JPH0472874B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula () 3,4-dihydro-6-hydroxy-
The present invention relates to an organic composition containing a 2H-benzopyran derivative as a stabilizer. In the above general formula (), R ¹ represents a hydrogen atom or a lower alkyl group such as a methyl group, ethyl group, propyl group, or butyl group. R ² and R ³ are the same or different and each represents a hydrogen atom; a lower alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group; or a lower alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group; or
R ² and R ³ are together −CH=CH−CH=CH−
form a group. A is (-CH ₂ ) _-o group, phenylene group,
−CH ₂ SCH ₂ − group, −CH ₂ CH ₂ SCH ₂ − group, −
CH ₂ CH ₂ SCH ₂ CH ₂ − group, −CH ₂ S−SCH ₂ − group, −
CH ₂ CH ₂ S−SCH ₂ CH ₂ − group, −CH ₂ SCH ₂ SCH ₂ −
group, -CH ₂ CH ₂ SCH ₂ SCH ₂ CH ₂ - group,

【formula】

[Formula] and

Represents a group selected from the group consisting of [Formula]. Here n means an integer greater than or equal to 1,
It is preferably an integer of 1 to 14, more preferably an integer of 1 to 8, in view of the ease of obtaining dicarboxylic acid as a raw material. R ⁵ and R ⁶ are the same or different and represent a hydrogen atom or a lower alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, or
R ⁵ and R ⁶ together represent a -(CH ₂ ) ₄ - group.
R ⁷ and R ⁸ are together

【formula】

【formula】

【formula】

[Formula] or

[In the formula, A has the same meaning as in the general formula (). ]

