CN107108399B - 1,3-丁二烯合成 - Google Patents
1,3-丁二烯合成 Download PDFInfo
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- CN107108399B CN107108399B CN201580068620.1A CN201580068620A CN107108399B CN 107108399 B CN107108399 B CN 107108399B CN 201580068620 A CN201580068620 A CN 201580068620A CN 107108399 B CN107108399 B CN 107108399B
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- CN
- China
- Prior art keywords
- ruthenium
- bis
- dichloride
- tricyclohexylphosphine
- ylidene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 230000015572 biosynthetic process Effects 0.000 title description 11
- 238000003786 synthesis reaction Methods 0.000 title description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 53
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 18
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 17
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000003624 transition metals Chemical class 0.000 claims abstract description 15
- -1 (tricyclohexylphosphine) [ (phenylthio) methylene ] ruthenium (II) dichloride Chemical compound 0.000 claims description 34
- 239000003446 ligand Substances 0.000 claims description 34
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 30
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 29
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 29
- 239000005977 Ethylene Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 9
- 239000007791 liquid phase Substances 0.000 claims description 9
- 239000007858 starting material Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 claims description 4
- FCDPQMAOJARMTG-UHFFFAOYSA-M benzylidene-[1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene]-dichlororuthenium;tricyclohexylphosphanium Chemical compound C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.CC1=CC(C)=CC(C)=C1N(CCN1C=2C(=CC(C)=CC=2C)C)C1=[Ru](Cl)(Cl)=CC1=CC=CC=C1 FCDPQMAOJARMTG-UHFFFAOYSA-M 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- RUKVGXGTVPPWDD-UHFFFAOYSA-N 1,3-bis(2,4,6-trimethylphenyl)imidazolidine Chemical group CC1=CC(C)=CC(C)=C1N1CN(C=2C(=CC(C)=CC=2C)C)CC1 RUKVGXGTVPPWDD-UHFFFAOYSA-N 0.000 claims description 2
- 239000007983 Tris buffer Substances 0.000 claims description 2
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims description 2
- 150000001350 alkyl halides Chemical class 0.000 claims description 2
- HVJJUDAMOHYMRL-UHFFFAOYSA-L dichloro-[(2-propan-2-yloxyphenyl)methylidene]ruthenium Chemical compound CC(C)OC1=CC=CC=C1C=[Ru](Cl)Cl HVJJUDAMOHYMRL-UHFFFAOYSA-L 0.000 claims description 2
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 claims description 2
- LURVUWBWEGPODG-UHFFFAOYSA-L dichlororuthenium;tricyclohexylphosphane Chemical compound [Cl-].[Cl-].[Ru+2].C1CCCCC1P(C1CCCCC1)C1CCCCC1 LURVUWBWEGPODG-UHFFFAOYSA-L 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000007302 alkyne metathesis reaction Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 28
