USOO6197990B1 (12) United States Patent (10) Patent No.: US 6,197,990 B1 Oda et al. (45) Date of Patent: Mar. 6, 2001

(54) PROCESS FOR THE PREPARATION OF (56) References Cited CYCLOPENTADIENYL METAL SALT AND PROCESS FOR THE PREPARATION OF U.S. PATENT DOCUMENTS DERVATIVE OF CYCLOPENTADIENE 6,046,346 * 4/2000 Yokoyama et al...... 556/53 USING THE SAME 6,066,704 * 5/2000 Katayama et al...... 526/127 (75) Inventors: Yoshiaki Oda, Toyonaka; Kazuhiro FOREIGN PATENT DOCUMENTS Yamauchi, Ibaraki; Hidenori Hanaoka, Osaka; Hiroshi Souda, Ibaraki, all of 6-279477 10/1994 (JP). (JP) OTHER PUBLICATIONS (73) Assignee: Sumitomo Chemical Company, Wiesenfeldt et al., Journal of Organometallic Chemistry, vol. Limited, Osaka (JP) 369, pp. 359-370, 1989.* Chem. Ber, 124, 1991, pp. 2185-2190, “Mono-, Bis-and (*) Notice: Subject to any disclaimer, the term of this Tris (cyclopentadienyl) Compounds-Syntheses of New patent is extended or adjusted under 35 Polydentate Ligands and their Molybdenum and Tungsten U.S.C. 154(b) by 0 days. Complexes”, Plenio, H. (21) Appl. No.: 09/341,498 Journal of Organometallic Chemistry, 495, 1995, pp. 195-202, “Synthesis and Characterization of Titanium Com (22) PCT Filed: Jan. 14, 1998 plexes Containing the 1-(3-Butenyl)-2,3,4,5-Tetramethyl (86) PCT No.: PCT/TP98/00110 cyclopentadienyl Ligand’, Okuda, J. et al. S371 Date: Jul. 13, 1999 * cited by examiner S 102(e) Date: Jul. 13, 1999 Primary Examiner Porfirio Nazario-Gonzalez (87) PCT Pub. No.: WO98/30567 (74) Attorney, Agent, or Firm-Sughrue, Mion, Zinn, Macpeak & Seas, PLLC PCT Pub. Date:Jul. 16, 1998 (57) ABSTRACT (30) Foreign Application Priority Data A cyclopentadienyl metal Salt is prepared by reacting a Jan. 14, 1997 (JP) ...... 9-005036 cyclopentadiene and a metal hydride in the presence of an Jan. 14, 1997 (JP) ...... 9-005037 amine compound. Furthermore, a derivative of a cyclopen (51) Int. Cl." ...... C07F 7/04 tadiene in which a phenyl group is bonded to its cyclopen (52) U.S. Cl...... 556/478; 556/87; 585/350; tadienyl moiety through an element of the 14 group of the 585/390 Periodic Table is prepared using Such a reaction. (58) Field of Search ...... 585/350, 390; 556/87, 478 20 Claims, No Drawings US 6, 197990 B1 1 2 PROCESS FOR THE PREPARATION OF CYCLOPENTADENYL METAL SALT AND (3) PROCESS FOR THE PREPARATION OF R6 Cp DERVATIVE OF CYCLOPENTADIENE R5D1 R7 USING THE SAME R4 A.

FIELD OF THE INVENTION R3 R1 The present invention relates to a process for the prepa 1O ration of a cyclopentadienyl metal Salt and a process for the R2 preparation of a cyclopentadiene derivative using the same. wherein BACKGROUND ART A is an atom of the 16 group of the Periodic Table, 15 B is an atom of the 14 group of the Periodic Table, Cyclopentadienyl metal Salts and derivatives of cyclopen R", R. R. R, R and R are the same or different and tadiene derived from Such metal Salts are important inter independently represent a hydrogen atom, a fluorine atom, a mediates which are used in various fields Such as the C-C alkyl group which may optionally be Substituted preparation of medicines, agrochemicals, metallocenes, etc. with a fluorine atom, a C7-Co aralkyl group which may An effective proceSS for the preparation of cyclopentadienyl optionally be Substituted with a fluorine atom, a Co-Co aryl metal Salts comprises removing hydrogen atoms from cyclo group which may optionally be Substituted with a fluorine pentadiene with bases to Synthesize corresponding metal atom, a C-C Substituted Silyl group, a C-C alkoxyl group which may optionally be Substituted with a fluorine Salts, and for example, Such a process using butyl lithium is atom, a C7-Caralkyloxyl group which may optionally be known (J. Organomet. Chem., 462, 1993, 57-67). 25 Substituted with a fluorine atom, a Co-Co aryloxyl group However, the process using butyl lithium has disadvan which may optionally be substituted with a fluorine atom, or tages Such that (1) used reagents are expensive, (2) it a C-Co di-Substituted amino group which may optionally be substituted with a fluorine atom, provided that any two or requires low-temperature facilities to perform the reaction, more of R', R,R,R,R and R may together form a ring, and (3) the reaction should be carried out at the low R’ is a hydrocarbon group which may optionally be concentration of reagents in an industrial Scale, and thus the substituted with a fluorine atom, or a tri-substituted silyl productivity decreases, Since the desired product cannot group, and effectively be obtained if the reaction is not carried out at a Cp is a cyclopetadiene ring comprising the Step of react low temperature, although the amount of reaction heat is ing a halide compound of the formula (1): large. As a matter of course, cyclopentadiene derivatives 35 derived from cyclopentadienyl metal Salts have the same (1) problems. Also, a process using an alkali metal hydride is known. However, this process has disadvantages Such that (1) the 40 kinds of Substrates are extremely limited, (2) mineral oils, which are usually contained as a Stabilizer in marketed alkali metal hydrides, should be beforehand removed, and thus the use of the alkali metal hydrides is unfavorable from the 45 Viewpoint of disaster measures, and the number of proceSS Steps in the industrial production. wherein A, B, R. R. R. R", R, R and R7 are the same DISCLOSURE OF THE INVENTION as defined above, and Y is a chlorine atom, a bromine atom 50 or an iodine atom In View of the above circumstances, the present inventors with a cyclopentadiene of the formula (2): extensively Studied a proceSS which can easily produce a cyclopentadienyl metal Salt without the use of expensive HCp (2) reagents and low-temperature facilities, and has no Substrate wherein Cp is the Same as defined above, in the presence of Specificity. As a result, it has been found that Such an object 55 a metal hydride and an amine compound. can be accomplished by the reaction of a cyclopentadiene Here, the proceSS according to the first aspect of the and a metal hydride in the presence of an amine compound, present invention, that is, the preparation process of a and thus the present invention has been completed. cyclopentadienyl metal Salt by the reaction of a cyclopen Accordingly, the present invention provides 60 tadiene and a metal hydride in the presence of an amine compound, will be explained. 1. a process for the preparation of a cyclopentadienyl Cyclopentadienes used in the present invention may be metal Salt comprising the Step of reacting a cyclopen any compounds having a cyclopentadienyl moiety. For tadiene and a metal hydride in the presence of an amine example, a cyclopentadiene of the formula (2), which is used compound, and 65 in the processes according to the first and Second aspects of 2. a process for the preparation of a cyclopentadiene the present invention, may be a compound of the formula derivative of the formula (3): (2a): US 6, 197990 B1 3 4 biscyclopentadienylpropane, biscyclopentadienylbutane, (E)m biscyclopentadienylpentane, biscyclopentadienylhexane, b is cyclop ent a die nyl dimethylsilane, b is cyclop ent a die nyl dip he nyl Silane, b is methylcyclop ent a die nyl dimethylsilane, b is dimethylcyclope nt a die nyl dimethylsilane, b is trimethylcyclop ent a die nyl dimethylsilane, wherein m is an integer of 0 to 5, E groups are the same or biStetra methylcyclop entadienyldimethylsilane, different and independently represent a C-C alkyl group, biscyclopentadienyltetramethyldisilane, etc.; a phenyl group, a naphthyl group, or a tri-Substituted Silyl bisindene compounds Such as bisindenylmethane, group having Substituents Selected from the group consisting bisindenylethane, bisindenylpropane, bisindenylbutane, of a C-C alkyl group and a phenyl group, provided that, b is in denylp entane, b is in de nyl he Xane, when two E groups are present on adjacent carbon