JPH06104647B2 - Ferulic acid derivative, method for producing the same, and ultraviolet absorber - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel ferulic acid derivative, a method for producing the same and an ultraviolet absorber comprising the compound.

[0002]

2. Description of the Related Art Benzophenone-based, benzotriazole-based, and salicylic acid-based compounds are well known as ultraviolet absorbers. However, since the benzophenone-based and benzotriazole-based ultraviolet absorbers are produced from petroleum, their toxicity is a problem. The salicylic acid-based UV absorber has no toxicity problem, but has a problem of low UV absorption ability.

On the other hand, the present inventor previously proposed a method for extracting ferulic acid from rice bran. Ferulic acid extracted is
Although it has no toxicity problem and can be used as an ultraviolet absorber by itself, it is not suitable for preventing deterioration of plastics and the like because it is water-soluble.

[0004]

Therefore, as a result of studying a ferulic acid derivative having good compatibility with plastics and the like,
The inventors have found that the novel ferulic acid derivative represented by the following formula is compatible with plastics and serves as an excellent ultraviolet absorber, and completed the present invention.

[0005]

The ferulic acid derivative of the present invention is represented by the following chemical formula 6.
The general formula shown in

[0006]

[Chemical 6] (In the formula, R represents a substituent selected from the group consisting of a hydrogen atom, a lower alkyl group, a halogen, a methoxy group, a nitro group and an amino group.). Examples of the novel ferulic acid derivative of the present invention include the following. (1) Benzyl 3- (4'-benzyloxy-3'-methoxyphenyl) -2-propenoate. (2) 3- {4 '-(4 "-nitrobenzyloxy)
-3'-methoxyphenyl} -2-propenoic acid 4 ''
´-Nitrobenzyl. The novel compound according to the present invention is

[0007]

[Chemical 7]

Compound (ferulic acid: extinction coefficient, λ _max = 322 nm, ε _max = 1.0 × 10 ⁴ )
Is reacted with an alkaline compound such as sodium hydroxide, potassium hydroxide, sodium metal, sodium hydride, and the resulting alkali salt is represented by the general formula

[0009]

[Chemical 8]

(In the formula, R is a hydrogen atom, a lower alkyl group,
Halogen, methoxy group, nitro group, amino group, X represents a substituent selected from the group consisting of chlorine atom, bromine atom and iodine atom. ) It synthesize | combines by making it react with the compound shown.

As the solvent for this reaction, many organic solvents such as benzene, chlorobenzene, toluene, dioxane, N, N-dimethylformamide, dimethylsulfoxide and alcohol can be used.

When an aromatic solvent such as benzene is used, when a quaternary ammonium salt such as tetrabutylammonium bromide or benzyltrimethylammonium chloride or a tertiary amine such as triethylamine is used as a catalyst. It is preferable because the reaction rate is increased.

The novel compounds of this invention are UV, especially organic.
Light region that deteriorates or destroys substances, 310 to 380 nm
Since it strongly absorbs ultraviolet rays, it cannot be mixed with plastic.
And helps prevent its deterioration. For example, when R = H
Compound (3- (4'-benzyloxy-3'-methoxyphen
Nyl) -2-benzyl propeneate), λ_max= 326n
m, ε_max= 2.67 × 10^Four And R = NO₂Place
Compound (3- {4 '-(4 "-nitrobenzyloxy)-
3'-methoxyphenyl} -2-propenoic acid 4 '' '-
Nitrobenzyl), λ_max= 325 nm, ε_max= 2.
07 x 10^Four Is. Moreover, the method of the present invention comprises one step.
Therefore, it is very easy to manufacture.

The compound of the present invention is not toxic, has an excellent ability to absorb ultraviolet rays, has a high solubility in organic solvents (oil solubility), and is insoluble in water. Therefore, it is effective as an ultraviolet absorber for synthetic resins and natural resins. It can also be used in cosmetics. When the compound of the present invention is used as an ultraviolet absorber, the amount thereof used varies depending on the material used, but is usually 0.1 to 1.0% by weight, preferably 0.
The effect is exhibited by adding 3 to 0.5% by weight. As a method of use, various methods such as mixing with a resin and coating on the surface can be applied.

[0015]

Embodiments of the present invention will be described below. Example 1

In a three-necked flask equipped with a condenser,
Luluric acid (1.94 g, 0.01 mol) potassium hydroxide
(1.32 g, 0.024 mol), and benzyl chloride
Add trimethylammonium (0.186g) and
Zen (30 mL) was added, and the mixture was stirred at room temperature for 1 hr. That
After that, benzyl chloride (2.78 g, 0.022 mol) was added.
Then, the mixture was stirred at 80 ° C. for 7 hours. After the reaction, add 30 mL of water
Then, the pH was adjusted to 7 with dilute sulfuric acid. Separate the benzene layer
It was dried over water magnesium sulfate. When benzene is distilled off
3.74 g (yield, 100%) of 3- (4'-benzyl)
Oxy-3'-methoxyphenyl) -2-propenoic acid
Obtained. The compound obtained in Example 1 has a melting point
77 ° C (recrystallized from ethanol), UV absorption 270-3
80 nm (in 95% ethanol), ε_max= 2.67 × 1
0^Four (Λ_max= 326 nm) IR (KBr): 3060, 1705, 1695, 1635, 1600, 1510, 13
80, 1300, 1250, 1180, 1140, 1000 cm^-1.

