CN106632509B - 膦配体和以此为基础用于烯属不饱和化合物的烷氧基羰基化的钯催化剂 - Google Patents
膦配体和以此为基础用于烯属不饱和化合物的烷氧基羰基化的钯催化剂 Download PDFInfo
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- CN106632509B CN106632509B CN201610826997.5A CN201610826997A CN106632509B CN 106632509 B CN106632509 B CN 106632509B CN 201610826997 A CN201610826997 A CN 201610826997A CN 106632509 B CN106632509 B CN 106632509B
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- Prior art keywords
- butene
- ethylenically unsaturated
- palladium
- reaction
- ferrocene
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 53
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 15
- 239000003446 ligand Substances 0.000 title abstract description 47
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title abstract description 37
- 229910000073 phosphorus hydride Inorganic materials 0.000 title abstract description 19
- 238000007083 alkoxycarbonylation reaction Methods 0.000 title abstract description 16
- 239000003054 catalyst Substances 0.000 title abstract description 7
- -1 ethylene, propylene, 1-butene Chemical class 0.000 claims description 64
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 60
- 238000000034 method Methods 0.000 claims description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
- 239000000203 mixture Substances 0.000 claims description 24
- ILPBINAXDRFYPL-UHFFFAOYSA-N 2-octene Chemical compound CCCCCC=CC ILPBINAXDRFYPL-UHFFFAOYSA-N 0.000 claims description 14
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 11
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 10
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 claims description 10
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 claims description 10
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 9
- 239000011541 reaction mixture Substances 0.000 claims description 9
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 claims description 8
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 8
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 8
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 8
- WGLLSSPDPJPLOR-UHFFFAOYSA-N 2,3-dimethylbut-2-ene Chemical group CC(C)=C(C)C WGLLSSPDPJPLOR-UHFFFAOYSA-N 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 claims description 4
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 4
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 4
- QMMOXUPEWRXHJS-HWKANZROSA-N (e)-pent-2-ene Chemical compound CC\C=C\C QMMOXUPEWRXHJS-HWKANZROSA-N 0.000 claims description 3
- QMMOXUPEWRXHJS-HYXAFXHYSA-N (z)-pent-2-ene Chemical compound CC\C=C/C QMMOXUPEWRXHJS-HYXAFXHYSA-N 0.000 claims description 3
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 claims description 3
- 125000000490 cinnamyl group Chemical group C(C=CC1=CC=CC=C1)* 0.000 claims description 3
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 claims description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 3
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 claims description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 2
- RBYGDVHOECIAFC-UHFFFAOYSA-L acetonitrile;palladium(2+);dichloride Chemical compound [Cl-].[Cl-].[Pd+2].CC#N.CC#N RBYGDVHOECIAFC-UHFFFAOYSA-L 0.000 claims description 2
- RRHPTXZOMDSKRS-PHFPKPIQSA-L (1z,5z)-cycloocta-1,5-diene;dichloropalladium Chemical compound Cl[Pd]Cl.C\1C\C=C/CC\C=C/1 RRHPTXZOMDSKRS-PHFPKPIQSA-L 0.000 claims 1
- KCHQXPGUJBVNTN-UHFFFAOYSA-N 4,4-diphenylbut-3-en-2-one Chemical compound C=1C=CC=CC=1C(=CC(=O)C)C1=CC=CC=C1 KCHQXPGUJBVNTN-UHFFFAOYSA-N 0.000 claims 1
