JPS61109784A - Production of arene oxide - Google Patents

Abstract

PURPOSE:The reaction of a polycyclic aromatic compound with a hypochlorite salt is carried out in a specific inert solvent under phase transfer conditions at specific temperature under reflux to produce the titled compound of high purity which is used as an intermediate of medicines in high yield economically with industrial advantage. CONSTITUTION:Under phase-transfer conditions, the reaction between a polycyclic aromatic compound such as phenanthrene, pyrene or benzo[a]pyrene and a hypochlorite salt such as sodium hypochlorite is conducted in an inert solvent such as chlorinated or nitrated hydrocarbon such as methylene dichloride or chloroform, at 35-55 deg.C under reflux to give an arene oxide. The phase transfer condition is made by using tetra-n-butyl ammonium chloride as a cata lyst.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention is directed to a method for producing allene oxide by hypochlorite oxidation of polycyclic aromatic compounds. Specifically, when a polycyclic aromatic compound is reacted with hypochlorite under phase transfer conditions, a chlorinated or nitrated hydrocarbon compound is used as an inert solvent, and the reaction temperature is refluxed at normal pressure or under reduced pressure. The present invention relates to an industrially advantageous method for producing allene oxide by carrying out oxidation while maintaining the temperature at 35 to 55°C.

Allene oxide is useful as an intermediate raw material for pharmaceuticals, agricultural chemicals, dyes, and various other industrial products, and has a wide range of uses.

[Conventional technology]

Allene oxide, particularly allene oxide, is a compound obtained by known methods. Examples are J, Am, Ch
@w, Soc, Magazine 1977 Vol. 99 No. 24 8121
As described in the miscellaneous text on pages 3 to 3, K domain polycyclic aromatic compounds were prepared using sodium hypochlorite and tetra-h-butylammonium bipurphate in a liquid-liquid independent system of chloroform solution and water. P at 10℃ or room temperature
It can be easily oxidized while keeping H at 8 to 9, and can be easily oxidized with a high yield of K and kana. However, in the above method, in order to achieve high yield, it is necessary to use 30 molar equivalents of sodium hypochlorite relative to the reaction substrate (K domain polycyclic aromatic compound), which is economically difficult. The above oxidation reaction is a large exothermic reaction, and in order to remove the reaction heat, it is necessary to oxidize while cooling on a water bath, and if the reaction is not controlled incorrectly, there is a risk of explosion, so it is technically difficult. However, it cannot be used as an industrial method.

[Problem that the invention seeks to solve]

As mentioned above, the known methods have economical and technical problems and are difficult to be used as industrial methods.

The present invention solves these problems and industrially advantageously produces allene oxide, 4? K y enanthrene-9,10-
The present invention provides a method for obtaining oxides, particularly by reducing the amount of hypochlorite used.
Furthermore, the present invention provides a method for safely obtaining allene oxide, particularly phenanthrene-9110-oxide, by efficiently removing reaction heat and overcoming technical difficulties.

[Means of problem solving]

As a result of intensive research aimed at solving these problems, the present inventors have established an industrially advantageous method for producing allene oxide by oxidizing polycyclic aromatic compounds with hypochlorite. In other words, the present invention involves the production of allene oxide by carrying out a liquid-liquid-independent reaction of a polycyclic aromatic compound with hypochlorite under phase transfer conditions, in the coexistence of a chlorinated or nitrated hydrocarbon compound as an inert solvent. , reaction, 35-55
It is carried out under reflux at normal pressure and - at a temperature in the range of °C, and at reduced pressure.
This method is the first known method to produce K-region allene oxide, which is characterized by using the heat of vaporization of the refluxing solvent to carry out the oxidation reaction while removing the heat of reaction. various problems have been solved.

[Action of the invention]

The polycyclic aromatic compound which is a raw material in the method of the present invention is contained in, for example, a tar fraction, and is easily found by means such as fractional distillation.