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 21
- 125000003118 aryl group Chemical group 0.000 description 20
- 239000000203 mixture Substances 0.000 description 19
- 125000000217 alkyl group Chemical group 0.000 description 14
- 125000000753 cycloalkyl group Chemical group 0.000 description 14
- 230000001681 protective effect Effects 0.000 description 11
- 230000035484 reaction time Effects 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 229910052736 halogen Inorganic materials 0.000 description 7
- 150000002367 halogens Chemical class 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 4
- 150000003871 sulfonates Chemical class 0.000 description 4
- 150000003568 thioethers Chemical class 0.000 description 4
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000004644 alkyl sulfinyl group Chemical group 0.000 description 3
- 125000000304 alkynyl group Chemical group 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000002274 desiccant Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 3
- 150000003003 phosphines Chemical class 0.000 description 3
- 125000005538 phosphinite group Chemical group 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 description 2
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 description 2
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003302 alkenyloxy group Chemical group 0.000 description 2
- 125000003282 alkyl amino group Chemical group 0.000 description 2
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 2
- 125000004414 alkyl thio group Chemical group 0.000 description 2
- 125000005133 alkynyloxy group Chemical group 0.000 description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 2
- 125000005110 aryl thio group Chemical group 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- 125000002619 bicyclic group Chemical group 0.000 description 2
- 150000001718 carbodiimides Chemical class 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- KMKCJXPECJFQPQ-UHFFFAOYSA-L dichloro-[(2-propan-2-yloxyphenyl)methylidene]ruthenium;tricyclohexylphosphane Chemical compound CC(C)OC1=CC=CC=C1C=[Ru](Cl)Cl.C1CCCCC1P(C1CCCCC1)C1CCCCC1 KMKCJXPECJFQPQ-UHFFFAOYSA-L 0.000 description 2
- NMUNQTSQYLEOMN-UHFFFAOYSA-L dichloro-[4,5-dimethyl-1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene]-(thiophen-2-ylmethylidene)ruthenium;tricyclohexylphosphane Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1.C=1C=CSC=1C=[Ru](Cl)(Cl)=C1N(C=2C(=CC(C)=CC=2C)C)C(C)=C(C)N1C1=C(C)C=C(C)C=C1C NMUNQTSQYLEOMN-UHFFFAOYSA-L 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011984 grubbs catalyst Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 238000007172 homogeneous catalysis Methods 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000003041 laboratory chemical Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- LJDZFAPLPVPTBD-UHFFFAOYSA-N nitroformic acid Chemical compound OC(=O)[N+]([O-])=O LJDZFAPLPVPTBD-UHFFFAOYSA-N 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-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
