Organic compounds -- part of the class 532-570 series – Organic compounds – Borate esters
Reexamination Certificate
2002-09-04
2004-11-16
Vollano, Jean F. (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Borate esters
C562S007000
Reexamination Certificate
active
06818785
ABSTRACT:
TECHNICAL FIELD
The present invention relates to a method for producing a fluoroaryl borane derivative and a bis (fluoroaryl) borane derivative such as a pentafluorophenyl boronic acid and a bis (pentafluorophenyl) borinic acid, which are useful as a polymerization catalyst, a polymerization co-catalyst, a catalyst for photopolymerization of silicone, an intermediate thereof, and an intermediate of a medicine or an agricultural chemical, for example.
BACKGROUND ART
Fluoroaryl borane derivatives and bis (fluoroaryl) borane derivatives such as pentafluorophenyl boronic acid and bis (pentafluorophenyl) borinic acid, are compounds useful as polymerization catalysts, polymerization co-catalysts, catalysts for photopolymerization of silicone, intermediates thereof, and intermediates of medicines or agricultural chemicals, for example.
For instance, as a manufacturing method of pentafluorophenyl boronic acid, J. Chem. Soc (1965) 3933-3939 discloses a method in which dichloropentafluorophenyl borane is added to acetone/water solution at a temperature of −78° C., then the acetone solution is concentrated, so that the pentafluorophenyl boronic acid is sublimated for purification, so as to be isolated. Further, as a manufacturing method of bis (pentafluorophenyl) borinic acid, it discloses a method in which a solution of bis (pentafluorophenyl) chloro borane in acetone is added to acetone/water solution at a temperature of −20° C., then the acetone solution is concentrated, so that the bis (pentafluorophenyl) borinic acid is sublimated for purification, so as to be isolated. Furthermore, the dichloropentafluorophenyl borane which is a precursor of pentafluorophenyl boronic acid, and the bis (pentafluorophenyl) chloro borane, which is a precursor of bis (pentafluorophenyl) borinic acid are synthesized by reacting pentafluorophenyl trimethyl tin or bis (pentafluorophenyl) dimethyl tin with boron trichloride. Upon synthesizing the dichloropentafluorophenyl borane, trimethyl tin chloride is produced as a by-product, and upon synthesizing the bis (pentafluorophenyl) chloro borane, dimethyl tin dichloride is produced as a by-product. However, it is difficult to purify dichloropentafluorophenyl borane and bis (pentafluorophenyl) chloro borane by distillation for the following reason: when these reaction mixtures are distilled so as to purify dichloropentafluorophenyl borane and bis (pentafluorophenyl) chloro borane as objects, trimethyl tin chloride reacts with an excess of boron trichloride so as to produce dimethyl tin dichloride which is identical to the by-product produced upon synthesizing bis (pentafluorophenyl) chloro borane, so that the dimethyl tin dichrolide is sublimed. Thus, it is difficult to purify dichloropentafluorophenyl borane and bis (pentafluorophenyl) chloro borane with high yield.
Moreover, J. Molecular Catalysis A: Chemical 144 (1999) 137-150 and WO 0037376 (2000) disclose that bis (pentafluorophenyl) borinic acid is prepared by heating a tris (pentafluorophenyl) borane hydrate.
However, the method disclosed in the above-mentioned J. Molecular Catalysis A: Chemical 144 (1999) 137-150 discloses only how to manufacture bis (pentafluorophenyl) borinic acid, and fails to recite how to isolate bis (pentafluorophenyl) borinic acid from a reaction mixture.
J. Molecular Catalysis A: Chemical 144 (1999) 137-150 recites only that it was confirmed by
19
F-NMR that bis (pentafluorophenyl) borinic acid was prepared by adding water to a toluene-d8 solution of tris (pentafluorophenyl) borane so as to prepare a tris (pentafluorophenyl) borane hydrate, then heating the solution of the tris (pentafluorophenyl) borane hydrate.
