JPH0617325B2 - Method for producing 3-methylbutene-1 - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing 3-methylbutene-1 which is a raw material of a useful polymer.

[Conventional technology]

Conventionally, it is known that 3-methylbutene-1 is produced by partial hydrogenation of isoprene. However, when isoprene is catalytically hydrogenated, in most cases, paraffin (2 -Methylbutane). Even when partial hydrogenation of hydrogenating only one double bond was successful, the main component was hydrogenated 2-methylbutene-2, which is a 1,4-adduct, or a double bond with less steric hindrance. 2-
Methylbutene-1 and the desired 3-methylbutene-1
The generation ratio of is very small.

The relatively good selectivity resulting example partially hydrogenated by 3-methylbutene-1 of isoprene, _{^{(b) Co (CN) ▲ 3- 2}} ▼ method according catalyst (ORa between et al, B
all. Chem. Soc. Jpn, 45 , 2723
(1972)), _{(ii) CoBr (PPh 3) 3 -BF} 3 · OEt 2 method by the catalyst (Mizorogi et, Chem.Lett., 847
(1976)), and _{(c) PdCl 2 (PPh 3) 2} -SnCl method according ₂ catalyst (Itaya et al., Ind.Eng.Chem.Prod.
Res. Dev. 11, No. 2, 146 (197)
2)), etc. are known.

[Problems to be solved by the invention]

However, among these, the methods of (a) and (c) do not have sufficiently high selectivity for 3-methylbutene-1, and the method of (b) has insufficient reaction rate and catalytic activity. It is not enough to use.

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-methylbutene-1 is at most 15%. is there.

Moreover, even in a reaction system having a high selectivity for 3-methylbutene-1 among these, an isomerization reaction of 3-methylbutene-1 that is rapidly generated occurs when the reaction rate of isoprene becomes high, and as a result, the main component is 2- It had the drawback of becoming methylbutene-2. This means that when the reaction rate of isoprene increases, the amount of isoprene present in the system decreases,
It is considered that 3-methylbutene-1 is coordinated with the catalyst instead of isoprene, and the isomerization reaction of 3-methylbutene-1 to 2-methylbutene-2 occurs preferentially. On the other hand, when the reaction rate of isoprene is low, a larger amount of isoprene is present, and it is considered that isoprene is coordinated with the catalyst and the hydrogenation reaction of isoprene occurs preferentially.

[Means for solving problems]

The present inventors have found that 3-methylbutene-1 is produced at a high selectivity and a high reaction rate by the partial hydrogenation reaction of isoprene, and even when the conversion of isoprene is high, 3
The present invention has been achieved as a result of extensive studies to find out a catalyst system and reaction conditions capable of maintaining high selectivity of -methylbutene-1.

That is, the present invention is a method for producing 3-methylbutene-1 by partial hydrogenation of isoprene in the presence of a catalyst composed of a cobalt compound, an organic phosphine compound and an aluminum compound, in which cis-olefin compound is added to the reaction system. Method for producing 3-methylbutene-1 characterized by being present, and partial hydrogenation of isoprene in the presence of a catalyst comprising 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. Reaction of 3-methylbutene-1
A method for producing 3-methylbutene-1 characterized in that a cis-olefin compound is present in the reaction system.

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 of bis (acetylacetonato) cobalt, tris (acetylacetonato) cobalt, etc .; chlorotris (triphenylphosphine) Examples thereof include organic phosphorus compound complexes such as cobalt, bromotris (triphenylphosphine) cobalt, dichlorobis (triphenylphosphine) cobalt, and dibromobis (triphenylphosphine) cobalt.

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-i
Mixed alkylaryl phosphines such as so-propylphosphine, 1-diphenylphosphino-2-trimethylsilylethane, 1,2-bis (diphenylphosphino) ethane; polymer phosphines such as crosslinked oligomers of triphenylphosphine Etc.

Further, as the aluminum compound, trimethyl aluminum, triethyl aluminum, and tree iso-
Butyl aluminum, tri-n-butyl aluminum,
Tree n-propyl aluminum, tree n-hexyl aluminum, diethyl aluminum hydride, di-i
So-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 organic aluminum compound and the inorganic aluminum compound described above 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 protonic acid having a pKa of 1 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, include two methanol product _(BF 3 · _2CH 3 OH) and the like.

Further, as the proton acid having a pKa of 1 or less, inorganic protonic acids such as sulfuric acid, hydrochloric acid, hydrobromic acid, nitric acid, phosphoric acid, perchloric acid, tetrafluoroboric acid and thiocyanic acid; trifluoroacetic acid, trichloroacetic acid, trichloromethane Organic protic acids such as sulfonic acid, trifluoromethanesulfonic acid, and p-toluenesulfonic acid can be used. Among the above, the organic protonic acid is more preferably used.

