JPS5933569B2 - Method for producing O-alkoxy-P-allylphenol - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improvement in a method for producing 0-alkoxy p-allylphenol by reacting a known 0-alkoxyphenol with an allyl halide in the presence of an alkali (earth) metal compound in an aqueous medium. .

In the known method, for example, it is the object. -alkoxy=
In addition to p-allylphenol [formula (1)], 2-alkoxyphenyl allyl ether [formula (2)], 2-
There is a drawback that a large amount of alkoxy 4-allylphenylallyl ether [formula (3)] and the like are produced as by-products, and furthermore, the reaction requires a long time (for example, 100 hours) and the reaction rate is low. KER(1) CH2CH=CH2 In the formula, R is a methyl or ethyl group0CH2CH=CH2 d0R(2) In the formula, R is a methyl or ethyl group0CH2CH=CH2 V0R(3) CH2CH=CH2 In the formula R is a methyl or ethyl group.The purpose of the present invention is to increase the reaction rate and suppress the production of by-products.The purpose of the present invention is to increase the reaction rate and suppress the production of by-products. The inventor's research has revealed that a significant improvement can be achieved by allowing a double salt to coexist in the reaction system.

That is, the present invention provides a method for producing o-alkoxy-p-allyl phenol by reacting o-alkoxyphenol with allyl halide in the presence of an alkali (earth) metal compound in an aqueous medium, using a copper compound and an ammonium salt or copper as a catalyst. It is characterized by the coexistence of a compound and a double salt of an ammonium salt.

-A method for producing alkoxy-p-allylphenol. ．． The word "allyl" used in this specification does not mean only the CH2-CH-CH2- group in the meaning of the ogi, but also broadly refers to the structural unit〉C-C-C
means a group containing H2-.

Examples of groups containing such structural units include crotyl (
2-butenyl) or methallyl (2-methylallyl) groups. "o-alkoxy" as used herein means 0 methoxy or o-ethoxy.

Allyl halide is preferably used in a proportion of 1 to 1.5 moles per mole of o-alkoxyphenol.

Examples of alkali (earth) metal compounds that can be used include Li.
K. Na. ．． Ca,. Ba. Mg. There are various hydroxides of Zn and their weak acid salts, and particularly preferred are Zn hydroxides and their weak acid salts. Each hydroxide of Na.

The preferred usage amounts of these are: o-alkoxyphenol 1
A ratio of 0.9 to 1.2 gram equivalents per mole is preferred. The alkali (earth) metal compound can be used either as a solid or as an aqueous solution, and in that case, the concentration can be any.

There is no limit to the amount of water used as the reaction medium, but if too much water is used and the reaction is carried out in a diluted state, the reaction rate will decrease, so generally the amount of water used is 200% per mole of alkoxyphenol. Preferably, ~400 ml of water is used.

Both inorganic and organic copper compounds are used as the catalyst, such as copper acetate, copper borate, copper silicate, copper halide, copper oxide, copper sulfate, copper nitrate, copper carbonate,
Copper phosphate etc. are used.

A suitable amount of copper compound to be used is 0.01 to 0.2 gram ion, more preferably 0.05 to 0.1 gram ion of copper ion per gram equivalent of base. The ammonium salt may be either an organic acid salt or an inorganic acid salt.

Further, the inorganic acid may be a weak acid or a strong acid. For example, ammonium sulfite, ammonium hydrogen phosphite, ammonium chloride, ammonium chlorate, ammonium perchlorate, ammonium nitrate, ammonium carbonate, ammonium hydrogen carbonate, ammonium thiosulfate, ammonium metavanadate, ammonium metaborate, ammonium sulfate, ammonium hydrogen sulfate, ammonium phosphate. , ammonium hydrogen phosphate. The preferred amount of ammonium salt to be used is 1 to 4 moles per gram of copper ions, more preferably 1 to 4 moles in terms of ammonia molecules.
2 moles.

When a copper salt and an ammonium salt coexist, it is thought that in some cases, a double salt is formed.

For example, copper ammonium chloride (CuCl2.2NH4C1
・2H20) double salt is the same as this double salt; as a result of carrying out this reaction by simultaneously adding copper chloride (CuCl2.2H20) and ammonium chloride as catalysts so that the composition is almost the same. The reaction temperature at which the results were obtained (see Examples 6 and 11) was 0 to 60°C, preferably 20 to 60°C.
It is best to do this at 35°C.

The reaction time is 5 to 180 minutes, preferably 10 to 60 minutes. The reaction product is conveniently separated, for example, by the following method A or B.

Method A: The reaction solution is neutralized with mineral acid and extracted with an organic solvent (ether, benzene, carbon tetrachloride, chloroform, petroleum ether, methylisobutylcaine (MIBK)).

Next, the extract (which contains all the organic matter) is distilled and separated into components. Method B: Without neutralizing the reaction solution, the reaction solution is directly subjected to extraction with the same organic solvent as in Method A.

The extract contains high-boiling substances such as unreacted allyl halide, the target orthoalkoxy paraallyl phenol, by-product 2-alkoxyphenyl allyl ether, some 2-alkoxy-4-allylphenyl allyl ether, and others. It is distilled and separated into each component. The raffinate (aqueous layer) is neutralized with mineral acid and extracted with the same organic solvent.
This extract contains unreacted ortho alkoxyphenol, the target ortho alkoxy paraallyl phenol, and some high-boiling substances, so it is separated into each component by distillation. Next, the present invention will be explained in detail with reference to Examples and Comparative Examples.

Example 1 Guaiacol 10.007, caustic soda 3,227,
Allyl chloride 6.807, cupric chloride (CuCl2.2H
20) 1.377, ammonium chloride (Nfl4Cl)
A mixture of 1.727 and 30 ml of water was reacted for 15 minutes at 25° C. with stirring.

Next, the reaction solution was neutralized with hydrochloric acid, and the neutralized solution was diluted with ether 30
ml was extracted about 5 times, and the extract was distilled to extract 4.73y of unreacted guaiacol and 4.73y of the target eugenol.
707 was obtained. The yield of the by-product o-allylguaiacol was 1.48y. The reaction rate was 52.7%, and the selectivity for eugenol was 67.5%. Comparative example
1 guaiacol 10.00y1 caustic soda 3.227,
A mixture of 6.807 ml of allyl chloride and 30 ml of water was reacted with stirring at 25° C. for 15 minutes.

Next, the reaction solution was neutralized with hydrochloric acid, and the neutralized solution was diluted with ether 30
Extracted about 5 times with M1 and distilled the extract to obtain 9.83'F7 of unreacted guaiacol and 0.83'F7 of the target eugenol.
Obtained 07y. The yield of the by-product o-allylguaiacotyl was 0.10y. The reaction rate was 1.7%, and the selectivity for eugenol was 32.4%. Example 2~
14 Five reactions were carried out under exactly the same conditions as in Example 1, except that the type and amount of the ammonium salt and copper compound used were changed.

The results are shown in Table 1 together with Example 1 and Comparative Example. Examples 15 to 17 A *ε reaction was carried out under exactly the same conditions as in Example 1, except that another potassium salt was used in place of the caustic soda in Examples.

The results are shown in Table 2.

Claims (1)

[Claims] 1. O-alkoxyphenol is reacted with allyl halide in the presence of an alkali (earth) metal compound in an aqueous medium.
- A method for producing o-alkoxy-p-allylphenol, which comprises coexisting a copper compound and an ammonium salt or a double salt of a copper compound and an ammonium salt as a catalyst.