JP3213366B2 - Cinnamic acid derivatives - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a cinnamic acid derivative,
In particular, the present invention relates to a novel cinnamic acid derivative which can be highly blended with a silicone material and has high ultraviolet absorption performance, and an intermediate thereof.

[0002]

BACKGROUND OF THE INVENTION Cinnamic acids have been known to be effective as ultraviolet absorbers for cosmetics and various plastics. However, this material has limited solubility in cosmetic materials and various plastics because its solubility and dispersibility are not so good.
Bleeding occurs due to poor dispersibility,
As a result, there were drawbacks that the expected ultraviolet absorption performance was not sufficiently exhibited. In various fields such as cosmetics,
Despite the use of silicone-based materials such as silicone oils and silicone resins, conventional cinnamic acids have the disadvantage that they have particularly poor solubility in silicone-based materials.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and to provide a novel cinnamic acid derivative having excellent solubility in silicone-based materials and high UV-absorbing performance, and its production. To provide intermediates for

[0004]

That is, the present invention provides a compound represented by the general formula

[0005]

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Wherein R ¹ is a hydrogen atom or an alkoxy group, R ² is a substituted or unsubstituted monovalent hydrocarbon group, Y is an alkoxy group, an aryloxy group or a hydroxyl group;
Represents an integer of 0 to 3), and a general formula useful for synthesizing the cinnamic acid derivative:

[0007]

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(Wherein R ¹ is the same as described above).

In the compound (I) of the present invention, R ¹ is a hydrogen atom or an alkoxy group. R ¹ is, for example, a hydrogen atom; methoxy group, ethoxy group, propoxy group, isopropoxy group, methoxyethoxy group, butoxy group, sec
And alkoxy groups such as -butoxy group, isobutoxy group, t-butoxy group, cyclohexyloxy group and 2-ethylhexyloxy group. Among these, a methoxy group is particularly preferable from the viewpoint of availability of raw materials and ultraviolet absorption performance. In the compound (I) of the present invention, R ² is a substituted or unsubstituted monovalent hydrocarbon group. The R ^2,
For example, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and dodecyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group Aralkyl groups such as 2-phenylethyl group and 2-phenylpropyl group; aryl groups such as phenyl group and tolyl group; alkenyl groups such as vinyl group and allyl group; Such as chloromethyl, chlorophenyl, 3,3,3-trifluoropropyl, aminoethyl, and cyanoethyl groups in which hydrogen atoms bonded to carbon atoms are partially substituted with halogen atoms, amino groups, cyano groups, etc. And substituted hydrocarbon groups. Among these, a saturated hydrocarbon group having 1 to 4 carbon atoms, particularly a methyl group, is preferable because the raw material can be easily obtained and synthesized. In the compound (I) of the present invention, Y is, for example, a methoxy group, an ethoxy group, a propoxy group,
Isopropoxy group, methoxyethoxy group, butoxy group,
sec-butoxy group, isobutoxy group, t-butoxy group,
Examples are an alkoxy group such as a cyclohexyloxy group; an aryloxy group such as a phenoxy group; and a hydroxyl group. Among these, an ethoxy group and a methoxy group are particularly preferable from the viewpoint of ease of synthesis, stability, appropriate reactivity, and the like.

The method for producing the compound (I) of the present invention will be described below. That is, the compound (I) of the present invention can be obtained by subjecting another compound of the present invention represented by the general formula (II) to an addition reaction with a silane compound represented by the general formula (III).
The chemical reaction formula is shown in equation (1).

[0011]

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(Wherein R ¹ , R ² , Y and n are the same as described above) Here, as the silane compound (III) used as a raw material, for example, trimethoxysilane, triethoxysilane,
Monohydrogenalkoxysilanes such as methyldimethoxysilane and dimethylethoxysilane; monohydrogenphenoxysilanes such as methyldiphenoxysilane; and monohydrogensilanols such as diethylsilanol, diphenylsilanol and methylphenylsilanol. Among these, trimethoxysilane and triethoxysilane are particularly preferable in terms of availability of raw materials, ease of synthesis, reactivity, and the like. In the addition reaction formula (1), the intermediate (II) and the silane compound (III)
There is no particular limitation on the proportion used, but one mole of the hydrosilyl group of the silane compound (III) reacts with one mole of the vinyl group of the intermediate (II). preferable. As the catalyst for the addition reaction of the formula (1), a platinum complex having a siloxane derivative of an olefin as a ligand is preferable, and among them, 1,3,5,7-tetravinyl-
Platinum complexes having 1,3,5,7-tetramethylcyclotetrasiloxane as a ligand are particularly preferred. The amount of the platinum complex used is not particularly limited, but is preferably in the range of 2 ppm or more and less than 2000 ppm as platinum atoms with respect to the amount of the intermediate (II). If it is less than 2 ppm, the reaction is slow and a good yield cannot be obtained in a short time. Further, the use of 2,000 ppm or more has no particular effect. In the addition reaction formula (1), the use of an organic solvent is not essential, but when the intermediate (II) is a solid, it is preferable to use an organic solvent that dissolves the intermediate (II) in terms of reaction control. As such an organic solvent, those which are inert to the reactants are desirable, for example, aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as hexane and heptane; and oils such as cyclohexane. Cyclic hydrocarbons; ethers such as dibutyl ether; and halogenated hydrocarbons such as 1,2-dichloroethane; ketones such as methyl ethyl ketone. These organic solvents may be used alone or as a mixture of two or more. The amount of the organic solvent used is not particularly limited, but is preferably in the range of 10% by weight or more and 1000% by weight or less based on the total weight of the reactants. This addition reaction is a method in which an intermediate (II), a catalyst and an organic solvent are charged, the intermediate (II) is dissolved by heating to a required temperature, and a silane compound (III) is added dropwise to the reaction. Can be done by
It is preferable from the viewpoint of reaction control. The reaction temperature of this addition reaction is 10-20
0 ° C, more preferably in the range of 40 to 120 ° C. The reaction time depends on the amount of catalyst used, reaction temperature, raw material molar ratio, etc.
It can be changed in the range of ~ 100 hours. This reaction can be carried out either under normal pressure or under pressure. The compound (I) of the present invention can be isolated and purified from the reaction mixture thus obtained by a method generally used in the field of synthetic organic chemistry. The compound (I) can be isolated by removing the components by distillation and, if necessary, using purification means such as solvent extraction, recrystallization, and column chromatography.

