JPS62258331A - Method for producing 3-alkenylcatechol - Google Patents

Abstract

PURPOSE:To readily obtain the titled substance which is an intermediate for insecticide parent chemicals at a high reaction rate and low temperature using a small amount of a catalyst, by the presence of a specific bidentate compound in a reaction system of a 2-halo-6-alkenylphenol, copper compound catalyst and an aqueous solution of an alkali and hydrolyzing the result reaction product. CONSTITUTION:A 2-halo-6-alkenylphenol as a raw material is hydrolyzed in the presence of a copper compound catalyst and an aqueous solution of an alkali (preferably caustic soda or caustic potash is used in a molar amount of 2-8 times, preferably 2-4 times based on the above-mentioned raw material and the concentration of the aqueous solution is preferably 2-10wt%) and further in the presence of a bidentate compound having O and/or N in an aromatic ring and/or at a position directly linked to the aromatic ring, preferably at 130-170 deg.C to afford the aimed compound. Examples of the bidentate compound include 8-hydroxyquinoline, etc., and particularly preferred compound is a compound capable of providing a chelate with a central metal in forming a complex.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing 3-alkenylcatechol. More specifically, Ichinomaro 4-flukenylphenol was dissolved in alkaline water in the presence of a copper compound catalyst,
The present invention relates to an improvement in a method for producing 3-alkenylcatechol by hydrolysis.

3-Alkenylcatechol For example, 3-isobutenylcatechol is λ, --dimethyl-13-dihydrobenzo-
7-furanylmethyl carbamate, which is an important compound as an intermediate for the pesticide active ingredient known as carbofuran.

[Conventional technology]

Conventionally, as a method for producing 3-alkenylcatechol, such as 3-imbutenylcatechol, a method is known in which coro-6-inbutenylphenol is hydrolyzed with an aqueous solution of caustic soda in the presence of cuprous chloride (JP-A-Show! RG-17'
AJ No. 39).

However, this method requires a high reaction temperature such that the hydrolysis reaction rate of chlorophenols is slow <i'to-iroc, and it is necessary to use a large amount of copper compound as a catalyst. A decrease in selectivity occurs.

In addition, this method is not necessarily industrially advantageous because of problems such as high reaction pressure, reduction and precipitation of copper compounds, and lower economic efficiency due to the large amount of copper used.

As a result of extensive research into a method for producing 3-alkenylcatechol by hydrolyzing two-halo 6-alkenylphenol in the presence of a copper compound catalyst, the present inventor has determined to include a compound that has a chelating effect on certain metals. It has been found that the hydrolysis reaction rate is significantly increased, and therefore the reaction temperature can be lowered and the amount of catalyst can be reduced.

[Means for solving problems]

Summary of this project qU In a method for producing 3-alkenylcatechol by hydrolyzing ni-halo-6-alkanylphenol in an alkaline aqueous solution in the presence of a copper compound catalyst, aromatic rings and/or aromatic rings are present in the reaction system. The present invention relates to a method for producing 3-alkenylcatechol, characterized by the presence of a double coordination compound having an oxygen atom and/or a nitrogen atom at a position directly connected to the 3-alkenylcatechol.

The present invention will be explained in more detail below.

Two-halo 6-alkenylphenol, which is a raw material for the reaction of the present invention, is represented by the following general formula (I).

(wherein, , coke claw 6-isoptenylphenol/l/, J-fa
Mot, -inbutenylphenol.

Nichloro-6-vinylphenol, Nibromo-6-
Vinylphenol, Coco-Cro-6-probenylphenol, Coco-Cro-6-propenylphenol, Coco-Cro-6-Ptenylphenol, Cocypromo-4-P?
Nilphenol, dichloro-6-(cornyl-l-
butenyl) phenol, kneepromo1. -(2-methyl-t-7'tenyl)phenol, nichloro-6-(
Niethyl-l-butenyl)phenol, -promo-
6-(2-ethyl-7-butenyl)phenol, nichlorob-(/-methyl-7-butenyl)phenol,
Cobro%-t, -(t-methyl-l-butenyl)phenol, nichloro-&-(/-ethyl-inbutenyl)phenol, copromo-4-(t-ethyl-inbutenyl)phenol, etc. are mentioned, but preferably The alkenyl group has - to 6 carbon atoms, and X is a chlorine atom or a bromine atom.

Particularly preferred is KJ-chloro-6-imptenylphenol.

The copper compounds used as catalysts in the present invention are monovalent copper compounds,
Any divalent copper compound may be used, such as sulfate steel, nitrate steel,
Examples include chlorinated steel, cuprous chloride, cupric oxide, cuprous oxide, and hydroxide steel. The amount of these copper compounds used is usually 0.00/-/gram atom of copper per 1 mol IC of nihalo-6-alkenylphenol, preferably o,
oi ~ 0.2 gram atom.