- 150000002940 palladium Chemical class 0.000 abstract description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 60
- 239000000243 solution Substances 0.000 description 41
- 238000006243 chemical reaction Methods 0.000 description 40
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 38
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 35
- 125000004432 carbon atom Chemical group C* 0.000 description 28
- 150000001336 alkenes Chemical class 0.000 description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 22
- 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
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 16
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000010586 diagram Methods 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 11
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 10
- 238000004679 31P NMR spectroscopy Methods 0.000 description 9
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000006063 methoxycarbonylation reaction Methods 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 229930192627 Naphthoquinone Natural products 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 150000002791 naphthoquinones Chemical class 0.000 description 8
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 8
- 229920002554 vinyl polymer Polymers 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- IEHIOXQFWRLVGR-UHFFFAOYSA-N methyl 7-methyloctanoate Chemical compound COC(=O)CCCCCC(C)C IEHIOXQFWRLVGR-UHFFFAOYSA-N 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 5
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- 125000003118 aryl group Chemical group 0.000 description 4
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/576—Six-membered rings
- C07F9/58—Pyridine rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5022—Aromatic phosphines (P-C aromatic 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
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Abstract
本发明涉及膦配体和以此为基础用于烯属不饱和化合物的烷氧基羰基化的钯催化剂。具体地,本发明涉及式(1)所示的化合物
Description
技术领域
本发明涉及一种改进的膦配体及其在烷氧基羰基化反应中的用途。
背景技术
烯属不饱和化合物的烷氧基羰基化反应是一种越来越重要的工艺。所谓烷氧基羰基化反应指的是烯烃之类的烯属不饱和化合物与一氧化碳和醇在一种金属或金属配合物和配体存在的情况下转化成相应的酯的反应:
示意图1:通用的烯属不饱和化合物的烷氧基羰基化反应方程式
在烷氧基羰基化反应中,乙烯-甲氧基羰基化反应形成3-甲基丙酸酯是制备甲基丙烯酸甲酯的重要中间步骤(S.G.Khokarale,E.J.García-Suárez,J.Xiong,U.V.Mentzel,R.Fehrmann,A.Riisager,Catalysis Communications 2014,44,73-75)。以甲醇作为溶剂,使用一种膦配体改性的钯催化剂在温和条件下进行乙烯-甲氧基羰基化反应。
Lucite(现在属于Mitsubishi Rayon公司)开发了一种非常好的催化体系,使用一种基于1,2-双(二叔丁基膦甲基)苯(DTBPMB)的配体(W.Clegg,G.R.Eastham,M.R.J.Elsegood,R.P.Tooze,X.L.Wang,K.Whiston,Chem.Commun 1999,1877-1878)。
例如在EP 0 662 467 A1就描述了将甲氧基羰基化反应应用于长链基料。该专利说明书描述了从3-戊烯酸甲酯制备己二酸二甲酯的工艺。使用乙酸钯(II)作为钯源。适用的双齿膦配体主要是例如1,1′-双(二苯基膦基)二茂铁、1-(二苯基膦基)-1′-(二异丙基膦基)二茂铁和1,1′-双(异丙基苯基膦基)二茂铁。然而,这些配体在烯烃尤其是2-辛烯和二正丁烯之类的长链烯烃的甲氧基羰基化反应过程中只能获得不够充分的产率。
发明内容
本发明的技术任务在于提供用于烷氧基羰基化反应的改进配体。这些配体尤其应可改善2-辛烯或二正丁烯之类的长链烯烃反应的产率,尤其应可提高烷氧基羰基化反应的时空产率。
可通过式(1)所示的膦配体解决这一任务
结果令人惊奇,本发明所述的膦配体1,1′-双(叔丁基苯基膦基)二茂铁与EP 0662 467 A1中所述结构类似的配体相比改善了特性。本发明所述的配体尤其能在2-辛烯和二正丁烯之类的长链烯烃的烷氧基羰基化反应过程中实现更高的产率。
本发明还涉及包含Pd和本发明的膦化合物的配合物。在这些配合物中,本发明的膦配体用作金属原子的二齿配体。所述配合物例如用作烷氧基羰基化的催化剂。使用本发明的配合物可以在大量不同的烯属不饱和化合物的烷氧基羰基化中实现高的产率。
本发明的配合物另外可以包含在金属原子上配位的配体。其例如是烯属不饱和化合物或阴离子。合适的额外的配体例如是苯乙烯、乙酸根阴离子、马来酰亚胺(例如N-甲基马来酰亚胺)、1,4-萘醌、三氟乙酸根阴离子或氯阴离子。优选的是选自N-甲基马来酰亚胺、苯乙烯和萘醌的其它配体。
在一个实施方案中,本发明所述的配合物选自以下配合物K1至K3:
钯金属原子可以与双键、双键体系(如芳烃或者其它共轭体系)或者自由电子对配位。
本发明还涉及本发明的膦配体用于催化烷氧基羰基化反应的用途。在此,本发明的膦配体特别可以用作本发明的金属配合物。
此外,本发明涉及包含下列方法步骤的方法:
a)首先添加烯属不饱和化合物;
b)或者添加本发明的膦配体和包含Pd的化合物,
