WO1997042158A1 - Synthese d'un compose de cyclopentadiene substitue - Google Patents

Synthese d'un compose de cyclopentadiene substitue Download PDF

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Publication number
WO1997042158A1
WO1997042158A1 PCT/NL1997/000197 NL9700197W WO9742158A1 WO 1997042158 A1 WO1997042158 A1 WO 1997042158A1 NL 9700197 W NL9700197 W NL 9700197W WO 9742158 A1 WO9742158 A1 WO 9742158A1
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group
cyclopentadiene
mol
stirring
mmol
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PCT/NL1997/000197
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English (en)
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Gerardus Johannes Maria Gruter
Johannes Antonius Maria Van Beek
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Dsm N.V.
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Priority to AU23109/97A priority Critical patent/AU2310997A/en
Publication of WO1997042158A1 publication Critical patent/WO1997042158A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/25—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
    • 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
    • C07F17/00—Metallocenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated

Definitions

  • the invention relates to a process for substituting a cyclopentadiene with at least one group of the form -RDR' n by deprotonating a cyclopentadiene compound already substituted with at least one other group through reaction with a base, sodium or potassium and then reacting the cyciopentadienyl anion formed with a compound containing a sulphonyl group.
  • cyclopentadiene will be abbreviated as "Cp”.
  • Cp cyclopentadiene
  • the same abbreviation will be used for a cyciopentadienyl group if it is clear from the context whether cyclopentadiene itself or the anion thereof is meant.
  • the object of the invention is to provide a simple method for synthesizing a substituted Cp compound of which at least 1 substituent has the form - RDR' n , the conversion being as high as possible and as few geminal products as possible being formed.
  • the invention is characterized in that the sulphonyl-group-containing compound is a compound according to the formula (R' n D-R-Sul) , wherein R is a linking group, R' is a substituent, D is a heteroatom from group 15 or 16 of the Periodic System of the Elements, n is the number of R' groups bound to D and Sul is a sulphonyl group.
  • a further advantage of the synthesis process according to the invention is that, in contrast to the process which is carried out by Szymoniak and Jutzi for attaching one or more substituents of the form -RDR' n to a substituted Cp compound, only one synthesis step needs to be carried out.
  • Another advantage of the synthesis process according to the invention is that yields greater than or equal to 95% are achieved.
  • geminal product is formed only in part.
  • the geminal products can easily be isolated by converting the product from the above synthesis into a salt by reaction with potassium, sodium or a base, after which said salt is washed with a dispersant in which the salt of the nongeminal products hardly dissolves.
  • the substituted Cp compound can be used as ligand in a metal complex.
  • Cp compounds are understood as meaning Cp itself and substituted Cp, in which case two substituents may form a closed ring.
  • a substituted Cp compound contains at least 1 alkyl, alkenyl and/or aralkyl substituent.
  • the alkyl substituents may be linear, branched or cyclic alkyl groups.
  • one or more heteroatoms from the groups 14 - 17 of the Periodic System for example 0, N, Si or F, may also occur in the substituents.
  • suitable substituents are methyl, ethyl, (iso)propyl, secondary butyl, secondary pentyl, secondary hexyl and secondary octyl, (tertiary) butyl and higher homologs, cyclohexyl, benzyl. Combinations of these substituents on the Cp compound are also possible.
  • Substituted Cp compounds can, for instance, be prepared by reacting a halide of the substituting compound in a mixture of the Cp compound and an aqueous solution of a base in the presence of a phase-transfer catalyst.
  • a virtually equivalent amount with respect to the Cp-compound of the halogenated substituting compound can be employed.
