CN1066736C - 桥接的环戊二烯基衍生物和它们的制备方法 - Google Patents
桥接的环戊二烯基衍生物和它们的制备方法 Download PDFInfo
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- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims description 28
- 238000002360 preparation method Methods 0.000 title claims description 14
- -1 hydrocarbyl radical Chemical class 0.000 claims abstract description 46
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 25
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 38
- 229930195733 hydrocarbon Natural products 0.000 claims description 23
- 150000002430 hydrocarbons Chemical class 0.000 claims description 23
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 17
- 239000004215 Carbon black (E152) Substances 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 10
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims description 8
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 4
- PGTKVMVZBBZCKQ-UHFFFAOYSA-N Fulvene Chemical compound C=C1C=CC=C1 PGTKVMVZBBZCKQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 150000003509 tertiary alcohols Chemical class 0.000 claims description 3
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 2
- 239000003513 alkali Substances 0.000 claims 1
- 150000003254 radicals Chemical class 0.000 abstract description 3
- HPYIUKIBUJFXII-UHFFFAOYSA-N Cyclopentadienyl radical Chemical compound [CH]1C=CC=C1 HPYIUKIBUJFXII-UHFFFAOYSA-N 0.000 abstract 1
- 230000001588 bifunctional effect Effects 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 description 33
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 150000002431 hydrogen Chemical class 0.000 description 11
- HYPABJGVBDSCIT-UHFFFAOYSA-N cyclododecene Chemical compound C1CCCCCC=CCCCC1 HYPABJGVBDSCIT-UHFFFAOYSA-N 0.000 description 9
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- 239000004913 cyclooctene Substances 0.000 description 8
- 239000003446 ligand Substances 0.000 description 7
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- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical class C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