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 description 1
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 description 1
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 description 1
- ZRPFJAPZDXQHSM-UHFFFAOYSA-L 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazole;dichloro-[(2-propan-2-yloxyphenyl)methylidene]ruthenium Chemical compound CC(C)OC1=CC=CC=C1C=[Ru](Cl)(Cl)=C1N(C=2C(=CC(C)=CC=2C)C)CCN1C1=C(C)C=C(C)C=C1C ZRPFJAPZDXQHSM-UHFFFAOYSA-L 0.000 description 1
- UUFQTNFCRMXOAE-UHFFFAOYSA-N 1-methylmethylene Chemical compound C[CH] UUFQTNFCRMXOAE-UHFFFAOYSA-N 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical class CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 1
- ATRQECRSCHYSNP-UHFFFAOYSA-N 2-(trifluoromethyl)pyridine Chemical class FC(F)(F)C1=CC=CC=N1 ATRQECRSCHYSNP-UHFFFAOYSA-N 0.000 description 1
- TXBIZRLVIDXDGB-UHFFFAOYSA-N 2-methylpropylphosphane Chemical compound CC(C)CP TXBIZRLVIDXDGB-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical class CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- HLTDBMHJSBSAOM-UHFFFAOYSA-N 2-nitropyridine Chemical class [O-][N+](=O)C1=CC=CC=N1 HLTDBMHJSBSAOM-UHFFFAOYSA-N 0.000 description 1
- HWWYDZCSSYKIAD-UHFFFAOYSA-N 3,5-dimethylpyridine Chemical class CC1=CN=CC(C)=C1 HWWYDZCSSYKIAD-UHFFFAOYSA-N 0.000 description 1
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical class CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 1
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical class CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical group O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- OXLURKCRXVAJQS-UHFFFAOYSA-L [1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene]-dichloro-[[5-(dimethylsulfamoyl)-2-propan-2-yloxyphenyl]methylidene]ruthenium Chemical compound CC(C)OC1=CC=C(S(=O)(=O)N(C)C)C=C1C=[Ru](Cl)(Cl)=C1N(C=2C(=CC(C)=CC=2C)C)CCN1C1=C(C)C=C(C)C=C1C OXLURKCRXVAJQS-UHFFFAOYSA-L 0.000 description 1
- ZDJCARGGZRTYFH-UHFFFAOYSA-L [1,3-bis(2-methylphenyl)imidazolidin-2-ylidene]-dichloro-[(2-propan-2-yloxyphenyl)methylidene]ruthenium Chemical compound CC(C)OC1=CC=CC=C1C=[Ru](Cl)Cl.CC1=CC=CC=C1N1CCN(C=2C(=CC=CC=2)C)[C]1 ZDJCARGGZRTYFH-UHFFFAOYSA-L 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000005360 alkyl sulfoxide group Chemical group 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 229940111121 antirheumatic drug quinolines Drugs 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical class [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000002047 benzodioxolyl group Chemical group O1OC(C2=C1C=CC=C2)* 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- ODCVQJURXOWOJD-UHFFFAOYSA-L benzylidene(dichloro)ruthenium;1,3-bis(2-methylphenyl)imidazolidin-2-ide;tricyclohexylphosphane Chemical compound Cl[Ru](Cl)=CC1=CC=CC=C1.CC1=CC=CC=C1N1[CH-]N(C=2C(=CC=CC=2)C)CC1.C1CCCCC1P(C1CCCCC1)C1CCCCC1 ODCVQJURXOWOJD-UHFFFAOYSA-L 0.000 description 1
