JPH06293750A - Production of methylenedioxy aromatic compound - Google Patents

Abstract

PURPOSE:To produce the subject compound useful as an intermediate for synthesis of a perfume, an insecticide, etc., in a high yield in a short time without formation of a colored substance as a by-product by reacting a 1,2-dioxy aromatic compound with methylene chloride in the presence of a specified catalyst. CONSTITUTION:The objective methylenedioxy aromatic compound is synthesized by reacting a compound of formula I (R is H, a 1 to 4C alkyl, aldehyde, carboxyl, an alkoxy, a halogen or nitro) with methylene chloride in the presence of a quaternary ammonium salt (e.g. tetrabutylammonium bromide) of formula II [M is N or P; (x) is Cl, Br or I; R<1> to R<2> are each a lower alkyl, an allyl or an allyl-lower-alkyl) or a quaternary phosphonium salt (e.g. tetraethylphosphonium chloride) in an aqueous caustic alkali solution (e.g. caustic soda) at 95 to 130 deg.C without using an iodine compound as a cocatalyst. Methylene chloride, the caustic alkali and the quaternary ammonium salt are used respectively in an amount of 1.2 to 5.0mol, 2.0 to 2.2mol and 0.005 to 0.10mol based on the compound of formula I.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel method for producing a methylenedioxy aromatic compound (ortho-methylenedioxy aromatic compound) which is useful as an intermediate for producing perfumes, insecticides and the like.

[0002]

Description of the Prior Art As a method for producing a methylenedioxy aromatic compound, the following Japanese Patent Application Laid-Open No. 52-113967,
Japanese Patent Publication No. 59-46949 can be mentioned. SUMMARY OF THE INVENTION 1,2-dioxyaromatic compound and methylene chloride in an aqueous solution of caustic alkali salt in the presence of a quaternary ammonium salt or quaternary phosphonium salt catalyst at 70 to 80 ° C.
Yield 70-83 by reacting at room temperature for 3-5 hours.
The methylenedioxy aromatic compound is obtained in%. And in the above temperature range, the yield is 8 more than at 70 ° C.
Since it is lower at 0 ° C., it suggests that the yield decreases when the temperature is 80 ° C. or higher.

Japanese Patent Publication No. 59-46949. In the above method, an iodine compound (iodine, alkyl iodide, metal iodide salt, etc.) is further used as a cocatalyst, and the reaction is carried out at 70 to 90 ° C. for 8 to 11 hours. Attempts to increase the yield (yield 61-93%). In the above temperature range, the yield is best around 80 ° C., and the yield decreases around 80 ° C. or above.

However, even in the above-mentioned method, which is an improvement of the above-mentioned method, the reaction time is long even when the yield of the desired product is high, and further, the iodine compound is easily oxidized by air to exhibit a coloring characteristic of iodine. In order to obtain a target product of high quality by the above-mentioned method, a post-treatment step for preventing coloring after the reaction is necessary. Therefore, as a method for producing a methylenedioxy aromatic compound, not only the yield of the target product is simply increased, but also the production process and reaction time are
There is a need for further improvement.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel method for producing a methylenedioxy aromatic compound which is useful as an intermediate for producing perfumes and insecticides.

[0006]

Means for Solving the Problems As a result of research to solve the above problems, the present inventors have found that a 1,2-dioxyaromatic compound and methylene chloride are quaternized in an aqueous solution of a caustic alkali salt. By reacting at 95 to 130 ° C. in the presence of an ammonium salt or a quaternary phosphonium salt and not an iodine compound as a cocatalyst, a high yield and a short time of methylenediene formation can be achieved without producing a coloring substance. The present invention has been completed by finding that an oxyaromatic compound can be produced.

That is, the present invention is as follows. Formula (I):

[0008]

[Chemical 3]

(In the formula, R is a hydrogen atom, and has 1 to 4 carbon atoms.
Represents an alkyl group, an aldehyde group, a carboxy group or an alkoxy group, a halogen atom or a nitro group. ) 1,2-dioxy aromatic compound and methylene chloride in an aqueous solution of caustic alkali represented by the following formula (II):

[0010]

[Chemical 4]

(In the formula, M represents a nitrogen atom or a phosphorus atom; X represents a chlorine atom, a bromine atom or an iodine atom; R
^{1 to} R ⁴ each represent the same or different lower alkyl group, allyl group or allyl lower alkyl group. ) In the presence of a quaternary ammonium salt or quaternary phosphonium salt, without the presence of an iodine compound as a promoter,
The present invention relates to a method for producing a methylenedioxy aromatic compound, which comprises reacting at 95 to 130 ° C.

The present invention will be described in detail below. The methylenedioxy aromatic compound is obtained by placing methylene chloride and a quaternary ammonium salt (or quaternary phosphonium salt) in a pressure-resistant reaction vessel, stirring the mixture with heat, and then neutralizing the caustic alkali with 1,2-dioxyaromatic compound. It can be obtained by adding an aqueous solution of an alkali salt over time and reacting at 95 to 130 ° C.

Examples of the quaternary ammonium salt include tetramethylammonium, tetraethylammonium,
Tetrabutylammonium, trimethylphenylammonium, triethylphenylammonium, tributylphenylammonium, trimethylbenzylammonium, triethylbenzylammonium, tributylbenzylammonium, trimethylphenylethylammonium, triethylphenylethylammonium, tributylphenylethylammonium chloride, bromide or iodide Examples thereof include tetrabutylammonium chloride and tetrabutylammonium bromide, and tetrabutylammonium bromide is more preferable.