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- 229910003002 lithium salt Inorganic materials 0.000 description 4
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HYPABJGVBDSCIT-UPHRSURJSA-N cyclododecene Chemical compound C1CCCCC\C=C/CCCC1 HYPABJGVBDSCIT-UPHRSURJSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical group CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 description 1
- WZMBDCNQLGWPRC-UHFFFAOYSA-N C[SiH](C)C1C=C2CCCCCCCCCCC2=C1 Chemical compound C[SiH](C)C1C=C2CCCCCCCCCCC2=C1 WZMBDCNQLGWPRC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QFHMNFAUXJAINK-UHFFFAOYSA-N [1-(carbamoylamino)-2-methylpropyl]urea Chemical group NC(=O)NC(C(C)C)NC(N)=O QFHMNFAUXJAINK-UHFFFAOYSA-N 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 238000002512 chemotherapy Methods 0.000 description 1
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- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- FNIATMYXUPOJRW-UHFFFAOYSA-N cyclohexylidene Chemical group [C]1CCCCC1 FNIATMYXUPOJRW-UHFFFAOYSA-N 0.000 description 1
- PWAPCRSSMCLZHG-UHFFFAOYSA-N cyclopentylidene Chemical group [C]1CCCC1 PWAPCRSSMCLZHG-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000003756 stirring Methods 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
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- VIPCDVWYAADTGR-UHFFFAOYSA-N trimethyl(methylsilyl)silane Chemical compound C[SiH2][Si](C)(C)C VIPCDVWYAADTGR-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
- C07C13/62—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with more than three condensed rings
- C07C13/64—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with more than three condensed rings with a bridged ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
- C07C13/54—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings
- C07C13/605—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings with a bridged ring system