- FCDPQMAOJARMTG-UHFFFAOYSA-L benzylidene-[1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene]-dichlororuthenium;tricyclohexylphosphane Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1.CC1=CC(C)=CC(C)=C1N(CCN1C=2C(=CC(C)=CC=2C)C)C1=[Ru](Cl)(Cl)=CC1=CC=CC=C1 FCDPQMAOJARMTG-UHFFFAOYSA-L 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000005752 bromopyridines Chemical class 0.000 description 1
- QNRMTGGDHLBXQZ-UHFFFAOYSA-N buta-1,2-diene Chemical compound CC=C=C QNRMTGGDHLBXQZ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000005753 chloropyridines Chemical class 0.000 description 1
- 125000003016 chromanyl group Chemical group O1C(CCC2=CC=CC=C12)* 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000110 cooling liquid Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
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- 238000010494 dissociation reaction Methods 0.000 description 1
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- 150000002902 organometallic compounds Chemical class 0.000 description 1
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- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
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- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
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- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
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- 150000003248 quinolines Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
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- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 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
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- FICPQAZLPKLOLH-UHFFFAOYSA-N tricyclohexyl phosphite Chemical compound C1CCCCC1OP(OC1CCCCC1)OC1CCCCC1 FICPQAZLPKLOLH-UHFFFAOYSA-N 0.000 description 1
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- NZIQBDROTUFRHZ-UHFFFAOYSA-N tritert-butyl phosphite Chemical compound CC(C)(C)OP(OC(C)(C)C)OC(C)(C)C NZIQBDROTUFRHZ-UHFFFAOYSA-N 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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Abstract
本发明涉及一种用于通过在至少一种元素钌的过渡金属催化剂上的烯‑炔复分解来制备1,3‑丁二烯的方法。
Description
技术领域
本发明涉及一种用于通过在至少一种元素钌的过渡金属催化剂上进行烯-炔复分解来制备1,3-丁二烯的方法。
背景技术
1,3-丁二烯(CAS号106-99-0)通常是通过饱和烃的热离解(蒸汽裂解)制备的,其中石脑油或在从C2至C4范围内的烃通常用作原料。在裂解过程中形成的混合物的处理中,获得不仅含有1,3-丁二烯而且还含有1,2-丁二烯、正丁烷、丁烯、1-丁炔、丁烯炔和丙烯的C4馏分。
从裂解炉产物中分离1,3-丁二烯的缺点是以石脑油为代价,始终使用较多乙烷作为裂解炉原料。然而,乙烷的裂解仅产生最少量的1,3-丁二烯,使得后者不断变得更稀少并且更昂贵。然而,来自裂解过程的另外的主要产物是乙烯。
在重要基础化学品的工业制备中的另一种重要起始材料是乙炔(acetylene),也称为乙炔(ethyne),它是通过在2000℃下高温热解轻质或中等石油馏分或天然气而工业制备的。在热解后,所形成的气体混合物迅速冷却(淬灭)至低于200℃,以避免产物分解成元素碳和氢。
US-A 3,671,604披露了乙炔与单烯烃的催化共聚作用,其中使用来自下组的酸催化剂,该组由以下各项组成:乙酸锌、氧化锌、氧化镉、乙酸镉、氧化镍、乙酸镍、氧化钴和乙酸钴。在US-A 3,671,604的方法中测试的反应温度是在从150℃至325℃的范围内,其中仅在从250℃至300℃的范围内的温度导致可测量的产物产率。反应产物是从三十至四十种组分的混合物。
发明内容