3,4-dihydro-6-hydroxy-2H- represented by the general formula () by reacting with a dicarboxylic acid represented by or a reactive derivative thereof
Benzopyran derivatives can be produced. Here, examples of reactive derivatives of 2-substituted ethyl alcohol include halides, alkanesulfonates, arenesulfonates, and carboxylates. Reactive derivatives of dicarboxylic acids include lower alkyl esters, acid halides, acid anhydrides or mixed acid anhydrides, alkali metal salts, silver or organic tertiary
and quaternary base salts. The reaction between the 2-substituted ethyl alcohol represented by the general formula () or its reactive derivative and the dicarboxylic acid represented by the general formula () or its reactive derivative is carried out under conventionally known general ester synthesis reaction conditions. A typical example of the ester synthesis reaction will be shown below. Reaction example (a) Reaction between alcohol and dicarboxylic acid dihalide Alcohol () and halide of dicarboxylic acid (), preferably dicarboxylic acid dichloride, are mixed in an inert solvent such as benzene, toluene, ether, or chloroform at a ratio of 1 to 3% relative to the alcohol. Molar equivalents of pyridine, triethylamine, etc.
The desired 3,4-dihydro-6-hydroxy-2H-benzopyran derivative () is obtained by reacting at room temperature in the presence of a grade amine. Reaction example Reaction between alcohol and acid anhydride or mixed acid anhydride Alcohol () and acid anhydride of dicarboxylic acid () or dicarboxylic acid () and pivalic acid, p
- a mixed acid anhydride such as toluenesulfonic acid in an inert solvent such as benzene, toluene, xylene, hexane, etc., preferably in the presence of an acid such as p-toluenesulfonic acid or a tertiary amine such as pyridine or triethylamine; Below, the desired 3,4-dihydro-6-hydroxy-2H-benzopyran derivative () is obtained by reacting at room temperature or under heating, and further dehydration condensation if necessary. Reaction example C. Reaction between alcohol and dicarboxylic acid Alcohol () and dicarboxylic acid () are mixed with dicyclohexylcarbodiimide or 2-chloro-1-methylpyridinium iodide in an inert solvent such as benzene, toluene, or xylene. In the presence of a dehydration condensation agent such as triethylamine,
The desired 3,
A 4-dihydro-6-hydroxy-2H-benzopyran derivative () is obtained. Reaction example Reaction between alcohol and lower alkyl ester of dicarboxylic acid Alcohol () and lower alkyl ester of dicarboxylic acid () are transesterified using a suitable transesterification catalyst,
For example, by performing a heating reaction in an inert solvent such as toluene or xylene in the presence of a titanium compound such as p-toluenesulfonic acid or tetramethyl titanate, and removing the generated low-boiling alcohol from the reaction system. Target 3,4-dihydro-
6-hydroxy-2H-benzopyran derivative ()
get. Reaction example Reaction of alcohol halide, alkanesulfonate or arenesulfonate with alkali metal salt, silver salt or salt of organic tertiary or quaternary base of dicarboxylic acid Halide of alcohol (), alkanesulfonate or arenesulfonate and dicarban The desired 3,4- A dihydro-6-hydroxy-2H-benzopyran derivative () is obtained. 3,4 obtained by the above ester synthesis reaction
The -dihydro-6-hydroxy-2H-benzopyran derivative can be separated and recovered by a conventional method. For example, water is added to the reaction mixture, then extracted with ether etc., the extract is washed with water, dried, the solvent is distilled off, and the residue is recrystallized or purified by column chromatography. A 3,4-dihydro-6-hydroxy-2H-benzopyran derivative represented by the formula () can be obtained. 2- represented by the general formula () used as a raw material
Most substituted ethyl alcohols are compounds known per se (see JP-A-49-88876 and JP-A-56-145282), but according to the method previously discovered by the present inventors, General formula () [In the formula, R ¹ , R ² and R ³ have the same meanings as in the general formula (), and R represents a hydrogen atom or a protective group. ] Hydroquinone or its derivative shown and 4-
It can be easily obtained by reacting methyl-5,6-dihydro-2H-pyran in the presence of a Lewis acid (see Japanese Patent Application No. 57-83654). Examples of Lewis acids used in this condensation reaction include boron trifluoride/ether complex, aluminum chloride, aluminum bromide, ferrous chloride, ferric chloride, stannous chloride, stannic chloride, zinc chloride, and sulfuric acid. , p-toluenesulfonic acid, etc., but preferably aluminum chloride,
It is a boron trifluoride/ether complex. The amount of Lewis acid used is approximately 0.1 to 2 times the molar amount of hydroquinone or its derivative represented by the general formula (),
Preferably it is about 0.5 to 1.0 times the molar amount. This condensation reaction is preferably carried out in a solvent, for example 1,2
- Hydrogen halides such as dichloroethane, dichloromethane, chloroform, 1,1,2-trichloroethylene, carbon tetrachloride, chlorobenzene;
Hydrocarbons such as benzene, toluene, xylene, cyclohexane, n-hexane, ligroin;
Nitrogen-containing compounds such as nitromethane, nitrobenzene, benzonitrile, and acetonitrile; oxygen-containing compounds such as methyl ethyl ketone, ethyl acetate, butyl acetate, and mixtures thereof can be used as the solvent, and 1,2-dichloroethane is particularly preferred. The amount of solvent used is approximately 2 to 100% of the hydroquinone or its derivative represented by the general formula ().
twice the weight, preferably about 5 to 20 times the weight. This condensation reaction is usually carried out at -40°C to 150°C, preferably at 0°C.
Perform at ~100°C. The 2-substituted ethyl alcohol represented by the general formula () can be converted into the above-mentioned 2-substituted ethyl alcohol reactive derivative by halogenating, alkanesulfonylating, arenesulfonylating or acylating it in a conventional manner. . The dicarboxylic acid represented by the general formula (), which is one of the raw materials, is a known compound, such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, corkic acid, azelaic acid, sebacic acid, brassic acid, tapsin. acid, phthalic acid, isophthalic acid, terephthalic acid, thiodiglycolic acid, thiodipropionic acid, 3-thia-1,6-hexanedioic acid, 3,4-dithia-1,6-hexanedioic acid,
4,5-dithia-1,8-octanedioic acid, 3,5
-dithia-1,7-heptanedioic acid, 4,6-dithia-1,9-nonanedioic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, 4-cyclohexene-1,2-dicarboxylic acid, 4- Methyl-4-
Cyclohexene-1,2-dicarboxylic acid, 1-cyclohexene-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, 5-norbornene-2,3-dicarboxylic acid, 5-methyl-5-norbornene-2, 3-dicarboxylic acid, 1,4,
5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic acid, narbornane-2,
