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4,4’7,7′-Teteramethylbis(1-indenyl) has been synthesised for the first time.This compound exists as two diastereoisomers (meso and d,l) which have been separated.These two forms are isomerized to 4,4′,7,7′-tetramethylbis(3-indenyl) in the presence of triethylamine.The three isomers are polymerized by the action of TiCl4.A new mechanism of propagation is proposed for the duplicate 1-1′ structure.

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7-Amino-5,8-dimethylisoquinoline gave various 7-anilino-5,8- dimethylisoquinolines via a palladium-catalyzed coupling reaction with bromobenzenes having electron-attracting groups (NO2, F).

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Syntheses of the phosphinoindenes 1-(diphenylphosphino)-3-methylindene (1b), 3-(diphenylphosphino)-2-methylindene (1c), 1-(diphenylphosphino)-2,3-dimethylindene (1d), 4,7-dimethyl-3-(diphenylphosphino)indene (1e), 1-(diphenylphosphino)-3,4,7-trimethylindene (1f) and 3-(diisopropylphosphino)indene (1i) were carried out by treatment of the appropriate indenide with the appropriate chlorophosphine. The silylphosphinoindene 3-(diphenylphosphino)-1-(trimethylsilyl)indene (1h) was prepared by treatment of the indenide of 3-(diphenylphosphino)indene (1a) with trimethylsilylchloride. These indenes, in addition to 1a, were then used, after deprotonation with BuLi, to prepare the corresponding indenyl ferrocenes, 2a-2e, 2h and 2i, by treatment with ferrous chloride in a 2:1 ratio. These compounds were characterized by 1H, 13C, and 31P NMR spectroscopy, as well as by mass spectrometry, except for the highly-sensitive diisopropylphosphine 2i that could only be characterized by 31P NMR spectroscopy. All of these ferrocene complexes are bisplanar chiral systems that can potentially form rac and meso isomers. In all cases both isomers were observed but for 2b and 2h only one could be isolated. The rac isomers of complexes 2a, 2b, 2d, and 2e, as well as the meso isomer of 2e, were studied by X-ray crystallography. Only complexes 2a and 2i were observed to undergo rac/meso isomerization processes at ambient temperature in THF solvent. We were unable to prepare the sterically congested hexamethylferrocene 2f. Generally, it was found that increasing substitution on the indenyl ring increases the reactivity and sensitivity of the ferrocene.

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It is possible to prepare substantially amorphous polymers of propylene endowed with high molecular weights, operating at temperatures of industrial interest, by carrying out the polymerization reaction of propylene in the presence of metallocene catalysts comprising particular bis-indenyl or bis-4,5,6,7-tetrahydroindenyl compounds substituted in the 2-position on the indenyl or tetrahydroindenyl groups.

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The present invention provides a high-activity and selectivity of propylene dimerization method, comprises the following steps: to methylaluminoxane (MAO) or modified methylaluminoxane (MMAO) as cocatalyst, propylene in the ethylenedioxy group bridged substituted two yinyin titanium families metal complex catalyst under catalysis of dimerization reaction; states Asia ethyl bridged substituted two yinyin titanium families metal complex catalyst is meso (meso -) of the ethylenedioxy-based bridged substituted two yinyin titanium families metal complex catalyst or racemic (rac -) of the ethylenedioxy-based bridged substituted two yinyin titanium families metal complex catalyst. Compared with the prior art, the present invention provides for the dimerization of a high catalytic activity, dimerization high selectivity, to achieve 99%, avoids the many follow-up separation relatively high degree of operation steps of the product, reduces industrialization cost, can meet the needs of industrial production. (by machine translation)

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The compounds of the formula I or Ia STR1 in which R1 is alkyl, aryl, alkoxy, alkenyl, arylalkyl, alkylaryl, aryloxy, fluoroalkyl, halogenoaryl, alkynyl, trialkylsilyl or a heteroaromatic radical, R2, R3 and R4, in addition to hydrogen, have the meanings given under R1 and R5 is hydrogen, alkyl, fluoroalkyl or alkenyl, can be obtained in a one-stage process by reaction of a compound II STR2 with (substituted) cyclopentadiene in the presence of a base. The compounds I and Ia are suitable as ligands for metallocene complexes which are used as catalysts in olefin polymerization.

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Process for the preparation of crystalline vinylaromatic polymers with a predominant syndiotactic structure which involves polymerizing vinylaromatic monomers in the presence of a catalytic system comprising: a titanium complex having general formula (I): STR1 wherein R1, R2, R3 and R4, the same or different, represent a hydrogen atom or a C1 -C20 alkyl radical or a C6 -C20 arylalkyl or aryl radical, on the condition that at least one of these is different from hydrogen.

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We report a Ni-catalyzed regioselective alpha-carbonylalkylarylation of vinylarenes with alpha-halocarbonyl compounds and arylzinc reagents. The reaction works with primary, secondary, and tertiary alpha-halocarbonyl molecules, and electronically varied arylzinc reagents. The reaction generates gamma,gamma-diarylcarbonyl derivatives with alpha-secondary, tertiary, and quaternary carbon centers. The products can be readily converted to aryltetralones, including a precursor to Zoloft, an antidepressant drug.

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The synthesis of a series of indenyl amido titanium dimethyl complexes, by means of the direct synthesis from the ligand, a 2-fold excess of MeLi, and TiCl4 is reported. The 1H NMR spectra of the complexes show a quartet structure for the metal-bound methyl groups, due to through-metal proton-proton coupling. Coupling of Ti-methyl protons with protons on the Cp ring is also revealed by COSY 2D-NMR. The performance of the Ti complexes in propylene polymerization, including [Me2Si(Me4C5)(t-BuN)]TiMe2 (1-TiMe2), [Me2Si(Ind) (t-BuN)]TiMe2(2-TiMe2) and six other methyl titanium complexes bearing substituted indenyl ligands, has been investigated with different cocatalysts and at different polymerization temperatures and propylene concentrations. All complexes produce amorphous polypropylene (am-PP). The catalytic activity and molecular weight strongly depend on the substitution of the Cp ring: 2-TiMe2 gives polymers of lower molecular weight, while the presence of a methyl group in position 2 (as in 3-TiMe2) determines up to 4-fold increase in molecular weight. The type of cocatalyst influences mainly the catalytic activity, the borates being better activators than MAO, but also molecular weight, with again the borates giving higher molecular weights than MAO. DeltaDeltaE? 2-TiMe2 = 3.4 kcal mol-1, DeltaDeltaE? 5-TiMe2 = 3.8 kcal mol-1, DeltaDeltaE? 3-TiMe2 = 6.3 kcal mol-1. Even if all the polymers produced are amorphous, 2-TiMe2 and 5-TiMe2 show a microstructure unbalanced towards isotacticity, while 3-TiMe2, 6-TiMe2 and 8-TiMe2 are syndiotactic-enriched. Chiral induction comes mainly from a weak enantiomorphic site control.

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Process for preparing 2-aryl-substituted indenes

A process is disclosed for preparing 2-aryl-substituted indenes by reacting an indene with an arene compound substituted with an halogen atom, preferably a iodine atom, or with an organosulphonate group, said reaction being carried out in a basic medium in the presence of a palladium catalyst. The compounds obtainable by this process can be used to prepare metallocene compounds with transition metals such as titanium, zirconium or hafnium, which are useful as catalyst components in the polymerization of olefins.

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