从这个现有技术出发,本发明的一个目的是提供一种用于以针对性方式从起始材料乙炔和乙烯制备1,3-丁二烯的方法,这些起始材料在工业上可大量获得,其中该方法还以显著低于现有技术的温度进行。
这个目的是通过一种用于在至少一种元素钌的过渡金属催化剂的存在下通过使乙烯和乙炔相互反应来制备1,3-丁二烯的方法来实现的。这是烯-炔复分解。
为了清晰起见,可以说本发明的范围以任何组合的形式涵盖了以下在一般意义上或以优选范围所提及的所有定义和参数。
本发明进一步涉及元素钌的过渡金属催化剂用于从乙烯和乙炔制备1,3-丁二烯的用途。
根据本发明的从乙炔和乙烯进行的1,3-丁二烯的合成优选在均相的元素钌的过渡金属催化剂上进行。
均相催化的特征是在反应条件下,反应物或起始材料、产物以及催化剂存在于吉布斯相律含义内的单相中。此相可以是气体、液体或超临界流体。是迄今为止在均相催化中最重要的并且因此根据本发明是优选的催化剂是分子地溶解在液相中的金属-有机化合物。
出于这个原因,根据本发明的1,3-丁二烯合成优选通过在至少一种均相的元素钌的过渡金属催化剂的存在下使乙烯和乙炔在液相中反应来进行。这里,该至少一种元素钌的过渡金属催化剂在溶液中使用。适用于该方法的溶剂溶解该均相催化剂但不会使其分解。作为溶剂,优选使用至少一种选自由卤烷烃组成的组的溶剂,这些卤烷烃在室温下为液体,其中室温指的是23+/-2℃。特别优选的是二氯甲烷。
本发明的方法的反应温度取决于要使用的催化剂的分解温度。它可以由本领域技术人员基于常规考虑来选择。在优选的实施例中,根据本发明的1,3-丁二烯合成因此在从-70℃至50℃的范围内、特别优选在从-64℃至45℃的范围内、非常特别优选在从-50℃至40℃的范围内、特别是在从15℃至40℃的范围内的温度下进行。与以上引用的现有技术相比,这些低的温度使本发明的方法显著地更经济。
本发明的1,3-丁二烯合成优选在没有超大气压的情况下进行。这意味着在优选的实施例中,本发明的方法在1013.25hPa+/-5%的大气压下进行。
根据本发明的1,3-丁二烯的合成既可以分批进行又可以连续进行。本发明的1,3-丁二烯合成优选分批进行。在分批程序中,优选的反应时间为在从0.5小时至4小时的范围内,其中反应时间被定义为引入反应气体的总时间。
均相催化剂通常对氧化和/或水解极其敏感,使得在本发明的方法的优选实施例中,该方法在缺氧条件下,优选在保护气体下进行。优选使用氮气或稀有气体、尤其是氮气作为保护气体。
大多数金属-有机催化剂络合物是具有限定的结构和化学计量的过渡金属化合物。在已经详尽研究的方法中,在分子基础上的反应过程可以(实际上)被完全理解,这是催化剂的针对性定制开发的基础。反应位点通常是金属原子(离子),不直接参与催化的配体(旁观者配体(spectator ligand),控制配体(control ligand))也配位到该金属原子(离子)上。从对该反应位点周围的电子和/或空间条件施加针对性影响的角度来看,这些配体的变化(配体调整)是关于活性、选择性和稳定性的催化剂优化的基础。
出于这个原因,根据本发明,优选具有至少一种有机配体的均相的元素钌的过渡金属催化剂。
作为根据本发明使用的过渡金属催化剂,优选使用通式(A)的那些,
其中
基团L是相同或不同的配体、优选不带电荷的电子供体,或L是与钌配位的取代基R的氧原子,并且
基团R是相同或不同的并且各自为氢、烷基、环烷基、烯基、炔基、芳基、羧酸酯基、烷氧基、烯氧基、炔氧基、芳氧基、烷氧基羰基、烷基氨基、烷硫基、芳硫基、烷基磺酰基或烷基亚磺酰基,其中这些基团可以各自任选被一个或多个烷基、卤素、烷氧基、芳基或杂芳基取代,或作为替代方案,这两个基团R桥联到包括在内的与它们结合的公共碳原子上以形成环状基团,该环状基团可以是脂肪族或芳香族性质的并且任选地被取代并且可以含有一个或多个杂原子。
优选通式(A)中的基团R在每种情况下彼此独立地是氢、C1-C30-烷基、C3-C20-环烷基、C2-C20-烯基、C2-C20-炔基、C6-C24-芳基、C1-C20-羧酸酯基、C1-C20-烷氧基、C2-C20-烯氧基、C2-C20-炔氧基、C6-C24-芳氧基、C2-C20-烷氧基羰基、C1-C30-烷基氨基、C1-C30-烷硫基、C6-C24-芳硫基、C1-C20-烷基磺酰基或C1-C20-烷基亚磺酰基,其中这些基团可以在每种情况下任选被一个或多个C1-C6-烷基,卤素,C1-C6-烷氧基,优选异丙氧基,芳基或杂芳基取代,或者作为替代方案,这两个基团R桥联到包括在内的与它们结合的公共碳原子上以形成环状基团,该环状基团可以是脂肪族或芳香族性质的并且任选地被取代并且可以含有一个或多个杂原子。
在优选实施例中,这两个配体L可以彼此独立地是膦、磺化的膦、磷酸酯、次亚膦酸酯、亚膦酸酯、醚、胺、酰胺、亚砜、羧基、亚硝酰基、吡啶、硫醚或咪唑烷(“Im”)的配体。
优选这两个配体L彼此独立地是C6-C24-芳基膦、C1-C10-烷基膦或C3-C20-环烷基膦的配体,磺化的C6-C24-芳基膦或磺化的C1-C10-烷基膦的配体,C6-C24-芳基次亚膦酸酯或C1-C10-烷基次亚膦酸酯的配体,C6-C24-芳基亚膦酸酯或C1-C10-烷基亚膦酸酯的配体,C6-C24-芳基亚磷酸酯或C1-C10-烷基亚磷酸酯的配体,C6-C24-芳基胂或C1-C10-烷基胂的配体,C6-C24-芳基胺或C1-C10-烷基胺的配体,吡啶配体,C6-C24-芳基亚砜或C1-C10-烷基亚砜的配体,C6-C24-芳基醚或C1-C10-烷基醚的配体或C6-C24-芳基酰胺或C1-C10-烷基酰胺的配体,它们各自可以被苯基取代,该苯基进而任选地被卤素、C1-C5-烷基或C1-C5-烷氧基取代,或L是与钌配位的取代基R的氧原子。
术语“膦”具体涵盖PPh3、P(p-Tol)3、P(o-Tol)3、PPh(CH3)2、P(CF3)3、P(p-FC6H4)3、P(p-CF3C6H4)3、P(C6H4-SO3Na)3、P(CH2C6H4-SO3Na)3、P(异丙基)3、P(CHCH3(CH2CH3))3、P(环戊基)3、P(环己基)3、P(新戊基)3以及P(新苯基)3。
出于本发明的目的,“烷基”表示直链或支链的饱和烃基。在一些实施例中,使用具有从1至6个碳原子的烷基,并且该烷基可以被称为“低级烷基”。优选的烷基是甲基(Me)、乙基(Et)、丙基(特别是正丙基和异丙基)、丁基(特别是正丁基、异丁基、仲丁基、叔丁基)、戊基(特别是正-戊基、异戊基、新戊基)、己基等。
出于本发明的目的,“芳基”表示单环芳香烃环体系或者其中稠合两个或更多个的芳香烃环或者与一个或多个环烷基和/或环杂烷基环稠合的至少一个芳香单环烃环的多环环体系。芳基可以在它的环体系中具有从6至24个碳原子(例如,C6-20芳基),并且包含多个稠环。在一些实施例中,芳基或亚芳基可以是具有从8至24个碳原子的多环芳基。优选的具有芳香族碳环体系的芳基是苯基、1-萘基(二环的)、2-萘基(二环的)、蒽基(三环的)、菲基(三环的)、并五苯基(五)以及类似基团。其他优选的芳基是苯并二噁烷基、苯并二氧杂环戊烯基、苯并二氢吡喃基、二氢吲哚基和类似物。在一些实施例中,芳基,特别是苯基,如在此所述,可以特别地被异-丙氧基取代。在一些实施例中,芳基可具有一个或多个取代基。特别优选的芳基是苯基。