Further, in the present invention, a cis-olefin compound is present in the reaction system.

Among the cis-olefin compounds, the general formula (In the formula, R ₁ and R ₂ represent an alkyl group, a silyl group, or an aryl group, and both may be bonded to each other to form a ring).

In addition, among the above, R ₁ and R ₂ are bonded to each other to form a bridged olefin compound, and the carbon atom adjacent to the olefin portion is a bridgehead carbon atom, cis-olefin, and R ₁ and R ₂ Is more preferably cis-olefin in which is a tertiary alkyl group, a tertiary silyl group or an aryl group.

Specifically, 2-norbornene, 2,5-norbornadiene, dicyclopentadiene, bicyclo [2.2.2]
Oct-2-ene, Bicyclo [2.2.2] octa
2,5,7-triene, bicyclo [2.1.1] hex-2-ene, bicyclo [2.2.0] hexa-2,5-
Arashi bridge olefins such as dienes; cis-tertiary alkyl substituted olefins such as cis-di-t-butylethylene; cis-
Cis-tertiary silyl-substituted olefins such as bis (trimethylsilyl) ethylene; cis-stilbene, cis-1,2
-Cis-aryl substituted olefins such as dinaphthylethylene and the like.

The cobalt compound is 1 mol of raw material isoprene,
The amount of cobalt atom added is usually 1 to 0.00001 mol, preferably 0.1 to 0.0001 mol.

The organic phosphine compound is usually 0.1 m as a phosphorus atom for 1 mol of cobalt in the cobalt compound.
ol or more, preferably 1 to 1000 mol, more preferably 1 to 100 mol, particularly preferably 1 to 20 mol.

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

The cis-olefin compound is usually used in an amount of 1 to 100 mol per 1 mol of cobalt atom in the cobalt compound.
It is preferably added in the range of 3 to 20 mol.

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 of 1 or less is used, it is usually added in an amount of 1 to 100 mol, preferably 1 to 10 mol, per 1 mol of cobalt atom in the cobalt compound.

As the reaction temperature, a temperature of 50 ° C. or lower is usually adopted. At a temperature higher than 50 ° C, the production ratio of the above-mentioned isomers other than the desired product, 3-methylbutene-1, 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, for example, toluene,
Chlorobenzene, bromobenzene, etc. can be used.

The reaction can be carried out in a batch system, a semi-continuous system, or a continuous system. The reaction product, that is, the desired 3-methylbutene-1, its isomer, 2-methylbutane, etc., can be separated by a conventional separation method such as distillation, extraction,
It can be separated by adsorption or the like. Especially when separated by distillation, the distillation residue can be recycled as a catalyst liquid.

[Work]

The reason why the high selectivity of 3-methylbutene-1 can be maintained even when the isoprene conversion is high by the presence of the cis-olefin compound in the reaction system according to the present invention is not clear, but it is probably cis. -When the olefin compound has a higher coordination rate to the catalyst than isoprene and acts competitively with 3-methylbutene-1 as a compound stronger than 3-methylbutene-1, in the case where the isoprene reaction rate is high. It is presumed that this is because the coordination of 3-methylbutene-1 to the catalyst is suppressed.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist thereof is not exceeded.

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

IP: isoprene 3MB1: 3-methylbutene-1 2MB1: 2-methylbutene-1 2MB2: 2-methylbutene-2 2MB: 2-methylbutane (*) Reduction products: 3MB1, 2MB1, 2MB2 and 2MB Comparative Example-1 59 mg (0.2 mmol) of cobalt (II) acetylacetonate dihydrate and 157 mg (0. 6 mMol),
After thoroughly purging the system with nitrogen, 20 ml of chlorobenzene was added. 0.42 ml (0.46 ml) of a 14.5 wt% toluene solution of triethylaluminum in a chlorobenzene solution.
(mmol) was added dropwise with stirring under ice cooling. Furthermore, 0.52 ml (0.34 mmol) of a 18.4 wt% toluene solution of ethylaluminum sesquichloride was added dropwise, and finally 0.3 ml (3.0 mmol) of isoprene was added, the system was replaced with hydrogen, and then cooled with ice. Hydrogen was introduced at normal pressure with vigorous stirring. After the introduction, hydrogen absorption started and hydrogenation reaction proceeded. When the reaction liquid was analyzed by gas chromatography when the hydrogen absorption amount was about 90% of the theoretical amount,
The reaction rate was 90%, and the production rate of 3MB1 was 82%. Further, the hydrogenation reaction was continued, and when the reaction liquid was analyzed when absorption of a hydrogen amount close to the theoretical amount was observed, the IP reaction rate increased to 98%, but the production rate of 3MB1 was 0.4%. Almost disappeared, and conversely, the production ratio of 2MB2 increased to 87.9%. The production rate of reduction products other than 3MB1 and 2MB2 was 7.6% for 2MB1 and 4.1% for 2MB.