或者添加包含Pd和本发明的膦配体的本发明配合物;
c)添加醇;
d)导入CO;
e)加热所述反应混合物,其中所述烯属不饱和化合物反应生成酯。
在此,所述方法步骤a)、b)、c)和d)可以以任意顺序进行。然而,通常在步骤a)至c)中预先加入反应物质之后添加CO。步骤d)和e)可以同时或相继地进行。此外,也可以在多个步骤中导入CO,从而例如首先导入一部分CO,然后加热和接着导入另一部分CO。
在本发明的方法中用作反应物的烯属不饱和化合物包含一个或多个碳碳双键。这些化合物在下文中为了简单起见也称为烯烃。所述双键可以是末端的或内部的。
优选地,所述烯属不饱和化合物具有2至30个碳原子,优选2至22个碳原子,更优选2至12个碳原子。
在一个实施方案中,所述烯属不饱和化合物包含4至30个碳原子,优选6至22个碳原子,还优选8至22个碳原子,更优选8至12个碳原子,最优选8个碳原子。
除了一个或多个双键,所述烯属不饱和化合物还可以包含其它的官能团。优选地,所述烯属不饱和化合物包含选自下列的一个或多个官能团:羧基、硫代羧基、磺基、亚磺酰基、羧酸酐、酰亚胺、羧酸酯、磺酸酯、氨基甲酰基、氨磺酰基、氰基、羰基、硫代羰基、羟基、氢硫基、氨基、醚、硫代醚、芳基、杂芳基或硅烷基和/或卤素取代基。其中,所述烯属不饱和化合物优选总共包含2至30个碳原子,优选2至22个碳原子,更优选2至12个碳原子。
在一个实施方案中,所述烯属不饱和化合物不包含除了碳碳双键之外的其它官能团。
在一个特别优选的实施方案中,所述烯属不饱和化合物是具有至少一个双键和2至30个碳原子,优选6至22个碳原子,还优选8至22个碳原子,更优选8至12个碳原子,最优选8个碳原子的非官能化的烯烃。
合适的烯属不饱和化合物例如是:
乙烯;
丙烯;
C4烯烃,例如1-丁烯、顺式-2-丁烯、反式-2-丁烯、顺式-和反式-2-丁烯的混合物、异丁烯、1,3-丁二烯;萃余液I至III、裂解物-C4
C5烯烃,例如1-戊烯、2-戊烯、2-甲基-1-丁烯、2-甲基-2-丁烯、2-甲基-1,3-丁二烯(异戊二烯)、1,3-戊二烯;
C6烯烃,例如四甲基乙烯、1,3-己二烯、1,3-环己二烯;
C7烯烃,例如1-甲基环己烯、2,4-庚二烯、降冰片二烯;
C8烯烃,例如1-辛烯、2-辛烯、环辛烯、二正丁烯、二异丁烯、1,5-环辛二烯、1,7-辛二烯;
C9烯烃,例如三丙烯;
C10烯烃,例如二环戊二烯;
十一烯;
十二烯;
内部C14烯烃;
内部C15至C18烯烃;
直链或支化的,环状、非环状或部分环状的,内部C15至C30烯烃;
三异丁烯、三正丁烯;
萜,例如柠檬烯、香叶醇、金合欢醇、蒎烯、月桂烯、香芹酮、3-蒈烯;
具有18个碳原子的多重不饱和化合物,例如亚油酸或亚麻酸;
不饱和羧酸的酯,例如乙酸或丙酸的乙烯基酯、不饱和羧酸的烷基酯、丙烯酸或甲基丙烯酸的甲基酯或乙基酯、油酸酯(例如油酸甲酯或油酸乙酯)、亚油酸或亚麻酸的酯;
乙烯基化合物,例如乙酸乙烯酯、乙烯基环己烯、苯乙烯、α-甲基苯乙烯、2-异丙烯基萘;
2-甲基-2-戊醛、甲基-3-戊烯酸酯、甲基丙烯酸酐。
在所述方法的一个变型方案中,所述烯属不饱和化合物选自丙烯、1-丁烯、顺式-和/或反式-2-丁烯,或者它们的混合物。
在所述方法的一个变型方案中,所述烯属不饱和化合物选自1-戊烯、顺式-和/或反式-2-戊烯、2-甲基-1-丁烯、2-甲基-2-丁烯、3-甲基-1-丁烯,或者它们的混合物。
在一个优选的实施方案中,所述烯属不饱和化合物选自乙烯、丙烯、1-丁烯、顺式-和/或反式-2-丁烯、异丁烯、1,3-丁二烯、1-戊烯、顺式-和/或反式-2-戊烯、2-甲基-1-丁烯、3-甲基-1-丁烯、2-甲基-2-丁烯、己烯、四甲基乙烯、庚烯、正辛烯、1-辛烯、2-辛烯,或者它们的混合物。
在一个变型方案中,使用烯属不饱和化合物的混合物。在本发明中,所述混合物是指包含至少两种不同的烯属不饱和化合物的组合物,其中每种烯属不饱和化合物的含量为优选至少5重量%,基于所述混合物的总重量。
优选使用分别具有2至30个碳原子,优选4至22个碳原子,更优选6至12个碳原子,最优选8至10个碳原子的烯属不饱和化合物的混合物。
合适的烯属不饱和化合物的混合物是所谓的萃余液I至III。萃余液I包含40%至50%异丁烯、20%至30%1-丁烯、10%至20%顺式-和反式-2-丁烯、最多1%1,3-丁二烯和10%至20%正丁烷和异丁烷。萃余液II是在石脑油裂解中生成的C4级分的一部分和基本上由从萃余液I除去异丁烯之后的正丁烯异构体、异丁烷和正丁烷组成。萃余液III是在石脑油裂解中生成的C4级分的一部分和基本上由正丁烯异构体和正丁烷组成。
另外合适的混合物是二正丁烯,也称为二丁烯、DNB或DnB。二正丁烯是C8烯烃的异构体混合物,其由1-丁烯、顺式-2-丁烯和反式-2-丁烯的混合物的二聚化而生成。在工业中,萃余液II或萃余液III料流通常经受催化低聚化,其中所包含的丁烷(n/iso)未改变地出现和所包含的烯烃完全或部分地反应。除了二聚的二正丁烯,通常也生成更高级的低聚物(三丁烯C12、四丁烯C16),其在反应之后通过蒸馏而分离。这些同样可以用作反应物。
在一个优选的变型方案中,使用包含异丁烯、1-丁烯、顺式-和反式-2-丁烯的混合物。优选地,所述混合物包含1-丁烯、顺式-和反式-2-丁烯。
本发明的烷氧基羰基化通过本发明的Pd配合物催化。在此,在方法步骤b)中可以将Pd配合物作为包含Pd和本发明的膦配体的预成型的配合物添加,或者所述Pd配合物原位地由包含Pd的化合物和游离的膦配体而形成。其中,包含Pd的化合物也称为催化剂前体。
在原位形成催化剂的情况下,可以加入过量的配体,从而在反应混合物中也存在未结合的配体。
在开始时才添加配合物的情况下,也可以添加另外的配体,从而在反应混合物中也存在未结合的配体。
在一个变型方案中,包含Pd的化合物选自二氯化钯(PdCl2)、乙酰基丙酮化钯(II)[Pd(acac)2]、乙酸钯(II)[Pd(OAc)2]、二氯(1,5-环辛二烯)钯(II)[Pd(cod)2Cl2]、双(二苯亚甲基丙酮)钯[Pd(dba)2]、双(乙腈)二氯钯(II)[Pd(CH3CN)2Cl2]、(肉桂基)二氯化钯[Pd(肉桂基)Cl2]。
优选地,包含Pd的化合物是PdCl2、Pd(acac)2或Pd(OAc)2。特别合适的是Pd(acac)2。
在方法步骤c)中的醇可以是支化的或直链的,环状的、脂环族的、部分环状或脂环族的,和特别是C1-至C30-烷醇。可以使用一元醇或多元醇。
在方法步骤c)中的醇包含优选1至30个碳原子,更优选1至22个碳原子,特别优选1至12个碳原子。它们可以是一元醇或多元醇。
除了一个或多个羟基之外,所述醇可以包含另外的官能团。优选地,所述醇还包含选自下列的一个或多个官能团:羧基、硫代羧基、磺基、亚磺酰基、羧酸酐、酰亚胺、羧酸酯、磺酸酯、氨基甲酰基、氨磺酰基、氰基、羰基、硫代羰基、氢硫基、氨基、醚、硫代醚、芳基、杂芳基或硅烷基和/或卤素取代基。
在一个实施方案中,所述醇除了羟基之外不包含另外的官能团。
所述醇可以包含不饱和的和芳族的基团。然而,优选的是脂族的醇。
在本发明中,脂族的醇是指不包含芳族基团的醇,例如烷醇、烯醇或炔醇。
在一个实施方案中,所述醇是具有一个或多个羟基和1至30个碳原子,优选1至22个碳原子,更优选1至12个碳原子,最优选1至6个碳原子的烷醇。
在所述方法的一个变型方案中,在方法步骤c)中的醇选自一元醇的类型。
在所述方法的一个变型方案中,在方法步骤c)中的醇选自:甲醇、乙醇、1-丙醇、异丙醇、异丁醇、叔丁醇、1-丁醇、2-丁醇、1-戊醇、2-戊醇、3-戊醇、1-己醇、环己醇、苯酚、2-乙基己醇、异壬醇、2-丙基庚醇。
在一个优选的变型方案中,在方法步骤c)中的醇选自甲醇、乙醇、1-丙醇、1-丁醇、1-戊醇、1-己醇、2-丙醇、叔丁醇、3-戊醇、环己醇、苯酚,或其混合物。
在所述方法的一个变型方案中,在方法步骤c)中的醇选自多元醇的类型。
在所述方法的一个变型方案中,在方法步骤c)中的醇选自:二元醇、三元醇、四元醇。
在所述方法的一个变型方案中,在方法步骤c)中的醇选自:环己烷-1,2-二醇、1,2-乙二醇、1,3-丙二醇、丙三醇、1,2,4-丁三醇、2-羟基甲基-1,3-丙二醇、1,2,6-三羟基己烷、季戊四醇、1,1,1-三(羟基甲基)乙烷、儿茶酚、雷琐酚和羟基氢醌。
