CN110997611A - 用于将甲醇转化为甲酸甲酯和氢气的均相铁催化剂 - Google Patents
用于将甲醇转化为甲酸甲酯和氢气的均相铁催化剂 Download PDFInfo
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- CN110997611A CN110997611A CN201880050139.3A CN201880050139A CN110997611A CN 110997611 A CN110997611 A CN 110997611A CN 201880050139 A CN201880050139 A CN 201880050139A CN 110997611 A CN110997611 A CN 110997611A
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- Prior art keywords
- catalyst
- methyl formate
- formula
- hydrogen
- base
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 102
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 19
- 239000001257 hydrogen Substances 0.000 title claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title abstract description 16
- 229910052742 iron Inorganic materials 0.000 title abstract description 5
- 239000003446 ligand Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims description 32
- 239000012041 precatalyst Substances 0.000 claims description 22
- 125000003118 aryl group Chemical group 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 19
- 230000007935 neutral effect Effects 0.000 claims description 18
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical group [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 16
- -1 nitrogen-containing compound Chemical class 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 125000004947 alkyl aryl amino group Chemical group 0.000 claims description 7
- 125000004104 aryloxy group Chemical group 0.000 claims description 7
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 7
- 125000004986 diarylamino group Chemical group 0.000 claims description 7
- 125000002373 5 membered heterocyclic group Chemical group 0.000 claims description 6
- 125000004070 6 membered heterocyclic group Chemical group 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 150000002170 ethers Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 4
- 125000000732 arylene group Chemical group 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000003161 (C1-C6) alkylene group Chemical group 0.000 claims description 3
- 150000004703 alkoxides Chemical class 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 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 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 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 claims 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 30