atoms, bisindenyldimethylsilane, bisindenyldiphenylsilane, they may be bonded at their ends to form a benzene ring, a cyclohexane ring or a cyclohexene ring, which is condensed b is methyl in denyl dimethylsilane, 15 b is dimethyl in denyl dimethylsilane, with the cyclopentadienyl ring, bisindenyltetramethyldisilane, etc.; G is a hydrogen atom when m is 5, or when m is 0 to 4, bisfluorene compounds Such as bisfluorenylmathane, G is a hydrogen atom or a group of the formula (2b): bisfluorenylethane, bisfluorenylpropane, bisfluorenylbutane, b is fluore nylp entane, b is fluore nyl he Xane, bisfluorenyldimethylsilane, bisfluorenyldiphenylsilane, | | f 2-(E), bisfluorenyltetramethyldisilane, etc.; sy comple X compounds Such S cyclop ent a die nyl in de nyl me thane, cyclop ent a die nyl in denyle thane, 25 cyclop ent a die nyl in de nyl prop a ne, wherein p is an integer of 1 or 2, q is an integer of 0 to 4, cyclop ent a die nyl in denylbutane, X is a carbon atom or a silicon atom, X and X are the cyclop ent a die nyl in denylp ent ane, Same or different and independently represent a hydrogen cyclop ent a die nyl in de nyl he Xane, atom, a C-C alkyl group or a phenyl group, E' is a cyclop ent a die nyl in de nyl dimethylsilane, substituent selected from those defined for E, provided that cyclop ent a die nyl in denyldip he nyl Silane, when X is a Silicon atom, X and X are not hydrogen methylcyclope intadienylindenyldimethylsilane, atOmS. dimethylcyclop entadienylindenyldimethylsilane, Herein, the cyclopentadienyl group includes a mixture of trimethylcyclopentadienylindenyldimethylsilane, its tautomers, which is usually obtained. The chemical tetramethylcyclopentadienylindenyldimethylsilane, Structures in this specification represent a part of tautomers 35 cyclopen tadienyl in denyltetra methyl disilane, as typical examples. cyclop ent a die nyl flu ore nyl me thane, Examples of cyclopentadienes, which are compounds cyclop ent a die nyl flu ore nyl ethane, having a cyclopentadienyl moiety, include cyclop ent a die nyl flu ore nyl prop a ne, cyclopentadiene compounds Such as cyclopentadiene, cyclop ent a die nyl flu ore nylbutane, methylcyclopentadiene, dimethylcyclopentadiene, 40 cyclop ent a die nyl flu ore nylp entane, trimethylcyclopentadiene, tetramethylcyclopentadiene, cyclop ent a die nyl flu ore nyl he Xane, pentamethylcyclopentadiene, ethylcyclopentadiene, cyclop ent a die nyl flu ore nyl dimethylsilane, n-propylcyclopentadiene, isopropylcyclopentadiene, cyclop ent a die nyl flu ore nyl dip he nyl Silane, n-butylcyclopentadiene, Sec.-butylcyclopentadiene, tert.- methylcyclopentadienylfluorenyldimethylsilane, butylcyclopentadiene, n-pentylcyclopentadiene, 45 dimethylcyclopentadienylfluorenyldimethylsilane, neopentylcyclopentadiene, n-hexylcyclopentadiene, trimethylcyclopentadienylfluorenyldimethylsilane, n-octylcyclopentadiene, phenylcyclopentadiene, tetramethylcyclopentadienylfluorenyldimethylsilane, naphthylcyclopentadiene, trimethylsilylcyclopentadiene, cyclopentadienylfluorenyltetramethyldisilane, etc. trie thylsilyl cyclop ent a die ne, tert. - The process of the present invention can easily produce butyldimethylsilylcyclopentadiene, etc.; 50 desired compounds at a high yield, when cyclopentadiene indene compounds Such as indene, methylindene, compounds having two or more Substituents are used. dimethylindene, ethylindene, n-propylindene, isopropyl Examples of metal hydrides include alkali metal hydrides indene, n-butylindene, Sec.-butylindene, tert-butylindene, Such as lithium hydride, Sodium hydride, potassium hydride, n-pentylindene, neopen tylindene, n-hexylindene, etc.; and alkaline earth metal hydrides Such as calcium n- octylindene, n - de cylinde ne, phenylindene, 55 hydride, etc. The amount of a metal hydride is usually from methylphenylindene, naphthylindene, trimethylsilylindene, 0.5 to 3 moles, preferably from 0.9 to 2.0 moles, per one triethylsilylindene, tert.-butyldimethylsilylindene, mole of the compound (2). Sodium hydride and potassium tetrahydroindene, etc.; hydride can be used in the form of a marketed product fluorene compounds Such as fluorene, methylfluorene, containing mineral oils, although they may be used after ethylfluorene, n-propylfluorene, isopropylfluorene, 60 washing the mineral oils off with hydrocarbon solvents such n-butylfluorene, Sec.-butyl fluorene, tert.-butyl fluorene, as hexane, etc. n-pentylfluorene, neopentylfluorene, n-hexylfluorene, AS an amine compound, a compound of the following n-octylfluorene, n-decylfluorene, n-dodecylfluorene, formula (4) is exemplified: phenylfluorene, naphthylfluorene, trimethylsilylfluorene, QQQN triethylsilylfluorene, tert-butyldimethylsilylfluorene, etc.; 65 b is cyclop ent a die ne compound S. Such as wherein Q, Q and Q are the Same or different and biscyclopentadienylmethane, biscyclopentadienylethane, independently represent a hydrogen atom, a C-C alkyl US 6, 197990 B1 S 6 group, or a C-Cs cycloalkyl group; or a phenyl group, a The reaction is usually carried out in a Solvent which is naphthyl group, a benzyl group, a naphthylmethyl group or inactive to the reaction. Examples of Solvents are aprotic a pyridyl group, which may optionally be Substituted with at Solvents, for example, aromatic hydrocarbon Solvents Such least one Substituent Selected from the group consisting of a as benzene, toluene, Xylene, etc., aliphatic hydrocarbon halogen atom, a C-C alkyl group, a C-C alkoxyl group, Solvents Such as pentane, hexane, heptane, octane a carboxyl group, a C-C alkoxycarbonyl group, a nitro cyclohexane, etc., ether Solvents Such as diethyl ether, group, an amino group, a phenyl group, a naphthyl group methyl tert.-butyl ether, tetrahydrofuran, 1,4-dioxane, etc.; and a benzyl group; or the terminals of Q and Q are bonded each other to form a C-C alkylene group which may amide Solvents Such as hexamethylphosphoric amide, optionally be Substituted with at least one C-C alkyl dimethyl form amide, dimethylace tamide, group, or a group of the formula: (-CHCH-)-O or N-methylpyrrollidone, etc.; halogen-containing Solvents (-CHCH-)-N-Q in which Q is a substituent selected Such as chlorobenzene, dichlorobenzene, etc. These Solvents from those defined for Q, or Q may be an ethylene group may be used Singly or in admixture of two or more Solvents. or a group of the formula: -(CH)N= and bonded to a The amount of a solvent is usually from 1 to 200 wt. parts, ring formed by Q and Q, provided that Q, Q and Q are preferably from 3 to 30 wt. parts, per 1 wt. part of a not hydrogen atoms at the Same time. 15 cyclopentadiene. Specific examples of amine compounds are To carry out the reaction, a cyclopentadiene, a metal primary amines including primary amines, for example, hydride and an amine compound are mixed at the same time primary amines Such as aniline, chloroaniline, bromoaniline, in a Solvent, or a metal hydride and an amine compound are fluoroaniline, dichloroaniline, dibromo aniline, firstly mixed, and then a cyclopentadiene is added to the difluoroaniline, trichloroaniline, tribromoaniline, mixture. trifluoroaniline, tetrachloroaniline, tetrabromoaniline, A reaction temperature is not limited, but is preferably in tetrafluoroaniline, pentachloroaniline, pentafluoroaniline, a range in which no low-temperature facilities are necessary, nitro aniline, dinitroaniline, hydroxyaniline, for the industrial production. For example, a reaction tem phenylene diamine, anisidine, dimethoxyaniline., perature is usually in the range between 0 and 70° C., trimethoxyaniline, ethoxyaniline, diethoxyaniline, triethoxyaniline, n-propoxyaniline, isopropoxyaniline, 25 preferably between 10 and 60° C. n-butoxyaniline, Sec.-butoxyaniline, isobutoxyaniline, tert.- The above reaction effectively provides a desired cyclo butoxyaniline, phenoxyaniline, methylaniline, ethylaniline, pentadienyl metal Salt. The obtained cyclopentadienyl metal n-propylaniline, isopropylaniline, n-butylaniline, Sec.