JPS6050198B2 - Method for producing organomagnesium complex - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing organomagnesium complexes.

An organic magnesium compound obtained by reacting an organic halide and metallic magnesium in the presence of an ether is known as a so-called Grignard reagent, and is widely used as a raw material for organic synthesis or as a catalyst component.

This compound can also be synthesized by reacting it in a hydrocarbon medium in the absence of ether, and further modified compounds can be synthesized depending on the purpose of use. For example, British Patent No. 1003551 discloses a complex of aluminum alkoxide and organomagnesium and states that it can be used in place of organolithium catalyst 7. As a result of research on organomagnesium compounds useful as catalyst raw materials for the production of polyolefins using the Ziegler method, the present inventors discovered a novel method for producing an organoboron-magnesium complex soluble in a hydrocarbon medium, resulting in the present invention. That is, the present invention has the general formula R^"nBX
3-n (in the formula, R^゛ is a hydrocarbon group having 1 to 10 carbon atoms, X is a halogen, OR^2, OSIR^゜R^'R^
゜ represents a group, R^'' is a hydrocarbon group having 1 to 16 carbon atoms, R3, R4, and R5 are hydrogen atoms or hydrocarbon groups having 1 to 10 carbon atoms, and n is an integer of 0 to 3; Te, n
is 2, X can be hydrogen) and MgR? or R6MgY (wherein R6 is a hydrocarbon group having 1 to 10 carbon atoms, Y is halogen, 0R2
, 0SiR3R4R5, R2, R3, R
4, R5 is the same as above) is reacted with magnesium compound B represented by the general formula BaMgβRlpR6qXr.
Ys (where α, β are numbers larger than 1, β/α is 0.5 to 10, P, q, r, s are O or numbers larger than 0, p+q+r+s=3α+2β, r+s/β< 0.
8, R1 and R6 are the above-mentioned hydrocarbon groups, and X and Y are the above-mentioned groups other than halogen.

General formula RlnBX3- used in the above reaction.

Compound A represented by will be explained. The hydrocarbon group having 1 to 10 carbon atoms represented by R1 is an alkyl group, and methyl, ethyl, propyl, butyl, hexyl, and octyl groups are used.

X represents a halogen, 0R2, 0SjR3R4R5 group. As the halogen, chlorine, bromine, and iodine are used. R2 is a hydrocarbon group having 1 to 16 carbon atoms,
An alkyl group, a cycloalkyl group, or a phenyl group is used. Examples of these include, for example, methyl,
Ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, hexadecyl, cyclohexyl, phenyl and the like are preferred. R3, R4, and R5 are hydrogen atoms or carbon atoms! There are 1 to 10 hydrocarbon groups. The hydrocarbon group is an alkyl group, a cycloalkyl group, or an allyl group, such as methyl, ethyl, propyl, butyl, amyl, hexyl, decyl, cyclohexyl, phenyl group, and the like. Examples of these chemical compounds are as follows. B (C ratio) 3, B (C2H5) 3
, B(C3H7)3, B(C4H9)3, B(C2H5
)2H. ．． B(1-C4H9)2H. ．． B (C2H5)
2 (0C2H5), B (C3H7) 2 (0C3H7),
B(C2H5)2Cf. B(C2H5)2Br. ．． B(
C2H5)24(0SiH0CH3●C2H5), BC
2H5Ce2BC2H5 (0C2H5)2, BC2H5
(0C4H9)2, B(0C4H9)3, B(0C2H
5) 3, BCr3, BF3, BI3.

Next, compound B represented by the formulas MgRS and R6MgY (wherein R6 and Y have the above-mentioned meanings) will be explained. In the above formula, the hydrocarbon group R6 having 1 to 10 carbon atoms is an alkyl group, cycloalkyl group, or allyl group, and methyl, ethyl, propyl, butyl, amyl, hexyl, decyl, cyclohexyl, phenyl group, etc. are preferable.

Y is 0R2, 0SjR3R4R5 or a halogen atom. As R2, R3, R4, R5, and the halogen atom, the groups or atoms described above are preferable.
Examples of these compounds are as follows. Mg
(C2H5)2, Mg(C3H7)2, Mg(C4H9
)2, Mg(C6Hl3)2, Mg(C6FI5)2,
Mg(C2H5)BrlMg(C4H9)Ce. ．． Mg
(C4H9)Br. ．． Mg7(C4H9)INMg(C
6Hl3) Br. Mg(C8Hl7)C', n-C3H
7Mg (0C21-15), n-C4H9Mg (0C8
H17), n-C4H9Mg (0C2H5), n-C3
H7Mg (0C2H5), n-C4H9Mg (0S1H
CH3・C4H9), C2H5Mg(0SiH-CH3
・C2H5).

In use, mixtures of these compounds may be used, and in particular Grignard reagents produced by the reaction of metallic magnesium and halogenated hydrocarbons are preferably used. The reaction where A<15B is carried out at a temperature of room temperature to 200°C, preferably 30 to 150°C, for a period of 0.5 to 2 (b).

In carrying out this reaction, it is advantageous to increase the reaction concentration of component A within a range that does not interfere with reaction operation. Component B can be used at a concentration of 0.05 to 5 mol/e.
A. The inert hydrocarbon medium soluble organomagnesium complex obtained by the reaction of 15B has a Mg/Al molar ratio of 0.5 to 1.
The composition has a composition of 0, and this composition can be arbitrarily changed within the above range by changing the amount of component B relative to component A. As the reaction medium for carrying out the reaction of A and B, aliphatic hydrocarbons such as hexane and heptane,
Aromatic hydrocarbons such as benzene, toluene, xylene,
Alicyclic hydrocarbons such as cyclohexane and methylcyclohexane can be used. The complex of the present invention is obtained in the form of a hydrocarbon solution, and is presumed to be a single complex or a mixture of multiple complexes.