  • An equivalent amount is understood as meaning an amount in moles which corre ⁇ sponds to the desired substitution level, for example 2 mol per mol of Cp compound if disubstitution with the respective substituent is intended.
  • trisubstituted to hexasubstituted Cp compounds can be obtained. If reaction is carried out with a tertiary halide of a substituting compound, only trisubstituted Cp compounds can as a rule be obtained, but with primary and secondary halide of a substituting compound, tetrasubstitution and usually even penta- substitution or hexasubstitution can generally be achieved. Because a substitute of the form -RDR' n is additionally introduced in a second step by means of the process according to the invention, four substituents are introduced in said first step as a maximum.
  • the substituents are preferably used in the process in the form of their halides.
  • a disubstitution may first be carried out with the aid of a certain halide of a substituting compound and, in the same reaction mixture, a third substitution can be carried out with another substituting compound by adding a second, different halide of a substituting compound to the mixture after a certain time. This can be repeated, so that it is also possible to prepare Cp derivatives containing three or more different substituents.
  • the substitution takes place in a mixture of the Cp compound and an aqueous solution of a base.
  • concentration of the base in the solution is between 20 and 80w%.
  • Hydroxides of an alkali metal, for example K or Na, are very suitable as a base.
  • the base is present in an amount of 5 - 60 mol per mol of Cp compound.
  • phase-transfer catalyst which is capable of trans ⁇ ferring OH ions from the aqueous phase to the, Cp-con- taining and halide-containing, organic phase which react therein with an H atom which can be cleaved from the Cp compound.
  • the phase-transfer catalysts are used in an amount of 0.01 - 2 equivalents with respect to the amount of Cp-compound.
  • a Cp compound already substituted with at least one other group is deprotonated by reaction with a base, sodium or potassium.
  • a base sodium or potassium.
  • a Cp compound already substituted with at least one other group is deprotonated by reaction with a base, sodium or potassium.
  • a base sodium or potassium.
  • R 3 Li organolithium compounds
  • R 3 MgX organomagnesium compounds
  • R 3 an alkyl, aryl or aralkyl group
  • X halide, such as, for example, n-butyllithium or isopropylmagnesium chloride.
  • Potassium hydride, sodium hydride, inorganic bases, such as NaOH and KOH, and alcoholates and amides of Li, K and Na can also be used as base. Mixtures of the abovementioned compounds can also be used.
  • Said reaction can be carried out in a polar dispersant, such as, for example, an ether.
  • a polar dispersant such as, for example, an ether.
  • ethers are tetrahydrofuran (THF) or dibutyl ether.
  • THF tetrahydrofuran
  • Nonpolar solvents such as, for example, toluene can also be used.
  • the cyciopentadienyl anion formed then reacts, during a second step of the synthesis route, with a compound according to the formula (R' n D-R-Sul) , wherein
  • R is a linking group
  • R' is a substituent
  • D is an electron-donating heteroatom from group 15 or
  • n is the number of R' groups bound to D and Sul is a sulphonyl group.
  • the R group forms the link between the Cp compound and the DR' n group.
  • the length of the shortest link between the Cp and D is critical to the extent that, if the Cp compound is used as ligand in a metal complex, it is decisive for the accessibility of the metal by the DR' n group in order thus to facilitate any intramolecular coordination.
  • An unduly short length of the R group (or bridge) may cause the donor to be unable to coordinate well as a result of ring tension.
  • the R' groups may each separately be a hydrocarbon radical containing 1 - 20 carbon atoms (such as alkyl, aryl, arylalkyl and the like). Examples of such hydrocarbon radicals are methyl, ethyl, propyl, butyl, hexyl, decyl, phenyl, benzyl and p-tolyl.
  • R' may also be a substituent which contains one or more heteroatoms from group 14 - 16 of the Periodic System of the Elements in addition to or instead of carbon and/or hydrogen.
