MXPA96005395A - Cylopentadienile derivatives of bridge and procedure for its preparation - Google Patents

Abstract

The present invention relates to bridge cyclopentadienyl derivatives having the general formula (I): AXB (I) wherein 1) A is a monofunctional hydrocarbyl radical having the general formula (II): characterized in that R and R * are selected from: - H, monofunctional alkyl radicals having from 1 to 3 carbon atoms, - monofunctional alkylaryl and aryl radicals, provided that the number of R is different from H and is not greater than 2 and that at least one of R * is H; 2) n is an integer from 2 to 20; 3) -X- is the bridge between A and B and consists of a bifunctional radical selected from: a) a linear C2-C10 alkylene group, branched or cyclic, b) an alkyl or substituted silanylene group having from 1 to 2 silicon atoms, c) a substituted alkyl silalene group, d) a siloxasilanylene group or -Si (R1) 2-O-Si (R2) 2 - tetraalkyl or substituted tetraaryl; 4) B is a monofunctional hydrocarbon radical selected from: e) any of the radicals A defined above nte; f) a cyclopentadienic radical

Description

CYLOPENTADIENILE BRIDGE DERIVATIVES AND PROCEDURE FOR PREPARATION DESCRIPTION OF THE INVENTION The present invention relates to novel bridge compounds of the cyclopentadienyl type, and to the process for their preparation. It is known that most soluble catalysts for homo- and copolymerization of alpha-olefins consist of zirconium or titanium complexes having bis-indenyl, bis-fluoronyl, or mixed ligands, such as fluorenyl-cyclopentadienyl ligands ( Pc Mohring, NJ Coville, J. Organomet, Chem. 479, 1, 1994). Ligands can be bridged or unbridged. The best results, particularly in terms of high molecular weights, are obtained with bridge ligands (see, J.C.W. Chien and D. He, Journal of Polymer Science; Part A: Polymer Chemistry, Vol. 29 (1991), page 1585). The tetrahydroindenyl derivatives are more efficient than the corresponding unsaturated derivatives, particularly in the incorporation of co- and ter-monomers, and therefore, they are currently among the most widely selected catalysts.

However, there is a problem that while ligands of the indenyl and fluorenyl type are readily available, the corresponding tetrahydroindenyl derivatives are obtained by the direct hydrogenation of the zirconium complex, as such it is difficult to chemoselectively hydrogenate the starting ligands. The process of hydrogenation of the complex with zirconium has several disadvantages. In fact, as indicated by several experts (see E. Samuel, Bull. Soc. Chim: Fr. 3548, 1966 and S. Collins et al., In J. Organo etallic Chem., 342, 21, 1988) there are difficulties for carry out this hydrogenation due to the low productions and / or drastic conditions. In addition, the hydrogenation process of zirconium indenyl complexes yields two identical tetrahydroindenyl type ligands; in fact, it is not possible to obtain, with this method, asymmetric complexes having a tetrahydroindenyl ligand and an indenyl ligand. Currently, new bridge cyclopentadienyl derivatives have been found, which overcome the aforementioned disadvantages, belonging to the fact that, as a result of their structure, they do not need the previous hydrogenation step. Accordingly, the present invention relates to cyclopentadienyl bridge derivatives having the general formula (I) A-X-B (I) wherein 1) A is a monofunctional hydrocarbyl radical having the general formula (II) wherein R and R 'are selected from: - H, - monofunctional alkyl radicals having from 1 to 3 carbon atoms, - monofunctional alkylaryl or o-aryl radicals, provided that: - the number of R different from H be no more than 2; - at least one of R * is H; preferably all R = H and R * is selected from H and CH3; 2) n is an integer from 2 to 20, preferably is selected from 3, 4, 5, 6, 10; 3) -X- is the bridge between A and B and consists of a bifunctional radical selected from: a) a linear, branched or cyclic C2-C20 alkylene group; b) an alkyl or substituted aryl silanylene group having 1 to 2 silicon atoms; c) a substituted alkyl sialkylene group; d) a siloxasylanylene group or -Si (R1) 2-0-Si (R2) 2"tetraalkyl or substituted tetraaryl; 4) B is a monofunctional hydrocarbyl radical selected from: (e) any of the radicals A defined above; ) A cyclopentadienyl radical The groups A are monofunctional cyclopentadienyl radicals, whose corresponding hydrocarbons, hereinafter later referred to as AH, are described in copending patent application IT-A-MI 95A 002707. Typical examples of hydrocarbons AH, which have both R * = H, are indicated in Table 1. The names of the previous hydrocarbons were obtained using the autonomous program of the Beilstein Institute, Beilstein Information System and the number of carbons is the same as in the formula (bundle): In one embodiment, the hydrocarbons AH and thus the corresponding monofunctional hydrocarbyl radicals A are selected from: - 2,4,5,6,7,8-hexahydroazulene (R * = R = H and n = 5), - 4, 5, 6, 7, 8, 9-hexahydro-2H-cyclopentacyclooctene (R * = R = H and n = 6), 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 - decahydro-2H-cyclopenta-cyclododecene (R * = R = H and n = 10), l-methyl-4,5,6,7,8,9,10,11,12,13-decahydro-2H-10-cyclopentacyclododecene (R * = CH3, R = H, n = 10). In one embodiment, -X- is a cyclic branched linear alkylene radical, having from 2 to 20 carbon atoms. Typical examples of linear -X- are ethylene, propylene, butylene, pentylene, hexylene. Typical examples of -X-branched are isopropylidene (CH3-C-CH), isobutylidene (CH3-C-C2H5), 3-pentylene (C2H5-C-C2H5), diphenylmethylene (CgH5-C-CgH5). Typical examples of the -X-cyclic alkylene radical are cyclobutylene, cyclopentylene, cyclohexylene.

