The method of obtaining ferrimagnetic derivative and method for producing (foradil) boranova connection (options)

 

(57) Abstract:

The invention relates to a method of obtaining new fluorinated ariminium derivatives by reacting fluorinated aromatic compounds with halogenated hydrocarbon and magnesium in an ether solvent or in a mixture with hydrocarbons. In accordance with this method, the target compound can be obtained efficiently in the one-step reaction at a low price. Received oilmagnate derivatives are used as reagents for the introduction of the fluorinated aromatic groups in a variety of organic compounds. The invention relates also to a method for porarily derivatives of boron by adding an ethereal solution of fluorinated kilmanjaro derived and the ether solution of boron halide to hydrocarbons having a higher boiling point than the ether solvent, and interaction kilmanjaro derived from the boron halide as evaporation of the ether solvent. This method makes it possible to selectively obtain the desired compounds of boron at a low price that gives him the advantage, when used in industrial production. The compounds of boron are used as cockatoos get ferrimagnetic derivative, which is widely used, for example as reactant (organic synthetic reagent for the introduction of ftoruridina group in various organic compounds. The present invention also relates to a method for obtaining (foradil)Baranovich compounds, such as Tris(foradil)borane and bis(foradil)boryl halide, servants, such as excellent socializaton for metallocene catalyst (polymerization catalyst) used in the polymerization reaction, catalyzed by cationic complex.

BACKGROUND OF THE INVENTION

Ferrimagnet derived, which is one of Grignard reagents, as is well known, for example as excellent reactant (organic synthetic reagent for the introduction of ftoruridina group in various organic compounds. In addition, recently ferrimagnetism derived pays considerable attention as synthetic material to obtain Tris(foradil)boranova compounds used as excellent socialization for metallocene catalyst (polymerization catalyst).

The method of obtaining ferrimagnetic derived disclosed, for example, in J. Org. Chem. , 29, 2385 (1964). He is vigotovlennyu by dissolving pentafluorobenzoyl in the ether solvent, such as tetrahydrofuran (THF). Therefore, panafcortelone derived receive as ferril magnesium derivative. Japanese Laid-open Patent Application N 247976/1994 (Tokukaihei 6-247976) discloses another method of obtaining. In this way panafcortelone derivative is obtained by addition of a solution of pentafluorobenzene in the ether solvent to the solution allylanisole derived in the ether solvent.

In these ways panafcortelone derivative is obtained as a result of the exchange reaction in which an alkyl group allylanisole derivative substituted on pentafluorophenyl group.

However, in these methods, the alkyl magnesium derivative to get the above-mentioned exchange reaction. In other words, as alkylamine derivative is prepared separately, to obtain panafcortelone derivative, the reaction is a two-step.

To solve the above problem, the present invention in one aspect is effective, cheap and easy way to get ferrimagnetic derived, in fact at one stage.

(Foradil)boranova connection, in particular Tris(pentafluorophenyl)borane, known is Aligator polymerization), used in the polymerization, the current flowing through the mechanism of formation of the cationic complex, and, more recently, the metallocene catalyst has received considerable attention as a catalyst for polymerization of polyolefin.

An example of a method of obtaining the above-mentioned Tris(pentafluorophenyl)borane disclosed in Proc. Chem. Soc., 1963 (July), 212. Namely, pentafluorobenzoyl lithium, produced by the interaction of bromopentafluorobenzene and butyl lithium reacts with trichloride boron, resulting Tris(pentafluorophenyl)borane. However, in this method, the reaction system must be cooled to -78oC, which makes this method unsuitable for industrial use.

To solve this problem, a method is proposed that uses the reaction of the Grignard reagent, which is disclosed in Z. Naturforsch., 20b, 5 (1965) as another example of a method of producing Tris(pentafluorophenyl)borane. In accordance with this method, for example, pentafluorobenzylbromide and diethylether of boron TRIFLUORIDE interact with each other in an acyclic ether solvent. In this case, it is not necessary to cool the reaction system to -78oC, which makes this process more profitable than the previously mentioned reaction. Gave annihalating derivative and boron halide in an acyclic ether solvent or in a mixture of acyclic ether solvent and an aromatic hydrocarbon solvent.

However, as in the above conventional procedure using acyclic ether solvent having a relatively low boiling point, such as diethyl ether, the reaction system must be cooled. Thus, when receiving (foradil)Baranovich compounds in industrial production is absolutely necessary cooling apparatus, etc., moreover, diethyl ether is a flammable liquid. In addition, in the above conventional procedure is difficult to control the reaction because of the formation of side products such as Quaternary boron compound, Tetra(foradil)borate derivative. This makes it difficult for selective receipt (foradil)Baranovich compounds, such as Tris(foradil)borane and bis(ferril boryl halide. In addition, an acyclic ether solvents are more expensive than the cyclic ether solvents.

Thus, the above-mentioned traditional methods of obtaining are not readily used in industry, not only due to the fact that solvents are difficult to handle, but also due to the fact that (foradil)boranova compounds such as Tris(foradil)borane and bis(foradil)Borel halo is the appropriate fields in the above conventional procedure may cause adverse reactions, for example, the ring opening and subsequent polymerization of the cyclic ether solvent. In addition, the use of only an aromatic hydrocarbon solvent in the above-mentioned conventional method of obtaining lowers output (foradil)Baranovich compounds, such as Tris(foradil)borane and bis(foradil)boryl halide.

Thus, to solve the above problems in its second aspect the present invention relates to a method for producing (foradil)Baranovich compounds, such as Tris(foradil)borane and bis(foradil)boryl halide, selectively, at a low price and simple way.

DETAILED DESCRIPTION OF THE INVENTION

For the implementation of the first aspect of the invention the authors conducted a thorough research on the method of production ferrimagnetic derived and found that ferrimagnet derivative can be obtained an effective, cheap and simple way, in fact at one stage, the result of the interaction of ferarra, hydrocarbon halide and magnesium with each other in the ether solvent or in a mixture of ether and hydrocarbon solvents.

Specifically, to solve this problem, in this application presents SUB>2, R3and R4represents a hydrogen atom, a fluorine atom, a hydrocarbon group or alkoxy group, and Xa represents a chlorine atom, bromine or iodine,

and the way to obtain is in the interaction:

(a) aryl fluoride having the General formula (1):

< / BR>
where each of R2, R3and R4represents a hydrogen atom, a fluorine atom, a hydrocarbon group or alkoxy group;

(b) hydrocarbon halide having the General formula (2):

R0Xa (2)

where Rorepresents a hydrocarbon group, and Xa represents a chlorine atom, bromine or iodine; and

(C) magnesium in an ether solvent or in a mixture of ether and hydrocarbon solvents.

The reaction corresponding to the specified process, is actually at one stage, which makes possible an efficient, cheap and easy getting ferrimagnetic derived.

For carrying out another aspect of the application, the authors of the present invention conducted thorough research on the method of production (foradil)Baranovich compounds and found that (foradil)boranova compounds such as Tris(foradil)borane and bis(foradil)boryl halide can be obtained selek is rastvoritele and solution of boron halide in an ether solvent and hydrocarbon solvent, having a higher boiling point than the ether solvent, so that ferrimagnet derivative and boron halide interact with each other as the ether solvent evaporates. The authors further found that (foradil)boranova compounds can be obtained from halftoned in fact, the one-step reaction (so-called "one pot") by the interaction ferrimagnetic derivative obtained by the above method, the boron halide in situ, which makes it possible to obtain (foradil)Baranovich compounds cheap and simple way.

In other words, to solve the above problems, the present invention provides a method of obtaining (foradil)Baranovich compounds having the General formula (6):

< / BR>
where each of R1, R2, R3, R4and R5represents a hydrogen atom, a fluorine atom, a hydrocarbon group or alkoxy group, and at least one of R1-R5represents a fluorine atom, Xb represents a chlorine atom, bromine or iodine, and n may be equal to 2 or 3,

and the way to obtain is that the mixed solution ferrimagnetic derivative, having the General is>and R5represents a hydrogen atom, a fluorine atom, a hydrocarbon group or alkoxy group, and at least one of R1-R5represents a fluorine atom, and Xa represents a chlorine atom, bromine or iodine,

and a solution of boron halide having the General formula (5) below, in the ether solvent:

BXb3(5)

where Xb represents a fluorine atom, chlorine, bromine or iodine,

with a hydrocarbon solvent having a higher boiling point than the ether solvent, so that ferrimagnet derivative and boron halide interact with each other as to evaporate the ether solvent.

In addition, to solve the above problems, the present invention provides a method of production (foradil)Baranovich compounds described by the General formula (6) above, which consists in mixing a solution ferrimagnetic derivative having the General formula (4) above, in the ether solvent, with a solution of boron halide described General formula (5) above, in the ether solvent at 80oC or below, and further mixing the obtained mixed solution of hydrocarbon will dissolve the boron halide interact with each other as to evaporate the ether solvent.

