Formula V and Formula IV, A indicates C or N；
In Formula V, R is expressed as methyl, ethyl, isopropyl, tert-butyl, cyclopenta, cyclohexyl or phenyl；
R1It is expressed as H, methyl, ethyl, benzyl or 2- picolyl；
R3、R4、R5And R6Independently indicate H, C1~C6Alkyl, C1~C6Alkoxy, phenyl, C1~C6Alkyl substituted benzene
Base, halogen, benzyl, hydroxyl, naphthalene, furyl or thienyl；
In Formula IV, R7、R8And R9Independently indicate H, C1~C6Alkyl, C1~C6Alkoxy, phenyl, C1~C6Alkyl takes
For phenyl, halogen, benzyl, hydroxyl, naphthalene, furyl or thienyl.
The structural formula of the PNP ligand is as shown in Formula VII:
In Formula VII, R is expressed as methyl, ethyl, isopropyl, tert-butyl, cyclopenta, cyclohexyl or phenyl；
R1It is expressed as H, methyl, ethyl, benzyl or 2- picolyl.
In the present invention, C1~C6Alkyl refers specifically to methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, uncle
Butyl, n-pentyl, isopentyl, neopentyl, sec-amyl, tertiary pentyl, cyclopenta, n-hexyl, isohesyl, new hexyl, Sec-Hexyl, uncle
Hexyl or cyclohexyl.
C1~C6Alkoxy is methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy, tertiary fourth oxygen
It is base, n-pentyloxy, isoamoxy, neopentyl oxygen, secondary amoxy, tertiary amoxy, cyclopentyloxy, positive hexyloxy, dissident's oxygroup, new
Hexyloxy, secondary hexyloxy, tertiary hexyloxy or cyclohexyloxy.
Manganese complex of the present invention is specifically as shown in formula 1- formula 16, preferred formula 2, formula 3, formula 8, formula 11 and formula 12:
In various, tBu indicates that tert-butyl, Ph indicate that phenyl, Cy indicate that cyclohexyl, iPr indicate isopropyl.
Invention further provides the preparation methods of the manganese complex, include the following steps:
Under the protection of inert atmosphere, pentacarbonyl halogenation manganese salt is reacted with the NNP ligand or the PNP ligand,
Up to the manganese complex；
The chemical formula of the pentacarbonyl halogenation manganese salt is Mn (CO)5X3, wherein X3Indicate Cl, Br or I.
In above-mentioned preparation method, the molar ratio of the pentacarbonyl halogenation manganese salt and the NNP ligand or the PNP ligand
It can be 1:1.05~1.1, such as 1:1.1；
The temperature of the reaction can be 70~110 DEG C, and the time can be 6~20 hours, and it is small that 8~20 are reacted such as at 70 DEG C
When, 8 hours, 15 hours or 20 hours.
In above-mentioned preparation method, the reaction carries out in a solvent, and the solvent can be toluene, dimethylbenzene and tetrahydro furan
At least one of mutter.
Manganese complex of the present invention is capable of the Guerbet reaction of catalysis ethanol, the chemical combination of the butanol of acquisition and its more advanced alcohol
Object can be used as the additive in gasoline.
The reaction equation of the Guerbet reaction is specifically such as formula (1)
Wherein, [Mn] indicates the manganese complex；
In the Guerbet reaction, the mole dosage of the manganese complex can be the 0.00001%~0.01% of ethyl alcohol,
Concretely 0.01%, the mole dosage of the ethyl alcohol can 50mmol~1300mmol；
The temperature of the Guerbet reaction can be 100~180 DEG C, and the time can be 2~168 hours, anti-such as at 160 DEG C
It answers 24 hours；
It is carried out under the conditions of Guerbet reaction is existing for the sodium ethoxide；
The concentration of sodium ethoxide described in the system of the Guerbet reaction can be 0.1~2M, concretely 1M.
Based on manganese complex of the present invention, provides a kind of ethyl alcohol coupling based on the catalysis of cheap metal manganese and prepare butanol
Method, show very high catalytic activity (TON=114120, wherein before 12h TOF be 3078h-1) and 92% butanol
Selectivity (Fig. 1)；The present invention will efficiently utilize biomass resource, especially to the production of high-quality bio-fuel, biomass platform
The catalytic activation of compound and conversion and corresponding cheap, effective catalyst design, provide important technical support and theory and refer to
It leads.