  • a substituent may be a group containing N, 0 and/or Si.
  • the R group may be a hydrocarbon group containing 1 - 20 carbon atoms (such as alkylidene, arylidene, arylalkylidene and the like). Examples of such groups are methylene, ethylene, propylene, butylene, phenylene, optionally having a substituted side chain.
  • the R 2 groups may each be H or a group as defined for R'.
  • the R-group has the structure -CR 2 2 -(ER 2 2 -) p _ 1 so that the R-group is linked to the Cp-compound with a carbon atom.
  • the main chain of the R group may thus contain silicon or germanium in addition to carbon.
  • R groups are: dialkylsilylene, dialkylgermylene, tetraalkyldisilylene or dialkylsilaethylene (-(CH 2 ) (SiR 2 2 )-) .
  • the alkyl groups (R 2 ) in such a group preferably have 1 - 4 C atoms and are, more preferably, a methyl or ethyl group.
  • the DR' n group comprises a heteroatom D chosen from group 15 or 16 of the Periodic System of the Elements and one or more substituent(s) R' bound to D.
  • the heteroatom D is chosen from the group comprising nitrogen (N) , oxygen (0), phosphorus (P) or sulphur (S); more preferably, the heteroatom is nitrogen (N) .
  • the R' group is also preferably an alkyl, more preferably an n-alkyl group containing 1 - 20 C atoms.
  • the R' group is an n-alkyl containing 1 - 10 C atoms.
  • Another possibility is that two R' groups in the DR' n group are joined to each other to form a ring-type structure (so that the DR' n group may be a pyrrolidinyl group).
  • the DR' n group may bond coordinatively to a metal.
  • the sulphonyl group has the form -0S0 2 R 6 , wherein R 6 is a hydrocarbon radical containing 1 - 20 carbon atoms (such as alkyl, aryl, aralkyl and the like). Examples of such hydrocarbon radicals are butane, pentane, hexane, benzene and naphthalene. R 6 may also contain one or more heteroatoms from group 14 - 17 of the Periodic System of the Elements, such as N, 0 or F, in addition to or instead of carbon and/or hydrogen.
  • sulphonyl groups are: phenylmethanesulphonyl , benzenesulphonyl, 1-butanesulphonyl, 2, 5-dichlorobenzenesulphonyl, 5-dimethylamino-l-naphthalenesulphonyl, pentafluoro- benzenesulphonyl, p-toluenesulphonyl, trichloromethane- sulphonyl, trifluoromethanesulphonyl, 2,4,6- triisopropylbenzenesulphonyl, 2,4,6- trimethylbenzenesulphonyl, 2-mesitylenesulphonyl, methanesulphonyl, 4-methoxybenzenesulphonyl, 1- naphthalenesulphonyl, 2-naphthalenesulphonyl , ethane- sulphonyl, 4-fluorobenzenesulphonyl and
  • the sulphonyl group is p-toluene ⁇ sulphonyl or trifluoromethanesulphonyl.
  • the second reaction step can be carried out in a polar dispersant, such as, for example, an ether.
  • a polar dispersant such as, for example, an ether.
  • ethers are THF or dibutyl ether.
  • Nonpolar solvents such as, for example, toluene, can also be used.
  • the temperature at which the reaction is carried out is -60 to 80°C.
  • the upper limit for the temperature is determined in part by the boiling point of the compound (R' n D-R-Sul) and the boiling point of the solvent.
  • D is a nitrogen atom
  • the compound according to the formula (DR' n -R-Sul) is formed in situ by reacting an aminoalcohol compound (R' 2 NR-0H) consecutively with a base (such as described above), potassium or sodium and a sulphonyl halide (Sul-X).
  • geminal products may in part be formed.
  • a geminal substitution is a substitution in which the number of substituents increases by 1, but in which the number of substituted carbon atoms does not increase.
  • the amount of geminal products formed is low if the synthesis is carried out starting from a substituted Cp compound containing 1 substituent and increases as the substituted Cp compound contains more substituents. If sterically large substituents are present on the substituted Cp compound, geminal products are not, or are scarcely, formed. Examples of sterically large substituents are secondary or tertiary alkyl substituents.
  • the amount of geminal product formed is also low if the second step of the reaction is carried out under the influence of a Lewis base whose conjugated acid has a dissociation constant, pK a , of -2.5 or less.
