CN102264746A - 取代的四氢茚基络合物的合成 - Google Patents
取代的四氢茚基络合物的合成 Download PDFInfo
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- CN102264746A CN102264746A CN2009801525733A CN200980152573A CN102264746A CN 102264746 A CN102264746 A CN 102264746A CN 2009801525733 A CN2009801525733 A CN 2009801525733A CN 200980152573 A CN200980152573 A CN 200980152573A CN 102264746 A CN102264746 A CN 102264746A
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- dihydro
- alkyl
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- -1 tetrahydroindenyl Chemical class 0.000 title claims description 15
- 230000015572 biosynthetic process Effects 0.000 title abstract description 6
- 238000003786 synthesis reaction Methods 0.000 title abstract 2
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- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
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- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 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
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- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 12
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- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
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- BZKFMUIJRXWWQK-UHFFFAOYSA-N Cyclopentenone Chemical compound O=C1CCC=C1 BZKFMUIJRXWWQK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
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- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- UCIKZESDXASJNG-UHFFFAOYSA-L [Cl-].[Cl-].C1=CC=C2C([Zr+2])C=CC2=C1 Chemical class [Cl-].[Cl-].C1=CC=C2C([Zr+2])C=CC2=C1 UCIKZESDXASJNG-UHFFFAOYSA-L 0.000 description 2
- DDDRMZMSFMQPPC-UHFFFAOYSA-L [Cl-].[Cl-].C1C=CC=C2C([Zr+2])CCC21 Chemical class [Cl-].[Cl-].C1C=CC=C2C([Zr+2])CCC21 DDDRMZMSFMQPPC-UHFFFAOYSA-L 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- DBYQHFPBWKKZAT-UHFFFAOYSA-N lithium;benzene Chemical compound [Li+].C1=CC=[C-]C=C1 DBYQHFPBWKKZAT-UHFFFAOYSA-N 0.000 description 2