在所述方法的一个变型方案中,在方法步骤c)中的醇选自:蔗糖、果糖、甘露糖、山梨糖、半乳糖和葡萄糖。
在所述方法的一个优选的变型方案中,在方法步骤c)中的醇选自甲醇、乙醇、1-丙醇、1-丁醇、1-戊醇、1-己醇。
在所述方法的一个特别优选的变型方案中,在方法步骤c)中的醇选自:甲醇、乙醇。
在所述方法的一个特别优选的变型方案中,在方法步骤c)中的醇是甲醇。
在所述方法的一个变型方案中,在方法步骤c)中的醇过量使用。
在所述方法的一个变型方案中,在方法步骤c)中的醇同时作为溶剂使用。
在所述方法的一个变型方案中,使用另一种选自下列的溶剂:甲苯、二甲苯、四氢呋喃(THF)和二氯甲烷(CH2Cl2)。
在步骤d)中,优选在0.1至10MPa(1至100bar),优选1至8MPa(10至80bar),更优选2至4MPa(20至40bar)的CO分压下导入CO。
在本发明的方法步骤e)中,将所述反应混合物优选加热到10℃至180℃,优选20至160℃,更优选40至120℃的温度,从而使所述烯属不饱和化合物反应生成酯。
在步骤a)中预先添加的烯属不饱和化合物与在步骤c)中添加的醇的摩尔比为优选1∶1至1∶20,更优选1∶2至1∶10,更优选1∶3至1∶4。
Pd与在步骤a)中预先添加的烯属不饱和化合物的质量比为优选0.001至0.5重量%,优选0.01至0.1重量%,更优选0.01至0.05重量%。
本发明的膦配体与Pd的摩尔比为优选0.1∶1至400∶1,优选0.5∶1至400∶1,更优选1∶1至100∶1,最优选2∶1至50∶1。
优选地,所述方法在添加酸的情况下进行。在一个变型方案中,所述方法因此另外包括步骤c′):将酸添加到反应混合物中。在此,优选的是布朗斯特酸或路易斯酸。
合适的布朗斯特酸的酸强度优选为pKa≤5,优选pKa≤3。所给出的酸强度pKa基于标准条件(25℃,1.01325bar)下测定的pKa值。在本发明中,对于多质子酸,所述酸强度pKa基于第一个质子迁移步骤的pKa值。
优选地,所述酸不是羧酸。
合适的布朗斯特酸例如是高氯酸、硫酸、磷酸、甲基膦酸和磺酸。优选地,所述酸是硫酸或磺酸。合适的磺酸例如是甲磺酸、三氟甲磺酸、叔丁烷磺酸、对甲苯磺酸(PTSA)、2-羟基丙烷-2-磺酸、2,4,6-三甲基苯磺酸和十二烷基磺酸。特别优选的酸是硫酸、甲磺酸、三氟甲磺酸和对甲苯磺酸。
使用的路易斯酸例如可以是三氟甲磺酸铝。
在一个实施方案中,在步骤c′)中添加的酸的量为0.3至40mol%,优选0.4至15mol%,更优选0.5至5mol%,最优选0.6至3mol%,基于在步骤a)中使用的烯属不饱和化合物的物质的量。
具体实施方式
下面的实施例具体阐述本发明。
通用操作说明
所有下列的制备使用标准Schlenk技术在保护气体下进行。溶剂在使用前通过合适的干燥剂干燥(Purification of Laboratory Chemicals,W.L.F.Armarego(作者),Christina Chai(作者),Butterworth Heinemann(Elsevier),第六版,Oxford2009)。
三氯化磷(Aldrich)在使用前在氩气下蒸馏。所有制备工作在预热过的容器中进行。产物的表征通过NMR光谱法进行。化学位移(δ)以ppm为单位给出。31P NMR信号参照如下:SR31P=SR1H*(BF31P/BF1H)=SR1H*0.4048(Robin K.Harris,Edwin D.Becker,SoniaM.Cabral de Menezes,Robin Goodfellow,和Pierre Granger,Pure Appl.Chem.,2001,73,1795-1818;Robin K.Harris,Edwin D.Becker,Sonia M.Cabral de Menezes,PierreGranger,Roy E.Hoffman和Kurt W.Zilm,Pure Appl.Chem.,2008,80,59-84)。
核磁共振谱的记录在Bruker Avance 300或Bruker Avance 400上完成,气相色谱分析在Agilent GC 7890A上进行,元素分析在Leco TruSpec CHNS和Varian ICP-OES 715上进行,和ESI-TOF质谱法在Thermo Electron Finnigan MAT 95-XP和Agilent 6890 N/5973仪器上进行。
制备1,1′-双(叔丁基苯基膦基)二茂铁
示意图2:合成1,1′-双(叔丁基苯基膦基)二茂铁
在250ml三颈烧瓶中将3g二茂铁在氩气氛围下溶解于70ml庚烷之中。加入5.3ml四甲基乙二胺(TMEDA),接着加入22ml 1.6N丁基锂己烷溶液。将反应混合物在室温下静置24小时,接着去掉浮在上面的溶剂。向残留物加入70ml庚烷。将6.1ml氯-叔丁基苯基瞵溶解于20ml庚烷中,并且将该溶液滴加到三颈烧瓶内的溶液中。将反应混合物加热1小时,接着冷却到室温并且进行水相处理。将有机相浓缩至变干。从热甲醇中结晶产物并且过滤。产率为4g。
31P NMR(CD2Cl2,121MHz),s 8.1ppm
1H NMR(CD2Cl2,300MHz),7.65-7.55m(4H),7.35-7.25m(6H),4.2-4.15m(1H),4.2-4.15m(1H),4.15-4.0m(1H),4.0-3.95m(2H),3.9-3.85m(3H),0.8dJ=12.4Hz,(18H)
13C(CD2Cl2,75MHz),137.7d,J=14Hz,137.4d,J=12.4Hz,136.1d,J=1.9Hz,135.8d,J=1.5Hz,129.3d,J=4.2Hz,127.9d,J=9Hz,77.6d,J=33.9Hz,77.0d=31.8Hz,75.1d,J=16.8Hz,72.9s,72.8s,72.6s,72-71.8m,31-30.8m,28.2d,J=14.8Hz。
化合物1的可选合成途径
示意图3:合成1,1′-双(叔丁基苯基膦基)二茂铁
在50mL THF中加入1,1′-二溴二茂铁(5.22g,15.2mmol)。然后在-60℃温度下在大约15分钟之内滴加丁基锂溶液(9.5mL,15.2mmol,1.6M己烷溶液)。接着将反应溶液继续搅拌大约15分钟,并且将其略微加热(-30℃)。然后重新冷却到-60℃,在大约15分钟之内加入氯-叔丁基苯基膦溶液(3.05g,15.2mmol,10mL THF溶液),接着加热到室温。将这重复一次。反应之后去除溶剂,并且替换成***(50mL)。然后使用25mL H2O洗涤两次,并且通过MgSO4进行干燥。经过浓缩析出铁锈色沉淀物,使用低温***洗涤沉淀物。可以得到7.28g(71%)产物。分析方法,参见之前的试验。
制备1-(二苯基膦基)-1′-(二异丙基膦基)二茂铁(对比化合物)
示意图4:合成1-(二苯基膦基)-1′-(二异丙基膦基)二茂铁
将1.13mmol(565μl)苯基锂(PhLi)加入到具有磁搅拌子和氮气阀的50mL圆底烧瓶中,通过注射泵缓慢滴加1.03mmol(300mg)环状膦的20ml庚烷溶液。使用庚烷将锂盐洗涤两次,并且加入6ml庚烷。在室温下将0.8eq(0.824mmol,131μl)ClPiPr2的庚烷溶液滴加到7ml庚烷中形成的悬浮液。红棕色悬浮液几乎没有变色。经过20分钟搅拌之后,将悬浮液回流加热1.5小时。固体物质略微变亮。完全去除溶剂,将棕红色残留物放在H2O和***之中。使用H2O将有机相洗涤两次,并且通过Na2SO4干燥有机相。从***相记录31P光谱。光谱表现出2个单峰。氯膦已完全用尽。将***相干燥,得到300mg(产率:61%)棕黄色的油,其可在65℃温度下溶解于水浴上的MeOH之中。将溶液放入低温冷冻机中过夜(-78℃)。析出76mg棕黄色的油,使用NMR光谱法对其进行研究。
1H NMR(300MHz,CDCl3)δ7.46-7.23(m,10H,Ph),4.36(m,2H,Cp),4.21(m,2H,Cp),34.24(m,4H,Cp),1.88(m,2H,iPr),1.15-0.96(m,12H,iPr).