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000006227 byproduct Substances 0.000 abstract description 4
- 239000002815 homogeneous catalyst Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 238000005481 NMR spectroscopy Methods 0.000 description 22
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 19
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 19
- 239000002585 base Substances 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 8
- 230000010354 integration Effects 0.000 description 8
- 239000003039 volatile agent Substances 0.000 description 8
- 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 7
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229910021575 Iron(II) bromide Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012018 catalyst precursor Substances 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- UHOVQNZJYSORNB-MICDWDOJSA-N deuteriobenzene Chemical compound [2H]C1=CC=CC=C1 UHOVQNZJYSORNB-MICDWDOJSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 2
- 230000006315 carbonylation Effects 0.000 description 2
- 238000005810 carbonylation reaction Methods 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000011997 shvo catalyst Substances 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 125000005270 trialkylamine group Chemical group 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L Cs2CO3 Substances [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910017147 Fe(CO)5 Inorganic materials 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 229910004039 HBF4 Inorganic materials 0.000 description 1
- 229910004713 HPF6 Inorganic materials 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 229910021579 Iron(II) iodide Inorganic materials 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 229910000025 caesium bicarbonate Inorganic materials 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical group 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000004636 glovebox technique Methods 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- BQZGVMWPHXIKEQ-UHFFFAOYSA-L iron(ii) iodide Chemical compound [Fe+2].[I-].[I-] BQZGVMWPHXIKEQ-UHFFFAOYSA-L 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
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910000032 lithium hydrogen carbonate Inorganic materials 0.000 description 1
- AZVCGYPLLBEUNV-UHFFFAOYSA-N lithium;ethanolate Chemical compound [Li+].CC[O-] AZVCGYPLLBEUNV-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 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