In another embodiment, -X- is a silanylene alkyl or substituted aryl group, having 1 to 2 silicon atoms, for example dimethylsilanylene or -Si (CH3) 2-, diethyl silanylene, tetramethyl disilanylene, or -Si (CH3) 2-Si (CH 3) 2, dimethyl diethyl disylanylene, preferably dimethylsilanylene. In another form of embodiment, the group -X- consists of Silicon-Carbon sequences, ie a substituted sialkylene alkyl group, for example; -Si (R1) 2-C (R1 ') 2-wherein R' is a lower alkyl and R "is hydrogen or a lower alkyl. Typical examples of sialkylene groups are: 1-sila-l, 1-dimethylethylene, -2-sila-2,2-dimethylpropylene, -1,3-disilayl, 1,3,3-tetramethylpropylene. In another embodiment, the group X is a substituted tetraalkyl or tetraaryl siloxasilanylene, ie, -Si (R2) 2-0-Si (R2) 2, wherein R1 and R2 are the same or different, and may be alkyl or aril. In the preferred embodiment -X- is selected from linear or branched alkylene derivatives and dialkylsilanylenes, most preferably selected from ethylene isopropylene and dimethylsilanylene. As for B, this is a monofunctional hydrocarbyl radical selected from: (e) any of the radicals A defined above, (f) a cyclopentadienyl radical. When B is equal to any of the derivatives A, defined above, the product having the general formula (I) will consist of two A or cyclopentadienyl derivatives, the same or different, joined together in position 2 from the bridge -X- . These structures will be called A-X-A ', where A and A', equal or different, both have the general formula (II), with the specification that, in the bridge product AXA ', the double bonds of the cyclopentadienyl ring can be located in positions 3,3a- and 1, (n + 3) a- or in positions 1,2- and 3a, (n + 3) a-, where n has the meaning defined above and the number of positions, represented in the general formula (lia) is obtained from the autonomous program mentioned above. Typical examples of the structures A-X-A ', where A1 is the same as or different from A, are indicated in tables 2a, 2b, 2c, 2d. When B does not belong to the hydrocarbyl radicals having the general formula (II), B is a monofunctional cyclopentadienyl radical (f) selected from cyclopentadienyl, indenyl, fluorenyl and the relative substituted alkyl, aryl, trialkylsilyl derivatives; (F) preferably it is selected from cyclopentadienyl, indenyl and fluorenyl. For simplicity, these compounds will be referred to as A-X-C. It should be noted that, as previously specified for AXA 'products, in the AXC bridge product, the double bonds of the cyclopentadienyl ring of the hydrocarbyl radical A can be placed at positions 3,3a- and l (n + 3) a- or 1,2- and 3a, (n-3) a-, where n has the meaning defined above and the number of positions, represented in the general formula lia, is obtained from the autonomous program mentioned above. The corresponding hydrocarbons will be referred to as the monofunctional cyclopentadienyl radicals (f) FH. The point of attachment to the bridge -X- of the cyclopentadienyl derivatives (f) is that which is usually obtained in the known art. For example, the indene will be linked to the bridge -X- in position 1 and the fluorene in the only non-condensed position of the 5-term cycle. Tables 3a-3d provide examples of structures of type A-X-C, where C is any of the monofunctional cyclopentadienyl radicals (f). A further object of the invention relates to a process for the preparation of the compounds having the general formula (1) wherein -X- is selected from branched or cyclic alkylene derivatives and dialkyl substituted silanylenes. The above compounds are prepared by starting from the hydrocarbons AH as defined above (ie, from hydrocarbons corresponding to the radicals A having the general formula Ia), and with a process that varies according to the structure