JP3360410B2 - Method for producing epoxy compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an epoxy compound. More specifically, the present invention relates to a method for producing an epoxy compound from an olefin and oxygen, which can be applied to a wide variety of olefins, generates less by-products, and has excellent selectivity to the target epoxy compound. And a method for producing an epoxy compound.

[0002]

2. Description of the Related Art A method for producing ethylene oxide from ethylene and oxygen using silver as a catalyst is known. However, this method has a problem that when applied to olefins other than ethylene, for example, propylene, hydrogen of the methyl group is preferentially oxidized, and therefore, the selectivity to the target epoxy compound is poor.

[0003]

In such a situation,
The problem to be solved by the present invention is that, for a wide variety of olefins such as propylene, 1-hexene, cyclohexene, and styrene, in addition to ethylene, the generation of by-products from olefins and oxygen is small, and the desired epoxy compound Another object of the present invention is to provide a method for producing an epoxy compound having excellent selectivity to an epoxy compound.

[0004]

That is, the present invention relates to a method for producing an epoxy compound by reacting an olefin with oxygen in the presence of the following (A) and (B), wherein the lanthanoid compound is a europium (Eu) compound Wherein the reducing agent is zinc, and a method for producing an epoxy compound in which a protonic acid coexists during the reaction. (A): Lanthanoid compound (B): Reducing agent

Examples of the olefin include ethylene, propylene, butene, pentene, hexene, octene, decene, 3-methyl-1-butene, 2,3-dimethyl-1-butene, and 2,3-dimethyl-2. -Butene, 4-
Aliphatic olefins such as methyl-1-pentene and allyl chloride; alicyclic olefins such as cyclopentene, cyclohexene, 1-methylcyclohexene, norbornene and dicyclopentadiene; and aromatic substituted olefins such as styrene and α-methylstyrene. Can be.

[0006] The epoxy compound, which is the target product obtained from the above-mentioned olefin, includes ethylene oxide, propylene oxide, butene oxide, pentene oxide, hexene oxide, octene oxide, decene oxide, 3-methyl-1,2-epoxybutane. ,
2,3-dimethyl-1,2-epoxybutane, 2,3-
Dimethyl-2,3-epoxybutane, 4-methyl-1,
2-epoxypentane, epichlorohydrin, 1,2-
Epoxycyclopentane, 1,2-epoxycyclohexane, 1-methyl-1,2-epoxycyclohexane,
2,3-epoxynorbornane, dicyclopentene oxide, styrene oxide and α-methylstyrene oxide.

(A): The lanthanoid compound is a europium (Eu) compound .

The lanthanoid compound (A) includes, specifically, a halide of the above lanthanoid,
Nitrate, carbonate, sulfate, oxalate, acetate, perchlorate, fluoride and the like can be mentioned. As these salts and compounds, hydrates containing water of crystallization may be used.
Preferred lanthanoid compounds include europium chloride, europium nitrate and europium carbonate.

[0009] The amount of the (A) lanthanoid compound used is usually 0.0001 to 0.1 mol / l, preferably 0.001 to 0.05 mol / l, in the reaction mixture. If the amount is too small, a sufficient reaction rate may not be obtained. On the other hand, if the amount is too large, the selectivity to the desired epoxy compound may decrease.

(B) The reducing agent is zinc.

The amount of the reducing agent (B) is usually 1 to 10 mol, preferably 1 to 5 mol, per 1 mol of the olefin. If the amount is too small, a sufficient reaction rate may not be obtained, while if the amount is too large, mixing may be difficult.

[0012] (B) The reducing agent includes
Bonic acid or inorganic acid is used at the same time. This allows the reaction rate and selectivity to be kept high. Specific examples of the carboxylic acid include acetic acid, propionic acid, butyric acid, isobutyric acid, and the like. Specific examples of the inorganic acid include hydrochloric acid and sulfuric acid. Preferably, it is acetic acid, propionic acid or butyric acid. The amount of the carboxylic acid to be used is generally 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, per 1 part by weight of the reducing agent. If the amount is too small, a sufficient reaction rate may not be obtained,
On the other hand, if the amount is too large, the selectivity to the target epoxy compound may decrease.

As a method of reacting olefin and oxygen, specifically, a method of supplying olefin and oxygen to a reaction solution containing (A) a lanthanoid compound, (B) a reducing agent and, if necessary, a carboxylic acid is used. I can give it.

Examples of the solvent used in the reaction include methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, acetonitrile, diethyl ether, tetrahydrofuran, acetone and the like. Preferred are methylene chloride, 1,2-dichloroethane and diethyl ether. In addition, when using a liquid olefin, it can also be implemented without using a solvent.

The oxygen used may be used alone.
It may be used by mixing with a gas other than oxygen. Examples of the gas other than oxygen include an inert gas such as nitrogen, helium, and argon. Air may be used as the oxygen source.

The amount of oxygen is usually 0.1 to 1 as oxygen partial pressure.
0 atm, preferably 0.1 to 5 atm. If the amount is too small, a sufficient reaction rate may not be obtained. On the other hand, if the amount is too large, the air-fuel mixture enters an explosion range, which is not preferable for safety.

The reaction temperature is usually 0-100 ° C, preferably 30-80 ° C. If the temperature is too low, a sufficient reaction rate may not be obtained, while if the temperature is too high, the selectivity to the target epoxy compound may be reduced.