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- BIEBZGCKLFWMCR-UHFFFAOYSA-N 2,3,3a,4-tetrahydro-1h-indene Chemical class C1C=CC=C2CCCC21 BIEBZGCKLFWMCR-UHFFFAOYSA-N 0.000 description 1
- KDABDTDIGVTUBT-UHFFFAOYSA-N 2-(4-tert-butylphenyl)-4,5-dihydro-1H-cyclopenta[a]naphthalene Chemical compound C1=CC(C(C)(C)C)=CC=C1C1=CC(CCC2=CC=CC=C22)=C2C1 KDABDTDIGVTUBT-UHFFFAOYSA-N 0.000 description 1
- KZLPHRBSXYGAQN-UHFFFAOYSA-N 2-methyl-4,5-dihydro-3ah-cyclopenta[a]naphthalene Chemical compound C1=CC=C2C3=CC(C)=CC3CCC2=C1 KZLPHRBSXYGAQN-UHFFFAOYSA-N 0.000 description 1
- VYTXLSQVYGNWLV-UHFFFAOYSA-N 4-(2-thienyl)butyric acid Chemical compound OC(=O)CCCC1=CC=CS1 VYTXLSQVYGNWLV-UHFFFAOYSA-N 0.000 description 1
- APLQEOKEPDXWGV-UHFFFAOYSA-N 7-phenyl-5,5a-dihydro-4h-cyclopenta[e][1]benzothiole Chemical compound C=1C2CCC=3SC=CC=3C2=CC=1C1=CC=CC=C1 APLQEOKEPDXWGV-UHFFFAOYSA-N 0.000 description 1
- IXXBOTCOBLYKPV-UHFFFAOYSA-N 8-tert-butyl-2-phenyl-4,5-dihydro-1H-cyclopenta[a]naphthalene Chemical compound C12=CC(C(C)(C)C)=CC=C2CCC(C=2)=C1CC=2C1=CC=CC=C1 IXXBOTCOBLYKPV-UHFFFAOYSA-N 0.000 description 1
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- DWWZPYPYUFXZTL-UHFFFAOYSA-N lithium;2h-inden-2-ide Chemical compound [Li+].C1=CC=C2[CH-]C=CC2=C1 DWWZPYPYUFXZTL-UHFFFAOYSA-N 0.000 description 1
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 239000012041 precatalyst Substances 0.000 description 1
- XOJVVFBFDXDTEG-UHFFFAOYSA-N pristane Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 description 1
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- VGKDLMBJGBXTGI-SJCJKPOMSA-N sertraline Chemical compound C1([C@@H]2CC[C@@H](C3=CC=CC=C32)NC)=CC=C(Cl)C(Cl)=C1 VGKDLMBJGBXTGI-SJCJKPOMSA-N 0.000 description 1