In accordance with the above process, due to the fact that the reaction is easily controlled, the ether solvent is not limited to acyclic ether solvent. In other words, cyclic ether solvents, which are more easy to handle, can also be used. In addition, because the resulting (foradil)boranova compounds such as Tris(foradil)borane and bis(foradil)arilgalogenide, do not form any complexes or Quaternary compounds (foradil)boranova connection can be easily isolated in pure form. Therefore, it becomes possible to obtain (foradil)boranova compounds such as Tris(foradil)borane and bis(foradil)boryl halide, selectively, cheap and easy way. In other words, the method of obtaining provided by the present invention is more advantageous than traditional industrial applications and makes it possible to obtain (foradil)boranova compounds such as Tris(foradil)borane and bis(foradil)boryl halide, high yield and high selectivity.

Further, to solve the above problems, the application provides a method of production (foradil)Baranovich compounds described General Faure is a hydrocarbon group or alkoxy group, and Xb represents a fluorine atom, chlorine, bromine or iodine, and n may be 2 or 3,

method of production lies in the interaction obtained using the above procedure ferrimagnetic derivative having the General formula (3) above with a boron halide having the General formula (5) below:

BXb3(5)

where Xb represents a fluorine atom, chlorine, bromine or iodine.

With regard to the above process, in addition to the previously mentioned various effects (foradil)boranova connection can be obtained from halftoned actually in the process of one-step reaction (so-called "one pot"), which makes it possible to obtain (foradil)boranova connection at a low price in an easy way.

The following description represents the invention in detail.

First explained is a method of obtaining ferrimagnetic derived.

The method of obtaining ferrimagnetic derivative, the above-described General formula (3), (hereinafter referred to as ferrimagnet derivative (3)), is a process in which eilperin, the above-described General formula (1), the hydrocarbon halide described above is portly solvents.

Eilperin, the above-described General formula (1), in which the present invention is used as a source connection for receiving ferrimagnetic derivative (3), is a compound, the substituents of which, designated as R2, R3and R4represent respectively a hydrogen atom, a fluorine atom, a hydrocarbon group or alkoxy group.

Hydrocarbon group refers to aryl group, an unbranched, branched hydrocarbon chain, or cyclic alkyl group having up to 12 carbon atoms, an unbranched, branched or cyclic alkeneamine group having from 2 to 12 carbon atoms, etc., the Hydrocarbon group may include a functional group that is inactive in the reaction in this invention. Examples of such functional groups are: methoxy, timetolive, N,N-dimethylamino, anise, p-anisic, trimethylsilyl, t-butyldimethylsilyl, triptoreline etc.

Alkoxy group has the General formula (A):

-ORa(A)

where Rarepresents a hydrocarbon group. Examples of the hydrocarbon groups indicated in the formula as Ra, allanah atoms, an unbranched, branched or cyclic alkeneamine group having from 2 to 12 carbon atoms. In addition, the hydrocarbon group may include functional groups that remain inactive in the reaction in this invention.

Examples of alkoxy groups, the above-described General formula (A) are: methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, cyclohexyloxy group, allyloxy group, phenoxy group, etc.

Examples of aristeidou are pentafluorobenzoyl, 1,2,3,5-tetrafluorobenzene, 1,2,4,5-tetrafluorobenzene, 1,2,4-triftorbyenzola, 1,3,5-triptorelin, 1,3-differental, 2,3,5,6-tetrachordal, 2,3,4,6-tetrachordal, 2,3,5-triptorelin, 2,4,6-triptorelin, 2,4-dipertua, 2,3,5,6-teratornis, 2,3,4,6-tetrachordal, 2,4,5-triparanol, 2,4,6-triparanol, 2,4-differenital, 3,5-differenital, etc.

The hydrocarbon halides, the above-described General formula (2) are compounds in which Xa represents a chlorine atom, bromine or iodine, and the substituents denoted as R0represent a hydrocarbon group. Examples of hydrocarbon gr carbon atoms, an unbranched, branched or cyclic alkeneamine group having from 2 to 12 carbon atoms, etc. in Addition, the hydrocarbon group may include functional groups that remain inactive in the reaction in this invention. Examples of such functional groups are: methoxy group, a methylthio group, N,N-dimethylamino group, o-anisic group, p-anisic group, trimethylsilyl group, t-butyldimethylsilyloxy group, triptoreline group, etc.

Examples of the above hydrocarbon halides are methyl chloride, methyl bromide, methyliodide, ethylchloride, ethylbromide, ethyliodide, n-propylchloride, n-propyl bromide, n-propyliodide, isopropylchloride, isopropylphenyl, isopropylate, n-butyl chloride, n-butylbromide, n-butylated, isobutylene, isobutyramide, isobutylene, sec-butyl chloride, sec-butylbromide, second-butylated, t-butyl chloride, t-butylbromide, t-butylated, vexilloid, Hexi bromide, hexalite, cyclohexylidene, cyclohexylamine, cycloheximide, allylchloride, allylbromide, allride, chlorobenzene, Brabanthal, idental, etc. From all these examples of the halides of the most preferred hydrocarbons are a and allibiotic. One substance or a mixture of two or more substances selected from these examples can be used effectively.

The quantitative ratio of the halide of a hydrocarbon to aristeidou not specifically limited. However, the preferred ratio in equivalents is 0.5 or higher. This ratio in equivalents, more preferably in the range between 0.5 and 3.0, and most preferred in the range from 0.8 to 1.5, equivalents. If the ratio of the hydrocarbon halide in equivalents is less than 0.5, it is too much unreacted halftoned to effectively get ferrimagnet derivative (3).

For the further reaction of the magnesium is preferably used in a form having a large surface area, such as powders, granules and fine strips.

The ratio of magnesium to aristeidou not specifically limited. However, the preferred ratio in equivalents is 0.5 or higher. This ratio in equivalents, more preferably in the range between 0.5 and 3.0, and most preferred in the range from 0.8 to 1.5, equivalents. If the ratio of magnesium equivalents is less than 0.5, it is too much unreacted aryl is specialno not limited to, until it is liquid and is inactive to the reaction, in this invention, and in which eilperin, the halide of magnesium and ferrimagnets derived as the target substance can be dissolved. Examples of the ether solvents are:

acyclic ethers, such as diethyl ether, DIPROPYLENE ether, diisopropyl ether, disutility ether, Diisobutyl ether, daintily ether, diisopentyl ether, 1,2-dimethoxy ethane, 1,2-diethoxy ethane, di(2-methoxyethoxy) ether;

cyclic ethers, such as tetrahydrofuran, tetrahydropyran, 1,4-dioxane, etc.

One substance or mixture of two or more substances selected from these examples can be used effectively. From all these examples of preferred compounds are diethyl ether and tetrahydrofuran, as they contribute to a better reaction. If a mixture of two or more substances selected from these examples, it is preferred inclusion in ether solvents at least diethyl ether or tetrahydrofuran.

The amount of volatile solvent is not specifically limited. However, preferred is a number, in which concentric manutoo hydrocarbon solvent is not specifically limited, while it remains a liquid substance that is inactive to the reaction, in the present invention. Examples of the hydrocarbon solvents are:

an unbranched, branched or cyclic aliphatic hydrocarbons, such as pentane, isopentane, hexane, cyclohexane, heptane, octane, Nanan, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, octadecane, paraffin and petroleum ether;

aromatic hydrocarbons, such as benzene, toluene, o-xylene, m-xylene, p-xylene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 1,2,5-trimethylbenzene, 1,3,5-trimethylbenzene, ethylbenzene, propylbenzene, butylbenzoyl etc.

Effectively can be one or a mixture of two or more substances selected from these examples of the compounds.

The ratio in a mixture of ether and hydrocarbon solvent is not specifically limited, as long as both solvent form a homogeneous mixture. However, preferred is a ratio between 1:0 and 1:10 by volume. The amount of the mixed solvent is also not specifically limited. However, preferred is such a number, in which the concentration of the final product ferrimagnetic derivative (3) between the magnesium when mixed with the ether solvent or a mixture of ether and hydrocarbon solvents (hereinafter referred to simply as the solvent, when referring to both types of solvents) is not specifically limited. The order of mixing is represented by the following examples:

1) halftoned, the hydrocarbon halide and magnesium are mixed with the solvent almost at the same time;

2) halftoned and magnesium are mixed with the solvent and then add the hydrocarbon halide;

3) halftoned first mixed with the solvent and then the hydrocarbon halide and magnesium are mixed with the solvent almost at the same time;

4) magnesium is first mixed with the solvent and then halftoned and the hydrocarbon halide is mixed with the solvent in virtually one and the same time;

5) magnesium, halftoned and the hydrocarbon halide is mixed with the solvent sequentially in this order; and

6) halftoned and the hydrocarbon halide is mixed with the solvent and then add the magnesium.

From all these examples, the procedure for adding substances is preferable mixing halftoned and magnesium followed by the addition of the hydrocarbon halide. Accordingly, the order of mixing ferrimagnet derivative can be obtained more effektivnosti way.

The method of mixing aristoi the th dropwise eilperin and/or the hydrocarbon halide is continuously or sequentially (portions), because in this case the reaction can be more easily controlled. A method of adding dropwise not specifically limited, and halftoned or the hydrocarbon halide can be added dropwise directly to the solvent or diluted with a solvent before precapitalism.