13C NMR(75MHz,CDCl3)δ139.9(J=9.8Hz,Ph),133.4(J=19.2Hz,Ph),128.4,128.1,128.0(Ph),77.1,76.8,76.2,76.1(Cp),73.5(J=14.5Hz,Cp),72.8(J=2.9Hz,Cp),71.9(J=10.5Hz,Cp),72.1(Cp),23.3(J=11.0Hz,iPr),20.1,20.0,19.9,19.8(iPr).
31P NMR(121MHz,C6D6)δ=0.88和-16.62。
制备1-(二苯基膦基)-1′-(二环己基膦基)二茂铁(对比化合物)
示意图5:合成1-(二苯基膦基)-1′-(二环己基膦基)二茂铁
化学配方:0.6ml 2M/THF苯基锂,0.25ml二环己基氯膦,50ml庚烷,20ml THF,30ml***,20ml甲醇
在100ml Schlenk烧瓶中将原料溶解于30ml庚烷之中。将苯基锂加入到100ml三颈烧瓶中。现在向苯基锂缓慢滴加所述溶液,然后静置1小时。然后将反应溶液浓缩到大约15ml。然后静置30分钟。去掉浮在上面的液体。向残留物加入20ml庚烷。将PCy2Cl溶解于20ml THF之中,并且将其在半小时之内加入。现在将反应溶液回流煮沸1小时。现在将反应溶液冷却到室温,并且将溶剂换成***。然后进行水相处理。抽出Et2O。将残余物溶解于热甲醇中。过滤尚且很热的溶液。在低温状态下析出黄色的沉淀物。产率为300mg。
31P(CDCl3,121MHz),-7.2s,-16.8s
13C(75MHz,CDCl3),133.4(d,J=19.3Hz),128.5s,128.2(d,J=6.8Hz),73.6(d,J=14.4Hz),72.9(d,J=4.9Hz),72.3(d,J=10.5Hz),71.2bs,69.1s,33.5(d,J=11.5Hz),30.4(d,J=4.9Hz),30.2(d,J=10.2Hz),27.4(dd),26.4s
1H(300MHz,CDCl3),7.3-7.2m(10H),4.2(t,J=1.7Hz,2H),4.13t,J=1.7Hz,2H),3.98(quint,J=1.8Hz,4H),1.8-1.5(m,11H),1.8-1.2m,11H)。
制备1-(二苯基膦基)-1′-(二金刚烷基膦基)二茂铁(对比化合物)
示意图6:合成1-(二苯基膦基)-1′-(二金刚烷基膦基)二茂铁(Ad:金刚烷基)
在具有磁搅拌子和氮气阀的100ml圆底烧瓶中加入565μl(1.13mmol,1.1eq)PhLi(2M)。使用注射泵(0.1系数10,10ml注射器)在2小时之内滴加300mg(1.03mmol)桥联膦和20ml庚烷构成的溶液。在加入1/3溶液之后析出橙色的固体物质。在滴加之后继续搅拌一小时。滗析暗色的溶液,并且各用6ml庚烷洗涤两次。向橙色固体物质加入6ml庚烷,并且在0℃温度下滴加溶解于7ml THF中的氯膦(1.1eq.)形成悬浮液。过夜搅拌将溶液加热到室温。悬浮液变成橙红色的透明溶液。加入200μl水之后,将溶液干燥,并且将残留物放在***和水中。水相呈强碱性(pH试纸)。在洗涤红色有机相之后,用水洗涤两次并且通过Na2SO4进行干燥。抽出***之后留下橙色的固体物质。
回流加热2小时完成反应。Ad2PCl的量从1.1eq下降到1.0eq。根据31P-NMR尽管有回流仍然不再转化。对磷信号积分之后,得到50mol%所需的产物,28mol%Ad2PCl,也许还有13mol%单取代产物。从溶液中析出红色晶体(红色晶体产率160mg),这就是所需的目标产物。
31P NMRδ=26.0,-17.0;
ESI:C42H49FeP2:计算值671.26542,实测值671.2664
1H NMR(300MHz,C6D6)δ7.31-7.13(m,10H,Ph),4.28(m,2H,Cp),4.19(m,2H,Cp),4.01(m,2H,Cp),3.99(m,2H,Cp),1.94-1.61(m,18H,Ad),1.54(m,12H,Ad).