出于本发明的目的,“环烷基”表示含有环化的烷基、烯基或炔基的非芳香族碳环基团。在不同的实施例中,环烷基含有从3至24个碳原子、优选从3至20个碳原子,例如C3-14环烷基。环烷基可以是单环的(例如环己基)或者另外多环的(如在例如桥联的和/或螺环体系中),其中这些碳原子能够在该环体系的内部或外部存在。该环烷基的每个适当的环位置可以共价地结合到所定义的化学结构上。优选的环烷基是环丙基、环丁基、环戊基、环己基、环庚基、环戊烯基、环己烯基、环己二烯基、环庚三烯基、降冰片基、降蒎基、降蒈基、金刚烷基、以及螺[4.5]癸基基团,以及还有它们的同系物、异构体等。在一些实施例中,这些环烷基可以是取代的。根据本发明,优选未取代的环烷基。
出于本发明的目的,“芳烷基”表示烷基-芳基,其中芳烷基经由烷基被共价地结合到所定义的化学结构上。根据本发明优选的芳烷基是苄基(-CH2-C6H5)。根据本发明的芳烷基可任选地是取代的,即,或者芳基和/或烷基可以是取代的。
术语“次亚膦酸酯”涵盖,例如,次亚磷酸三苯酯、次亚磷酸三环己酯、次亚磷酸三异丙酯以及次亚磷酸甲基二苯酯。
术语“亚磷酸酯”具体涵盖亚磷酸三苯酯、亚磷酸三环己酯、亚磷酸三叔丁酯、亚磷酸三异丙酯以及亚磷酸甲基二苯酯。
术语“磺酸酯”具体涵盖三氟甲磺酸酯、甲苯磺酸酯以及甲磺酸酯。
术语“亚砜”具体涵盖(CH3)2S(=O)以及(C6H5)2S=O。
术语“硫醚”具体涵盖CH3SCH3、C6H5SCH3、CH3OCH2CH2SCH3以及四氢噻吩。
出于本专利申请的目的,术语“吡啶”旨在作为对于所有含氮配体的集合性术语,如Grubbs在WO-A-03/011455中所提及的。实例是:吡啶、甲基吡啶(α-、β-和γ-甲基吡啶)、二甲基吡啶(2,3-、2,4-、2,5-、2,6-、3,4-以及3,5-二甲基吡啶)、三甲基吡啶(2,4,6-三甲基吡啶)、三氟甲基吡啶、苯基吡啶、4-(二甲氨基)吡啶、氯吡啶、溴吡啶、硝基吡啶、喹啉、嘧啶、吡咯、咪唑以及苯基咪唑。
如果式(A)中的配体L的一个或两个是咪唑烷基团(Im),则它通常具有通式(IIa)或(IIb)的结构,
其中
R1、R2、R3、R4是相同的或不同的并且各自为氢、直链或支链的C1-C30-烷基、C3-C20-环烷基、C2-C20-烯基、C2-C20-炔基、C6-C24-芳基、C1-C20-羧酸酯基、C1-C20-烷氧基、C2-C20-烯氧基、C2-C20-炔氧基、C6-C20-芳氧基、C2-C20-烷氧基羰基、C1-C20-烷硫基、C6-C20芳硫基、C1-C20-烷基磺酰基、C1-C20-烷基磺酸酯、C6-C20-芳基磺酸酯或C1-C20-烷基亚磺酰基。
基团R1、R2、R3、R4中的一个或多个可彼此独立地任选被一个或多个取代基,优选直链或支链C1-C10-烷基、C3-C8-环烷基、C1-C10-烷氧基或C6-C24-芳基取代,其中这些上述取代基进而能够被一个或多个基团所取代,这些基团优选选自下组,该组由以下各项组成:卤素(特别是氯或溴)、C1-C5-烷基、C1-C5-烷氧基和苯基。
仅为了清楚的目的,应该补充的是,在通式(IIa)和(IIb)中描述的咪唑烷基的结构等同于在文献中对于这种咪唑烷基(Im)描述的结构,这些结构强调了咪唑烷基的卡宾特性。这还类似地适用于以下描述的相关的优选结构(IIIa)-(IIIf)。
在具有至少一个作为配体L的咪唑烷基(Im)的通式(A)的催化剂的优选实施例中,R1和R2彼此独立地各自为氢、C6-C24-芳基、特别优选苯基、直链或支链C1-C10-烷基、特别优选丙基或丁基,或与包括在内的与它们结合的碳原子一起形成环烷基或芳基,其中所有上述基团进而任选能够被一个或多个另外的选自由直链或支链C1-C10-烷基、C1-C10-烷氧基、C6-C24-芳基所组成的组的基团,以及选自由羟基、硫醇、硫醚、酮、醛、酯、醚、胺、亚胺、酰胺、硝基、羧酸、二硫化物、碳酸酯、异氰酸酯、碳二亚胺、烷氧羰基、氨基甲酸酯和卤素所组成的组的官能团取代。
在具有至少一个作为配体L的咪唑烷基(Im)的通式(A)的催化剂的优选实施例中,基团R3和R4是相同或不同的并且各自为直链或支链C1-C10-烷基,特别优选异丙基或新戊基,C3-C10-环烷基,优选金刚烷基,C6-C24-芳基,特别优选苯基,C1-C10-烷基磺酸酯,特别优选甲烷磺酸酯,C6-C10-芳基磺酸酯,特别优选对甲苯磺酸酯。
作为R3和R4含义的上述基团任选地被一个或多个另外的选自由直链或支链C1-C5-烷基、特别是甲基、C1-C5-烷氧基、芳基所组成的组的基团,以及选自由羟基、硫醇、硫醚、酮、醛、酯、醚、胺、亚胺、酰胺、硝基、羧酸、二硫化物、碳酸酯、异氰酸酯、碳二亚胺、烷氧羰基、氨基甲酸酯和卤素所组成的组的官能团取代。
特别地,基团R3和R4可以是相同或不同的并且各自为异-丙基、新戊基、金刚烷基、三甲苯基或2,6-二异丙基苯基。
配体L中特别优选的咪唑烷基(Im)具有以下结构(IIIa)至(IIIf),其中Ph在每种情况下是苯基,Bu是丁基并且Mes在每种情况下为2,4,6-三甲基苯基,或作为替代方案,Mes在所有情况下为2,6-二异丙基苯基。
式(A)的催化剂的多种代表物原则上是已知的,例如从WO-A-96/04289和WO-A-97/06185。
作为优选的Im基团的替代方案,通式(A)中的配体L的一个或两个还优选是相同或不同的三烷基膦配体,其中烷基中的至少一个为仲烷基或环烷基,优选异丙基、异丁基、仲丁基、新戊基、环戊基或环己基。
通式(A)中的一个或两个配体L具体是三烷基膦配体,其中烷基中的至少一个为仲烷基或环烷基,优选异丙基、异丁基、仲丁基、新戊基、环戊基或环己基。
在优选的实施例中,使用式(B)的基于钌的过渡金属催化剂,
其中
Y为氧(O)或硫(S),优选氧,
R5、R6、R7和R8是相同或不同的并且各自是氢、有机或无机基团,优选氢或-SO2-N(CH3)2或-NH-CO-CF3,
R9是烷基、环烷基、烯基、炔基、芳基、烷氧基、烯氧基、炔氧基、芳氧基、烷氧基羰基、烷基氨基、烷硫基、芳硫基、烷基磺酰基或烷基亚磺酰基,优选异丙基,其中的每个都可以任选地被一个或多个烷基、卤素、烷氧基、芳基或杂芳基所取代,
并且
L是具有与对于式(A)指示的相同含义的配体。
式(B)的催化剂原则上是已知的。这类化合物的代表是由Hoveyda等人在US 2002/0107138 A1和应用化学国际版(Angew.Chem.Int.Ed.)2003,42,4592中描述的催化剂以及由Grela在WO-A-2004/035596、欧洲有机化学(Eur.J.Org.Chem)2003,963-966和应用化学国际版2002,41,4038和有机化学杂志(J.Org.Chem.)2004,69,6894-96和欧洲化学期刊(Chem.Eur.J)2004,10,777-784中描述的催化剂。式(B)催化剂是可商购的或者可以根据所指出的这些文献参考制备的。
