JPH01283279A - Production of epoxidie - Google Patents

Abstract

PURPOSE:To facilitate the separation of a V2O5 catalyst from a reaction product and to obtain an epoxide in high yield and purity by reacting a specific monohydric alcohol with tertbutyl hydroperoxide at room temperature using V2O5 as a catalyst. CONSTITUTION:The objective compound of formula II useful as a raw material for glycols, ethers, cyclic acetals, etc., can be produced by reacting 100mol of a monohydric alcohol of formula I (R1 is H or CH3; R2 is cyclohexyl, n- dodecyl, phenyl, 3-butenyl or 4-methyl-3-pentenyl) such as geraniol with 50-300mol of tertbutyl hydroperoxide in the presence of 100-500mol of a V2O5 catalyst in a solvent (e.g., methylene chloride) preferably in an inert gas atmosphere such as N2 gas at room temperature (about 10-35 deg.C) for about 2hr and purifying the product by column chromatography, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing epoxides. More specifically, the present invention relates to a method for producing epoxides useful as raw materials for compounds such as glycols, ethers, and cyclic acetals.

[Prior Art] In recent years, various studies have been conducted on epoxide manufacturing methods, and among these, the so-called Sharpless (S
harpress) oxidation method (K.B. Sharpless (K, B, 5harpress)).

Journal of the American Chemical Society (J, Am, Chem, 'Soc,), 102.5
974 (1980) and 103.484 (1981)
) is an asymmetric product with high yield and high optical purity by regioselectively and stereoselectively oxidizing the double bond near the hydroxyl group of allyl alcohol, which has two double bonds, such as geraniol. This method is particularly popular because it allows epoxide to be mixed.

However, the sharpless oxidation method has a major drawback in that it is extremely difficult to separate the epoxide product from the catalyst after the reaction.

On the other hand, as a method for easily separating the product epoxide and the catalyst after the reaction, for example, 1-octene is
There is a method to obtain an epoxide by reacting with tert-butyl hydroxyperoxide in the presence of an i-3iO2 solid catalyst (R.A. Jelton (R, A, 5h).
eldon), Journal of Molecular Catalysis (J, Mol.

Cat, ), 71107 (1980)). According to this method, it is easy to separate the product from the catalyst, and the catalyst can be reused even if it is deactivated. reaction conditions are required.

[Problems to be Solved by the Invention] In view of the above-mentioned prior art, the present inventors have discovered that it is possible to easily separate the product after the reaction from the catalyst, etc., and that it is possible to easily separate the product after the reaction from the catalyst, etc. No conditions required,
In order to develop an epoxide manufacturing method with excellent productivity,
As a result of intensive research focusing on epoxide reactions of olefins using solid inorganic metal oxides as catalysts, we have discovered a completely new method for producing epoxides that satisfies all of the above requirements, and have completed the present invention.

[Means for Solving the Problems] That is, the present invention has the general formula (I): (wherein R+ is a hydrogen atom or a methyl group, R2 is a cyclohexyl group, an n-decyl group, a phenyl group, a 3-butenyl group, or General formula (■) characterized in that a monohydric alcohol represented by 4-methyl-3-pentenyl group is reacted with tert-butyl hydroperoxide in the presence of v205: (wherein R1 and R2 are The present invention relates to a method for producing an epoxide represented by (same as above).

[Function and Examples] According to the method for producing an epoxide of the present invention, the general formula (■); or 4-methyl-3pentenyl group) is a monohydric alcohol represented by the general formula (I) (wherein R1 and R2 are the same as above);
It can be obtained by reacting with tertiary-butyl hydroperoxide (hereinafter referred to as TBHP) in the presence of TBHP.

