JPS59225177A - Coumarone derivative and its preparation - Google Patents

Abstract

NEW MATERIAL:The coumarone derivative of formula I (R1-R3 are H or methyl; the dotted line represents the presence of one pi-electron). EXAMPLE:dl-2,5,7,8-Tetramethyl-2-(4'-methyl-4'-pentenyl)-6-chromanol. USE:An antioxidant for organic substance. PREPARATION:The compound of formula I can be prepared by reacting the hydroquinone compound of formula II with myrcene hydrochloride (geranyl chloride, neryl chloride or their mixture). Myrcene hydrochloride is obtained by adding hydrochloric acid to myrcene which is available easily and economically from a natural product.

Description

[Detailed description of the invention] The present invention relates to the general formula CI) 1 ) This invention relates to a chroman derivative represented by and a method for producing the same.

α-Tocopherol, which is one of the chroman derivatives, has been known as an antioxidant for synthetic resins, foods, feeds, and the like. This compound is usually obtained through the condensation reaction of trimethylhydroquinone and isophytol, but one raw material, isophytol, is generally obtained using acetone or acetylene as a starting material, and requires at least a complex reaction process beyond the IO process. Because it is synthesized through a process, processing costs are high and it is extremely expensive. As a special example, a method of synthesizing isophytol using isoprene as a starting material is also known, but in this case as well, the number of steps is long and the reaction results in each step are not very good. Rather, the current situation is that value is being found in the use of by-products generated during the synthesis process.

The present inventors have conducted intensive studies on a compound that should be substituted for the expensive α-tocopherol and a method for producing the same, and have found that a compound that can be obtained with good results by adding hydrochloric acid to miljon, which is easily and inexpensively obtained from natural products. From the condensation reaction of myrcene hydrochloride and hydroquinones, a
- It has been discovered that a chroman derivative that is more useful than tocopherol can be obtained, and the present invention has been completed.

The chroman derivative represented by the general formula (I) of the present invention is believed to be a new compound, and can be used as an antioxidant for organic substances.
It has extremely good effects.

Specific examples of the compound represented by the general formula CI) of the present invention are as follows.

d/-2,5,7,8-tetramethyl-2-(4'-methyl-4'-pentenyl)-6-chromanol, dl! -2,5,7,8-tetramethyl-2-(4'-
Methyl-5'-pentenyl)-6-chromanol, dI! -2,5,8-trimethyl-2-(4'-methyl-47-pentenyl)-6-chromanol, d7-2.5.8-trimethyl-2-(4'-methy/l/-5 '-pentenyl)-6-chromanol,
d7-2,8-dimethyl-2-(4'-methyl-4'
-pentenyl)-6-chromanol, dl! -2,8-
Dimethyl-2-(4'-methyl-5'-pentenyl)-
6-Chromanol Q In all of these compounds, the group attached to the 7th carbon atom of chroman is an OB group, as shown in general formula (I), but this group is Depending on the purpose, chromanol can be treated with acetic anhydride to convert it into a compound represented by the following general formula (m) as in the case of α-tocopherol.

In the present invention, the reaction between hydroquinone represented by general formula (11) and myrcene hydrochloride is usually carried out in a solvent. Examples of such solvents include halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, and ethylene chloride; aromatic hydrocarbons such as tetralin, benzene, toluene, and xylene; methyl acetate, ethyl acetate, and isopropyl acetate. , carboxylic acid esters represented by isobutyl acetate, ethyl formate, benzyl acetate, methyl benzoate, etc., ethers represented by diethyl ether, dioxane, etc., and non-polar organics such as ligroin, petroleum ether, hexane, petroleum benzyl, etc. Examples include solvents, but ethyl acetate is particularly preferred.

Generally, Lewis acids and Bronsted acids can be used as the catalyst of the present invention. As acid, zinc chloride, aluminum chloride, tin tetrachloride, titanium tetrachloride,
Although zeolite, silica alumina, etc. can be used, zinc chloride and aluminum chloride are particularly preferred.