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- 159000000000 sodium salts Chemical class 0.000 description 1
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- 125000001424 substituent group Chemical group 0.000 description 1
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 1
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- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 238000012725 vapour phase polymerization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
- C07F7/0814—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring is substituted at a C ring atom by Si
-
- 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
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
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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
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- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
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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
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- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/0827—Syntheses with formation of a Si-C bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
本发明涉及取代的四氢茚基的合成以及该合成的络合物在乙烯和α-烯烃的均聚和共聚中的用途。
Description
本发明涉及取代的四氢茚基的合成。
C2对称的茂金属催化剂组分可表现为两种立体异构形式:外消旋形式和内消旋形式。立体定向催化剂用于制备有规立构聚烯烃。通常知晓:当将催化剂组分用于烯烃聚合反应时,外消旋形式诱使引入单体的可再现取向。这对于制造全同立构聚烯烃是合乎期望的。
已经尝试避免内消旋异构体的产生或者将所需的外消旋异构体与内消旋异构体分离,但是,分离步骤成本高且已经观察到在纯化之后,在光或者热的作用下,体系中再次引入内消旋异构体。催化剂组分的氢化避免内消旋异构体的形成和/或在光或热的作用下其“再形成”。因而,氢化的茂金属催化剂组分已知可用于烯烃聚合。
在基于桥接双茚基的茂金属的具体范围中,本领域中已知:这些导致形成两种具有不同催化性能的异构茂金属(外消旋和内消旋)。非立体定向的内消旋组分促进不期望的低分子量无规立构聚合物级分的形成,而外消旋组分产生高度有规立构的聚合物级分。此外,从纯的外消旋成分开始,热和光诱使部分的外消旋预催化剂转变为内消旋异构体,从而导致在活化之后以及聚合期间形成较低分子量的“可溶物”。这在乙烯/丙烯共聚物的制造中是特别有害的。
已经观察到:茚基环的氢化使在茂金属合成的最终步骤期间内消旋异构体的产生减少,但是,到目前为止,仅对最终催化剂进行了氢化,而且,对于未取代的双茚基组分,氢化已经成功,对于单取代的双茚基组分,氢化稍有成功。