- 239000012454 non-polar solvent Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
-
- 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
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Abstract
由螯配体支撑的铁基均相催化剂用于甲醇的催化脱氢偶联,以生产甲酸甲酯和氢气。由于甲醇和甲酸甲酯都是挥发性材料,因此可以通过在室温下应用真空将其容易地与催化剂分离。可以分离出反应的氢气副产物,并将其用作其他化学转化的原料。
Description
技术领域
本发明大体涉及有机化学领域。其特别涉及甲醇的催化脱氢偶联,以生产甲酸甲酯。
背景技术
甲酸甲酯是甲酸生产中的关键中间体。它也是C1化学中有用的构件分子。目前,甲酸甲酯在工业上是通过使用甲醇钠作为催化剂并用干燥的CO作为羰基化试剂将甲醇羰基化而生产的。然而,通过羰基化途径生产甲酸甲酯有几个主要缺点。例如,甲酸甲酯的百分比产率相对较低,并且该反应通常在相对较高的CO压力下进行。此外,该方法依赖于使用危险且易燃的CO气体,其难以大量运输。因此,需要更有效和更绿色的方法以由甲醇合成甲酸甲酯,特别是不使用有毒的CO气体。
本发明解决了这种需求以及其它需求,这将在以下描述和所附权利要求中变得明显。
发明内容
本发明如在所附权利要求中阐述的。
简言之,本发明提供了一种制备甲酸甲酯和氢气的方法。该方法包括:在反应器中,于有效形成甲酸甲酯和氢气的条件下,使无水甲醇与式(I)的催化剂接触
其中,
R1和R2各自独立地为具有1至12个碳原子的烷基、芳基、烷氧基、芳氧基、二烷基氨基、二芳基氨基或烷基芳基氨基;
如果E是氮,则R3和R4各自独立地为具有1至12个碳原子的烷基或芳基;
如果E是磷,则R3和R4各自独立地为具有1至12个碳原子的烷基、芳基、烷氧基、芳氧基、二烷基氨基、二芳基氨基或烷基芳基氨基;
R1、R2和P可以连接以形成5或6元杂环;
R3、R4和E可以连接以形成5或6元杂环;
R5和R6各自独立地为C1-C6亚烷基或亚芳基;
E是磷或氮;以及
L是中性配体。
具体实施方式
令人惊讶地发现,通过在含有三齿螯配体的均相铁催化剂存在下进行甲醇的脱氢偶联(dehydrogenative coupling、DHC或dehydrocoupling)反应,可以直接以高产率生产甲酸甲酯。该反应不需要使用有毒、加压的CO气体,并且具有作为唯一副产物的联产二氢的附加价值。在该反应中仅生成甲酸甲酯。在粗反应混合物中,通过1H NMR光谱未检测到其他副产物,例如甲醛或二甲氧基甲烷。相当出乎意料的是,与相同条件下的相应的钌基催化剂比较,铁催化剂显示出优异的反应性。
因此,一方面,本发明提供了用于制备甲酸甲酯和氢气的方法。该方法包括这样的步骤:在反应器中,于有效形成甲酸甲酯和氢气的条件下,使无水甲醇与式(I)的催化剂接触
式(I)中的R1和R2各自独立地为具有1至12个碳原子的烷基、芳基、烷氧基、芳氧基、二烷基氨基、二芳基氨基或烷基芳基氨基。
如果E是氮,则式(I)中的R3和R4各自独立地为具有1至12个碳原子的烷基或芳基。
如果E是磷,则式(I)中的R3和R4各自独立地为具有1至12个碳原子的烷基、芳基、烷氧基、芳氧基、二烷基氨基、二芳基氨基或烷基芳基氨基。
式(I)中的R5和R6各自独立地为C1-C6亚烷基或亚芳基。
式(I)中的E为磷或氮。
式(I)中的L为中性配体。
式(I)中的R1、R2和P可以连接以形成5或6元杂环。
式(I)中的R3、R4和E可以连接以形成5或6元杂环。
R1、R2、R3和R4中的一个或多个可取代有选自醚、酯和酰胺的一个或多个基团。如果有的话,R1、R2、R3和R4上的取代基可以相同或不同。
醚基的例子包括甲氧基、乙氧基、异丙氧基等。
酯基的例子包括甲酸酯基、乙酸酯基、丙酸酯基等。
酰胺基的例子包括二甲基氨基、二乙基氨基、二异丙基氨基等。
如本文所用,术语“烷基”是指直链、支化或环状烷基。这些基团的例子包括甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、正戊基、叔戊基、新戊基、异戊基、仲戊基、3-戊基、环戊基、正己基、异己基、环己基等。
术语“芳基”是指苯基或萘基。
术语“亚烷基”是指二价烷基。
术语“亚芳基”是指二价芳基。
术语“烷氧基”是指-OR基团,例如-OCH3、-OEt、-OiPr、-OBu、-OiBu等。
术语“芳氧基”是指-OAr基团,例如-OPh、-O(取代的Ph)、-O萘基等。
术语“二烷基氨基”是指-NR'R"基团,例如二甲基氨基、二乙基氨基、二异丙基氨基等。
术语“二芳基氨基”是指-NAr'Ar"基团,例如二苯基氨基。
术语“烷基芳基氨基”是指-NRAr基团,例如甲基苯基氨基。
术语“中性配体”是指具有中性电荷的配体。中性配体的例子包括一氧化碳、醚化合物、酯化合物、膦化合物、胺化合物、酰胺化合物、腈化合物和含N杂环化合物等。中性膦配体的例子包括三甲基膦、三环己基膦、三苯基膦等。中性胺配体的例子包括三烷基胺、烷基芳基胺和二烷基芳基胺,例如三甲胺和N,N-二甲基苯胺。中性腈配体的例子包括乙腈。中性含N杂环配体的例子包括吡啶和1,3-二烷基-或二芳基-咪唑碳烯。
在一实施例中,R1、R2、R3和R4都是异丙基。在另一实施例中,R1、R2、R3和R4都是苯基。
在一实施例中,R5和R6都是-(CH2CH2)-。
在一实施例中,E是磷。
在多种实施例中,式(I)的催化剂具有式(1c):
其中iPr代表异丙基。