The temperature of mixing, in which eilperin and/or the hydrocarbon halide is mixed with the solvent is not specifically limited. However, when mixing of the hydrocarbon halide with the solvent, the preferred temperature is in the range between -20oC and temperature phlegmy solution. More preferred is a temperature of the mixing set in the range between -20oC and 100oC, and most preferred is in the range between 20oC and 70oC. Because when mixing the hydrocarbon halide with the solvent in the above temperature range the reaction is easier to control. Subsequently, it can be possible to get ferrimagnet derivative (3) more effectively in a simple way. The temperature of mixing below -20oC does not give significant effects, and therefore is not suitable for use in industrial production, in contrast to those cases, comparator mixing exceeds the temperature phlegmy solution, it becomes difficult to control the reaction. The temperature of mixing is easy to install in the range between -20oC and temperature phlegmy solution, suitable for use in industry.

Eilperin, the hydrocarbon halide and magnesium begin to interact with each other when mixed with the above-mentioned anhydrous solvent and subsequent stirring. During the reaction the magnesium gradually dissolves in the solvent. If during the course of the reaction system water is present, the resulting ferrimagnet derivative (3) interacts with water and begins to decompose. For this reason, it is desirable that this reaction proceeded in an atmosphere of inert gas, such as nitrogen. It is desirable to replace the air inert gas, such as nitrogen, within the reaction system, namely in the reaction vessel. In addition, it is desirable that the solvent, eilperin and a halide of a hydrocarbon does not contain water. Drying method of halftoned, hydrocarbon halide and the solvent is not specifically limited.

The reaction temperature is preferably set in the range between 30oC and temperature phlegmy solution. More preferably , - in the interval between 30oC and 70oC. as a result, it becomes possible to obtain ferrimagnetic derivative (3) more effectively in a simple way. Setting the reaction temperature below 30oC is undesirable because the reaction becomes too slow to efficiently retrieve ferrimagnetic derived. On the other hand, if the reaction temperature exceeds the temperature phlegmy solution becomes difficult to control the reaction.

The reaction time is set arbitrarily, so that the reaction proceeded completely, depending on the reaction temperature, quantities of halftoned and hydrocarbon halide, etc., the Reaction pressure is also not specifically limited, and the reaction may proceed at normal, reduced or increased pressure.

In the result of the above process get ferrimagnet derivative (3), namely the solution ferrimagnetic derived. In addition, as a by-product is produced hydrocarbon, expressed by the General formula (B) below:

RoH (IN)

where Rorepresents a hydrocarbon group. This solution is used when necessary in situ in the reaction at the stage of obtaining (AE needed and the separation method is not specifically limited.

In accordance with the above-described process may be actually one stage, and ferrimagnets derivative can be obtained with high yield and high selectivity. Therefore, it becomes possible to obtain ferrimagnet derivative (3) effectively, at low cost and in a simple way. Ferrimagnet derivative (3) can be used, for example as reactant (organic synthetic reagent for the introduction of ftoruridina groups in various kinds of organic compounds or synthetic material to obtain Tris(foradil)Baranovich compounds, which are great socialization for metallocene catalyst (polymerization catalyst). Further, when using pentafluorophenol as halftoned panafcortelone derivative (3) can be obtained efficiently at a low price, simple way. It is desirable to contain the target ferrimagnet derivative (3) in an atmosphere of inert gas, such as nitrogen, to prevent reaction with water.

Next will be described a method of obtaining (foradil)boranova connection.

The method of obtaining (foradil)boranova connection is oterom solution ferrimagnetic derivative, the above-described General formula (4) (hereinafter referred to as ferrimagnet derivative (4)), in the ether solvent and a solution of boron halide, the above-described General formula (5), in the ether solvent is mixed with a hydrocarbon solvent having a higher boiling point than the ether solvent, so that ferrimagnet derivative (4) and boron halide interact with each other as the ether solvent evaporates.

Furthermore, the method of obtaining (foradil)boranova compounds of the present invention, the above-described General formula (6) represents a reaction process in which solutions ferrimagnetic derivative and boron halide, the above-described General formula (5), in the ether solvent are mixed with each other at a temperature of 80oC or below, and the obtained mixed solution is mixed with a hydrocarbon solvent having a higher boiling point than the ether solvent, so that ferrimagnet derivative (4) and boron halide interact with each other as the ether solvent evaporates.

Next, the method of obtaining (foradil)boranova compounds of the present invention, the above-described obiturary magnetoacoustic (3) and boron halide, the above-described General formula (5) interact with each other in situ.

Ferrimagnet derivative (4) used in the present invention as the starting material to obtain (foradil)boranova compounds in which the substituents denoted as R1, R2, R3, R4and R5respectively represent one of the following groups: a hydrogen atom, a fluorine atom, a hydrocarbon group and alkoxy group, and at least one of the substituents R1-R5represents a fluorine atom, and Xa represents a chlorine atom, bromine or iodine. Examples of the hydrocarbon groups are basically the same as in the above examples of the hydrocarbon groups. Similarly, examples of alkoxy groups are basically the same as in the above examples of alkoxy groups.

Examples ferrimagnetic derivative (4) are: pantothenicacid, pentafluorobenzylbromide, pentafluorophenyl magnesium iodide, 1,2,3,5-tetraferriphlogopite, 1,2,4,5-tetracarbonylnickel, 1,2,4-tryptophansynthroid, 1,3,5-Cryptosporidium, 2,3,5,6-titrator-4-methylphenylamine, 2.5-differentialalgebraic, 2.5-debtor-3-methylphenylamine, 2,3,4,6-those who RAID, 2,3,6-Cryptor-5-methoxyphenylacetone, 2,4,6-Cryptor-5-methoxyphenylacetamide, 2.5-debtor-3-methoxyphenylacetone, 2.5-debtor-4-methoxyphenylacetamide, 2-performancebased, 4-performancebased, 2-fluoro-4-methylphenylamine, etc. From all these examples ferrimagnetic derivative (4) the most preferred is pentafluorobenzylbromide. Now you can use one or a mixture of two or more substances selected from these examples.

The method of obtaining ferrimagnetic derivative (4) is not specifically limited. For example, ferrimagnet derivative (4) can be obtained by the reaction of magnesium and ferril of halide, such as ferrichloride, forreverse and ferralitic.

Ferrimagnet derivative, the above-described General formula (4), in which at least two Deputy designated as R1and R5represent a fluorine atom, and thus is ferrimagnetism derivative (3) can be obtained by the above explained method of obtaining. In other words, ferrimagnet derivative (3) can be obtained by the interaction of (i) halftoned having fluorine atoms in at least two positions (ortho-panida hydrocarbon, the above-described General formula (2), and (iii) magnesium with each other.

The boron halide, the above-described General formula (5), is a compound in which Xb represents a fluorine atom, chlorine, bromine or iodine, examples of which are boron TRIFLUORIDE, trichloride boron, tribromide boron and triiodide boron. From these examples, the most preferred is boron TRIFLUORIDE. You can effectively use one or a mixture of two or more substances selected from these examples. Alternatively, the boron halide may be in the form of essential complexes, such as diethyl ether complex and tertrahydrofuran ring complex.

The state of the ether solvent is not specially limited, while it is a liquid substance that is inactive to the reaction, in the present invention, and which can dissolve ferrimagnet derivative (4) and boron halide. Examples of the ether solvents are mostly the same as the aforementioned examples of acyclic and cyclic solvents. You can effectively use one or a mixture of two or more substances selected from these examples. The most preferred of all of these examples of the compounds are Diatlov is more substances selected from these examples, prefer the ether solvent include at least diethyl ether or tetrahydrofuran. In the method of obtaining (foradil)boranova compounds of the present invention as the ether solvent may be used cyclic ether. Further, the above-mentioned hydrocarbon solvent can be used instead of ether solvent to such an extent so as not to have an adverse effect on the reaction taking place in the present invention.

The amount of volatile solvent is not specifically limited. However, preferred is such a number, in which the concentration ferrimagnetic derivative (4) or boron halide is in the range between 0.1 and 80 weight percent. Method of dissolution ferrimagnetic derivative (4) or boron halide in an ether solvent is not specifically limited. That is, the method of preparing a solution by dissolving ferril magnetoliposomes (4) in the ether solvent and method of preparing another solution by dissolving the boron halide in an ether solvent is not specifically limited.

The molar ratio ferrimagnetic derivative (4) and halide which is the ratio between 1.0 and 5.0. Additional restriction molar ratio interval from 2.5 to 5.0, inclusive, more preferably the interval from 2.7 to 4.0 inclusive, and most preferred is the interval from 2.8 to 3.7 inclusive, makes possible the selective receipt (foradil)boranova compounds in which n in the above General formula (6) is equal to 3, i.e. Tris(foradil)borane. Furthermore, an additional constraint molar ratio interval from 1.0 to 2.5 inclusive, not including this value, more preferably the interval from 1.2 to 2.4 inclusive, and most preferred is the interval from 1.3 to 2.3 inclusive, makes it possible for mainly (foradil)boranova compounds in which n in the above General formula (6) is equal to 2, i.e. bis(foradil)boryl of halide. If the molar ratio is less than 1.0, there's too much unreacted boron halide. On the other hand, if the molar ratio is greater than 5.0, there's too much unreacted ferrimagnetic derivative (4). In the effective receipt (ferril Baranovich compounds, such as Tris(foradil)borane and bis(foradil)boryl halide, become impossible.