- Salt may be used in the form of a reaction mixture, or may butylaniline, isobutylaniline, tert.-butylaniline, be isolated from the reaction mixture. In general, the reac dimethylaniline, diethylaniline, di-n-propylaniline, tion mixture as Such can Satisfactorily be used. diisopropylaniline, di-n-butylaniline, di-Sec.-butylaniline, Now, the process according to the Second aspect of the diisobutylaniline, di-tert.-butylaniline, trimethylaniline, present invention, that is, the preparation process of a triethylaniline, diisopropylaniline, phenylaniline, cyclopentadiene derivative of the formula (3) by the reaction benzylaniline, aminobenzoic acid, methyl aminobenzoate, of a halide compound of the formula (1) and a cyclopenta ethyl aminobenzoate, n-propyl aminobenzoate, isopropyl 35 diene of the formula (2) in the presence of a metal haride and aminobenzoate, n-butyl aminobenzoate, isobutyl an amine compound will be explained. aminobenzoate, Sec.-butyl aminobenzoate, tert.-butyl Examples of an atom of the 16 group of the Periodic aminobenzoate, etc.; as well as naphthylamine, Table, which is represented by “A” in the formula (1), naphthylmethylamine, benzylamine, propylamine, include an oxygen atom, a Sulfur atom, a Selenium atom, etc. butylamine, pentylamine, hexylamine, cyclohexylamine, 40 An oxygen atom and a Sulfur atom are preferable, and an he pty la mine, octylamine, 2-amin opy ridine, oxygen atom is more preferable. 3-aminopyridine, 4-aminopyridine, etc., Examples of an atom of the 14 group of the Periodic Secondary amine S Such as N-methylaniline, Table, which is represented by “B”, include a carbon atom, N-ethylaniline, diphenylamine, N-methylchloroaniline, a Silicon atom, a germanium atom, etc. A carbon atom and N-methylbro moaniline, N-methylfluoroaniline, 45 a Silicon atom are preferable. N-methyla nisidine, N-methyl methyla niline, Examples of a C-C alkyl group for R', R. R. R", R N-methylethylaniline, N-methyl-n-propylaniline, or R' include a methyl group, an ethyl group, a n-propyl N-methylisopropylaniline, diethylamine, diproylamine, group, an isopropyl group, a n-butyl group, a Sec.-butyl diisopropylamine, dip enty lamine, dihexylamine, group, a tert-butyl group, a n-pentyl group, a neopentyl dicyclohexylamine, diheptylamine, dioctylamine, 50 group, an amyl group, a n-hexyl group, a n-Octyl group, a morpholine, piperidine, 2,2,6,6-tetramethylpiperidine, n-decyl group, a n-dodecyl group, a n-pentadecyl group, a pyrrollidine, 2-methyla minopy ridine, n-eicosyl group, etc. Among them, a methyl group, an ethyl 3-methylaminopyridine, 4-methylaminopyridine, etc., group, an isopropyl group, a tert-butyl group and an amyl tertiary amines such as N,N-dimethylaniline, N,N- group are preferable. dimethylchloroaniline, N,N-dimethylbromoaniline, N,N- 55 Any one of these alkyl groups may optionally be Substi dimethylfluoro aniline, N,N-dimethylanisidine, tuted with one or more fluorine atoms. Examples of a N-methylmethylaniline, N,N-dimethylethylaniline, N,N- fluorinated C-C alkyl group include a fluoromethyl dimethyl-n-propylaniline, N,N-dimethylisopropylaniline, group, a difluoromethyl group, a trifluoromethyl group, a 2-dimethylaminopyridine, 3-dimethylaminopyridine, fluoroethyl group, a difluoroethyl group, a trifluoroethyl 4-dimethylaminopyridine, 1,4-diazabicyclo2.2.2]octane, 60 group, a tetrafluoroethyl group, a pentafluoroethyl group, a 1,5-diazabicyclo4.3.0non-5-ene, 1,8-diazabicyclo5.4.0) perfluoropropyl group, a perfluorobutyl group, a perfluoro undec-7-ene, etc. pentyl group, a perfluorohexyl group, a perfluorooctyl Among them, primary and Secondary amines are prefer group, a perfluorodocecyl group, a perfluoropentadecyl ably used. More preferably, primary anilines are used. group, a perfluoroeicosyl group, etc. The amount of an amine compound is usually from 0.001 65 Examples of a C-Co aralkyl group for R', R, R, R", to 2 moles, preferably from 0.01 to 0.5 mole, per one mole R or R include a benzyl group, a (2-methylphenyl)methyl of a metal hydride. group, a (3-methylphenyl)methyl group, a (4-methylphenyl) US 6, 197990 B1 7 8 methyl group, a (2,3-dimethylphenyl)methyl group, a (2,4- n-propoxy group, an isopropoxy group, a n-butoxy group, a dimethylphenyl)methyl group, a (2,5-dimethylphenyl) Sec.-butoxy group, a tert-butoxy group, a n-pentyloxy methyl group, a (2,6-dimethylphenyl)methyl group, a (3,4- group, a neopentyloxy group, a n-hexyloxy group, a dimethylphenyl)methyl group, a (4,6-dimethylphenyl) n-octyloxy group, a n-dodecyloxy group, a n-pentadecyloxy methyl group, a (2,3,4-trimethylphenyl)methyl group, a group, a n-elicocyloxy group, etc. Among them, a methoxy (2,3,5-trimethylphenyl)methyl group, a (2,3,6- group, an ethoxy group and a tert.-butoxy group are pref trimethylphenyl)methyl group, a (3,4,5-trimethylphenyl) methyl group, a (2,4,6-trimethylphenyl)methyl group, a erable. Any one of these alkoxyl groups may optionally be (2,3,4,5-tetramethylphenyl)methyl group, a (2,3,4,6- Substituted by one or more fluorine atoms. tetramethylphenyl)methyl group, a (2,3,5,6-tetramethyl Examples of a C-C aralkyloxyl group for R', R, R, phenyl)methyl group, a (pentamethylphenyl)methyl group, R", R or Rinclude a benzyloxy group, a (2-methylphenyl) an (ethylphenyl)methyl group, a (n-propylphenyl)methyl methoxy group, a (3-methylphenyl)methoxy group, a group, an (isoproy plphenyl)methyl group, a (n-butylphenyl) (4-methylphenyl)methoxy group, a (2,3-dimethylphenyl) methyl group, a (Sec.-butylphenyl)methyl group, a (tert.- methoxy group, a (2,4-dimethylphenyl)methoxy group, a butylphenyl)methyl group, a (n-pentylphenyl)methyl group, (2,5-dimethylphenyl)methoxy group, a (2,6- a (neopentylphenyl)methyl group, a (n-hexylphenyl)methyl 15 dimethylphenyl)methoxy group, a (3,4-dimethylphenyl) group, a (n-octylphenyl)methyl group, a (n-decylphenyl) methoxy group, a (3,5-dimethylphenyl)methoxy group, a methyl group, a (n-tetradecylphenyl)methyl group, a naph (2,3,4-trimethylphenyl)methoxy group, a (2,3,5 thylmethyl group, an anthracenylmethyl group, etc. Among -trimethylphenyl)methoxy group, a (2,3,6-trimethylphenyl) them, a benzyl group is preferable. Any one of these aralkyl methoxy group, a (2,4,5-trimethylphenyl)methoxy group, a groups may optionally be Substituted by one or more fluo (2,4,6-trimethylphenyl)methoxy group, a (3,4,5- rine atoms. trim ethyl phenyl)methoxy group, a (2,3,4,5- Examples of a Co-Co aryl group for R', R. R. R", R tetra methylphenyl)methoxy group, a (2,3,4,6- or R' include a phenyl group, a a 2-tolyl group, a 3-tolyl tetra methylphenyl)methoxy group, a (2,3,5,6- group, a 4-tolyl group, a 2,3-Xylyl group, a 2,4-Xylyl group, tetramethylphenyl)methoxy group, a (pentamethylphenyl) a 2.5-xylyl group, a 2,6-Xylyl group, a 3,4-xylyl group, a 25 methoxy group, an (ethylphenyl)methoxy group, a 3,5-Xylyl group, a 2,3,4-trimethylphenyl group, a 2,3,5- (n-propylphenyl)methoxy group, an (isopropylphenyl) trimethylphenyl group, a 2,3,6-trimethylphenyl group, a methoxy group, a (n-butylphenyl)methoxy group, a (Sec.- 2,4,6-trimethylphenyl group, a 3,4,5-trimethylphenyl group, butylphenyl)methoxy group, a (tert-butylphenyl)methoxy a 2,3,4,5-tetra methylphe nyl group, a 2,3,4,6- group, a (n-hexylphenyl)methoxy group, a (n-octylphenyl) tetramethylphenyl group, a 2,3,5,6-tetramethylphenyl methoxy group, a (n-decylphenyl)methoxy group, a group, a pentamethylphenyl group, an ethylphenyl group, a (n-tetradecylphenyl)methoxy group, a naphthylmethoxy n-propylphenyl group, a isopropylphenyl group, a group, an anthracenylmethoxy group, etc. Among them a n-butylphenyl group, a Sec.-butylphenyl group, a tert.