3-dicarboxylic acid, etc. These dicarboxylic acids can be easily converted into reactive derivatives of the dicarboxylic acids such as lower alkyl esters, acid halides, acid anhydrides, mixed acid anhydrides, alkali metal salts, silver salts, or organic tertiary or quaternary bases by conventional methods. can be guided to Further, according to the present invention, hydroquinone or a derivative thereof represented by the general formula () and the general formula () [In the formula, Y represents a halogen atom, and A has the same meaning as in the general formula (). ] The 3,4-dihydro-6-hydroxy-2H-benzopyran derivative represented by the general formula () can be produced by reacting the dicarboxylic acid ester represented by the following in the presence of a Lewis acid. Examples of Lewis acids used in this condensation reaction include boron trifluoride/ether complex, aluminum chloride, aluminum bromide, ferrous chloride, ferric chloride, stannous chloride, stannic chloride, and zinc chloride. Zinc chloride is preferred. The amount of Lewis acid used is approximately
The amount is 0.0001 to 1 times the molar amount, preferably about 0.001 to 0.1 times the molar amount. This condensation reaction is preferably carried out in a solvent, and hydroquinone or its derivative represented by the above general formula () and 4-methyl-5,6
The solvents used in the condensation reaction with -dihydro-2H-pyran are likewise used. The amount of the solvent to be used is about 2 to 100 times the weight of the hydroquinone or its derivative represented by the general formula (), preferably about 5 times the weight.
~20 times the weight. This condensation reaction usually starts at -40℃
It is carried out at 150°C, preferably 0°C to 100°C. The dicarboxylic acid ester represented by the general formula () used as a raw material is prepared by combining 4-methyl-5,6-dihydro-2H-pyran and a dicarboxylic acid halide represented by the above general formula () in the presence of a Lewis acid. It can be easily obtained by reaction. This condensation reaction can be carried out in the presence of the same Lewis acid used in the condensation reaction between hydroquinone or its derivative represented by the general formula () and the dicarboxylic acid ester represented by the general formula () above. The amount of Lewis acid used is 4-methyl-
0.001 to 5,6-dihydro-2H-pyran
The amount is 0.5 times the molar amount, preferably 0.01 to 0.5 times the molar amount. This condensation reaction is preferably carried out in a solvent, and the solvent used in the condensation reaction between hydroquinone or its derivative represented by the general formula () and the dicarboxylic acid ester represented by the general formula () above can be similarly used. . The amount of solvent used is approximately 2 to 4-methyl-5,6-dihydro-2H-pyran.
~100 times the weight, preferably about 5 to 20 times the weight.
This condensation reaction is usually carried out at -5°C to 70°C, preferably at 0°C.
Perform at ℃~50℃. The reaction mixture containing the dicarboxylic acid ester represented by the general formula () thus obtained can also be directly subjected to the reaction with the hydroquinone represented by the general formula () or a derivative thereof. A dicarboxylic acid ester represented by the general formula () is obtained by reacting 4-methyl-5,6-dihydro-2H-pyran with a dicarboxylic acid halide represented by the general formula (), and then the dicarboxylic acid ester represented by the general formula A preferred embodiment for producing a 3,4-dihydro-6-hydroxy-2H-benzopyran derivative represented by the general formula () by reacting it with hydroquinone or its derivative represented by () is as follows. show. 4-methyl-5,
6-dihydro-2H-pyran and Lewis acid are dissolved or suspended in a solvent, and then a dicarboxylic acid halide represented by the general formula () is added to give a dicarboxylic acid halide of about 0.5 to
By continuing stirring for 4 hours, a reaction mixture containing a dicarboxylic acid ester represented by the general formula () is obtained. From this reaction mixture, for example, a dicarboxylic acid ester represented by the general formula () is isolated by distillation. Next, hydroquinone or its derivative represented by general formula () and a Lewis acid are dissolved or suspended in a solvent, and while stirring and heating under an inert gas atmosphere such as nitrogen, hydroquinone or its derivative represented by general formula () is dissolved or suspended in a solvent. A dicarboxylic acid ester represented by the general formula () is added in an amount of 0.5 to 0.6 times the molar amount of the dicarboxylic acid ester represented by the general formula () over a period of about 0.5 to 8 hours and allowed to react. After adding the dicarboxylic acid ester represented by the general formula (), stirring is continued for about 0.5 to 4 hours to obtain the 3,4 ester represented by the general formula ().
A reaction mixture containing a -dihydro-6-hydroxy-2H-benzopyran derivative is obtained. The 3,4-dihydro-6-hydroxy-2H-benzopyran derivative can be easily separated and recovered from this reaction mixture by the method described above. 2-substituted ethyl alcohol represented by the general formula () or a reactive derivative thereof used as a raw material in the method for producing a 3,4-dihydro-6-hydroxy-2H-benzopyran derivative represented by the general formula () of the present invention; The dicarboxylic acid ester represented by the general formula () is easily derived from 4-methyl-5,6-dihydro-2H-pyran as described above.
-Dihydro-2H-pyran is produced in large amounts as a by-product when producing isobrene from isobutene and formalin, and can also be synthesized by reacting tertiary butanol with an aqueous formaldehyde solution in the presence of an acid catalyst. It can be easily and inexpensively obtained. Synthesis examples, test examples, and examples of the 3,4-dihydro-6-hydroxy-2H-benzopyran derivative represented by the general formula () used as a stabilizer in the present invention are shown below, but the present invention is not limited to these. It's not something you can do. Synthesis example 1 A mixture of 2.5 g of 3,4-dihydro-2-(2-hydroxyethyl)-2,5,7,8-tetramethyl-2H-benzopyran-6-ol, 0.79 g of pyridine, and 10 ml of methylene chloride was cooled on ice. Then, 50 mmol of succinic acid chloride was added dropwise, and the mixture was stirred at room temperature overnight. Water was added to the resulting reaction solution, extracted with diethyl ether, and the extract was washed with water.
It was dried over anhydrous magnesium sulfate and concentrated. By purifying the concentrated solution by silica gel column chromatography, di[2-(3,4-dihydro-6-hydroxy-
2.54 g of 2,5,7,8-tetramethyl-2H-benzopyranyl)ethyl]succinate was obtained (yield: 87.3%). NMR spectrum (90MHz) δHMS CDCl ₃ : 1.23 (s,
6H); 1.53-2.2 (m, 26H); 2.4-2.75 (m,
8H); 4.05-4.43 (m, 4H); 4.72 (br.s, 2H) Synthesis Examples 2-9 In Synthesis Example 1, 5 mmol of succinic acid chloride
Dicarboxylic acid chloride 5 shown in Table 1 instead of
The corresponding 3,4-
A dihydro-6-hydroxy-2H-benzopyran derivative was obtained. The yield, NMR spectrum, and FD mass spectrum of each are shown in Table 1.

