JPH0586381B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing allyl ethers of phenols by effectively utilizing 1,2-dichloropropane.

More specifically, the decomposition products obtained by decomposing 1,2-dichloropropane, mainly consisting of allyl chloride and chloropropenes, are treated as a mixture with alkali metal salts of phenols, or with phenols and alkali metal hydroxides. This invention relates to a method for producing allyl ethers of phenols by reacting with.

In addition, the allyl ether of phenols itself or by subjecting the allyl ether to Claisen rearrangement to obtain C-allyl phenols,
Various intermediates for organic synthesis of Fine Chemicals,
It is a compound useful as a raw material for polymer production, a polymer modifier, etc.

(Prior art) 1,2-dichloropropane is a by-product (generally (5% to 15% of allyl chloride and propylene oxide), but its use is limited to demand as a cheap solvent and is hardly used effectively as a raw material for the chemical industry. is the current situation.

A method of dehydrochlorinating 1,2-dichloropropane by a method such as thermal decomposition to produce allyl chloride with high utility value (e.g.
135712), but this method has a selectivity of about 50 to 75% for allyl chloride (boiling point 45.1°C), and chloropropenes, that is, trans-1
- Chloropropene (boiling point 37.4°C), cis-1-chloropropene (boiling point 32.8°C), 2-chloropropene (boiling point 22.6°C) and other by-products are produced in considerable amounts; In particular, since the boiling point of the trans isomer is close to that of allyl chloride, it is quite difficult to purify to obtain highly pure allyl chloride, and thus it has little practical value.

As described above, the reality is that 1,2-dichloropropane is not utilized effectively in the true sense of the word.

(Problems to be Solved by the Invention) As mentioned above, chloropropenes can be extracted from a mixture of allyl chloride and chloropropenes obtained by decomposing 1,2-dichloropropane by ordinary means such as distillation. It is extremely difficult to economically separate and remove allyl chloride to obtain high purity allyl chloride that can be used as a raw material for the chemical industry.

Therefore, a method can be considered in which either allyl chloride or chloropropenes is selectively reacted in the mixture, and the other unreacted component is separated (so-called reaction separation method). However, for example, methods such as addition reaction of chlorine or hydrogen chloride, chlorohydrination reaction, etc. cannot achieve the purpose because allyl chloride and chloropropenes will co-react with each other.

Therefore, there is currently a need to develop a reaction separation method that can selectively react with either allyl chloride or chloropropenes and still yield a product with high utility value.

(Means for Solving the Problems) In view of the above situation, the present inventors have proposed a method for effectively utilizing 1,2-dichloropropane, in which allyl chloride obtained by decomposing 1,2-dichloropropane and chloro As a result of intensive studies on a method of selectively reacting only allyl chloride in a mixture with propenes and obtaining a product with high utility value, we found that the mixture can be directly reacted with alkali metal salts of phenols, or The inventors have discovered that only allyl chloride can be selectively converted to allyl ether of phenols by reacting with phenols and alkali metal hydroxides, leading to the completion of the present invention.

That is, the present invention provides a method for converting a decomposition product mainly consisting of allyl chloride and chloropropenes obtained by decomposing 1,2-dichloropropane into an alkali metal salt of a phenol, or a phenol and an alkali metal aqueous solution, as a mixture. This is a method for producing allyl ether of phenols, which is characterized by reacting with an oxide.

Next, the present invention will be explained in detail.

The decomposition products of 1,2-dichloropropane used in the method of the present invention include the method of thermally decomposing 1,2-dichloropropane in the presence or absence of a catalyst, sodium hydroxide, potassium hydroxide, hydroxide It can be easily obtained by various methods such as a method of reacting with an alkali such as calcium.

The decomposition product of 1,2-dichloropropane obtained by the above method usually contains 50 to 75% allyl chloride and chloropropenes (trans-1-
Chloropropene, cis-1-chloropropene, and 2-chloropropene (generic term) consists of about 25 to 50% composition. Depending on the decomposition method and decomposition rate of 1,2-dichloropropane, it may also contain by-products such as benzene and unreacted 1,2-dichloropropane. 1,2-
Dichloropropane (boiling point 96.4°C) can also be removed by distillation), but there is no particular problem even if these compounds are contained.

Moreover, it goes without saying that any product having the same composition as the decomposition product obtained in this way can be used in the method of the present invention.

Next, examples of the alkali metal salts of phenols used in the method of the present invention include phenol, o-
Cresol, m-cresol, p-cresol,
o-chlorophenol, p-chlorophenol,
Phenols represented by monovalent phenols such as 2,4-dichlorophenol and p-nitrophenol, polyvalent phenols such as catechol, resorcinol, hydroquinone, bisphenol A, bisphenol F, pyrogallol, and phloroglucin; and lithium; It can be prepared by reacting an alkali metal such as sodium or potassium, an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide, potassium hydroxide, or the like.

Moreover, instead of the alkali metal salts of these phenols, the various phenols mentioned above and alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, etc. can also be used in combination.

The ratio of the decomposition product of 1,2-dichloropropane to the alkali metal salt of phenols or the phenol and alkali metal hydroxide mentioned above is the stoichiometric amount in terms of allyl chloride in the decomposition product. It is best to use an equal amount or a slight excess of allyl chloride.