- benzyloxy group is preferable. Any one of these aralkyloxyl butylphenyl group, a n-pentylphenyl group, a neopentylphe groups may optionally be Substituted by one or more fluo nyl group, a n-hexylphenyl group, a n-Octylphenyl group, a 35 rine atoms. n-decylphenyl group, a n-dodecylphenyl group, a tetrade Examples of an aryloxyl group for R', R,R,R,R or cylphenyl group, a naphthyl group, an anthracenyl group, Rinclude Co-Co aryloxyl groups such as a phenoxy group, etc. Among them, a phenyl group is preferable. Any one of a 2-methylphenoxy group, a 3-methylphenoxy group, a these aryl groups may optionally be Substituted by one or 4-methylphenoxy group, a 2,3-dimethylphenoxy group, a more fluorine atoms. 40 2,4-dimethylphenoxy group, a 2,5-dimethylphenoxy group, A substituted silyl group for R', R. R. R", R or R a 2,6-dimethylphenoxy group, a 3,4-dimethylphenoxy means a silyl group which is Substituted by one or more group, a 3,5-dimethylphenoxy group, a 2,3,4- hydrocarbon groups. Here, examples of hydrocarbon groups trimethylphenoxy group, a 2,3,5-trimethylphenoxy group, a include C-Cohydrocarbon groupS. Such as a methyl group, 2,3,6-trimethylphenoxy group, a 2,4,5-trimethylphenoxy an ethyl group, a n-propyl group, an isopropyl group, a 45 group, a 2,4,6-trimethylphenoxy group, a 3,4,5- n-butyl group, a Sec.-butyl group, a tert.-butyl group, an trimethylphenoxy group, a 2,3,4,5-tetramethylphenoxy isobutyl group, a n-pentyl group, a n-hexyl group, a cyclo group, a 2,3,4,6-tetramethylphenoxy group, a 2,3,5,6- hexyl group, etc., aryl groupS. Such as a phenyl group, etc. tetramethylphenoxy group, a pentamethylphenoxy group, an Examples of a C-C Substituted silyl group include mono ethylphenoxy group, a n-propylphenoxy group, an isopro Substituted silyl groups having 1 to 20 carbon atoms Such as 50 pylphenoxy group, a n-butylphenoxy group, a Sec.- a methylsilyl group, an ethylsilyl group, a phenylsilyl group, butylphenoxy group, a tert.-butylphenoxy group, a etc., di-Substituted silyl groups having 2 to 20 carbon atoms n-hexylphenoxy group, a n-octylphenoxy group, a Such as a dimethylsilyl group, a diethylsilyl group, a diphe n-decylphenoxy group, a n-tetradecylphenoxy group, a nylsilyl group, etc., tri-Substituted silyl groups having 3 to naphthoxy group, an anthracenyloxy group, etc. Any one of 20 carbon atoms Such as a trimethylsilyl group, a triethyl 55 these aryloxyl groups may optionally be Substituted by one silyl group, a tri-n-propylsilyl group, a triisopropylsilyl or more fluorine atoms. group, a tri-n-butylsilyl group, a tri-Sec.-butylsilyl group, a A Ca-Co disubstituted amino group for R', R, R, R", tri-tert-butylsilyl group, a triisobutylsilyl group, a tert.- R or R' means an amino group which is substituted by two butyldimethylsilyl group, a tri-n-pentylsilyl group, a tri-n- hydrocarbon groups. Here, examples of hydrocarbon groups heXylsilyl group, a tricyclohexylsilyl group, a triphenylsilyl 60 include C-C hydrocarbon groupS. Such as a methyl group, group, etc. Among them, a trimethylsilyl group, a tert.- an ethyl group, a n-propyl group, an isopropyl group, a butyldimethylsilyl group and a triphenylsilyl group are n-butyl group, a Sec.-butyl group, a tert.-butyl group, an preferable. Any one of the hydrocarbon groups of these isobutyl group, a n-pentyl group, a n-hexyl group, a cyclo Substituted Silyl groups may optionally be Substituted by one hexyl group, etc., aryl groupS Such as a phenyl group, etc. or more fluorine atoms. 65 Examples of the C-Co disubstituted amino group include Examples of a C-Co alkoxyl group for R', R, R, R", a dimethylamino group, a diethylamino group, a di-n- R or R' include a methoxy group, an ethoxy group, a propylamino group, a diisopropylamino group, a di-n- US 6, 197990 B1 10 butylamino group, a di-Sec.-butylamino group, a di-tert.- plified compounds in which a methoxy or allyloxy group is butylamino group, a diisobutylamino group, a tert.- replaced by a benzyloxy group, an ethoxy group, a trimeth butylisopropylamino group, a di-n-hexylamino group, a ylsilyloxy group, a tert.-butyldimethylsilyloxy group or a di-n-octylamino group, a di-n-decylamino group, a diphe methoxymethoxy group, or propane is replaced by methane, nylamino group, a bistrimethylsilylamino group, a bis-tert.- ethane, butane, pentane, hexane, phenylmethane or diphe butyldimethylsilylamino group, etc. Among them, a dim nylmethane; or a bromo moiety is replaced by an iodo ethylamino group and a diethylamino group are preferable. moiety. Any one of these disubstituted amino groups may optionally Examples of the compound (1) in which B is a silicon be substituted by one or more fluorine atoms. atom include chloro(2-methoxyphenyl)dimethylsilane, Any two or more groups of R', R. R. R", Rand R may chloro(2-methoxy-3-methylphenyl)dimethylsilane, chloro optionally bond each other to form a ring or rings. (2-methoxy-3,5-dimethylphenyl)dimethylsilane, (3-tert.- Examples of a hydrocarbon group for R' include C-Co butyl-2-methoxyphenyl)chlorodimethylsilane, (3-tert.- alkyl groupS Such as a methyl group, an ethyl group, a propyl butyl-2-methoxy-5-methylphenyl)chlorodimethylsilane, group, a hexyl group, a decyl group, etc.; C-Co alkenyl (3,5-di-tert.-butyl-2-methoxyphenyl)chlorodimethylsilane, groupS Such as a Vinyl group, an allyl group, a propenyl 15 chloro(2-methoxy-3-phenylphenyl)dimethylsilane, chloro group, a 2-methyl-2-propenyl group, a homoallyl group, a (2-methoxy-5-methyl-3-phenylphenyl)dimethylsilane, hexenyl group, a decenyl group, etc.; alkoxyalkyl groups (3-tert.-butyl dimethylsily 1-2-methoxyphenyl) Such as a methoxymethyl group, a methoxyethoxymethyl chlorodimethylsilane, (3-tert.-butyldimethylsilyl-2- group, etc.; C7-C2 aralkyl groupS Such as a benzyl group, methoxy-5-methylphenyl)chlorodimethylsilane, chloro(2- a (4-methylphenyl)methyl group, a (2,4,6-trimethylphenyl) methoxy-3-trimethylsilylphenyl)dimethylsilane, chloro(2- methyl group, etc. Any one of these hydrocarbon groups methoxy-5-methyl-3-trimethylsilylphenyl)dimethylsilane, may optionally be Substituted by one or more halogen atoms. (3,5-diamyl-2-methoxyphenyl)chlorodimethylsilane, Examples of halogen-Substituted hydrocarbon groups (3-tert.-butyl-2,5-dimethoxyphenyl)chlorodimethylsilane, include a 2-chloro-2-propenyl group, and the like. (3-tert-butyl-5-chloro-2-methoxyphenyl) Examples of a tri-Substituted Silyl group include a trim 25 chloro dimethylsilane, (2 - allyl oxyphenyl) ethylsilyl group, a triethylsilyl group, a tri-n-propylsilyl chlorodimethylsilane, (2-allyloxy-3-methylphenyl) group, a triisopropylsilyl group, a tri-n-butylsilyl group, a chlorodimethylsilane, (2-allyloxy-3,5-dimethylphenyl) tri-Sec.-butylsilyl group, a tri-tert.-butylsilyl group, a tri chlorodimethylsilane, (2-allyloxy-3-tert.-butylphenyl) isobutylsilyl group, a tert-butyldimethylsilyl group, a tri-n- chlorodimethylsilane, (2-allyloxy-3-tert.-butyl pentylsilyl group, a tri-n-hexylsilyl group, a tricyclohexyl 5-methylphenyl)chlorodimethylsilane, (2-allyloxy-3,5-di silyl group, a triphenylsilyl group, etc. tert.-butylphenyl)chlorodimethylsilane, (2-allyloxy-3- Specific examples of the compound (1) in which B is a phenylphenyl) chlorodimethylsilane, (2-allyloxy-5-methyl carbon atom include 2-bromo-2-(2-methoxyphenyl) 3-phenylphenyl)chlorodimethylsilane, (2-allyloxy-3-tert propane, 2-bromo-2-(2-methoxy-3-methylphenyl)propane, butyl dimethylsilyl phenyl)chlorodimethylsilane, 2-bromo-2-(2-methoxy-3,5-dimethylphenyl)propane, 35 (2-allyloxy-3-tert.-butyldimethylsilyl-4-methylphenyl) 2-bromo-2-(3-tert.-butyl- 2-methoxyphenyl)propane, chlorodimethylsilane, (2-allyloxy-3-trimethylsilylphenyl) 2-bromo-2-(3-tert.-butyl-2-methoxy-5-methylphenyl) chlorodimethylsilane, (2-allyloxy-5-methyl-3- propane, 2-bromo-2-(3,5-di-tert.-butyl-2-methoxyphenyl) trimethylsilylphenyl)chlorodimethylsilane, (2-allyloxy-3,5- propane, 2-bromo-2-(2-methoxy-3-phenylphenyl)propane, diamylphenyl)chlorodimethylsilane, (2-allyloxy-3-tert.