- C07C13/61—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings with a bridged ring system with a bridged indene ring, e.g. dicyclopentadiene
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/14—All rings being cycloaliphatic
- C07C2602/22—All rings being cycloaliphatic the ring system containing eight carbon atoms, e.g. pentalene
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/14—All rings being cycloaliphatic
- C07C2602/24—All rings being cycloaliphatic the ring system containing nine carbon atoms, e.g. perhydroindane
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/14—All rings being cycloaliphatic
- C07C2602/26—All rings being cycloaliphatic the ring system containing ten carbon atoms
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/14—All rings being cycloaliphatic
- C07C2602/32—All rings being cycloaliphatic the ring system containing at least eleven carbon atoms
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Abstract
具有以下通式(Ⅰ)的桥接的环戊二烯基衍生物:
A-X-B(Ⅰ)
其中
1)A是具有以下通式(Ⅱ)的单官能化烃基
2)-X-是在A和B之间的桥接基并由选自亚烷基、亚硅烷基、烷基取代的亚硅碳烷基、亚硅氧烷硅烷基的双官能度基团组成;
3)B是选自以下基团的单官能度烃基;
(e)以上定义的A基团中的任何一个;
(F)环戊二烯基。
Description
本发明涉及新型的桥接的环戊二烯基类型化合物和它们的制备方法。
α-烯烃的均聚和共聚合反应的最有用的可溶性催化剂已知是由有双茚基、双芴基类型或混合型(如芴基环戊二烯基配位体)配位体的锆或钛的配合物组成(P.c.Mohring,N.J.Coville,J.Organomet.Chem.479,1,1994)。
配位体能够是桥接的或非桥接的。尤其就高分子量来说,用桥接的配位体可获得最佳结果,(参见J.C.W.Chien and D.He,Journal ofPolymer Science,Part A:Polymer Chemistry,Vol.29(1991),PP1585)。
四氢茚基衍生物比相应的不饱和衍生物更有效,尤其在引入共聚单体和第三种单体方面,因而目前属于最广泛选择的催化剂。
然而,有一个问题,尽管茚基和芴基类型的配位体易获得,但相应的四氢茚基衍生物是由锆配合物的直接氢化获得的,很难化学选择性氢化起始配位体。
有锆的配合物的氢化方法具有各种缺点。事实上,正如几个专家所指出的那样(参见E.Samuel,Bull.Soc.Chim.Fr,3548,1966和S.Collins等人,J.Organometallic Chem.,342,21,1988),在进行这一氢化方法时有许多困难,归因于低产率和/或激烈的条件。还有,锆的茚基配合物的氢化方法产生两种相同的四氢茚基类型的配位体;事实上不可能用这一方法获得有一个四氢茚基和一个茚基配位体的非对称配合物。
现已发现新型的桥接环戊二烯基衍生物,它们克服了上述缺点,是由于这样的事实:由于它们结构上的原因,它们不需要上述氢化步骤。
据此,本发明涉及具有以下通式(Ⅰ)的环戊二烯基的桥接衍生物:
A-X-B (Ⅰ)其中
1)A是具有以下通式(Ⅱ)的单官能化烃基其中R和R*选自:-H,-具有1-3个碳原子的单官能度烷基,-单官能度的烷基芳基或芳基,前提条件是:-不同于H的R的数目不超过2;-至少一个R*是H;优选地,所有R=H和R*是选自H和CH3;
2)n是整数2-20,并优选地选自3,4,5,6,10;