The composition of the complex can be determined by analyzing the solution, and the average composition can be determined by measuring the molecular weight. Generally, organic Mg-II compounds are insoluble in inert hydrocarbon media, but this complex is soluble in inert hydrocarbon media and is obtained in the form of a solution, so it is easy to handle and cannot be used on an industrial scale. extremely suitable for
The present invention will be explained in more detail below with reference to Examples.

Example 1 13.80 g of di-n-butylmagnesium and 1.63 g of triethyl boron were placed in a 500 ml flask together with 200 mL of 2-heptane, and reacted with stirring at 50° C. for 2 hours.

As time passed, the amount of solid di-n-butylmagnesium decreased and a homogeneous solution was obtained. Thus the composition Mg6(C2H
5) A solution containing a complex of 3(n-C4H9)12 was obtained. The concentration of Mg was 0.53 mol/e. Example 2 Composition (n-C4H9) 1.25Mg (0Si-H-CH
3・n-C4H9).

．． 6.2 g of magnesium compound No. 75 and 1.63 g of triethyl boron were heated at 80° C. in the same manner as in Example 1.
By reacting with stirring for a period of time, the composition Mg2(C
2H5)3(n-C4H9)2.5(0SI-H-CH
A solution containing 1.5 complexes of 3.n-C4H9) was obtained. The concentration of Mg was 0.17 mol/e. Example 3 13.80 g of di-n-butylmagnesium and 2.85 g of ethyldiethoxyboron were prepared in the same manner as in Example 1.
By reacting at 0°C for 1 hour, the composition βMg4(C
A solution containing a complex of 2H5)(n-C4FI9)8(0C2H5)2 was obtained.

The concentration of Mg was 0.61 mol/e. Example 4 7.6 g of magnesium powder (4) was placed in a 50017 L flask under a nitrogen atmosphere. To this was added 30 mt of a 200 ml dry heptane solution containing 0.30 mole n-butyl chloride.

The flask was heated to the boiling point of the contents while stirring, and after the reaction started, the remaining n-butyl chloride was added over 3 sips, and after the addition was complete, the flask was heated under reflux for an additional 1 hour. By adding 1.4 g of ethyldiethoxyboron to the obtained reaction mixture and reacting at 120'C for 3 hours, the composition Mg9.5(C2H5)(n-C4Fl9)19(0C
A solution containing a complex of 2H5)2 was obtained.

The Mg concentration was 0.48 mol/'. Example 5 In the same manner as in Example 4, 7.6 g of magnesium powder and 0.3 mol of ethyl bromide were reacted.

7.0 g of tributoxyboron was added to the obtained reaction mixture, and the mixture was reacted at 100°C for 2 hours. The obtained solution is
Composition Mg5. l(C2H5)10.2(0C4H9)
It contained 3 complexes. The concentration of Mg is 0.63 mol/
It was e. Example 6 8.3 g of diethylmagnesium and trichlorboron 4.
0g was reacted with 200ml of toluene at 60°C for 5 hours in the same manner as in Example 1, and a homogeneous solution was separated.

This solution has the composition Mgl. It contained 5.2 complexes of 1(C2H5). The concentration of Mg was 0.32 mol/e. Example 7 21.1 g of n-butylmagnesium octoxide and 6.1 g of tributyl boron were added to 20 g in the same manner as in Example 1.
The reaction was carried out in 0 mL of hexane at 700 C for 2 hours to obtain a homogeneous solution.

The composition of the complex is BMg3(n-C4H9)6(0C8H1
7) 3, and the Mg concentration was 0.48 mol/e.

Example 8 11.2 g of n-propylmagnesium ethoxide and 4.9 g of triethyl boron were mixed to 80 g in the same manner as in Example 1.
The reaction was carried out at ℃ for 2 hours to obtain a homogeneous solution.

The composition of the complex is BMg2(C2H5)3(n-C3H7)
2(0C2H5)2, and the Mg concentration was 0.52 mol/l. Example 9 19.4 g of di-n-hexylmagnesium and composition 5 (C2
H5) 3.2 g of a boron compound of 2B (0Si-H-CH3.C2H5) was heated at 60°C in the same manner as in Example 1.
A homogeneous solution was obtained by reacting for a period of time.

Claims (1)

[Claims] 1 General formula R^1_nBX_3_-_n (wherein R^1 is a hydrocarbon group having 1 to 10 carbon atoms,
represents a group such as halogen, OR^2, OSiR^3R^4R^5, R^2 is a hydrocarbon group having 1 to 16 carbon atoms, and R^3, R^4, R^5 is a hydrogen atom or carbon a hydrocarbon group having 1 to 10 atoms, n is an integer of 0 to 3, and n
is 2, X can be hydrogen) and MgR^2_6 or R^6MgY (in the formula,
R^6 represents a hydrocarbon group having 1 to 10 carbon atoms, Y represents a halogen, OR^2, OSiR^3R^4R^5, R^2, R^3, R^4, R^5 is the same as above) is reacted with magnesium compound B represented by the general formula B_αMg_βR^1_pR^6_qX_rY_s (where α and β are numbers larger than 1, and β/α is 0.5 to
10, p, q, r, s are 0 or a number larger than 0, p
+q+r+s=3α+2β, r+s/β≦0.8, R^1 and R^6 are the aforementioned hydrocarbon groups, and X
, Y is the aforementioned group other than halogen).