  • the pK a values are based on D. D. Perrin: Dissociation Constants of Organic Bases in Aqueous Solution, International Union of Pure and Applied Chemistry, Butterworths , London 1965. The values have been determined in aqueous H 2 S0 4 solution. Ethers may be mentioned as examples of suitable Lewis bases.
  • geminal products have formed during the process according to the invention, said products can easily be separated from the nongeminal products by converting the mixture of geminally and nongeminally substituted products into a salt by reaction with potassium,, sodium or a base, after which the salt is washed with a dispersant in which the salt of the nongeminal products is insoluble or sparingly soluble.
  • the compounds mentioned above may be used as base.
  • Suitable dispersants are nonpolar dispersants, such as alkanes.
  • suitable alkanes are: heptane and hexane.
  • the substituted Cp compounds, of which at least one substituent has the form -RDR' n are very suitable for use as ligand in a metal complex.
  • the metal complexes with the Cp compounds as ligands are suitable as catalyst component.
  • Said cata- lyst components are, together with a cocatalyst, used in the polymerization of olefins.
  • Complexes were characterized using a Kratos MS80 mass spectrometer or a Finnigan Mat 4610 mass spectrometer.
  • Comparable tosylates can be prepared in an analogous way.
  • a tosylate is always coupled to alkylated Cp compounds.
  • geminal coupling also takes place in addition to the required substitution reaction.
  • it was possible to separate the geminal isomers from the nongeminal isomers by converting the nongeminal isomers into their sparingly soluble potassium salt, followed by washing of said salt with a solvent in which said salt is not soluble or is sparingly soluble.
  • the characterization was carried out with the aid of GC , GC-MS, 13 C- and ⁇ -NMR.
  • the bis(2-dimethylaminoethyl)tri(2- propyl)cyclopentadiene was obtained with a yield of 35% via column chromatography.
  • a double-walled reactor having a capacity of 1 1 and provided with baffles, cooler, top stirrer, thermometer and dropping funnel was filled with 600 g of clear 50% NaOH (7.5 mol), after which cooling was carried out to 8°C. Then 20 g (49 mmol) of Aliquat 336 and 33 g (0.5 mol) of freshly cracked cyclopentadiene were added. The reaction mixture was vigorously stirred for several minutes. Then 172 g of cyclohexyl bromide (1.05 mol) were added. During this process, the mixture was cooled with water. After stirring for 2 hours at room temperature, the reaction mixture was heated to 70°C, after which stirring was carried out again for 6 hours.
  • the characterization was carried out with the aid of GC, GC-MS, 13 C- and ⁇ -NMR.
  • Example IVa Preparation of a di- and tri(2- pentyl )cyclopentadiene
  • a double-walled reactor having a capacity of 1 1 and provided with baffles, cooler, top stirrer, thermometer and dropping funnel was filled with 900 g (11.25 mol) of clear 50% NaOH. Then 31 g (77 mmol) of Aliquat 336 and 26.8 g (0.41 mol) of freshly cracked cyclopentadiene were added. The reaction mixture was vigorously stirred for several minutes. Then 155 g
  • the characterization was carried out with the aid of GC, GC-MS, 13 C- and t ⁇ -NMR.
  • Example IVc Preparation of (dimethylaminoethyl)tri ( 2- pentyl)cvclopentadiene The reaction was carried out in the same way as for (dimethylaminoethyl)tri(2-propyl)cyclopentadiene (Example lib). The conversion was 90%. The nongeminal (dimethylaminoethyl)tri(2-pentyl)cyclopentadiene was obtained distillatively in a yield of 54%.
  • the (dimethylaminoethyl)tri(2-pentyl)cyclopentadiene was obtained after preparative silica gel column purification using petroleum ether (40 - 60°C) and THF consecutively, with a yield of 57%.
  • Example Vb Preparation of (dimethylaminoethyl)di (2- propyl)cvclopentadiene The reaction was carried out in the same way as for (dimethylaminoethyl)tri(2-propyl)cyclopentadiene (Example lib). The conversion was 97%. The (dimethyl ⁇ aminoethyl)di(2-propyl)cyclopentadiene was obtained distillatively with a yield of 54%.
  • Example VI Example Via: Preparation of di (2-butyl )cvclopentadiene
