METHOD FOR PRODUCING HALOGENATED HYDROCARBON MAGNESIUM COMPOUND AND METHODS FOR PRODUCING TERTIARY ALCOHOL COMPOUND AND ORGANOSILICON COMPOUND

Abstract

Provided is a method for producing a halogenated hydrocarbon magnesium compound, the method including bringing a halogenated hydrocarbon compound into contact with magnesium having a specific surface area of 1×10.sup.−5 to 2×10.sup.−4 m.sup.2/g. Also provided are methods for producing a tertiary alcohol compound and an organosilicon compound, wherein said production method is utilized.

Claims

1. A method for producing a halogenated hydrocarbon magnesium compound, the method comprising contacting a halogenated hydrocarbon compound with magnesium having a specific surface area of 1×10.sup.−5 to 2×10.sup.−4 m.sup.2/g.

2. The method for producing a halogenated hydrocarbon magnesium compound according to claim 1, wherein the halogenated hydrocarbon compound is at least one selected from a mono-halogenated alkyl compound and a di-halogenated alkyl compound represented by the following formula (1):
[Chem. 1]
X—R—X  (1) wherein R represents a linear or branched alkyl group having 1 to 8 carbon atoms and X represents a halogen atom.

3. The method for producing a halogenated hydrocarbon magnesium compound according to claim 1, wherein the halogenated hydrocarbon compound is a hydrocarbon bromide compound.

4. The method for producing a halogenated hydrocarbon magnesium compound according to claim 1, wherein the halogenated hydrocarbon compound is contacted with the magnesium at a temperature between −78° C. and 100° C.

5. The method for producing a halogenated hydrocarbon magnesium compound according to claim 1, wherein a solution containing the halogenated hydrocarbon compound is contacted with the magnesium.

6. The method for producing a halogenated hydrocarbon magnesium compound according to claim 5, wherein the solution containing the halogenated hydrocarbon compound is passed through a packed tower filled with the magnesium.

7. The method for producing a halogenated hydrocarbon magnesium compound according to claim 6, wherein the solution containing the halogenated hydrocarbon compound is repeatedly passed through the packed tower filled with the magnesium.

8. The method for producing a halogenated hydrocarbon magnesium compound according to claim 6, wherein a plurality of packed towers each filled with the magnesium exist and the solution containing the halogenated hydrocarbon compound is passed through the plurality of packed towers.

9. The method for producing a halogenated hydrocarbon magnesium compound according to claim 6, wherein the solution containing the halogenated hydrocarbon compound has a temperature between −78° C. and 100° C.

10. A method for producing a tertiary alcohol compound, comprising: producing a halogenated hydrocarbon magnesium compound by the method according to claim 1, and contacting the halogenated hydrocarbon magnesium compound with a ketone compound.

11. A method for producing a tertiary alcohol compound, comprising contacting a halogenated hydrocarbon compound, a ketone compound, and magnesium having a specific surface area of 1×10.sup.−5 to 2×10.sup.−4 m.sup.2/g.

12. A method for producing an organosilicon compound, comprising: producing a halogenated hydrocarbon magnesium compound by the production method according to claim 1, and contacting the halogenated hydrocarbon magnesium compound with a silicon compound selected from a chlorosilane compound and an alkoxysilane compound.

13. A method for producing an organosilicon compound, comprising contacting a halogenated alkyl compound, a silicon compound selected from a chlorosilane compound and an alkoxysilane compound, and magnesium having a specific surface area of 1×10.sup.−5 to 2×10.sup.−4 m.sup.2/g.

Description

EXAMPLES

[0063] Hereinafter, representative examples of the present invention will be shown and specifically described, but the present invention is not limited thereto in any way. In the analysis of components in the Examples and Comparative Examples, a gas chromatograph device (manufactured by Agilent Co., Ltd., 6890N) was used. As an analysis column, column DB-1 manufactured by J&W was used. Further, specific surface areas of magnesium in the Examples and Comparative Examples were determined by measuring weights and surface areas per particle using a precision balance and optical microscope observation with a magnification of 10 times as described above, calculating the specific surface area of each particle, and then calculating an average value of 10 particles.