of - X-. When -X- is a difunctional derivative of the type R3-C-R4 wherein R3 and R4 are selected from monofunctional c rad-c5 alkyl radicals, phenyl, or R3 and R4 together form an alkylene radical of C4-C5, the reaction takes place in two steps. Accordingly, the present invention relates to a process for the preparation of compounds having the general formula AXB, wherein A and B have the meaning defined above and -X- is a radical of the type R3-C-R4, wherein R3 and R4 have the above meaning, which involves the following steps: i) The condensation between the compound having the general formula AH defined above and a ketone having the general formula R3-CO-R4 to give the fulvene compound that has the general formula (III): ii) The addition to the fulvene compound obtained in step (i) of the hydrocarbon BH, the above hydrocarbon BH being selected from any of the hydrocarbons AH and FH defined above. Step (i) of the above reaction takes place in a basic environment, preferably with an alcoholate of a tertiary alcohol, most preferably with potassium terbutylate. Step (ii) of the above process is preferably carried out by preparing the hydrocarbon anion BH and subsequently interacting the previous anion with the product (III) obtained in step (i). It should be noted that the procedure described above allows the preparation of compounds, where -X- forms a bridge between radical A always in position 2 and the cyclopentadienyl radical B in the position specified by the prior art. A further object of the present invention relates to intermediates, of the fulvene type, having the general formula (III), wherein n, R, R *, R3 and R4 have the meanings mentioned above; preferably R = H, R * is selected from H and CH3, R3 = R4 = CH3 or CgH5, n is selected from 3,4,5,6,10. Another object of the present invention relates to a process for obtaining the compounds having the general formula Al-X-Al wherein X is a dialkylsilanylene and the Al radicals, the same among them, are selected from the radicals A defined above, which comprise the reaction of the hydrocarbon A1H with a dialkyl dihalogen silane, preferably a dialkyl dichlorosilane, in a molar ratio of AlH / dialkyl dihalogen silane of about 2/1. In a preferred embodiment, the process is carried out by preparing the hydrocarbon anion A1H, preferably with an alkyl lithium, and the anion thus prepared is interacting with the dihalogen silane. A further object of the present invention relates to a process for obtaining the compounds having the general formula Al-X-B wherein: -X- is a dialkylsilylene; Al is a monofunctional hydrocarbyl radical selected from the radicals A defined above; B is selected from: - A2, where A2 is any of the radicals A defined above provided it is different from Al, - a cyclopentadienyl radical (f), the above procedure is carried out in two steps, the first (step a) comprises the reaction of the compound AlH with a dialkyl dihalogen silane, preferably a dialkyl dichlorosilane, in a molar ratio of AlH / dialkyl dihalogen silane of about l / l; the second step comprises the reaction of the compound obtained in step (a) with a hydrocarbon BH in an essentially equimolar ratio with respect to the product obtained in step (a). In the preferred embodiment, the process is carried out by preparing the hydrocarbon anion AlH, preferably with alkyl lithium, and subsequently reacting, in the first step, the above anion with the dihalogen silane, in a molar ratio consisting essentially of l / l. In the second step, the anion of the hydrocarbon BH is prepared, preferably with an alkyl lithium and the above anion is reacted with the compound obtained in the first step, in a molar ratio of about 1/1. The following examples provide a better illustration of the present invention.