The V2O5 is a metal oxide that acts as a solid catalyst. Other than the above ■205, for example, T i 02,'
When a metal oxide such as IrJO3 or SiO2 is used as a solid catalyst, epoxide cannot be absorbed at room temperature. The above-mentioned 205 has the property of selectively epoxidizing the monohydric alcohol represented by the general formula (■) in a short time even at room temperature, and this fact was discovered for the first time by the present inventors. It was. ■When using 205, the reason why the -hydric alcohol is epoxidized in a short time even at room temperature is not yet clear, but it is probably because the hydroxyl group of the -hydric alcohol and T
It is thought that the reaction progresses as BI(P interacts with the surface of 205).

The method for producing epoxide of the present invention will be explained below.

The blending ratio of TBIIP to the monohydric alcohol represented by (1) is usually 50 to 800 parts by mole, preferably 150 to 800 parts by mole per 100 parts by mole of the alcohol.
It is 250 mole parts. If the blending ratio of T B HP is less than 50 mole parts, a large amount of unreacted monohydric alcohol tends to remain, and if it exceeds 300 mole parts, diol or decomposition products tend to be produced. be.

In addition, V2O used as a solid catalyst in the present invention
The blending amount of No. 5 is 100 to 500 mol parts, preferably 250 to 350 mol parts, based on 100 mol parts of the above-mentioned -hydric alcohol. When the amount of V2O5 blended is less than 100 mole parts, a large amount of unreacted monohydric alcohol tends to remain, and when it exceeds 500 mole parts, diols or decomposition products tend to be produced.

The -hydric alcohol, T B II P and V2O5
After weighing a predetermined amount, the ingredients may be added all at once, or after mixing two of these ingredients, the remaining ingredients may be added, and the present invention is not limited to such a preparation method. .

In addition, when reacting the above-mentioned -hydric alcohol and T B HP, it is desirable to replace the atmosphere with an inert gas such as nitrogen gas or argon gas in advance.

A solvent is used when charging the -hydric alcohol, T B HP and V2O5, and examples of such a solvent include methylene chloride. There is no particular limitation on the amount of the solvent, and it is preferably adjusted as appropriate depending on the amount to be charged.

As soon as the -hydric alcohol, TBHP and V2O5 are mixed, the reaction proceeds rapidly. In the present invention, the reaction proceeds at room temperature and is completed in about 2 hours, although it varies depending on the amount charged. Note that the above-mentioned room temperature refers to a temperature of about 10 to 35°C, and when the temperature is lower than 10°C, the reaction does not proceed sufficiently, and when it is higher than 35°C, the diol or decomposition occurs. tends to produce products.

After the reaction is complete, the product is filtered, the filtrate is taken out and washed with saturated brine, the solvent is removed and concentrated, and the crude product is then dried using, for example, anhydrous sodium sulfate. It will be collected.

The crude product thus obtained is recovered as a purified product, for example by passing it through column chromatography.

Next, the method for producing epoxide of the present invention will be explained in more detail based on Examples, but the present invention is not limited to these Examples.

Example 1 and Comparative Examples 1 to 5 Geraniol 0.17 ml (1 mmol), metal oxide 0.5 g shown in Table 1, 3M-TBHP toluene solution 0.67 ml (TBHP concentration: 2 mmol)
1) and CH2C1C121O were added to a 20 ml eggplant-shaped flask whose interior was purged with nitrogen gas, and the mixture was stirred and reacted at room temperature (approximately 20° C.) for the reaction time shown in Table 1. Next, the contents of the flask were taken out and subjected to column chromatography (n-hexane/acetone = 411 (
It was purified using a mixed solution (volume ratio). Next, for the products whose products were changed, the products were identified according to the following method.

(Measurement of 'H-NMR spectrum) Measurement was performed using a 111-NMR spectrometer PM, model X60SI (60 MHz) manufactured by JEOL Ltd.

In addition, CDC63 was used as a solvent, and tetramethylsilane was used as an internal standard.

(Measurement of IR spectrum) Using an infrared spectrophotometer model IRA-1 manufactured by JASCO ■
It was measured by the aCf liquid film method and the KBr tablet method.

