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Ep 1 072 606 A1 Europäisches Patentamt (19) European Patent Office Office européen des brevets (11) EP 1 072 606 A1 (12) EUROPEAN PATENT APPLICATION published in accordance with Art. 158(3) EPC (43) Date of publication: (51) Int. Cl.7: C07F 17/00 31.01.2001 Bulletin 2001/05 (86) International application number: (21) Application number: 98913757.5 PCT/ES98/00094 (22) Date of filing: 15.04.1998 (87) International publication number: WO 99/52918 (21.10.1999 Gazette 1999/42) (84) Designated Contracting States: • SANCHO ROYO, José BE DE ES FR GB IT NL E-28003 Madrid (ES) • MENDEZ LLATAS, Luis (71) Applicant: REPSOL QUIMICA S.A. E-28935 Mostoles (ES) E-28046 Madrid (ES) (74) Representative: (72) Inventors: Del Santo Abril, Natividad • PARELLADA FERRER, M Dolores Oficina Garcia Cabrerizo, S.L., E-28820 Coslada (ES) Vitruvio, 23 • BARRIO CALLE, Juan Antonio 28006 Madrid (ES) E-28007 Madrid (ES) (54) PROCESS FOR PREPARING AROMATIC DERIVATIVES OF TITANOCENE (57) Procedure for the preparation of aromatic OR4 where R4 is an alkyl group of 1 to 4 carbon derivatives of titanocene, useful as catalysts for the atoms; at least one of the R1, R2 or R3 is hydrogen. polymerisation and hydrogenation of polymers, charac- The preparation is carried out by the reaction of the terised by the use of a Grignard reagent. This proce- titanocene dichloride with the corresponding Grig- dure allows to easily prepare compounds with the nard reagent. This method substantially enhances general formula : safety, reproducibility, yield and cost of that carried out via lithium compounds. where: L, which can be equal to or different one from the other, are cyclopentadiene, or pentamethylcy- clopentadiene; preferably at least one L is cyclopentadiene; R1, R2, R3, equal or different from one another, are selected from the group consisting of: hydrogen, alkyl group from 1 to 4 carbon atoms, EP 1 072 606 A1 Printed by Xerox (UK) Business Services 2.16.7 (HRS)/3.6 12EP 1 072 606 A1 Description yield and cost of the method which is carried out via lith- ium compounds. [0001] This invention refers to a procedure for the preparation of aromatic compounds of titanocene. More Description of the invention particularly it refers to a procedure of synthesis of 5 bis(aryl) and bis(cyclopentadienyl) titanium derivatives [0007] The procedure of this invention is character- via the Grignard reagent. ised by the use of an organo magnesium for the manu- facturing of compounds which have the following State of the Art formula: 10 [0002] The alkyl and aryl compounds derived from titanocene are very useful in numerous organic reac- tions, for instance as catalysts for the polymerisation and hydrogenation of polymers. The large number of publications (U.S. Patent 2,952,670 (1960) ; Gevaert- 15 Agfa, Neth. Patent 6,603,202 (1966) ; Natta, G., et al, Chim. Ind. (Milan) 39, 1032 (1957) ; U.S. Patent Appl. 3,000,870 (1958); Ryabov, A. V., et al., Vysokomol. Soedin, Ser. Bll, 49 (1969)), evidences the interest aroused by bis(cyclopentadienyl) bis(phenyl) titanium 20 as catalyst together with titanium tetrachloride or an alkyl aluminium compound for the polymerisation of eth- ylene. [0003] On the other hand, the hydrogenation cata- lyst activity of polymers of bis(cyclopentadienyl) 25 bis(alkylphenil)titanium described in patent GB where: 2159819 or bis(cyclopentadienyl) bis(alcoxyphenyl) tita- nium claimed in patent EP 0 601 953 is well known. L, which can be equal or different one from the [0004] The efforts to prepare organotitanium com- other, are cyclopentadiene, or pentamethylcy- pounds with σ bonds date back to more than a century 30 clopentadiene; preferably at least one L is ago, but it was not until 1952 that Herman et al., J. cyclopentadiene; R1, R2, R3, are equal or different Amer., Chem. Soc. 