Examples of polycyclic aromatic compounds include phenanthrene, pyrene, pen:/[:a] l'rene, penz[8] anthracene, dibenz(a%h) anthracene, chrysene, phenanthroline, and acenaphthene. Since these are generally solids, it is necessary to use them in the method of the present invention by dissolving them in an organic solvent inert to the reaction.

As the organic solvent, chlorinated or nitrated hydrocarbon compounds are effectively used, and suitable examples include methylene dichloride, chloroform, ethylene chloride, trichlene, chlorobenzene, and nitrobenzene.

As mentioned earlier, the reaction of the present invention is based on removing the reaction heat using the heat of vaporization of the solvent, so it is an essential condition that the reaction be carried out at the reflux temperature of the solvent. . The reaction temperature is set at a temperature in the range of 35 to 55°C. The above organic solvents may be used alone to maintain the reflux temperature at 35 to 55°C, or the above organic solvents may be used as a mixture in an appropriate ratio without any problem in the reaction. In particular, in the present invention, methylene dichloride is the best #*.

If the reaction is carried out at a temperature exceeding 55° C., the hypochlorite used will decompose rapidly and the conversion rate will drop significantly, making it unsuitable. On the other hand, a temperature lower than 35° C. is undesirable because the reaction rate is slow and industrially uneconomical.

The method of the present invention requires that the reaction be carried out under phase transfer conditions, that is, using a phase transfer catalyst, such as tetra-n-butylammonium chloride, tetra-n-butylammonium bromide, tetra- n-Butylammonitum vinylphate, benzyltri-n-butylammonium chloride, benzyltri-n-butylammonium bromide, tri-n-octylmethylammonium chloride, N-lacrylpyridium chloride, etc. can be used. , tetra-n-butylammonium bromide, tetra-n-butylammonium bipurphate, oyohihenzil) I) -n-butylammonium 9
Muchloride is most preferred. The amount of the phase transfer catalyst used is 0.1 to 50 mol, preferably 0.5 to 10 mol, relative to the polycyclic aromatic compound. If the amount is less than 0.1 mol, the reaction will be slow, and if the amount exceeds 50 mol, it is economically unfavorable.

The pH of the reaction solution in the method of the present invention is in the range of 8 to 10, preferably 8.2 to 9.2, and if it exceeds this, the reaction will be slow (9), which is not preferred.

The hypochlorite used in the method of the present invention is generally used in the form of an aqueous sodium salt solution, but a bleaching powder may also be suspended in water. The effective chlorine concentration of the aqueous solution or suspension of hypochlorite is from 1 to 15, preferably from 5 to 13,6. Effective chlorine concentration! At low concentrations, the efficiency of the reaction equipment is poor, and the effective chlorine concentration is 15%.
If the concentration exceeds 100%, the decomposition of hypochlorite will be severe and both are unfavorable. The amount of hypochlorite used is 1.5 to 5.0%, preferably 1.5% to 1 mole of the polycyclic aromatic compound.
7 to 3.0% #. If the molar ratio is less than 1.5, the conversion rate may be low, and if the molar ratio exceeds 5.0, it is economically unfavorable.

The reaction time in the method of the present invention varies depending on the reaction conditions, but is from 1 minute to 5 hours, but the reaction time can be freely adjusted by changing the amount of catalyst used, reaction temperature, etc. be.

The reaction mode in the method of the present invention is a liquid-liquid independent system, and either a batchwise or continuous system is possible.

In liquid-liquid independent reactions, the stirring efficiency has a large effect on the reaction rate, and the reaction is generally carried out under high-speed stirring.

In the method of the present invention, since the reaction is carried out under reflux, the stirring efficiency is improved when the solvent boils, and the reaction can be carried out without high-speed stirring. After carrying out the reaction of the present invention, there are very few minerals and by-products, and allene oxide can be easily obtained in high yield by conventional unit operations such as liquid-liquid separation, water washing, 11-condensation, -filtration, and drying. be able to. Further, the oxide solution obtained by liquid-liquid separation and washing of the organic layer with water may be used as it is in the next reaction.