3)-X-是在A和B之间的桥接基和由选自以下基团的双官能度基团组成:a)直链的,支链的或环状的C2-C20亚烷基;b)具有1-2个硅原子的、烷基或芳基取代的亚硅烷基;c)烷基取代的亚硅碳烷基(silalkylene);d)亚硅氧烷硅烷基(siloxasilanylene)或-Si(R1)2-O-Si(R2)2-四烷基或四芳基取代;
4)B是选自以下基团的单官能度烃基:(e)以上定义的A基团中的任何一个;(f)环戊二烯基。
基团A是单官能度环戊二烯基,它的相对应的烃类(下面简单称作AH)已描述在待审查的专利申请IT-A-MI 95A 002707。两R*=H的烃AH的典型实例在表1中指定。通过使用Beilstein Institute-BeilsteinInformation System的Autonom程序获得以上烃类的名称并且碳原子数与通式(Ⅱa)中一样:
在一实施方案中,烃类AH,和因而相应的单官能度烃基A,选自:-2,4,5,6,7,8-六氢甘菊环(R*=R=H和n=5),-4,5,6,7,8,9-六氢-2H-环戊二烯并环辛烯(R*=R=H和n=6),-4,5,6,7,8,9,10,11,12,13-十氢-2H-环戊二烯并环十二碳烯(R*=R=H和n=10),-1-甲基-4,5,6,7,8,9,10,11,12,13-十氢-2H-环戊二烯并环十二碳烯(R*=CH3,R=H和n=10)。
在一个实施方案中,-X-是直链、支链或环状的具有2-20个碳原子的亚烷基。直链-X-的典型实例是亚乙基,亚丙基,亚丁基,亚戊基,亚己基。支链-X-的典型实例是亚异丙基(CH3-C-CH3),亚异丁基(CH3-C-C2H5),3-亚戊基(C2H5-C-C2H5),二苯基亚甲基(C6H5-C-C6H5)。环状亚烷基-X-的典型实例是亚环丁基,亚环戊基和亚环己基。
在另一实施方案中,-X-是具有1-2个硅原子的、烷基或芳基取代的亚硅烷基,例如二甲基亚硅烷基,或-Si(CH3)2-,二乙基亚硅烷基,四甲基二亚硅烷基,或-Si(CH3)2-Si(CH3)2,二甲基二乙基二亚硅烷基,优选二甲基亚硅烷基。
在实施方案的另一种形式中,-X-基团由硅-碳序列组成,即烷基取代的亚硅碳烷基,例如-Si(R’)2-C(R”)2-,其中R’是低级烷基和R”是氢或低级烷基。亚硅碳烷基的典型实例是:-1-硅杂-1,1-二甲基亚乙基,-2-硅杂-2,2-二甲基亚丙基,-1,3-二硅杂-1,1,3,3-四甲基亚丙基。
在另一实施方案中,基团X是四烷基或四芳基取代的硅氧烷基亚硅烷基,即-Si(R1)2-O-Si(R2)2,其中R1和R2相同或不同,可以是烷基或芳基。
在优选的实施方案中,-X-是选自直链或支链亚烷基衍生物和二烷基亚硅烷基,甚至更优选地,它选自亚乙基、亚异丙基和二甲基亚硅烷基。
至于B,这是选自以下基团的单官能度烃基:
(e)以上所定义的A基团的任何一种,
(f)环戊二烯基。
当B等同于以上所定义的A衍生物中任何一种时,具有通式(Ⅰ)的产物由两个相同或不同的、从桥基-X-连接于各自的2位的环戊二烯基A衍生物组成。
我们称这些结构为A-X-A’,其中A和A’可以相同或不同,都具有通式(Ⅱ),需要说明的是,在桥接产物A-X-A’中,环戊二烯基环的双键能够在3,3a-和1,(n+3)a-位或在1,2-和3a,(n+3)a-位被取代,其中n具有以上的定义和在通式(Ⅱa)中给出的位数是从上述Autonom程序获得的。
其中A’与A相同或不同的A-X-A’结构的典型实例在表2a,2b,2c,2d中指定。
当B不属于具有通式(Ⅱ)的烃基时,B是单官能度环戊二烯基(f),该(f)选自环戊二烯基,茚基,芴基和相关的烷基、芳基、三烷基甲硅烷基取代的衍生物;优选地,(f)是选自环戊二烯基,茚基和芴基。为简便起见,我们称这些化合物为A-X-C。
应该注意的是,正如以上对于A-X-A’产物所说明的,在桥接产物A-X-C中,烃基A的环戊二烯基环的双键能够在3,3a-和1,(n+3)a-位或在1,2-和3a,(n+3)a-位被取代,其中n具有以上的定义和在通式Ⅱa中给出的位数是从上述Autonom程序获得的。我们称对应于单官能度环戊二烯基(f)的烃类为FH。
连接于以上环戊二烯基衍生物(f)的桥基-X-的连接点是通常在已知技术中获得的那些。例如,茚在1位被连接于桥基-X-和芴仅仅连接于5-员环(5-term cycle)的非稠合位。
表3a-3d提供了A-X-C类型结构的实例,其中C是单官能度环戊二烯基(f)的任何一种。
本发明的再一目的涉及具有通式(Ⅰ)的化合物的制备方法,其中-X-选自支链或环状亚烷基衍生物和选自二烷基取代的亚硅烷基。
上述化合物是从所定义的烃类A-H(即从对应于具有式Ⅱa的基团A的烃类)开始和使用一种方法(该方法根据-X-的结构来改变)来制备的。