Examples of the Brønsted acid include para-toluenesulfonic acid, pencenesulfonic acid, para-toluenesulfochloride, trifluoroacetic acid, trifluoroacetic anhydride, and inorganic acids. is particularly preferred.

When these Lewis acids and Brønsted acids are used as catalysts, the amount used should be 1 to 10% compared to hydroquinone.
50% by weight is preferred.

The reaction temperature in the present invention is usually in the range from room temperature to the reflux temperature of the solvent used, but in most cases the reaction is carried out at the reflux temperature. The concentration of the reaction raw material in the solvent in the present invention is generally 5 to 90% by weight, particularly 80 to 90% by weight.
80 weight ratio is preferred. The thus obtained chroman derivative represented by the general formula (I) of the present invention is useful as an antioxidant for organic substances, and is useful in oils and fats, medicines, cosmetic products,
It is particularly useful for preventing oxidation of foods, feeds, and synthetic polymers. Further, the chroman derivative represented by the general formula (I) is useful for preventing the oxidation of organic substances even when used alone, but it can also be used in combination with other antioxidants. The present invention will be explained below with reference to Examples.

Example 1 100 equipped with stirrer, thermometer, cooling tube and dropper
- 2,8° 5-trimethylhydroquinone 21! i' (0.14 mol), zinc chloride5.
After charging IP, aluminum chloride 2.3z and ethyl acetate 21- and replacing the air in the container with nitrogen, the temperature was raised and when the reaction temperature reached 80°C, myrcene hydrochloride obtained by adding hydrochloric acid to myrcene was added. (2nd, 5th day B,
P, 71-86°C) 809 was added dropwise. After dropping, 80℃
The reaction was carried out at a temperature of about 3 hours. After the reaction, the reaction solution is cooled,
To this was added 5 (11 nl) of ethyl acetate, and then 100-
of water was added to separate the oil-water phase. The oil phase was washed with 5% carbonated water, then water, and finally dehydrated with Glauber's salt. Ethyl acetate was distilled off from this liquid by evaporation, and then distilled under reduced pressure. As a result, the HP was 0.8 mHP.

As the main fraction at 155-160°C, dI! -2.

5.7.8-tetramethyl-2-(4'-methyl-4'
-pentenyl)-6-chromanol 8751- was obtained. The main fraction obtained here is redistilled, and the purified liquid product is dl! It was confirmed from the following analysis results that it was -2,5,7,8-tetramethyl-2-(4'-methyl-4'-pentenyl)-6-chromanol.

a) Elemental analysis result Calculated value C within 0; 79.68% (79,17%) 11ii 9.96% (9,72ch) b) Mass spectrometry result (7QeV) m/e=288 The spectrum is shown in Figure 1 shows.

C) Infrared absorption spectrum Figure 2 shows the spectrum.

Example 2 Purified methacrylic acid (25%) was charged into a 50 ml cylindrical glass container, and 0.59% of each of the various compounds shown in Table 1 was added thereto.

After replacing the gas phase of each container with nitrogen gas, the containers were placed in a hot water bath at 80° C., and the oxidation stability of methacrylic acid was tested. The results are shown in Table-1.

Table-1 Oxidation stability test and conclusion

[Brief explanation of drawings]

FIG. 1 shows a mass spectrometry spectrum of the compound of the present invention, and FIG. 2 shows an infrared absorption spectrum.

Claims (2)

[Claims] (1) General formula (I) ordinary ) A chroman derivative represented by (2) A hydroquinone compound represented by the general formula (1) (wherein R1, R2, and R3 represent a hydrogen atom or a methyl group) and mil dihydrochloride (geranyl chloride, neryl chloride, or a mixture thereof) Indicates the presence of 1 represented by general formula (I), which is characterized by reacting with. ] Method for producing chroman derivatives.