JPS5929043B2 - Addition reaction method between polyhalogenated alkanes and olefins - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for addition reaction between polyhalogenated alkanes and olefins, and its purpose is to allow the reaction to proceed under mild conditions and to obtain a 1:1 addition reaction product in high yield. The present invention provides a novel catalyst that can be obtained.

As a catalyst for the addition reaction between polyhalogenated alkanes and olefins, there are redox catalysts represented by a mixture of ιL diethylamine hydrochloride, iron chloride, and benzoin (M, Asscheretal, J, Chem,
Soc, 1887 (1963)).

Although these catalysts have higher activity than conventional peroxide or azo compound catalysts, their catalytic activity cannot be fully demonstrated unless the reaction temperature is relatively high, and the addition reaction product of 1.1 The yield is insufficient and the catalyst cannot be recovered and reused. As a result of intensive research to overcome these drawbacks, the present inventors have discovered that a mixture of a quaternary phosphonium salt and metallic iron can carry out the addition reaction between polyhalogenated alkanes and olefins under relatively mild reaction conditions. As the reaction progresses, the present inventors have discovered that the catalyst can provide a 1:1 addition reaction product in high yield, leading to the completion of the present invention. That is, the present invention is an addition reaction method characterized by reacting a polyhalogenated alkane and an olefin in the presence of a catalyst consisting of a quaternary phosphonium salt and metal iron. It has been found that the catalyst component used in the reaction of polyhalogenated alkanes and olefins in the present invention can be recovered in high yield as a complex salt consisting of a quaternary phosphonium salt and a ferric halide after the reaction.

Furthermore, although the above-mentioned complex salt consisting of quaternary phosphonium salt and ferric halide itself does not have catalytic activity for the reaction between polyhalogenated alkali and olefins, combining this complex salt with benzophenone Thus, the catalytic function can be restored. Therefore, the present invention is advantageous in that the catalyst can be easily recovered and reused in another form. Among the catalyst components used in the present invention, quaternary phosphonium salts include [R4P3X (R is an alkyl group or an aryl group,
X is a halogen), and is particularly derived from triphenylphosphine [Ph3P-R1
] Quaternary phosphonium salts represented by X (Ph is a phenyl group, R1 is an alkyl group or an aryl group) such as triphenylchloromethylphosphonium chloride and triphenylbenzylphosphonium chloride are preferred. Further, as for the metal iron which is another catalyst component, it is preferable that it is granular and has a smaller particle size, and generally iron powder of 20 mesh or less, especially 200 mesh or less is suitably used. The mixing ratio of the quaternary phosphonium salt of the above-mentioned catalyst component and metallic iron is generally in the range of 0.01 to 10 milligram atoms of metallic iron per 1 mmole of quaternary phosphonium salt. In order to recover a complex salt of a class phosphonium salt and metallic iron, it is desirable to use the two in an equimolar ratio. The temperature of the catalyst in the reaction system of the present invention varies somewhat depending on the type of polyhalogenated alkane and olefins used in the reaction, and cannot be absolutely limited, but generally the ratio of the quaternary phosphonium salt to the olefins is 0. If it is present in an amount of 1 mol % or more, the reaction will proceed sufficiently. Of course, the larger the amount of the catalyst added, the better the reaction results will be obtained, but if it exceeds 5 mol % based on the olefins, no significant difference will be observed.
Furthermore, the catalytic activity can be further increased by carrying out the reaction of the present invention in a reaction system containing an appropriate solvent.

That is, among the catalyst components of the present invention, metallic iron exists in a heterogeneous state in the reaction system, but it is desirable that the quaternary phosphonium salt exists uniformly in the reaction system. Therefore, the solvent to be added to the reaction system may be one that dissolves the quaternary phosphonium salt of the catalyst component, and in particular alcohols with relatively low boiling points such as methanol, ethanol, isopropanol, and n-butanol, acetonitrile, Preferred are aprotic polar solvents such as dimethylformamide, as well as methyl acetate, ethyl acetate, and the like. The polyhalogenated alkanes used in the reaction in the present invention include compounds used as telogens in so-called telomerization reactions, such as perhalogenated alkanes such as carbon tetrachloride, carbon tetrabromide, and carbon monochloride tribromide, as well as chloroform, 1
-l-1-3-tetrachloropropane, bromoform, etc.

Examples of olefins include α-olefins such as ethylene, propylene, and isobutylene, vinyl halides, allyl alcohol, 1-octene, and styrene, which are used as taxogens in so-called telomerization reactions. Double bond (ethylene bond)
The above compounds having the following are collectively referred to as olefins.
In addition, in the reaction of the present invention, the charging ratio of polyhalogenated alkane and olefin can be arbitrarily selected within the range of 1 to 10 moles per 1 mole of polyolefin. In addition, the conditions for the reaction of the present invention are not particularly limited, and the reaction may be carried out using ordinary equipment and means, and it is generally most effective to carry out the reaction under normal pressure to increased pressure, at a temperature of 50 to 150°C, for 1 to 10 hours. It is true.
Example 1 0.2 mol of carbon tetrachloride, 0.1 mol of styrene, 2 mmol of various quaternary phosphonium salts shown in Table 1 as a catalyst, 2 mmol of iron powder, and 20 ml of ethanol as a solvent were mixed in a round tank equipped with a reflux device. It was placed in a bottom flask.