Hydrocarbon RA in the present invention, and has a higher boiling point than the ether solvent, and in which the target (ferril boranova compounds such as Tris(foradil)borane and bis(foradil)boryl halide may be dissolved. Examples of the hydrocarbon solvent is basically the same as the aforementioned aliphatic and aromatic hydrocarbons. Now you can use a single substance or a mixture of two or more substances selected from these examples. In addition, it is desirable that the hydrocarbon solvent had a boiling point of 60oC or higher. If the hydrocarbon solvent includes aromatic hydrocarbons, it is desirable to use it in such a way that it does not adversely effect the reaction in this invention. In addition, it is desirable that no hydrocarbon or ether solvent does not form azeotropic composition.

Suitable combinations of ether and hydrocarbon solvents are:

diethyl ether and hexane, diethyl ether and cyclohexane, diethyl ether and heptane, diethyl ether and octane, diethyl ether and IsoparE of Exxon Corp. (mixture isoparaffins having about 10 carbon atoms), diethyl ether and Dean, diethyl ether and Oct is IsoparE, tetrahydrofuran and Dean, tetrahydrofuran, and octadecan, tetrahydrofuran and liquid paraffin, etc.

The amount of hydrocarbon solvent is not specifically limited. However, this quantity must be such that the concentration of the target (foradil)Baranovich compounds, such as Tris(foradil)borane and bis(foradil)boryl halide, preferably ranged between 0.1 and 80 weight percent, and more preferably in the range between 0.1 and 50 weight percent when ferrimagnet derivative (4) and boron halide interact with each other as the ether solvent pariveda. In particular, the limitation of the concentration range from 0.1 to 50 percent by weight makes it possible to obtain a cleaner (foradil)boranova connection. The method of fixing the concentration is not specifically limited. However, preferred are a method of adding a hydrocarbon solvent to the reaction system, while ferrimagnet derivative (4) communicates with the boron halide, as the evaporation of the ether solvent, and a method of fractionation of hydrocarbon and ether solvents, which allows to return a hydrocarbon solvent in reactionsa (referred to hereinafter as solution of the magnesium derivative), and boron halide in an ethereal solvent (hereinafter referred to as the solution of a boron halide) when mixed with the hydrocarbon solvent is not specifically limited. However, preferred are the following examples of mixing: a solution of the magnesium derivative solution and the solution of the boron halide is mixed with a hydrocarbon solvent almost simultaneously and the solution of the magnesium derivative solution and the solution of the boron halide is first mixed

with each other, and then the resulting solution is mixed with a hydrocarbon solvent.

If too long a contact ferrimagnetic derivative (4) and boron halide in the presence of an ether solvent begins adverse reaction and result in significantly reduced yield and selectivity obtain (ferril Baranovich compounds, such as Tris(foradil)borane and bis(foradil)boryl halide. Thus, in the case when the solution of the magnesium derivative solution and the solution of the boron halide is first mixed with each other, preferably the mixture is mixed with a hydrocarbon solvent as quickly as possible.

Next, the temperature of mixing of solutions of magnesium derivative and boron halide, preferably mouth is preferably in the range -20oC to 50oC, as adverse reactions can be prevented in case the solutions of magnesium derivative and boron halide to mix with each other at 80oC or below. At the temperature of mixing exceeding 80oC, hard to control side reactions, therefore, decreases the yield and selectivity of receipt (foradil)Baranovich compounds, such as Tris(foradil)borane and bis(foradil)boryl halide. The temperature of mixing below -40oC has no significant effects, and therefore it is disadvantageous when used in industrial production compared with those cases where the temperature of the mix is set at a higher temperature range.

Any method of mixing solutions of magnesium derivative and boron halide with a hydrocarbon solvent or a method of mixing solutions of magnesium derivative and boron halide with each other is not specifically limited. But I prefer adding dropwise continuous or portions.

The reaction between ferrimagnetism derivative (4) and boron halide carried out as follows: mix solutions of magnesium derivative and boron halide with the above besly in the reaction system during the reaction water is present, ferrimagnet derivative (4) interacts with it and begins to decompose. Therefore, it is desirable that the above-mentioned reaction proceeded in an atmosphere of inert gas, such as nitrogen. It is also desirable to replace the air inert gas, such as nitrogen, within the reaction system, namely in the reaction vessel. It is also desirable that the ether solvent, a hydrocarbon solvent and boron halide did not contain water. The method of drying the ether solvent, a hydrocarbon solvent and boron halide is not specifically limited.

The ether solvent evaporates completely before the reaction between ferrimagnetism derivative (4) and boron halide. Examples of timing evaporation of the ether solvent include the following, but not only them: 1) after mixing the solution of the magnesium derivative and/or a solution of a boron halide with a hydrocarbon solvent, and 2) when the solution of the magnesium derivative and/or a solution of a boron halide is mixed with a hydrocarbon solvent (mixing and evaporation competitive conduct (at a time)); and so on, But note that preferably the solvent was evaporated as quickly as possible, for the reason explained above. This is one and/or solution of a boron halide with a hydrocarbon solvent.

The temperature at which the evaporated ether solvent, preferably set in the range from 30oC to 200oC, and more preferably in the range from 30oC to 150oC. Consequently, the residual amount of volatile solvent can be reduced. In particular, if the temperature is set in the range from 30oC to 150oC, you can get a cleaner (foradil)boranova connection. The ether solvent was evaporated can be at normal (atmospheric), low and high pressure.

The reaction temperature is preferably set in the range from 30oC to 200oC, more preferably in the range from 30oC to 170oC, and most preferably in the range from 30oC to 150oC. Desirable to set the reaction temperature below 30oC, the reaction becomes too slow to efficiently retrieve (foradil)Baranovich compounds, such as Tris(foradil)borane and bis(foradil)boryl halide. On the other hand, if the reaction temperature exceeds 200oC, the reaction becomes difficult to control.

The reaction time can be set arbitrarily so that the reaction proceeded completely according to the Oia, etc. The pressure of the reaction is not specifically limited, and the reaction may proceed at normal (atmospheric), reduced or increased pressure.

In the result of the above process receive (foradil)boranova compound expressed by General formula (6) above. As a by-product also receive a halide of magnesium, described below General formula (C):

MgXaXb ()

where Xa represents a chlorine atom, bromine or iodine, and Xb represents a fluorine atom, chlorine, bromine or iodine. If necessary, the magnesium halide can be separated from (foradil)boranova connection method is not specifically limited. When using a mixture of two or more kinds ferrimagnetic derivatives receive a mixture of several species (foradil)Baranovich connections.

In the above process, the ether solvent is not limited acyclic ether solvents as the reaction is easy to control. In other words, you can also use a cyclic ether solvent, which is more easy to handle. In addition, as the target (foradil)boranova compounds such as Tris(foradil)borane and bis(foradil)boryl halide, do not form any complexes or chetverti possible to obtain (foradil)boranova connection such as Tris(foradil)borane and bis(foradil)boryl halide, selectively, at a low price, simple way. In other words, the method of obtaining of the present invention has the advantage when used in industrial production compared to traditional and gives the opportunity to get (foradil)boranova compounds such as Tris(foradil)borane and bis(foradil)boryl halide, high yield and high selectivity. (Foradil)boranova compounds, in particular Tris(pentafluorophenyl) borane is used, for example, as acetalization metallocene catalyst (polymerization catalyst). Further, when using pentafluorobenzylbromide as ferrimagnetic derivative (4), get (pentafluorophenyl)boranova compounds such as Tris(pentafluorophenyl) borane and bis(pentafluorophenyl)boryl halide, efficiently, at a low price, simple way.

Next, (foradil)boranova connection, the above-described General formula (10), get the result of the interaction of ferril magnesium derivative (3) obtained in the above manner, with the boron halide, the above-described General formula (5) in situ. The molar ratio ferrimagnetic derivative (3) and boron halide with the Method of mixing solutions ferrimagnetic derivative (3) and boron halide is not specifically limited. The boron halide may be added to the solution all at once, or add dropwise continuously or in portions. The boron halide can be mixed with the solution directly or dissolved in a solvent before mixing with the solution.

The temperature of the mix, which mix the solutions ferrimagnetic derivative (3) and boron halide, or the reaction temperature is not specifically limited. However, it is desirable to set the temperature of the mixing and reaction temperature in the above-mentioned intervals, respectively. The reaction time can be set arbitrarily, so that the reaction proceeded completely, depending on the reaction temperature, the combination of quantities ferrimagnetic derivative (3) and boron halide, etc., the Pressure of the reaction is not specifically limited, and the reaction may proceed at normal (atmospheric), reduced or increased pressure.

(Foradil)boranova connection, the above-described General formula (10), receive the above method. In addition, as a byproduct get the magnesium halide, the above-described General formula (C). If necessary, you can separate the halide of magnesium (foradil)boranova connection with the method is executed by the above-mentioned various effects, (foradil)boranova connection can be obtained from halftoned in one stage (the so-called reaction in one vessel"). Therefore, it becomes possible to obtain (foradil)boranova connection at a low price in an easy way.

Other aspects of the nature and advantages of the invention are explained in the following description. The effects of the present invention are explained in the following description.

Below the present invention will be explained in detail a number of examples. However, the present invention is not limited by the examples below.