[Table] Synthesis example 10 Ethyl malonate 1.60g, 3,4-dihydro-2
-(2-Hydroxythiethyl)-2,5,7,8-tetramethyl-2H-benzopyran-6-ol
A mixed solution consisting of 4.76 g of p-toluenesulfonic acid, 0.3 g of p-toluenesulfonic acid, and 100 ml of toluene was heated, and 50 ml of toluene was gradually added while the generated ethanol and toluene were gradually distilled off. After stirring at 170°C for 1 hour, the mixture was cooled, toluene and diethyl ether were added, and the mixture was washed successively with 6N hydrochloric acid and brine. The obtained organic layer was dried, concentrated, and purified by silica gel column chromatography to obtain di[2-(3,4-dihydro-6-hydroxy-2,5,7,8-tetramethyl- 2H−
2.61 g of benzopyranyl)ethyl)malonate was obtained (yield 48.3%). FD mass spectrum: [M] ⁺ 568 Synthesis Examples 11-17 In Synthesis Example 1, 3,4-dihydro-2-(2
-Hydroxyethyl)-2,5,7,8-tetramethyl-2H-benzopyran-6-ol (2.5 g) was replaced with 10 mmol of 2-substituted ethyl alcohol shown in Table 2 below, and 5 m of succinic acid chloride was used.
The corresponding 3,4-dihydro-6-hydroxy-2H-benzopyran derivatives were obtained by carrying out the reaction and separation and recovery in the same manner as in Synthesis Example 1 except that 5 mmol of adipic acid chloride was used instead of mol. The results are shown in Table 2.