The present invention achieves following technical effect:
1, the present invention, which provides, reports a new class of manganese-NNP or the ethanol condensed reaction at butanol of PNP complex catalysis,
Synthesis butanol Compound that can be highly selective, the complex compound have high catalytic activity, have very high researching value and answer
Use prospect.
2, the present invention also provides a kind of methods for preparing manganese-NNP perhaps PNP complex compound by the NNP of three teeth or
PNP ligand with manganese salt react in a solvent by heating stirring, and filtering gained precipitating is novel manganese-NNP or PNP complex compound, system
It is standby simple, it is easy to operate.
Detailed description of the invention
Fig. 1 is the homogeneous catalyst and its catalytic effect that the Guerbet reaction of ethyl alcohol can be achieved.
Fig. 2 is the structural formula and its x-ray crystal structure of manganese complex shown in formula 7.
Fig. 3 is the structural formula and its x-ray crystal structure of manganese complex shown in formula 9.
Fig. 4 is the structural formula and its x-ray crystal structure of manganese complex shown in formula 11.
Fig. 5 is the structural formula and its x-ray crystal structure of manganese complex shown in formula 15.
Specific embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.
In following embodiment, Me indicates that methyl, tBu indicate that tert-butyl, nBu indicate that normal-butyl, Ph indicate phenyl, Bn table
Show that benzyl, Cy indicate that cyclohexyl, iPr indicate that isopropyl, PE indicate that petroleum ether, EA indicate that ethyl acetate, TLC indicate thin layer color
Spectrum, NMR indicate nuclear magnetic resonance.
In following embodiments bis- [2- (di-t-butyl phosphino-) ethyl] amine of ligand (tBuPNP), bis- [2- (dicyclohexylphosphontetrafluoroborates
Base) ethyl] amine (CyPNP) and bis- [2- (diisopropyl phosphino-) ethyl] amine (iPrPNP), bought from Alfa-Aesar Reagent Company,
Purity > 95%；The equal bibliography synthesis of remaining ligand: (Organometallics2003,22,445.；
Organometallics, 2009,28,6331.；Organometa-llics2012,31,5239.；Dalton Trans.,
2011,40,10397.)。
Mn(CO)5Br is bought from Alfa-Aesar Reagent Company, purity > 97%, is directly used.
Solvent for use is bought from Shanghai traditional Chinese medicines Reagent Company, purifies drying with standard method using preceding.
One, the preparation of Py-NNP ligand:
1,2- chloro-N, N- bis- (trimethyl silicon substrate) ethylamine is synthesized
2- chloro ethylamine hydrochloride (4.6g, 40mmol), NEt are successively added into Shrek bottle3(18mL,132mmol)
The methylene chloride 50mL of sum.Reaction be stirred at room temperature in the case where, toward the system be added trim,ethylchlorosilane (90mmol, 9.8g,
Dichloromethane solution (20mL) 11.4mL).Reaction is stirred overnight at room temperature, and after reaction, excessive triethylamine is removed under reduced pressure,
The n-hexane of 60mL is added into resulting residue for trim,ethylchlorosilane and methylene chloride, and reaction is stirred at room temperature 30 minutes, mistake
Filter out NEt3·HCl.After filtrate concentration, target product (6.0g, 68%) is obtained by vacuum distillation.1H NMR(400MHz,
CDCl3)δ3.37–3.21(m,2H),3.18–2.99(m,2H),0.14(s,18H).13C NMR(101MHz,CDCl3)δ
47.38,44.83,1.89.
2,2- isopropyl phosphine ethamine borane complex is synthesized
Under the conditions of argon gas, into the Shrek bottle of 100mL, diisopropyl phosphine (2.92g, 20mmoL) and n-hexane is added
Above-mentioned mixed liquor is cooled to -78 degree, n-BuLi (2.5M, 8.8mL, 22mmoL) is added dropwise into the system by (20ml).
After adding, reaction is warmed to room temperature, and is continued after stirring 1h, is obtained LiPiPr2White suspended things.