当-X-是R3-C-R4类型的二官能度衍生物,其中R3和R4是选自单官能度C1-C5烷基,苯基,或R3和R4连接在一起形成C4-C5亚烷基,该分两步进行。
据此,本发明涉及具有通式A-X-B的化合物的制备方法,其中A和B具有以上定义和-X-是R3-C-R4类型的基团,其中R3和R4具有以上意义,它包括以下步骤:
ⅱ)烃BH加成到在步骤(ⅰ)中获得的富烯化合物,以上烃BH是选自烃类AH和以上定义的FH中的任何一种。
上述反应的步骤(ⅰ)在碱性环境中进行,优选使用叔醇的醇化物,甚至更优选使用叔丁醇钾。
上述反应的步骤(ⅱ)优选通过如下来进行:制备烃BH的阴离子和随后让该阴离子与在步骤(ⅰ)中获得的产物(Ⅲ)发生相互作用。
应该指出的是,上述方法使得这样的化合物的制备成为可能,其中-X-形成了在基团A(总是在2位)和环戊二烯基B(在已知技术所规定的位置)之间的桥基。
本发明的又一目的涉及具有通式(Ⅲ)的富烯类型的中间体,其中n,R,R*,R3和R4具有以上定义;优选地,R=H,R*选自H和CH3,R3=R4=CH3或C6H5,n选自3,4,5,6,10。
本发明的另一目的涉及获得通式Al-X-Al的化合物的方法,其中X是二烷基亚硅烷基,和Al基相互相同,是选自以上定义的A基团,该方法包括烃AlH与二烷基二卤硅烷(优选二烷基二氯硅烷)按AlH/二烷基二卤硅烷摩尔比约2/1的反应。
在一优选的实施方案中,该方法是通过如下进行的:通过制备烃AlH的阴离子,优选使用烷基锂,和让如此制备的阴离子与二卤硅烷发生相互作用。
本发明的再一目的涉及获得通式Al-X-B的化合物的方法,其中:
-X-是二烷基亚硅烷基;
A1是选自以上定义的A基团的单官能度烃基;
B是选自:-A2,其中A2是以上定义的基团A中的任何一种,前提是它不同于A1,-环戊二烯基(f),
以上方法分两步进行,第一步(步骤a)包括化合物AlH与二烷基二卤硅烷(优选二烷基二氯硅烷)按AlH/二烷基二卤硅烷摩尔比约1/1的反应;第二步包括在步骤(a)中获得的化合物与烃BH按基本上与在步骤(a)中获得的产物等摩尔比的反应。
在一优选的实施方案中,该方法如下进行:制备烃AlH的阴离子,优选使用烷基锂,和随后,在第一步中,上述阴离子与二卤硅烷基本上按1/1的摩尔比进行反应。在第二步中,制备烃BH的阴离子,优选使用烷基锂,和以上阴离子与在第一步获得的化合物按摩尔比约1/1进行反应。
下面的实施例是为了更好地说明本发明。
实施例1-双(2,4,5,6,7,8-六氢甘菊环-2-基)二甲基硅烷的合成
在室温下将12ml的正丁基锂在己烷中的2.5M溶液加入到一种在100ml THF中含有4.1g(0.03摩尔)2,4,5,6,7,8-六氢甘菊环(按照在同一申请人的IT-A-MI 95A 002707的待审查专利申请中描述的方法制得)的溶液中。这是一个放热反应,形成白色固体。混合物在搅拌下放置2小时,然后冷却至-70℃和经约20分钟的时间加入1.93g(0.015摩尔)二甲基二氯硅烷。在整夜中任温度上升,最终获得一黄色溶液。
在蒸发溶剂之后,产物通过用石油醚洗脱,在硅胶柱上提纯。
所获得的产物被起始二烯烃污染,通过在机械真空下保持该级分24小时而将二烯烃除去。
获得2.2g产物(45%收率),经NMR和GC分析表明它是纯净的。
1H-NMR谱(CDCl3,相对于TMS的ppm)如下:6.03(bs,4H),3.07(bs,2H),2.50(m,8H),1.90-1.50(bs,12H),-0.2(s,6H)。
实施例2-2-[1H-茚-1-基)-1-甲基-乙基]-1,4,5,6,7,8-六氢-甘菊环的合成。
在10ml MeOH和10ml丙酮中制备4.5g(0.033摩尔)2,4,5,6,7,8-六氢甘菊环和0.3g叔丁醇钾的溶液。以上溶液在回流温度下保持20小时,在这段时间结束后,再加入2.7g的叔丁醇钾。混合物在回流温度再保持25小时,在这段时间结束后将混合物倾入水中并用乙醚萃取。
在中和和脱水之后,蒸发乙醚萃取液,残余物通过在硅胶柱上用石油醚洗脱来提纯。
获得3.8g黄色固体形式的富烯衍生物2-亚异丙基-2,4,5,6,7,8-六氢-甘菊环(66%收率)。这一化合物的1H-NMR谱(CDCl3,相对于TMS的ppm)如下:6.13(s,2H),2.47(m,4H),2.09(s,6H),1.64(m,6H)。
制备茚(4.0g,0.034摩尔)的醚溶液(100ml)。添加12ml的丁基锂在己烷中的2.5M溶液,混合物在搅拌下保持3小时。
然后将富烯衍生物加入到以上溶液,冷却至-70℃。任温度上升和混合物在搅拌下保持48小时。
然后让反应混合物在水中水解并用乙醚萃取,在蒸发之后,得到一种固体,在硅胶柱上用作为洗脱液的石油醚加以提纯。
