JPH0639398B2 - Method for partial hydrogenation of cyclic dienes - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention is a raw material of a useful polymer, and is a partial hydrogen of a cyclic diene for producing an olefinic compound which is a raw material for various organic phoine derivatives. It relates to the method of conversion.

[Conventional technology]

Various methods of hydrogenating olefins having a plurality of double bonds, that is, polyenes are known, but generally, complete hydrogenation of all double bonds and partial hydrogenation of double bonds at unspecified positions ( For example, it is known that non-selective partial hydrogenation from diene to monoene) and regioselective partial hydrogenation (selective hydrogenation of only double bond at a specific position) are difficult in this order.

Conventionally, an example of partial hydrogenation of isoprene is known as an example of the partial hydrogenation reaction corresponding to the above. As an example of a relatively high selectivity produces a partially hydrogenated to 3-methyl-1-butene isoprene, _{^{(b) Co ▲ (CN) 3- 5}} ▼ method according catalyst (ORa inter al, Bu
ll.Chem.Soc.Jpn, 45 , 2723 (1972)), (b) CoBr (PPh ₃ ) _3- BF ₃ OEt ₂ catalyst method (Mizorogi et al., Chem. Lett., 847 (1976)), and (C) PdCl ₂ (PPh ₃ ) _2- SnCl ₂ catalyst method (Itaya et al., In
d.Eng.Chem.Prod.Res.Dev. 11 , No. 2,146 (1972)) and the like are known.

[Problems to be solved by the invention]

However, of these, the methods (a) and (c) above do not have sufficiently high selectivity for 3-methyl-1-butene,
In addition, the method (b) is not sufficient for industrial use because the reaction rate and the catalytic activity are not sufficient.

On the other hand, there is a method of partially hydrogenating isoprene in the presence of a catalyst composed of a cobalt compound-phosphorus compound-organoaluminum compound (Japanese Patent Publication No. 45-22322), but the production ratio of 3-methyl-1-butene is at most 15. %.

Moreover, even in a reaction system having a high selectivity for 3-methyl-1-butene among these, the isomerization reaction of the produced 3-methyl-1-butene suddenly occurs when the conversion of isoprene becomes high, and as a result, It has a drawback that the main component is 2-methyl-2-butene.

Moreover, with respect to dienes other than isoprene, for example, cyclic dienes, there is almost no known method for selectively hydrogenating one double bond.

[Means for solving problems]

In view of the above facts, the inventors of the present invention have diligently studied to find out a catalyst system and reaction conditions that can partially hydrogenate only one double bond of cyclic dienes, and have reached the present invention. Is.

That is, an object of the present invention is to provide a method for selective partial hydrogenation of cyclic dienes, in which the cyclic dienes are heated to 50 ° C or lower in the presence of a catalyst composed of a cobalt compound, an organic phosphine compound and an aluminum compound. Method for partial hydrogenation of cyclic dienes, characterized by hydrogenating at a temperature of 1 to obtain a partial hydride in which one double bond is hydrogenated, and a cobalt compound, an organic phosphine compound, an aluminum compound, and a halogenated compound In the presence of a catalyst composed of a boron compound and / or a protonic acid having a pKa of 1 or less, the cyclic dienes are hydrogenated at a temperature of 50 ° C. or less to obtain a partial hydride in which one double bond is hydrogenated. And a method for partial hydrogenation of cyclic dienes.

Hereinafter, the present invention will be described in more detail.

In the process of the invention, a catalyst system consisting of a cobalt compound, an organic phosphine compound and an aluminum compound is used.