Under protection of argon gas, just by 2- chloro-N, N- bis- (trimethyl silicon substrate) ethylamine (4.46g, 20mmoL) and 20mL
Hexane is added in Shrek bottle, under agitation, above-mentioned LiPiPr is added toward the mixture2Suspension.React room temperature
After stirring 30min, it is heated to reflux 8h.After reaction, the H of 10mL de aerated water and 2M 10mL is added into reaction2SO4Solution,
Reaction is stirred at room temperature one hour, and 11mL 4M NaOH solution is added into the reaction later, and reaction continues stirring one hour.Separation
Organic phase, water phase are dried, filtered with n-hexane extraction (2 × 15mL), merging organic phase, anhydrous sodium sulfate, and crude product is obtained after draining
2- isopropyl phosphine ethamine.
By obtained 2- isopropyl phosphine ethylamine in the THF (30mL) of degassing, the boron of 1M is added into the solution
Alkane tetrahydrofuran solution, reaction be stirred at room temperature 2 hours after, drain, residue through column chromatography for separation obtain target product (0.75g,
41%).1H NMR(400MHz,CDCl3) δ 2.98 (td, J=8.7,6.2Hz, 2H), 1.99 (ddt, J=14.3,10.4,
7.1Hz, 1H), 1.84-1.69 (m, 2H), 1.35 (s, 2H), 1.18 (ddd, J=10.9,7.1,4.3Hz, 12H), 0.82-
0.11(brs,3H).δ13C NMR(101MHz,CDCl3) δ 37.55,23.46 (d, J=29.1Hz), 22.08 (d, J=
33.5Hz), 16.91 (d, J=20.3Hz)31P NMR(162MHz,CDCl3)δ29.42(q).HR-MS(ESI)calcd.for
C14H29BN2P[M+H]+:176.1734；found:176.1720.
3-1, the borane complex for synthesizing Py-NNP ligand
Under the conditions of argon gas, into Shrek bottle, 2- pyridine carboxaldehyde (0.44g, 4.14mmol) and 5mLTHF is added, it is past to be somebody's turn to do
THF (5mL) solution of 2- wopropyl ethyl amine borane complex (0.73g, 4.14mmol) is added in solution.Reaction stirring 0.5h,
THF solvent is drained, the borane complex of gained pyridine-imine-NNP ligand is direct plungeed into without purifying to react in next step
In.
Under the conditions of ice-water bath, 20mL first is added into the borane complex of above-mentioned resulting pyridine-imine-NNP ligand
The toluene solution (1.3mL, 1.56mmoL) of the DIBAL of 1.2M is slowly added dropwise into the solution for benzene.It is small that reaction is stirred at room temperature 0.5
Shi Hou is added 3mL water quenching and goes out, and toluene is extracted twice (2 × 5mL), merges organic phase.Sodium sulphate dries, filters, and solvent is drained
Afterwards, the borane complex (0.65g, 59%) of pure pyridine NNP ligand is obtained through column chromatography for separation.1H NMR(400MHz,
CDCl3) δ 8.55 (d, J=4.8Hz, 1H), 7.64 (td, J=7.7,1.8Hz, 1H), 7.37-7.26 (m, 1H), 7.16 (dd, J
=7.4,4.9Hz, 1H), 3.93 (d, J=4.9Hz, 2H), 2.93 (dt, J=12.0,7.1Hz, 2H), 1.99 (ddt, J=
14.3,10.4,7.1Hz, 3H), 1.83 (ddd, J=11.0,9.6,8.1Hz, 2H), 1.17 (ddd, J=12.1,7.1,
5.5Hz,12H),0.75–0.14(brs,3H).13C NMR(101MHz,CDCl3)δ159.09,149.31,136.51,
122.28,122.05,54.75,44.34,22.11 (d, J=33.4Hz), 19.87 (d, J=30.2Hz), 16.94 (d, J=
21.8Hz).31P NMR(162MHz,CDCl3)δ32.25(q).HR-MS(ESI)calcd.for C14H29BN2P[M+H]+:
267.2155；found:267.2136.
3-2, synthesis Py-NNP ligand
Borane complex (0.32g, 1.2mmol) containing Py-NNP ligand is dissolved in the Et of degassing2NH, will be above-mentioned molten
Liquid is added under protection of argon gas in Schlenk bottles of 20mL, and reaction carries out 24 hours at 95 degree.After reaction, Et is drained2NH,
Residue again argon gas protect lower column separation (eluent ratio: petrol ether/ethyl acetate=3:1to petrol ether/ethyl acetate/
Methanol=3:1:0.2), obtain target product (0.22g, 72%).
