JPS6055519B2 - Method for producing a solution containing an organomagnesium compound - Google Patents

Description

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

Organomagnesium compounds are useful as starting materials for the synthesis of various organometallic or organic compounds, and so-called Grignard reagents synthesized in ethereal media are particularly well known and used.

This compound is also useful as a polymerization catalyst for vinyl monomers or olefins, but since the contamination of polar compounds such as ethers is avoided in these polymerization systems, synthesis in an inert hydrocarbon medium has been considered. However, organomagnesium compounds are insoluble or sparingly soluble in inert hydrocarbon media, which poses a problem in handling on an industrial scale, and a countermeasure has been desired. As a method for making this compound soluble in an inert hydrocarbon medium and making it easier to handle, alcohol is present in the organomagnesium synthesis system by the reaction of magnesium metal and a halogenated hydrocarbon, and a solution of alkyl alkoxymagnesium is prepared. A method was proposed to obtain it. (0.B
．． SmithChem. c0mmunficati0n
5591966)Alkylalkoxymagnesium shows some solubility in aromatic hydrocarbons, alicyclic hydrocarbons, etc., but it is not sufficient, and its solubility in aliphatic hydrocarbons is extremely low, especially in lower alkyl hydrocarbons. Or, in the case of lower alkoxymagnesium, the solubility is particularly low. Industrially, aliphatic hydrocarbons are significantly cheaper than aromatic hydrocarbons and alicyclic hydrocarbons, and are suitable as reaction media used in large quantities. The availability of organomagnesium compounds in the form of this solution is therefore extremely advantageous. As a result of our studies on this point, the present inventors have found that by reacting the reaction mixture with a specific organometallic compound after synthesizing alkyl alkoxymagnesium, it is possible to increase the concentration of the organomagnesium compound in the solution. The present inventors have discovered that it is possible to increase the That is, the present invention provides magnesium metal (a), formula R″x″(
halogenated hydrocarbon compound (b) represented by the formula (in which R'' is an alkyl group x'' is a halogen atom) and the formula R3O
The alcohol compound (c) represented by H (wherein R3 is an alkyl group or an alicyclic hydrocarbon group) is reacted in an aliphatic or alicyclic hydrocarbon medium, and then the alcohol compound (c) of the formula MR
rlXm-n (where M represents beryllium, zinc, or aluminum; R is an alkyl group having 1 to 4 carbon atoms; by adding and reacting an organometallic compound (d) having the formula [RlMg(0R3)]p[M
RnYm-n], (where Y is hydrogen, alkoxy, or siloxy group, p is a number greater than 0, R,.Rl,
R3, m1 and n have the above-mentioned meanings).

The magnesium metal (a) used in the synthesis of the organomagnesium solution of the present invention has a shape generally used in the synthesis of so-called Grignard reagents, such as cut pieces, ribbon-like pieces, and powder particles.

Next, as the halogenated hydrocarbon compound (b), the general formula R
A compound represented by lXl (wherein R1 is an alkyl group and X1 is a halogen atom) is used. Hydrocarbon group R1
represents aliphatic, aromatic, and alicyclic hydrocarbons, and chlorine, bromine, and iodine are used as the halogen atom X1. Examples of these compounds include ethyl chloride, propyl chloride, butyl chloride, amyl chloride, hexyl chloride, ethyl bromide, butyl bromide, butyl iodide, and the like. Alcohol compound (c
) is an alcohol in which R3 of the formula λ°CH is an alkyl group or an alicyclic hydrocarbon.

Examples of these compounds are as follows. Methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, decyl alcohol, cyclohexyl alcohol. Magnesium metal (a), halogenated hydrocarbon compound (b), and alcohol compound (c) are mixed in an aliphatic or alicyclic hydrocarbon medium at a temperature from room temperature to 200°C until the reaction of the three components is completed. be carried out for a sufficient period of time.

Inert hydrocarbon media include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane,
Alicyclic hydrocarbons such as methylcyclohexane are used.

Considering the use of this compound, aliphatic hydrocarbons are particularly preferred. Synthesis temperature is 50-150℃, especially 80-120℃
℃ is preferable for controlling the reaction. The reaction ratio is 1 atomic equivalent of magnesium metal to 0 halogenated hydrocarbon.
．． It is recommended to use 8 to 1.2 moles, preferably 0.9 to 1.0, and 112 equivalents of the halogenated hydrocarbon based on the hydroxyl group, i.e., 0.4 to 0.6 equivalents of the organic compound containing hydroxyl groups. How to make the reaction (a), (b), (c)
The three components may be reacted simultaneously, or the reaction may be carried out by reacting components (a) and (b) and then adding component (c). Subsequently, an organometallic compound of the general formula MRrlXm-n [where MlR, . X. ．． m and n have the above-mentioned meanings].