31P NMR(121MHz,C6D6)δ=26.04和-17.00。
制备1-(二苯基膦基)-1′-(叔丁基苯基膦基)二茂铁(对比化合物)
示意图7:合成1-(二苯基膦基)-1′-(叔丁基苯基膦基)二茂铁
化学配方:
0.53ml 2M/THF苯基锂,0.19ml叔丁基(苯基)氯膦,50ml庚烷,20ml THF,30ml***,20ml甲醇
在100ml Schlenk烧瓶中将原料溶解于30ml庚烷之中。在100ml三颈烧瓶中加入苯基锂。在-70℃温度下向苯基锂缓慢滴加所述溶液,然后静置1小时。然后将反应溶液浓缩到大约15ml。然后静置30分钟。去掉浮在上面的液体。向残留物加入20ml庚烷。将叔丁基(苯基)氯膦溶解于20ml THF之中,并且在半小时之内加入。现在将反应溶液回流煮沸1小时。现在将反应溶液冷却到室温,并且将溶剂换成***。然后进行水相处理。抽出Et2O。将残余物溶解于热甲醇中。过滤尚且很热的溶液。在低温状态下析出黄色的沉淀物。
31P(CDCl3(121MHz))8.1s,-16.8s。
制备1,1′-双(异丙基苯基膦基)二茂铁(对比化合物)
示意图8:合成1,1′-双(异丙基苯基膦基)二茂铁
在配有温度计、磁搅拌器和回流冷却器的100ml三颈烧瓶中将0.93g二茂铁溶解于50ml纯净庚烷之中。在室温下利用注射器加入1.3g TMEDA(1.6ml)和7.5ml 1,6-正丁基锂/己烷。将溶液静置5小时,析出很大的橙棕色二锂化二茂铁晶体。利用注射器去除上清液,并且加入20ml纯净庚烷。接着滴加溶解于10ml庚烷中的氯膦。回流加热一小时。冷却之后分别用10ml脱气水将有机相洗涤三次。将其浓缩变干,并且加入10ml***。使用***作为溶剂,通过10cm硅凝胶60在氩气氛围下过滤该溶液,将其浓缩变干,并且从不太热的甲醇结晶出目标产物,未优化的产率大约为50%。
31P(121MHz,CDCl3),-7.8s,-8.15s,
13C(75MHz,CDCl3);137.77,(d,J=12Hz),137.4(d,J=11.3Hz),134.2(d,J=20.3Hz),129.1s,128.1(d,J=7.5Hz),77.4(d,J=11.3Hz),75.0(d,J=26.2Hz),74.0(d,J=22.3Hz),72.1bs,71.9-71.5m,71.1s,69.0s,27.6(d,J=10Hz),27.558d,J=10Hz),20.3-19.9m
1H(300MHz,CDCl3):7.52-7.44(m,4H),7.33-7.23(m,6H),4.23(sept,J=1.2Hz,1H),4.1-4.0(m,4H),3.93-3.9(m,1H),3.87-3.84(m,1H),3.58-3.54(m,1H),2.1-1.9(m,2H),0.99(d,J=7Hz,3H),0.94(d,J=7Hz,3H),0.83-0.7(m,6H)
制备1,1′-双(二(1,4-二-三氟甲基苯基)膦基)二茂铁(对比化合物)
示意图9:合成1,1′-双(二(1,4-二-三氟甲基苯基)膦基)二茂铁
化学配方:0.3g二茂铁,0.61ml TMEDA,2.45ml丁基锂,1.75ml PClR2。
将二茂铁在100ml三颈烧瓶中溶解于15ml庚烷之中。然后加入TMEDA。同样在加入TMEDA之后加入丁基锂。装有反应混合物的100ml烧瓶在室温下静置24小时。经过24小时之后去掉浮在上面的溶剂。然后向残留物加入20ml庚烷。首先将PClR2溶解于10ml庚烷中,然后将其滴加到烧瓶之中。然后加热到70℃反应30分钟。然后冷却到室温并且进行水相处理。将有机相浓缩直至变干,然后从热甲醇中析出晶体。产率:850mg
分析:
31P(CD2Cl2;121MHZ),-14.7s,
HRMS计算值1129.00242,实测值:1129.00236
MS EI 70eV)M/z(%),1098(M+,17)930(63),670(81),473(100),319(9,88)261(16),195(71),97(13),69(23)。
其它对比化合物
以下使用的对比化合物1-(二叔丁基膦基)-1′-(二苯基膦基)二茂铁和1,2-双(二叔丁基膦甲基)苯均可在市面上买到。
制备[Pd((Cp2Fe)1,1′-(PPh(叔丁基))2)(η2-苯乙烯)](苯基-η2-乙烯)(配合物K1)
示意图10:合成配合物K1
将109.6mg(0.517mmol)(η3-烯丙基)-(η5-环戊二烯基)钯溶解于大约10ml庚烷中,并且通过硅藻土过滤。将溶解于10ml庚烷中的250.8mg(0.486mmol)二茂铁配体与55.8μl(0.486mmol)苯乙烯一起在室温下滴加到透明的深红色溶液之中。深红色溶液经过几分钟搅拌之后变得清亮。经过一小时之后,熔化NMR样品并且记录31P NMR。配体已完全转化。将溶液继续搅拌四小时,然后在-28℃温度下存放。没有晶体形成。然后在高真空中剧烈浓缩反应溶液,析出黄色的固体物质。将悬浮液放入-28℃低温冷冻机中过夜完成反应。滗析浮在上面的溶液,使用庚烷将黄色固体物质洗涤三次,并且在油泵上干燥。产率:40-60%。磷谱表现出各自略微***成双峰的两个强信号和两个较宽的信号。
1H NMR(300MHz,C6D6)δ8.53-6.,71(m,10H,Ph),5.03-3.27(m,8H,Cp),1.47-1.04(m,18H,tBu).
31P NMR(121MHz,C6D6)δ=44.91(d,J=20.3Hz),41.27(d,J=20.3Hz),44.01(br),39.89(br)。
这些磷信号表明因为非对映异构体配体也出现了非对映异构体配合物。
制备[Pd((Cp2Fe)1,1′-(PPh(叔丁基))2)(η2-萘醌)](配合物K2)
使用萘醌合成配合物,以获得易于结晶的配合物。
示意图11:合成配合物K2
该反应的关键是在反应之前使得萘醌升华(100℃和1·10-3mbar)。升华的萘醌是一种黄色结晶固体物质。将109.6mg(0.516mmol)钯前体(参见示意图11)溶解于10ml庚烷之中,并且通过硅藻土过滤到25ml圆底烧瓶中。在室温下将250.8mg(0.487mmol)二茂铁配体和76.86mg(0.485mmol,1.1eq)新鲜升华的萘醌(溶解于15ml庚烷中)滴加到深红色的透明溶液中。含有配体和萘醌的溶液透明并且呈橙色。为了完全溶解萘醌,必须使用水浴将溶液加热到60℃(必要时利用超声波浴实现完全溶解)。反应溶液变得清亮,并且析出红棕色的固体物质。搅拌过夜。在沉淀之后滗析溶液,并且使用庚烷将红棕色固体物质洗涤两次。在真空中干燥之后得到红棕色固体物质(50-70%)。