  • a double-walled reactor having a capacity of 1 1 and provided with baffles, cooler, top stirrer, thermometer and dropping funnel was filled with 600 g of clear 50% NaOH (7.5 mol), after which the contents were cooled to 10°C. Then 30 g of Aliquat 336 (74 mmol) and 48.2 g (0.73 mol) of freshly cracked cyclopentadiene were added. The reaction mixture was vigorously stirred for several minutes. Then 200 g (1.46 mol) of 2-butyl bromide were added in half an hour. During this process, the mixture was cooled with water.
  • a double-walled reactor having a capacity of 1 1 and provided with baffles, cooler, top stirrer, thermometer and dropping funnel was filled with 400 g (5.0 mol) of clear 50% NaOH . Then 9.6 g (24 mmol) of Aliquat 336 and 15.2 g (0.23 mol) of freshly cracked cyclopentadiene were added. The reaction mixture was vigorously stirred for several minutes. Then 99.8 g (0.73 mol) of 2-butyl bromide were added in half an hour. During this process, the mixture was cooled with water. After stirring for half an hour at room temperature, the reaction mixture was heated to 70°C, after which stirring was carried out again for three hours. Stirring was stopped and phase separation was awaited.
  • a double-walled reactor having a capacity of 1 1 and provided with baffles, cooler, top stirrer, thermometer and dropping funnel was filled with 430 g (5.4 mol) of clear 50% NaOH. Then 23 g (57 mmol) of Aliquat 336 and 27 g (0.41 mol) of freshly cracked cyclopentadiene were added. The reaction mixture was vigorously stirred for several minutes. Then 150 g (1.0 mol) of 3-pentyl bromide were added in one hour. During this process, the mixture was cooled with water. After stirring for 1 hour at room temperature, the reaction mixture was heated to 70°C, after which stirring was again carried out for 3 hours. Stirring was stopped and phase separation was awaited.
  • Example VIIIc Preparation of (di-n-butylaminoethyl )- di (3-pentyl )cyclopentadiene
  • Example IXa Preparation of di(2- propyl)cyclohexylcyclopentadiene 150 g of clear 50% NaOH (1.9 mol), 7 g
  • a double-walled reactor having a capacity of 1 1 and provided with baffles, cooler, top stirrer, thermometer and dropping funnel was filled with 600 g (7.5 mol) of clear 50% NaOH, after which the mixture was cooled to 8°C. Then 20 g (49 mmol) of Aliquat 336 and 33 g (0.5 mol) of freshly cracked cyclopentadiene were added. The reaction mixture was vigorously stirred for several minutes. Then 256 g (1.57 mol) of cyclohexyl bromide were added. During this process, the mixture was cooled with water. After stirring for 1 hour at room temperature, the reaction mixture was heated to 70°C, after which stirring was carried out again for 2 hours.
  • a double-walled reactor having a capacity of 1 1 and provided with a baffle, cooler, top stirrer, thermometer and dropping funnel was filled with 1050 g (13.1 mol) of clear 50% NaOH, after which the mixture was cooled to 10°C. Then 32 g (79 mmol) of Aliquat 336 and 51 g (0.77 mol) of freshly cracked cyclopentadiene were added. The reaction mixture was vigorously stirred for several minutes. Then 344 g (3.19 mol) of ethyl bromide were added gradually in 1 hour. During this process, the mixture was cooled with water. After stirring for 1 hour at room temperature, the reaction mixture was heated to 35°C, after which stirring was carried out again for 6 hours.
  • Example Xlla Preparation of tetraoctylcyclopentadiene A double-walled reactor having a capacity of
  • Example XIII Example Xllla: Preparation of tetrapropylcyclopentadiene
  • a double-walled reactor having a capacity of 1 1 and provided with a baffle, cooler, top stirrer, thermometer and dropping funnel was filled with 1000 g (12.5 mol) of clear 50% NaOH, after which the mixture was cooled to 10°C. Then 30 g (74 mmol) of Aliquat 336 and 50 g (0.75 mol) of freshly cracked cyclopentadiene were added. The reaction mixture was vigorously stirred for several minutes. Then 373 g (3.03 mol) of propyl bromide were added in one hour. During this process, the mixture was cooled with water. After stirring for 1 hour at room temperature, the reaction mixture was heated to 35°C, after which stirring was carried out again for 6 hours.
  • the crude product isopropoxyethyltetramethyl- cyclopentadiene was added dropwise to a cooled (0°C) suspension of potassium hydride (0.55 g; 12.3 mmol) in THF (100 ml) under a nitrogen atmosphere in a three- neck round-bottom flask. After stirring for half an hour at 0°C, the mixture was slowly brought to room temperature (in four hours).