【table】

[Table] Synthesis example 18 3,4-dihydro-2-(2-
Heating a mixture consisting of 5.0 g of (hydroxyethyl)-2,5,7,8-tetramethyl-2H-benzopyran-6-ol, 1.78 g of thiodipropionic acid, 0.3 g of p-toluenesulfonic acid and 100 ml of toluene, The mixture was refluxed for 20 hours with azeotropic dehydration. The reaction solution was concentrated and purified by silica gel column chromatography to obtain di[2-(3,4-dihydro-6-hydroxy-2,
5,7,8-tetramethyl-2H-benzopyranyl)ethyl]3,3'-thiodipropionate
5.27g was obtained (yield 82%). NMR spectrum (90MHz) δHMS CDCl ₃ : 1.2 (s,
6H); 1.68-2.17 (m, 26H); 2.37-2.9 (m,
12H); 3.7-4.5 (m, 6H) FD-Mass spectrum: [M] ⁺ 6.42 Synthesis Examples 19-25 In Synthesis Example 18, 3,4-dihydro-2-(2
Synthesis Example 18 except that 20 mmol of 2-substituted ethyl alcohol shown in Table 3 below was used instead of 5.0 g of -hydroxyethyl)-2,5,7,8-tetramethyl-2H-benzopyran-6-ol. The corresponding thiodipropionic acid esters were obtained by carrying out the reaction and separation and recovery in the same manner. The results are shown in Table 3.

【table】

[Table] Synthesis example 26 3,4-dihydro-2-(2-hydroxyethyl)-2,5,7,8-tetramethyl-2H-benzopyran-6-ol 2.5 g, thiodiglycolic acid 5 mmol, p-toluenesulfonic acid 0.1 g, While heating a solution consisting of 100 ml of toluene under reflux, the water produced was distilled out of the system. After the resulting reaction solution was cooled, diethyl ether was added thereto, and the mixed solution was then washed with water, dried over anhydrous magnesium sulfate, and concentrated. By purifying the concentrated solution by silica gel column chromatography, di[2-(3,4-dihydro-
1.79 g of 6-hydroxy-2,5,7,8-tetramethyl-2H-benzopyranyl)ethyl thiodiacetate was obtained (yield 58%). FD mass spectrum: [M] ⁺ 614 NMR spectrum (90MHz) δCDCl ₃ HMS: 1.22 (s,
6H); 1.55-2.2 (m, 26H); 2.56 (t, J=6
Hz, 4H); 3.3 (s, 4H); 4.05-4.53 (m, 6H) Synthesis examples 27-31 In Synthesis Example 26, 5 mmol of thiodiglycolic acid
3-thia-1,6-hexanedioic acid, 3, instead of
4-dithia-1,6-hexanedioic acid, 4,5-dithia-1,8-octanedioic acid, 3,5-dithia-
1,7-heptanedioic acid, 4,6-dithia-1,9
- Synthesis example except that 5 mmol of each nonanedioic acid was used
The corresponding dicarboxylic acid diesters were obtained by carrying out the reaction and separation and recovery in the same manner as in 26. Respective yields and NMR spectra,
The FD mass spectra are shown in Table 4.

