JPH02167291A - Silicone-based cinnamic acid derivative, production thereof and ultraviolet light absorber - Google Patents

Abstract

NEW MATERIAL:A compound which is a siloxane having a unit shown by formula I [R<1> is 1-4C alkyl, phenyl or trimethylsiloxy; R<2> is bifunctional hydro carbon (hydrocarbon containing plural oxygen atoms is included) containing at least two carbons; X is alkoxy; n is 0-3; a is 2 or 3; R<3> is 1-4C alkyl, phenyl or trimethylsiloxy; m is 0-3] and has another unit shown by formula II existing in the siloxane. EXAMPLE:[3-Bis(trimethylsiloxy)methylsilyl-1-methylpropyl]-3,4,5-trime thoxy cinnamate shown by formula III. USE:An ultraviolet light absorber soluble in silicone oil, having excellent water resistance and oil resistance. PREPARATION:A cinnamic ester shown by formula IV [Y is monofunctional hydrocarbon containing at least two carbons and olefinic unsaturated bond (hydrocarbon containing plural oxygen atoms is included)] is reacted with a siloxane containing units shown by formula V and VI in an organic solvent in the presence of a flux.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel silicone-based cinnamic acid derivative, a method for producing the same, and a novel ultraviolet absorber.

More specifically, the present invention relates to a novel silicone-based cinnamic acid derivative that is soluble in silicone oil, has excellent water and oil resistance, and has ultraviolet absorption characteristics in wavelengths in the UV-B region.

[Prior Art] It is known that ultraviolet rays cause various changes in the skin. Dermatologically, the working wavelength is 400-320 r.
Classified into long wavelength ultraviolet rays of + m, medium wavelength ultraviolet rays of 320-290 nm, and short wavelength ultraviolet rays of 290 nm or less.
They are called UV-A, UV-B and UV-C, respectively.

Normally, most of the ultraviolet rays that humans are exposed to are from sunlight, but the ultraviolet rays that reach the ground are UV-A and UV-B.
UV-C is absorbed in the ozone layer and almost never reaches the ground. Among the ultraviolet rays that reach the ground, UV-B causes changes such as erythema and water spots when the skin is irradiated with more than a certain amount of light, as well as increased melanin formation and pigmentation. bring about.

Therefore, protecting the skin from UV-B is extremely important in terms of preventing the acceleration of skin aging and preventing the occurrence and aggravation of age spots and freckles.
-B absorbers have been developed.

As existing UV-B absorbers, PABA derivatives, cinnamic acid derivatives, salicylic acid derivatives, camphor derivatives, urocanic acid derivatives, pendaphenone 1 bald conductor, and heterocyclic derivatives are known.

These UV-B absorbers are used exclusively by being incorporated into external preparations such as cosmetics and quasi-drugs.

On the other hand, it is well known that silicone bases such as low molecular weight dimethylpolysiloxane are widely used as bases for external preparations.

This is largely due to the silicone base's excellent usability, such as good spreadability, light feel, and non-stickiness, and excellent functionality, such as not being easily washed away by sweat or water.

However, existing UV-B absorbers have extremely low compatibility with silicone bases.

Therefore, in order to incorporate it into a silicone-based external preparation, it is necessary to further add an oily base, which has the disadvantage that the usefulness of the silicone-based base described in Y11 cannot be fully demonstrated.

Furthermore, it also had the disadvantage of being inferior in water resistance and oil resistance.

On the other hand, patents for silicone having ultraviolet absorbing ability include Japanese Patent Publication No. 44-29866, Japanese Patent Application Publication No. 60-58991, and Japanese Patent Application Publication No. 60-108431.

However, these chemical structures have a basic skeleton of unsubstituted cinnamic acid, and in silicone oil, UV-C
The absorption maximum wavelength was on the side, and the UV-B absorption ability was insufficient. (Figure 3 shows the UV absorption spectrum of 3-bis(trimethylsiloxy)methylsilyl-2methylpropyl-cinnamate.As a UV-B absorber,
It can be seen that it does not have an appropriate wavelength range. ) Under these circumstances, there has been a strong desire to develop an ultraviolet absorber that dissolves in silicone oil, has excellent water and oil resistance, and provides sufficient protection against wavelengths in the UV-B region.

As a result of intensive research aimed at obtaining an ultraviolet absorber that dissolves in silicone oil, has excellent water resistance and oil resistance, and has an appropriate UV-B wavelength range, the present inventors discovered that the silicone-based cinnamic acid according to the present invention The inventors have discovered that the derivative is a compound that satisfies the above-mentioned properties, and have completed the present invention.