- 2-bromo-2-(2-methoxy-5-methyl-3-phenylphenyl)propane, 40 butyl-5-methoxyphenyl)chlorodimethylsilane, (2-allyloxy 2-bromo-2-(3-tert.-butyldimethylsilyl-2-methoxyphenyl) 3-tert.-butyl-5-chlorophenyl)chlorodimethylsilane, propane, 2-bromo-2-(3-tert-butyldimethylsilyl-2-methoxy (1-allyloxynaphthalen-2-yl)chlorodimethylsilane, etc. 5-methylphenyl)propane, 2-bromo-2-(2-methoxy-3- Examples of the compound (1) in which B is a silicon trimethylsilylphenyl)propane, 2-bromo-2-(2-methoxy-5- atom also include analogous compounds to the above exem methyl-3-trimethylsilylphenyl)propane, 2-bromo-2-(3,5- 45 plified compounds in which a methocy group or an allyloxy diamyl-2-methoxyphenyl)propane, 2-bromo-2-(3-tert.- group is replaced by a benzyloxy group, an ethoxy group, a butyl-2,5-dimethoxyphenyl)propane, 2-bromo-2-(3-tert.- trimethylsilyloxy group, a tert-butyldimethylsilyloxy group butyl-5-chloro-2-methoxyphenyl)propane, 2-bromo-2-(2- or a methoxymethoxy group, or a chlorodimethylsilane allyloxyphenyl)propane, 2-bromo-2-(2-allyloxy-3- group is replaced by a chlorodiethylsilane group, a chlo methylphenyl)propane, 2-bromo-2-(2-allyloxy-3,5- 50 rodiphenylsilane group, chlorodimethoxysilane group, a dimethylphenyl)propane, 2-bromo-2-(2-allyloxy-3-tert.- bromodimethylsilane group or a dimethyliodosilane group. butylphenyl)propane, 2-bromo-2-(2-allyloxy-3-tert-butyl The compound (2) may be any compound having a 5-methylphenyl)propane, 2-bromo-2-(2-allyloxy-3,5-di cylopentadineyl moiety. Examples of the compound (2) may tert.-butylphenyl)propane, 2-bromo-2-(2-allyloxy-3- be the same as those exemplified for the compound (2a). phenylphenyl)propane, 2-bromo-2-(2-allyloxy-5-methyl-3- 55 Examples of an amine compound may be the same as phenylphenyl)propane, 2-bromo-2-(2-allyloxy-3-tert.- those used in the process according to the first asepct of the butyldimethylsilylphenyl)propane, 2-bromo-2-(2-allyloxy present invention. 3-tert.-butyldimethylsilyl-4-methylphenyl)propane, The reaction is usually carried out in a Solvent which is 2-bromo-2-(2-allyloxy-3-trimethylsilylphenyl)propane, inactive to the reaction. Examples of Such Solvents are 2-bromo-2-(2-allyloxy-5-methyl-3-trimethylsilylphenyl) 60 aprotic Solvents, for example, aromatic hydrocarbon Sol propane, 2-bromo-2-(2-allyloxy-3,5-diamylphenyl)propane, vents Such as benzene, toluene, Xylene, etc., aliphatic hydro 2-bromo-2-(2-allyloxy-3-tert.-butyl-5-methoxyphenyl) carbon Solvents Such as pentane, hexane, heptane, octane, propane, 2-bromo-2-(2-allyloxy-3-tert.-butyl-5- cyclohexane, etc., ether Solvents Such as diethyl ether, chlorophenyl)propane, 2-bromo-2-(1-allyloxynaphthalen-2- methyl tert.-butyl ether, tetrahydrofuran, 1,4-dioxane, etc.; yl)propane, etc. 65 amide Solvents Such as hexamethylphosphoric amide, Examples of the compound (1) in which B is a carbon dimethyl form amide, dimethylace tamide, atom also include analogous compounds to the above exem N-methylpyrrollidone, etc.; halogen-containing Solvents US 6, 197990 B1 11 12 Such as chlorobenzene, dichlorobenzene, etc. These Solvents m-triethylsilylcyclopentadienyl group, a m-tert.- may be used Singly or in admixture of two or more Solvents. butyldimethylsilylcyclopentadienyl group, a m-indenyl The amount of a solvent is usually from 1 to 200 wt. parts, group, a m-methylindenyl group, a m-dimethylindenyl preferably from 3 to 30 wt. parts, per 1 wt. part of a group, a m-ethylindenyl group, a m-n-propylindenyl group, cyclopentadiene. a m-isopropylindenyl group, a m-n-butylindenyl group, a This reaction is usually carried out by mixing a metal m-sec.-butylindenyl group, a m-tert-butylindenyl group, a hydride, an amine compound and the compound (2) in a m-n-pentylindenyl group, a m-neopentylindenyl group, a Solvent, and then adding the compound (1), although the mn-hexylindenyl group, a m-n-octylindenyl group, a m-n- desired compound (3) can be Synthesized by mixing all the decylindenyl group, a m-phenylindenyl group, a compounds at the same time. mi-methylphenylindenyl group, a m-naphthylindenyl A reaction temperature is not limited, but is preferably in group, a m-trimethylsily lin denyl group, a a range in which no low-temperature facilities are necessary, m-trie thylsily linde nyl group, a m-tert. - for the industrial production. For example, a reaction tem butyldimethylsilylindenyl group, a m-tetrahydroindenyl perature is usually in the range between 0 and 70° C., group, a m-fluorenyl group, a m-methylfluorenyl group, a preferably between 10 and 60° C. 15 m-dimethylfluorenyl group, a m-ethylfluorenyl group, a The amount of the compound (2) is usually in the range m-diethylfluorenyl group, a m-n-propylfluorenyl group, a between 0.5 and 5 moles, preferably between 0.8 and 3 m-di-n-propylfluorenyl group, a m-isopropylfluorenyl moles, per one mole of the compound (1). group, a m-diisoproylfluorenyl group, a m-n-butylfluorenyl Examples of metal hydrides include alkali metal hydrides group, a m-sec.-butylfluorenyl group, a m-tert.- Such as lithium hydride, Sodium hydride, potassium hydride, butylfluorenyl group, a m-di-n-butylfluorenyl group, a etc.; and alkaline earth metal hydrides Such as calcium m-di-sec.-butylfluorenyl group, a m-di-tert-butylfluorenyl hydride, etc. The amount of a metal hydride is usually from group, a m-n-p enty 1 flu ore nyl group, a 0.5 to 3 moles, preferably from 0.9 to 2.0 moles, per one m-neopentylfluorenyl group, a m-n-hexylfluorenyl group, a mole of the compound (2). Sodium hydride and potassium m-n-octylfluorenyl group, a m-n-decylfluorenyl group, a hydride can be used in the form of a marketed product 25 m-n-dodecylfluorenyl group, a m-phenylfluorenyl group, a containing mineral oils, although they may be used after m-diphenylfluorenyl group, a m-methylphenylfluorenyl washing the mineral oils off with hydrocarbon solvents such group, a m-naphthylfluore nyl group, a as hexane, etc. m-trimethylsilyl fluore nyl group, a m-bis The amount of an amine compound is usually from 0.001 trimethylsilylfluorenyl group, a m-triethylsilylfluorenyl to 2 moles, preferably from 0.01 to 0.5 mole, per one mole group, a m-tert-butyldimethylsilylfluorenyl group, etc. of a metal hydride. Specific examples of the cyclopentadiene derivative (3) After the completion of the reaction, water, or an acidic include 2-(cyclope inta-1,4-dienyl)methyl)-1- aqueous Solution Such as the aqueous Solution of ammonium methoxybenzene, 2-(cyclopenta-1,4-dienyl)methyl)-1- chloride or hydrochloric acid is added to the reaction mix methoxy-4,6-dimethylbenzene, 2-tert-butyl-6-(cyclopenta ture. Then, the mixture was separated to an organic phase 35 1,4-dienyl)methyl-1-methoxy-4-methylbenzene, and an aqueous phase, and the Solution of the compound (3) 6-(cyclopen ta-1,4-dienyl)methyl-1-methoxy-2- is recovered in the form of the organic phase. phenylbenzene, 1-tert-butyldimethylsilyl-3-(cyclopenta-1, When a solvent miscible with water is used in the reaction 4-dienyl)methyl)-2-methoxy-5-methylbenzene, or when a reaction mixture cannot be separated to an organic 3-(cyclopenta-1,4-dienyl)methyl)-2-methoxy-5-methyl-1- phase and an aqueous phase since the amount of a Solvent 40 trimethylsilylbenzene, 2-tert.-butyl-6-(cyclopenta-1,4- used in the reaction is low, an organic Solvent, which is dienyl)methyl-1,4-dimethoxybenzene, 3-tert.-butyl-1- insoluble in water Such as toluene, ethyl acetate, chloroben chloro-5-(cyclop enta-1,4-dienyl)methyl-4- Zene and the like, can be added to the reaction mixture, and methoxybenzene, 2-tert.-butyl-6-(cyclopenta-1,4-dienyl) then the reaction mixture is Separated to an organic phase methyl-1-methoxybenzene, 2-1-(cyclopenta-1,4-dienyl)- and an aqueous phase. 45 1-methylethyl-1-methoxybenzene, 2-1-(cyclopenta-1,4- The compound (3) can be isolated from the organic phase dienyl)-1-methylethyl-1-methoxy-4,6-dimethylbenzene, by concentration. If desired, the compound (3) can be 6-tert-butyl-2-1-(cyclopenta-1,4-dienyl)-1-methylethyl)-1- purified by distillation, column chromatography, etc. methoxy-4-methylbenzene, 6-1-(cyclopenta-1,4-dienyl)-1- In the obtained compound (3), examples of a group methylethyl-1-methoxy-2-phenylbenzene, 1-tert.