所涉及的是一种异构体混合物,该混合物在31P-NMR中表现出6个不同的磷信号并且提示3种非对映异构体配合物。
1H NMR(300MHz,C6D6)δ8.40-8.27(m,1.5H,CH芳烃),8.17(m,0.5H,CH芳烃),8.09-87.99(m,1H,CH芳烃),7.69-7.59(m,1H,CH芳烃),7.49(m,1H,CH芳烃),7.30-7.12(m,7H,CH芳烃),7.08(m,1H,CH芳烃),6.94-6.66(m,3H,CH芳烃),5.21-4.98(m,2H,CH乙烯基),4.34(m,0.5H,Cp),4.10(m,1H,Cp),4.02(m,1H,Cp),3.95(m,0.5H,Cp),3.90-3.81(m,1H,Cp),3.79(m,0.5H,Cp),3.75(m,1H,Cp),3.66(m,0.5H,Cp),3.60(m,1H,Cp),3.48(m,1H,Cp),1.26-1.06(m,18H,叔丁基)。
31P NMR(121MHz,C6D6)δ=50.89(d,Hz,J=25.,8Hz),47.37(d,Hz,J=25.8Hz),49.58(s),46.73(s)。
元素分析计算值C40H42FeO2P2Pd:C,61.67;H,5.43;P,7.95。实测值:C,61.36;H,5.56;P,7.65。
制备[Pd((Cp2Fe)1,1′-(PPh(叔丁基))2)(η2-N-甲基马来酰亚胺)](配合物K3)
同样也可以使用N-甲基马来酰亚胺制备钯配合物:
示意图12:合成配合物K3
该反应的关键是预先使得马来酰亚胺升华(100℃和1·10-3mbar)。升华的N-甲基马来酰亚胺是一种白色结晶固体物质。类似于使用萘醌合成(参见试验50),得到287mg(80%)产物作为黄色固体产物,如下所述很容易让其结晶:
将42mg配合物K3溶解于1~2ml甲苯中。将6ml庚烷加入到黄色的透明溶液中。溶液没有变混浊。将体积缩小三分之一,析出黄色的固体物质。再次加入一些甲苯,并且在水浴上加热到60℃。通过硅藻土过滤几乎透明的溶液,将透明的黄色滤液放入3℃冰箱中。经过4天之后,形成了X射线可透过的黄棕色晶体。
1H NMR(400MHz,C6D6)δ8.07(m,1H,CH芳烃),7.98(m,1H,CH芳烃),7.64-7.53(m,2H,CH芳烃),7.23-7.12(m,3H,CH芳烃),6.98(m,3H,CH芳烃),4.49-4.36(m,2H,Cp或者乙烯基),4.36-4.28(m,1H,Cp或者乙烯基),4.10(m,0,5H,Cp或者乙烯基),4.08-4.00(m,2H,Cp或者乙烯基),3.88-3.81(m,2H,Cp或者乙烯基),3.75(m,1.5H,Cp或者乙烯基),3.59(m,1H,Cp或者乙烯基),3.13(s,1H,CH3),3.05(s,1.5H,CH3),2.99(s,0.5H,CH3),1.33-1.16(m,18H,叔丁基)
31P NMR(161MHz,C6D6)δ=48.83(d,Hz,J=17.4Hz),47.8(d,Hz,J=17.4Hz),47.23(s),46.54(s)
HRMS(ESI)m/z+计算值C35H41FeNO2P2Pd(M+Na)+754.09044。
所涉及的是一种异构体混合物,该混合物在31P NMR中表现出6个不同的磷信号并且提示3种非对映异构体配合物。
晶体结构由两个非对映异构体配合物构成。
高压实验
原料:
甲醇(MeOH)。
二正丁烯是C8烯烃的异构体混合物,其由1-丁烯,顺式-2-丁烯和反式-2-丁烯的混合物的二聚化而生成。在工业中,萃余液II或萃余液III料流通常经受催化低聚化,其中所包含的丁烷(n/iso)未改变地出现和所包含的烯烃完全或部分地反应。除了二聚的二正丁烯,通常也生成更高级的低聚物(三丁烯C12、四丁烯C16),其在反应之后通过蒸馏而分离。
用于C4烯烃低聚化的工业实践化的方法是所谓的″OCTOL方法"。在专利文献中,例如DE102008007081A1描述了基于OCTOL方法的低聚化。
EP1029839A1涉及在OCTOL方法中生成的C8烯烃的分馏。
工业的二正丁烯通常由5%至30%的正辛烯,45%至75%的3-甲基庚烯和10%至35%的3,4-二甲基己烯组成。优选的料流包含10%至20%正辛烯,55%至65%3-甲基庚烯和15%至25%3,4-二甲基己烯。
在下文中,PTSA总是表示对甲苯磺酸一水合物。
用于分批试验中的反应的通用试验描述:
将相应量的基料、钯盐、酸和醇在氩气和磁搅拌下在50ml Schlenk容器中混合。
将100ml钢制高压釜(出自Parr公司,配备有气体进口和气体出口阀、数字压力记录器、温度感应器和球阀以及用于取样的嵌入毛细管)通过三次抽真空和氮气吹扫而除去氧气。然后将Schlenk容器中的反应溶液借助毛细管以氩气的逆流通过球阀而填充到高压釜中。然后在室温下压入相应量的CO和再加热到反应温度(不在恒压下进行的反应),或者首先加热到反应温度和再通过量管(借助减压装置与高压釜相连)压入CO。然后将该量管再用CO填充至大约100bar和在反应过程中在恒定压力下提供所需的CO。该量管的死容积为大约30ml和配备有数字压力记录器。然后,将该反应在所需的温度下在搅拌的情况下实施相应的时间。在此,借助软件(Spec View公司的Specview)和Parr公司的4870过程控制器和4875功率控制器记录在高压釜中和在玻璃量管中的压力变化数据。由这些生成Excel表格,从而以后可以制成图表,该图表可以描绘气体消耗(和因此转化率)随时间的变化。如果需要,可以通过毛细管收集GC样品并且分析。为此,在反应之前向Schlenk容器中一起加入合适的准确量(2-10ml)的异辛烷作为内部标准物。由此也可以获知反应进程。在反应结束时,将高压釜冷却至室温,小心地释放压力,如果需要的话加入异辛烷作为内部标准物和进行GC分析或者对于新的产物也进行GC-MS分析。
用于玻璃瓶中的高压釜试验的通用试验说明:
使用300ml Parr反应器。与之相匹配的是相应尺寸的自造的铝模块,其适合于通过市购可得的磁搅拌器(例如Heidolph公司的)加热。对于高压釜的内部,制成厚度大约1.5cm的圆形金属板,其包括相应于玻璃瓶外周长的6个孔。为了匹配这些玻璃瓶,它们配备有小的磁搅拌器。这些玻璃瓶配备有螺旋盖和合适的隔膜,并且使用在玻璃吹制间制成的特殊装置在氩气下填充相应的反应物、溶剂和催化剂和添加剂。为此,同时填充6个容器,这可以在相同的温度和相同的压力下在一个实验中进行6个反应。然后,将该玻璃容器使用螺旋盖和隔膜密闭和分别通过隔膜***合适大小的小的注射针管。这样可以以后在反应中实现气体交换。将这些瓶放置在金属板中和将其在氩气下转移到高压釜中。该高压釜用CO吹扫和在室温下以预定的CO压力填充。然后,借助磁搅拌器在磁搅拌下加热到反应温度和将该反应进行相应的时间。然后,冷却到室温和缓慢地释放压力。然后,将高压釜用氮气吹扫。将所述瓶从高压釜中取出和加入确定量的合适标准物。进行GC分析,由其结果确定产率和选择性。