This compound is a new compound that has not been described in any literature, and is an extremely useful substance as an ultraviolet absorber or an intermediate thereof.

[Means to solve the problem]

That is, the present invention according to claim 1 provides: - Format (1) The invention according to claim 2 provides siloxanes having at least one unit represented by the general formula, which may be present in the siloxane. a cinnamic acid ester represented by a silicone-based cinnamic acid derivative characterized in that the unit is represented by the -format 0.4-07□StR3m; m 5
1. The method for producing a silicone-based cinnamic acid derivative according to claim 1, wherein the silicone-based cinnamic acid derivative is reacted with a siloxane having 10 (4-s)/2 units in an organic solvent in the presence of a catalyst.

The invention according to claim 3 is an ultraviolet absorber comprising the silicone-based cinnamic acid derivative according to claim 1, and is a use invention of the silicone-based cinnamic acid derivative according to claim 1.

The present invention will be explained in detail below.

The silicone-based cinnamic acid derivative of the present invention is composed of a unit represented by the -format (1) and a unit represented by -i2〇(4-111/□5iR3+*, and in the formula Examples of defined R1 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, L-butyl, phenyl group, trimethylsiloxy group, etc. However, due to the ease of obtaining raw materials, methyl group or its It is preferable that a part thereof is a phenyl group or a trimethylsiloxy group. n represents the number of substitutions of R1.

Examples of R2 include, for example, CI□CI□=, -CH2C)12CH2--CH2C
HCN, --CCH2CH□(jb (CH:1)2 --C112CH2C1(-, --CH2CH2CH2CH
2-, -CH2C1(20C)H2C)12C1(.

Examples include hexylene, cyclohexylene, decylene groups, etc., but alkylene groups having 2 to 4 carbon atoms are preferred, particularly -CH□CH, CH-, since they cause relatively few side reactions in the hydrosilylation reaction.

CH, is good Delicious.

Examples of X include methoxy, ethoxy, isopropoxy, and the like. Although there is no significant difference in solubility in silicone bases and UV-B absorption wavelengths, methoxy groups are particularly preferred from the viewpoint of easy availability of reagents. a represents the number of substitutions of X.

In the siloxane unit represented by the general formula 0.4-0zzsiR", R3 is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, L
Examples thereof include -butyl, phenyl group, trimethylsiloxy group, etc., but it is preferable that the methyl group or a part thereof is a phenyl group or a trimethylsiloxy group for reasons such as availability of raw materials. m is the number of substitutions of R3.

The silicone-based cinnamic acid derivative of the present invention can be synthesized by the manufacturing method described in claim 2.

- The ester of format (2) is obtained by converting the corresponding substituted cinnamic acid derivative into an acid chloride by a conventional method, and then reacting it with a monohydric alcohol having an olefinically unsaturated bond in the presence of an amine. . Usual organic solvents can be used as reaction solvents, among which toluene,
Aromatic organic solvents such as benzene and xylene are preferred, and the reaction temperature is high, with reflux temperature being particularly preferred.

Depending on the alcohol used in the reaction, Y in -a formula (2)
are different, but are monovalent hydrocarbon groups (including those with a heteroatom O) having at least 2 carbon atoms and an olefinically unsaturated bond: for example, as a straight-chain hydrocarbon group , CHz=CH-CH2CHCH! -,
CH2=CHCH2CH2-CHz=CH-CHzCH
CHz=CH-CH(Me) as a branched hydrocarbon group such as zCHz-, CHz"CH-CHzOCHzCHz-, etc.
CHz=CH-C(Me)z-, CH,=CH-CH(
Et)CH2CH2(Et)z-, CHz”C)ICH
zCH(Me)-CHz=CI(CH(Me) CHt
-, CHz=C(Me)CHz-, etc., and some have a double bond at the end.

Also, MeCH=CH-, MeCH=C)ICHz-,
(Me)zc=c)I-.

(Me)zC=CHCHz-1MeCH:CHCHz-
, MeCHzCH=CH-, etc., which have a double bond inside, and CI (z=cH-CH=CHz-, CH2=C(Me)
CH=CHz-.

There are also those with two double bonds such as MeCH=CI-CH=C)Iz-, but due to the superiority of the esterification reaction and hydrosilylation reaction and from these esters, 6
A Stability of silicone cinnamic acid g 84 to be observed (
An ester having one double bond at the terminal is preferable due to factors such as photostability (including photostability).