THE PREFERRED EMBODIMENT OF THE INVENTION

Example 1

Air inside a reaction vessel equipped with a thermometer, dropping funnel, stirrer, sum of nitrogen and condenser phlegmy, replacing with nitrogen in a satisfactory degree. Then 2,187 g (0,090 moles) of magnesium, 15,131 g (0,090 moles) of pentafluorobenzene as halftoned and 15 ml of diethyl ether as solvent (ether solvent) is placed in the reaction vessel. A mixed solution prepared by mixing 11,624 g (0,095 moles) of Isopropylamine, a halide of a hydrocarbon with 10 ml of diethyl ether are placed in an addition funnel. As the ratio of 1.06 in equivalents.

The mixed solution is added dropwise to the contents of the reaction vessel over 0.5 hour with stirring in a stream of nitrogen. The temperature of this content is 25oC at the beginning of the addition and increases to 57.5oC in the process of adding dropwise (which indicate how the temperature of mixing).

Upon completion of the addition, the reaction liquid leave until completion of the reaction for three hours at 57,5oC (reaction temperature) with stirring in a stream of nitrogen. The result is pentafluorobenzylbromide as ferrimagnet derivative (3) in the form of a solution in diethyl ether.

The output of pentafluorobenzylbromide determined using 19F-NMR. More precisely, at the end of the reaction are selected portion of the reaction liquid and prepare the sample for analysis by mixing aliquots of the reaction liquid with laterobasal in nitrogen atmosphere. Shooting range 19F-NMR when pre-determined conditions. After that first received19F-NMR spectrum calculate the integral of a fluorine atom in the meta-position of pentafluorobenzene and the integral of a fluorine atom in the meta-position pentafluorophenyl group pentafluorobenzylbromide, then from these data, calculate the quantity pentafluorophenyl 83,1 molar percent.

Example 2

The air in the reaction container of the same type as in example 1, replacing with nitrogen in a satisfactory degree. Then 2,183 g (0,090 moles) of magnesium, 15,126 g (0,090 moles) of pentafluorobenzene as halftoned and 15 ml of tetrahydrofuran as solvent (ether solvent) is placed in the reaction vessel. A mixed solution prepared by mixing 11,646 g (0,095 moles) of Isopropylamine a halide of a hydrocarbon with 10 ml of tetrahydrofuran are placed in an addition funnel. As the ratio of isopropyl bromide to pentafluorobenzene, and the ratio of magnesium to pentafluorobenzene, approximately 1.06 in equivalents.

The mixed solution is added dropwise to the contents of the reaction vessel for 50 minutes under stirring in a stream of nitrogen. The temperature of this content is 25oC at the beginning of the addition and increases to 50.0oC in the process of adding dropwise (which indicate how the temperature of mixing).

Upon completion of the addition, the reaction liquid leave until completion of the reaction for 3 hours at 50,0oC (reaction temperature) with stirring in a stream of nitrogen.

The result is pentafluorobenzylbromide in the form of a solution in tetrahydrofuran. molar percent.

Example 3

The air in the reaction container of the same type as in example 1, replacing with nitrogen in a satisfactory degree. Then 2,217 g (0,091 moles) of magnesium, 15,318 g (0,091 moles) of pentafluorobenzene, 15 ml of tetrahydrofuran as the ether solvent and 5 ml of toluene as the hydrocarbon solvent is placed in the reaction vessel. A mixed solution prepared by mixing 12,364 g (0,101 mole) of isopropyl bromide with 10 ml of diethyl ether are placed in an addition funnel. The ratio of isopropyl bromide to pentafluorobenzene approximately 1,11 in equivalents, and the ratio of magnesium to pentafluorobenzene approximately 1.00 per equivalents.

The mixed solution is added dropwise to the contents of the reaction vessel over 0.5 hour with stirring in a stream of nitrogen. The temperature of this content is 25oC at the beginning of the addition and increased to 61.0oC in the process of adding dropwise (which is referred to as the temperature of the mix). The ratio of diethyl ether and toluene in the mixture is 5:1 by volume.

Upon completion of the addition, the reaction liquid leave until completion of the reaction for 3 hours at 61,0oC (reaction temperature) with stirring in a stream of nitrogen. tx2">

The reaction output pentafluorobenzylbromide defined in the same manner as in example 1, amounted to 80 mole percent.

Example 4

The reaction and is measured in the same manner as in example 3, except the reaction time, which increases from 3 to 5 hours, the reaction yield pentafluorobenzylbromide is 82,2 molar percent.

Example 5

Here as a vessel for mixing used a 4-neck flask of 100 ml equipped with a thermometer, dropping funnel, stirrer, sum of nitrogen and refrigerator, Dimroth (Dimroth). The air in the vessel for mixing displace nitrogen for some time, and then 35 ml of tetrahydrofuran as the ether solvent, 1,8159 g (12,81 mole) tertrahydrofuran ring complex of boron TRIFLUORIDE as the boron halide is placed in a container for mixing. 35 ml of tertrahydrofuran ring solution of the magnesium derivative) containing 37.9 mmol of pentafluorobenzylbromide as panafcortelone derivative (4) is placed in the addition funnel. The molar ratio of pentafluorobenzylbromide and tertrahydrofuran ring complex of boron TRIFLUORIDE here is 3.0.

Then Tetra is an increase of 15 min at 25oC (temperature mixing) with stirring under a stream of nitrogen, to obtain a mixed solution. Then immediately perform the reaction using the obtained mixed solution.

As the reaction vessel here use 4-neck flask of 300 ml equipped with a thermometer, dropping funnel, a stirrer, a system for the supply of nitrogen and refrigerator Liebig. The receiver is attached to the outlet of the refrigerator Liebig, which is connected to a vacuum pump or other similar equipment. After the air in the reaction vessel displace nitrogen for some time in the reaction vessel was placed 200 ml IsoparE of Exxon Corp. as the hydrocarbon solvent. The above mixed solution was placed in an addition funnel. At this point in the reaction vessel, more precisely in the reaction system, support normal blood pressure.

Then the hydrocarbon solvent is heated to 60oC with stirring under a stream of nitrogen, after which the mixed solution is added dropwise to a hydrocarbon solvent, the temperature of which is supported by 60oC. After picapau about half of the mixed solution, the pressure in the reaction system gradually oleaut was added dropwise. Thus, adding a mixed solution complete in 1.5 hours. The pressure in the reaction system by this time reduced to 250 mm Hg.

Upon completion of the addition, the reaction liquid leave until completion of the reaction for 3 hours at 60oC (reaction temperature) with stirring under a stream of nitrogen, while the pressure in the reaction system continues to decrease. By the end of the reaction the pressure is reduced to 80 mm Hg.

Upon completion of the reaction, the reaction liquid is cooled to room temperature and filtered in a nitrogen atmosphere. The result is Tris(pentafluorophenyl)borane as (foradil)boranova connection, in the form of a solution in a hydrocarbon solvent.

The yield of Tris(pentafluorophenyl)borane is determined using19F-NMR. Specifically,19F-NMR spectrum measured under certain conditions using p-vtortola as an internal standard. Then first calculate the number of fluorine atoms p-Tortolla and the number of fluorine atoms in the ortho-position of pentafluorophenyl group of Tris(pentafluorophenyl)borane is calculated using the previous calculations. Thus, calculated yield of Tris(pentafluorophenyl)borane is 76,8 molar percent.

the which time, then 35 ml of tetrahydrofuran and 1,7712 g (12,49 mmol) tertrahydrofuran ring complex of boron TRIFLUORIDE is placed in a container for mixing. In addition, 35 ml of tertrahydrofuran ring solution containing 37,81 mmole of pentafluorobenzylbromide, placed in an addition funnel. The molar ratio of pentafluorobenzylbromide and tertrahydrofuran ring complex of boron TRIFLUORIDE is 3.0.

Then tertrahydrofuran ring solution is added dropwise to the contents of the vessel for mixing for 5 minutes at 25oC (temperature mixing) with stirring under a stream of nitrogen to obtain a mixed solution. Then immediately perform the reaction using the thus obtained mixed solution.

The air in the reaction vessel of the same type as in example 5, replacing with nitrogen for some time, after which 200 ml IsoparE of Exxon Corp. as the hydrocarbon solvent is placed in the reaction vessel. In addition, the above-mentioned mixed solution was placed in an addition funnel. The pressure in the reaction vessel, more precisely in the reaction mixture at this point is normal.

Then the hydrocarbon solvent is heated to 85oC with stirring under a stream of nitrogen, after which red 85oC. After adding about half of the mixed solution of the pressure inside the reaction system is gradually reduced in order tetrahydrofuran began to evaporate and the residue mixed solution at this time continue dropwise. So, adding the mixed solution is carried out for 1.5 hours. The pressure in the reaction system by this time reduced to 450 mm Hg.

Upon completion of the addition, the reaction liquid leave until completion of the reaction for 1 hour at 60oC (reaction temperature) with stirring under a stream of nitrogen, while the pressure in the reaction system continues to decrease. By the end of the reaction the pressure is reduced to 80 mm Hg.

Upon completion of the reaction, the reaction liquid is cooled to room temperature and filtered in a nitrogen atmosphere. The result is Tris(pentafluorophenyl)borane as (foradil)boranova connection in the form of a solution in a hydrocarbon solvent.

The yield of Tris(pentafluorophenyl)borane, defined in the same manner as in example 5, was 69.2 molar percent. Next, using diethyl ether, the extract from the solid residue (insoluble matter) obtained by filtration, and the amount of Tris(pentagonmaterial)borane, corresponding to 22.5 mole percent relative to theoretical yield. Thus, the total yield of Tris(pentafluorophenyl)borane in this case 91.7 mole percent.

