JPS58157738A - Production of o-methallyloxyphenol - Google Patents

Abstract

PURPOSE:The etherification reaction between catechol and methallyl chloride is carried out in a water-ketone mixed solvent in the presence of a specific base and an iodide of alkali metal as catalysts to produce selectively the titled compound used as starting compound of carbofuran insecticides. CONSTITUTION:In the production of o-methallyloxyphenol by reaction between catechol and methallyl chloride, a catalyst consisting of a base selected from car bonates, bicarbonates of alkali metals and alkaline earth metals such as potassium bicarbonate and of an iodide of an alkali metal such as sodium iodide as well as a mixed solvent consisting of a ketone of R<1>COR<2> (R<1> is alkyl; R<2> is alkyl, phenyl, R<1> and R<2> bind to form 4-8C alkylene where acetone, methyl ethyl ketone and diethyl ketone are excluded) such as cyclohexanone, and of water are used. EFFECT:The recovery of unreacting starting materials and catalyst can be done easily.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improved method for producing ortho-methallyloxyphenol using catechol and methallyl chloride as raw materials.

Orthometallyloxyphenol is a compound known as a raw material for carborane insecticides, and the rearrangement and cyclization reactions of this compound result in 2,3-dihydro-, which is a raw material for agricultural chemicals.
It is known that 2,2-dimethyl-7-hydroxybenzofuran is produced.

Conventionally, various methods for producing ortho-methallyloxyphenol (hereinafter referred to as monoether) using catechol and methallyl chloride as raw materials have been developed, but these conventional methods have a low yield of the desired monoether. or, even if the yield is high, there are many by-products of orthodimethallyloxybenzene (hereinafter referred to as diether), oxidation of catechol, or formation of polymers such as dimers, which is economically disadvantageous. .

That is, etherification of monohydroxybenzene such as thiphenol is usually easily carried out in good yield without any particular difficulty. In the etherification of dihydroxybenzene such as Shikashi catechol, both of the two hydroxy groups 3-1 can participate in the etherification, so selective etherification of only one hydroxy group is extremely difficult. Furthermore, when the etherification reagent is relatively unreactive such as an alkyl derivative, the alkylation reaction to the benzene nucleus is small;
When allyl derivatives, particularly methallyl chloride, which are more reactive than alkyl derivatives, are used as an etherification agent, an alkylation reaction of the benzene nucleus occurs, and control of this reaction is extremely difficult. Therefore, the formation of diethers and aromatic alkylated derivatives leads to a decrease in the yield of monoethers and the production of mixed products, and it is difficult and economically disadvantageous to separate and produce monoethers from this mixture. The conventional technology for producing the monoether of the present invention from catechol and methallyl chloride is as follows.

(1) Japanese Patent Publication No. 4L-12263 (U.S. Patent No. 3.4)
74.171) In the most elementary technique, catechol and methallyl chloride are reacted in equimolar amounts in the presence of 2CO3 and Kl in ~4-dry acetone, and the mixture is allowed to react under reflux for 30 hours. , ortho-methallyloxyphenol was obtained, but the amount of acetone, base, and catalyst used was not considered at all, and the yield was as low as 45%, so how could the production of diether be suppressed? There is no indication at all whether the desired monoether can be obtained in high yield.

(2) Unexamined Japanese Patent Publication No. 5O-95230 (U.S. Patent Nos. 3 and 9)
27.1'18) This method describes the selective monoetherification of dihydroxybenzene, combining hydroxyphenol and an alkylating agent with sulfoxide or sulfone groups in the presence of an alkali hydroxide or an alkaline earth metal oxide. Alternatively, the reaction is carried out in a dipolar neutral medium containing an amide group. However, this method uses a specific solvent with a relatively expensive and high boiling point as mentioned above, and referring to the various examples described in the specification, the amount of carbon dioxide per mole of starting material catechol is at most It is understood that selective monoetherification was achieved using 0.5 moles of methallyl chloride. However, in such a method, the yield of monoether is necessarily less than 50%, and in practice it is less than 40%.
The yield is low, less than %. Furthermore, it has the disadvantage that a delicate and expensive separation process is required to recover expensive unreacted catechol from the reaction mixture.

(3) JP-A-54-1064.38 (German Published Publication No. 2,845,429) This method attempts to avoid the disadvantages associated with the use of the overused catechol, but the amide group.

It is characterized in that an aprotic solvent containing sulfoxide groups, ether groups, etc., particularly N-methylpyrrolidone, is used as the solvent, and a specific amount of alkali metal carbonate or bicarbonate is used. However, this method produces a relatively large amount of diether as a by-product, and separating the monoether from the selected solvent by distillation is problematic; the monoether is thermally unstable, and the solvent has a high boiling point. Therefore, it is difficult.