(Measurement of mass spectrometry values) (■ Hitachi Seisakusho new product, gas chromatography eea-ao
mold (PID) and stainless steel column (diameter: 3 cm
, Length: 1m1 Column packing material: Made by Nippon Chromato Kogyo ■,
5ilicon 0V-173%).

[Margin below (Identification of epoxide obtained in Example 1) (a) IH-
NMR spectrum (CDCN3) δ (ppm):
1.30 (s, 3H), 1.47 (m, 2H), 1.
61 (s, 3H), 1.68 (s, 311), 2.08
(m, 2H), 2.49 (b, IH), 2.98 (m,
LH), 3.75 (m, 211), 5.08 (m, LH
) (b) II? Spectrum (NaCN liquid film method) ν (cm
-1): 3400 (011), 29 [10 (CH
3), 2920(-C)I2), 1θTo <;c
-c (□), 1030 (; CH-CH2-OH)
, 1240.850.750 (epoxide C-0-C) (tX) Mass spectrometry value publication 170 From the above results, TiO2,5j02 as a metal oxide
It can be seen that when WO3 is used, the product cannot be obtained at all, and only when 205 is used, the product can be obtained.

It is also seen that no product was obtained without using T B HP.

-11 Example 2 In a 100 ml flask equipped with Starcy, 2052 g of V, 240 ml of purified C112C, geraniol O, [19 ml (0.62 g: 4 mmol)
), 2.7 ml of 3M) toluene solution of TBHP (
TBIIP (8 mmol) was charged under nitrogen flow and stirred at room temperature (approximately 20'C) for 2 hours.

After the reaction was completed, the contents were immediately taken out and filtered to collect the filtrate. Next, the filtrate was washed twice with water, and CthC12
After the layers were extracted and dried overnight using anhydrous Na2SO4, the solution was concentrated to yield 0.85 g of crude product.

The obtained crude product was passed through column chromatography (n-hexane/acetone-4/1 (volume ratio) mixed solvent) to obtain 0.49 g of product. The yield of the product obtained is 7
It was 2%. The identification data of the product obtained is shown below.

(a) 111-NMR spectrum (CD0g3) δ(
ppffl): 1.30 (s, 3H), 1, 47 (
m, 2H), 1.61(s, 3)1), l, ti
8 (s, 311), 2.08 (m, 2] (), 2
．． 49 (b, 111), 2.98 (m, l] (), 3.
75 (m, 21+), 5,08 (m, LH) (b) IR spectrum (NaCj liquid film method) ν (cm
-1): 3400 (OH), 2960 (CI-I
3), 2920(-CH2-), te7o<
:; c-c < , □), cH-c+2- at 1030
on), 1240.850.75[1(Epoxide C-0-C)
(I\) Mass spectrometry molecular weight: 170 Example 3 In Example 2, geraniol O, 17ml (1mm
ol) instead of nerol O, f39ml (0,62
0.35 g of the product nerol oxide was obtained in the same manner as in Example 1 except that 4 mmol) was used. The yield of nerol oxide obtained was 52%.

The identification data of nerol oxide obtained is described below.

(a) 'H-NMR spectrum (CDCN3) δ(p
pm): 1.33 (s, 3H), 1.69 (s, 3H)
), 1.76 (s, 3H), 2, 23 (d, 2
)1),2.8[l(b,1)1),3,OB(m,L
H), 3.80 (m, 2H), 5.16 (m, IH),
(b) IR spectrum (Na0g liquid film method) ν (cm-1
): 3400 (011); 2950 (CH3)
;2!1110(CH2);1870('CC-
CCH), 1025 (CH-CH2-011);
1210.830,750 (Epoxy FC-0-C)C
\) Mass spectrometry molecular weight = 170 Example 4 Cinnamyl alcohol 0.77ml (0.80g: [
in+mol), 3M-TBHP) toluene solution 4 m
l (TBHP: 12 mmol), V20S 3g
and CH2C12 [10 m1 nitrogen-substituted 10
The yield of 0.45 g of the product was 50% in the same manner as in Example 1 except that it was placed in a 0 ml eggplant-shaped flask.