获得4.5g的产物(74%收率)。
它的1H-NMR谱(CDCl3,相对于TMS的ppm)如下:7.4-7.0(m,4H),6.8(dd,11H),6.45(dd,11H),5.95(s,1H),3.60(bs,1H),3.10(bs,2H),2.40(m,6H),1.23(s,3H),0.94(s,3H)。
实施例3-双(十氢环戊二烯并环十二烯-2-基)二甲基硅烷的合成。
将22ml的在己烷中的2.5M BuLi溶液加入到11g的4,5,6,7,8,9,10,11,12,13-十氢-2H-环戊二烯并环十二烯(按照在同一申请人的IT-A-MI95A 002707的待审查专利申请中描述的方法制得)在100ml戊烷中的溶液中。混合物在搅拌下过夜,所获得的固体经过滤和干燥,获得9.0g相应的锂盐。
在THF(100ml)中制备3.4g(0.16摩尔)以上锂盐的溶液。
在-70℃下经约20分钟,向在THF中的这一溶液添加1.0g(0.008摩尔)的二甲基二氯硅烷。在整夜中任温度上升,最终获得黄色溶液。
在溶剂蒸发之后,添加乙醚,混合物用稀盐酸水解。乙醚萃取液被洗涤至中性,干燥和蒸发。残余物在硅胶柱上用石油醚洗脱加以提纯。
获得2.2g(62%收率)的产物,经NMR分析证明是双(4,5,6,7,8,9,10,11,12,13-十氢-2H-环戊二烯并环十二烯-2-基)二甲基硅烷的混合物。1H-NMR(CDCl3,相对于TMS的ppm):6.62(s),6.39(bs),6.21(bs),6.12(bs),3.23(m),2.91(s),2.35(m),1.88-0.84(m),0.08(bs),-0.21(bs)。
13C-NMR(CDCl3,相对于TMS的ppm):153.35,146.07,146.02,141.49,141.04,138.44,132.29,132.01,127.09,125.09,124.89,121.46,61.37,46.25,39.49,32.30,30.96,30.76,28.94,28.90,24.30。
实施例4-1,2-双-(1-甲基-4,5,6,7,8,9,10,11,12,13-十氢-2-H-环戊二烯并环十二烯-2-基)-二甲基硅烷的合成。
将28ml(70.10-3摩尔)BuLi在己烷中的溶液加入到已用100ml戊烷稀释的15.1g(69.2.10-3摩尔)1-甲基-4,5,6,7,8,9,10,11,12,13-十氢-2H-环戊二烯并环十二烯(按照在IT-A-MI 95A 002707中的实施例4制得)。混合物搅拌过夜,然后过滤。分离固体并干燥:获得12g的相应的锂盐。
向5.6g(25.7.10-3摩尔)的以上锂盐(已溶于100ml无水THF并冷却至-70℃)中加入1.7g(13.2.10-3摩尔)二氯硅烷;在一夜的时间内让温度升高至20℃,在蒸发溶剂剂后添加乙醚,反应混合物用稀HCl水解。有机相被洗涤至中性,干燥和蒸发。残余物在硅胶柱上用石油醚洗脱加以提纯。
获得3.5g(55%收率)的1,2-双-(1-甲基-4,5,6,7,8,9,10,11,12,13-十氢-2-H-环戊二烯并环十二烯-2-基)-二甲基硅烷。
表1
1,2-双-(2,4,5,6-四氢并环戊二烯-2-基)乙烷1,2-双-(2,4,5,6,7,8-六氢甘菊环-2-基)乙烷1,2-双-(4,5,6,7,8,9-六氢-2H-环戊二烯并环辛烯-2-基)乙烷1,1-双-(2,4,5,6,7,8-六氢甘菊环-2-基)-1-甲基-乙烷1,1-双-(4,5,6,7,8,9-六氢-2H-环戊二烯并环辛烯-2-基)-1-甲基-乙烷双-(2,4,5,6-四氢并环戊二烯-2-基)二甲基硅烷双-(2,4,5,6,7,8-六氢甘菊环-2-基)二甲基硅烷1,2-双-[1,1,2-三甲基-(2,4,5,6,7,8-六氢甘菊环-2-基)]丙烷
表2a
2-[二甲基-(2,4,5,6-四氢-并环戊二烯-2-基)-甲硅烷基]-2,4,5,6,7,8-六氢-甘菊环2-[2-(2,4,5,6-四氢-并环戊二烯-2-基)-乙基]-2,4,5,6,7,8-六氢-甘菊环2-[1-甲基-1-(2,4,5,6-四氢-并环戊二烯-2-基)-乙基]-2,4,5,6,7,8-六氢-甘菊环2-[二甲基-(4,5,6,7-四氢-2H-茚-2-基)-甲硅烷基]-2,4,5,6,7,8-六氢-甘菊环2-[1-甲基-1-(4,5,6,7-四氢-2H-茚-2-基)-乙基]-2,4,5,6,7,8-六氢-甘菊环2-[二甲基-(2,4,5,6-四氢-并环戊二烯-2-基)甲硅烷基]-4,5,6,7,8,9-六氢-2H-环戊二烯并环辛烯2-[1-(2,4,5,6,7,8-六氢-甘菊环-2-基)-1-甲基-乙基]-4,5,6,7,8,9-六氢-2H-环戊二烯并环辛烯2-[(2,4,5,6,7,8-六氢-甘菊环-2-基)-二甲基-甲硅烷基]-4,5,6,7,8,9-六氢-2H-环戊二烯并环辛烯2-[(2,4,5,6,7,8-六氢-甘菊环-2-基)-二甲基-甲硅烷基]-4,5,6,7,8,9,10,11,12,13-十氢-2H-环戊二烯并环十二烯2-[1-(2,4,5,6,7,8-六氢-甘菊环-2-基)-1-甲基-乙基]-4,5,6,7,8,9,10,11,12,13-十氢-2H-环戊二烯并环十二烯2-[1-甲基-1-(2,4,5,6-四氢-并环戊二烯-2-基)-乙基]-4,5,6,7,8,9,10,11,12,13-十氢-2H-环戊二烯并环十二烯