There is no need to use a reaction solvent, and the chloropropenes in the decomposition product of 1,2-dichloropropane have the effect of acting as a solvent. However, in general, chain or cyclic ethers such as diethyl ether, dibutyl ether, tetrahydrofuran, and dioxane, alcohols such as ethanol, n-propyl alcohol, and isopropyl alcohol, ketones such as acetone and methyl ethyl ketone, and various organic solvents thereof are used. Favorable reaction results are often obtained when an aqueous solution or the like is used as a solvent.

The decomposition product of 1,2-dichloropropane may be charged into the reactor together with other raw materials, or the decomposition product may be continuously supplied after the other raw materials are charged into the reactor in advance. Any method can be adopted.

The reaction temperature is usually preferably about 50 to 150°C.
Further, the reaction pressure is preferably about 0 to 10 kg/cm ² G.

After the reaction is complete, unreacted chloropropenes, unreacted allyl chloride, solvent, generated inorganic salts (alkali metal halides), etc. are removed using a combination of methods such as distillation and filtration to obtain the desired phenol. Allyl ethers of the following types can be obtained.

(Example) The present invention will be explained below in more detail with reference to Examples.

Reference example Thermal decomposition of 1,2-dichloropropane A quartz tube with an electric heater wrapped around it (inner diameter 2.5
1,2-dichloropropane was continuously charged from one end of the quartz tube at a flow rate of 400 g/hr while controlling the temperature inside the tube at 510°C.
Thermal decomposition of 1,2-dichloropropane was carried out.

The decomposition products that come out in gas form from the other end of the quartz tube are condensed in a condenser cooled with ice water, the hydrogen chloride contained is removed by water washing, and then dried, followed by simple distillation for decolorization. A decomposition product was obtained at a rate of 260 g/hr.

Analysis of the decomposition product by gas chromatography revealed that its composition was 60.5% by weight of allyl chloride, 34.7% by weight of 1-chloropropene (total of trans and cis forms), 2.0% by weight of 2-chloropropene, and 0.3% by weight of benzene. and 2.5% by weight of unreacted dichloropropane.

Example 1 In an autoclave equipped with a stirrer and a thermometer, 116 ml of the previously prepared sodium salt of phenol was added.
(1 mol) and 400 g of methyl ethyl ketone, and while controlling the internal temperature at 90°C, 139 g (1.1 mol as allyl chloride) of the thermal decomposition product of 1,2-dichloropropane obtained in the reference example was added over 1 hour. After continuous charging, the reaction was continued at the same temperature for an additional 4 hours.

After the reaction was completed, the autoclave was cooled to room temperature and the reaction product was taken out. Subsequently, after separating the by-product sodium chloride crystals, methyl ethyl ketone and unreacted chloropropenes, etc. were distilled off.
The evaporation residue was washed with water and dried to obtain 117 g (0.873 mol) of allyl phenyl ether.

Example 2 Completely the same method as in Example 1 except that 130 g (1 mol) of p-cresol sodium salt was used instead of the sodium salt of phenol in Example 1.
As a result of reaction and post-treatment under the following conditions, allyl-4
126 g (0.851 mol) of -methyl phenyl ether (ie allyl ether of p-cresol) were obtained.

Example 3 114 g (0.5 mol) of bisphenol A, 41.2 g (1.03 mol) of flaky sodium hydroxide, and 400 g of isopropyl alcohol were placed in the same autoclave as in Example 1, and while controlling the internal temperature at 90°C, the same procedure was carried out as in the reference example. After continuously charging 139 g (1.1 mol as allyl chloride) of the obtained thermal decomposition product of 1,2-dichloropropane over 1 hour,
The reaction was continued for an additional 6 hours at the same temperature.

Post-treatment was carried out in accordance with Example 1 (however, isopropyl alcohol was distilled off instead of methyl ethyl ketone), and as a result, 128 g (0.416 mol) of diallyl ether of bisphenol A was obtained.

(Effects of the Invention) As detailed above, the method for producing allyl ether of phenols of the present invention produces decomposition products mainly consisting of allyl chloride and chloropropenes obtained by decomposing 1,2-dichloropropane. is reacted as a mixture with an alkali metal salt of a phenol, or a phenol and an alkali metal hydroxide, thereby selectively reacting only allyl chloride in the decomposition product,
Allyl ethers of phenols with high utility value can be produced, and unreacted chloropropenes can also be obtained at a purity that can be used industrially.

Furthermore, in the method of the present invention, allyl chloride in the decomposition product of 1,2-dichloropropane provides reaction results comparable to commercially available pure allyl chloride.

Therefore, according to the present invention, 1,2-dichloropropane, which has not been used effectively in the past, can be used!
It can be used effectively in many ways, and has high industrial utility value.

Claims (1)

[Scope of Claims] 1. A decomposition product mainly consisting of allyl chloride and chloropropenes obtained by decomposing 1,2-dichloropropane is treated as a mixture with an alkali metal salt of a phenol, or a phenol and an alkali metal. A method for producing allyl ether of phenols, which comprises reacting with a hydroxide. 2. The method for producing allyl ether of phenols according to claim 1, wherein the decomposition product of 1,2-dichloropropane is a thermal decomposition product of 1,2-dichloropropane.