无水甲醇可以以多种等级商购获得,例如,甲醇>99wt%、甲醇99-100wt%、甲醇99.7wt%、甲醇99.8wt%和甲醇100wt%。这些等级中的任何一种可用于DHC反应。
优选地,基于反应混合物的总重量,反应混合物含有如下含量的水:小于1wt%、小于0.5wt%、小于0.4wt%、小于0.3wt%、小于0.2wt%、小于0.1wt%、小于0.05wt%、小于0.01wt%、小于0.005wt%或小于0.001wt%。在一实施例中,DHC反应在无水情况下进行。
式(I)的催化剂可以以多种方式制备。例如,催化剂可原位形成:通过将式(IIa)或(IIb)的预催化剂引入反应器中
并将该预催化剂暴露于热、酸、碱或其组合,以形成式(I)的催化剂。
式(IIa)或(IIb)中的R1、R2、R3、R4、R5、R6、E和L如式(I)中所定义。
式(IIa)中的Z为R7或X。
R7为氢或烷基或芳基。
X为[BH4]-或卤化物。
式(IIb)中的L2为中性配体。
R7所代表的烷基或芳基可含有1至12个碳原子。
X所代表的卤化物包括氯化物、溴化物和碘化物。在一实施例中,X是氯化物或溴化物。
中性配体L2的例子包括醚化合物、酯化合物、酰胺化合物、腈化合物和含N杂环化合物等。
在一实施例中,当X是卤化物时,将预催化剂暴露于碱中,并且可选地暴露于热,以产生催化剂。
在另一实施例中,当X为[BH4]-时,将预催化剂暴露于热,但可选地不存在碱,以产生催化剂。
如本文所用,“不存在”这一表述是指不从外部来源添加所提及的组分,或者,如果添加的话,不以在可察觉的程度上影响DHC反应的量添加,例如这样的量——可以使甲酸甲酯的产率改变超过10%、超过5%、超过1%、超过0.5%或超过0.1%。
在多种实施例中,式(IIa)的预催化剂具有式(1a):
其中iPr代表异丙基。
在多种实施例中,式(IIb)的预催化剂具有式(1b):
其中iPr代表异丙基。
或者,式(I)的催化剂可以通过以下步骤原位形成:
(a)将下述物质引入反应器中以形成预催化剂混合物:(i)包含中性配体(L)的铁盐或铁络合物,(ii)式(III)的配体
可选地,和(iii)中性配体(L);以及
(b)可选地,将预催化剂混合物暴露于热、酸、碱或其组合,以形成式(I)的催化剂。
式(III)中的R1、R2、R3、R4、R5、R6和E如式(I)中所定义。
适于制备式(I)催化剂的铁盐的例子包括[Fe(H2O)6](BF4)2、Fe(CO)5、FeCl2、FeBr2、FeI2、[Fe3(CO)12]、Fe(NO3)2、FeSO4等。
包含中性配体(L)的铁络合物可通过本领域已知的方法制备和/或商购获得。
式(III)的配体可通过本领域已知的方法制备和/或商购获得。
用于产生催化剂的所采用的热没有特别限制。它可以与用于DHC反应的热相同。例如,可将预催化剂或预催化剂混合物暴露在升高的温度下,例如40至200℃、40至160℃、40至150℃、40至140℃、40至130℃、40至120℃、40至100℃、80至160℃、80至150℃、80至140℃、80至130℃、80至120℃或80至100℃,以形成催化剂。
用于形成催化剂的酸没有特别限制。合适的酸的例子包括甲酸、HBF4、HPF6、HOSO2CF3等。
用于形成催化剂的碱没有特别限制。无机碱和有机碱均可使用。合适的无机碱的例子包括Na、K、NaH、NaOH、KOH、CsOH、LiHCO3、NaHCO3、KHCO3、CsHCO3、Li2CO3、Na2CO3、K2CO3、Cs2CO3等。合适的有机碱包括金属醇盐和含氮化合物。合适的金属醇盐的例子包括碱金属C1-C6醇盐,例如LiOEt、NaOEt、KOEt和KOt-Bu。在一实施例中,碱是甲醇钠(NaOMe)。在另一实施例中,碱是乙醇钠(NaOEt)。含氮碱的例子包括三烷基胺,例如三乙胺。
通常,使用1:1摩尔当量的碱与催化剂前体来产生催化剂。可以使用大于1:1的摩尔当量比,例如,碱与催化剂前体的比为2:1。然而,应避免使用大量过量的碱,因为它可能会抑制甲酸甲酯的形成。
有效形成甲酸甲酯的条件包括升高的温度。有利于DHC反应的温度可以例如在40至200℃的范围内、40至160℃的范围内、40至150℃的范围内、40至140℃的范围内、40至130℃的范围内、40至120℃的范围内、40至100℃的范围内、80至160℃的范围内、80至150℃的范围内、80至140℃的范围内、80至130℃的范围内、80至120℃的范围内或80至100℃的范围内。
可以进行脱氢偶联反应的压力没有特别的限制。例如,压力可以在大气压至2MPa的范围内。反应可以在开放的反应器中进行,其中,随着反应进行,可以将所生产的氢气取出。或者,反应可以在密封的反应器中进行,其中,生产的氢气保留在反应器中。
优选地,接触步骤/脱氢偶联反应在不存在碱的情况下进行。反应期间的碱性条件可趋于抑制甲酸甲酯的形成。
脱氢偶联反应可以在存在或不存在溶剂的情况下进行。在一实施例中,接触步骤/DHC反应在溶剂存在下进行。在另一实施例中,接触步骤/DHC反应在不存在溶剂的情况下进行。
如果需要,DHC反应可以在普通的非极性溶剂中进行,例如脂族或芳族的烃,或者在弱极性、非质子溶剂中进行,例如醚和酯。脂族溶剂的例子包括戊烷和己烷。芳族溶剂的例子包括苯、二甲苯、甲苯和三甲苯。醚的例子包括四氢呋喃、二噁烷、乙醚和聚醚。酯的例子包括乙酸乙酯。
在一实施例中,溶剂是甲苯。在另一实施例中,溶剂是均三甲苯。
如果使用,溶剂可以以相对于甲醇的量1:1至100:1,或1:1至20:1(v/v)的量加入。
如上文提到的,为了将甲醇转化为甲酸甲酯和氢气,通常将反应混合物加热至升高的温度,例如40至160℃。在一实施例中,反应在大气压下在回流的苯、二甲苯、均三甲苯或甲苯中进行。