EXAMPLE 1 Synthesis of bis (2, 4, 5, 6, 7, 8-hexahydroazulene-2-yl) dimethylsilane. 12 ml was added to a solution of 2.5 M n-butyllithium in hexane at room temperature, to a solution in 100 ml of THF containing 4.1 grams (0.03 mole) of 2, 4, 5, 6, 7, 8-hexahydroazulene (prepared as described in the co-pending patent application of the same applicant IT-A-MI 95A 002707). An exothermic reaction occurs with the formation of a white solid. The mixture is allowed to stir for 2 hours and then cooled to -70 ° C and 1.93 grams (0.015 moles) of dimethyldichlorosilane are added over a period of about 20 minutes. The temperature is allowed to rise overnight and finally a yellow solution is obtained. After evaporation of the solvent, the product is purified on a column of silica gel eluting with petroleum ether. The product obtained is contaminated with the starting diene which is removed maintaining the fraction under mechanical vacuum for 24 hours. 2.2 grams of the product are obtained (yield 45%), which is pure under NMR and GC analysis.

The spectrum of iH-NMR (CDC13, ppm reí to TMS) is as follows: 6.03 (broad s, 4H), 3.07 (broad s, 2H), 2.50 (m, 8H), 1.90-1.50 (s broad, 12H ), -0.2 (s, 6H).

EXAMPLE 2 Synthesis of 2- [lH-Inden-1-yl) -1-methyl-ethyl] -1,4,5,6,7,8-hexahydro-azulene A solution was prepared in 10 ml of MeOH and 10 ml of acetone, 4.5 grams (0.033 moles) of 2,4,5,6,7,8-hexahydroazulene and 0.3 grams of potassium terbutylate. The above solution is left at reflux temperature for 20 hours, at the end of which, an additional 2.7 grams of potassium terbutylate is added. The mixture is maintained at reflux temperature for another 25 hours, after which the mixture is poured into water and extracted with ethyl ether. After neutralization and anhydrification, the ether extract is evaporated and the residue is purified by elution on a column of silica gel with petroleum ether. 3.8 grams of a fulvene derivative of 2-isopropylene-2,4,5,6,7,8-hexahydroazulene were obtained as a yellow solid (66% yield). The 1H-NMR spectrum of this compound (CDC13, ppm reí to TMS) is as follows: 6.13 (s, 2H), 2.47 (, 4H), 2.09 (s, 6H), 1.64 (m, 6H).

An ether solution (100 ml) of indene (4.0 grams, 0.034 moles) was prepared. 12 ml of a 2.5 M solution in butyl lithium hexane was added and the mixture was left under stirring for 3 hours. Then, the fulvene derivative was added to the above solution, cooled to about -70 ° C. The temperature was allowed to rise and the mixture was left under stirring for 48 hours. The reaction mixture was then hydrolyzed in water and extracted with diethyl ether which, after evaporation, gave a solid which was purified on a column of silica gel using petroleum ether as eluent. 4.5 grams of the product were obtained (74% yield). Its spectrum of ^ -H-NMR (CDC13, ppm reí to TMS) is as follows: 7.4-7.0 (m, 4H), 6.8 (dd, 1H), 6.45 (dd, 1H), 5.95 (s, 1H) , 3.60 (broad s, 1H), 3.10 (broad s, 2H), 2.40 (m, 6H), 1.23 (s, 3H), 0.94 (s, 3H).