1H NMR(400MHz,CDCl3) δ 8.48 (d, J=4.2Hz, 1H), 7.56 (td, J=7.7,1.8Hz, 1H), 7.24
(d, J=7.8Hz, 1H), 7.08 (dd, J=6.7,5.2Hz, 1H), 3.86 (s, 2H), 2.81-2.56 (m, 2H), 2.10 (s,
2H),1.79–1.60(m,2H),1.60–1.48(m,2H),0.95-1.03(m,12H).13C NMR(101MHz,CDCl3)δ
(159.09,149.31,136.51,122.28,122.05,54.75,44.34,22.11 d, J=33.4Hz), 19.87 (d, J=
30.2Hz), 16.94 (d, J=21.8Hz)31P NMR(162MHz,CDCl3)δ-0.91(s).HR-MS(ESI)called for
C14H26N2P[M+H]+:253.1828；found:253.1828.
Two, the preparation of N-Me-PNP (Cy) ligand
Under protection of argon gas, into the Schlenk bottle of 50mL, dicyclohexylphosphontetrafluoroborate (1.00g, 5mmol) and degassing THF is added
(10mL), by above-mentioned solution be cooled to -20 degree, be slowly added into above-mentioned solution nBuLi (2.2mL, 2.5M in hexanes,
5.5mmol), it is slowly increased to room temperature after adding and flows back 1 hour.Under protection of argon gas, into the Schlenk bottle of another 50mL
MeN (CH is added2CH2Cl)2Above-mentioned solution is cooled to -20 degree, up by HCl (0.49g, 2.52mmol) and THF (10mL)
State and be slowly added to nBuLi (1.1mL, 2.5M in hexanes, 2.52mmol) in solution, be slowly increased to after adding room temperature and after
Continuous stirring 2 hours.Later by above-mentioned solution under -78 degree, the THF solution for the dicyclohexylphosphontetrafluoroborate lithium being slowly added to reacts later
Liquid is slowly increased to room temperature, and heated overnight at reflux.After reaction, THF is drained, 5mL de aerated water, solution are added into raffinate
Three times (3 × 10mL) with the extraction of degassing ether, merge organic phase, anhydrous sodium sulfate dries, filters, and organic phase is concentrated into
5mL, has a large amount of white solids to be precipitated after putting -20 degree refrigerator 30min, and the filtering of low temperature argon gas obtains white solid (0.45g, 38%).
1H NMR(400MHz,Tol-d8) δ 2.71 (dt, J=9.4,6.2Hz, 4H), 2.31 (s, 3H), 2.13 (dt, J=4.3,
2.1Hz,4H),1.91–1.74(m,24H),1.56(m,4H),1.25(m,18H).13C NMR(101MHz,Tol-d8)δ56.76
(d, J=29.4Hz), 41.65,33.58 (d, JC-P=14.9Hz), 30.51 (d, JC-P=15.4Hz), 29.14 (d, JC-P=
8.7Hz),27.32(d,JC-P=5.5Hz), 26.63.20.61,20.41,20.22,20.03,19.84,19.76,19.65,
19.46.31P NMR(162MHz,Tol-d8)δ-8.00(s).HR-MS(ESI)called for C29H56NP2[M+H]+:
480.3883；found:480.3880.
Embodiment 1, pyridine synthesis NNP-Mn (CO)2Br complex compound (shown in formula 7)
Reaction equation is as follows:
Under argon atmosphere, into the Schlenk bottle of 25mL, [Mn (CO) is added5Br] (129mg, 0.47mmol), [Py-
NNP-iPr] L5 (132mg, 0.52mmol) and degassing THF (10mL), reaction is stirred overnight at room temperature.With reaction time into
Row, solution are gradually precipitated by faint yellow solid.After reaction, argon gas filters, and filter cake is eluted with degassing ether, after vacuum drying
It obtains light yellow solid (192mg, 87%).
Nuclear-magnetism:1H NMR(400MHz,CD2Cl2) δ 8.62 (d, J=4.9Hz, 1H), 8.20 (s, 1H), 7.72 (d, J=
7.0Hz, 1H), 7.33 (d, J=6.8Hz, 1H), 7.29-7.25 (m, 1H), 4.79 (d, J=18.7Hz, 1H), 3.88 (d, J=
17.8Hz, 1H), 3.11-2.79 (m, 2H), 2.41 (m, 1H), 2.08 (t, J=13.6Hz, 1H), 1.62-0.94 (m, 14H)
.13C NMR(101MHz,CD2Cl2)δ162.54,152.49,138.92,124.66,121.87,59.99,29.67,24.43
(d, J=17.0Hz), 24.05,23.84 (d, J=17.8Hz), 20.26,19.32 (d, J=2.3Hz), 18.85,17.82 (d,
J=6.0Hz)31P NMR(162MHz,CD2Cl2)δ77.54(s).