Examples of the quaternary phosphonium salt include tetraethylphosphonium, tetramethylphosphonium,
Tetrabutylphosphonium, trimethylphenylphosphonium, triethylphenylphosphonium, tributylphenylphosphonium, trimethylbenzylphosphonium, triethylbenzylphosphonium, tributylbenzylphosphonium, trimethylphenylethylphosphonium, triethylphenylethylphosphonium, tributylphenylethylphosphonium chloride, bromide or iodide Can be mentioned.

The amount of the quaternary ammonium salt (or quaternary phosphonium salt) used is sufficient to be 0.005 to 0.10 mol based on the 1,2-dioxy aromatic compound.
Examples of the 1,2-dioxy aromatic compound include catechol, 4-methylcatechol, 4-ethylcatechol, 4,5-dimethylcatechol, 4-propylcatechol, 4-propenylcatechol, 4-formylcatechol and the like. I'm dying.

Examples of the caustic alkali include caustic soda and caustic potash. The amount of caustic used is 1 mol of 1,2-dioxy aromatic compound,
The amount is 2.0 to 2.2 mol, preferably 2 mol. The amount of methylene chloride is preferably 1.2 to 5.0 mol with respect to the 1,2-dioxy aromatic compound.

1,2-dioxyaromatic compounds, caustic, quaternary ammonium salts and quaternary phosphonium salts are
Both can be obtained as commercial products. The amount of water as a solvent is 7 to 14 mol, preferably 8 to 10 mol, based on 1 mol of the 1,2-dioxyaromatic compound. The reaction temperature is 95 to 130 ° C., preferably 95 to 1
The temperature is preferably 25 ° C, more preferably 100 to 120 ° C.

The dropping time of the aqueous solution of the caustic alkali salt of 1,2-dioxyaromatic compound is 1 to 5 hours, preferably 2 to 3 hours, and the reaction is completely completed in 1 to 2 hours after the dropping. finish.

The methylenedioxy aromatic compound which is the object compound of the present invention can be produced, for example, by the following reaction formula.

[0020]

[Chemical 5]

The methylenedioxy aromatic compound produced as described above is subjected to usual post-treatments such as extraction, concentration and filtration after completion of the reaction, and if necessary, known distillation such as distillation and various chromatographies. It can be appropriately purified by means.

EXAMPLES The present invention will be described below with reference to Examples and Comparative Examples. It should be noted that these examples do not limit the scope of the present invention. Example 1 A glass autoclave container (300 cc) equipped with a stirrer and a dropping device was charged with methylene chloride [127 g.
(1.5 mol)] and tetrabutylammonium bromide [6.5 g (0.02 mol)] were charged, and the temperature of the reaction vessel was raised to 110 ° C. and maintained while stirring. next,
Caustic soda [62.5 g (purity 96
%, 1.5 mol)] and catechol [82.5 g (0.
75 mol)] was dissolved in a nitrogen gas atmosphere, and an aqueous sodium salt solution of catechol was added dropwise over 3 hours by a micrometer pump.

After completion of dropping, the reaction was completed by heating and stirring at the same temperature for 2 hours, and the reaction solution was cooled to room temperature. After cooling, the reaction solution was extracted twice with toluene (200 cc).
+150 cc) and the extract was distilled to obtain colorless and transparent 1,2-methylenedioxybenzene (87 g) (yield 95%). This product was identified by NMR spectrum, MS spectrum, IR spectrum and the like.

Example 2 A colorless and transparent 1,2-methylenedioxybenzene (84 g) was obtained by the same procedure as in Example 1 except that the reaction temperature was changed to 100 ° C. %).

Example 3 A colorless and transparent 1,2-methylenedioxybenzene (86 g) was obtained by the same procedure as in Example 1 except that the reaction temperature was changed to 120 ° C. %).

Example 4 A colorless and transparent 1,2-methylenedioxybenzene was prepared in the same manner as in Example 2 except that caustic soda was changed to caustic potash [98.8 g (purity 85%, 1.5 mol)]. (86 g) was obtained (yield 94%).

Comparative Example 1 Tetrabutylammonium bromide [6.5 g (0.
02 mol)], and further potassium iodide [3.3 g
(0.02 mol)] and charged in the same manner as in Example 1 except that the reaction temperature was changed to 100 ° C., to obtain light yellow 1,2-methylenedioxybenzene (69.5 g). ) Was obtained (yield 66%).

Comparative Example 2 1,2-Methylenedioxybenzene (47.6 g) was obtained in the same manner as in Example 1 except that the reaction temperature was changed to 80 ° C. (yield 52%). ).

[0028]

According to the present invention, it is possible to produce a methylenedioxy aromatic compound which is useful as an intermediate for producing fragrances, insecticides, etc., in a high yield and in a short time, without producing a coloring substance. it can.

Claims (1)

[Claims] 1. The following formula (I): (In the formula, R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aldehyde group, a carboxy group or an alkoxy group, a halogen atom or a nitro group.) And a 1,2-dioxy aromatic compound. In a caustic aqueous solution, methylene chloride and the following formula (II): (In the formula, M represents a nitrogen atom or a phosphorus atom; X represents a chlorine atom, a bromine atom or an iodine atom; and R ^{1 to} R ⁴ are
They represent the same or different lower alkyl groups, allyl groups or allyl lower alkyl groups. ) In the presence of a quaternary ammonium salt or quaternary phosphonium salt, and without the presence of an iodine compound as a co-catalyst,
A method for producing a methylenedioxy aromatic compound, which comprises reacting with.