也能以相应的方式在Parr公司的600ml反应器中进行试验,其中使用具有12个孔的金属板,其可装载12个反应容器。
分析:
GC分析2-辛烯:使用Agilent公司的色谱分析仪GC Agilent 7890A,利用30m HP5柱进行GC分析。温度分布:35℃,10分钟;以每分钟10℃的速率加热到200℃;注射体积为1μl,分流比为50∶1。
2-辛烯和产物的保留时间:10.784-13.502分钟
以下将由2-辛烯形成的酯称作MINO(异壬酸甲酯)。
未知异构体分布的***产物的保留时间:15.312、17.042、17.244、17.417分钟
iso-C9酯的保留时间:19.502-20.439分钟(主峰:19.990分钟)
n-C9酯的保留时间:20.669、20.730、20.884、21.266分钟。
n/iso比例表示末端转化成酯的烯烃与内部转化成酯的烯烃之比。
以下所述的n选择性涉及末端甲氧基羰基化反应相对于甲氧基羰基化反应产物总产率的比例。
只要没有其它说明,以下相对的物质的量mol-%均涉及烯烃(基料)物质的量。
2-辛烯与不同配体的甲氧基羰基化反应
将Pd(acac)2(1.95mg,6.4μmol)、MeSO3H(6.4μL,98.55μmol)和MeOH(10mL,24.69mmol)装入25mL Schlenk容器之中。将0.16mol-%所述的配体(相对于2-辛烯的物质的量)装入4mL小瓶并且加入磁搅拌子。然后用注射器注入1.25mL透明的黄色母液和2-辛烯(315μL,2mmol)。Pd(acac)2相对于2-辛烯的物质的量的摩尔百分比为0.04mol%,MeSO3H为0.6mol%。将小瓶放在样品架上,在氩气氛围下再将其放入Parr Instruments公司的300mL高压釜之中。用氮气将高压釜吹扫三次之后,将CO压力调整到40bar。反应在120℃温度下进行5小时。在反应结束之后,将高压釜冷却到室温并且小心卸压。加入异辛烷作为内部GC标准物。利用GC确定壬酸甲酯的产率和区域选择性。在下表中总结了测量结果:
实施例 | 配体 | 产率 | n/iso比例 |
1* | 1,1′-双(叔丁基苯基膦基)二茂铁 | 85% | 83/17 |
2(VB) | 1-(二苯基膦基)-1′-(二金刚烷基膦基)二茂铁 | 53% | 75/25 |
3(VB) | 1-(二苯基膦基)-1′-(二环己基膦基)二茂铁 | 36% | 75/25 |
4(VB) | 1,1′-双(异丙基苯基膦基)二茂铁 | 55% | 77/23 |
5(VB) | 1-(二苯基膦基)-1′-(二异丙基膦基)二茂铁 | 47% | 73/27 |
6(VB) | 1-(二苯基瞵基)-1′-(叔丁基苯基膦基)二茂铁 | 65% | 70/30 |
7(VB) | 1,1′-双(二(1,4-二-三氟甲基苯基)膦基)二茂铁 | 0% |
VB:对比实施例
*:本发明所述的实施例
该试验证明使用本发明所述的配体1,1′-双(叔丁基苯基膦基)二茂铁与现有技术公开的具有类似结构的二茂铁基配体相比能够实现明显更高的产率和更大的n/iso特异性。
二正丁烯与不同配体的甲氧基羰基化反应
将Pd(acac)2(3.9mg,12.9μmol)、MeSO3H(甲磺酸)(13μL,197.1μmol)和MeOH(20mL)装入50mL Schlenk容器之中。将0.16mol-%所述的配体(相对于二正丁烯的物质的量)装入4mL小瓶并且加入磁搅拌子。然后用注射器注入1.25mL透明的黄色母液和二正丁烯(315μL,2mmol)。Pd(acac)2相对于2-辛烯的物质的量的摩尔百分比为0.04mol%,MeSO3H为0.6mol%。将小瓶放在样品架上,在氩气氛围下再将其放入600mL Parr高压釜之中。用氮气将高压釜吹扫三次之后,将CO压力调整到40bar。反应在120℃温度下进行20小时。在反应结束之后,将高压釜冷却到室温并且小心卸压。加入异辛烷作为内部GC标准物。利用GC确定异壬酸甲酯(MINO)的产率和区域选择性。在下表中总结了测量结果:
实施例 | 配体 | 产率 | n/iso比例 |
1* | 1,1′-双(叔丁基苯基膦基)二茂铁 | 73% | 86/14 |
2(VB) | 1,2-双-(二叔丁基膦甲基)苯 | 49% | 94/6 |
3(VB) | 1-(二叔丁基膦基)-1′-(二苯基膦基)二茂铁 | 18% | 79/21 |
4(VB) | 1-(二苯基膦基)-1′-(二异丙基膦基)二茂铁 | 12% | 78/22 |
5(VB) | 1-(二苯基膦基)-1′-(叔丁基苯基膦基)二茂铁 | 16% | 77/23 |
6(VB) | 1,1′-双(异丙基苯基膦基)二茂铁 | 22% | 80/20 |
VB:对比实施例
*:本发明所述的实施例
即使在该试验中也能利用本发明所述的配体实现与类似结构的二茂铁基配体或者已知的配体DTBPMB相比明显更好的产率和更高的n/iso选择性。
二正丁烯与预先形成的配合物的甲氧基羰基化反应
在氩气氛围下向100ml钢制高压釜装入0.04mol-%所述的配合物和1,1′-双(叔丁基苯基膦基)二茂铁(29.6mg,0.12mol%)。接着加入MeOH(30ml)和二正丁烯(7.54ml,48mmol)和PTSA(54.7mg,0.6mol%)。在室温下向高压釜加入纯度4.7的40bar CO,并且在120℃温度下进行20小时反应。接着让高压釜冷却下来,并且缓慢泄放压力。将高压釜内容物转移到Schlenk容器中。加入5ml异辛烷作为内部标准物,并且利用GC分析法确定异壬酸甲酯(MINO)的产率和区域选择性。在下表中总结了测量结果:
*:本发明所述的实施例
该试验表明,使用预先形成的配合物同样能实现与原位形成的配合物一样好的结果。
Claims (3)
2.根据权利要求1的方法,
其中在方法步骤b)中包含Pd的化合物选自二氯化钯、乙酰丙酮钯(II)、乙酸钯(II)、二氯(1,5-环辛二烯)钯(II)、双(二苯亚甲基丙酮)钯、双(乙腈)二氯钯(II)、(肉桂基)二氯化钯。
3.根据权利要求1或2的方法,
其中在方法步骤c)中的醇选自甲醇、乙醇、1-丙醇、1-丁醇、1-戊醇、1-己醇、2-丙醇、叔丁醇、3-戊醇、环己醇、苯酚,或其混合物。
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