High-resolution: HR-MS (ESI) called for C17H25MnN2O3P[M]+:391.0978；found:391.0979.
It is infrared: IR:3029,2905,2018,1924,1459,1104,1056,779,682,640,618cm-1.
X-ray crystal structure is as shown in Figure 2.
Target manganese complex structure prepared known to result is correct from the above analysis.
Embodiment 2, synthesis N-Me-PNP (iPr)-Mn (CO)2Br complex compound (shown in formula 9)
Under argon atmosphere, into the Schlenk bottle of 25mL, [Mn (CO) is added5Br] (120mg, 0.44mmol), [N-
Me-PNP-iPr] (153mg, 0.48mmol) and degassing toluene (10mL), it reacts and is heated to 100 degree, be stirred overnight.Reaction
After, drain toluene, 10mL be added and deaerates n-hexane, argon gas filtering, after filter cake vacuum drying light yellow solid (175mg,
78%).
Nuclear-magnetism:1H NMR(400MHz,C6D6) δ 3.46 (t, J=10.9Hz, 2H), 3.07 (dt, J=14.7,7.3Hz,
2H),2.26–2.13(m,2H),2.07(s,3H),1.74–1.63(m,8H),1.51(m 3H),1.41–1.28(m,8H),
1.26–1.10(m,11H).13C NMR(101MHz,C6D6) δ 232.06,227.14,58.59 (t, J=4.5Hz), 48.34,
28.31 (t, J=10.2Hz), 25.71 (t, J=8.1Hz), 24.79 (t, J=5.3Hz), 20.72,19.31,19.21,
18.85.31P NMR(162MHz,C6D6)δ77.82(s).
High-resolution: HR-MS (ESI) called for C19H39MnNO2P2[M]+:430.1831；found:430.1834.
It is infrared: IR:2907,2871,1900,1807,1458,1053,1021,925,816,739,686,65 2,621cm-1.
X-ray crystal structure is as shown in Figure 3.
Target manganese complex structure prepared known to result is correct from the above analysis.
Formula 1, formula 2, formula 3, formula 4, formula 5,10 institute of formula 6, formula 8 and formula has been prepared according to method same as Example 2
Show cobalt complex.
Embodiment 3, synthesis PNP-Mn (CO)2Complex compound (shown in formula 11)
Under argon atmosphere, into the Schlenk bottle of 10mL, PNP is successively addediPr-Mn(CO)2Br(0.15g,
0.3mmol), sodium ethoxide (61mg, 0.9mmol) and anhydrous and oxygen-free THF (4mL).Reaction is stirred at room temperature 2 hours, with reaction
It carries out, solution gradually becomes red from yellow, after reaction, drains solvent.Then 5mL anhydrous and oxygen-free is added into residue
N-hexane, argon gas filtering, gained filtrate are drained, as amino manganese complex formula 11 (87mg, 69%).
Nuclear-magnetism:1H NMR(400MHz,C6D6) δ 2.96 (s, 1H), 1.99 (d, J=4.7Hz, 1H), 1.38 (s, 1H),
0.98 (d, J=5.7Hz, 3H), 0.84 (d, J=4.2Hz, 3H)13C NMR(101MHz,C6D6) 64.89 (J=of δ
10.1Hz), 26.29 (J=10.1Hz), 22.85 (J=5.6Hz), 18.08,17.48.31P NMR(162MHz,C6D6)δ
112.99(s).
X-ray crystal structure is as shown in Figure 4.
Target manganese complex structure prepared known to result is correct from the above analysis.
Embodiment 4, synthesis PNP-Mn (CO)2OAc complex compound (shown in formula 15)
Under argon atmosphere, into the Schlenk bottle of 10mL, PNP is successively addediPr-Mn(CO)2(0.1mmol,
41.4mg), anhydrous and oxygen-free n-hexane (2mL) and acetic acid (0.3mmol, 18mg).Reaction is stirred at room temperature 0.5 hour, will mix later
It closes liquid and is put into -20 degree refrigerator overnights, upper layer hexane solution is siphoned away, pale yellow crystals (36mg, 75%) is obtained.