Example 7

The air in the vessel for mixing the same type as in example 5, replacing with nitrogen for some time. Then 10 ml of diethyl ether as solvent of ethyl and 3,395 g (23,90 mmol) diethylamino complex of boron TRIFLUORIDE as a boron halide is placed in a container for mixing. In addition, 35 ml of diethyl ether containing 38,57 mmole of pentafluorobenzylbromide, placed in an addition funnel. The molar ratio of pentafluorobenzylbromide and diethylaminoacetate Bora 1.6.

Then diethylamine solution is added dropwise to the contents of the vessel for mixing for 30 minutes at 25oC (temperature mixing) with stirring under a stream of nitrogen to obtain a mixed solution. Then immediately perform the reaction using the thus obtained mixed solution.

In this case, as the reaction vessel using a 4-neck flask equipped with thermometer, dropping funnel, stirrer, sum of nitrogen and conden nitrogen for some time, 200 ml IsoparE as the hydrocarbon solvent is placed in the reaction vessel. In addition, the above-mentioned mixed solution was placed in an addition funnel. The pressure in the reaction vessel, more precisely in the reaction mixture at this point is normal.

Then the hydrocarbon solvent is heated to 90oC with stirring under a stream of nitrogen, after which the mixed solution is added dropwise to a hydrocarbon solvent for 1 hour, the temperature of the hydrocarbon solvent support equals 90oC. Evaporation of diethyl ether and adding a mixed solution simultaneously. So, adding the mixed solution is carried out for 1.5 hours. The pressure in the reaction system by this time reduced to 450 mm Hg.

Upon completion of the addition, the reaction liquid is heated to 110oC (reaction temperature) under a stream of nitrogen and leave until completion of the reaction for 1 hour with stirring under a stream of nitrogen, the temperature at this time support 110oC.

Upon completion of the reaction, the reaction liquid is cooled to room temperature and filtered in a nitrogen atmosphere. The result of bis(pentafluorophenyl)boryl halide as (foradil)Tofranil)boryl of halogen, defined in the same manner as in example 5, is of 92.5 mole percent.

Example 8

In this case, as the reaction vessel using 4-necked flask equipped with a thermometer, two drip funnel, a stirrer, a system of deciding nitrogen and a Liebig condenser. The receiver is attached to the outlet of the condenser Liebig, which is connected to a vacuum pump or other similar equipment. After the air in the reaction vessel displace nitrogen for some time, 200 ml IsoparE of Exxon Corp. as the hydrocarbon solvent is placed in the reaction vessel. In addition, 35 ml of tetrahydrofuran and 1,8128 g (12,79 mmol) tertrahydrofuran ring complex of boron TRIFLUORIDE placed in one of the funnels and drip at the same time 35 ml tertrahydrofuran ring solution containing 37,30 mmol of pentafluorobenzylbromide placed in the other addition funnel. The molar ratio of pentafluorophenyl magnesium bromide and tertrahydrofuran ring complex of boron TRIFLUORIDE is 2.9. The pressure in the reaction vessel, more precisely in the reaction mixture at this point is normal.

Then the hydrocarbon solvent is heated to 64oC with stirring under a stream of nitrogen, after which tetragonisca at the same time, in this case, the temperature of the hydrocarbon solvent support 64oC. After adding about half the number of tertrahydrofuran ring solution from each drip funnel the pressure in the reaction system is gradually reduced in order to begin to evaporate tetrahydrofuran, while the remaining mixed solution continue to add dropwise from both drip funnels. Adding the mixed solution is carried out for 1 hour. At the end of this process the pressure in the reaction system is 250 mm Hg and the temperature was 55oC.

Upon completion of the addition, the reaction continued for two hours at 55oC (reaction temperature) with stirring under a stream of nitrogen, the pressure in the reaction system continues to decrease. At the end of the reaction the pressure is 80 mm Hg.

Upon completion of the reaction, the reaction liquid is cooled to room temperature and filtered in a nitrogen atmosphere. The result is Tris(pentafluorophenyl)borane as (foradil)boranova connection in the form of a solution in a hydrocarbon solvent.

The yield of Tris(pentafluorophenyl)borane, defined in the same manner as in example 5, is 41,9 molar percent. On the first broadcast. The amount of Tris(pentafluorophenyl)borane in the extract determined in the same manner as in example 5. It turned out that the extract contains Tris(pentafluorophenyl)borane in a quantity equal to 21.4 mole percent relative to theoretical yield. Thus, in this case, the overall yield of Tris(pentafluorophenyl)borane is 63,3 molar percent.

Example 9

(Foradil)boranova connection receive, using as the starting material halftoned. In a reaction vessel equipped with thermometer, dropping funnel, stirrer, the supply of nitrogen and reflux condenser, the air is replaced with nitrogen in a satisfactory degree. Then 2,320 g (0,095 moles) of magnesium, 15,110 g (0,090 moles) of pentafluorobenzene as halftoned and 20 ml diethyl ether as the ether solvent is placed in the reaction vessel. A mixed solution obtained by mixing 11,707 g (0,095 moles) of Isopropylamine a halide of a hydrocarbon with 5 ml of diethyl ether are placed in the addition funnel. The ratio of Isopropylamine to pentafluorobenzene and the ratio of magnesium to pentafluorobenzene approximately 1.06 in equivalents.

The mixed solution is added dropwise to the contents of the reaction is going in for three hours at 65oC (reaction temperature) with stirring under a stream of nitrogen. Upon completion of the reaction, the reaction liquid was diluted with 20 ml diethyl ether. The result is pentafluorobenzylbromide as ferrimagnetic derived in the form of a solution in diethyl ether.

The reaction output pentafluorobenzylbromide defined in the same manner as in example 1, is 88,0 molar percent. The following reaction is performed using the received pentafluorobenzylbromide in the form of a solution in diethyl ether.

The air in the reaction vessel equipped with thermometer, dropping funnel, stirrer, the supply of nitrogen and a reflux condenser, replace nitrogen in a satisfactory degree. Then 3,198 g diethylaminoacetate boron and 20 ml of diethyl ether are placed in a reaction vessel. Pentafluorobenzylbromide in the form of a solution in diethyl ether are placed in the addition funnel. The molar ratio of pentafluorobenzylbromide and detragiache of boron TRIFLUORIDE is 3.5.

Then the solution from the dropping funnel is added dropwise to the contents of the reaction vessel over 0.5 hour with stirring under a stream of nitrogen. The temperature of this content to nachane).

Upon completion of addition the reaction continue for 3 hours at 37oC (reaction temperature) with stirring under a stream of nitrogen. The result is Tris(pentafluorophenyl)borane as (foradil)boranova connection in the form of a solution in diethyl ether.

The yield of Tris(pentafluorophenyl)borane expectations for boron TRIFLUORIDE, determined as in example 5, is 88,7 molar percent.

Example 10

(Foradil)boranova connection receive, using as the starting material halftoned. In a reaction vessel equipped with thermometer, dropping funnel, stirrer, the supply of nitrogen and reflux condenser, the air is replaced with nitrogen in a satisfactory degree. Then 2,184 g (0,090 moles) of magnesium, 15,128 g (0,090 moles) of pentafluorobenzene and 15 ml of diethyl ether are placed in a reaction vessel. A mixed solution obtained by mixing 12,189 g (0,099 moles) of Isopropylamine with 10 ml of diethyl ether are placed in the addition funnel. The ratio of Isopropylamine to pentafluorobenzene and the ratio of magnesium to pentafluorobenzene approximately 1.00 per equivalents.

Then the mixed solution is added dropwise to the contents roleout hold for 4 hours at 61oC (reaction temperature) with stirring under a stream of nitrogen. The result is pentafluorobenzylbromide as ferrimagnetic derivative (3) in the form of a solution in diethyl ether.

The reaction output pentafluorobenzylbromide defined in the same manner as in example 1, is of 85.7 mole percent. The following reaction is performed using the received pentafluorobenzylbromide in the form of a solution in diethyl ether.

The air in the reaction vessel equipped with thermometer, dropping funnel, stirrer, the supply of nitrogen and a reflux condenser, replace nitrogen in a satisfactory degree. Then 2,994 g (0,021 mole) of diethylaminoacetate boron and 20 ml of diethyl ether are placed in the vessel for mixing. Pentafluorobenzylbromide in the form of a solution in diethyl ether and 25 ml of diethyl ether are placed in the addition funnel. The molar ratio of pentafluorobenzylbromide and diethylaminoacetate boron is 3,66.

Then the solution from the dropping funnel is added dropwise to the contents of the vessel for mixing within 80 min with stirring under a stream of nitrogen. After the addition is obtained mixed solution is kept permasalahannya solution.

The air in the reaction vessel equipped with thermometer, dropping funnel, stirrer, sum of nitrogen and a reflux condenser, replacing with nitrogen in a satisfactory degree, after which 300 ml IsoparE of Exxon Corp. placed in the reaction vessel as a hydrocarbon solvent. The mixed solution obtained in the above manner, is placed in the addition funnel.