【table】

[Table] Synthesis Examples 32 to 38 In Synthesis Example 26, 3,4-dihydro-2-(2
-hydroxyethyl)-2,5,7,8-tetramethyl-2H-benzopyran-6-ol 2-substituted ethyl alcohol 10 shown in Table 5 instead of 2.5 g
The corresponding thiodiglycolic acid diesters were obtained by performing the reaction and separation and recovery in the same manner as in Synthesis Example 26 except that mmol was used. The results are shown in Table 5.

【table】

[Table] Synthesis example 39 3,4-dihydro-2-(2-hydroxyethyl)-2,5,7,8-tetramethyl-2H-benzopyran-6-ol 10 g, dimethyl maleate
A solution consisting of 3.16 g of p-toluenesulfonic acid, 0.6 g of p-toluenesulfonic acid, 0.16 g of hydroquinone, and 100 ml of toluene was heated, and the methanol produced was gradually distilled out of the system. The resulting reaction solution was poured into water and extracted with diethyl ether. After washing the extract with water and drying, the low-boiling substances were distilled off under reduced pressure, and the resulting concentrate was purified by silica gel column chromatography to obtain di[2-
(3,4-dihydro-6-hydroxy-2,5,
7,8-tetramethyl-2H-benzopyranyl)
5.93g of ethyl]maleate was obtained (yield 51%). FD mass spectrum: [M] ⁺ 580 NMR spectrum (90MHz) δHMS CDCl ₃ : 1.2 (s,
6H); 1.6-2.3 (m, 26H); 2.56 (t, J=7
Hz, 4H); 4.1-4.6 (m, 6H); 6.1-6.25 (m,
2H) Synthesis example 40 Di[2-(3,4 −
9.04 g of dihydro-6-hydroxy-2,5,7,8-tetramethyl-2H-benzopyranyl)ethyl itaconate (yield 76%). FD mass spectrum: [M] ⁺ 594 NMR spectrum (90MHz) δHMS CDCl ₃ : 1.22 (s,
6H); 1,6-2.2 (m, 26H); 2.57 (t, J=
7Hz, 4H); 3.3 (s, 2H); 4.1~4.5 (m,
6H); 5.67 (s, 1H); 6.3 (s, 1H) Synthesis example 41 3,4-dihydro-2-(2-hydroxyethyl)-2,5,7,8-tetramethyl-2H-benzopyran-6-ol 5.0 g, 4-cyclohexene-1,2-dicarboxylic acid 1.70 g, p - A solution consisting of 0.16 g of toluenesulfonic acid, 0.04 g of hydroquinone and 100 ml of toluene was heated, and the water produced was distilled out of the system. After cooling, water was added and extracted with diethyl ether, and the resulting extract was washed with water.
The concentrate obtained by drying over anhydrous magnesium sulfate and distilling off low-boiling substances under reduced pressure was purified by silica gel column chromatography to obtain di[2-(3,4-dihydro- 6-
Hydroxy-2,5,7,8-tetramethyl-
5.12 g of 2H-benzopyranyl)ethyl 4-cyclohexene-1,2-dicarboxylate was obtained (yield 81%). FD mass spectrum: [M] ⁺ 634 NMR spectrum (90MHz) δHMS CDCl ₃ : 1.2 (s,
6H); 1.6-3.1 (m, 36H); 4.06-4.4 (m, 6H);
5.62 (s, 2H) Synthesis example 42 3,4-dihydro-2-(2-hydroxyethyl)-2,5,7,8-tetramethyl-2H-benzopyran-6-ol 5.0 g, 5-norbornene-2,3-dicarboxylic anhydride 1.64 g A solution consisting of 0.1 g of p-toluenesulfonic acid, 0.1 g of hydroquinone, and 100 ml of toluene was heated, and the water produced was distilled out of the system. After cooling, water was added and extracted with diethyl ether, and the resulting extract was washed with water. The concentrate obtained by drying over anhydrous magnesium sulfate and distilling off low-boiling substances under reduced pressure was purified by silica gel column chromatography to obtain di[2-(3,4-dihydro-
5.1 g of 6-hydroxy-2,5,7,8-tetramethyl-2H-benzopyranyl)ethyl5-norbornene-2,3-dicarboxylate (yield 79%). FD mass spectrum: [M] ⁺ 646 NMR spectrum (90MHz) δHMS CDCl ₃ : 1.2 (s,
6H); 1.4-3.3 (m, 36H); 4.0-4.5 (m,
4H); 4.6-4.83 (m, 2H); 4.87 (s, 2H) Synthesis Examples 43-49 In Synthesis Example 42, 5-norbornene-2,3-
Instead of 1.64 g of dicarboxylic anhydride, 1.52 g of 1-cyclohexene-1,2-dicarboxylic anhydride, 1.54 g of cyclohexane-1,2-dicarboxylic anhydride
g, citraconic anhydride 1.12g, norbornane-
2,3-dicarboxylic anhydride 1.66g, 1,4,
3.71 g of 5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic anhydride, 1,66 g of 4-methyl-4-cyclohexene-1,2-dicarboxylic anhydride or 5-methyl-5 - By carrying out the reaction and separation and recovery in the same manner as in Synthesis Example 42 except that 1,78 g of norbornene-2,3-dicarboxylic acid anhydride was used, the corresponding 3,4-dihydro-6-hydroxy-2H-benzopyran A derivative was obtained. The results are shown in Table 6.