表2b
2-[二甲基-(2,4,5,6-四氢-并环戊二烯-2-基)-甲硅烷基]-4,5,6,7,8,9,10,11,12,13-十氢-2H-环戊二烯并环十二烯2-[(4,5,6,7,8,-六氢-2H-环戊二烯并环辛烯-2-基)-二甲基-甲硅烷基]-4,5,6,7,8,9,10,11,12,13-十氢-2H-环戊二烯并环十二烯2-[1-(4,5,6,7,8,9-六氢-2H-环戊二烯并环辛烯-2-基)-1-甲基-乙基]-4,5,6,7,8,9,10,11,12,13-十氢-2H-环戊二烯并环十二烯2-[1-(4,5,6,7,8,9-六氢-2H-环戊二烯并环辛烯-2-基)-1-苯基-乙基]-4,5,6,7,8,9,10,11,12,13-十氢-2H-环戊二烯并环十二烯2-[1-甲基-1-(2,4,5,6-四氢-并环戊二烯-2-基)-乙基]-4,5,6,7,8,9-六氢-2H-环戊二烯并环辛烯2-[(4,5,6,7,8,9-六氢-2H-环戊二烯并环辛烯-2-基)-二苯基-甲基]-4,5,6,7,8,9,10,11,12,13-十氢-2H-环戊二烯并环十二烯2-[2-(2,4,5,6,7,8-六氢-甘菊环-2-基)-乙基]-4,5,6,7,8,9-六氢-2H-环戊二烯并环辛烯2-[2-(4,5,6,7,8,9-六氢-2H-环戊二烯并环辛烯-2-基)-乙基]-4,5,6,7,8,9,10,11,12,13-十氢-2H-环戊二烯并环十二烯2-[2-(2,4,5,6-四氢-并环戊二烯-2-基)-乙基]-4,5,6,7,8,9-六氢-2H-环戊二烯并环辛烯
表2c
双-(1-甲基-2,4,5,6,7,8-六氢甘菊环-2-基)二甲基硅烷双-(1-甲基-4,5,6,7,8,9-六氢-2H-环戊二烯并环辛烯-2-基)二甲基硅烷1,1-双-(1-甲基-2,4,5,6,7,8-六氢甘菊环-2-基)-1-甲基-乙烷1,1,-双-(1-甲基-4,5,6,7,8,9-六氢-2H-环戊二烯并环辛烯-2-基)-1-甲基-乙烷1,2-双-(1-甲基-2,4,5,6,7,8-六氢甘菊环-2-基)四甲基二硅烷双-(1-甲基-4,5,6,7,8,9,10,11,12,13-十氢-2H-环戊二烯并环十二烯-2-基)-二甲基硅烷
表2d
2-(1-环戊-2,4-二烯基-1-甲基-乙基)-2,4,5,6,7,8-六氢甘菊环2-(环戊-2,4-二烯基-二甲基-甲硅烷基)-2,4,5,6,7,8-六氢-甘菊环2-(2-环戊-2,4-二烯基-乙基)-2,4,5,6,7,8-六氢甘菊环2-(2-环戊-2,4-二烯基-1,1,2-三甲基-丙基)-2,4,5,6,7,8-六氢甘菊环2-[二甲基-(3-甲基-环戊-2,4-二烯基)-甲硅烷基]-2,4,5,6,7,8-六氢甘菊环2-[1-甲基-1-(3-甲基-环戊-2,4-二烯基)-乙基]-2,4,5,6,7,8-六氢甘菊环2-[1-(3-叔丁基-环戊-2,4-二烯基-1-甲基-乙基)-2,4,5,6,7,8-六氢甘菊环2-[1-(1-甲基-1-(3-三甲基甲硅烷基-环戊-2,4-二烯基)-乙基]-2,4,5,6,7,8-六氢甘菊环
表3a
2-[二甲基-(3-三甲基甲硅烷基-环戊-2,4-二烯基)-甲硅烷基]-2,4,5,6,7,8-六氢甘菊环2-[1-甲基-1-(2,3,4,5-四甲基-环戊-2,4-二烯基)-乙基]-2,4,5,6,7,8-六氢甘菊环2-[二甲基-(2,3,4,5-四甲基-环戊-2,4-二烯基)-甲硅烷基]-2,4,5,6,7,8-六氢甘菊环2-[2-(2,3,4,5-四甲基-环戊-2,4-二烯基)-乙基]-2,4,5,6,7,8-六氢甘菊环2-[1,1,2-三甲基-2-(2,3,4,5-四甲基-环戊-2,4-二烯基)-丙基]-2,4,5,6,7,8-六氢甘菊环2-[1-(1H-茚-1-基)-1-甲基-乙基]-1,4,5,6,7,8-六氢甘菊环2-[2-(1H-茚-1-基)-1,1,2-三甲基-丙基]-2,4,5,6,7,8-六氢甘菊环
表3b