The hydrolysis reaction of the 2-halo-6-alkenylphenol represented by the general formula CI) is carried out in an alkaline aqueous solution. Examples of the alkali include caustic soda, caustic potash, and calcium hydroxide, with caustic soda and caustic potash being preferred.

The amount used is 1 to 1 times the mole, preferably 1 to 1 times the amount of co^-rho-6-alkenylphenol.

Caustic alkali is usually added to the reaction system as an alkaline aqueous solution, and the concentration of the added caustic alkali aqueous solution is usually O,
S~20 weight strength, preferably 1~10 weight strength.

In this Q, ld, 2-halo-6-alkenylphenol,
It is an essential requirement that a double coordination compound having an oxygen atom and/or a nitrogen atom in an aromatic ring and/or in a position directly connected to an aromatic ring be present in a reaction system consisting of a copper compound catalyst and an aqueous alkali solution.

Examples of divalent coordination compounds having an oxygen atom and/or a nitrogen atom in the aromatic group and in a position directly connected to the aromatic ring include j-hydroxyquinoline, g-aminoquinoline,
Naphthyridine, j-sulfonaphthylamine, aminonaphthol, l-hydroxyphenazine, ! ,! '−
Dipyridyl, u! '-dipyridylamine, 2.2
'-dipyridyl ether, J,! '-dipyridyl thioether, 2'-dipyridyl ketone, bivirazine,
J, J-bis(neepyridyl)pyrazine, l, IQ-
Examples include 7-enanthroline, dihydroxypyridine 1, co-aminopyridine, co-hydroxymethylpyridine, 0-aminophenol, 0-aminobenzoic acid, catechol, methoxycatechol, salicylic acid, J-(4(-pyrazolyl)-aminopropionic acid) These compounds further contain an alkyl group of C, %C, C, S-C,
alkenyl group + C, ~CIo aralkyl group, hydroxyl group, C1-C6 alkoxy group, amino group, C
Substituents such as 5 to C2 alkylamino groups, sulfo groups, C1 to C4 alkylsulfonyl groups, nitro groups, halogen atoms, carboxy groups, preferably C1 to C5 alkyl groups, hydroxy groups, sulfo groups, nitro groups, It may be substituted with a halogen atom, a carboxy group, etc. Such compounds include, for example, cortacyl-t-hydroxyquinoline, ψ,t-dihydroxyquinoline, d-alkoxyj-hydroxyquinoline,! -amino-t-hydroxyquinoline% j-sulfo-j-hydroxyquinoline,! −
Nitro t-Hydroxy Norin, J-10 Rho J-Hydroyashikino 1. ), cocarboxy t-hydroxyquinoline, j17-dichloro-g-hydroxyquinoline, cocarboxylic acid, t-dihydroxyquinoline, and the like. Among the bivalent coordination compounds of the present invention, compounds in which a complex is formed and the chelate with the central metal forms a j- to six-membered ring are particularly preferred.

These two-wheel coordination compounds have a certain stoichiometric relationship with the copper compound as a catalyst in the reaction system, so they form a complex.The amount of the coordination compound used is 0.07 to 700 times the amount of the copper compound, preferably 1 to 0 times the mole is required.

In the present invention, instead of adding the copper compound catalyst and the two-wheel coordination compound alone to the reaction system, the copper complex formed by the copper compound and the two-wheel coordination compound is prepared in advance by a known method [ For example, in the case of g-hydroxyquinoline, Sp@atr
o Chlm, Aeta g(iqs6)/] and may be added to the reaction system.

The hydrolysis reaction of the present invention is usually carried out at a temperature of 100 to 00C1, preferably 13θ to 70C.

The pressure may be any pressure that can maintain the reaction mixture in a liquid phase.1 Usually, the reaction is carried out at normal pressure, under the self-generated pressure of the hydrolysis reaction, or under the pressure of an inert gas such as nitrogen,
At the above temperature, about t-tqkg/cd! It is. If the reaction temperature is too low, the reaction rate will be slow; on the other hand, if the reaction temperature is too high, the copper-binary coordination compound complex in the reaction system will become unstable, leading to precipitation of copper and impeding the yield of the target J-alkenylcatechol. This is not preferable because the rate also decreases. Further, the reaction time is usually about 0.5 to io hours.

In the reaction of the present invention, a small amount of copper may precipitate as metal steel from the copper complex compound in the reaction system during the reaction, and this may adhere to the reactor. 1. It is desirable to use one in which the inner wall surface in contact with the reactor is made of fluororesin.