The hydrocarbon solvent is heated to 115oC under stirring in a stream of nitrogen, and then the mixed solution is added dropwise to a hydrocarbon solvent for 1 hour, the temperature of which at the same time supporting equal 115oC. Evaporation of the solvent containing diethyl ether, begins simultaneously with precapitalism mixed solution. After the addition was evaporated to continue solvents containing diethyl ether while the temperature in the reaction vessel continue to gradually increase to 123oC (reaction temperature) under a stream of nitrogen.

Upon completion of the reaction, the reaction liquid is cooled to room temperature and filtered in a nitrogen atmosphere. The result is Tris(pentafluorophenyl)borane as (foradil)boranova connection in the form of a solution (fileto the boron TRIFLUORIDE, defined in the same manner as in example 5, is 73,1 molar percent.

Example 11

Here as a vessel for mixing use a 4-neck flask with a volume of 1000 ml equipped with a thermometer, dropping funnel, stirrer, sum of nitrogen and refrigerator, Dimroth (Dimroth). The air inside the vessel for mixing displace nitrogen for some time, and then 350 ml of diethyl ether and 33,7127 g (237,53 mmole) of diethylaminoacetate boron is placed in a container for mixing. In addition, 360 ml of a solution containing 707,4 mmole of pentafluorobenzylbromide in diethyl ether are placed in the addition funnel. The molar ratio of pentafluorobenzylbromide and diethylaminoacetate boron is 3.0. At this point, the pressure in the vessel for mixing normal.

Then diethylamine solution from a dropping funnel is added dropwise to the contents of the vessel for mixing for one hour with stirring under a stream of nitrogen. The temperature in the vessel for mixing at the beginning of the addition is equal to the 25oC, and in addition it increases to 34oC. the result 670,8 grams of the mixed solution. The following reaction is carried out immediately after this PR is 4-neck flask with a volume of 3000 ml, equipped with thermometer, dropping funnel, stirrer, sum of nitrogen and rectifying Oldershaw column with efficiency, estimated by dozens of plates. The receiver is connected to specific pre-position so that it was going distillate from the fractionation column. After displacement of the air from the reaction vessel with nitrogen 1056,0 g IsoparE of Exxon Corp. placed in the reaction vessel as a hydrocarbon solvent. Previously obtained mixed solution was placed in an addition funnel. The pressure inside the reaction vessel, namely in the reaction system is at this point normal.

Then the hydrocarbon solvent is heated to 95oC with stirring under a stream of nitrogen, after which the mixed solution is added dropwise to a hydrocarbon solvent for 1 hour, the temperature of the hydrocarbon solvent are supported equal 95oC. Evaporation of diethyl ether and adding a mixed solution begins at the same time. At the end of the addition the temperature in the reaction vessel is gradually increased to 125oC (reaction temperature) to continue evaporation, while the reaction is performed within a predefined time at 125the silt ether is to 92.1 percent by weight. After the reaction, the concentration of pentacarbonyliron in the reaction liquid, defined in the same manner as in example 5, makes 12.9 weight percent.

Upon completion of the reaction, the reaction liquid was diluted with 2275,7 g IsoparE. Diluted the reaction liquid is cooled to room temperature and filtered in a nitrogen atmosphere. The result is Tris(pentafluorophenyl)borane as (foradil)boranova connection in the form of a solution (filtrate) in a hydrocarbon solvent. The yield of Tris(pentafluorophenyl)borane, defined in the same manner as in example 5, is 95.9 molar percent. The residual quantity of diethyl ether into the solution (the filtrate) is determined using the1H-NMR, using p-forfour as an internal standard. The residual quantity of diethyl ether is 4.7 mole percent relative to the expected Tris(pentafluorophenyl)borane.

The essence of the present invention described in the embodiment and the examples in the section "the Best embodiments of the invention, but the above examples should not be construed as limiting the invention. Within the letter and spirit of the invention allowed different modificazioni the present invention, allows the reaction to almost one stage, thus making it possible to take ferrimagnetic derived efficiently at a low price, simple way. Ferrimagnet derived using, for example, as reactant (organic synthetic reagent for the introduction of ftoruridina groups in organic compounds of various types.

The method of obtaining (foradil)Baranovich compounds presented in this invention, allows to obtain (foradil)boron, such as Tris(foradil)borane and bis (foradil)boryl halide, selectively, at a low price, simple way. In other words, the production method, presented in this invention, when used in industrial production has advantages compared with the traditional methods and provides the ability to get (foradil)boron, such as Tris(foradil)borane and bis(foradil)boryl halide, high yield and high selectivity. (Foradil)boranova connection is used, for example, as a wonderful socializaton for metallocenes (polymerization catalysts) used in the polymerization reaction, catalyzed by cationic complex.

Moreover, the above-described CSP is (foradil)Baranovich compounds from halftoned almost in one stage (the so-called reaction in one vessel"). Thus, (foradil)boranova connections can be obtained at low cost by a simple method.

1. The method of obtaining ferrimagnetic derived, expressed the General formula 3

< / BR>
where R2, R3and R4represents each a hydrogen atom, a fluorine atom, aryl group, cycloalkyl group or alkoxy group, and XA represents a chlorine atom, bromine or iodine, characterized in that halftoned formula 1

< / BR>
where R2, R3and R4as described above, interacts with the hydrocarbon halide of General formula 2: R0Xa, where R0represents a carbon unbranched, branched or cyclic alkyl or alkenylphenol group; Ha described above; and with magnesium in an ether solvent or in a mixture of ether and hydrocarbon solvent.

2. The method of obtaining ferrimagnetic derived under item 1, characterized in that the ether or a mixed solvent mixed with aelfthryth and magnesium and then add the hydrocarbon halide.

3. The method of obtaining ferrimagnetic derived under item 1, characterized in that the temperature of mixing, in which ether or a mixed solvent mixed with the hydrocarbon halide is a Method of obtaining ferrimagnetic derived under item 1, characterized in that the reaction temperature set in the range -20oC and temperature phlegmy used ether or a mixed solvent.

5. The method of obtaining ferrimagnetic derived under item 1, characterized in that the ratio of hydrocarbon halide to cryptolib is the equivalent of 0.5 or higher.

6. The method of obtaining ferrimagnetic derived under item 1, characterized in that the ratio of magnesium to cryptolib is the equivalent of 0.5 or higher.

7. The method of obtaining ferrimagnetic derived under item 1, characterized in that the ratio in a mixture of ether and hydrocarbon solvent is between 1 : 0 and 1 : 10 by volume.

8. The method of obtaining ferrimagnetic derived under item 1, characterized in that the take this amount of ether or a mixed solvent so that the concentration ferrimagnetic derived ranged between 0.1 and 80 wt.%.

9. The method of obtaining ferrimagnetic derived under item 1, characterized in that eilperin is pentafluorobenzoyl.

10. The method of obtaining ferrimagnetic derived under item 1, characterized in that halogen is, ethylbromide, ethyliodide, Isopropylamine, Isopropylamine, isopropylidene, lillolita, allylbromide and allided.

11. The method of obtaining ferrimagnetic derived under item 1, characterized in that the ether solvent contains diethyl ether and/or tetrahydrofuran.

12. The method of obtaining (foradil)boranova compounds of General formula 6

< / BR>
where each of R1- R5represents a hydrogen atom, a fluorine atom, cycloalkyl or alkoxygroup, and if one of R1- R5represents a fluorine atom, b represents an atom of fluorine, chlorine, bromine or iodine, and n may be equal to 2 or 3, by mixing the solution ferrimagnetic derived, General formula 4 in the ether solvent

< / BR>
where R1- R5described above, and XA represents a chlorine atom, bromine or iodine, and a solution of boron halide, the General formula 5 in the ether solvent

BXb3< / BR>
where b described above, with a hydrocarbon solvent having a higher boiling point than the ether solvent, characterized in that the solution ferrimagnetic derived and a solution of boron halide in an ether solvent is mixed with a hydrocarbon solvent at the same time aetsa ether solvent.

13. The method of obtaining (foradil)boranova connection on p. 1, characterized in that the temperature at which interact ferrimagnet derivative and boron halide as the evaporation of the ether solvent, set in the interval between 30 and 200oC.

14. The method of obtaining (foradil)boranova connection on p. 12, wherein the ether solvent is a cyclic ether.

15. The method of obtaining (foradil)boranova connection on p. 12, characterized in that the take this amount of volatile solvent so that the concentration ferrimagnetic derived or boron halide ranged between 0.1 and 80 wt.%.

16. The method of obtaining (foradil)boranova connection on p. 12, characterized in that the boiling point of the hydrocarbon solvent 60oC or higher.

17. The method of obtaining (foradil)boranova connection on p. 12, characterized in that the take this amount of hydrocarbon solvent to the concentration (foradil)boranova compounds were in the range between 0.1 and 50 wt.%, in that time, as ferrimagnet derivative and boron halide interact with each other as the evaporation of the ether solvent.

19. The method of obtaining (foradil)boranova connection on p. 12, characterized in that ferrimagnet derivative is pentafluorobenzylbromide.

20. The method of obtaining (foradil)boranova connection on p. 12, wherein the boron halide is boron TRIFLUORIDE.

21. The method of obtaining (foradil)boranova connection on p. 12, wherein the boron halide is an essential complex.

22. The method of obtaining (foradil)boranova connection on p. 12, wherein the ether solvent contains diethyl ether and/or tetrahydrofuran.