Example 1

[0064] To a well-dried 2 L three necked flask, 800 mL of tetrahydrofuran (water content: 10 ppm) and 4.0 g of granular magnesium having an average specific surface area of 5.8×10.sup.−5 m.sup.2/g were charged, and a mixed solution of 200 mL of tetrahydrofuran (water content: 10 ppm) and 14.8 g of 1-bromopropane was added dropwise using a dropping tube while stirring with a magnetic stirrer. Since the solution generated heat with the dropping, the dropping rate was adjusted so that the temperature of the reaction solution was maintained at 55° C. while cooling the flask in a water bath, and the dropping was completed over 2 hours. After completion of the dropwise addition, the conversion ratio to propylmagnesium bromide was determined by analyzing propylmagnesium bromide using gas chromatography, and the conversion ratio was found to be 83%.

Example 2

[0065] To a well-dried 500 mL glass three necked flask, 200 mL of tetrahydrofuran and 2.4 g of methyl ethyl ketone were charged, and a mixed solution of 5 g of propylmagnesium bromide synthesized in Example 1 and 100 mL of tetrahydrofuran was added dropwise over 1 hour under an argon atmosphere using a dropping tube. .sup.1H-NMR of the reaction product confirmed that 2-ethyl-2-pentanol was produced. The synthesis yield was confirmed using gas chromatography, and found to be 72%.

Example 3

[0066] To a well-dried 500 mL glass three necked flask, 200 mL of tetrahydrofuran and 4.4 g of dichlorodimethylsilane were charged, and a mixed solution of 5 g of propylmagnesium bromide synthesized in Example 1 and 100 mL of tetrahydrofuran was added dropwise over 1 hour under an argon atmosphere using a dropping tube. .sup.1H-NMR of the reaction product confirmed that chlorodimethylpropylsilane was produced. The yield was confirmed by gas chromatography, and the synthesis yield was found to be 76%.

<Preparation of Magnesium Packed Tower>

[0067] The magnesium packed towers used in the following Examples had a straight tube structure having an internal flow path length of 200 mm and a circular cross section of 20 mm in diameter, and was made of a polytetrafluoroethylene resin. When passing a liquid through the magnesium packed tower, the packed tower was held and fixed vertically, and liquid passing was carried out in a manner that the liquid was introduced into the tower from the lower part of the flow path and came out of the upper part. Additionally, the packed tower was provided with type K thermocouple inserted from the side surface in the lower part of the packed tower, which is the inlet of liquid, and in the upper part, which is the outlet, so that temperatures at the inlet and outlet of the packed tower could be measured. Supply of a liquid to the magnesium packed tower was carried out using a plunger pump having a liquid contact portion made of polytetrafluoroethylene, regardless of the number of connected packed towers. ¼ inch PFA tubes were used for connecting from the pump to the packed tower and connecting between packed towers, when multiple packed towers were used.

Example 4

[0068] To a well-dried 10 L glass bottle, 7.5 L of tetrahydrofuran (water content: 10 ppm) and 150 g of 1-bromopropane were charged and mixed by shaking. The glass bottle was placed in a water bath at 30° C. After the magnesium packed tower was filled with 6.0 g of granular magnesium having an average specific surface area of 5.8×10.sup.−5 m.sup.2/g, the mixed solution in the 10 L glass bottle was supplied at a constant flow rate of 400 mL/min, and the magnesium and the solution were brought into contact with each other. During the solution supply, the solution temperature at the outlet of the packed tower was measured with the thermocouple, to be 42° C. to 45° C. The conversion ratio to propylmagnesium bromide was confirmed by analysis of the solution by gas chromatography, and found to be 7%. The solution was passed through the magnesium packed tower under the same conditions. The conversion ratio to propylmagnesium bromide in the solution having passed the packed tower was analyzed by gas chromatography and was confirmed to be 13%.