EXAMPLE 3 Synthesis of bis (decahydrocyclopentacyclododecene-2-yl) dimethylsilanes 22 ml of 2.5 M BuLi in hexane was added to a solution of 11 grams of 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 -decahydro-2H-cyclopentacyclododecene, prepared as described in co-pending patent application of the same applicant IT-A-MI 95A 002707, in 100 ml of pentane. The mixture was left under stirring overnight, the solid obtained was filtered and dried to obtain 9.0 grams of the corresponding lithium salt. A solution in THF (100 ml) of 3.4 grams (0.16 moles) of the above lithium salt was prepared. 1.0 grams (0.008 moles) of dimethyldichlorosilane were added at -70 ° C in about 20 minutes to this solution in THF. Then the temperature was allowed to rise overnight, obtaining at the end a solution of yellow color. After evaporation of the solvent, ethyl ether was added and the mixture was hydrolyzed with dilute hydrochloric acid. The ether extract was washed neutral, dried and evaporated. The residue (3.7 grams) was purified on a column of silica gel eluting with petroleum ether. 2.2 grams were obtained (62% yield), which under NMR analysis proved to be a mixture of bis (2,4,5,6,7,8,9,10,11,12,13-decahydro-2H- cyclopenta-cyclododecene-2-yl) dimethyl silane. 1H-NMR (CDC13, ppm reí to TMS) 6.62 (s), 6.39 (s broad), 6.21 (s broad), 6.12 (s broad), 3.23 (m), 2.91 (s), 2.35 (m), 1.88-0.84 (m), 0.08 (s broad), -0.21 (s broad). 13 C-NMR (CDC13, ppm re to TMS): 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.