可以以≥25ppm(0.0025mol%)的催化剂负载量发生DHC反应。例如,反应可以以如下催化剂负载量进行:50至20000ppm(0.005至2mol%)、100至15000ppm(0.01至1.5mol%)、100至10000ppm(0.01至1mol%)、100至1000ppm(0.01至0.1mol%)或100至500ppm(0.01至0.05mol%)。
根据本发明的一实施例,将催化剂或催化剂前体与甲醇——可选地以及溶剂——以1:10至1:100000的重量比在反应器中混合。将混合物在搅拌(mixing)下加热至40至160℃的温度,为期1-6小时,在此期间放出氢气(H2),并且氢气可以从反应器中除去或不除去。可以将反应进行到完全转化,但是由于速率和反应压力,限制转化可能是有利的。
产物甲酸甲酯可在适度的温度下(甲酸甲酯b.p.=32℃)与甲醇或其它挥发性产物(例如,低于60℃)一起从产物溶液中除去,并用多种冷凝器设计在0℃左右的温度方便地冷凝。
氢气易于与反应液分离,反应液在此温度下冷凝,并且氢气可以纯化和压缩以用于其他的用途。这些操作可以分批或以连续方式进行。含催化剂的浓缩物可通过添加新鲜甲醇而进行再循环。
根据本发明的方法可以生产甲酸甲酯,其产率为至少50%、至少60%、至少70%、至少80%或至少90%。可得到这些产率的反应时间包括6小时或更短、5小时或更短、4小时或更短、3小时或更短、2小时或更短或者1小时或更短。
本发明包括并明确地考虑了本文公开的实施例、特征、特性、参数和/或范围的任何的和所有的组合。也就是说,本发明可由本文提到的实施例、特征、特性、参数和/或范围的任何组合来限定。
如本文所用,不定冠词“一(个/种)”是指一个/种或者多个/种,除非上下文另外明确地指出。类似地,名词的单数形式包括其复数形式,反之亦然,除非上下文另外明确地指出。
尽管已经尝试精确,但是本文描述的数值和范围应被认为是近似值(即使在没有用术语“约”限定的情况下)。这些值和范围可以根据其声称的数值而变化,这取决于本发明试图获得的期望特性以及在测量技术中发现的由标准偏差引起的变化。此外,本文描述的范围旨在并且具体地预期为包括所声称范围内的所有子范围和值。例如,50至100的范围旨在描述并包括该范围内的所有值,包括子范围,例如60至90以及70至80。
本文引用的所有文献的内容,包括专利和非专利文献,均通过引用其全文而并入本文。在任何并入的主题与本文的任何公开内容相矛盾的程度上,本文的公开内容应优先于并入的内容。
本发明可以通过其优选实施例的以下实例进一步说明,但是应当理解,除非另有明确说明,仅是出于说明的目的而包括这些实例,并不旨在限制本发明的范围。
实例
总体实验信息
除非另有说明,否则所有的有机金属化合物都是在氮气气氛下使用标准Schlenk(施兰克)和手套箱技术制备和处理的。无水甲醇(99.7%分析纯)和均三甲苯(98%)购自西格玛奥德里奇公司(Sigma Aldrich),使用时无需进一步纯化。苯-d6购自剑桥同位素实验室(Cambridge Isotope Laboratory),并保存在干燥的分子筛中。1H NMR光谱在Bruker Avance-500 MHz光谱仪上记录。1H NMR光谱中的化学位移值是内部参考残余溶剂共振(苯-d6为δ7.16)。先前已经在文献中报道了化合物2-4。它们根据文献步骤合成(参见:Kuriyama et al.,Org.Process Res.Dev.2012,16,166;Werkmeister et al.,Chem.Eur.J.2015,21,12226以及其中引用的参考文献;Chakraborty et al.,Acc.Chem.Res.2015,48,1995以及其中引用的参考文献;Zhang et al.,J.Am.Chem.Soc.2005,127,10840;Gunanathan et al.,J.Am.Chem.Soc.2009,131,3146;Zhang et al.,Organometallics 2011,30,5716;以及Alberico et al.,Angew.Chem.Int.Ed.2013,52,14162)。Shvo催化剂购自Strem Chemicals,使用时无需进一步纯化。
制备Fe-MACHO催化剂的总体步骤
催化剂通过Chakaraborty et al.,J.Am.Chem.Soc.2014,136,8564中描述的方法制备。
1a[(iPrPNHP)Fe(H)(CO)(Br)]的改良合成
在手套箱中,在氮气气氛下,向200-mL的烘箱干燥的Schlenk烧瓶中装入络合物[iPrPNHP]FeBr2(CO)(850mg,1.545mmol)、NaBH4(60mg,1.545mmol,纯度98%)和100mL干燥EtOH。将所得的黄色溶液在室温下搅拌18小时,通过Celite(赛力特)过滤,并将滤液蒸发至干,得到纯的1a(分离产率83%)。1a的1H和31P{1H}NMR光谱与报道值(参见Chakraborty etal.,J.Am.Chem.Soc.2014,136,7869)非常吻合。
1b[(iPrPNHP)Fe(H)(CO)(BH4)]的改良合成
在手套箱中,在氮气气氛下,向200-mL的烘箱干燥的Schlenk烧瓶中装入络合物[iPrPNHP]FeBr2(CO)(850mg,1.545mmol)、NaBH4(131mg,3.399mmol,纯度98%)和100mL干燥EtOH。将所得的黄色溶液在室温下搅拌18小时,通过Celite过滤,并将滤液蒸发至干,得到纯的1b(分离产率92%)。1b的1H和31P{1H}NMR光谱与报道值(参见Chakraborty et al.,J.Am.Chem.Soc.2014,136,7869)非常吻合。