(4) JP-A-55-7291 This method involves the preparation of specific quaternary ammonium derivatives or phosphonium derivatives in a two-phase reaction medium consisting of a mixed solvent of water and a water-immiscible inert organic solvent with a boiling point of 50°C or higher. Although this method is characterized by reacting catechol and methallyl chloride in the presence of catechol, it generally has a low monoether yield based on the starting catechol and also requires the use of special quaternary ammonium derivatives or phosphonium derivatives as mentioned above. It must be used as a transfer catalyst.

(5) JP-A-55-76833 This method consists of quite complicated steps, in which two phases exist in the first region, one being an organic solvent and the other being water, and a base and a quaternary ammonium derivative or phosphonium After mixing with the derivative, the organic layer is separated from the aqueous phase, and the monoether is obtained by heating the organic layer to the reaction temperature in a second region using a strainer.However, this method basically consists of the above-mentioned =7- This method is the same as the method described in JP-A-55-7291, and uses a special quaternary ammonium derivative or phosphonium derivative, and the reaction is performed separately in the first and second regions, making the operation complicated. Furthermore, referring to Examples, the yield based on converted catechol is about 90%, but the conversion rate of catechol is all about 60% or less.

(6) JP-A-56-29584 This method uses a polyhydroxyalkyl ether containing at least one OH group as a solvent, a base such as sodium carbonate or sodium bicarbonate, and sodium dithionite as a reducing agent. , is a monoether production method that removes CO□ gas and water, but it uses a special polyhydroxyalkyl ether as a solvent, and the 2,3-dihydro- It is used as a raw material for the production of -2,2-dimethyl-7-benzofuranol. However, in this method, unreacted 8-catechol is transferred to the next step and kept at a high temperature of about 180°C, making it difficult to recover and reuse it.

As described above, conventional methods for producing monoethers use relatively expensive and high-boiling solvents, or use specific quaternary ammonium derivatives or phosphonium derivatives through two-phase heterogeneous reactions. Both have their own drawbacks as mentioned above.

The purpose of the present invention is to perform a simple operation using a homogeneous reaction using an inexpensive and easily available mixed solvent of ketones and water, without using any special quaternary ammonium derivatives, phosphonium derivatives, etc. An object of the present invention is to provide a method for selectively producing the monoether of the present invention.

Another object of the present invention is to provide a method for producing the monoether of the present invention in which unreacted raw materials and catalysts can be easily recovered and reused, and post-treatment of the reaction solution is extremely easy.

The most distinctive feature of the present invention is that the etherification reaction is carried out in a water-ketone mixed solvent.

When a ketone solvent alone is used, the expensive iodide contained in the reaction solution is separated as a precipitate. However, it is very difficult to selectively extract iodide from the precipitate. Furthermore, regeneration of unreacted energy remaining in the ketone solvent requires a troublesome process, which is not desirable. The situation changes completely when water is added to the ketone solvent to carry out the etherification reaction. That is, by adding water, the catalyst and base are dissolved in the solvent, so that even with a small amount of catalyst, the etherification can be completed in a short time.

As the reaction progresses, the reaction solution separates into two layers: an organic layer containing ethers and an aqueous layer containing unreacted catechol and expensive iodide. After removing the ketone and unreacted methallyl chloride by concentration, the organic layer can be distilled under reduced pressure to easily obtain a high-quality monoether. On the other hand, most of the unreacted catechol and iodide contained in the aqueous layer can be easily recovered because there is no need for regeneration treatment, which is unique. Note that it is of course possible to reuse the unreacted base remaining in the aqueous layer. In the present invention, it is usually clever to add the consumed base and reuse it after removing the chloride precipitate.

In the present invention, it is preferable to separate the reacted mixture into an aqueous layer and an organic layer, and to use the aqueous layer containing the catalyst again in the reaction after treatment.

As a method for treating the aqueous layer described above, for example, (a) the chloride produced in the aqueous layer is cooled, filtered and separated as a solid, and then a raw material base is newly added.

(b) Add the raw material base to the aqueous layer, and then chloride is separated as it is or cooled and solidified.

(c) The chloride produced in the aqueous layer is sodium carbonate.

Sodium bicarbonate or sodium hydroxide is added to cause an exchange reaction to form the raw material base and sodium chloride, and sodium chloride is precipitated using the difference in solubility caused by changes in lagoonal temperature, followed by filtration.

etc. can be mentioned.

In the present invention, the amount of water and ketone used as a solvent is preferably 1 to 10 parts by weight of water and 1 to 10 parts by weight of ketone per 1 part by weight of catechol. carbonate.

Mention may be made of bicarbonates or bicarbonates of alkaline earth metals, specific examples of which are 2CO3 and Na2CO3.