Example-1 Triethylaluminum 10.0 wt% toluene solution 0.60 ml as a toluene solution of triethylaluminum
(0.46 mmol) as a toluene solution of ethylaluminum sesquichloride, ethyl aluminum sesquichloride 10.0 wt% toluene solution 0.96 ml (0.34
Comparative Example- except that 151 mg (1.6 mmol) of 2-norbornene was added after the addition of isoprene.
The reaction was carried out in the same manner as in Example 1, and when the hydrogen absorption amount was about 90% of the theoretical amount, the reaction solution was analyzed. As a result, the IP reaction rate was 90% and the 3MB1 production ratio was 81%. Further IP
When the reaction rate was increased and absorption of a hydrogen amount close to the theoretical amount was observed, the reaction solution was analyzed, and the following results were obtained.

IP reaction rate 97% 3MB1 production ratio 81% 2MB1 〃 5.8% 2MB2 〃 13% 2MB 〃 0.2% Example-2 2-diphenyl pentadiene 0.11 ml (0.8 mmol) was used instead of 2-norbornene. Example 1 except that
The reaction is carried out in the same manner as above, and the hydrogen absorption amount is about 9 of the theoretical amount.
When the reaction solution was analyzed at 0%, the IP reaction rate was 90%, and the 3MB1 production ratio was 79%. When the IP reaction rate was further increased and absorption of a hydrogen amount close to the theoretical amount was observed, the reaction solution was analyzed and the following results were obtained.

IP reaction rate 97% 3MB1 production ratio 78% 2MB1 〃 4.7% 2MB2 〃 17% 2MB 〃 0.3% Example-3 In place of 2-norbornene, 2,5-norbornadiene 0.08 ml (0.8 mmol) Example except that was used
The reaction was carried out in the same manner as in Example 1, and when the hydrogen absorption amount was about 90% of the theoretical amount, the reaction solution was analyzed. As a result, the IP reaction rate was 90% and the 3MB1 production ratio was 82%. Further IP
When the reaction rate was increased and the absorption of the amount of hydrogen close to the theoretical amount was observed, the reaction solution was analyzed, and the following results were obtained.

IP reaction rate 95% 3MB1 production ratio 54% 2MB1 〃 6.5% 2MB2 〃 38% 2MB production ratio 1.5% Example-4 In place of 2-norbornene, cis-stilbene 0.2
The reaction was carried out in the same manner as in Example 1 except that 8 ml (1.6 mmol) was used, and when the hydrogen absorption amount was about 90% of the theoretical amount, the reaction solution was analyzed.
%, The production ratio of 3MB1 was 82%. When the IP reaction rate was further increased and absorption of a hydrogen amount close to the theoretical amount was observed, the reaction solution was analyzed, and the following results were obtained.

IP reaction rate 96% 3MB1 generation rate 58% 2MB1 〃 6.6% 2MB2 〃 35% 2MB 〃 0.4% Comparative example-2 Trans-stilbene 28 instead of 2-norbornene 28
The reaction was carried out in the same manner as in Example 1 except that 8 mg (1.6 mmol) was used, and when the hydrogen absorption amount was about 90% of the theoretical amount, the reaction solution was analyzed.
%, The production ratio of 3MB1 was 81%. When the IP reaction rate was further increased and absorption of a hydrogen amount close to the theoretical amount was observed, the reaction solution was analyzed and the following results were obtained.

IP reaction rate 95% 3MB1 production ratio 0.2% 2MB1 〃 7% 2MB2 〃 90% 2MB 2.8% [Effect of the invention] According to the method of the present invention, it is selectively higher than isoprene which is a cheap raw material. Since the yield and the reaction rate are sufficiently fast to produce 3-methylbutene-1, and the high selectivity of 3-methylbutene-1 can be maintained at a high isoprene reaction conversion rate, the method of the present invention is industrial. Extremely high value.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location B01J 31/22 X 7821-4G 31/24 X 7821-4G C07B 61/00 300

Claims (2)

[Claims] 1. A partial hydrogenation reaction of isoprene in the presence of a catalyst composed of a cobalt compound, an organic phosphine compound and an aluminum compound to give 3-methylbutene-1.
The method for producing 3-methylbutene-1 characterized in that the cis-olefin compound is present in the reaction system. 2. A partial hydrogenation reaction of isoprene in the presence of a catalyst comprising a cobalt compound, an organic phosphine compound, an aluminum compound, a boron halide compound and / or a protonic acid having a pKa of 1 or less to produce 3-methylbutene-1. In the method, the cis-olefin compound is present in the reaction system.
A method for producing methylbutene-1.