NMR (CDCl ₃ ) δ 3.89 (3H,
_{s, OCH 3), 5.17 (} 2H, s, CH 2), 5.
_{23 (2H, s, CH 2} ), 6.2-7.7 (15H,
m) ppm. Solubility in solvent (25 ° C) Water Methanol Acetone Toluene 0.0g / 100mL 1.23g / 100mL 10.2g / 100mL 15.3g / 100mL Analytical value C, 77.03%; H, 6.01%. Calculated value C ₂₄ H ₂₂ O ₄ : C, 76.98%; H, 5.92%. Example 2

The reaction was conducted in the same manner as in Example 1 except that p-nitrobenzyl bromide was used in place of benzyl chloride to give 3- {4 '-(4 "-nitrobenzyloxy) -3. ′ -Methoxyphenyl} -2-propenoic acid 4 ″ ″-nitrobenzyl was obtained with a yield of 100%. Melting point 159-160 ° C. (from mixed solvent of ethanol and CHCl ₃ ) UV absorption 250-380 nm (in CHCl ₃ ), ε _max = 2.34
× 10 ⁴ (Λ _max = 285 nm), ε _max = 2.07 × 10 ⁴ (Λ _max
= 325nm) IR (KBr): 1715, 1635, 1605, 1585, 1520, 1380, 134
5, 1310, 1275, 1180, 1140, 1035, 810, 740 cm ^-1 . NMR (CDCl ₃ ): δ3.94 (3H, s, OC
H ₃ ), 5.23 (2H, s, CH ₂ · C ₆ H ₅ ) 5.33 (2H, s, CH ₂ · C ₆ H ₅ ) 6.38 (1H, d, C H ═CH—CO, J = 15.83HZ) 7.69 (1H, d, CH = C H -CO, J = 15.83Hz), 6.
8 to 8.3 (11H, m, Arom). Solubility in solvent (25 ℃) Solubility Water Methanol Acetone CHCl ₃ Toluene 25 ℃ 0g / 100mL 0.18g / 100mL 0.54g / 100mL 4.94g / 100mL 0.24g / 100mL Analytical value C, 62.15%, H, 4.37%, N , 6.11%. Calculated value C ₂₄ H ₂₀ N ₂ O ₈ : C, 62.06%, H, 4.34
%, N, 6.03

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Koji Kato 22-14, Shiroyamadai, Hashimoto-shi, Wakayama 22 (72) Inventor Yasuhisa Tanaka 9 Nagata, Koga-cho, Naga-gun, Wakayama (72) Inventor Chieko Hayashi 150 at 277 Nagayama, Kazakawa-cho, Naga-gun, Wakayama

Claims (7)

[Claims] 1. A general formula represented by the following chemical formula 1 (In the formula, R represents a substituent selected from the group consisting of a hydrogen atom, a lower alkyl group, a halogen, a methoxy group, a nitro group and an amino group.). 2. The compound according to claim 1, which is benzyl 3- (4′-benzyloxy-3′-methoxyphenyl) -2-propenoate. 3. The compound according to claim 1, which is 4- {4 ′-(4 ″ -nitrobenzyloxy) -3′-methoxyphenyl} -2-propenoic acid 4 ″ ″-nitrobenzyl. 4. A general formula represented by the following chemical formula: The compound represented by the formula (1) is reacted with an alkaline compound, and the obtained compound into which an alkali metal is introduced is represented by the following general formula: (In the formula, R represents a hydrogen atom, a lower alkyl group, a halogen, a methoxy group, a nitro group, an amino group, and X represents a substituent selected from the group consisting of a chlorine atom, a bromine atom and an iodine atom.) The compound represented by the following general formula: (In the formula, R is the same as the substituent of claim 1.) A method for producing a compound represented by the formula. 5. A general formula represented by the following chemical formula 5 (In the formula, R represents a substituent selected from the group consisting of a hydrogen atom, a lower alkyl group, a halogen, a methoxy group, a nitro group and an amino group.) An ultraviolet absorber containing an effective amount of the compound represented by the formula. 6. The ultraviolet absorbent according to claim 5, which contains an effective amount of benzyl 3- (4′-benzyloxy-3′-methoxyphenyl) -2-propenoate. 7. The ultraviolet ray according to claim 5, which contains an effective amount of 4- {4 ′-(4 ″ -nitrobenzyloxy) -3′-methoxyphenyl} -2-propenoic acid 4 ″ ″-nitrobenzyl. Absorbent.