For use in the production of the compound (I) of the present invention,
Intermediate (II), another compound of the present invention, is synthesized by the following method. That is, cinnamic acid (IV) and 3-chloro-2
-Dehydrohalogenation with chloromethylpropene in the presence of a base, for example a tertiary amine such as triethylamine, 1,8-diazabicyclo [5,4,0] -7-undecene. This is shown in chemical reaction formula (2).

[0014]

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(Wherein R ¹ is the same as above and B is a tertiary amine) In the reaction formula (2), cinnamic acid (I
V) are known substances, for example, cinnamic acid, 2-hydroxycinnamic acid, 3-hydroxycinnamic acid, 4-hydroxycinnamic acid, 2-methoxycinnamic acid, 3-methoxycinnamic acid, Examples include methoxycinnamic acid and 4-butoxycinnamic acid. Among these, 4-methoxycinnamic acid is particularly preferred from the viewpoint of industrial availability and ultraviolet absorption performance. Also, in the reaction formula (2), 3-chloro-2-chloromethylpropene used as a raw material is also a known substance. For example, a method of chlorinating 3-chloro-2-methylpropene with sulfuryl chloride (European Patent No. 1595
No. 08) or a method of reacting chlorine gas with methylenecyclopropane (R. Koester, P. Binger; Justus
Liebibs Ann. Chem., 10, 1619 (1973)). The reaction of reaction formula (2) is carried out in an aromatic hydrocarbon solvent in a cinnamic acid (IV), tertiary amine and 3-chloro-
The reaction can be carried out by heating and stirring the mixture of 2-chloromethylpropene at 40 ° C. to the reflux temperature of the solvent. The ratio of the reactants used is not particularly limited, but the stoichiometric amount is economically preferable. Examples of the aromatic hydrocarbon solvent used in this reaction include benzene, toluene, xylene and the like, and toluene is particularly preferably used from the viewpoint of reaction control and safety. The isolation and purification described in the addition reaction formula (1) can be applied to the isolation and purification of the intermediate (II) from the reaction mixture.

[0016]

The compound (I) of the present invention has a cinnamic acid structure in its molecular structure, so that it has a high ultraviolet absorption performance, and has a silyl group, so that it has very high solubility in silicone-based materials such as silicone oil. There are features that are excellent. Further, since the silyl group of the compound (I) of the present invention is hydrolyzable, it imparts adhesion to a substrate of a silicone-based material such as glass, metal, and plastic, and is a raw material for producing a silicone oil having an ultraviolet absorbing function. It is also useful.

[0017]

The present invention will be described in more detail with reference to the following examples. The scope of the present invention is not limited only to the following examples. Example 1 Synthesis of 2-methylene-1,3-di (p-methoxycinnamoyloxy) propane p-Peptide was placed in a 500 ml flask equipped with a stirrer, thermometer, dropping funnel, reflux condenser and oil bath. 25.0 g (0.14 mol) of methoxycinnamic acid and 100 g of toluene were charged, and stirring was started. Add 14g of triethylamine
(0.14 mol) was added dropwise from a dropping funnel at a liquid temperature of 40 to 45 ° C. over 10 minutes. Then, from the dropping funnel, 3-chloro-2-
Add 8.8 g (0.07 mol) of chloromethylpropene at a liquid temperature of 45-50.
At 15 ° C. over 15 minutes, and further heated and stirred at a liquid temperature of 80 to 85 ° C. for 15 hours. The peak of p-methoxycinnamic acid almost disappeared by liquid chromatography analysis, and the reaction product 2-methylene- It was confirmed that 1,3-di (p-methoxycinnamoyloxy) propane was produced. next,
After cooling to room temperature, triethylamine hydrochloride was filtered off, and the filtrate was washed twice with 100 ml of a saturated saline solution, and dried over anhydrous sodium sulfate. After drying, low boiling components such as toluene were distilled off to obtain white crude crystals. The crystals were recrystallized from 70 ml of ethanol and dried under reduced pressure at room temperature for 4 hours. As a result, white powdery 2-methylene-1,3-di (p-methoxycinnamoyloxy)
22.8 g (80.0% yield) of purified crystals of propane were obtained. The results of liquid chromatography analysis, melting point measurement, elemental analysis, infrared absorption spectrum analysis, ¹ H nuclear magnetic resonance absorption analysis, and mass spectrum analysis of this product are as described below, and it was confirmed that the molecular structure was as follows: .