1c[(iPrPNP)Fe(H)(CO)]的改良合成
在手套箱中,在氮气气氛下,向200-mL的烘箱干燥的Schlenk烧瓶中装入络合物1a(500mg,1.06mmol)、NaOtBu(106mg,1.07mmol,纯度97%)和60mL干燥THF。立即得到深红色溶液,将其在室温下再搅拌30分钟。之后,在真空下除去溶剂,将所要产物萃取到戊烷中,并通过Celite塞过滤,以除去NaBr。真空下蒸发所得滤液,提供纯的1c(分离产率72%)。1c的1H和31P{1H}NMR光谱与报道值(参见Chakaraborty et al.,J.Am.Chem.Soc.2014,136,8564)非常吻合。
甲醇催化脱氢偶联成甲酸甲酯的总体步骤
在惰性气氛下,向配备有搅拌棒和冷水冷凝器的10-mL的Schlenk烧瓶中装入催化剂(25μmol,1mol%)、甲醇钠(如果需要的话,50μmol)、无水甲醇(101μL,2.5mmol)和苯-d6(~1mL)。将所得溶液回流特定的时间(1-3小时),然后将烧瓶冷却至0℃,并将所有挥发物真空转移至冷冻过的J.Young NMR管中,管中含有内标物——均三甲苯(177μL,1.25mmol)。用1H NMR光谱分析所得无色溶液,通过均三甲苯的芳族CH共振(δ~6.70,3H)和甲酸甲酯的OCHO共振(δ~7.50,1H)的相对1H NMR积分确定甲酸甲酯的百分比产率。使用以下公式计算甲酸甲酯的百分比NMR产率:
比较例1
在氮气气氛下,向配备有搅拌棒和冷水冷凝器的10-mL的Schlenk烧瓶中装入具有以下结构的Shvo催化剂(27mg,25μmol,1mol%)、无水甲醇(101μL,2.5mmol)和苯-d6(~1mL)
将所得溶液回流1小时,然后将烧瓶冷却至0℃,并将所有挥发物真空转移至冷冻过的J.Young NMR管中,管中含有内标物——均三甲苯(177μL,1.25mmol)。用1H NMR光谱分析所得无色溶液,通过均三甲苯的芳族CH共振与甲酸甲酯的甲酰基质子的相对积分确定甲酸甲酯的百分产率。在该反应中没有生成甲酸甲酯(产率0%)。
比较例2
在氮气气氛下,向配备有搅拌棒和冷水冷凝器的10-mL的Schlenk烧瓶中装入Milstein(米尔斯坦)钌预催化剂2a(12mg,25μmol,1mol%)、甲醇钠(3mg,50μmol)、无水甲醇(101μL,2.5mmol)和苯-d6(~1mL)。将所得溶液回流1小时,然后将烧瓶冷却至0℃,并将所有挥发物真空转移至冷冻过的J.Young NMR管中,管中含有内标物——均三甲苯(177μL,1.25mmol)。用1H NMR光谱分析所得无色溶液,通过均三甲苯的芳族CH共振与甲酸甲酯的甲酰基质子的相对积分确定甲酸甲酯的百分比NMR产率(17%)。
实例1
在氮气气氛下,向配备有搅拌棒和冷水冷凝器的10-mL的Schlenk烧瓶中装入Fe-MACHO预催化剂1a(12mg,25μmol,1mol%)、NaOMe(3mg,50μmol)、无水甲醇(101μL,2.5mmol)和苯-d6(~1mL)。将所得溶液回流1小时,然后将烧瓶冷却至0℃,并将所有挥发物真空转移至冷冻过的J.Young NMR管中,管中含有内标物——均三甲苯(177μL,1.25mmol)。用1H NMR光谱分析所得无色溶液,通过均三甲苯的芳族CH共振与甲酸甲酯的甲酰基质子的相对积分确定甲酸甲酯的百分比NMR产率(91%)。
比较例3
在氮气气氛下,向配备有搅拌棒和冷水冷凝器的10-mL的Schlenk烧瓶中装入Ru-MACHO催化剂3a(15.2mg,25μmol,1mol%)、NaOMe(3mg,50μmol)、无水甲醇(101μL,2.5mmol)和苯-d6(~1mL)。将所得溶液回流1小时,然后将烧瓶冷却至0℃,并将所有挥发物真空转移至冷冻过的J.Young NMR管中,管中含有内标物——均三甲苯(177μL,1.25mmol)。用1H NMR光谱分析所得无色溶液,通过均三甲苯的芳族CH共振与甲酸甲酯的甲酰基质子的相对积分确定甲酸甲酯的百分比NMR产率(43%)。
实例2
在氮气气氛下,向配备有搅拌棒和冷水冷凝器的10-mL的Schlenk烧瓶中装入Fe-MACHO-BH预催化剂1b(10mg,25μmol,1mol%)、无水甲醇(101μL,2.5mmol)和苯-d6(~1mL)。将所得溶液回流1小时,然后将烧瓶冷却至0℃,并将所有挥发物真空转移至冷冻过的J.Young NMR管中,管中含有内标物——均三甲苯(177μL,1.25mmol)。用1H NMR光谱分析所得无色溶液,通过均三甲苯的芳族CH共振与甲酸甲酯的甲酰基质子的相对1H NMR积分确定甲酸甲酯的百分比NMR产率(84%)。
实例3
重复实例2,只是将所得溶液回流2小时。所有的甲醇都转化为甲酸甲酯。在这个反应中没有形成其它副产物。
比较例4
在氮气气氛下,向配备有搅拌棒和冷水冷凝器的10-mL的Schlenk烧瓶中装入Ru-MACHO-BH催化剂3b(14.7mg,25μmol,1mol%)、无水甲醇(101μL,2.5mmol)和苯-d6(~1mL)。将所得溶液回流5小时,然后将烧瓶冷却至0℃,并将所有挥发物真空转移至冷冻过的J.Young NMR管中,管中含有内标物——均三甲苯(177μL,1.25mmol)。用1H NMR光谱分析所得无色溶液,通过均三甲苯的芳族CH共振与甲酸甲酯的甲酰基质子的相对积分确定甲酸甲酯的百分比NMR产率(74%)。
实例4
重复实例2,只是Fe-MACHO-BH预催化剂1b浓度降低到0.1mol%。将1b的浓度降低至0.1mol%,在3小时内提供了甲酸甲酯79%的产率。
实例5