J.Organomet.Chem.(1982),232,233-247描述了亚乙基双(4,5,6,7-四氢-1-茚基)二氯化钛的合成。这通过使用负载在木炭上的钯的氢化催化剂或PtO2氢化催化剂的亚乙基双(茚基)二氯化钛的氢化进行。该氢化反应据称基本上得到以足够纯的形式的手性化合物。但是,实际上,需要色谱分离以除去非手性的内消旋异构体,该非手性的内消旋异构体占产物的主要部分。
EP-A-344887涉及手性的硅桥接的茂金属催化剂,其使α-烯烃以高的全同立构规整度、以最小量的反转(inversion)和在高的催化剂活性等级下聚合。在实施例1中,制备了化合物1,1′-二甲基亚硅烷基桥接的双(茚基)二氯化锆。此外,通过加入二氯甲烷以及铂黑或氧化铂(IV)制备了该化合物的四氢茚基衍生物。在氢化之后,滤出不溶解的外消旋异构体并使其结晶。类似地,在实施例7中,制备了四甲基二硅氧烷桥接的双(四氢茚基)二氯化锆。
对如上概述的现有技术的状态进行概括,US5883275承认:氢化或部分氢化的茂金属的合成通常从具有芳族配体的相应茂金属开始。其进一步声称:已知的用于使茂金属的芳族配体骨架氢化的合成程序大体上全部遵循相同的路线。将茂金属溶解或悬浮在二氯甲烷中并在铂黑或二氧化铂的存在下在高的氢气压力下氢化。但是,US5883275宣称这些已知程序具有一些缺点。但是,US5883275公开了用于合成氢化茂金属的替代方法。与在先前已知的方法中一样,它们的程序也从具有芳族配体的相应茂金属开始。但是,公开了用于氢化的新方法,其中待在氢化催化剂的存在下用氢气处理的茂金属处于非卤化溶剂中。为了使得使用非常活泼的氢化催化剂以在相对低的氢气压力下进行氢化反应和在高于0℃的温度下工作成为可能,该非卤化溶剂是必要的。
此外,J.Organomet.Chem.,604(2000),12-19报道了将双(茚基)二氯化锆氢化成相应的双(四氢茚基)二氯化锆。但进一步承认:对茚基金属络合物中的六元环进行氢化的能力并不普遍。该文献报道了从“被预先还原”的双(四氢茚基)配体直接合成双(四氢茚基)氯化镧的不同方法。2-甲基-4,5,6,7-四氢茚基锂的合成示于该文献的方案1中。甲硅烷基桥接的双(四氢化茚)的合成示于方案2中。
鉴于以上文献,应当理解:需要进一步且优选改善的用于制造氢化茂金属催化剂组分的方法,所述氢化茂金属催化剂组分优选使α-烯烃聚合至高的全同立构规整度。
本发明的目的在于提供桥接的取代的双四氢茚基催化剂组分的制备方法。
因此,本发明公开取代的双四氢茚基配体的制备方法,包括以下步骤:
a)制备通式I或通式I′的络合物
b)使络合物I或I′与R″Li反应,随后用稀酸进行酸化以分别制备络合物II或络合物II′
c)任选地,在nBuLi的存在下,使络合物II或络合物II′与R* 2SiX2反应以制备配体III或配体III′
其中R、R′、R″、Ra和Rb各自独立地选自氢、或具有最高达10个碳原子的烃基,
其中R*和R**各自独立地选自未取代的或取代的具有最高达8个碳原子的烷基或芳基,包括多核稠合芳环,
其中Y为周期表第13、14、15或16族的金属,
其中X为卤素或具有最高达6个碳原子的烷基,和
其中n为0、1或2。
优选地,不省去步骤c)且存在甲硅烷基桥。
优选地,Ra和Rb相同且为氢。
优选地,n等于0。
优选地,R、R*或R**的至少一个的体积至少与tBu一样大。
本发明的第二方面提供式IV或IV′的氢化茂金属催化剂组分
式IV或IV′的茂金属催化剂组分通过式III或III′的配体的经由式MX′4的金属盐的金属化反应制备,其中,M为周期表第4族的金属且X′为卤素或具有最高达6个碳原子的烷基。
本发明特别涉及柄型(ansa)-茂金属的制备,所述柄型-茂金属包含在环戊二烯基上和/或在苯基片断(fragment)上的带有大体积取代基的茚基。据信,这导致外消旋络合物对于在溶液中的差向异构化的非常高的稳定性。
本发明的第三方面提供包含式IV或IV′的催化剂组分以及具有电离作用的含有铝或硼的活化剂的催化剂体系。
合适的含铝活化剂包括铝氧烷、烷基铝化合物和/或路易斯酸。
可用于本发明的铝氧烷是公知的且优选包括低聚的线型和/或环状的烷基铝氧烷,低聚的线型铝氧烷由式(A)表示:
和低聚的环状铝氧烷由式(B)表示
其中,n为1-40、优选10-20;m为3-40、优选3-20;且R为C1-C8烷基、优选甲基。通常,在由例如三甲基铝和水制备铝氧烷时,获得线型和环状的化合物的混合物。
可有用地在固体负载催化剂的制备中采用的铝氧烷和茂金属的量可在宽范围内变化。通常,铝与过渡金属的摩尔比为200∶1~2000∶1、优选500∶1~1000∶1。