Example 5

[0069] Four magnesium packed towers described above were connected in series using PFA tubes, and the tubes connecting the packed towers were each immersed in a water bath at 30° C., so that the liquid temperature at the inlet of the second or later tubes was 30° C. The mixed solution of tetrahydrofuran and 1-bromopropane described in Example 4 was supplied at 400 mL/min, and the mixed solution was brought into contact with magnesium in each packed tower. During the solution supply, the sample immediately after passing through each packed tower was taken from the sampling valve provided between the packed towers, and the conversion ratio to propylmagnesium bromide was confirmed by analysis by gas chromatography. The conversion ratio was 8% after passing the first tower, 15% after passing the second tower, 24% after passing the third tower, and 33% after passing the fourth tower.

Example 6

[0070] The total amount of the solution obtained in Example 5 was further supplied into the four magnesium packed towers connected in series under the same conditions as Example 5 two times. The conversion ratios were 62% after the first supply and 87% after the second supply.

Example 7

[0071] To a well-dried 10 L glass bottle, 7.5 L of tetrahydrofuran (water content: 10 ppm), 150 g of 1-bromopropane, and 157 g of dichlorodimethylsilane were charged and mixed by shaking. The resulting mixed solution was supplied to the four magnesium packed towers connected in series under the same conditions as Example 5 three times. Each time the solution was passed through the four magnesium packed towers, a sample was collected and the conversion ratio of the raw material to chlorodimethylpropylsilane was measured by gas chromatography. The conversion ratio was 28% after the first supply, 54% after the second supply, and 84% after the third supply. The temperatures and the results of conversion ratios of the solution discharged from the magnesium packed towers in Example 7 are shown in Table 1.

Example 8

[0072] To a well-dried 10 L glass bottle, 7.5 L of tetrahydrofuran (water content: 10 ppm), 246 g of 1,3-dibromopropane, and 315 g of dichlorodimethylsilane were weighed and mixed by shaking. The resulting mixed solution was supplied into four magnesium packed towers connected in series under the same conditions as Example 5 three times. Each time the solution was passed through the four magnesium packed towers, a sample was collected and subjected to analysis. .sup.1H-NMR and .sup.29Si-NMR analyses of the solutions after the reaction confirmed that the product was 1,3-di-(dimethylchlorosilyl)propane. The conversion ratio at each stage was determined by the internal standard method (internal standard substance was toluene) according to .sup.1H-NMR. As a result, the conversion ratio was 26% after the first supply, 49% after the second supply, and 71% after the third supply.

Example 9

[0073] To a well-dried 10 L glass bottle, 7.5 L of tetrahydrofuran (water content: 10 ppm) and 150 g of 1-bromopropane were weighed and mixed by shaking. The glass bottle was placed in a water bath at 30° C. After the magnesium packed tower was filled with 6.0 g of granular magnesium having an average specific surface area of 9.0×10.sup.−5 m.sup.2/g, the mixed solution in the 10 L glass bottle was supplied at a constant flow rate of 400 mL/min, and the magnesium and the solution were brought into contact with each other. During the solution supply, the temperature of the solution at the outlet of the packed tower was measured with a thermocouple, to be 48° C. to 52° C. The conversion ratio to propylmagnesium bromide in the solution was confirmed by analysis using gas chromatography and found to be 5%. The solution was passed through the magnesium packed tower under the same conditions. The conversion ratio to propylmagnesium bromide in the solution having passed the packed tower was confirmed by analysis using gas chromatography and found to be 11%.

Example 10

[0074] Four magnesium packed towers described above were connected in series using PFA tubes, and the tubes connecting the packed towers were each immersed in a water bath at 30° C., so that the liquid temperature at the inlet of the second or later tubes was 30° C. The mixed solution of tetrahydrofuran and 1-bromopropane described in Example 9 was supplied at 400 mL/min, and the mixed solution was brought into contact with magnesium in each packed tower. During the solution supply, the sample immediately after passing through each packed tower was taken from the sampling valve provided between the packed towers, and the conversion ratio to propylmagnesium bromide was confirmed by analysis by gas chromatography. The conversion ratio was 7% after passing the first tower, 12% after passing the second tower, 20% after passing the third tower, and 29% after passing the fourth tower.