【table】

[Table] Synthesis examples 50 Fumaric acid dichloride was added to a solution consisting of 5.0 g of 3,4-dihydro-2-(2-hydroxyethyl)-2,5,7,8-tetramethyl-2H-benzopyran-6-ol, 1.6 g of pyridine and 40 ml of methylene chloride. 1.53g was added dropwise and stirred at room temperature for 4 hours.
The resulting reaction solution was poured into water and extracted with diethyl ether. The extract was washed with water and dried, and then the low-boiling substances were distilled off under reduced pressure. The resulting concentrate was purified by column chromatography to obtain di[2-(3) ,4-
5.14 g of dihydro-6-hydroxy-2,5,7,8-tetramethyl-2H-benzopyranyl)ethyl fumarate was obtained (yield: 89%). FD mass spectrum: [M] ⁺ 580 Synthesis Examples 51-57 Also in Synthesis Example 39, 3,4-dihydro-2-
(2-hydroxyethyl)-2,5,7,8-tetramethyl-2H-benzopyran-6-ol 10g
2-substituted ethyl alcohol shown in Table 13 instead of
The corresponding 3,4-dihydro-6-hydroxy-2H-benzopyran derivatives were obtained by carrying out the reaction and separation and recovery in the same manner as in Synthesis Example 39, except that 40 mmol was used. The results are shown in Table 7.

[Table] Test Examples 1 to 19 The test compounds shown in Table 8 were added to ethyl linoleate at 0.020 g per 100 g of the ethyl linoleate.
g was added and mixed to create a sample solution. 20 ml of these samples were tested using an AOM (Antioxygen method) test device under AOM conditions (97.8 g, aeration 2.33
cc/sec) and POV (peroxide value)
The time to reach 100meq/Kg was measured. The results are shown in Table 8.

【table】

【table】

[Table] Test Examples 20 to 32 The test compounds shown in Table 9 were added to ethyl linoleate at 0.020 g per 100 g of the ethyl linoleate.
g was added and mixed to create a sample solution. 20ml of these samples were tested using an AOM (Antioxygen method) test device under AOM conditions (97.8°C, aeration 2.33°C).
cc/sec) and POV (peroxide value)
The time to reach 100meq/Kg was measured. The results are shown in Table 9.