或者如EP-A-0277004(第6页第30行至第7页第7行)中所述的下列通式的那些:
本发明还提供乙烯和α-烯烃的均聚或共聚方法,包括以下步骤:
a)向反应器中注入本发明的活性催化剂体系;
b)向该反应器中注入单体和任选的共聚单体;
c)保持在聚合条件下;
d)收取聚合物。
优选的单体为乙烯和丙烯,且优选的共聚单体为丙烯、1-丁烯和1-己烯。
本发明还提供能通过前述方法获得的聚烯烃。
本发明的催化剂体系可用于任何聚合方法如淤浆聚合、溶液聚合或气相聚合,条件是不损害所需的催化活性。在本发明的优选实施方式中,该催化剂体系用于均相的溶液聚合法、或非均相的淤浆法。在溶液法中,典型的溶剂包括具有4-7个碳原子的烃,例如庚烷、甲苯或环己烷。在淤浆法中,必须将催化剂体系固定在惰性载体上。
使用本发明的氢化催化剂体系制备的聚烯烃与使用它们的非氢化对应物获得的那些相比具有更少的区域缺陷(regio-defect)且更为立构规整。
附图说明
图1表示二氯[3,3′-双(二甲基硅烷二基)二(η5-[2-(3,5-二甲基苯基)-4,5-二氢-3H-环戊二烯并[a]萘-3-基]]锆的在CD2Cl2中的1H NMR谱图。
图2为二氯[3,3′-双(二甲基硅烷二基)二(η5-[2-(3,5-二甲基苯基)-4,5-二氢-3H-环戊二烯并[a]萘-3-基]]锆的分子结构的ORTEP图,其中,热椭球以50%概率水平绘制。
图3表示二氯[3,3′-双(二甲基硅烷二基)二(η5-[2-(4-叔丁基苯基)-4,5-二氢-3H-环戊二烯并[a]萘-3-基]]锆在CD2Cl2中的1H NMR谱图。
图4为二氯[3,3′-双(二甲基硅烷二基)二(η5-[2-(4-叔丁基苯基)-4,5-二氢-3H-环戊二烯并[a]萘-3-基]]锆的分子结构的ORTEP图,其中,热椭球以50%概率水平绘制。
图5表示二氯[3,3′-双(二甲基硅烷二基)二(η5-(8-叔丁基-2-苯基-4,5-二氢-3H-环戊二烯并[a]萘-3-基)]锆的在CD2Cl2中的1H NMR谱图。
图6为二氯[3,3′-双(二甲基硅烷二基)二(η5-(8-叔丁基-2-苯基-4,5-二氢-3H-环戊二烯并[a]萘-3-基)]锆的分子结构的ORTEP图。
图7表示二[η5-(2-苯基-4,5-二氢-3H-环戊二烯并[c]菲-3-基)二氯化锆的在CD2Cl2中的1H NMR谱图。
图8为二[η5-(2-苯基-4,5-二氢-3H-环戊二烯并[c]菲-3-基)二氯化锆的分子结构的ORTEP图。
图9表示二氯[6,6′-双(二甲基硅烷二基)二(η5-(7-苯基-5,6-二氢-4H-茚并[5,4-b]噻吩-6-基)]锆的在CD2Cl2中的1H NMR谱图。
图10为二氯[6,6′-双(二甲基硅烷二基)二(η5-(7-苯基-5,6-二氢-4H-茚并[5,4-b]噻吩-6-基)]锆的分子结构的ORTEP图。
实施例
实施例1
2-(3,5-二甲基苯基)-4,5-二氢-1H-环戊二烯并[a]-萘和2-(3,5-二甲基苯基)
-4,5-二氢-3H-环戊二烯并[a]-萘的制备、以及二氯[3,3′-双(二甲基硅烷二基)
二(η
5
-[2-(3,5-二甲基苯基)-4,5-二氢-3H-环戊二烯并[a]萘-3-基]]锆的制备。
所述制备由以下方案示出:
在0℃的温度下、在二乙醚(Et2O)的存在下,对α-四氢萘酮进行2小时的溴化。其后,在回流下用乙酰乙酸乙酯的钠盐处理4小时,然后,在碱KOH-H2O的存在下、在回流下进行3-氧代-2-(1-氧代-1,2,3,4-四氢化萘-2-基)丁酸乙酯的环化6小时,从而以62%的产率获得所需的环戊烯酮。用MeLi处理该环戊烯酮并使所形成的醇脱水,从而以43%的产率形成2-甲基-4,5-二氢-3aH-环戊二烯并[a]萘。然后,使3,3a,4,5-四氢-2H-环戊二烯并[a]-萘-2-酮与3,5-二甲基苯基锂在醚中反应。该反应混合物的酸化得到配体2-(3,5-二甲基苯基)-4,5-二氢-3H-环戊二烯并[a]-萘和2-(3,5-二甲基苯基)-4,5-二氢-1H-环戊二烯并[a]萘的混合物,产率为66%。