- having a cyclopentadiene moiety, which is represented by 50 butyldimethylsilyl-3-1-(cyclopenta-1,4-dienyl)-1- Cp, may be the groups exemplified for the compound (2a). methylethyl)-2-methoxy-5-methylbenzene, 3-1- In particular, examples of Such a group include a (cyclopenta-1,4-dienyl)-1-methylethyl)-2-methoxy-5- m-cyclopentadienyl group, a m-methylcyclopentadienyl methyl-1-trimethylsilylbenzene, 6-tert-butyl-2-1- group, a m-dimethylcyclopentadienyl group, a (cyclopen ta-1,4-dienyl)-1-methylethyl-1,4- m-trimethylcyclopent a die nyl grO up, 55 dimethoxybenzene, 5-tert-butyl-1-chloro-3-1-cyclopenta m-tetra methylcyclop ent a die nyl group, a 1,4-dienyl)-1-methylethyl-4-methoxybenzene, 6-tert.- m-ethylcyclop ent a die nyl group, a m-n- butyl-2-1-cyclopenta-1,4-dienyl)-1-methylethyl)-1- propyl cyclop ent a die nyl grO up, methoxybenzene, 1-methoxy-2-1-(4-methylcyclopenta-1, m-isopropylcyclopen tadienyl group, a m-n- 4-dienyl)-1-methylethylbenzene, 1-methoxy-4,6-dimethyl butyl cyclop ent a die nyl group, a m-Sec. - 60 2-1-(4-methylcyclopenta-1,4-dienyl)-1-methylethyl butyl cyclop ent a die nyl group, a m-tert. - benzene, 6-tert.-butyl-1-methoxy-4-methyl-2-1-(4- butylcyclopentadienyl group, a m-n-pentylcyclopentadienyl methylcyclopenta-1,4-dienyl)-1-methylethylbenzene, group, a m-neopentylcyclopentadienyl group, a m-n- 1-methoxy-6-1-(4-methylcyclopenta-1,4-dienyl)-1- hexylcyclopentadienyl group, a m-n-octylcyclopentadienyl methylethyl)-2-phenylbenzene, 1-tert.-butyldimethylsilyl-2- group, a m-phenylcyclopentadienyl group, a 65 methoxy-5-methyl-3-1-(4-methylcyclopenta-1,4-dienyl)-1- m-naphthylcyclop ent a die nyl grO up, methylethylbenzene, 2-methoxy-5-methyl- 3-1-(4- m-trim ethylsilyl cyclop ent a die nyl group, a methylcyclopen ta-1,4-dienyl)-1-methylethyl)-1-

US 6, 197990 B1 19 20 (2-allyloxy-3,5-di-tert.-butylphenyl)(2,3,4,5- phenylphenyl)(inden-1-yl)climethylsilane, (2-allyloxy-5- tetramethylcyclop enta-1,3-dienyl) dimethylsilane, methyl-3-phenylphenyl)(inden-2-yl) dimethylsilane, (2-allyloxy-5-methyl-3-phenylphenyl)(2,3,4,5- (2-allyloxy-5-methyl-3-trimethylsilylphenyl)(inden-1-yl) tetramethylcyclop enta-1,3-dienyl) dimethylsilane, dimethylsilane, (2-ally loxy-5-methyl-3- (2-allyloxy-5-methyl-3-trimethylsilylphenyl)(2,3,4,5- trimethylsilyl phenyl) (inden-2-yl) dimethylsilane, tetramethylcyclop enta-1,3-dienyl) dimethylsilane, (2-allyloxy-3-tert.-butyldimethylsilyl-5-methylphenyl) (2-allyloxy-3-tert.-butyldimethylsilyl-5-methylphenyl)(2,3, (inden- 1-yl) dimethylsilane, (2-allyloxy-3-tert.- 4,5-tetramethylcyclopenta-1,3-dienyl)dimethylsilane, butyl dimethylsilyl-5-methylphenyl) (inden-2-yl) (2-ally loxy-3,5-diamylphenyl)(2,3,4,5- dimethylsilane, (2-allyloxy-3,5-diamylphenyl)(inden-1-yl) tetramethylcyclop enta-1,3-dienyl) dimethylsilane, dimethylsilane, (2-allyloxy-3,5-diamylphenyl)(inden-2-yl) (2-allyloxy-3-tert.-butyl-5-methoxyphenyl)(2,3,4,5- dimethylsilane, (2-allyloxy-3-tert-butyl-5-methoxyphenyl) tetramethylcyclop enta-1,3-dienyl) dimethylsilane, (inden-1-yl)dimethylsilane, (2-allyloxy-3-tert.-butyl-5- (6-allyloxy-5-tert.-butyl-3-chlorophenyl)(2,3,4,5- methoxyphenyl)(inden-2-yl)climethylsilane, (6-allyloxy-5- tetramethylcyclop enta-1,3-dienyl) dimethylsilane, tert.-butyl-3-chlorophenyl)(inden-1-yl)dimethylsilane, (2-allyloxyphenyl)(tert.-butylcyclopenta-1,3-dienyl) 15 (6-allyloxy-5-tert.-butyl-3-chlorophenyl)(inden-2-yl) dimethylsilane, (2-allyloxy-3-methylphenyl)(tert.- dimethylsilane, (2-allyloxyphenyl)(9H-fluoren-9-yl) butylcyclopenta-1,3-dienyl)dimethylsilane, (2-allyloxy-3,5- dimethylsilane, (2-allyloxy-3-methylphenyl)(9H-fluoren-9- dimethylphenyl)(tert.-butylcyclopenta-1,3-dienyl) yl)dimethylsilane, (2-allyloxy-3,5-dimethylphenyl)(9H dimethylsilane, (2-allyloxy-3-tert.-butylphenyl)(tert.- fluoren-9-yl) dimethylsilane, (2-allyloxy-3-tert.- butylcyclopenta-1,3-dienyl)dimethylsilane, (2-allyloxy-3- butylphenyl)(9H-fluoren-9-yl)dimethylsilane, (2-allyloxy tert.-butyl-5-methylphenyl)(tert.-butylcyclopenta-1,3- 3-tert.-butyl-5-methylphenyl)(9H-fluoren -9-yl) dienyl)dimethylsilane, (2-allyloxy-3,5-di-tert-butylphenyl) dimethylsilane, (2-allyloxy-3,5-di-tert.-butylphenyl)(9H (tert.butylcyclope inta- 1,3-dienyl) dimethylsilane, fluoren-9-yl)dimethylsilane, (2-allyloxy-5-methyl-3- (2-ally loxy-5-methyl-3-phenylphenyl) (tert.- phenylphenyl)(9H-fluoren-9-yl)climethylsilane, (2-allyloxy butylcyclopenta-1,3-dienyl)dimethylsilane, (2-allyloxy-5- 25 5-methyl-3-trimethylsilylphenyl)(9H-fluoren-9-yl) methyl-3-trimethylsilylphenyl)(tert.-butylcyclopenta-1,3- dimethylsilane, (2-allyloxy-3-tert.-butyldimethylsilyl-5- dienyl) dimethylsilane, (2-ally loxy-3-tert.- methylphenyl)(9H-fluoren-9-yl)dimethylsilane, (2-allyloxy butyldimethylsilyl-5-methylphenyl)(tert.-butylcyclopenta 3,5-diamylphenyl)(9H-fluoren-9-yl)dimethylsilane, 1,3-dienyl)dimethylsilane, (2-allyloxyp-3,5-dimaylhenyl) (2-allyloxy-3-tert.-butyl-5-methoxyphenyl)(9H-fluoren-9- (tert.-butylcyclopenta-1,3-dienyl) dimethylsilane, yl)dimethylsilane, (6-allyloxy-5-tert-butyl-3-chlorophenyl) (2-allyloxy-3-tert.-butyl-5-methoxyphenyl)(tert.- (9H-fluoren-9-yl)climethylsilane, (1-allyloxynaphthalen-2- butylcyclopenta-1,3-dienyl)dimethylsilane, (6-allyloxy-5- yl)dimethyl(1,2,3,4-tetramethylcyclopentadienyl)silane, etc. tert.-butyl-3-chlorophenyl)(tert.-butylcyclopenta-1,3- analogous compounds to the above compounds in which a die nyl) dimethylsilane, (2-allyl oxyphenyl) ethoxy or an allyloxy group is replaced by a benzyloxy (trimethylsilylcyclopenta-1,3-dienyl) dimethylsilane, 35 group, an ethoxy group, a trimethylsilyloxy grou, a tert.- (2-allyloxy-3-methylphenyl)(trimethylsilylcyclopenta-1,3- butyldimethylsilyloxy group or a methoxymethoxy group; dienyl)dimethylsilane, (2-allyloxy-3,5-dimethylphenyl) or a dimethylsilane group is replaced by a diethylsilane (trimethylsilylcyclopenta-1,3-dienyl) dimethylsilane, group, a diphenylsilane group or a dimethoxysilane group; (2-allyloxy-3-tert-butylphenyl)(trimethylsilylcyclopenta-1, or a cyclopentadienyl group is replaced by a dimethylcy 3-dienyl) dimethylsilane, (2-allyloxy-3-tert.-butyl-5- 40 clopentadienyl group, a trimethylcyclopentadienyl group, a methylphenyl)(trimethylsilylcyclopenta-1,3-dienyl) n-propylcyclopentadienyl group, an isopropylcyclopentadi dimethylsilane, (2-allyloxy-3,5-di-tert.-butylphenyl) enyl group, a n-butylcyclopentadienyl group, an isobutyl (trimethylsilylcyclopenta-1,3-dienyl) dimethylsilane, cyclopentadienyl group, a Sec.-butylcyclopentadienyl group, (2-ally loxy-5-methyl-3-phenylphenyl) a tert.-butyldimethylsilylcyclopentadienyl group, a phenyl (trimethylsilylcyclopenta-1,3-dienyl) dimethylsilane, 45 cyclopentadienyl group or a methylindenyl group, or a (2-ally loxy-5-methyl-3-trimethylsilyl phenyl) 2-methoxyphenyl group is replaced by a 3-phenyl-2- (trimethylsilylcyclopenta-1,3 -dienyl)dimethylsilane, methoxyphenyl group, a 3-trimethylsilyl-2-methoxyphenyl (2-allyloxy-3-tert.-butyldimethylsiyl-5-methylphenyl) group or a 3-tert.-butyldimethylsilyl-2-methoxyphenyl (trimethylsilylcyclopenta-1,3-dienyl) dimethylsilane, grOup. (2-allyloxy-3,5-diamylphenyl)(trimethylsilylcyclopenta-1, 50 Such compounds (3) may contain a plurality of isomers 3-dienyl) dimethylsilane, (2-allyloxy-3-tert.-butyl-5- which are due to the positions of Substituents and/or the methoxyphenyl)(trimethylsilylcyclopenta-1,3-dienyl) positions of double bonds in a cyclopentadiene moiety of the dimethylsilane, (6-allyloxy-5-tert.