Chemistry of carbon compounds – Miscellaneous organic carbon compounds – C-metal
Reexamination Certificate
1999-10-22
2001-05-22
Shaver, Paul F. (Department: 1621)
Chemistry of carbon compounds
Miscellaneous organic carbon compounds
C-metal
C568S001000, C558S287000, C558S294000, C558S295000
Reexamination Certificate
active
06235222
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a method for manufacturing fluoroaryl magnesium halide which is a useful compound as a Grignard reagent used in various types of organic synthetic reactions. The present invention also relates to a method for manufacturing a fluoroaryl borane derivative which is a useful compound as a cocatalyst for a metallocene catalyst (polymerization catalyst) used in a cation complex polymerization reaction or a catalyst for silicone photo-polymerization, for example.
BACKGROUND OF THE INVENTION
Fluoroaryl magnesium halide is a useful compound as a Grignard reagent used in various types of organic synthetic reactions, for example. Also, the fluoroaryl magnesium halide is a useful compound, for example, as an intermediate of a fluoroaryl borane derivative, used in manufacturing a cocatalyst which promotes an activity of a metallocene catalyst (polymerization catalyst) used in a cation complex polymerization reaction, or a catalyst for silicone photo-polymerization. Recently, the metallocene catalyst has been receiving considerable attention as a polyolefin polymerization catalyst.
Various proposals have been made as a method of synthesizing the fluoroaryl magnesium halide. For example, J. Chem. Soc., 166 (1959) discloses a method of synthesizing pentafluorophenyl magnesium bromide, which is a species compound of the fluoroaryl magnesium halide, by reacting bromopentafluorobenzene with magnesium using diethyl ether as a solvent.
Also, J. Organometal. Chem., 11, 619-622 (1968) and J. Organometal. Chem., 26, 153-156 (1971) disclose a method of synthesizing pentafluorophenyl magnesium halide, which is a species compound of the fluoroaryl magnesium halide, by a Grignard exchange reaction of fluoroaryl halide (chloropentafluorobenzene, bromopentafluorobenzene, and iodopentafluorobenzene) and ethyl magnesium halide using tetrahydrofuran (THF) as a solvent. Also, U.S. Pat. No. 5,693,261 discloses a method of synthesizing pentafluorophenyl magnesium halide by a Grignard exchange reaction of chloropentafluorobenzene and isopropyl magnesium halide.
On the other hand, Japanese Laid-open Patent Application No. 295985/1997 (Japanese Official Gazette, Tokukaihei No. 9-295985, published on Nov. 18, 1997) discloses a method of preparing fluoroaryl magnesium halide (Grignard reagent) by reacting fluoroaryl halide with magnesium using alkyl halide as a catalyst.
However, in the method of synthesizing pentafluorophenyl magnesium bromide disclosed in J. Chem. Soc., 166 (1959) supra, the synthesis pentafluorophenyl magnesium bromide is colored considerably with coloring components produced by the side reaction or the like. For this reason, when a fluoroaryl borane derivative is synthesized by using the pentafluorophenyl magnesium bromide as a Grignard reagent, a colored fluoroaryl borane derivative is produced as the final product unless the coloring components are removed.
The method for manufacturing pentafluorophenyl magnesium halide disclosed in J. Organometal. Chem., 11, 619-622 (1968) and J. Organometal. Chem., 26, 153-156 (1971) supra use THF as the solvent. However, the fluoroaryl borane derivative synthesized using a THF solution of the resulting pentafluorophenyl magnesium halide includes strong Lewis acids, for example. Thus, there is a problem that the resulting fluoroaryl borane derivatives trigger ring-opening polymerization of THF used as the solvent or causes a large amount of by-product to be produced.
Also, the method for manufacturing pentafluorophenyl magnesium halide disclosed in U.S. Pat. No. 5,693,261 supra has a problem that, because chloropentafluorobenzene has poor reactivity, chloropentafluorobenzene has to be used excessively with respect to isopropyl magnesium halide. Further, this method has another problem that it demands a step of removing the excessively used chloropentafluorobenzene from the final product (commercial goods).
