Organic compounds -- part of the class 532-570 series – Organic compounds – Boron containing
Reexamination Certificate
2001-02-09
2002-04-30
Vollano, Jean E. (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Boron containing
C568S001000
Reexamination Certificate
active
06380435
ABSTRACT:
TECHNICAL FIELD
The present invention relates to {circle around (1)} a purifying process of tetrakis(fluoroaryl)borate.magnesium halide. The present invention also relates to {circle around (2)} a tetrakis(fluoroaryl)borate.ether complex, which is useful as, for example, a co-catalyst of a metallocene catalyst (polymeric catalyst) used in a cationic complex polymerization reaction, a photopolymeric catalyst for silicone, a cationic polymerization initiator used in the polymerization of a functional polymer or monomer with photochemical activation or irradiation of electron beams, and an intermediate for producing tetrakis(pentafluorophenyl)borate derivatives of various kinds, and to a process of producing the same; and to {circle around (3)} a process of producing a tetrakis(fluoroaryl)borate derivative. Further, the present invention relates to {circle around (4)} a tetrakis(fluoroaryl)borate derivative.ether complex useful as an intermediate for producing the tetrakis(fluoroaryl)borate derivative and a process of producing the same, and to {circle around (5)} a process of producing tetrakis(fluoroaryl)borate.
TECHNICAL BACKGROUND
A tetrakis (fluoroaryl) borate derivative is an useful compound as, for example, a co-catalyst for promoting the activity of a metallocene catalyst (polymeric catalyst) used in a cationic complex polymerization reaction, or a photopolymeric catalyst for silicone. Also, tetrakis(fluoroaryl)borate.magnesium halide is an useful compound as an intermediate for producing the tetrakis(fluoroaryl)borate derivative. Recently, the metallocene catalyst has been receiving considerable attention as a polyolefin polymeric catalyst.
A producing process of tetrakis(pentafluorophenyl)borate.magnesium bromide, which is a kind of tetrakis(fluoroaryl)borate.magnesium halide, from bromopentafluorobenzene through the Grignard reaction is disclosed in, for example, Japanese Laid-open Patent Application No. 247980/1994 (Tokukaihei No. 6-247980).
Also, in Japanese Laid-open Patent Application No. 247981/1994 (Tokukaihei No. 6-247981), a process of synthesizing tetrakis(pentafluorophenyl)borate.lithium from pentafluorobenzene using an organic lithium compound and boron halide first, and thence reacting the resulting compound with N,N-dimethylaniline.hydrochloride is disclosed as a process of producing a tetrakis(pentafluorophenyl)borate derivative, which is a kind of the tetrakis(fluoroaryl)borate derivative.
Further, a process of producing the tetrakis(pentafluorophenyl)borate derivative by reacting tetrakis(pentafluorophenyl)borate.magnesium bromide with N,N-dimethylaniline.hydrochloride is disclosed in U.S. Pat. No. 398,236.
However, Japanese Laid-open Patent Application No. 247980/1994 (Tokukaihei No. 6-247980) neither discloses nor implies the separation/removal of magnesium halide, a by-product produced with tetrakis(pentafluorophenyl)borate.magnesium bromide, from the reaction series. If the tetrakis(pentafluorophenyl)borate derivative is produced from tetrakis(pentafluorophenyl)borate.magnesium bromide containing magnesium halide as impurities, and used as a co-catalyst of the metallocene catalyst, for example, the activity of the metallocene catalyst deteriorates considerably. The process disclosed in Japanese Laid-open Patent Application No. 247980/1994 (Tokukaihei No. 6-247980) is a producing process of tetrakis(pentafluorophenyl)borate.magnesium bromide containing magnesium halide as impurities. Thus, tetrakis(pentafluorophenyl)borate.magnesium bromide obtained through this process can not be used as an adequate intermediate for producing the tetrakis(pentafluorophenyl)borate derivative.