作为特别优选的钌过渡金属催化剂,来自下组的至少一种催化剂
M1=苯亚甲基[1,3-双(2,4,6-三甲基苯基)-2-咪唑烷叉]二氯(三环己基膦)钌(格鲁布斯II催化剂,CAS号246047-72-3)、
M2=双(三环己基膦)[(苯硫基)亚甲基]二氯化钌(II)(CAS号219770-99-7)、
M3=1,3-双(2,4,6-三甲基苯基)-4,5-二氢咪唑-2-叉[2-(异丙氧基)-5-(N,N-二-MeNH2SO2)苯基]亚甲基二氯化钌(II)(詹氏催化剂1B,CAS号918870-76-5)、
M4=双(三环己基膦)-3-苯基-1H-茚-1-叉基二氯化钌(II)(CAS号250220-36-1)、
M5=苯亚甲基双(三环己基膦)二氯化钌(格鲁布斯I催化剂,CAS号172222-30-9)、
M6=二氯(邻-异丙氧基苯基亚甲基)-(三环己基膦)钌(II)(荷维达-格鲁布斯催化剂I,CAS号203714-71-0)、
M7=(1,3-双(2,4,6-三甲基苯基)-2-咪唑烷叉)二氯(邻-异丙氧基苯基亚甲基)钌(荷维达-格鲁布斯催化剂II,CAS号301224-40-8)、
M8=三环己基膦[4,5-二甲基-1,3-双(2,4,6-三甲基苯基)咪唑-2-叉][2-噻吩基亚甲基]二氯化钌(II),至少95%(CAS号1190427-50-9)、
M9=三环己基膦[1,3-双(2,4,6-三甲基苯基)咪唑-2-叉][3-苯基-1H-茚-1-叉基]二氯化钌(II),至少95%(CAS号254972-49-1)、
M10=[1,3-双(2,6-二-异-丙基苯基)-4,5-二氢咪唑-2-叉]-[2-异-丙氧基-5-(三氟乙酰胺基)苯基]亚甲基二氯化钌(II)(CAS号1212008-99-5)、
M11=三(异-丙氧基)膦(3-苯基-1H-茚-1-叉基)[1,3-双(2,4,6-三甲基苯基)-4,5-二氢咪唑-2-叉]二氯化钌(II)至少95%(施特雷姆化学品(Strem Chemicals)目录号44-7783)、
M12=三环己基膦[1,3-双(2,4,6-三甲基苯基)咪唑-2-叉][2-噻吩基亚甲基]二氯化钌(II),至少95%(CAS号1190427-49-6)、
M13=3-苯基-1H-茚-1-叉基[双(异-丁基膦配体)]二氯化钌(II)(CAS号894423-99-5)、
M14=二氯[1,3-双(2-甲基苯基)-2-咪唑烷叉](苯亚甲基)(三环己基膦)钌(II)(CAS号927429-60-5)、
M15=二氯[1,3-双(2-甲基苯基)-2-咪唑烷叉](2-异丙氧基苯基亚甲基)钌(II)(CAS号927429-61-6)
在本发明的1,3-丁二烯合成中使用。特别优选使用M5作为元素钌的过渡金属催化剂。
根据本发明使用的催化剂的制备对于本领域技术人员是已知的。可以在P.Schwab、R.H.Grubbs、J.W.Ziller,美国化学学会杂志(J.Am.Chem.Soc.),1996,118(1),第100-110页中找到实例。此外,催化剂M1至M15是从德国席泽(Seelze)的西格玛-奥德里奇实验室化学公司(Sigma-Aldrich Laborchemikalien GmbH)或德国克尔(Kehl)的施特雷姆化学品公司(Strem Chemicals Inc.)可商购的。
在反应混合物中根据本发明使用的元素钌的过渡金属催化剂的量通常是以要使用的全部催化剂的总和计算并且基于所使用的乙烯的量在从0.01摩尔%至10000摩尔%、优选从0.1摩尔%至100摩尔%、特别优选从0.2摩尔%至10摩尔%的范围内。
在1l的溶剂体积下,总气体流量(即作为起始材料要进料到反应装置中的乙烯和乙炔的混合物)优选在从200l/h至500l/h的范围内、特别优选在从200l/h至400l/h的范围内、非常特别优选在从200l/h至300l/h的范围内。本领域技术人员可以基于这些数字来计算用于较小或较大批次的相应参数。
在总气体流中,起始材料乙烯和乙炔优选以在从6:4至4:6范围内的比例、特别优选以在1:1范围内的比例存在。
在优选的实施例中,含有乙烯和乙炔的混合物的气体流在进入反应装置之前被干燥。合适的干燥剂是本领域技术人员已知的。优选使用至少一种来自下组的干燥剂来干燥根据本发明使用的气体混合物,该组由以下各项组成:浓硫酸、氢氧化钠和分子筛。特别地,连续使用所有这三种干燥剂。
本领域技术人员通常用于气体反应的任何类型的反应容器或装置都适用于本发明的1,3-丁二烯合成。优选搅拌釜反应器、流管或鼓泡塔反应器。这些优选由钢制成。对于相对较小的批次,也可以使用基于玻璃的反应器。术语反应容器、装置和反应器在本专利申请中同义使用。
通常,通过任选在冷却下而且在保护气体、特别是氮气下将该至少一种元素钌的过渡金属催化剂(在任选以预混形式的催化剂混合物的情况下,按原样或优选作为在上述溶剂的至少一种中的溶液)引入至少一个冷却的反应容器中来进行反应。
优选将该至少一个反应容器保持在从-70℃至50℃范围内的温度下、特别优选在从15℃至40℃范围内的温度下。当使用溶剂时,纯化的乙炔和乙烯的混合物通过入口引入,优选低于液面。
该气体混合物的未反应部分可以进料到该反应容器中,或者在替代实施例中,转移到至少一个第二反应容器中,该至少一个第二反应容器同样含有根据本发明使用的至少一种元素钌的过渡金属催化剂。同样在此,如果使用溶剂,则在液体表面以下进行乙烯和乙炔的起始混合物的引入。离开此容器的未反应的气体混合物可以进料回到该第一反应容器或进料回到该至少一个第二反应容器中,或者排放到周围的空气/废气中。
从安全角度看,乙炔的处理要求高,尤其在超大气压下,这就是为什么要在仅高达100毫巴表压的小的超大气压下使含有这些起始材料的气体混合物优选通过该含催化剂的溶剂。
在沸点为-4.5℃的情况下,1,3-丁二烯积聚在该溶剂中并且可以通过蒸馏从该溶剂和所形成的副产物中分离出来。根据本发明的从乙烯和乙炔合成1,3-丁二烯的终止以及反应产物的纯化可以通过本领域技术人员通常已知的方法进行。在已分离出反应产物后,该溶剂还可以用来使该至少一种催化剂再次可用于反应。
具体实施方式
实例
起始材料
乙烯,CAS号74-85-1,纯度99.9%,由林德集团(Linde AG)生产
乙炔,CAS号74-86-2,纯度99.5%,由林德集团生产
催化剂:M1至M15,根据德国席泽的西格玛-奥德里奇实验室化学公司或德国克尔的施特雷姆化学品公司的描述
保护气体:氮气
装置
图1通过举例示出了如用于本发明的框架内的实验的装置。图1中的参考号具有以下含义:
1 乙炔
2 H2SO4(95%-98%)
3 2N NaOH
5 乙烯
6 保护气体N2
7 气泡计
8 低温恒温器-20℃
9 加热浴