Nuclear-magnetism:1H NMR(400MHz,C6D6)δ8.16(s,1H),3.57(s,3H),2.95(s,2H),2.28–1.56(m,
11H),1.52–0.64(m,24H).13C NMR(101MHz,C6D6)δ67.45,52.44,31.58,27.42,26.46,
25.44,24.30,22.67,19.95 (d, J=24.3Hz), 18.14 (d, J=59.4Hz) .13.96.31P NMR(162MHz,
C6D6)δ87.68(s).
X-ray crystal structure is as shown in Figure 5.
Target manganese complex structure prepared known to result is correct from the above analysis.
Manganese complex shown in formula 12 and formula 16 has been prepared in the same manner as shown in Example 1
Embodiment 5, synthesizing cis PNPiPr-Mn(CO)2H complex compound (shown in formula 13)
In glove box, amino manganese complex formula 11 (0.01mmol, 4.1mg) and toluene (1mL) are added to containing syringe needle
Bottle in, bottle is put into 100mL autoclave later.The hydrogen of 10 atmospheric pressure is filled in kettle, room temperature reaction 14 is small
When.To the end of reacting, by phosphine spectrum tracking reaction product after hydrogen slow release.
31P NMR (162MHz, Toluene): 109.38ppm.
Target manganese complex structure prepared known to result is correct from the above analysis.
Embodiment 6, synthesis of trans PNPiPr-Mn(CO)2H complex compound (shown in formula 14)
In glove box, by amino manganese complex formula 11 (0.01mmol, 4.1mg), ethyl alcohol (0.3mmol, 13.8mg) and
Toluene (1mL) is successively added in the bottle containing syringe needle, after reacting 15min and forming ethyoxyl manganese complex (formula 12) completely,
Bottle is put into 100mL autoclave.The hydrogen of 30 atmospheric pressure is filled in kettle, is reacted at room temperature 14 hours.To the end of reacting,
By phosphine spectrum tracking reaction product after hydrogen slow release.
31P NMR (162MHz, Toluene): 106.86ppm.
Target manganese complex structure prepared known to result is correct from the above analysis.
The research of embodiment 7, different Mn catalysts to Guerbet reaction result[a]
The different Mn catalyst effects of table 1 compare
[a]Reaction condition: (6mL, 100mmol) ethyl alcohol, (6mmol) sodium ethoxide, (0.01mol%) catalyst is 25ml's
For 24 hours is reacted in pressure-resistant kettle[b]Total conversion ratio is the amount that ethyl alcohol is converted into higher alcohol, and yield is that the yield of butanol (is made with biphenyl
It is quantitative for internal standard GC)[c]Selectivity is the amount of the substance of butanol the mass ratio of the material shared in higher alcohols product[d]TON
It can be with total amount (mmol) of ethanol conversion to higher alcohols product for the catalyst of every mmol[e]The selectivity of crotonyl alcohol is
21%.
Under the protection of argon gas, by Mn catalyst (0.01mmol, 0.01mol%), sodium ethoxide (6mmol, 408.3mg,
6mol%) successively it is added in the 25mL pressure resistance kettle containing magnetic stir bar with ethyl alcohol (100mmol, 6mL), it is anti-at a temperature of given
It should for 24 hours.After reaction, cooling with ice water, the gas generated inside autoclave body is slowly released, biphenyl is added into reaction system
It as internal standard, is diluted with THF, the yield and its selectivity of product butanol is quantitatively obtained by GC.
By to screening of catalyst result it can be found that using the lesser cyclohexyl of steric hindrance and isopropyl PNP type
Pincer [Mn] (+1) catalyst (entry1-7) has preferable conversion ratio and yield to ethyl alcohol；Uncle biggish for steric hindrance
Butyl PNP catalyst or the weaker NNP catalyst and [Mn] (+2) catalyst of coordination ability fail successfully to make ethyl alcohol
Conversion (entry7-11) occurs.