The silicone-based cinnamic acid derivative of the present invention can be obtained by subjecting the ester of general formula (2) thus obtained to a hydrosilylation reaction with a siloxane. It is a silicon compound and is expressed as a siloxane having R'nSi○(3-n)/2 units and R'm5io +4-0/z units. For example, (CIEt
O), SiH, (Me:+SiO)zMesiH(Me
, 5iO), SiH, (MeJSi)MePhSiH.

(MetO5i)ELMeSill, (Me:+05
i) EtPhSiH.

H(Me)2SiO5t(Me)20Si(Me), H
etc., but 1.1.1, 3, 5, 5.5-
Hebutamethyltrisiloxane is preferred. However, the method is not limited to this as long as the silicone-based cinnamic acid derivative of the present invention can be produced.

As the reaction solvent, ordinary organic solvents can be used, but aromatic organic solvents such as toluene, benzene and xylene are particularly preferred, and the reaction temperature is preferably high, with reflux temperature being preferred.

As a catalyst for hydrosilylation, commonly known rhodium complexes (Wilkinson complex), ruthenium complexes, platinum complexes, chloroplatinic acid, etc. can be used, but these may be used depending on the ease of obtaining the catalyst and the operational simplicity of the synthetic reaction. A chloroplatinic acid catalyst is preferred from the viewpoint of properties.

The silicone-based cinnamic acid derivative of the present invention according to claim 1,
Depending on the purpose, by selecting various esters of type (2) and the above-mentioned siloxanes, they can be manufactured from low molecular weight to high molecular weight, and their properties range from liquid to resinous at room temperature. Including solid matter.

Although the ultraviolet absorber according to claim 3 has the development history as described above, the field of application thereof is not particularly limited.
According to the characteristics and purpose of the silicone-based cinnamic acid derivative according to claim 1. It can be used in various products that use ultraviolet absorbers.

The amount of compounding ingredients used in external preparations such as cosmetics and quasi-drugs varies depending on the dosage form, but is generally 0.1 to 20.
%, preferably 0.5-10%.

[Example] EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples.

Hereinafter, the present invention will be explained in more detail by giving examples of the synthesis of the novel silicone-based cinnamic acid derivative of the present invention and its physicochemical properties.

Synthesis Example 1 3.4.5-) 11.94 g of dimethoxycinnamic acid and thionyl chloride [ml were stirred in 8 od of benzene at reflux for 3 hours to form acid chloride, and after removing the solvent, 7.20 g
80 mL of toluene containing 1-buten-3-ol was added, the reaction system was cooled in a water bath, and 40 ml of toluene containing 5.25 g of triethylamine was slowly added and stirred for 1 hour. Further, the mixture was stirred at room temperature for 1 day.

After filtering and washing the toluene layer with water to remove water, 3,4.5-)dimethoxycinnamic acid ester 10.9 was purified by silica gel column chromatography using toluene as a medium.
3 g (74.6%) were obtained.

GC-MS M”292 NMR (CDCI: l) 7.60 (LH, d (
J=15.77Hz)), 6.36 (LH,d(
J=16, 14Hz)), 6.74 (2H,s)
, 5.92 (IH, m) , 5.49 (LH, m
), 5.29 (LH,d (J=17.60Hz
)) , 5.15 (LH, d (J=10.64H
z)), 3.85 (9H, s), 1.38 (3H,
d(J-6, 60Hz)).

Synthesis Example 2 2.9319 g of ester obtained in Synthesis Example 1 and siloxane (1,1,1,3,5,5,5-Heptameth
yltrisiloxane.

(hereinafter abbreviated as M) IM) 2.2270g to 50% toluene
2.3 drops of 0.1 M chloroplatinic acid isopropyl alcohol solution were added thereto, and the mixture was stirred at reflux temperature for 5 hours to carry out a hydrosilylation reaction. The product was isolated by silica gel column chromatography using toluene as a vehicle to obtain 3.0880 g (59.8%) of the silicone-based cinnamic acid derivative of the present invention in the form of an oil.

This substance was identified by the following analytical values.

Substance name [3-bis(trimethylsiloxy)methylsilyl-1methylpropyl 3-3.4.5-)rimethoxycinnamate GC-MS 514 NMR (CDCI3) 7.59 (IH, d (J
=16.13Hz)) , 6.35 (LH,d (
J=15.77Hz)), 6.75 (2H,s)
, 4.95 (LH, q) , 3.86 (9H,
s), 1.65 (2H, m), 1.29 (
3H,d(J=6.23Hz) ), 0.54(2
8, m), 0°11 (18H, s), 0.09 (3
H,s).