The reaction pressure is not particularly limited, but is usually 1 to 1.
The pressure is 50 atm, preferably 1 to 30 atm.

The reaction time is generally 0.1 to 10 hours, preferably 0.1 to 2 hours. If the time is too short, the conversion of the olefin may be insufficient, while if the time is too long, the selectivity to the target epoxy compound may decrease.

The type of the reaction may be either a batch system or a continuous system. In the case of a continuous system, the above reaction time refers to an average residence time.

[0021]

The present invention will be described below by way of examples. Example 1 2 m of methylene chloride as a solvent was placed in a glass flask.
l, 1 ml of 1-hexene as olefin (8 mmo
l), ₃₀ μmol of europium chloride (EuCl ₃ .6H ₂ O) as a lanthanoid compound and 2 ml of propionic acid as a carboxylic acid were charged, and the inside of the flask was replaced with oxygen. Next, 1 g of zinc powder was added to start the reaction. The temperature of the reaction solution was maintained at 40 ° C. by heating. After reacting for 1 hour, the inside of the flask was replaced with argon to terminate the reaction. The reaction solution was filtered, and the residue was washed with methylene chloride. The components of the combined filtrate and washing solution were analyzed by gas chromatography. As a result, hexene oxide 0.267 mm
ol, 1-hexen-3-ol 0.009 mmol,
0.022 mmol of 1,2-hexanediol, 0.004 mmol of 1-hexanal, 0.2 ml of 2-hexanol.
003 mmol, 1-hexanol 0.006 mmol
l and 0.035 mmol of others were detected. Than this,
2. Hexene oxide yield (= mol of hexene oxide obtained × 100 / mol of supplied 1-hexene)
3% and hexene oxide selectivity (= mol of hexene oxide obtained × 100 / total mol of product) 8
1% was obtained.

The experimental conditions are summarized below. (1) Amount of (A) lanthanoid compound used: 6 × 10 ⁻³ mol / l in reaction mixture (2) (B) Amount of reducing agent used: 1.96 mol per mol of olefin (3) Use of carboxylic acid Amount: 0.1 per part by weight of reducing agent.
99 parts by weight (4) Amount of oxygen: 1 atm in oxygen partial pressure (5) Reaction temperature: 40 ° C. (6) Reaction pressure: 1 atm (7) Reaction time: 1 hr

Examples 2 to 10 The same procedure as in Example 1 was carried out except that the conditions shown in Tables 1 and 2 were used. The results are shown in Tables 1 and 2.

[0024]

[Table 1]------------------------------------------------- O1 O1 O1 O1 O1 Catalyst * 2 L1 L1 L1 L1 L2 L3 Carboxylic acid * 3 A1 A2 A2 A2 A2 A2 Solvent * 4 Sl S2 S3 S4 S1 S1 Reaction temperature ℃ 40 40 40 40 40 40 Result Epoxy compound * 5 EP1 EP1 EP1 EP1 EP1 EP1 Epoxy yield% * 6 3.3 4.4 1.4 2.9 2.3 1.8 Epoxy selectivity% * 7 81 74 70 67 67 74 --------------- −−−−−−−−−−−

[0025]

Table 2 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Example 7 8 ^{* 8} 9 10 Olefin * 1 O1 O2 O3 O4 Catalyst * 2 L1 L1 L1 L1 Carboxylic acid * 3 A3 A2 A2 A2 Solvent * 4 S1 S1 S1 S1 Reaction temperature ℃ 40 30 20 40 Result Epoxy compound * 5 EP1 EP2 EP3 EP4 Epoxy yield% * 6 2.2 0.86 1.0 1.8 Epoxy selectivity% * 7 81 74 32 32 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−

* 1 Olefin O1: 1-Hexene O2: Propylene O3: Styrene O4: Cyclohexene

[0027] * 2 catalyst (lanthanide _{compound) L1: EuCl 3 · 6H 2} O L2: Eu (NO 3) 3 · 6H 2 O L3: Eu 2 (CO 3) 3 · nH 2 O

* 3 Carboxylic acid A1: propionic acid A2: acetic acid A3: butyric acid

* 4 Solvent S1: methylene chloride S2: 1,2-dichloroethane S3: diethyl ether S4: acetone

* 5 Epoxy compound EP1: hexene oxide EP2: propion oxide EP3: styrene oxide EP4: cyclohexene oxide

* 6 Epoxy yield: mol of epoxy compound obtained × 100 / mol of supplied olefin * 7 Epoxy selectivity: mol of epoxy compound obtained
× 100 / total mol of product × 100 * 8 Example 10: A propylene partial pressure of 0.7 atm and an oxygen partial pressure of 0.3 atm were used.

[0032]

As described above, according to the present invention, in addition to ethylene, a wide variety of olefins such as propylene, 1-hexene, cyclohexene, and styrene can be obtained.
It is possible to provide a method for producing an epoxy compound which is less likely to generate by-products from olefins and oxygen and has excellent selectivity to the target epoxy compound.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI // C07B 61/00 300 C07B 61/00 300

Claims (2)

(57) [Claims] 1. A presence of the following (A) and (B), a process for the preparation of the epoxy compound to be reacted with olefin and oxygen, lanthanoid compound europium (Eu) compound
A method for producing an epoxy compound, wherein the reducing agent is zinc and a protonic acid coexists in the reaction. (A): Lanthanoid compound (B): Reducing agent 2. The production method according to claim 1, wherein (B) the reducing agent is zinc, and a protonic acid coexists in the reaction.