K, HCO3, NaHCo3, Ca (HCO3)
2 etc. can be exemplified. An alkali metal iodide can be used as the straining catalyst, and a specific example thereof is KI.

Na1 etc. can be mentioned. The alkali metal carbonate and alkaline earth metal bicarbonate are usually in the range of about 0.43 to 1 mol, preferably about 0.04 to 1 mol of catechol.
The alkali metal bicarbonate is usually used in a range of about 0.6 to 3 moles, preferably about 0.8 to 1.0 moles, per mole of catechol.
It is used in a range of 4 moles. Further, the alkali metal iodide is usually used in an amount of about 0.01 to 1 mole, preferably about 0.3 to 0.7 mole, per mole of catechol.

The ketone used in the present invention has the general formula % (wherein R is an alkyl group having 1 to 6 carbon atoms, R2 is an alkyl group having 1 to 6 carbon atoms or a phenyl group,
2 is bonded to represent an alkylene group having 4 to 8 carbon atoms. (excluding acetone, methyl ethyl ketone, and diethyl ketone).

Preferred specific examples include methyl isobutyl ketone, dipentyl ketone, cyclohexanone, ayatophenone and the like.

In the present invention, the reaction is preferably carried out at a temperature of about 50-150°C. In the case of a reaction under pressure, the pressure is not particularly limited because the type of M medium and the reaction W + ii degree r (therefore, the pressure varies greatly).

Note that the present invention can be applied to either a batch method or a continuous method.

Next, embodiments of the present invention will be specifically explained.

In the present invention, catechol, water and ketone solvents, bases, catalysts, and methallyl chloride may be mixed at cold temperature and then added at a reflux width. Even if the refluxed metallyl chloride was gradually added, it would not work.

As the reaction progresses, the reaction solution separates into two layers: an aqueous layer and an organic layer containing monoether. The aqueous layer contains unreacted catechol, unreacted base and catalyst, as well as chloride produced by the reaction; however, the aqueous layer is reused. (2) After separation of the produced chloride by filtration, a new raw material base is added and then reused as a raw material. ■ Add the raw material base, then chloride as is or cool and solidify 1rJ4
Separate as a thing. The aqueous layer is then reused. α) The produced chloride is sodium carbonate, sodium bicarbonate, or hydroxide)) Add IJ cum to perform an exchange reaction to form the raw material base and sodium chloride, and precipitate the trichum to be chlorinated using the solubility difference due to temperature change, Perform filtration and separation. The water layer is reused. The organic layer is concentrated to recover the solvent ketone and methallyl chloride. On the other hand, the desired monoether is isolated from the concentrate by distillation under reduced pressure.

By the method of the present invention, the conventional problems of recovering unreacted catechol and catalyst have been solved at once.

It is well known that catechol is sensitive to heat due to its nature. Even if it is possible to recover catechol by extraction, prolonged heating causes deterioration of the catechol during subsequent solvent removal. In this respect, the present invention is an extremely excellent method because it does not require a complicated process of extraction and extraction solvent recovery, and does not cause deterioration of catechol due to heating.

Next, the present invention will be explained with reference to Examples.

Examples 1 to 3 5 g (45, s mmol) of catechol, water, and ketone were added to a glass reactor with a capacity of 1.00 m/m equipped with a width meter and a stirring device, and then a base and a catalyst were added and stirred, and the system was stirred. was made into a nitrogen gas atmosphere. This mixture is heated, and at a predetermined temperature, methallyl chloride 4.12y (45,5
mmol) was added dropwise over 30 minutes, and the reaction was continued at a predetermined temperature. After the reaction, the mixture was cooled and the oil and water layers were analyzed by high performance liquid chromatography, and the results shown in Table 1 were obtained.

The oil layer was washed with water, dried, and distilled under reduced pressure, and the identification of monoether and diether was confirmed by measuring the NMR spectrum and mass spectrum of the fraction.

The reaction results are shown as yield, selectivity, and mono/di ratio.

(2) Yield is the number of moles of monoether produced relative to the number of moles of catechol used in the reaction, expressed as a percentage.

(2) Selectivity is the number of moles of monoether produced relative to the number of moles of catechol consumed, expressed as a percentage.

■ The seven/di ratio indicates the number of moles of the monoether produced relative to the number of moles of the by-product diether.

Table 1 (from here on) Patent applicant: Otsuka Chemical Co., Ltd. Agent
Patent Attorney 1) Iwao Mura 19- Procedural Amendment (Voluntary) April 23, 1980 Commissioner of the Patent Office '66 Itsuki 15.1, Indication of the Case 1980 Patent Application No. 41872 3, Amendment Relationship with the case of the person who made the amendment Patent applicant Otsuka Chemical Co., Ltd. 4, attorney 6, number of inventions increased by amendment Contents of amendment 1 The scope of the patent claims is amended as shown in the attached sheet.