-butyl-3-chlorophenyl) substituent Cp. The compound (3) of the present invention (trimethylsilylcyclopenta-1,3-dienyl) dimethylsilane, includes all Such isomers. (2-ally loxyphenyl) (inden-1-yl) dimethylsilane, 55 (2-allyloxyphenyl)(inden-2-yl)climethylsilane, (2-allyloxy INDUSTRIAL APPLICABILITY 3-methylphenyl)(inden-1-yl)dimethylsilane, (2-allyloxy-3- According to the proceeses of the present invention, a methylphenyl)(inden-2-yl)climethylsilane, (2-allyloxy-3,5- wide variety of cyclopentadienyl metal Salts and also the dimethylphenyl)(inden-1-yl)dimethylsilane, (2-allyloxy-3, derivatives of cyclopentadiene can be prepared at a high 5-dimethylphenyl)(inden-2-yl)dimethylsilane, (2-allyloxy 60 3-tert-butylphenyl)(inden-1-yl)dimethylsilane, (2-allyloxy conversion and a high Selectivity without the use of expen 3-tert-butylphenyl)(inden-2-yl)dimethylsilane, (2-allyloxy Sive reagents and low-temperature facilities. 3-tert.-butyl-5-methylphenyl)(inden-1-yl)dimethylsilane, (2-allyloxy-3-tert.-butyl-5-methylphenyl)(inden-2-yl) EXAMPLES dimethylsilane, (2-allyloxy-3,5-di-tert-butylphenyl)(inden 65 The present invention will be illustrated by the following 1-yl)dimethylsilane, (2-allyloxy-3,5-di-tert.-butylphenyl) examples, which do not limit the Scope of the invention in (inden-2-yl)dimethylsilane, (2-allyloxy-5-methyl-3- any way. US 6, 197990 B1 21 22 Example 1 g) were added to the Solution of tetramethylcyclopentadiene Tetramethylcyclopentadiene (1.16 g; purity: 86%; pure (1.34 g; purity: 91.3%; pure compound: 1.22 g) dissolved in compound: 1.00 g) was dissolved in tetrahydrofuran (20 ml). tetrahydrofuran (6.73 g), and stirred at 50° C. for one hour. Then, sodium hydride (washed with hexane) (0.197 g) and Thus, tetramethylcyclopentadienylsodium was obtained in diisopropylamine (0.0828 g) were added to the solution, the form of a solution in tetrahydrofuran. followed by refluxing for 7 hours. Methyl iodide (2.8 g) was added to the obtained reaction After cooling the reaction mixture to room temperature, solution, and stirred for 30 minutes to convert tetramethyl dichlorodimethylsilane (3.16 g) was added to the reaction cyclopentadienylsodium to pentamethylcyclopentadiene. mixture, and stirred for 30 minutes to convert tetramethyl When the content of pentamethylcyclopentadiene was mea cyclop ent a die nyl Sodium to chloro dimethyl Sured by gas chromatography, the yield of tetramethylcy (tetramethylcyclopentadienyl)silane. Chlorodimethyl clopentadienylsodium was 83%. (tetramethylcyclopentadienyl)silane was quantitatively Example 7 analyzed by gas chromatography, and the yield of tetram ethylcyclopentadienylsodium was calculated. The yield was 15 The same procedures as those in Example 6 were repeated 53%. except that cyclopentadiene (0.661 g) was used in place of tetramethylcyclopentadiene, and butylamine (0.037 g) was Example 2 used in place of m-chloroaniline. The yield of cyclopenta The same procedures as those in Example 1 were repeated dienylsodium was 99%. except that 2.2,6,6-tetramethylpiperidine (0.0578 g) was used in place of diisopropylamine, and the refluxing time Example 8 was changed from 7 hours to 5 hours. The yield of tetram Sodium hydride (containing mineral oil; the content of ethylcyclopentadienylsodium was 33%. sodium hydride: 60%) (0.80 g) and aniline (0.046 g) were Example 3 added to the solution of trimethylcyclopentadiene (1.08 g) 25 dissolved in tetrahydrofuran (6.12 g), and stirred at 50° C. The same procedures as those in Example 1 were repeated for 3 hours. Thus, trimethylcyclopentadienylsodium was except that butylamine (0.0299 g) was used in place of obtained in the form of a solution in tetrahydrofuran. diisopropylamine, and the refluxing time was changed from Methyl iodide (2.8 g) was added to the obtained reaction 7 hours to 5 hours. The yield of tetramethylcyclopentadi solution, and stirred for 30 minutes to convert trimethylcy enylsodium was 18%. clopentadienylsodium to tetramethylcyclopentadiene. When Comparative Example 1 the content of tetramethylcyclopentadiene was measured by gas chromatography, the yield of trimethylcyclopentadienyl The same procedures as those in Example 1 were repeated Sodium was 90%. except that no diisopropylamine was used. The yield of tetramethylcyclopentadienylsodium was 0%. 35 Example 9 Comparative Example 2 The same procedures as those in Example 8 were repeated except that 2-cyclopentadienyl-2-fluorenylpropane (2.72 g) The same procedures as those in Example 1 were repeated was used in place of trimethylcyclopentadiene, the amount except that potassium tert-butoxide (1.84 g) was used in of tetrahydrofuran was changed from 6.12 g to 15.4g, the place of the combination of Sodium hydride and diisopro 40 pylamine. The yield of tetramethylcyclopentadienylsodium amount of Sodium hydride (containing mineral oil; the content of sodium hydride: 60%) was changed from 0.80 g was 0%. to 1.60 g, the amount of aniline was changed from 0.046 g Example 4 to 0.092 g, and the amount of methyl iodide was changed from 2.8 g. to 5.6 g. The yield of 2-cyclopentadienyl-2- Sodium hydride (containing mineral oil; the content of 45 sodium hydride: 60%) (0.41 g) and aniline (0.033 g) were fluorenylpropane disodium salt was 93%. added to the solution of tetramethylcyclopentadiene (0.63 g) Example 10 in tetrahydrofuran (15 ml), and stirred at 40° C. for 4 hours. Thus, tetramethylcyclopentadienylsodium was obtained in The same procedures as those in Example 8 were repeated the form of a solution in tetrahydrofuran. 50 except that bistrimethylcyclopentadienyldimethylsilane Methyl iodide (2.8 g) was added to the obtained reaction (2.73 g) was used in place of trimethylcyclopentadiene, the solution, and stirred for 30 minutes to convert tetramethyl amount of tetrahydrofuran was changed from 6.12 g to 15.5 cyclopentadienylsodium to pentamethylcyclopentadiene. g, the amount of Sodium hydride (containing mineral oil; the The content of pentamethylcyclopentadiene was 0.62 g, content of sodium hydride: 60%) was changed from 0.80 g when measured by gas chromatography. Thus, the yield of 55 to 1.60 g, the amount of aniline was changed from 0.046 g tetramethylcyclopentadienylsodium was 88%. to 0.092 g, and the amount of methyl iodide was changed from 2.8 g. to 5.6 g. The yield of bistrimethylcyclopentadi Example 5 enyldimethylsilane disodium salt was 88%. The same procedures as those in Example 4 were repeated Example 11 except that potassium hydride (containing mineral oil; the 60 content of potassium hydride: 35%) (1.17 g) was used in The same procedures as those in Example 8 were repeated place of sodium hydride. The yield of tetramethylcyclopen except that 1,2-bisindenylethane (2.58 g) was used in place tadienylpotassium was 90% of trimethylcyclopentadiene, the amount of tetrahydrofuran was changed from 6.12 g to 14.6 g., the amount of Sodium Example 6 65 hydride (containing mineral oil; the content of Sodium Sodium hydride (containing mineral oil; the content of hydride: 60%) was changed from 0.80 g to 1.60 g, the sodium hydride: 60%) (0.80 g) and m-chloroaniline (0.064 amount of aniline was changed from 0.046 g to 0.092 g, and US 6, 197990 B1 23 24 the amount of methyl iodide was changed from 2.8 g. to 5.6 the solution of (2-allyloxy-3-tert.-butyl-5-methylphenyl) g. The yield of 1,2-bisindenylethane disodium salt was 92%. chlorodimethylsilane (3.99 g; purity: 70.7%; pure com pound: 2.82 g) dissolved in tetrahydrofuran (3 ml) was Example 12 dropwise added, followed by stirring for one hour. 5 After adding water (15 ml) and hexane (15 ml) to the Sodium hydride (containing mineral oil; the content of reaction mixture, the mixture was separated. The organic sodium hydride: 60%) (3.30 g) and aniline (0.237 g) were layer was concentrated, and (2-allyloxy-3-tert.