A halogen atom represented by X, a hydrogen atom alkoxy,
Among siloxy groups, halogens include chlorine, bromine, and iodine, with chlorine being particularly preferred. As the alkoxy, those of the formula 0R2 in which R2 is methyl, ethyl, propyl, butyl, amyl, hexyl, octyl, decyl, dodecyl, etc. are used. As a siloxy group, the formula 0Si
R2, R3, and R4 in R2R3R4 are methyl,
Aliphatic hydrocarbons such as ethyl, propyl, butyl, amyl, hexyl, alicyclic hydrocarbons such as cyclohexyl, methylcyclohexyl, aromatic hydrocarbons such as phenyl, tolyl, xylyl, or R2, R3, R4. Those in which one or two of them are hydrogen are used. Specific examples of the compounds are as follows. A1(
C2H5)3, A1(C3H7)3,,Al(C4H9
),,A1(C2H5)2H,. A1(C4H9)2H
．． ．． A](1-C,H,)2H1A](C2H5)2(
0C2H5), AI(C4H9)(0C4H9)2,,
Al(C2H5)2(0C6H5), Al(C2H5
)2C1,A1(C2H5)Cl2,,A](C4H9
)2C1, A1(C2H5)2Br, . A1(C2H5
)211A1(C2H5)2(0Si-H-CH3・C
2H5),,Al(C4H9)2(0Si-H-CH3
・C4H,), A] (CH,)2 (0Si-H-C
H3・C6H5), A1(C2H5)2[0Si(CH
3) 2・C2H5], Be(CH,)2, Be(C2H
5) 2, Be(C2H5) (0C2H5), Be(C2
H5) (0Si-H-CH3・C2H5), Zn(C2
H5)2, Zn(C4H9)2, ZnH(C2H5),
Zn(C2H5)(0C2H5), Zn(C2H5)(
0SiHICH3●C2H5) These compounds can also be synthesized within the reaction system.

That is, a reaction mixture of compounds (a), (b) and (C) is added with MXpYm-p [in the formula X, . Y is the same or different and represents a halogen atom, alkoxy, siloxy, or an organic acid residue, P is the number of Om, M. ．． It is also possible to synthesize the above-mentioned compound and to dissolve the organomagnesium compound by carrying out an addition reaction with m having the above-mentioned meaning. Among the above compounds, hydride compounds such as dialkyl aluminum hydride have a high reaction rate,
and high yield, which is particularly preferred.

Alkoxy- and siloxy-containing compounds have the advantage that they have low reactivity to oxygen and moisture and are safe to handle, and that the compounds produced are stable and can be recovered and used in high concentrations. The reaction of components (a), (b) and (c) with the organometallic compound (d) is carried out in an aliphatic or cycloaliphatic hydrocarbon medium at a temperature of room temperature to 150°C.

As the aliphatic or alicyclic hydrocarbon medium, those used in the synthesis of components (a), (b) and (c), such as aliphatic and alicyclic hydrocarbons, can be used as they are. Among these, aliphatic hydrocarbons are particularly preferred from the viewpoint of cost and use of the resulting solution. Although the reaction proceeds satisfactorily at room temperature, it is preferable to use a temperature of 60 to 120°C in order to accelerate the reaction. The reaction ratio is in the range of 0.001 to 10 mol, preferably 0.02 to 1 mol, of the organometallic compound per 1 atomic equivalent of magnesium metal. The solution obtained by the reaction contains a complex consisting of an organomagnesium component and an organometallic component.

This complex has the general formula [where Y is alkoxy, siloxy, or hydrogen, p is a number greater than 0, and M. ．． R. ．． Rl
, R3, N. ．． m−n has the above-mentioned meaning].

The value of p can be greater than 0 and up to 100, but from the viewpoint of reaction yield and solubility of the complex, it is 0.5 to 2.
0 is preferred. The present invention will be explained in more detail using the following examples.