As the cobalt compound, cobalt chloride, cobalt sulfate, cobalt nitrate, cobalt carbonate, cobalt acetate, cobalt formate, cobalt naphthenate, cobalt oleate,
Salts of cobalt octoate, cobalt cyanide, cobalt fluoride, cobalt bromide, cobalt iodide, etc .; chelate compounds such as bis (acetylacetonato) cobalt, tris (acetylanato) cobalt; chlorotris (triphenylphosphine) cobalt , Bromotris (triphenylphosphine) cobalt, dichlorobis (triphenylphosphine) cobalt, dibromobis (triphenylphosphine) cobalt, and other organic phosphorus compound complexes.

Examples of the organic phosphine compound include triphenylphosphine, tris (p-methoxyphenyl) phosphine, tris (o-methoxyphenyl) phosphine, tris (p-trimethylsilylphenyl) phosphine, tri-p-tolylphosphine. And triarylphosphines such as tri-o-tolylphosphine; tri-n-butylphosphine, tri-n-propylphosphine, tri-iso-
Trialkylphosphines such as propylphosphine; Triaralkylphosphines such as tribenzylphosphine; Diphenyl-n-propylphosphine, diphenyl-iso
-Propylphosphine, 1-diphenylphosphino-2
Examples include mixed alkylaryl phosphines such as -trimethylsilylethane and 1,2-bis (diphenylphosphino) ethane; polymer phosphines such as crosslinked oligomers of triphenylphosphine.

Examples of the aluminum compound include trimethyl aluminum, triethyl aluminum, tri-iso-butyl aluminum, tri-n-butyl aluminum, tri-n-propyl aluminum, tri-n-hexyl aluminum, diethyl aluminum hydride, di-iso.
-Butyl aluminum hydride, diethyl aluminum chloride, di-iso-butyl aluminum chloride, diethyl aluminum bromide, ethyl aluminum dichloride, iso-butyl aluminum dichloride, ethyl aluminum dibromide, ethyl aluminum sesquichloride, iso-butyl aluminum sesquichloride, ethyl Examples include organic aluminum compounds such as aluminum sesquibromide; inorganic aluminum compounds such as aluminum chloride and aluminum bromide.

As the aluminum compound, it is preferable to use the above-mentioned organic aluminum compound and the inorganic aluminum compound in combination, or to use a plurality of organic aluminum compounds in combination. Further, it is more preferable to use an aluminum compound containing a halogen atom, that is, an organic aluminum compound or an inorganic aluminum compound containing a halogen atom, and an organic aluminum compound containing no halogen atom in combination.

In the present invention, it is effective to further use a boron halide compound and / or a protic acid having a pKa / or less as a catalyst component.

Examples of the boron halide compound include boron trifluoride,
Boron trichloride, boron tribromide, hydrofluoric boron trifluoride etherate (BF ₃ · OEt _2), three Hutu boron and secondary methanol product (BF ₃ · 2CH ₂ OH), and the like.

Further, as the protonic acid having a pKa / or less, sulfuric acid, hydrochloric acid,
Inorganic protonic acids such as hydrobromic acid, nitric acid, phosphoric acid, perchloric acid, tetrafluoroboric acid, thiocyanic acid; trifluoroacetic acid, trichloroacetic acid, trichloromethanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, etc. Examples of organic protonic acids include

Among the above, the organic protonic acid is more preferably used.

The cobalt compound is usually 1 to 0.00001 mol as a cobalt atom with respect to 1 mol of the starting cyclic diene,
It is preferably added in the range of 0.1 to 0.0001 mol.

The organic phosphine compound is added in an amount of usually 0.1 mol or more, preferably 1 to 1000 mol, more preferably 1 to 100 mol, particularly preferably 1 to 20 mol as a phosphorus atom with respect to 1 mol of the cobalt atom in the cobalt compound. To be done.

In addition, the aluminum compound is usually in the range of 1 to 100 mol, preferably 2 to 20 m as an aluminium atom with respect to 1 mol of the cobalt atom in the cobalt compound.
It is added in the range of ol.