[0018]

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Liquid chromatography analysis (UV detector; 254 nm): 98.7% of main component purity Melting point measurement: 70-71 ° C. Elemental analysis: actual measurement value C: 70.60% H: 5.80% O:
28.60% Calculated C: 70.57% H: 5.92% O: 28.51% · infrared absorption spectrum analysis (Ekimakuho): wavenumber (cm ^-1) Attribution 2940 C-H 1705 C = O 1595 C = C · 1 H Nuclear magnetic resonance absorption analysis (90 MHz, in CDCl ₃ ): Position Chemical shift δ (ppm) Integrated intensity Multiplicity a 4.05 6Hsb 6.95 to 7.80 8Hmc 6.67 2Hsd 6.40 2Hse 5.00 4Hsf5.55 2H s mass spectrometry (m / e): 408 (M ⁺ peak) Example 2 2- (p-methoxycinnamoyloxy) methyl-3-
Synthesis of (p-methoxycinnamoyloxy) propyltriethoxysilane 2-Methylene-methyl was added to a 200-ml flask equipped with a stirrer, thermometer, dropping funnel, reflux condenser and oil bath.
1,3-di (p-methoxycinnamoyloxy) propane
10.2 g (0.025 mol), toluene 10 g, and 1,3,5,7
-Platinum complex with tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane as ligand (platinum content 2
%), Stirring was started, and the solution was heated to 62 ° C. 4.1 g of triethoxysilane was added from the dropping funnel.
(0.025 mol) was added dropwise at a liquid temperature of 62 to 64 ° C over 10 minutes. After completion of the dropwise addition, the mixture was heated and stirred at a liquid temperature of 75 to 79 ° C. for 2 hours, and the peak of the raw material almost disappeared by liquid chromatography analysis.
It was confirmed that an addition reaction product was formed. After standing to cool, low boiling components such as toluene are removed by distillation, and yellow transparent liquid 2- (p-methoxycinnamoyloxy) methyl-
14.0 g (yield 98.0%) of 3- (p-methoxycinnamoyloxy) propyltriethoxysilane was obtained. The results of liquid chromatography analysis, elemental analysis, infrared absorption spectrum analysis, ¹ H nuclear magnetic resonance absorption analysis, ultraviolet absorption spectrum analysis, and mass spectrum analysis of this product are as described below, and the molecular structure of the following formula was confirmed. confirmed.

[0020]

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Liquid chromatography analysis (UV detector; 254 nm): 96.8% Elemental analysis: Actual measured value Si: 5.00% C: 62.90% H: 6.99% O: 2
5.11% Calculated value Si: 4.91% C: 62.91% H: 7.04% O: 2
5.14% and infrared absorption spectrum analysis (Ekimakuho): wavenumber (cm ^-1) Attribution 2940 C-H 1705 C = O 1595 C = C 1100~1080 Si-OCH 2 · 1 H nuclear magnetic resonance analysis (90 MHz , In CDCl ₃ ): Position Chemical shift δ (ppm) Integrated intensity Multiplicity a 4.00 6Hsb 6.90 to 7.88 8Hmc 6.67 2Hsd 6.40 2Hse 4.40 to 4.57 4Hdf 2.50 to 3.20 1Hmg 1.20 -1.50 2Hmh 3.80-4.36Hqi 1.30-1.69Ht ・ Ultraviolet absorption spectrum analysis (solvent; ethanol): absorption maximum wavelength λmax = 310 nm molar extinction coefficient εmax = 1.50 × 10 ⁴ dm ³ mol ^-1 cm ^-1 cm ^-1 Mass spectrometry (m / e): 572 (M ⁺ ) The compound obtained in this example was added to various silicone oils in 10
% Solubility at 25 ° C (○: soluble, ×:
Insoluble) are shown in Table 1. The case of methyl 4-methoxycinnamate is also shown as a comparative product.

[0022]

[Table 1]

Note) * 1) Methyl 4-methoxycinnamate

──────────────────────────────────────────────────の Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C07F 7/18 C07C 69/618 C07C 69/736 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A compound of the general formula (Wherein, R ¹ is a hydrogen atom or an alkoxy group, R ² is a substituted or unsubstituted monovalent hydrocarbon group, Y is an alkoxy group, an aryloxy group, or a hydroxyl group, and n represents an integer of 0 to 3. The cinnamic acid derivative represented by). 2. A compound of the general formula (Wherein R ¹ is the same as defined above).