The research of embodiment 8, different alkali and other reaction conditions to manganese catalysis Guerbet reaction result[a]
2 condition optimizing of table
[a]Reaction condition: (6mL, 100mmol) ethyl alcohol, (6-12mmol) sodium ethoxide, 0.01mol% [Mn]-formula 8 exist
160 DEG C of reaction 12-168h. conversion ratios in the pressure-resistant kettle of 25mLl, yield, selectivity and TON and calculation method one in example 1
Cause[b]The additional water that 10mmol is added[c]Reaction temperature is 180 DEG C of[d]0.02mol% [Mn]-formula 8.[e]0.1mol% [Mn]-
Formula 8.[f](12mL, 200mmol) ethyl alcohol, (12mmol) sodium ethoxide[g]60mL reaction kettle, (0.0025mmol) [Mn]-formula 8,
(30mL, 510mmol) ethyl alcohol, (30mmol) sodium ethoxide[h]60mL reaction kettle, (0.00125mmol) [Mn]-formula 8, (45mL,
765mmol) ethyl alcohol, (46mmol) sodium ethoxide[i]100mL reaction kettle, (0.00125mmol) [Mn]-formula 8, (75mL,
1275mmol) ethyl alcohol, (76mmol) sodium ethoxide[j]The selectivity of crotonyl alcohol is 11%.[i]100mL reaction kettle,
(0.00125mmol) [Mn]-formula 8, (75mL, 1275mmol) ethyl alcohol, (150mmol) sodium ethoxide
By carrying out condition optimizing discovery to the above reaction, using [Mn] (formula 8) is catalyst, is screened to alkali
(entry1-5), all there is preferable reaction result when using highly basic, when using weak base (such as sodium acetate) at that time, although the reaction
With preferable selectivity (entry 5), but its conversion ratio and yield are poor；Increase the dosage of alkali and the dosage of catalyst,
Its conversion ratio and yield can be further improved (entry 10-12)；It has also been found that, which is being reacted simultaneously
It, can for the selectivity of product ethanol when increasing the dosage of its substrate ethyl alcohol but identical other reaction conditions when device is identical
Increase with it (entry 1,13), it is believed that, when the space that can accommodate gas due to reaction kettle is less, generated in-situ hydrogen
Atmospheric pressure just will increase, and can accelerate the hydrogenation rate of reaction intermediate in this way, so that its conversion to higher alcohol be prevented (to pass through
GC detection is carried out to the gas generated in reaction system, in its gas phase 81%) content of hydrogen has reached as the result is shown.Finally,
After carrying out a series of optimization to reaction condition, which can obtain up to 114120 TON (entry 19), wherein preceding 12h
TOF be 3078h-1。
Embodiment 9 poisons experiment repercussion study
3 ligand of table poisons result and compares
Under the protection of argon gas, by catalyst [Mn] (formula 8) (0.01mmol, 0.01mol%), sodium ethoxide (408.3mg,
6mmol, 6mol%), the Hg or PMe of ethyl alcohol (100mmol, 6mL) and corresponding amount3Successively it is added to the 25mL containing magnetic stir bar
In pressure-resistant kettle, reacted for 24 hours at 160 DEG C.After reaction, cooling with ice water, the gas generated inside autoclave body is slowly released, to
Biphenyl is added in reaction system as internal standard, is diluted with THF, the yield and its selectivity of product butanol is quantitatively obtained by GC.
Poison reagent Hg or PMe the above result shows that being added3Do not have to the conversion ratio and yield of entire catalysis reaction
Any detrimental effect illustrates that catalysis reaction is the process of a homogeneous reaction.
Research of the Mn catalyst that embodiment 10, N-Me are protected in ethyl alcohol conversion process
Table 4N-Me catalyst result compares
Under the protection of argon gas, by catalyst [Mn] formula 9 or formula 10 (0.01mmol, 0.01mol%), sodium ethoxide
(408.3mg, 6mmol, 6mol%) and ethyl alcohol (100mmol, 6mL) are successively added to the 25mL pressure resistance kettle containing magnetic stir bar
In, it is reacted for 24 hours at 160 DEG C.After reaction, cooling with ice water, slowly release the gas generated inside autoclave body, Xiang Fanying
Biphenyl is added in system as internal standard, is diluted with THF, the yield and its selectivity of product butanol is quantitatively obtained by GC.
From the point of view of in 4 result of table, after N-H structure is become N-Me, strong influence is produced for the conversion of ethyl alcohol.
Its conversion ratio, yield and selectivity, which have, obviously to be declined, and therefore, the presence of N-H structure is for ethyl alcohol in ligand
Entire conversion to butanol plays very important effect.