EXAMPLE 4 Synthesis of 1,2-bis- (1-methyl-4, 5, 6, 7, 8, 9, 10-11-12-13-decahydro-2H-cyclopentacyclododecene-2-yl) -dimethyl silane 28 ml (70.10 moles) of BuLi in hexane was added to 15.1 g (69.2.10 -3 moles) of 1-methyl-4, 5, 6, 7, 8, 9, 10, 11, 12, 13 -decahydro- 2H-cyclopentacyclododecene, prepared according to examples 4 of IT-A-MI 95A 002707, diluted with 100 ml of pentane. The mixture was stirred overnight and then filtered. The solid was recovered and dried: 12 g of the corresponding lithium salt were obtained. To 5.6 g (27.7.10-3 moles) of the above lithium salt, dissolved in 100 ml of anhydrous THF and cooled to -70 ° C, was added 1.7 g (13.2.10-3 moles) of dichlorosilane; then, the temperature was allowed to rise to 20 ° C overnight. After evaporation of the solvent, diethyl ether was added and the reaction mixture was hydrolyzed with dilute HCl. The organic phase was washed neutral, dried and evaporated. The residue was purified on a column of silica gel eluting with petroleum ether. 3.5 g (55% yield), of 1,2 bis (1-methyl-4, 5,6,7,8,9,10,11,12, 13-decahydro-2-H-cyclopentacyclododecene-2) were obtained -yl) dimethylsilane. 1, 2.3.5-tetrahydro-pentalene '-H1 ** 11-1, 2,3,5-tßlrβhldro-pβntalene 2-? Rtet? L-1, 2,3,5-tßtrahldro-pßntalßr? O 4,5,6,7 C-t? Tra lchloro-2 H-lnd? T? O 7-mßtl-4,5,6,7-Cetrahydro-2H-inino-6-mel'l-4.5.6.7-tetrahldfs-2H-indefio 6-Fepyl-4,5,6,7-tetrahydro-2H-ir? Lepo 2, 8-phenyl-2,4,5,6,7,8-hexahydroazole , 5,6,7,8,9-l? ßxaM ro-2H-clclopßntaclciooc < ßno 4,5,6,7,8,9, 10.11 -octah¡dro-2H-cyclopefitac? Clodecene 4. 5.6.7.6.9,10.1 .12.13-d * caH? Dro-2H-cte »or? Rtrlclclododßc«? O Table 1. 1, 2-tx £ - (2,4,5,6 &? Trah? Dropental? N -2-? L)? 1, 2- * e- (24.5,8,7, ß-hexa? Drc? ßzuten-2-? L) ethane 1, 1 -bls-. { 2,4,5,6,7,8-? Exa l roazulen-2-ll) -1 -pethyl-ethane 1,1-b? S- (4, S, 6,7, ß, 9-hexa? Dro-2H-? Clopen-ac? Clooct? N-2-? L) -1-mebl-ßlano is- < 2,4,5,6-tetranidro? Eptatorv2-l) d? Metfls? Lano bis -. { 2.4.5, 6.7,8-hexeí ?? roaz? iefv2Hl) d? p? etíte? lano 1,2-blt- [1,1, 2- trtnßll 2.4.5.7,8-he »ldpoazulßt? -2-IO] propane Table 2a 2- Di-ethyl- (2> 4,5,6-tetrahydro-peplalen-2-4l > -silanyl) -2,4,5l6,7,8-hexahydro-azuk 8 2- (1-Me1yl-1- (2,4,5,6, -tetraht lro-pental? N-2-yl) -ethyl] -2I4,5,6,7,8-h? Xah¡dro- azuleno -[1 , 7,8-Hexahydro-azulen-2-yl) -1-methyl-ethyl] -4,5, β, 7,8,9-tβ-exahydro-2H-cyclopentacycloicytope 2- [1 - (2,4,5,6 > 7,8, .Hexahidro-azulen-2-ylmethyl-silaniq ^, 5,6,7,8I9,10,11,12,13 ^ lecahldro-2H - cyclopentacloclotene 2- [H2,4,5,6,7,8-Hexahldro-azu cahWro-2H cyclopentacyclooctene 2-11 -Methyl-1-. { 2,4,5,6-tetrahydro-pentalen-2? Tiq-4, S, 6. 