〔Effect of the invention〕

Thus, according to the method of the present invention, hypochlorite oxidation of polycyclic aromatic compounds, KJ:9, is possible to produce allene oxide in high yield and high purity, and economically and industrially. Therefore, it represents a major advance in this field of technology and application.

Next, the method of the present invention will be explained in more detail with reference to Examples. However, the following examples are not intended to limit the method of the invention.

Example 1 78.2 g (0.40 mol) of phenanthrene (M1 degree 91%), tetra-n-butyl in a cylindrical flask equipped with a reflux condenser, thermometer, addition funnel, PHIE < Ammonium bisulfate 1
．． 0 grams (o, o O3 moles), methylene dichloride 69
0 g, and 852 g (1.2 mol) of an aqueous solution of sodium hypochlorite with an available chlorine concentration of 104,
The temperature was raised to reflux temperature (40-43°C) while stirring.

Thereafter, stirring was continued and the same temperature was maintained until the end of the reaction.

Dripping funnel 35 salt @ 20 grams (0.19 mol)
was added dropwise over 20 minutes to adjust the pH of the reaction solution to 8.5 to start the reaction. When the reaction started, the pH of the reaction solution decreased, so the pH was kept at 8.5 ± 0.2 by dropping a 2N aqueous solution of sodium hydroxide and the reaction was continued for 1 hour @After the reaction was finished, the liquid was separated. The organic layer was washed with 100 g of water to obtain a methylene dichloride solution of phenanthrene-9,1O-oxide. As measured by internal standard method using gas chromatography, the conversion rate of phenanthrene was 100%, 72/threne-9.10-oxide was 9
It was produced in a yield of 6 molar width.

Example 2 In a 10 ton cylindrical flask equipped with a reflux condenser, thermometer, dropping funnel, PH electrode and stirrer, industrial sodium hypochlorite 1 with an effective chlorine concentration of 12.9% was added.
Add 651 grams (3.0 mol) and add 165 grams (0.30 mol) of #17 salt from the dripping port while stirring.
was added dropwise over 5 minutes to adjust PI to 9.0. Phenanthrene (91% pure i) 587/ram (3.0 mol) and tetra-n- Butylammonicum promide7.
25 grams (0,023 moles) were added over 20 minutes. Subsequently, 943 g (0.20 mol) of salt 17 was added dropwise over 5 minutes, and while adjusting the pH of the reaction solution to 8.7, it was heated on a water bath until it reached the reflux temperature (40-43°C). Thereafter, stirring and refluxing were continued until the reaction was completed. When the reaction starts, the pH of the reaction solution decreases, so the effective chlorine concentration is 12.9. Industrial sodium hypochlorite (PH12.5) 1
By dropping 982 grams (3.6 moles), the reaction proceeded while maintaining the pH of the reaction solution at 8.5±0.2. After adjusting the pH of the reaction solution to 8.7, add industrial hypochlorous acid). There was no need to heat the reaction mixture, and the reaction temperature was maintained at 42 to 43° C., and no problems were found regarding the removal of reaction heat. Approximately 2.5 to 3 to drip the entire amount of sodium hypochlorite
．． It took 0 hours. After dropping the entire amount, 2N-hydroxide was added to keep the pH of the reaction solution at 8.5 ± 0.2 for another 1 hour.)
The reaction was completed while dropping IJ Kum's water bath solution 70-. As measured by internal standard method using gas chromatography, the conversion rate of phenanthrene was 100%, and phenanthrene-9,10-oxide was produced in a yield of 98 molar width. As described above, under reflux, the reaction heat was removed and the two liquid layers were mixed very efficiently.