The condensation reaction research of embodiment 11, manganese catalysis acetaldehyde and crotonaldehyde
Under the protection of argon gas, by Mn catalyst formula 8 (0.01mmol) (or being added without catalyst), sodium ethoxide (1mmol),
Acetaldehyde or crotonaldehyde (1mL) are successively added in the 25mL pressure resistance kettle containing magnetic stir bar, react 4h at 160 DEG C.Reaction knot
Shu Hou, it is cooling with ice water, the gas generated inside autoclave body is slowly released, biphenyl is added into reaction system as internal standard, uses
THF dilution, the selectivity and yield of raw material condensation product are quantitatively obtained by GC.
From the point of view of above-mentioned acquired results, catalyst will be added and be added without condensation production of the catalyst to acetaldehyde or crotonaldehyde
Object is analyzed, and the selectivity of C4 does not have apparent difference, i.e. the introducing of catalyst fails to improve the selectivity of C4
To inhibit the generation of C4+ product.Therefore, it is presumed that, the conversion reaction for ethyl alcohol, the highly selective of product butanol be
Since condensation intermediate crotonaldehyde can efficiently occur caused by hydrogenation.
The hydrogenation research of embodiment 12, manganese catalysis acetaldehyde and crotonaldehyde
Under the protection of argon gas, by Mn catalyst-formula 8 or 9 (0.01mmol), sodium ethoxide (0.12mmol), acetaldehyde or bar
Beans aldehyde (2mmol) is successively added in the 25mL autoclave containing magnetic stir bar, using THF as solvent, is set with inert gas argon gas
10bar H is filled with after the gas changed in autoclave three times2, reacted for 24 hours at 160 DEG C.It is after reaction, cooling with ice water,
Autoclave body internal hydrogen is slowly released, biphenyl is added into reaction system as internal standard, is diluted with THF, is quantitatively obtained by GC
The selectivity and yield of hydrogenated products.
From the point of view of above-mentioned hydrogenation result, the addition of [Mn]-formula 8 has the C4 product of acetaldehyde or crotonaldehyde brighter
The selectivity of aobvious facilitation, C4 product is improved significantly, the result again illustrate acetaldehyde and hydrogen be ethyl alcohol to
The intermediate of butanol conversion process；In addition, using N-Me protect Mn catalyst formula 9, no matter for acetaldehyde or crotonaldehyde hydrogen
Change for reaction, all obtains lower C4 selectivity.Therefore, this also further illustrates its metal of the catalyst containing N-H structure
The mode that generation hydrogen migration is cooperateed with ligand is vital for the hydrogenation of its reaction intermediate crotonaldehyde.
As can be seen from the above-described embodiment, the present invention provides a kind of novel manganese catalysis ethanol condensations to generate the anti-of butanol
It answers, which shows very high catalytic activity (TON=114120, wherein the TOF of preceding 12h is 3078h-1) and 92% fourth
Alcohol selectivity, has very high researching value and application prospect.
In this description, the present invention is described referring to specific embodiment.But it is clear that can still make
Various modifications and alterations are without departing from the spirit and scope of the invention out.Therefore, the description and the appended drawings should be considered as illustrative
And not restrictive.
Claims (2)
1. manganese complex generates the application in butanol in the Guerbet reaction of manganese catalysis ethanol；
The reaction equation that the Guerbet of the manganese catalysis ethanol reacts to obtain butanol is as follows:
The Guerbet reaction carries out under the protection of inert atmosphere；
Wherein, [Mn] indicates the manganese complex；
The structural formula of the manganese complex is as shown in Formulas I, Formula II, formula III or formula IV:
Wherein, X2It is methyl, ethyl, isopropyl, cyclopenta or cyclohexyl for P, R；R1For H；
X and X1Independently selected from H, Cl, Br, I, CO, OEt and OMe, and X and X1It is not simultaneously CO.
2. application according to claim 1, it is characterised in that: in the Guerbet reaction, mole of the manganese complex
Dosage is the 0.00001%~0.01% of ethyl alcohol；
The temperature of the Guerbet reaction is 100~180 DEG C, and the time is 2~168 hours；
It is carried out under the conditions of Guerbet reaction is existing for the sodium ethoxide；
The concentration of sodium ethoxide described in the system of the Guerbet reaction is 0.1~2M.
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