74,2693 (1952) synthesised the first from one another, are selected from a group con- organotitanium compound. Somewhat latter, in 1954 sisting of: hydrogen, alkyl group of 1 to 4 carbon the first bis(aryl) derivatives of bis(cyclopentadienyl) atoms, OR4 where R4 is an alkyl group of 1 to 4 car- titanium were isolated by reaction of titanocene dichlo- 35 bon atoms; at least one of the R1, R2 or R3 is hydro- ride and the corresponding aryl lithium salt, being in this gen. way that L. Summers et al, (J. Amer., Soc. 76,2278 (1954) and J. Amer., Chem. Soc., 77,3604 (1955)) pre- [0008] The procedure for the preparation of said pared phenyl, 3-tolyl, 4-tolyl and 4- dimethylaminephe- titanocenes is characterised by the following steps: nyl derivatives with yields above 81%. Subsequently 40 Beachell and Butter (Inorg. Chem, 4,1133 1965) Preparation of the Grignard reagent by reaction of described the synthesis of the Cp2Ti (3- CF3C6H4)2 and magnesium metal with a compound with the for- Cp2Ti (4-XC6H4)2 derivatives where X= OCH3, F, Cl, Br, mula (II) : CF3) using the same synthesis path. The preparation of diaryl titanocene derivatives by reaction with aryl lithium 45 was again published by Liu et al. in J. Huaxue Tongbao, 10, 26, (1984). [0005] The use of lithium compounds involves the use of very volatile solvents, very low temperatures (- 70°C), extremely humidity sensitive reactants and pyro- 50 phoric products, which implies an important risk and complexity in the preparation of diaryl titanocene deriv- atives at industrial scale. [0006] On our side, we have discovered that, sur- prisingly, the bis(aryl) derivatives of titanocene can be 55 easily prepared by the reaction of titanocene dichloride 1 2 3 with the corresponding Grignard derivative. This BrC6H4R, where R , R and R have already been method substantially enhances safety, reproducibility, defined and Br is bromide, in a polar solvent such 2 34EP 1 072 606 A1 as tetrahydrofuran; nyl) (cyclopentadienyl) (pentamethylcyclopentadienyl) b) Reaction of the Grignard reagent in solution with titanium, bis(3-methoxyphenyl) (cyclopentadienyl) (pen- titanocene dichloride in a 2:1 ratio; tamethylcyclopentadienyl) titanium, bis(4-etoxyphenyl) (cyclopentadienyl) (pentamethylcyclopentadienyl) tita- Precipitation with a non-polar solvent, such as 5nium, bis(3-etoxyphenyl) (cyclopentadienyl) (pentame- cyclohexane, of the chlorobromomagnesium salts thylcyclopentadienyl) titanium, bis(4-methylphenyl) synthesised in the reaction medium and filtration of (cyclopentadienyl) (pentamethylcyclopentadienyl) tita- the same, obtaining a solution of the compound (I). nium, bis (phenyl) (cyclopentadienyl) (pentamethylcy- clopentadienyl) titanium, bis(4-ethylphenyl) [0009] Preferably the process according to the fol- 10 (cyclopentadienyl) (pentamethylcyclopentadienyl) tita- lowing invention refers to compounds which have the nium, bis(3-ethylphenyl) (cyclopentadienyl) (pentameth- formula ylcyclopentadienyl) titanium, bis(4-butylphenyl) (cyclopentadienyl) (pentamethylcyclopentadienyl) tita- nium, bis(3-butylphenyl) (cyclopentadienyl) (pentameth- 15 ylcyclopentadienyl) titanium, bis(3-ethyl,4- methylphenyl) (cyclopentadienyl) (pentamethylcy- clopentadienyl) titanium, bis(4-methoxyphenyl) bis(pen- tamethylcyclopentamethyl) titanium, bis (3- methoxyphenyl) bis(pentamethylcyclopentamethyl) tita- 20 nium, bis(4-ethoxyphenyl) bis (pentamethylcyclopen- tamethyl) titanium, bis(3-ethoxyphenyl) bis(pentamethylcyclopentamethyl) titanium, bis(4-meth- ylphenyl) bis(pentamethylcyclopentamethyl) titanium, bis(phenyl) bis(pentamethylcyclopentamethyl) titanium, 25 bis(4-ethylphenyl) bis(pentamethylcyclopentamethyl) titanium, bis(3-ethylphenyl) bis(pentamethylcyclopen- tamethyl) titanium, bis (4-ethylphenyl) bis (pentamethyl- cyclopentamethyl) titanium, bis (3-butylphenyl) bis(pentamethylcyclopentamethyl) titanium, bis(3- where: 30 ethyl,4-methylphenyl) bis (pentamethylcyclopentame- thyl) titanium. L, which can be equal or different one from the [0012] The products prepared by the method other, are cyclopentadiene, or pentamethylcy- described in this invention are obtained with quantitative clopentadiene; preferably at least one L is yields and with a purity of >97% . cyclopentadiene; 35 [0013] An additional advantage of this procedure is OR4 is an alcoxyle group, containing from 1 to 4 that the titanocene derivative is obtained in solution at carbon atoms. an adequate concentration for its direct use in polymer- isation or hydrogenation reactions. The solutions of [0010] The advantages posed by this method bis(aryl) derivatives are stable at room temperature for respect of those described in the preceding state of art, 40 long periods of time. are the use of less volatile solvents, reaction tempera- [0014] In the procedure described in this invention tures between 0 and 70°C, cheaper and not so humidity the reaction with the titanocene dichloride is carried out sensitive reactants, which makes operation more simple in the same reactor in which the intermediate Grignard and safe, and easy to be carried out at an industrial derivative has been synthesised, not being necessary scale. Preferably the solvents used are liquid with boil- 45 to isolate it, which simplifies and eases the operation . ing points higher than or equal to 65°C. [0015] Below are some explanatory examples of [0011] Specific examples of the compounds pre- the procedure subject matter of the invention which evi- pared are: bis(4-methoxyphenyl) bis (cyclopentadienyl) dence the advantages of the method compared to those titanium, bis(3-methoxyphenyl) bis(cyclopentadienyl) described in the preceding state of art. These examples titanium, bis(4-etoxyphenyl) bis(cyclopentadienyl) tita- 50 are not intended as limitations of the invention: nium,
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  • Titanocene Dichlorides
    Antiproliferative Activity of Some Polar Substituted Titanocene Dichlorides John Ronald Boyles A thesis submitted to the Department of Chemistry in conformity with the requirernents for the degree of Master of Science Queen's University Kingston, Ontario, Canada July, 1997 Copyright O John Ronald Boyles, 1997 National Library Bibliothèque nationale of Canada du Canada Acquisitions and Acquisitions et Bibliographic Services services bibliographiques 395 Wellington Street 395, rue Wellington Ottawa ON K1A ON4 ûttawaON K1AON4 Canada Canada The author has granted a non- L'auteur a accordé une licence non exclusive licence allowing the exclusive permettant a la National Library of Canada to Bibliothèque nationale du Canada de reproduce, loan, distriilbute or sell reproduire, prêter, distribuer ou copies of this thesis in microform, vendre des copies de cette thèse sous paper or electronic formats. la fome de microfiche/^ de reproduction sur papier ou sur format électronique. The author retains ownership of the L'auteur conserve la propriété du copyright in this thesis. Neither the droit d'auteur qui protège cette thèse. thesis nor substantial extracts fkom it Ni la thèse ni des extraits substantiels may be printed or otherwise de celle-ci ne doivent être imprimés reproduced without the author' s ou autrement reproduits sans son permission. autorisation. DEDICATION To the beautiful bride-to-be, Kathy ABSTRACT This work describes the cytotoxic activity of polar substituted titanocene dichlorides against small cell lung cancers. Two polar substituted metallocene dichloride compounds Cp(C,H,CO,Me)TiCI, and (C,H,CO,Me),TiCI2 as well as Cp2TiClz wece synthesized and tested for cytotoxicity against small celi lung cancer ce11 lines.
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