该配体的锂盐在四氢呋喃(THF)中用0.5当量的二氯二甲基硅烷处理以形成相应的双(环戊二烯基)二甲基硅烷。通过在Silica Gel 60上的急骤层析法,从粗产物中以低的产率分离出该双-环戊二烯基配体。所述配体的这些低的形成产率是在柄型-茂金属的合成中所遇到的主要困难。该螯合配体用在甲苯-己烷中的2当量的nBuLi和金属盐ZrCl4(THF)2进行金属化以合成所需的柄型-二茂锆。该混合物在室温下搅拌过夜,然后,通过玻璃粉过滤。收集在-30℃的温度下从滤液沉淀的晶体并且将其在真空中干燥。该结晶沉淀物的NMR谱图表明为纯的外消旋柄型-茂金属。该化合物(在CD2Cl2中)的1H NMR谱图示于图1中。分离该外消旋-络合物,产率为52%,这是由该异构体与其内消旋-对应物相比的高的稳定性引起的。
该柄型-二茂锆成功地由X-射线晶体结构分析表征。图2为包含2-(3,5-二甲基苯基)-4,5-二氢环戊二烯并[a]萘基片断的该络合物的分子结构的ORTEP图,其中,热椭球以50%概率水平绘制。
第一独立分子的关键几何参数如下:
-键长Zr-Cp(c)=2.234(1)埃;
-两个环戊二烯基平面之间的角度=61.0°。
第二独立分子的关键几何参数如下:
-键长Zr-Cp(c)=2.238(1)埃;
-两个环戊二烯基平面之间的角度=59.6°。
这两种独立分子代表相应的外消旋络合物。
实施例2
2-(4-叔丁基苯基)-4,5-二氢-1H-环戊二烯并[a]萘和2-(4-叔丁基苯基)-4,5-
二氢-3H-环戊二烯并[a]萘的制备、以及二氯[3,3′-双(二甲基硅烷二基)二
(η
5
-[2-(4-叔丁基苯基)-4,5-二氢-3H-环戊二烯并[a]萘-3-基]]锆的制备。
如在实施例1中那样进行所述制备,除了在配体制备的最后步骤中,向3,3a,4,5-四氢-2H-环戊二烯并[a]萘-2-酮中加入在醚中的1当量的4-叔丁基苯基锂,随后对该反应混合物进行酸化之外。最终配体为以76%的产率获得的2-(4-叔丁基苯基)-4,5-二氢-3H-环戊二烯并[a]萘和2-(4-叔丁基苯基)-4,5-二氢-1H-环戊二烯并[a]萘的混合物,如在以下方案中所示。
这些配体的锂盐在THF中用0.5当量的二氯二甲基硅烷处理以形成相应的双(环戊二烯基)二甲基硅烷。通过在Silica Gel 60上的急骤层析法,从粗产物中以低的产率分离出该双-环戊二烯基配体混合物。接着,该螯合配体用在甲苯-己烷中的2当量的nBuLi和金属盐ZrCl4(THF)2进行金属化。该混合物在室温下搅拌过夜,然后,通过玻璃粉过滤。收集在-30℃下从滤液沉淀的晶体并且将其在真空中干燥。基于NMR谱的证据,该结晶沉淀物是纯的内消旋柄型-茂金属。该化合物(在CD2Cl2中)的1H NMR谱图示于图3中。分离该内消旋-络合物,产率为16%。
该内消旋-络合物由X-射线晶体结构分析表征。其分子结构的ORTEP图可参见图4。该结构的关键几何参数如下:
-键长Zr-Cp(c)和Zr-Cp(c)′分别为2.234(1)埃和2.237(1)埃;
-键角Cp(c)-Zr-Cp(c)′为127.6°。
实施例3
2-苯基-8-叔丁基-4,5-二氢-1H-环戊二烯并[a]萘和2-苯基-8-叔丁基-4,5-
二氢-3H-环戊二烯并[a]萘的制备、以及二氯[3,3′-双(二甲基硅烷二基)二
(η
5
-(8-叔丁基-2-苯基-4,5-二氢-3H-环戊二烯并[a]萘-3-基)]锆的制备。
所述制备描述于以下方案中。
对起始材料叔丁基苯进行酰化以形成酮酸,随后,对该酮酸进行还原。然后,在AlCl3的存在下进行所得产物的环化以获得7-叔丁基-3,4-二氢化萘-1(2H)-酮且总产率为39%。对该产物进行溴化、随后进行烷基化、并在含水KOH中进行环化,得到8-叔丁基-3,3a,4,5-四氢-2H-环戊二烯并[a]萘-2-酮和7-叔丁基-2-(2-氧代丙基)-3,4-二氢化萘-1(2H)-酮的比例为1/3.5的混合物。分离不期望的7-叔丁基-2-(2-氧代丙基)-3,4-二氢化萘-1(2H)-酮并在含醇的KOH中进行处理,从而以中等(moderate)产率获得所需的8-叔丁基-3,3a,4,5-四氢-2H-环戊二烯并[a]萘-2-酮。使8-叔丁基-3,3a,4,5-四氢-2H-环戊二烯并[a]萘-2-酮在醚中与1当量的PhLi进一步反应,随后进行反应介质的酸化以获得2-苯基-8-叔丁基-4,5-二氢-1H-环戊二烯并[a]萘和2-苯基-8-叔丁基-4,5-二氢-3H-环戊二烯并[a]萘的混合物,如以下方案中所示。
