JP3003268B2 - Method for producing alkoxy alkadiene - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing an alkoxy alkadiene useful as a raw material for a polymer and an organic synthesis, a solvent, especially a paint or a varnish composition.

[0002]

2. Description of the Related Art It is known that an alkoxyalkadiene is formed by a telomerization reaction between an alcohol and an aliphatic conjugated diene. Conventionally, this reaction is carried out in the presence of a palladium compound. As the palladium compound, a zero-valent palladium complex (for example, Japanese Patent Publication No. 48-42606), a divalent palladium salt and a complex (for example, Japanese Patent Publication No. 47-20205)
And Japanese Patent Publication No. 49-31965).

[0003] However, zero-valent and divalent palladium complexes are very expensive, and many compounds lack stability, and cannot be implemented on an industrial scale. In addition, divalent palladium salts have lower reactivity than zero-valent and divalent palladium complexes. Therefore, a stable and highly reactive catalyst is desired for the telomerization reaction of an aliphatic conjugated diene.

[0004]

An object of the present invention is to carry out a telomerization reaction between an aliphatic conjugated diene and an alcohol,
It is to provide a method for producing an alkoxyalkadiene.

[0005]

That is, the present invention provides a compound represented by the following general formula (1):

[0006]

Embedded image (Wherein, R represents a hydrogen atom or an aromatic ring) in the presence of a catalyst comprising a palladium compound and a phosphine compound represented by the following formula:
The present invention relates to a method for producing an alkoxyalkadiene.

A feature of the production method of the present invention is that the catalyst is easy to prepare and extremely stable, has a high reaction rate, and has excellent catalytic activity, as compared with conventional catalysts.

Hereinafter, the present invention will be described in detail.

The palladium compound used in the present invention is, for example, a compound represented by the general formula (2) in the presence of a solvent:

[0010]

Embedded image (Wherein R represents a hydrogen atom or an aromatic ring), and can be easily synthesized by salt exchange between a compound represented by the following formula (1) and a palladium salt. Dried.

As the solvent, methanol, ethanol,
Examples thereof include alcohols such as propanol and butanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethers such as diethyl ether and tetrahydrofuran, and water, and one or more of these are used.

[0012] As the palladium salt, 2
Any preparation method may be used as long as it is in a valence state.In the case of palladium chloride, since it is difficult to dissolve in water alone, for example, an aqueous solution obtained by adding a compound such as lithium chloride or sodium chloride or potassium chloride to palladium chloride or the like Is used. The amount of the palladium salt used is 1 to 3 moles, preferably 1.5 to 2.5 moles per mole of the compound of the general formula (2).
The reaction is carried out within a range of 10 to 80 ° C., and the reaction is carried out at room temperature for convenience. The reaction is preferably performed under an inert gas such as nitrogen.

R can be a substituted or unsubstituted aromatic ring such as a hydrogen atom, a phenyl group, an o-tolyl group, a pp-tolyl group and the like. It is preferably an aromatic ring having 6 to 7 carbon atoms.

The amount of the palladium compound represented by the general formula (1) is usually 0.00001 to 1 gram atom, preferably 0.0001 to 0.5, in terms of palladium atom per mole of the aliphatic conjugated alkadiene. Use in the range of gram atoms.

Examples of the phosphine compound used as a cocatalyst in the present invention include trialkylphosphines such as tributylphosphine, tricyclohexylphosphine and tri-n-octylphosphine, triphenylphosphine, and the like.
Tri (o-tolyl) phosphine, tri (m-tolyl) phosphine, tri (p-tolyl) phosphine, diphenyl-p-chlorophenylphosphine, tris (p-methoxyphenyl) phosphine, sodium diphenylphosphinobenzene-m-sulfonate, 3 sodium Triarylphosphine such as mutris (m-sulfophenyl) phosphine, tris (carboxyphenyl) phosphine, bis (carboxyphenyl) phenylphosphine, carboxyphenyldiphenylphosphine, 1,2-bis (diphenylphosphino) ethane, 1, Examples include bidentate phosphines such as 3-bis (diphenylphosphino) propane and 1,4-bis (diphenylphosphino) butane, and one or more of these can be used. These phosphine compounds are generally used in an amount of 0.1 to 100 mol, preferably 0.2 to 20 mol, per gram atom of palladium.

The aliphatic conjugated alkadiene used in the present invention is 1,3-butadiene, 2-ethyl-1,3
Examples thereof include compounds having 4 to 8 carbon atoms, such as -butadiene, 2,3-dimethyl-1,3-butadiene, isoprene, 1,3-pentadiene, chloroprene, and 1,3-octadiene. Butadiene is particularly preferred, and an inexpensive BB fraction obtained from petroleum cracking gas can be used.