Moreover, WO 0037476 (2000) discloses preparation of bis (pentafluorophenyl) borinic acid by heating a tris (pentafluorophenyl) borane hydrate, and an isolation method of bis (pentafluorophenyl) borinic acid. Specifically, a toluene solution of tris (pentafluorophenyl) borane is heated up to 100° C. Then, to the solution, a toluene solution containing 2.5 equivalent amount of water is dropped so that reaction carried out at 100° C. After finishing the reaction, the reaction mixture is dried in vacuo so as to isolate bis (pentafluorophenyl) borinic acid. However, it is recited that the bis (pentafluorophenyl) borinic acid obtained by this method contains boroxine by 5% as impurities. In short, this method has such a problem that the isolated bis (pentafluorophenyl) borinic acid has a low purity.
Moreover, that patent also discloses a method in which alminium sulfate 18 hydrate is used instead of water. Specifically, aluminium sulfate 18 hydrate is added to a toluene solution of tris (pentafluorophenyl) borane. After the solution is refluxed, insoluble alminium sulfate is separated from the reaction mixture. A solvent of a filtrate is removed in vacuo. Toluene is added to the thus obtained residue. After stirring, the insoluble matter passes through a G4 sintered-glass so as to be separated. The solvent of the filtrate is again removed in vacuo. Heptane is added to the residue. The solution is stirred and filtered so that a cake is obtained. Finally, the thus obtained cake is washed with heptane, and dried in vacuo so as to isolate bis (pentafluorophenyl) borinic acid. However, this method has such a problem that it is necessary to remove the by-product alminium sulfate and its process is so complicated.
As described above, the prior methods have many problems to be improved. Although conditions of reduced pressure etc. are unexplained, boroxine is generated as impurity. Thus, in the case where the bis (fluoroaryl) borane derivative containing impurities is used as polymerization catalyst for example, there occur such problems that polymerization activity declines, etc.
Therefore, for industrial application of a fluoroaryl borane derivative and a bis (fluoroaryl) borane derivative, such as pentafluorophenyl boronic acid and bis (pentafluorophenyl) borinic acid, as catalysts or the like, there is a desire for a method by which the highly-purified fluoroaryl borane derivative and bis (fluoroaryl) borane derivative are easily isolated from a reaction mixture, and highly purified. Thus, the present invention, which is contrived in view of the foregoing problems, has an object of providing a method by which a fluoroaryl borane derivative and a bis (fluoroaryl) borane derivative can be produced, isolated, and highly purified with ease.
DISCLOSURE OF INVENTION
The present invention, in order to attain the above-mentioned object, carried out intensive studies on a method for purifying a fluoroaryl borane derivative and a bis (fluoroaryl) borane derivative, especially on a condition for filtrating, a condition for purifying, and the like. As a result, they found a method for purifying by which it is possible to readily separate the fluoroaryl borane derivative and the bis (fluoroaryl) borane derivative respectively as desired. Furthermore, they found a method for obtaining such an object that the content of a specific compound contained in the fluoroaryl borane derivative or the bis (fluoroaryl) borane derivative as impurities is not more than a specific amount, thus completing the present invention.
Compared with the prior arts, the fluoroaryl borane derivative and the bis (fluoroaryl) borane derivative obtained by the foregoing method for purifying are highly purified, so that it is possible to preferably use them as polymerization catalysts having high polymerization activity.
That is, in order to solve the foregoing problems, a method of the present invention for purifying a fluoroaryl borane derivative and a bis (fluoroaryl) borane derivative includes the steps of: precipitating the fluoroaryl borane derivative from a solution containing a fluoroaryl borane derivative, a bis (fluoroaryl) borane derivative, and a hydrocarbon solvent; performing first filtration; cooling a filtrate that has been obtained by the first filtration; precipitating the bis (fluoroaryl) borane derivative from the filtrate; and performing second filtration, and the fluoroaryl borane der
Iida Toshiya
Ikeno Ikuyo
Mitsui Hitoshi
Moriguchi Toshimitsu
Nippon Shokubai Co. , Ltd.
Vollano Jean F.
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