After the reaction is completed, the pressure of the mixture is usually lowered to normal pressure, and if metal steel is precipitated, it is separated by filtration. The pH of the p-liquid should be lower than 1) Form a crystal or oil layer containing J-alkenylcatechol and an aqueous layer, then separate this, and then recrystallize or distill the crystal or oil layer as necessary. By doing so, the target J-alkenylcatechol can be recovered. Also J-
The alkenylcatechol is separated, and the υ copper complex and/or the excess divalent coordination compound are recovered from the aqueous layer by a conventional method such as neutralization, and are used as a catalyst or reaction system for the hydrolysis of nihalo6-alkenylfetool. It can also be reused as a dicared coordination compound present in

〔Example〕

Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

Example 1 0.190f of Shiquinoline was added to this alkaline aqueous solution! Make sure to dissolve at θ~60C. Copper sulfate pentahydrate O, yu! 0?
An aqueous solution prepared by dissolving t-hydroxyquinoline in water coke was added to the above alkaline aqueous solution of t-hydroxyquinoline under stirring, and the mixture was stirred for O, S hours.
．． After adding Ast and dissolving it, the inside of the 808 pressurized reactor was purged with nitrogen. /jj''-/jThe SUS pressurized reactor was immersed in an oil bath whose temperature was adjusted to 4°C and heated and stirred for S hours. After the reaction was completed, the reaction solution was heated to 3j% under a nitrogen atmosphere.
Add the liberated oil to an aqueous solution containing hydrochloric acid (Q) and add it to a mixed solution of benzene/THF/(volume ratio).
As a result of extracting and quantifying the extract by liquid chromatography, the conversion rate of Coke 4-6-imptenylphenol was gos, and the yield of J-isobutenylcatechol was 6.
It was 1ch.

Comparative Example 1 The reaction was carried out in the same manner as in Example 1 except that t-hydroxyquinoline was removed. As a result, the conversion rate of Coke 4-row 6-imptenylphenol was
- The yield of isobutenylcatechol was only i%. It was found that the effect of g-hydroxyquinoline on the reaction rate was very large.

Examples 2-6 Table-! 1#ic of the j-hydroxyquinoline derivative described above.
Coke tetralo 6-imptenylphenol was hydrolyzed in the same manner as in Example 1, except that twice the mole of acid steel pentahydrate was used. The results are shown in Table-1.

Table-l Example Lycium, 2'-dipyridylamine 0. After dissolving J I J 54 in 20 - acetonitrile, cuprous chloride 0.09
9 fl- was added and stirred at room temperature for 1 hour, and then acetonitrile was distilled off under reduced pressure to prepare a copper complex of co,co'-dipyridylamine.

5O8-, 31 & 9 in a pressurized reactor! r%Na
OH, two? was dissolved in 5 scc of water, and then 3.6 cc of Coke 4-row 6-imptenylphenol was added. Added and dissolved. This corroro! --After adding the copper complex to an alkaline aqueous solution of iso7''f-nylphenol, SU
A pressurized reactor manufactured by S was repeatedly replaced with nitrogen, and the reactor was
The mixture was immersed in an oil bath whose temperature was adjusted to 1/C and heated and stirred for 3 hours. After the reaction was completed, the reaction solution was treated in the same manner as in Example 1, and the conversion rate of Coke 4-6-inputenylphenol was 9s%, and the yield of 3-inbutenylphenol was 67s%.

Example ff - / Comparative Example Coke coro-6-imbu was prepared in the same manner as in Example 1, except that cuprous chloride was used as the copper compound and a predetermined amount of the two-wheel coordination compound listed in Table 1 was used. The hydrolysis reaction of tenylphenol was carried out.

The results are shown in Table C.

〔Effect of the invention〕

According to the present invention, in a method for producing J-alkenylcatechol by hydrolyzing -1-halo-6-alkenylphenol in an alkaline aqueous solution in the presence of a copper compound catalyst, a specific bivalent coordination is provided in one reaction system. By having a compound present.

The hydrolysis reaction rate is significantly increased, and therefore it is possible to obtain the desired J-alkenylcatechol at a high conversion rate and high yield even with a small amount of catalyst.

Applicant: Mitsubishi Chemical Industries, Ltd. Agent: Patent Attorney Hase - (1 other person)

Claims (1)

[Claims] (1) In a method for producing 3-alkenylcatechol by hydrolyzing 2-halo-6-alkenylphenol in an alkaline aqueous solution in the presence of a copper compound catalyst, it is directly connected to the aromatic ring and/or to the reaction system. A method for producing 3-alkenylcatechol, characterized by the presence of a bidentate compound having an oxygen atom and/or nitrogen atom at the position