Example 11

[0075] The total amount of the solution obtained in Example 10 was further supplied into the four magnesium packed towers connected in series under the same conditions as Example 10 two times. The conversion ratio was 59% after the first supply and 84% after the second supply.

Example 12

[0076] To a well-dried 10 L glass bottle, 7.5 L of tetrahydrofuran (water content: 10 ppm), 150 g of 1-bromopropane, and 157 g of dichlorodimethylsilane were charged and mixed by shaking. The resulting mixed solution was supplied to the four magnesium packed towers connected in series under the same conditions as Example 5 three times. Each time the solution was passed through the four magnesium packed towers, the sample was collected and the conversion ratio of the raw material to chlorodimethylpropylsilane was measured by gas chromatography. The conversion ratio was 25% after the first supply, 57% after the second supply, and 89% after the third supply. The temperatures and the results of conversion ratios of the solution discharged from the magnesium packed towers in Example 12 are shown in Table 1.

Example 13

[0077] To a well-dried 10 L glass bottle, 7.5 L of tetrahydrofuran (water content: 10 ppm), 246 g of 1,3-dibromopropane, and 315 g of dichlorodimethylsilane were charged and mixed by shaking. The resulting mixed solution was supplied to the four magnesium packed towers connected in series under the same conditions as Example 5 three times. Each time the solution was passed through the four magnesium packed towers, the sample was collected and subjected to analysis. .sup.1H-NMR and .sup.29Si-NMR analyses of the solution after the reaction confirmed that the product was 1,3-di-(dimethylchlorosilyl)propane. The conversion ratio at each stage was determined by the internal standard method (internal standard substance was toluene) by .sup.1H-NMR. As a result, the conversion ratio was 24% after the first supply, 51% after the second supply, and 73% after the third supply.

Comparative Example 1

[0078] The same procedures as Example 4 were carried out except that 6.0 g of powdery magnesium having an average specific surface area of 3×10.sup.−3 m.sup.2/g was used as magnesium to be packed in the packed tower. During the solution supply, the temperature of the solution at the outlet of the packed tower was measured to be 55° C. to 62° C. Since gas contamination was observed in the tube that supplied liquid, it was found that the reaction solution boiled in the packed tower. The conversion ratio to propylmagnesium bromide of the solution after the reaction was analyzed, and found to be 2%.

Comparative Example 2

[0079] The same procedures as Example 7 were carried out except that 6.0 g of powdery magnesium having an average specific surface area of 3×10.sup.−3 m.sup.2/g was used as magnesium to be packed in the packed tower. Similarly to Comparative Example 1, since gas contamination was observed in the tube that supplied liquid, it was found that the reaction solution boiled in the packed tower. As with Example 7, analysis was performed to determine the conversion ratio to chlorodimethylpropylsilane, and it was found that the conversion ratio was 18% after the first supply, 24% after the second supply, and 28% after the third supply. The temperatures and the results of conversion ratios of the solution discharged from the magnesium packed towers in Comparative Example 2 are shown in Table 1.

TABLE-US-00001 TABLE 1 Comparative Example 7 Example 12 Example 2 Specific surface area of magnesium (m.sup.2/g) 5.8 × 10.sup.−5 9.0 × 10.sup.−5 3.0 × 10.sup.−3 First Solution First packed tower 42~44 44~46 59~61 supply temperature at the Second packed tower 42~46 45~49 58~62 outlet of each Third packed tower 43~45 50~52 59~63 packed tower (° C.) Fourth packed tower 44~48 51~54 31~43 Conversion ratio(%) 28 25 18 Second Solution First packed tower 38~44 42~46 32~34 supply temperature at the Second packed tower 39~43 43~44 33~35 outlet of each Third packed tower 40~42 42~45 32~36 packed tower (° C.) Fourth packed tower 37~43 40~44 32~34 Conversion ratio (%) 54 57 24 Third Solution First packed tower 35~39 38~42 32~34 supp1y temperature at the Second packed tower 34~35 39~41 33~34 outlet of each Third packed tower 36~37 35~39 32~36 packed tower (° C.) Fourth packed tower 32~34 31~36 32~33 Conversion ratio(%) 84 89 28