If typical alkali treatment is applied to tetrakis(pentafluorophenyl)borate.magnesium bromide to remove magnesium halide from tetrakis(pentaflurorphenyl)borate.magnesium bromide obtained by the process disclosed in the above publication, magnesium hydroxide is produced. Since magnesium hydroxide turns a post-treatment solution into gel, the solution can not be filtered. In other words, since magnesium halide can not be removed by the typical alkali treatment, it is difficult to separate tetrakis(pentafluorophenyl)borate.magnesium bromide obtained in the above process, or to obtain a highly-pure tetrakis(fluoroaryl)borate compound after the treatment.
Thus, there has been an increasing demand for a purifying process for separating/removing impurities, such as magnesium halide, from tetrakis(fluoroaryl)borate.magnesium halide readily and efficiently.
On the other hand, the process disclosed in Japanese Laid-open Patent Application No. 247981/1994 (Tokukaihei No. 6-247981) has the following problems:
(1) since the reaction series must be kept at −65° C. or below, not only special equipment is required, but also the cooling cost is high;
(2) the process demands an expensive organic lithium compound (t-butyl lithium), which is a dangerous compound because it may ignite when reacted with water and the like;
(3) the process also demands expensive boron halide (boron trichloride), which is very difficult to handle because it is in the gaseous state and corrosive. Thus, the process disclosed in the above publication can not be readily adopted for industrial use.
In the process disclosed in U.S. Pat. No. 5,473,036, magnesium hydroxide is produced as a by-product with the object product, that is, the tetrakis(pentafluorophenyl)borate derivative. Since magnesium hydroxide turns a post-treatment solution into gel, it is difficult to separate (isolate) the tetrakis(pentafluorophenyl)borate derivative from the solution. Thus, there arises a problem that the tetrakis(pentafluorophenyl)borate derivative can not be produced efficiently.
In other words, the conventional producing processes have a problem that an inexpensive and highly-pure tetrakis(fluoroaryl)borate derivative can not be produced efficiently. Hence, there has been an increasing demand for a process of producing an inexpensive and highly-pure tetrakis(fluoroaryl)borate derivative efficiently.
Therefore, it is a first object of the present invention to provide a purifying process of separating/removing impurities, such as magnesium halide, from tetrakis(fluoroaryl)borate.magnesium halide readily and efficiently. Also, it is a second object of the present invention to provide a process of efficiently producing an inexpensive and highly-pure tetrakis (fluoroaryl)borate derivative, which is useful as, for example, a co-catalyst of the metallocene catalyst or a photopolymeric catalyst for silicone.
A process of producing tetrakis(pentafluorophenyl)borate, which is useful as an intermediate for producing the tetrakis(pentafluorophenyl)borate derivatives of various kinds, has been known.
For example, a process of obtaining tetrakis(pentafluorophenyl)borate.lithium by reacting pentafluorophenyl lithium, which is produced by reacting pentafluorophenyl bromide with butyl lithium at −78° C. in dry pentane, with tris(pentafluorophenyl)borate at −78° C. in dry pentane is disclosed in p245, J. Organometallic. Chem., 2, (1964).
Also, aforementioned Japanese Laid-open Patent Application No. 247981/1994 (Tokukaihei No. 6-247981) discloses a process of preparing tetrakis(pentafluorophenyl)borate.lithium used in the producing process of N,N-dimethyl anilinium.tetrakis(pentafluorophenyl)borate from N,N-dimethylaniline.hydrochloride as follows.
That is, the above publication discloses a process of preparing, in which pentafluorophenyl lithium is produced initially by reacting pentafluorophenyl bromide with t-butyl lithium at −65° C. in dry diethyl ether, and then tetrakis(pentafluorophenyl)borate.lithium is prepared by reacting the resulting pentafluorophenyl lithium with boron trichloride at −65° C. to −55° C. in dry pentane.
However, the process disclosed in p245, J. Organometallic. Chem., 2, (1964) has a problem that the yield of tetrakis(pentafluorophenyl)borate.lithium is low (43%). Also, since the process disclosed in aforementioned Japanese Laid-open Patent Application No. 247981/1994 (Tokukaihei No. 6-247981
Ikeno Ikuyo
Mitsui Hitoshi
Ueno Tsunemasa
Yamamoto Naoko
Birch & Stewart Kolasch & Birch, LLP
Nippon Shokubai Co. , Ltd.
Vollano Jean E.
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