23. The method of obtaining (foradil)boranova compounds of General formula 6

< / BR>
where each of R1- R5represents a hydrogen atom, a fluorine atom, aryl, cycloalkyl or alkoxygroup, and if one of R1- R5represents a fluorine atom, b represents a fluorine atom, bromine or iodine, and n may be equal to 2 or 3, by mixing the solution ferrimagnetic derivative of General formula 4 in the ether solvent

< / BR>
where R1- R5described above, and XA represents a chlorine atom, bromine or iodine,

solution of a halide of boron, total formaldeh solvent, having a higher boiling point than the ether solvent, characterized in that the solution ferrimagnetic derived in the ether solvent is first mixed with a solution of a boron halide in an ethereal solvent, followed by mixing the resulting solution with a hydrocarbon solvent at 80oC so that ferrimagnetic compound and a boron halide interact with each other as to evaporate the ether solvent.

24. The method of obtaining (foradil)boranova connection on p. 23, characterized in that the solution ferrimagnetic derivative in a volatile solvent and a solution of boron halide in an ether solvent are mixed with each other in the temperature range from -40oC to 70oC.

25. The method of obtaining (foradil)boranova connection on p. 23, wherein the ether solvent is a cyclic ether.

26. The method of obtaining (foradil)boranova connection on p. 23, characterized in that the take this amount of volatile solvent so that the concentration ferrimagnetic derived or boron halide ranged between 0.1 and 80 wt.%.

27. The method of obtaining (foradil)boranova connection p. The method of obtaining (foradil)boranova connection on p. 23, characterized in that the take this amount of hydrocarbon solvent to the concentration (foradil)boranova compounds were in the range between 0.1 and 50 wt.%, at that time, as ferrimagnet derivative and boron halide interact with each other as the evaporation of the ether solvent.

29. The method of obtaining (foradil)boranova connection on p. 23, characterized in that the molar ratio of ferrimagnetic derivative and boron halide is in the range between 1.0 and 5.0.

30. The method of obtaining (foradil)boranova connection on p. 23, characterized in that ferrimagnet derivative is pentafluorobenzylbromide.

31. The method of obtaining (foradil)boranova connection on p. 23, wherein the boron halide is boron TRIFLUORIDE.

32. The method of obtaining (foradil)boranova connection on p. 23, wherein the boron halide is an essential complex.

33. The method of obtaining (foradil)boranova connection on p. 23, wherein the volatile solvent comprises diethyl ether and/or tetrahydrofuran.

where R0represents an unbranched or branched or cyclic alkyl or alkenylphenol group, and XA represents a chlorine atom, bromine or iodine; and

with magnesium in an ether solvent or in a mixture of ether and hydrocarbon solvents,

obtaining ferrimagnetic derivative of formula 3

< / BR>
where R2, R3and R4and Ha described above.

(C) interaction ferrimagnetic derivative of formula 3 obtained in stage (a) with the boron halide of formula 5,

b3< / BR>
where b described above.

35. The method of obtaining (foradil)boranova connection 34, characterized in that ferrimagnet derivative and boron halide interact with each other in the mixing solution ferrimagnetic carried the first solvent, as the evaporation of the ether solvent.

 

Same patents:

The invention relates to the production of deisopentanisation

The invention relates to a new organoboron compound having catalytic activity, of the formula I

[RjM-Xd-MRj]a-bAc+(I)

in which R are, independently of one another, identical and denote C1-C40alkyl; X is, independently from each other, equal or different and denote C1-C40alkyl; M is, independently of one another, identical or different and denote an element of IIIa, IVa, Va group of the Periodic system of elements, provided that one M is boron, a is a cation of an element Ia, IIa and IIIa groups of the Periodic system of elements, carbene-hydronium - or sulfonyl - cation or compound Quaternary ammonium, and a is an integer from 0 to 10, b is an integer from 0 to 10, C is an integer from 0 to 10 and a = C; d is 1; j is an integer from 1 to 3
The invention relates to the technology of organoboron compounds, in particular amine-Baranov, namely morpholine-borane, which can be used as a selective reducing agent in aqueous and organic media, as well as hydroporinae agent in fine organic synthesis

The invention relates to methods of producing a cyclic boron compounds which may find application in the synthesis of 1,4-butandiol, cyclic ketones, tertiary alcohols, ethers and other products used in thin organic and ORGANOMETALLIC synthesis

The invention relates to methods of producing a cyclic boron compounds which may find application in the synthesis of TRANS-2,3-dialkyl-1,4-butandiol, substituted cyclic ketones, alcohols, esters, and other practically important compounds used in thin organic and ORGANOMETALLIC synthesis

The invention relates to a new method of obtaining sulfur-containing imidazole derivatives of General formula (I) possess valuable pharmacological properties, and new intermediate products of the formula III, IV and V

(I)

where

R1- C1-C4-alkyl;

R2- alkylthiol containing 1-4 carbon atoms, possibly substituted by one or more substituents selected from halogen, hydroxyl, alkoxy, benzyloxy, and means phenylthio or mercapto;

R3- carboxyl, free or converted into a salt or an ester of linear or branched C1-C4-alkyl, or hydroxyalkyl;

R4- radical (CH2)m-SO2-X-R10where X is - NH-, NHCONH-, NHCO-O-; R10is hydrogen or C1-C3-alkyl, m = 0, 1;

the interaction of imidazole formula II

(II)

with the corresponding halogen derivatives - a compound of formula III

(III)

where

B is a boron atom;

X1and X2is hydroxyl or X1with X2form together with the boron atom to which they relate, zatem subjected to interaction with the compound of the formula V

(V)

where

X4is a halogen atom

The invention relates to pharmacology, in particular ORGANOMETALLIC compounds possessing biological activity, which can find application in drug development for the prevention and treatment of coronary heart disease

The invention relates to the field of production of new magnesium-organic compounds, which can find application in thin organic and ORGANOMETALLIC synthesis

The invention relates to organic chemistry, and in particular to methods of obtaining new compounds magyarkanizsa

The invention relates to methods for new magyarkanizsa compounds, particularly to a method of obtaining a 1-aryl(alkyl)-2-minihaloes [60] fullerenes General formula (1)

< / BR>
where n = 1 to 4;

C60- new allotropic modification of carbon;

R = Ph, n-C6H13n-C7H15;

Hal = Br, Cl

The invention relates to organic chemistry, and in particular to methods of obtaining new compounds magyarkanizsa

The invention relates to methods for new magyarkanizsa compounds, specifically, to a method for producing 1-(n - propyl)-2-minihaloes [60] fullerenes General formula (1):

< / BR>
where n = 1-6, C60- new allotropic modification of carbon;

Hal = Br, Cl

The invention relates to the production of alkenylsilanes used in the synthesis of Organoelement compounds

FIELD: organic synthesis.

SUBSTANCE: invention relates to preparation of novel organomagnesium compounds, which consists in reaction of alkylallenes with diethylmagnesium in presence of zirconacene dichloride as catalyst used in amount 0.2 to 0.6 mmole based on alkylallene in diethyl ether medium under argon atmosphere, reaction time being 8-12 h.

EFFECT: extended assortment of organomagnesium compounds, which can find use as components of catalytic systems in processes of oligo- and polymerization of olefin, diene, and acetylene hydrocarbons as well as in delicate organic and organometallic syntheses.

1 tbl, 8 ex

FIELD: chemistry of metalloorganic compounds, chemical technology.

SUBSTANCE: invention relates to a new method for preparing new magnesium-organic compounds of the general formula (1)

wherein R means (CH2)4, (CH2)5, (CH2)6; n = 3, 4, 5. Method is carried out by interaction of α,ω-diallenes with ethyl magnesium bromide and magnesium powder in the presence of titanocene dichloride as a catalyst in argon atmosphere in tetrahydrofurane medium. Reaction time is 8-12 h. The total yield of end substances is 77-98%. Proposed compounds can be used as components of catalytic system in processes for oligo- and polymerization of unsaturated compounds and in fine organic and organometallic synthesis also.

EFFECT: improved preparing method.

2 cl, 1 tbl, 11 ex

FIELD: metalloorganic synthesis, chemical technology.

SUBSTANCE: invention describes a method for synthesis of 2,3-dialkyl-5-alkylidenemagnesacyclopent-2-enes of the general formula (1): wherein R means C2H5, n-C3H7, n-C4H9; R' means n-C5H11, n-C7H15. Method involves interaction of disubstituted acetylene of the general formula: R-≡-R wherein R is given above with 1,2-alkadiene of the general formula: R'-=.= wherein R' is given above and butylmagnesium chloride of the formula: n-BuMgCl in the presence of zirconacene dichloride of the formula: Cp2ZrCl2 as a catalyst wherein these components are taken in the ratio R-≡-R : R'-=.= : n-BuMgCl : Cp2ZrCl2 = 10:(10-14):(22-26):(1.0-1.4), respectively, in argon atmosphere, under normal pressure, in tetrahydrofuran medium as a solvent for 10-14 h. Synthesized magnesium-organic compounds can be used as components of catalytic systems in oligomerization processes and polymerization of olefins and diene hydrocarbon in fine, industrial organic and metalloorganic synthesis, and in synthesis of biologically active preparations also.

EFFECT: improved method of synthesis.

1 tbl, 12 ex

Up!