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Abstract

Procédé de substitution d'un cyclopentadiène par au moins un groupe de formule -RDR'n, qui consiste à déprotoner le cyclopentadiène déjà substitué par au moins un autre groupe par réaction avec une base, du sodium ou du potassium, puis à mettre l'anion de cyclopentadienyle obtenu en réaction avec un composé contenant un groupe sulfonyle et représenté par la formule (R'nD-R-Sul) dans laquelle R représente un groupe de liaison, R' représente un substituant, D représente un hétéroatome du groupe 15 ou 16 du tableau périodique des éléments et Sul représente un groupe sulfonyle.
PCT/NL1997/000197 1996-05-03 1997-04-16 Synthese d'un compose de cyclopentadiene substitue WO1997042158A1 (fr)

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AU23109/97A AU2310997A (en) 1996-05-03 1997-04-16 Synthesis of a substituted cyclopentadiene compound

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NL1003009A NL1003009C2 (nl) 1996-05-03 1996-05-03 Synthese van een gesubstitueerde cp-verbinding.
NL1003009 1996-05-03

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0875507A1 (fr) * 1997-04-30 1998-11-04 Eli Lilly And Company Procédé pour la préparation d'intermédiaires de dérivés de l'acide benzoique et de médicaments benzothiophèniques
WO2002074745A1 (fr) * 2001-03-20 2002-09-26 Basell Polyolefine Gmbh Procede pour la production de composes cyclopentadiene substitues
JP2013530134A (ja) * 2010-04-28 2013-07-25 ユニベーション・テクノロジーズ・エルエルシー アルキルシクロペンタジエン化合物の合成

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0416815A2 (fr) * 1989-08-31 1991-03-13 The Dow Chemical Company Catalyseurs de polymérisation d'addition à géométrie restreinte, leur procédé de préparation, les précurseurs, procédés d'utilisation et polymères obtenus
DE4303647A1 (de) * 1993-02-09 1994-08-11 Basf Ag Cyclopentadiene mit funktionalisierter Kohlenwasserstoff-Seitenkette

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0416815A2 (fr) * 1989-08-31 1991-03-13 The Dow Chemical Company Catalyseurs de polymérisation d'addition à géométrie restreinte, leur procédé de préparation, les précurseurs, procédés d'utilisation et polymères obtenus
DE4303647A1 (de) * 1993-02-09 1994-08-11 Basf Ag Cyclopentadiene mit funktionalisierter Kohlenwasserstoff-Seitenkette

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JUTZI, PETER ET AL: "Dimethylaminoalkyl and methoxyalkyl substituted tetramethylcyclopentadienes: synthesis of novel polydentate ligands", SYNTHESIS (1993), (7), 684-6 CODEN: SYNTBF;ISSN: 0039-7881, 1993, XP000601948 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0875507A1 (fr) * 1997-04-30 1998-11-04 Eli Lilly And Company Procédé pour la préparation d'intermédiaires de dérivés de l'acide benzoique et de médicaments benzothiophèniques
WO2002074745A1 (fr) * 2001-03-20 2002-09-26 Basell Polyolefine Gmbh Procede pour la production de composes cyclopentadiene substitues
US6995267B2 (en) 2001-03-20 2006-02-07 Basell Polyolefine Gmbh Method for producing cyclopentadiene compounds
JP2013530134A (ja) * 2010-04-28 2013-07-25 ユニベーション・テクノロジーズ・エルエルシー アルキルシクロペンタジエン化合物の合成

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AU2310997A (en) 1997-11-26

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