The method of preparing the Grignard reagent disclosed in Japanese Laid-open Patent Application No. 295985/1997 supra has a problem that, although the coloring of the resulting Grignard reagent is slightly reduced if diethyl ether is used as the solvent (reaction solvent), the resulting Grignard reagent is still colored black. Also, the reaction hardly proceeds if any other kind of ether solvents is used.
Generally, diethyl ether is used as a solvent when preparing the Grignard reagent from fluoroaryl halide and magnesium. However, reaction heat produced in the reaction of bromopentafluorobenzene and magnesium is so large (89 Kcal/mol) that the reaction is not readily controlled. Particularly, diethyl ether involves a safety problem because it is a highly inflammable compound with a low boiling point.
SUMMARY OF THE INVENTION
The present invention is devised to solve the above problems and has an object to provide a method of safely, efficiently, and industrially manufacturing fluoroaryl magnesium halide containing no impurities, such as coloring components, by a relatively gradual reaction compared with the conventional reactions. The present invention has another object to provide a method of readily and efficiently manufacturing a fluoroaryl borane derivative at high purity, which is a useful compound as a cocatalyst for a metallocene catalyst or a catalyst for silicone photo-polymerization.
The inventors of the present invention conducted an assiduous study of the method for manufacturing the fluoroaryl magnesium halide and the method for manufacturing the fluoroaryl borane derivative. In due course, the inventors discovered that, by conducting a Grignard exchange reaction of hydrocarbon magnesium halide and fluoroaryl halide in a solvent containing a chain ether solvent, fluoroaryl magnesium halide containing no impurities, such as coloring components, can be manufactured safely, efficiently, and industrially by a relatively gradual reaction compared with conventional reactions. Also, the inventors discovered that the reaction proceeds particularly in a preferable manner in a solvent containing an ether solvent other than diethyl ether. Further, the inventors achieved the present invention when they discovered that, by reacting the fluoroaryl magnesium halide obtained by the above method with a boron compound, a highly-pure fluoroaryl borane derivative containing no impurities, such as coloring components, can be manufactured readily and efficiently.
More specifically, in order to solve the above problems, a method for manufacturing fluoroaryl magnesium halide of the present invention is a method for manufacturing fluoroaryl magnesium halide expressed by General Formula (1):
where each of R
1
, R
2
, R
3
, R
4
, and R
5
independently represents a hydrogen atom, a fluorine atom, a hydrocarbon group, or an alkoxy group, provided that at least three of R
1
-R
5
are fluorine atoms, and X
a
represents a chlorine atom, a bromine atom, or an iodine atom;
by reacting, in a solvent containing a chain ether solvent, hydrocarbon magnesium halide expressed by General Formula (2):
R
6
MgX
a
(2)
where R
6
represents a hydrocarbon group, X
a
represents a chlorine atom, a bromine atom, or an iodine atom;
with fluoroaryl halide expressed by General Formula (3):
where each of R
1
, R
2
, R
3
, R
4
, and R
5
independently represents a hydrogen atom, a fluorine atom, a hydrocarbon group, or an alkoxy group, provided that at least three of R
1
-R
5
are fluorine atoms, and X
b
represents a bromine atom or an iodine atom.
In order to solve the above problems, a method for manufacturing tris(fluoroaryl)borane of the present invention is a method for manufacturing tris(fluoroaryl)borane expressed by General Formula (5):
where each of R
1
, R
2
, R
3
, R
4
, and R
5
independently represents a hydrogen atom, a fluorine atom, a hydrocarbon group, or an alkoxy group, provided that at least three of R
1
-R
5
are fluorine atoms;
by reacting the fluoroaryl magnesium halide manufactured by the above method with a boron compound expressed by General Formula (4):
B(X
c
)
3
(4)
where X
c
repres
Ariyoshi Yukiko
Hirano Naoko
Iida Toshiya
Ikeno Ikuyo
Mitsui Hitoshi
Conlin David G.
Dike Bronstein, Roberts & Cushman LLP
Nippon Shokubai Co. , Ltd.
Shaver Paul F.
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