在氮气气氛下,向配备有搅拌棒和冷水冷凝器的10-mL的Schlenk烧瓶中装入Fe-MACHO活性催化剂1c(9.8mg,25μmol,1mol%)、无水甲醇(101μL,2.5mmol)和苯-d6(~1mL)。将所得溶液回流1小时,然后将烧瓶冷却至0℃,并将所有挥发物真空转移至冷冻过的J.Young NMR管中,管中含有内标物——均三甲苯(177μL,1.25mmol)。用1H NMR光谱分析所得无色溶液,通过均三甲苯的芳族CH共振与甲酸甲酯的甲酰基质子的相对1H NMR积分确定甲酸甲酯的百分比NMR产率(66%)。
实例6
基于实例1-2和5,在无碱条件下,Fe-MACHO-BH预催化剂1b显示出最佳催化性能。进行“连续添加(successive addition)”实验,以确定该预催化剂的耐用性。结果记录于表1中。
表1
使用1mol%预催化剂1b的连续添加实验
试验(run) | 添加的MeOH | 时间(hr) | MF产率(%) | TON |
1 | 101μL,2.5mmol | 2 | 100 | 100 |
2 | 101μL,2.5mmol | 2 | 96 | 96 |
3 | 101μL,2.5mmol | 2 | 81 | 81 |
从表1中可以看出,1b的催化活性在前两次连续的(consecutive)催化试验(run)中基本上没有变化,但是此后开始显示出减弱的反应性。然而,这些实验证明,使用1mol%的Fe-MACHO-BH预催化剂,可以在6小时内得到2.77×102的合计的催化转换数(turnovernumber,TON)。
在说明书中,已经公开了本发明的某些实施例,尽管采用了特定的术语,但是它们仅以一般性和描述性意义使用,而不是为了限制的目的,本发明的范围在伴随的权利要求中阐述。
Claims (17)
1.一种制备甲酸甲酯和氢气的方法,所述方法包括:在反应器中,于有效形成甲酸甲酯和氢气的条件下,使无水甲醇与式(I)的催化剂接触
其中,
R1和R2各自独立地为具有1至12个碳原子的烷基、芳基、烷氧基、芳氧基、二烷基氨基、二芳基氨基或烷基芳基氨基;
如果E是氮,R3和R4各自独立地为具有1至12个碳原子的烷基或芳基;
如果E是磷,R3和R4各自独立地为具有1至12个碳原子的烷基、芳基、烷氧基、芳氧基、二烷基氨基、二芳基氨基或烷基芳基氨基;
R1、R2和P可连接以形成5或6元杂环;
R3、R4和E可连接以形成5或6元杂环;
R5和R6各自独立地为C1-C6亚烷基或亚芳基;
E是磷或氮;以及
L是中性配体。
4.根据权利要求1所述的方法,其中,R1、R2、R3和R4中的一个或多个取代有选自醚、酯和酰胺的一个或多个基团。
5.根据权利要求1所述的方法,其中,R1、R2、R3和R4各自独立地为甲基、乙基、丙基、异丙基、丁基、戊基、异戊基、环戊基、己基、环己基或苯基。
6.根据权利要求5所述的方法,其中,R1、R2、R3和R4中的每一个为异丙基。
7.根据权利要求5所述的方法,其中,R1、R2、R3和R4中的每一个为苯基。
8.根据权利要求1所述的方法,其中,R5和R6中的每一个为-(CH2CH2)-。
9.根据权利要求1所述的方法,其中,E是磷。
10.根据权利要求1所述的方法,其中,L是一氧化碳、膦、胺、腈或含N杂环配体。
11.根据权利要求2所述的方法,其中,L2为醚、酯、酰胺、腈或含N杂环配体。
12.根据权利要求1所述的方法,其中,所述接触步骤在40至160℃的温度下进行。
13.根据权利要求1所述的方法,其中,所述接触步骤在溶剂的存在下进行。
14.根据权利要求1所述的方法,其中,所述接触步骤在不存在溶剂的情况下进行。
15.根据权利要求1所述的方法,其中,所述接触步骤在不存在碱的情况下进行。
16.根据权利要求2所述的方法,其中,所述碱是金属醇盐或含氮化合物。
17.根据权利要求16所述的方法,其中,所述碱为甲醇钠、乙醇钠或三乙胺。
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US20110104046A1 (en) * | 2008-05-16 | 2011-05-05 | Kamaluddin Abdur-Rashid | Method for the production of hydrogen from the dehydrocoupling of amine boranes |
WO2013079659A1 (en) * | 2011-12-01 | 2013-06-06 | Leibniz-Institut Für Katalyse E.V. An Der Universität Rostock | A process for producing ethyl acetate by dehydrogenation of ethanol using a homogenous catalyst system |
US20130281664A1 (en) * | 2010-10-19 | 2013-10-24 | David Milstein | Novel ruthenium complexes and their uses in processes for formation and/or hydrogenation of esters, amides and derivatives thereof |
WO2016035080A1 (en) * | 2014-09-04 | 2016-03-10 | Yeda Research And Development Co. Ltd. | Ruthenium complexes and their uses as catalysts in processes for formation and/or hydrogenation of esters, amides and related reactions |