2-[2-(1H-茚-1-基)-乙基]-2,4,5,6,7,8-六氢甘菊环2-[1-甲基-1-(4-甲基-1H-茚-1-基)-乙基]-1,4,5,6,7,8-六氢甘菊环2-[(4,7-二甲基-1H-茚-1-基)-二甲基-甲硅烷基]-2,4,5,6,7,8-六氢甘菊环2-[1-(4,7-二甲基-1H-茚-1-基)-1-甲基-乙基]-1,4,5,6,7,8-六氢甘菊环2-[(5,6-二甲基-1H-茚-1-基)-二甲基-甲硅烷基]-2,4,5,6,7,8-六氢甘菊环2-[1-(5,6-二甲基-1H-茚-1-基)-1-甲基-乙基]-1,4,5,6,7,8-六氢甘菊环9-[1-(3,4,5,6,7,8-六氢-甘菊环-2-基)-1-甲基-乙基]-9H-芴1-[1-甲基-1-(3,4,5,6-四氢-并环戊二烯-2-基)-乙基]-1H-茚9-[2-(2,4,5,6,7,8-六氢-甘菊环-2-基)-1,1,2-三甲基-丙基]-9H-芴
表3c
1-[1-甲基-1-(4,5,6,7-四氢-3H-茚-2-基)-乙基]-1H-茚2-[1-(1H-茚-1-基)-1-甲基-乙基]-4,5,6,7,8,9-六氢-1H-环戊二烯并环辛烯2-[1-(1H-茚-1-基)-1-甲基-乙基]-4,5,6,7,8,9,10,11,12,13-十氢-1 H-环戊二烯并环十二烯9-[1-甲基-1-(3,4,5,6-四氢-并环戊二烯-2-基)-乙基]-9H-芴9-[1-甲基-1-(4,5,6,7-四氢-3H-茚-2-基)-乙基]-9H-芴9-[1-(4,5,6,7,8,9-六氢-3H-环戊二烯并环辛烯-2-基)-1-甲基-乙基]-9H-芴
表3d
Claims (18)
1.具有以下通式(Ⅰ)的桥接的环戊二烯基衍生物:
A-X-B (Ⅰ)其中1)A是具有以下通式(Ⅱ)的单官能化烃基其中R和R*选自:-H,-具有1-3个碳原子的单官能度烷基,-单官能度的烷基芳基或芳基,前提条件是:不同于H的R的数目不超过2;和至少一个R*是H;2)n是整数3-10;3)-X-是在A和B之间的桥接基并由选自以下基团的双官能度基团组成:a)直链的、支链的或环状的C2-C20亚烷基;b)具有1-2个硅原子的烷基或芳基取代的亚硅烷基;c)烷基取代的亚硅碳烷基;4)B是选自以下基团的单官能度烃基:(e)以上定义的A基团中的任何一个;(f)环戊二烯基。
2.根据权利要求1的环戊二烯基衍生物,其中所有的R=H,R*是选自H和CH3。
3.根据权利要求1的环戊二烯基衍生物,其中n是选自3,4,5,6,10。
4.根据权利要求1的环戊二烯基衍生物,其中R=R*=H和n是选自5,6和10。
5.根据权利要求1的环戊二烯基衍生物,其中-X-是选自直链或支链亚烷基衍生物和二烷基亚硅烷基。
6.根据权利要求5的环戊二烯基衍生物,其中-X-是选自亚乙基,亚异丙基和二甲基亚硅烷基。
7.根据权利要求1的环戊二烯基衍生物,其中B是单官能度环戊二烯基(f),该(f)选自环戊二烯基,茚基,芴基和相关的烷基、芳基、三烷基甲硅烷基取代的衍生物。
8.根据权利要求7的环戊二烯基衍生物,其中B是选自环戊二烯基、茚基和芴基的单官能度环戊二烯基(f)。
10.根据权利要求9的方法,其特征在于:
步骤(ⅰ)在碱性环境中进行;
步骤(ⅱ)通过如下来进行:制备烃BH的阴离子和随后让该阴离子与在步骤(ⅰ)中获得的产物(Ⅲ)发生相互作用。
11.根据权利要求10的方法,其特征在于,所用碱为叔醇的醇化物。
12.根据权利要求11的方法,其特征在于,所用的叔醇的醇化物为叔丁醇钾。
13.根据权利要求9的方法,其中R*选自H和CH3,R=H,R3=R4=CH3或C6H5,n选自3,4,5,6,10。
14.根据权利要求13的方法,其中具有通式R3-CO-R4的酮是丙酮和n是选自5,6和10。
15.一种获得具有通式Al-X-Al的化合物的方法,其中-X-是二烷基亚硅烷基,和Al基,相互相同,是选自以上定义的A基团,该方法包括烃AlH与二烷基二卤硅烷按AlH/二烷基二卤硅烷摩尔比约2/1的反应。
16.根据权利要求15的方法,其中二烷基二卤硅烷是二烷基二氯硅烷。
17.一种获得具有以下通式Al-X-B的化合物的方法,其中:
-X-是二烷基亚硅烷基;
Al是选自以上定义的A基团的单官能度烃基;
B是选自:-A2,其中A2是以上定义的基团A中的任何一种,前提是它不同于Al,-环戊二烯基(f),
以上方法分两步进行,第一步(步骤a)包括化合物AlH与二烷基二卤硅烷按Al/H二烷基二卤硅烷摩尔比约1/1的反应;第二步包括在步骤(a)中获得的化合物与烃BH按基本上与在步骤(a)中获得的产物等摩尔比的反应。
18.根据权利要求17的方法,其中二烷基二卤硅烷是二烷基二氯硅烷。
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