7.8,9,10,11, 12,13, -decahydro-2H cyclopentacyclooctene Table 2b 2-pi etll- (2,4,5 > 6-tet? 1? Ldro-entalen-2-ll) -sulanil] -, 5,6,7,8,9, 10,11, 1, 13- decahydro-2H-cyclopentacyclododzecene -. { (4,5,6,7,8-hßxahydro-2H C-co lopßOntacyclocyte-2HCl) -dO-methyl-4,5,6,7,8,9, 0,11,12,13-decahldro- 2H-clclopen1acick > dodßceno - [1- (4,5, ß, 7,8,9l-hexahydro-2H-cyclopentacycloheten-2-yl) -1-methyl-ethyl-, 5,6,7,8,9,10,1,12 , 13-decahydro-2H-cyclopentacyclododzecene - | 1- < 4.5, ßl7,8,9, -hexahydro-2H-cyclopentacylclooc1ep-2-yl) -1-phenyl-ethyl] -4,5,6,7,8,9,10 , 1, 13-decahldro-2H-cyclopentacloclodedecene ethyl-1- (2,4,5, ß4etra idr? i > enta C Vfc im len-2Hl) -etiQ 4,5,6,7,8,9, heoxahidro-2H-c: kjp «ntac¡ck > C) teno .5 > 6,7,8,9, -hexahydro-2H-clck > pentaclclooctene 2- [2-. { 4,5,6,7,8,9-hexahldro-2 H -clclopentaclclo c te t »-2-yl) -etll] -4,5,6,7,8,9, 10,11. l2,13-decahydro-2H-cyclopeptacyclododecene 2-I2- (2A5, ß.-tetrahydro-pental-2-yl) -etiMIM, 5,6,7, 8,9-hexahydro-2H-cyclopentaclocyclohetene Table 2c bls-. { 1-metll-2,4,5, ß, 7l8-hexahldroazuleno-2-IQdlmetllsllat ?? bls- 1 -methyl-4, 6,6,7,8,9-hßxa h lro-2H-cict pentaclcloocten -2-il) d I medís lia no 1. 1-bis- (1-ethyl-2,4,5,6,7,8-hexaMdroazulen-2-il) -1- etll-etarto , 1 -bis- < 1 -metí I-4, 5,6,7,8,9-hexah idro-2H-clclopentacicloocten -2-IQ-1 -metll-eta no 1,2-bis-. { 1-pMethyl-2,4, S, 6l7, ß-l? Exahydroazulen-2-yl) tetramethyl i5-lane bis - (1-mßhl-4,5,6,7,8,9,10,11,12,13-dßcah l ro- 2H-clclopßntaciclododßcen-2-ll) -dlmetpsllano Table 2d ^ 1-ctcl Copánntan-2 & , 4.-dlenlli-1-met ° ll-etil) -2,4,5,6,7,8-hexahidro-azululno 2- (ciclopentan-2,4-d Ciep ¡ld me & f il-si lan¡l) -2t, 4, 5 °, 6,7,8-t? exahi ro-azuleno 2- (2-cyclopenta-2,4-dlepll- "tl l) -2.4, 5,6,7,8-exahldro-azulene 2- (2-cyclopenta-2,4-dienyl-1,1l C2-rlme < ilW-propiQ-2,4,5-.6Í, 7,8-hexa idro-azulene - (Dlme Otll- (3-fnetll-colclope-ntIa-2 ^, 4-dlenll) -s «ilanll] - 2) -2 4,5,6,7,8-hexahldro-azulene 2- (1-Metl - (3- eai-cyclopentan-2,4-dlenyl) -el_p-2,4,5,6,7,8-exahldro ^ azuler) 2 ^ H3-tert-Butyl- < rfclopenta-2.4-dienll) -1 netll'etll) -2,4l5.6.7,8-hexahldro-azuleno 2- 1- (1- ethyl-1- <3 & lmet «sllanll < l-aopenta-2,4-dlenll *) ^ tll) -2,4,5,6,7? ? exahldro-azulerv- Table 3a 2- [dl ßtlH3-trlmetilsllllanll-clclopenla-2,4-dlepll) -sllapll] -Z4,6, ß, 7.8-hexal? Ldro ^ blueßr > or 2- [1- «netJ -. { 2,3,4,5-totra? Netil-cyclopenta-2,4-diepil) - aQ-2,4, Sl6l7,8-hexahydro-azu [«no 2- [2- (2,3,4,5-tetrametll-cick > penta-2,4-dienll) -etill-2,4,5,6,7l8-hexahydro-azulene 2-. { 1,1 ^ -trimethyl ^ - (2,3,4l5-tefn methyl iclopepta-2,4-diepil > propyl] -2,4,8,6,7,8-hexat? Idro-azulepo 2- [1-. { 1H-lnden-1-yl) -lHn? Ethyl-etiq-1l4,5.6.7l8-hexahldro-azulene - [2- [1 H-lnder > -1-Jl 1, 1, 2- rimetlH3ropi -2.4, S.6,7,8-riexahldro-a2Uleno Table 3b 2-. { 2- (1H-lndßn-1-ll) -βdl] -2? 3,6,7,8, -hexahldro-azulßno 2- [1 -matfl-1 -. { 4 -metí H-lndßn-1 -H * HßH [] - 1, 4,5,6,7,8, -hexah idrs-azuleno 9- [2- (2.4.5,6,7, ß-t? Exa ldro ^ zulen-2-ll) -1, -tri e < ll-prop | -] - 9H-fluorene Table 3c -11 -metll-1 -. { 4, 5,6,7-tetrah idro-3H-lnden-2-yl '- «tJI] -1 H-Indeno 2- [1- (1Hlr? Dßn-1-ÍIH-meai-ßtil] -4, d, 6,7, ß.9-tetrahl lro-1H-clclopentaclocloctane 2- [1- < 1H nclen-1-JI) -1-metJI-etíQ-4,5,6,7,8,9, 10,11, 12,13 ^ ecahidro-1H-ciclop «ntacyclododecene 9- | 1-methyl-1- (3,4,5,6-tetrahydro-pephitalene-2-yl) -ethyl] 9H-fluorene 9- [1-methyl-1- (4? 6,7-tetrahydro-3 H-lden-2-yl) -etll] 9H-f-1-oren 9-. { 1-4? 8,7,8,9-hßxahydro-3H-ck; top «ptac '?; K > octßn-2-yl) -1-methyl-etl] 9M-fluorene Table 3

