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(12) United States Patent (10) Patent No.: US 6,197,990 B1 Oda Et Al

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(12) United States Patent (10) Patent No.: US 6,197,990 B1 Oda Et Al 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.
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