该配体的锂盐在THF中用0.5当量的Me2SiCl2处理以形成相应的双(环戊二烯基)二甲基硅烷。重复在Silica Gel 60上的急骤层析法,从粗产物中以18%的产率分离出该双-环戊二烯基配体。将其用在甲苯-己烷中的2当量的nBuLi然后用金属盐ZrCl4(THF)2进行金属化。该混合物在室温下搅拌过夜,然后,通过玻璃粉过滤。收集在-30℃的温度下从滤液沉淀的晶体并且将其在真空中干燥。基于1H NMR谱的证据,以21%的产率分离的该产物是外消旋-络合物和内消旋-络合物的比例为1∶4的混合物。该1H NMR谱图示于图5中。该内消旋-异构体由X-射线晶体结构分析表征。图6为该内消旋-络合物的分子结构的ORTEP图,其中热椭球以50%概率水平绘制。
该结构的关键几何参数为:
-键长Zr-Cp(c)和Zr-Cp(c)′分别为2.222(1)埃和2.221(1)埃;
-两个环戊二烯基平面之间的角度为56.4°。
实施例4
3,3a,4,5-四氢-2H-环戊二烯并[c]-菲-2-酮的制备和二[η
5
-(2-苯基-4,5-二氢
-3H-环戊二烯并[c]菲-3-基)二氯化锆的制备。
从萘开始并按照类似于实施例3的如下所示的方案制备该络合物。
该螯合配体用在甲苯-己烷中的2当量的nBuLi并随后加入金属盐ZrCl4(THF)2进行金属化以形成未桥接的金属络合物。
该外消旋-络合物通过如图7中所示的NMR谱并通过X-射线晶体结构分析清楚地表征。
图8为该外消旋络合物的分子结构的ORTEP图,其中,热椭球以50%概率水平绘制。该结构的关键几何参数为:
-Zr-Cp(c)和Zr-Cp(c)′的键长分别为2.229(2)埃和2.244(2)埃;
-Zr-Cp(A)与Zr-Cp′(A)轴之间的角度为132.70(6)°,
-Cp平面与Cp′平面之间的角度为50.91(6)°。
观察到,通过非常大体积的取代基的存在,该未桥接的金属络合物中的旋转受阻。
实施例5
二氯[6,6′-双(二甲基硅烷二基)二(η
5
-(7-苯基-5,6-二氢-4H-茚并[5,4-b]噻
吩-6-基)]锆的制备
所述制备描述于以下方案中。
通过如下获得6,7-二氢-1-苯并噻吩-4(5H)-酮,总产率为43%:以琥珀酸酐对噻吩进行酰化,随后对所形成的酮进行还原和在Iaton试剂的存在下对4-(2-噻吩基)丁酸进行环化。接着,由6,7-二氢-1-苯并噻吩-4(5H)-酮合成4,5,5a,6-四氢-7H-茚并[5,4-b]噻吩-7-酮,总产率为30%。使4,5,5a,6-四氢-7H-茚并[5,4-b]噻吩-7-酮在醚中与1当量的PhLi进一步反应,随后进行反应介质的酸化以获得7-苯基-5,5a-二氢-4H-茚并[5,4-b]噻吩和7-苯基-5,8-二氢-4H-茚并[5,4-b]噻吩的混合物,如以下方案中所示。
该配体的锂盐在THF中用0.5当量的Me2SiCl2处理以形成相应的双(环戊二烯基)二甲基硅烷。通过重复在Silica Gel 60上的急骤层析法,将该双-环戊二烯基配体作为包含约70%所需异构体的Me2Si-桥接配体的混合物分离,产率为17%。对其用在甲苯-己烷中的2当量的nBuLi并然后用金属盐ZrCl4(THF)2进行金属化。该混合物在室温下搅拌过夜,然后,通过玻璃粉过滤。收集在-30℃的温度下从滤液沉淀的晶体并且将其在真空中干燥。基于1H NMR谱的证据,以13%的产率分离的该产物是外消旋-络合物和内消旋-络合物的比例为1∶5的混合物。该1H NMR谱图示于图9中。该内消旋-异构体由X-射线晶体结构分析表征。图10为该内消旋-络合物的分子结构的ORTEP图,其中热椭球以50%概率水平绘制。
该结构的关键几何参数为:
-键长Zr-Cp(c)和Zr-Cp(c)′为2.239(1)埃;
-两个环戊二烯基平面之间的角度为59.2°。
Claims (10)
2.权利要求1的方法,其中,存在步骤c)。
3.权利要求1或2的方法,其中,Ra和Rb相同且为氢。
4.前述权利要求中任一项的方法,其中,R、R*或R**的至少一个的体积至少与叔丁基一样大。
5.前述权利要求中任一项的方法,其中,n为0。
6.通过权利要求1-5中任一项的方法获得的式III或式III′的配体。
8.活性催化剂体系,其包含权利要求7的茂金属催化剂组分和选自铝氧烷、烷基铝化合物、路易斯酸、或其组合的具有电离作用的活化剂。
9.乙烯和α-烯烃的均聚或共聚方法,包括以下步骤:
a)向反应器中注入权利要求8的活性催化剂体系;
b)向该反应器中注入单体和任选的共聚单体;
c)保持在聚合条件下;
d)收取聚合物。
10.权利要求9的方法,其中,所述单体为乙烯或丙烯且所述共聚单体为丙烯、1-丁烯和1-己烯。
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