Claims (17)

1. Bridged cyclopentadienyl derivatives having the general formula (I) A-X-B (I) wherein 1) A is a hydrocarbyl radical. monofunctional that has the general formula (II): characterized in that R and R * are selected from: - H, - monofunctional alkyl radicals having from 1 to 3 carbon atoms, - monofunctional alkylaryl and aryl radicals, provided that the number of R is different from H and is not greater than 2 and that at least one of R * is H; 2) n is an integer from 2 to 20; 3) -X- is the bridge between A and B and consists of a bifunctional radical selected from: a) a linear, branched or cyclic C2-C10 alkylene group; b) an alkyl or substituted aryl silanylene group having 1 to 2 silicon atoms; c) a substituted alkyl silalene group; d) a siloxasilanylene group or -Si (R- ^) 2-0-Si (R2) 2-, tetraalkyl or substituted tetraaryl; 4) B is a monofunctional hydrocarbon radical selected from: (e) any of the radicals A defined above; (f) a cyclopentadienyl radical.

2. The cyclopentadienyl derivatives according to claim 1, characterized in that R = H, R * is selected from H and CH3.

3. The cyclopentadienyl derivatives according to claim 1, characterized in that n is selected from 3,4,5,6,10.

4. The cyclopentadienyl derivatives according to claim 1, characterized in that R = R * = H and n is selected from 5, 6 and 10.

5. The cyclopentadienyl derivatives according to claim 1, characterized in that -X- is selected from linear or branched alkylene derivatives and dialkylsilanilenes.

6. The cyclopentadienyl derivatives according to claim 5, characterized in that -X- is selected from ethylene, isopropylidene and dimethylsilanylene.

7. The cyclopentadienyl derivatives according to claim 1, characterized in that B is a monofunctional cyclopentadienyl radical (f) selected from cyclopentadienyl, indenyl, fluorenyl and the alkyl, aryl derivatives; relative substituted trialkylsilyl.

8. The cyclopentadienyl derivatives according to claim 7, characterized in that B is a monofunctional cyclopentadienyl radical (f) selected from cyclopentadienyl, indenyl, fluorenyl.

9. A process for the preparation of the compounds having the general formula A-X-B, characterized in that A and B have the meaning given above, and -X- is a radical of the type R3-C-R4, wherein R3 and R4 are selected from alkyl radicals, monofunctional C ^ Cg, phenyl, or R3 and R4 together form an alkylene radical of 4-C5, which involves the following steps i) The condensation between the hydrocarbon having the general formula AH, defined above and a ketone having the general formula R3-CO-R4 to give the fulvene compound having the general formula (III). ii) The addition to. fulvene compound having the general formula (III) obtained in step (i), of the hydrocarbon BH, the hydrocarbon BH above selected from any of the hydrocarbons corresponding to the monofunctional hydrocarbyl radicals (e) and (f) defined in claim 1 .

10. The method according to claim 9, characterized in that: Step (i) takes place in a basic environment, preferably with an alcoholate of a tertiary alcohol, most preferably with potassium terbutylate; Step (ii) is carried out by preparing the hydrocarbon anion BH and subsequently interacting the previous anion with the fulvene intermediate (III) obtained in step (i).

11. The process according to claim 9, characterized in that R * is selected from H and CH3, R = H, R3 = R4 = CH3 or CgH5, n is selected from 3,4,5,6,10.

12. The process according to claim 11, characterized in that the ketone having the general formula R3-CO-R4 is acetone and n is selected from 5, 6 and 10.

13. Fulvene derivatives having the general formula (III) (neither) characterized because n, R *, R, R and R4 have the meaning defined above.

14. The fulvene derivatives according to claim 13, characterized in that R = H, R * is selected from H and CH 3, R 3 = R 4 = CH 3, n is selected from 3,4,5,6 and 10.

15. A process for obtaining the compounds having the general formula Al-X-Al, characterized in that -X- is a dialkylsilanylene and the Al radicals, the same among them, are selected from the radicals A defined above, comprising the reaction of the hydrocarbon AlH with a dialkyl dihalogen silane, in a molar ratio of AlH / dialkyl dihalogen silane of about 2. /1.

16. The process according to claim 15, characterized in that the dialkyldi-halogensilane is dialkyldichlorosilane.

17. A process for obtaining the compounds having the general formula Al-X-B characterized in that: -X- is a dialkisilanylene; Al is a monofunctional hydrocarbyl radical selected from the radicals A defined above; B is selected from: - A2, where A2 is any of the radicals A defined above provided it is different from Al, - a cyclopentadienyl radical (f), the above procedure is carried out in two stages, the first ( step a) comprises the reaction of the compound AlH with a dialkyl dihalogen silane, preferably a dialkyl dichlorosilane, in a molar ratio of AlH / dialkyl dihalogen silane of about l / l; the second step comprises the reaction of the compound obtained in step (a) with a hydrocarbon BH in an essentially equimolar ratio with respect to the product obtained in step (a).