Example 3 In an apparatus similar to that in Example 1, methylene dichloride 69
Phenanthrene (91% purity) dissolved in 0g
) 78.2 grams (0,40 mol), tetra-n-butylammonium bromide 0.97 grams (o, o 0
3 mol) and 10 g of water were added thereto, and the temperature was raised while stirring until it reached reflux temperature (40 to 43°C). Thereafter, stirring and refluxing were continued until the reaction was completed. 17% salt a here! 42 grams (0,196 mol) and 521 grams of industrial sodium hypochlorite (O,S a
mol) were simultaneously added dropwise from different dropping funnels over a period of 2 hours. At this time, the pH of the reaction solution was maintained at 8.6±0.2. After dropping the entire amount, the P of the reaction solution was further increased for 1 hour.
Hf: Maintained at 8.6 ± 0.2 (2N aqueous solution of sodium hydroxide 11- was added dropwise to complete the reaction. As measured by internal standard method using gas chromatography, the conversion rate of phenanthrene was 100%. So Fenanthren-9
．． 10-oxide was produced in a yield of 97 molar width.

Example 4 A device similar to that in Example IK was used with an effective chlorine concentration of 8.5.
168 grams of industrial sodium hypochlorite (0
, 20 mol) was added thereto, and while stirring, 9.5 grams (0,044 mol) of Chef's pot salt I1 was added dropwise over 5 minutes through the dropping funnel to adjust the pH to 9.0. Next, here are 173 grams of industrial methylene dichloride and 18 grams of industrial ethylene dichloride.
Dissolved in a mixed solution of 7 grams, 38.5 grams (o, zo mol) of phenanthrene (purity 92.5) and 0.48 grams of tetra-n-butylammonitum bromide.
3 grams (o, o 1 smol) were added over 5 minutes.

Subsequently, 5.3 grams (0,025 moles) of 17% hydrochloric acid
The reaction solution was added dropwise over a period of minutes, and while adjusting the pH of the reaction solution to 8.7, it was heated on a hot water bath until it reached the reflux temperature (53°C), and stirring and refluxing were continued until the reaction was completed. When the reaction starts, the pH of the reaction solution decreases, so adjust the pH to approximately 12 in advance.
of the reaction solution by adding dropwise 235 g (0.28 mol) of sodium hypochlorite with an available chlorine concentration of 8.5%. ) [ was maintained at 8.5±0.2 while the reaction proceeded. After dropping the entire amount of sodium hypochlorite (takes approximately 30 minutes), the pH is maintained at 8.5± for another 1 hour.
2N-sodium hydroxide water to keep it at 0.2 #! *5
- was added dropwise to complete the reaction. Fennans v as measured by internal standard method using gas chromatography
Phenanthrene-9,
10-oxide was produced in a yield of 95 mol.

Patent applicant Nippon Shokubai Kagaku Kogyo Co., Ltd. Procedure Amendment V (
Voluntary) December 61, 1982 Director General of the Patent Office Takashi Shiga1, Indication of the case Patent Application No. 230271 of 19822, Name of the invention Process for producing allene oxide3, Person making the amendment

Claims (6)

[Claims] (1) When producing the corresponding arene oxide by reacting a polycyclic aromatic compound with hypochlorite under phase transfer conditions, the polycyclic aromatic compound is chlorinated or nitrated as an inert solvent. 35°C to 55°C in the coexistence of hydrocarbon compounds
A method for producing allene oxide, characterized in that the reaction is carried out under reflux at a temperature in the range of . (2) The method according to claim (1), wherein the reaction is carried out under normal pressure or reduced pressure. (3) The polycyclic aromatic compound is at least one member selected from the group consisting of phenanthrene, pyrene, benzo[a]pyrene, benz[a]anthracene, dibenz[a,h]anthracene, chrysene, phenanthroline, and acenaphthylene. A claim characterized in that it is a species (
1) or the method described in (2). (4) Claims (1), (2), or (3) characterized in that the hypochlorite is sodium hypochlorite.
) method described. (5) The chlorinated or nitrated hydrocarbon compound as the inert solvent is at least one selected from the group consisting of methylene dichloride, chloroform, ethylene chloride, trichlene, chlorobenzene, and nitrobenzene. The method according to claim (1), (2), (3) or (4). (6) The target allene oxide is phenanthrene-9
, 10-oxide, the method according to claim (1), (2), (3), (4) or (5).