The identification data of the product obtained is shown below.

(a) IH-NMR spectrum (CDCN3) δ(p
pm): 2.55 (b, 111), 3.25 (m, LH
), 3.74 (IH), 3.95 (u+, 2H),
7.29 (s, 5H), (b) IR spectrum ν (cm −' ): 340D (OH), 3000 (−
C1 (2-), 1460 (-CH2-), 700 (Q)
, 1200.880,7[io(epoxide C-0-C
) (/Xun mass spectrometry molecular weight = 150 Examples 5 to 7 and Comparative Examples 6 to 9 1 mmol of raw materials shown in Table 2, 2 mmol of TBHP
, V2050.5 g and chloromethylene loml were added to a 20 ml eggplant-shaped flask whose interior was substituted with nitrogen, and the mixture was stirred and reacted at room temperature (approximately 20° C.) for the reaction time shown in Table 2. The reaction product obtained next was identified in the same manner as in Example 1. The results are shown below.

(Identification data of product obtained in Example 5) (a) 'H
-NMR spectrum (CDCL3) δ (ppm) 1
．． 30 (s, 3H), 1.47 (m, 2H), 1.61
(s, 3H), 1.68 (s, 3H), 2.08 (m,
2H), 2.49 (b, 1) I), 2,98 (m, LH
), 3.75 (m, 2H), 5.08 (m
, 1ll) (mouth IIR spectrum ν (cm-1) 3400 (leaf), 29+30 (C11
3) 2920 (-CH2-), 1670 <;c-c
4>, 1030 (;Cl-CH2-oll),
1240, 850, 750 (Epoxide C-0-C) (l\) Mass spectrometry molecular weight: 170 (Identification data of product obtained in Example 6) (a) I
H-NMR spectrum (CDCI!3) δ (ppm)
1.33 (s, 3H), 1.69 (s, 3H) 1.7
8(s, 3t(), 2.23(d, 2H), 2.60(
b, 111), 3.06 (m, LH), 3.80 (m
, 2H), 5.1B (m, LH) (b) IR spectrum ν (cm-1) 3400 (OR), 2950 (CH3
)2910(-C112-), 1θ7o <;C-C
Cn) 1025 (N Cll-CH2-0H), 12
IH
-NMR spectrum (CDC#3) δ (ppm) 2
．． 55 (b, 1ll), 3.25 (m, 1ll),
3.74 (m, LH), 3.95 (m, 211), 7.
29(s, 51() (b) IR spectrum ν(cm-1) 3400(011), 3000(-C
H2-), 880.760 (epoxide C-0-C) (
/ ~ Publication of mass spectrometry values 150 [Blank below] -19 = As is clear from the above results, the epoxidation reaction proceeds when the allyl position is a hydroxyl group, but when the allyl position is an ester or aldehyde group. In some cases, it can be seen that the reaction does not proceed.

Note that in Comparative Example 4, the yield was determined by a gas chromatogram of commercially available styrene oxide.

[Effects of the Invention] The method for producing epoxide of the present invention does not require reaction conditions such as heating, and a specific monohydric alcohol is heated at room temperature.
The epoxide can be extracted very simply by simply reacting it with T B HP in the presence of the epoxide, and the catalyst (205) can be easily separated from the obtained epoxide, making it possible to obtain a highly pure epoxide. This is an excellent method.

Claims (1)

[Claims] 1. General formula (I): ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1 is a hydrogen atom or a methyl group, R^2 is a cyclohexyl group, an n-decyl group, General formula (II) characterized in that a monohydric alcohol represented by a phenyl group, 3-butenyl group or 4-methyl-3-pentenyl group is reacted with tert-butyl hydroperoxide in the presence of V_2O_5 : ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) A method for producing an epoxide represented by (in the formula, R_1 and R_2 are the same as above).