10 低温冷却器
11 1250mL反应器,玻璃
12 隔板
13 2250mL反应器,玻璃
14 约100毫巴表压
15 废气
该实验装置由两个提供有磁力搅拌棒的反应器(250ml三颈玻璃烧瓶)、两个低温冷却器(保持在-20℃下的冷却液)、两个用于取样的隔板以及两个作为加热浴的油浴组成。首先将由先前纯化的乙炔(首先95-98%浓度H2SO4,然后2N NaOH,并且最后分子筛)和乙烯构成的气体混合物经由具有在从1.5mm到7mm范围内的直径的玻璃毛细管引入第一反应器中液体表面以下。进而将此气体混合物的未被反应消耗或未在反应器1的低温冷却器中冷凝的部分经由另一个毛细管输送到第二反应器中液体表面以下。在通过该第二低温冷却器后,使该气体混合物的未反应的或未在反应器2的低温冷却器中冷凝的部分进入废气中。
通过GC(气相色谱法)分析反应器1和反应器2的液体内含物。由于转换率低,评估只是定性的。然而,对于在本发明的框架内的实验,参考物质环己烷的存在允许通过丁二烯与环己烷的峰面积比来对比出所形成的丁二烯的量。
表1示出了发现它们各自保留时间的物质。通过与商业纯物质对比或通过GC-MS(MS=质谱法)进行鉴定。
表1
对比实例1(无催化剂)
在已预先通过N2而成为惰性的装有低温冷却器(冷却介质的温度为-20℃)的100ml玻璃容器中在保护气体下使50ml的二氯甲烷达到30℃。使空间成为惰性的是指通过引入惰性气体或蒸气将大气氧气或反应性或爆炸性气体或气体混合物从空间置换的程序。此外,加入1.0ml的环己烷作为对二氯甲烷的参照。随后在整个反应时间期间在搅拌的同时使以1:1比例的乙烯和乙炔的混合物通过该溶剂,并且以规则的间隔从液相中取出样品。没有形成丁二烯。
对比实例2(M4,无乙烯)
在已预先通过N2而成为惰性的具有低温冷却器(冷却介质的温度为-20℃)的容器中在保护气体下使50mg的催化剂M4(溶解在50ml的二氯甲烷中)达到30℃。此外,加入1.0ml的环己烷作为参照。随后在整个反应时间期间在搅拌的同时引入乙炔,并且以规则的间隔从液相中取出样品。没有形成丁二烯。
对比实例3(M5,无乙烯)
在已预先使得成为惰性的具有低温冷却器(冷却介质的温度为-20℃)的容器中在保护气体下使50mg的催化剂M5(溶解在50ml的二氯甲烷中)达到30℃。此外,加入1.0ml的环己烷作为参照。随后在整个反应时间期间在搅拌的同时引入乙炔,并且以规则的间隔从液相中取出样品。没有形成丁二烯。
实例1
在已预先通过N2而成为惰性的具有低温冷却器(冷却介质的温度为-20℃)的容器中在保护气体下使50mg的催化剂MX(其中MX在每种情况下是上述催化剂M1至M15中的一种)(溶解在50ml的二氯甲烷中)达到30℃。此外,加入1.0ml的环己烷作为参照。随后在整个反应时间期间在搅拌的同时将以1:1比例的乙烯和乙炔的混合物引入该溶剂中在液体表面以下。在反应时间期间以规则的间隔从液相中取出样品。通过气相色谱法在这些样品中检测丁二烯。
实例2(M5,-64℃)
在已预先通过N2而成为惰性的具有低温冷却器(冷却介质的温度为-20℃)的容器中在保护气体下使50mg的催化剂M5(溶解在50ml的二氯甲烷中)达到-64℃。此外,加入1.0ml的环己烷作为参照。随后在整个反应时间期间在搅拌的同时引入以1:1比例的乙烯和乙炔的混合物。在反应时间期间以规则的间隔从液相中取出样品。通过气相色谱法在这些样品中检测丁二烯。
实例3(M5,两倍催化剂量)
在已预先通过N2而成为惰性的具有低温冷却器(冷却介质的温度为-20℃)的容器中在保护气体(N2)下使100mg的催化剂M5(溶解在50ml的二氯甲烷中)达到30℃。此外,加入1.0ml的环己烷作为参照。随后在整个反应时间期间在搅拌的同时引入以1:1比例的乙烯和乙炔的混合物。在反应时间期间以规则的间隔从液相中取出样品。通过气相色谱法在这些样品中检测丁二烯。
对比实例1至3表明,两种组分对于进行本发明的方法是必要的:必须首先使乙炔与催化剂接触,并且其次与乙烯接触。
Claims (7)
1.一种用于制备1,3-丁二烯的方法,其特征在于乙烯和乙炔在至少一种元素钌的过渡金属催化剂的存在下相互反应,其中乙烯和乙炔以气体流起始材料的形式进料,其中乙烯和乙炔的比例在6:4至4:6的范围内,其特征在于该方法在使用至少一种溶剂的液相中进行,并且其中至少一种所述催化剂选自由以下组成的组:
M1=苯亚甲基[1,3-双(2,4,6-三甲基苯基)-2-咪唑烷叉]二氯(三环己基膦)钌、
M2=双(三环己基膦)[(苯硫基)亚甲基]二氯化钌(II)、
M3=1,3-双(2,4,6-三甲基苯基)-4,5-二氢咪唑-2-叉[2-(异丙氧基)-5-(N,N-二-MeNH2SO2)苯基]亚甲基二氯化钌(II)、
M4=双(三环己基膦)-3-苯基-1H-茚-1-叉基二氯化钌(II)、
M5=苯亚甲基双(三环己基膦)二氯化钌、
M6=二氯(邻-异丙氧基苯基亚甲基)-(三环己基膦)钌(II)、
M7=(1,3-双(2,4,6-三甲基苯基)-2-咪唑烷叉)二氯(邻-异丙氧基苯基亚甲基)钌、
M8=三环己基膦[4,5-二甲基-1,3-双(2,4,6-三甲基苯基)咪唑-2-叉][2-噻吩基亚甲基]二氯化钌(II)、
M9=三环己基膦[1,3-双(2,4,6-三甲基苯基)咪唑-2-叉][3-苯基-1H-茚-1-叉基]二氯化钌(II)、
M10=[1,3-双(2,6-二-异-丙基苯基)-4,5-二氢咪唑-2-叉]-[2-异-丙氧基-5-(三氟乙酰胺基)苯基]亚甲基二氯化钌(II)、
M11=三(异-丙氧基)膦(3-苯基-1H-茚-1-叉基)[1,3-双(2,4,6-三甲基苯基)-4,5-二氢咪唑-2-叉]二氯化钌(II)、
M12=三环己基膦[1,3-双(2,4,6-三甲基苯基)咪唑-2-叉][2-噻吩基亚甲基]二氯化钌(II)、
M13=3-苯基-1H-茚-1-叉基[双(异-丁基膦配体)]二氯化钌(II)、
M14=二氯[1,3-双(2-甲基苯基)-2-咪唑烷叉](苯亚甲基)(三环己基膦)钌(II)、
M15=二氯[1,3-双(2-甲基苯基)-2-咪唑烷叉](2-异丙氧基苯基亚甲基)钌(II)。
2.如权利要求1所述的方法,其特征在于使用在室温下为液体的卤烷烃作为该溶剂。
3.如权利要求1或2所述的方法,其特征在于该方法在从-70℃至50℃范围内的温度下进行。
4.如权利要求1或2所述的方法,其特征在于该方法在1013.25hPa+/-5%的大气压下进行。
5.如权利要求1所述的方法,其特征在于至少使用M5作为元素钌的过渡金属催化剂。
6.如权利要求1或2所述的方法,其特征在于以所使用的全部催化剂的总和计算并且基于所使用的乙烯的量,在反应混合物中的至少一种催化剂的量在0.01至10000mol%的范围内。
7.如权利要求1或2所述的方法,其特征在于该方法是分批进行的。
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