【table】

[Table] Tetraester test examples 33-51 Add the test compounds shown in Table 10 to ethyl linoleate at 0.020 g per 100 g of ethyl linoleate.
g was added and mixed to create a sample solution. 20ml of these samples were tested using an AOM (Antioxygen method) test device under AOM conditions (97.8°C, aeration 2.33°C).
cc/sec) and POV (peroxide value)
The time to reach 100meq/Kg was measured. The results are shown in Table 10.

【table】

【table】

[Table] Examples 1 to 9 Anti-aging test of polyisoprene rubber
parts of resin) containing high-cis-1,4-polyyprene rubber (manufactured by Clareisoprene Chemical Co., Ltd., Kuraprene 1R-10, viscosity average molecular weight
850,000) was subjected to an aging test for a certain period of time in an oven at 100°C, and the plasticity Pt of the aged polyisoprene rubber and the plasticity Po of the unaged polyisoprene rubber were measured using a Wallace plasticity meter. The residual plasticity rate PRI (%) = (Pt/Po) x 100 was determined. The results are shown in Table 11.

【table】

[Table] Examples 10 to 18 Anti-aging test of polypropylene Polypropylene containing 0.1 PHR of the test compound (manufactured by Mitsubishi Chemical Corporation, NOVATEC-P,
4500J, melting index: 8.0, specific gravity: 0.90) was kneaded in a Plastograph kneader at 30 rpm under heating at 240°C, and the change in melt-kneading torque (m, g) over time was investigated. The results are shown in Table 12.

【table】

【table】

[Table] Examples 19 to 22 Anti-aging test on polyethylene Polyethylene containing 1 PHR of the test compound (manufactured by Nippon Petrochemical Co., Ltd., LDPE F-22CE, melting index: 1.0, specific gravity: 0.924) was mixed with a Plastograph kneader at 320°C. While kneading at 30 rpm under heating at .degree. C., changes in melt-kneading torque (m, g) over time were investigated. The results are shown in Table 13.

[Table] Examples 23 to 25 Anti-aging test of polyurethane Polyurethane containing 1 PHR of the test compound [polytetramethylene glycol (molecular weight 2000), 4,
[Prepared by polymerizing 4'-methylenebis(phenylisocyanate) and 1,4-butanediol in a ratio of 1:5:4] was aged in an oven at 120°C for 750 hours, and its tensile strength was measured. The results are shown in Table 14. The tensile strength of the polyurethane before aging was 750 Kg/cm ² .

【table】

Claims (1)

[Claims] 1 General formula () [In the formula, R ¹ represents a hydrogen atom or a lower alkyl group. R ² and R ³ are the same or different and represent a hydrogen atom, a lower alkyl group, or a lower alkoxy group, or R ² and R ³ together represent -CH=CH-CH
Forms a =CH- group. A is ( _-CH2 ) _-o group, phenylene group _{, -CH2SCH2-} group _{, -CH2CH2SCH2- group} ,
−CH ₂ CH ₂ SCH ₂ CH ₂ − group, CH ₂ S−SCH ₂ − group, −
CH ₂ CH ₂ S−SCH ₂ CH ₂ − group, −CH ₂ SCH ₂ SCH ₂ −
group, -CH ₂ CH ₂ SCH ₂ SCH ₂ CH ₂ - group,
[Formula] represents a group selected from the group consisting of [Formula] and [Formula]. Here, n means an integer of 1 or more.
R ⁵ and R ⁶ are the same or different and represent a hydrogen atom or a lower alkyl group, or R ⁵ and R ⁶ together represent a -(CH ₂ ) ₄ - group. R ⁷ and R ⁸ together represent [Formula] [Formula] [Formula] [Formula] or [Formula], R ⁹ represents a hydrogen atom or a lower alkyl group, and X represents a halogen atom. ] 3,4-dihydro-6-hydroxy-
0.001~ using 2H-benzopyran derivative as stabilizer
Organic composition containing 20% by weight. 2 3,4-dihydro- represented by general formula ()
An organic composition according to claim 1, which contains a synergistic stabilizing agent in a proportion of about 50 to 500% by weight relative to the 6-hydroxy-2H-benzopyran derivative.