-butyl-5- added to the Solution of tetramethylcyclopentadiene (5.01 g) methylphenyl) dimethyl (2,3,4,5- dissolved in tetrahydrofuran (45ml), and stirred at 40° C. for tetramethylcyclopentadienyl)Silane (pure compound: 3.23 4 hours. Thus, tetramethylcyclopentadienylsodium was g) was obtained. The yield was 85% based on tetramethyl obtained in the form of a solution in tetrahydrofuran. cyclopentadiene. Methyl iodide (8.0 g) was added to the obtained reaction What is claimed is: solution, and stirred for 30 minutes to convert tetramethyl 1. A process for the preparation of a cyclopentadienyl cyclopentadienylsodium to pentamethylcyclopentadiene. metal Salt comprising the Step of reacting a cyclopentadiene The content of pentamethylcyclopentadiene was 4.80 g and a metal hydride in the presence of an amine compound. when measured by gas chromatography. Thus, the yield of 15 2. A process according to claim 1, wherein Said amine tetramethylcyclopentadienylsodium was 86%. compound is a primary amine or a Secondary amine. 3. A process according to claim 2, wherein Said primary Example 13 amine is a primary aniline. 4. A process according to any one of claims 1 to 3, Sodium hydride (containing mineral oil; the content of wherein an amount of said amine compound is from 0.001 sodium hydride: 60%) (2.50 g) and aniline (0.237 g) were to 2 moles per one mole of Said metal hydride. added to the Solution of tetramethylcyclopentadiene (5.01 g) 5. A process according to any one of claims 1 to 3, dissolved in tetrahydrofuran (28 ml), and stirred at 40° C. for wherein an amount of Said amine compound is from 0.01 to 4 hours. Thus, tetramethylcyclopentadienylsodium was 0.5 mole per one mole of said metal hydride. obtained in the form of a solution in tetrahydrofuran. 25 6. A process according to any one of claims 1 to 3, wherein an amount of said metal hydride is from 0.5 to 3 Methyl iodide (8.0 g) was added to the obtained reaction moles per one mole of Said cyclopentadiene. solution, and stirred for 30 minutes to convert tetramethyl 7. A process according to any one of claims 1 to 3, cyclopentadienylsodium to pentamethylcyclopentadiene. wherein Said metal hydride contains mineral oils. The content of pentamethylcyclopentadiene was 4.78 g 8. A process according to any one of claims 1 to 3, when measured by gas chromatography. Thus, the yield of wherein a reaction temperature is from 10 to 60° C. tetramethylcyclopentadienylsodium was 85%. 9. A process according to any one of claims 1 to 3, wherein Said cyclopentadiene is a compound of the formula Example 14 (2a): Sodium hydride (containing mineral oil; the content of 35 sodium hydride: 60 wt. %) (0.60 g) was suspended in (E)in tetrahydrofuran (6.91 g), and then aniline (0.047 g) was dropwise added to the Suspension at 25 C. After heating to 50 C., the suspension was stirred for 10 minutes. Thereafter, tetramethylcyclopentadiene (1.22 g) was drop wise added to the Suspension while maintaining the Suspen 40 sion at 50 C., followed by stirring for one hour. Thus, wherein m is an integer of 0 to 5, E groups are the same or tetramethylcyclopentadienylsodium was obtained. After different and independently represent a C-C alkyl group, cooling the above solution to 20 C., the solution of a phenyl group, a naphthyl group, or a tri-Substituted Silyl (2-ally loxy-3-tert.-butyl-5-methylphenyl) group having Substituents Selected from the group consisting 45 of a C-C alkyl group and a phenyl group, provided that, chlorodimethylsilane (3.86 g; purity: 73%; pure compound: when two E groups are present on adjacent carbon atoms, 2.82 g) in toluene was dropwise added to the above Solution, they may be bonded at their ends to form a benzene ring, a followed by stirring for 2 hours. cyclohexane ring or a cyclohexene ring, which is condensed After adding water (3 g) to the reaction mixture, the with the cyclopentadienyl ring, Solvent was evaporated off. Toluene (10 g) and water (3 g) 50 G is a hydrogen atom when m is 5, or when m is 0 to 4, were added to the residual oil, and the mixture was sepa G is a hydrogen atom or a group of the formula (2b): rated. The organic layer was concentrated, and (2-allyloxy 3-tert.-butyl-5-methylphenyl) dimethyl(2,3,4,5- tetramethylcyclopentadienyl)silane (4.97 g; purity: 63%; pure compound: 3.13 g) was obtained. The yield was 82% 55 based on tetramethylcyclopentadiene. Example 15 Potassium hydride (containing mineral oil; the content of wherein p is 1 or 2, q is an integer of 0 to 4, X is a carbon sodium hydride: 35%) (3.00 g) was suspended in tetrahy 60 atom or a Silicon atom, X and X are the same or different drofuran (18 ml), and then 4-methylaniline (0.056 g) was and independently represent a hydrogen atom, a C-C alkyl dropwise added to the suspension at 10 C., followed by group or a phenyl group, E' is a Substituent Selected from stirring for 10 minutes. Thereafter, the solution of tetram those defined for E, provided that when X is a Silicon atom, ethylcyclopentadiene (1.22 g) dissolved in tetrahydrofuran X and X are not hydrogen atoms. (6 ml) was dropwise added to the Suspension, and heated to 65 10. A process according to claim 9, wherein m is an 25 C., followed by stirring for one hour. Thus, tetrameth integer of 2 to 5, or m is 1 and G is a group of the formula ylcyclopentadienylpotassium was obtained. To this Solution, (2b). US 6, 197990 B1 25 26 11. A proceSS for the preparation of a cyclopentadiene derivative of the formula (3): (1) R6 Y (3) N B1 R7 5 R51 R6 C YB1. p R7 Rt A. R51 R A. R3 R1 1O R2 R3 R1 R2 wherein A, B, R', R,R,R,R, R and R7 are the same as defined above, and Y is a chlorine atom, a bromine atom or an iodine atom wherein 15 with a cyclopentadiene of the formula (2): HCp (2) A is an atom of the 16 group of the Periodic Table, wherein Cp is the Same as defined above, in the presence of B is an atom of the 14 group of the Periodic Table, a metal hydride and an amine compound. 12. A process according to claim 11, wherein Said cyclo R", R. R. R", R and R are the same or different and pentadiene of the formula (2) is reacted with Said metal independently represent a hydrogen atom, a fluorine hydride in the presence of Said amine compound, and then atom, a C-Co alkyl group which may optionally be reacted with said halide compound of the formula (1). Substituted with a fluorine atom, a C7-Co aralkyl 13. A process according to claim 11 or 12, wherein Said group which may optionally be Substituted with a cyclopentadiene of the formula (2) is a compound of the formula (2a) in claim 9. fluorine atom, a C-C aryl group which may option 25 14. A process according to claim 11 or 12, wherein Said ally be Substituted with a fluorine atom, a C-Co amine compound is a primary amine or a Secondary amine. Substituted Silyl group, a C-C alkoxyl group which 15. A proceSS according to claim 14, wherein Said primary may optionally be Substituted with a fluorine atom, a amine is a primary aniline. C7-Co aralkyloxyl group which may optionally be 16. A process according to claim 12, wherein an amount Substituted with a fluorine atom, a Co-Co aryloxyl of said amine compound is from 0.001 to 2 moles per one group which may optionally be Substituted with a mole of said metal hydride. 17. A process according to claim 12, wherein an amount fluorine atom, or a C-Co di-substituted amino group of said amine compound is from 0.01 to 0.5 mole per one which may optionally be substituted with a fluorine mole of said metal hydride. atom, provided that any two or more of R', R, R, R", 35 18. A process according to any one of claims 11 or 12, R and R may together form a ring, wherein an amount of said metal hydride is from 0.5 to 3 R" is a hydrocarbon group which may optionally be moles per one mole of Said compound of the formula (2). Substituted with a fluorine atom, or a tri-substituted 19. A process according to any one of claims 11 or 12, silyl group, and wherein a reaction temperature is from 10 to 60° C. 40 20. A proceSS according to any one of claims 11 or 12, Cp is a cyclopetadiene ring comprising the Step of react wherein Said metal hydride contains mineral oils. ing a halide compound of the formula (1): k k k k k