CN106163662A (zh) * | 2014-03-31 | 2016-11-23 | 宝洁公司 | 酯采用铁络合物作为催化剂的均相氢化 |
US20170088571A1 (en) * | 2014-06-09 | 2017-03-30 | Los Alamos National Security, Llc | Polydentate ligands and their complexes for molecular catalysis |
CN106660029A (zh) * | 2014-01-08 | 2017-05-10 | 多伦多大学管理委员会 | 包含三齿pnp配体的铁(ii)催化剂、它们的合成和其用途 |
-
2018
- 2018-07-24 US US16/043,303 patent/US20190039990A1/en not_active Abandoned
- 2018-07-31 EP EP18759448.6A patent/EP3661907A1/en active Pending
- 2018-07-31 WO PCT/US2018/044506 patent/WO2019027959A1/en unknown
- 2018-07-31 CN CN201880050139.3A patent/CN110997611A/zh active Pending
Patent Citations (7)
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US20110104046A1 (en) * | 2008-05-16 | 2011-05-05 | Kamaluddin Abdur-Rashid | Method for the production of hydrogen from the dehydrocoupling of amine boranes |
US20130281664A1 (en) * | 2010-10-19 | 2013-10-24 | David Milstein | Novel ruthenium complexes and their uses in processes for formation and/or hydrogenation of esters, amides and derivatives thereof |
WO2013079659A1 (en) * | 2011-12-01 | 2013-06-06 | Leibniz-Institut Für Katalyse E.V. An Der Universität Rostock | A process for producing ethyl acetate by dehydrogenation of ethanol using a homogenous catalyst system |
CN106660029A (zh) * | 2014-01-08 | 2017-05-10 | 多伦多大学管理委员会 | 包含三齿pnp配体的铁(ii)催化剂、它们的合成和其用途 |
CN106163662A (zh) * | 2014-03-31 | 2016-11-23 | 宝洁公司 | 酯采用铁络合物作为催化剂的均相氢化 |
US20170088571A1 (en) * | 2014-06-09 | 2017-03-30 | Los Alamos National Security, Llc | Polydentate ligands and their complexes for molecular catalysis |
WO2016035080A1 (en) * | 2014-09-04 | 2016-03-10 | Yeda Research And Development Co. Ltd. | Ruthenium complexes and their uses as catalysts in processes for formation and/or hydrogenation of esters, amides and related reactions |
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ELISABETTA ALBERICO ET AL.: "Selective Hydrogen Production from Methanol with a Defined Iron Pincer Catalyst under Mild Conditions", 《ANGEW. CHEM. INT. ED.》 * |
ELIZABETH A. BIELINSKI ET AL.: "Base-Free Methanol Dehydrogenation Using a Pincer-Supported Iron Compound and Lewis Acid Cocatalyst", 《ACS CATALYSIS》 * |
Also Published As
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US20190039990A1 (en) | 2019-02-07 |
WO2019027959A1 (en) | 2019-02-07 |
EP3661907A1 (en) | 2020-06-10 |
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