2. From the bottom of page 3 of the specification, the first line ``Subject'' is corrected to ``Improvement.''

3 Line 4 from the bottom of page 11 of the specification and line 2 from the bottom of page 12 “
Delete "unreacted catechol" and "unreacted catechol" respectively.

4 Line 4 from the bottom of page 15 of the specification “Unreacted catechol”
Delete certain.

5. In the specification, page 16, line 10, "from the concentrated liquid" is replaced with "After removing unreacted catechol from the concentrated liquid by washing with water,
” he corrected.

6. Add 1 and reflux condenser next to ``stirring device'' on page 17, line 7 of the specification.

7. Replace the phrase “alkaline earth” on page 6, line 11 of the specification with “
"alkaline earth metals".

8 Claim (1) characterized by the statement "by homogeneous reaction" on page 10, line 11 of the specification (1) When reacting catechol and methallyl chloride, the following C is used together with the base and catalyst shown in A and B below. A method for producing ortomecrylogycyphenol, which is characterized by using a mixed solvent of ketone and water shown below.

A The base is an alkali metal carbonate, bicarbonate or alkaline earth metal bicarbonate.

B The catalyst is an alkali metal iodide.

C ketone is a general 2 RICOH,2 (in the formula, R1 has a carbon number of 1
-6 alkyl group, R12 represents an alkyl group having 1 to 6 carbon atoms or a phenyl group, and R1 and R2 combine to represent an alkylene group having 4 to 8 carbon atoms. (excluding acetone, methyl ethyl ketone, and diethyl ketone).

(2. According to claim 1, the reacted mixed liquid is separated into an aqueous layer and an organic layer, and the aqueous layer containing the catalyst is directly used for the reaction. A method as claimed in claim 1.

(3) The method for treating an aqueous layer according to claim 2 includes () cooling the chloride generated in the aqueous layer, filtering it as a solid substance, separating it, and then adding a new raw material base. Become.

←) It consists of adding a raw material base to the aqueous layer, and then separating the chloride as it is or as a solid after cooling.

(c) The chloride produced in the aqueous layer is sulfur carbonate.

Sodium bicarbonate or sodium hydroxide is added to perform an exchange reaction to form the raw material base and sodium chloride, and sodium chloride is precipitated using the solubility difference due to temperature changes, f1
It consists of passing and separating.

The method according to claim 2, which is any one of the following.

(4) According to claim 1 or 2, the amount of water and chthone used is 0.1 to 10 parts by weight of water and I to 10 parts by weight of ketol per 1 part by weight of catechol. Method described.

(5) Alkali metal carbonate bicarbonate 2CO3゜NaHCO3, KHCO3 or NaHCO3,7/L/
2. A method according to claim 1, wherein the potassium earth metal bicarbonate is Ca(HCO3)2.

(6) The method according to claim 1, wherein the alkali metal iodide is KI or NaI.

26

Claims (1)

[Scope of Claims] (1) When reacting catechol and methallyl chloride, an ortho-containing method characterized in that a mixed solvent of ketone and water as shown in C below is used together with a base and a catalyst shown in A and B below. Production method of methallyloxyphenol. A The base is an alkali metal carbonate monobicarbonate or an alkaline earth metal bicarbonate. -B The catalyst is an alkali metal iodide. C ketone has the general formula RJ, COR2 (in the formula 1 (1 is an alkyl group having 1 to 6 carbon atoms, R2 is an alkyl group having 1 to 6 carbon atoms or a phenyl group, and I<1 and R2 are bonded to form a carbon It is a ketone represented by a number 4 to 8 alkylene group (excluding acetone, methyl edyl ketone, and diethyl ketone). (2. According to claim 1, the reacted mixture is The method according to claim 1, characterized in that the aqueous layer is separated into several layers, and the aqueous layer containing the catalyst is separated or treated and used again for the reaction. (3) Claims Scope The method for treating the aqueous layer described in item 2 consists of (a) cooling the chloride generated in the aqueous layer, filtering and separating it as a solid, and then adding a new raw material base. ) The raw material base is added to the aqueous layer, and then the chloride is separated as is or cooled and solidified. (c) The chloride produced in the aqueous layer is sodium carbonate. Sodium bicarbonate or This consists of adding sodium hydroxide and causing an exchange reaction to form the raw material base and sodium chloride, precipitating the sodium chloride by utilizing the solubility difference due to temperature change, and separating by filtration. The method according to claim 2. (4) The amount of water and ketone used is 1 to 10 parts by weight of water and 1 to 10 parts by weight of gutone per 1 part by weight of catechol. The method according to claim 2. The method according to claim 1, wherein the bicarbonate is Ca(HCO3)2. (6) The alkali metal iodide is KI or Nal.
The method according to claim 1.