Example 1 In a flask with a capacity of 500 m1, 1
A dry hexane solution containing 0.45 moles of n-butyl chloride and 0.225 moles of n-butyl alcohol containing 1.4y of magnesium powder (0.48 gram atoms)
Added 50ml out of 0ml.

Heating under reflux under pressure of 0.5k91cI1 of nitrogen (approximately 85°C
) was stirred and after the reaction started, the remaining hexane solution was added over 1 hour, and after the addition was completed, the mixture was further heated under reflux for 1 hour. The supernatant liquid was separated and M was determined by chelate titration method.
The amount of g atoms was determined to be 25m9'e. To this reaction mixture, 30 n1 of n-hexane solution containing 0.03 n101 triethylaluminum was added and reacted at 80°C for 2 hours.

It was confirmed that the amount of precipitate decreased over time and the Mg-Ihi compound was dissolved. The liquid phase was filtered and the solid portion was washed to obtain 250 ml of solution. The analytical value of Mg was 0.80 mol/e, which corresponds to a yield of 89%. As a result of the Al component (chelate titration), alkyl component (gas analysis) of this solution, and alcohol component (gas chromatography) of the decomposition liquid, the composition was determined as shown in the following formula. Example 2 A synthetic reaction was carried out in exactly the same manner as in Example 1, except that n-amyl bromide was used as the hydroxylated hydrocarbon and ethyl alcohol was used as the hydroxyl group-containing compound.

After the reaction was completed, the Mg atom content in the supernatant was 15m911. To this reaction mixture was added 50 ml of n-heptane solution containing 0.05 TrLm01 of diethylzinc.
The reaction was carried out at 0°C for 3 hours.

It was treated in the same manner as in Example 1 to obtain 270 ml of solution. The analytical value of Mg was 0.65 mol/e, which corresponds to a yield of 78%. As a result of the analysis, the composition of the complex was determined as follows. // Example 3 In exactly the same manner as in Example 1, n-butyl chloride magnesium and n-butyl alcohol were reacted.

The Mg concentration in the reaction supernatant was 18m91e. To this reaction mixture was added 100 ml of n-heptane solution containing 0.03 ml of dichloraluminum butoxide, and the mixture was reacted at 100° C. for 5 hours.

The liquid phase was filtered and the solid portion was washed to obtain 350 ml of solution. The concentration of Mg was 0.55n1011e. This corresponds to a yield of 86%. Examples 4 to 12 Magnesium metal, halogenated hydrocarbon, and alcohol were reacted using the same method as in the examples.

Claims (1)

[Claims] 1 Magnesium metal (a), formula R^1X^1 (in the formula R
^1 is an alkyl group, X^1 is a halogen atom) halogenated hydrocarbon compound (b) and formula R^3
An alcohol compound (c) of the formula OH (wherein R^3 is an alkyl group or an alicyclic hydrocarbon group) is reacted in an aliphatic or alicyclic hydrocarbon medium, followed by a reaction with the formula MR_nX_m_ -_n (where M is beryllium, zinc,
represents aluminum, R is a hydrocarbon group having 1 to 4 carbon atoms, X is a halogen atom, hydrogen atom, alkoxy, or siloxy group, m represents the valence of M, and n is a number from 1 to m. organometallic compound (d
) is added and reacted to form the formula [R^1Mg(OR
^3)]_p[MR_nY_m_-_n], (wherein Y is hydrogen, alkoxy, siloxy group, p is a number greater than 0, M, R, R^1, R^3, m and n has the above-mentioned meaning). 2. The method for producing a solution containing a magnesium compound according to claim 1, wherein the organometallic compound (d) represented by the formula MR_nX_m_-_n is a hydride compound. 3. The method for producing a solution containing a magnesium compound according to claim 1, wherein the organometallic compound (d) represented by the formula MR_nX_m_-_n is a compound containing a siloxy or alkoxy group. 4. A method for producing a solution containing a magnesium compound according to claim 1, 2 or 3, wherein the reaction is carried out in an aliphatic hydrocarbon medium. 5 Organometallic compound (d) of formula MR_nX_m_-_n
0.01 to 10 per 1 atomic equivalent of magnesium metal
A method for producing a solution containing a magnesium compound according to claim 1, 2, 3 or 4, which is subjected to a molar reaction. 6. A method for producing a solution containing a magnesium compound according to claim 1, 2, 3 or 4, in which an organometallic compound of the formula MR_nX_m_-_n is reacted with 0.02 to 1.0 mol per 1 atomic equivalent of magnesium metal. .