The other starting materials, alcohols, include those having 1 to 8 carbon atoms such as methanol, ethanol, n-propanol, butanol, 2-ethylhexanol and ethylene glycol. Alicyclic alcohols such as aliphatic alcohols, cyclohexanol and methylcyclohexanol;
And aromatic alcohols such as phenol, phenol and benzyl alcohol.

A solvent is not always required for the reaction between the aliphatic alkadiene and the alcohol, but a solvent inert to the reaction can be used. For example, ketones such as acetone and methyl ethyl ketone, and dioxane and the like can be used. Ethers, nitriles such as acetonitrile and propionitrile, hydrocarbons such as benzene, cyclohexane and n-hexane, sulfoxides such as dimethyl sulfoxide,
Examples include nitro compounds such as nitrobenzene and nitromethane, acetamide, propionamide, N, N-dimethylformamide, and N, N-dimethylacetamide.

The reaction temperature is usually in the range of 0 ° C. to 150 ° C., preferably 30 ° C. to 120 ° C. The reaction pressure is not particularly limited, and pressure conditions under normal pressure or under pressure can be appropriately selected and employed. The reaction time is from 0.1 to 10 hours, preferably from 0.2 to 6 hours. The telomerization reaction can be carried out by a continuous system or a batch system, but the industrial system is preferably a continuous system.

[0020]

According to the method of the present invention, an alkoxyalkadiene can be obtained with a high selectivity and a high yield. It is a useful compound.

[0021]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

EXAMPLE 1 N-benzoyl-N-phenylhydroxylamine palladium catalyst (64 mg, 0.1 ml) was added to a 50 ml autoclave.
2 mmol), 63 mg of triphenylphosphine (9.
24 mmol) and 16 ml of methanol, followed by purging with nitrogen. Next, 12 g of butadiene was added, and 7K
The reaction was performed at 60 ° C. for 1.5 hours at g / cm ² G. The conversion of butadiene was 85%, and the selectivity was as follows.

1-methoxy-2,7-octadiene (1-OMe) 79.2% 3-methoxy-1,7-octadiene (3-OMe) 6.3% Butadiene dimer (Dimer) 14.6% Example 2 The same procedure as in Example 1 was carried out except that the catalyst was changed to 67 mg (0.12 mmol) of N-benzoyl-No-tolylhydroxylamine palladium catalyst, and the conversion was 90%.
And the selectivity was as follows.

1-OMe 79.2% 3-OMe 5.9% Dimer 14.9% Examples 3-5 Performed in the same manner as in Example 1 except that triphenylphosphine was replaced with a phosphine compound shown in Table 1. Was. Table 1 shows the results
Shown in

[0025]

[Table 1] Examples 6 to 8 The same procedures as in Examples 3 to 5 were performed except that the palladium catalyst used in Example 2 was used. Table 2 shows the results.

[0026]

[Table 2] Comparative Examples 1-3 Palladium acetate 27 mg (0.
The procedure was the same as in Examples 3 to 5, except that 12 mmol) was used. Table 3 shows the results.

[0027]

[Table 3] Example 9 N-benzoyl-N-phenylhydroxylamine palladium catalyst (64 mg, 0.1 ml) was added to a 50 ml autoclave.
2mmol), 1,2-bis (diphenylphosphino)
47 mg (0.12 mmol) of ethane (dppe) and 16 ml of methanol were added, and the atmosphere was replaced with nitrogen. Next, 12 g of butadiene was added, and the mixture was reacted at 80 ° C. for 3 hours at 7 kg / cm ² G by nitrogen pressure. Butadiene conversion is 85
% And selectivity were as follows.

1-OMe 78.4% 3-OMe 7.7% Dimer 13.8% Examples 10, 11 Except that the phosphine compound was changed from dppe to the phosphine compound (0.12 mmol) described in Table 4. Performed similarly to 9. Table 4 shows the results.

[0029]

[Table 4] Examples 12 to 14 Except that the palladium catalyst used in Example 2 was used and the phosphine compounds were changed to the compounds shown in Table 5, the results were shown in Examples 9 to 14.
Performed similarly to 11. Table 5 shows the results.

[0030]

[Table 5] Comparative Examples 4 and 5 27 mg of palladium acetate (0.
Except for using 12 mmol), palladium was metallized after the completion of the reaction in the same manner as in Examples 9 to 11. Table 6 shows the results.

[0031]

[Table 6]

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-62-63538 (JP, A) JP-A-57-45137 (JP, A) JP-B-48-42606 (JP, B1) JP-B-47-47 20205 (JP, B1) JP-B-49-31965 (JP, B1) JP-B-49-46286 (JP, B1) JP-B-48-3605 (JP, B1) JP-B-47-20604 (JP, B1) (58) Field surveyed (Int.Cl. ⁷ , DB name) C07C 41/06 C07C 43/15 CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. A compound of the general formula (1) (Wherein, R represents a hydrogen atom or an aromatic ring) in the presence of a catalyst comprising a palladium compound and a phosphine compound represented by the following formula:
A method for producing an alkoxyalkadiene.