Furthermore, when a boron halide compound is used, it is usually 1 to 1 mol with respect to 1 mol of the cobalt atom in the cobalt compound.
It is added in an amount of 100 mol, preferably 1 to 10 mol. When a protonic acid having a pKa / or less is used, it is usually 1 for 1 mol of cobalt atom in the above cobalt compound.
It is added in the range of -100 mol, preferably 1-10 mol.

The present invention is directed to the use of cyclic zuenes as a reaction raw material and hydrogenation of only one double bond.

Examples of the cyclic diene as a raw material include 1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,3-cyclooctadiene, and 1,5-cyclooctadiene.

When the cyclic dienes exemplified above are hydrogenated according to the method of the present invention, one double bond is partially hydrogenated as shown in Table 1.

As the reaction temperature, a temperature of 50 ° C. or lower is adopted. 5
At temperatures higher than 0 ° C, the production ratio of isomers other than the target organism increases. The reaction temperature is preferably in the range of -20 ° C to 50 ° C, more preferably -5 ° C to 45 ° C.

The reaction pressure is usually from normal pressure to 100 kg / cm ² .

The reaction is usually performed in the presence of a solvent. As a solvent,
Any solvent inert to the reaction may be used, and for example, aromatic hydrocarbons such as toluene and halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, trichlorobenzene and bromobenzene can be used.

The reaction can be carried out in a batch system, a semi-continuous system, or a continuous system. The reaction product can be separated by a usual separation method, for example, distillation, extraction, adsorption and the like. Especially when separated by distillation, the distillation residue can be recycled as a catalyst liquid.

〔Example〕

Next, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to the following Examples unless it exceeds the gist.

The reaction rate and production rate were calculated by the following formulas.

Example-1 A flask having a volume of 100 ml was charged with 59 mg (0.2 mmol) of cobalt (II) acetylacetonate dihydrate and 157 mg (0.6 mmol) of triphenylphosphine, and the system was thoroughly replaced with nitrogen. , Chlorobenzene as solvent 20
ml was added. To a suspension of chlorobenzene, 0.60 ml of a 10.0 wt% toluene solution of triethylaluminum (0.46
mmol) was added dropwise with stirring under ice cooling. Further, 40 mg (0.3 mmol) of aluminum chloride was added, and finally 1,3-
After adding 0.37 ml (3.0 mmol) of cyclooctadiene and replacing the inside of the system with hydrogen, hydrogen was introduced at normal pressure while vigorously stirring under ice cooling. After the start of introduction, hydrogen absorption started and after reacting for 7 hours, the reaction liquid was analyzed by gas chromatography, and the following results were obtained.

1,3-Cyclooctadiene Reaction rate 88% Cyclooctene generation rate 100% Example-2 Except for using 1,5-cyclooctadiene 0.37 ml (3.0 mmol) instead of 1,3-cyclooctadiene. Was reacted in the same manner as in Example-1, and after reacting for 8 hours, the reaction liquid was analyzed by gas chromatography, and the following results were obtained.

1,5-Cyclooctadiene Reaction rate 100% Cyclooctene formation ratio 65% 1,3-Cyclooctadiene formation ratio 35% [Effect of the invention] According to the method of the present invention, cyclic diene is partially hydrogenated to form a cyclic monoene. Olefins can be selectively produced.

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Claims (2)

[Claims] 1. A catalyst comprising a cobalt compound, an organic phosphine compound and an aluminum compound,
A method for partial hydrogenation of cyclic dienes, which comprises hydrogenating the cyclic dienes at a temperature of 50 ° C. or lower to obtain a partial hydride in which one double bond is hydrogenated. 2. Hydrogenation of cyclic dienes at a temperature of 50 ° C. or lower in the presence of a catalyst consisting of a cobalt compound, an organic phosphine compound, an aluminum compound and a boron halide compound and / or a protonic acid having a pKa of 1 or less,
A method for partial hydrogenation of cyclic dienes, characterized in that a partial hydride in which one double bond is hydrogenated is obtained.