Next, while stirring with a magnetic stirrer,
The reaction was carried out at ℃ for 5 hours. After the reaction, the reaction solution was washed twice with water and separated into an organic layer and an aqueous layer.

By analyzing the organic layer by gas chromatography, the reaction rate of styrene and the ratio between carbon tetrachloride and styrene were determined.
The yield of 1,1,1,3-tetrachloro-3-phenylpropane, which is the addition reaction product of :1, was determined. In addition, by evaporating water and ethanol from the aqueous layer, a complex salt of a quaternary phosphonium salt and metallic iron, which is a catalyst component, was recovered and its yield was determined. The results are shown in Table 1.

In addition, the yields of complex salts in Haruka 1, 2, and 3 in Table 1 are based on [Ph3P-CH
Cl2]+FeCl4-, [Ph3P-CH2Cl]+
FeCl4-, [Ph3P-CH2Ph]+FeCl4
- yield.

Example 2 Under the same reaction conditions as in Example 1, reactions of carbon tetrachloride with 1-octene and allyl alcohol shown in Table 2 were carried out for predetermined times.

The results are shown in Table 2. In addition, carbon tetrachloride and 1-
The 1:1 addition reaction product with octane is 1 ・1 ・1
・3-tetrachlorononane, and the 1:1 addition reaction product of carbon tetrachloride and allyl alcohol are 2.4.4
-4-Tetrachloro-1-butanol.

Example 3 Using a 300 ml stainless steel autoclave, 1 mol of carbon tetrachloride, 20 k9/Cnl of ethylene, 5 mmol of quaternary phosphonium salt and 5 mg atoms of iron powder as catalyst components, and 20 ml of ethanol as a solvent were charged.
The reaction was carried out at 0° C. for 5 hours in the same manner as in Example 1.

The results are shown in Table 3. Example 4 Chloroform 0.
5 mol, 1-octene 0.25 mol, quaternary phosphonium salt [Ph3P-CH2Ph]+Cl-2 as catalyst
．． 5 mmol, 2.5 mg atoms of iron powder, and 50 ml of ethanol as a solvent were charged into a 300 ml stainless steel autoclave equipped with a magnetic stirrer.

Next, after purging the inside of the autoclave with nitrogen, the temperature was 130°C.
The reaction was allowed to proceed for 4 hours. After the reaction, the catalyst component and the reaction product were separated by washing twice with water. Analysis of the organic layer by gas chromatography revealed that the 1-octene reaction rate was 100 mol% and the yield of 1:1 addition product 1,1,3-trichlorononane was 85.2 mol%. In addition, from the aqueous layer, the catalyst component is a complex salt: [Ph3P-CH2Ph] + FeCl4
- was recovered with a yield of 95.2%.

Example 5 A reaction was carried out under exactly the same conditions as in Example 4, except that 0.5 mol of 1,1,1,3-tetrachloropropane was used instead of chloroform, and 20 kg/d of ethylene was used instead of 1-octene. .

Claims (1)

[Scope of Claims] 1. An addition reaction method characterized by reacting a polyhalogenated alkane and an olefin in the presence of a catalyst consisting of a quaternary phosphonium salt and metal iron. 2 The quaternary phosphonium salt is [Ph_3P-R]^+Cl^- (Ph is a phenyl group,
2. The addition reaction method according to claim 1, wherein R is a quaternary salt of triphenylphosphine represented by an alkyl group or an aryl group. 3. The addition reaction method according to claim 1, wherein the metallic iron is iron powder having a particle size of 20 mesh or less. 4. The addition reaction method according to claim 1, wherein the reaction is carried out by adding a solvent capable of dissolving the quaternary phosphonium salt. 5. The addition reaction method according to claim 4, wherein the solvent is an alcohol. 6. The addition reaction method according to claim 5, wherein the alcohol is at least one selected from methylenel, ethanol, isopropanol, and n-butanol. 7. The addition reaction method according to claim 1, wherein the polyhalogenated alkane is a perhalogenated alkane. 8. The addition reaction method according to claim 7, wherein the perhalogenated alkane is carbon tetrachloride. 9. The addition reaction method according to claim 1, wherein the olefin is an α-olefin. 10. The addition reaction method according to claim 1, wherein the olefin is styrene. 11. The addition reaction method according to claim 1, wherein the olefin is allyl alcohol. 12. The addition reaction method according to claim 1, wherein the reaction temperature is 50 to 150°C.