Figure 1 shows the UV spectrum at a concentration of 10 ppm (solvent, ethanol). From this, it was confirmed that the silicone-based cinnamic acid derivative, which is a new compound of the present invention, has an appropriate absorption wavelength in the UV-B wavelength region.

Synthesis Example 3 A hydrosilylation reaction was carried out according to Synthesis Example 2 except that benzene was used as a solvent. Similarly purified, the product was 3.15
'70g (61.1%) was obtained.

Synthesis Example 4 A hydrosilylation reaction was carried out in accordance with Synthesis Example 2, except that xylene was used as a solvent. Similarly purified, the product was 3.52
40 g (68.2%) were obtained.

Synthesis Example 5 10.48 g of 3.4-dimethoxycinnamic acid and thionyl chloride 11 were stirred in 200 d of benzene at reflux temperature for 2 hours to form acid chloride, and after removing the solvent, 3.63 g of 1-
80 d of toluene containing buten-3-ol was added, the reaction system was cooled in a water bath, and 40 d of toluene containing 5.10 g of triethylamine was slowly added and stirred under PA for 1 hour. Further, the mixture was stirred at room temperature for 1 day. After filtration and washing the toluene layer with water to remove water, 6.886 g (52.2%) of 3,4-dimethoxycinnamic acid ester was obtained by silica gel column chromatography using toluene as a vehicle.

GC-MS M'262 NMR (CDCI 3) 7.63 (LH, d (J=
15, 62Hz)), 6.32 (LH,d (
J-15, 62Hz)), 6.85 (IH, d
(J=8.30Hz), 7.05 (1)1. s
), 7.10 (ltl, d (J=8.30H
z) ) , 5.92 (IH, m) , 5.50 (
LH, m), 5.30 (LH, d (J=17.0
9Hz) ), 5.16(IH, d (J=10.
75Hz)), 3.90(6Hs), 1.29(
3)1. d(J=6.83Hz)).

Synthesis Example 6 2.6231 g of ester obtained in Synthesis Example 5 and siloxane (
2.2291 g of M HM ) was poured into 50 ml of toluene, and 2.3 drops of 0.1M chloroplatinic acid isopropyl alcohol solution was added, followed by stirring at reflux temperature for 5 hours to carry out a hydrosilylation reaction. The product was isolated by silica gel column chromatography using toluene as a solvent to obtain 2.9157 g (60.1%) of a silicone-based cinnamic acid derivative in the form of an oil.

This substance was identified based on the analytical values shown below.

Substance name [3-his(trimethylsiloxy)methylsilyl-1methylpropyl)-3,4-dimethoxycinnamate GC-MS N”484 HMR (CDC1z) 7.63 (LH, d(J=1
5.62Hz)), 6.32 (LH,d (J:
15, 62Hz)), 6.85 (LH,d (J
=8.30Hz), 7.05 ('IH,s),
7.10(1H,d(J=8.301(z)),
4.95 (LH, q), 3.90 (6H, s)
, 1.65 (2H, m), 1.29 (3H, d
(,I=6.83Hz)), 0.54(2t(,m
), 0.11 (18H,s), 0.09(3)1
．． s).

FIG. 2 shows the UV spectrum at a concentration of 10 ppm (solvent, ethanol).

From this, it can be seen that the silinine-based cinnamic acid derivative, which is the new compound of the present invention, has an absorption wavelength suitable for the UV-B wavelength region!Ii1! It has been certified.

Synthesis Example 7 3.4.5-1 rimethoxycinnamic acid 24.1550 g,
5. After stirring 22 ml of thionyl chloride in 160 ml of benzene at reflux temperature for 4 hours to form an acid chloride and removing the solvent.
160ml of toluene containing 8550g of allyl alcohol was added, the reaction system was cooled in a water bath, and 80ml of toluene containing 10.111g of triethylamine was slowly added and stirred for 12 hours. After filtration and washing the toluene layer with water to remove water, 20.3039 g (72.0%) of 3.4-5-) dimethoxycinnamic acid ester was obtained by silica gel column chromatography using toluene as a solvent. It is a white crystal with a melting point of 67.0-68.2°C, and has an MS (
M” 278).

Synthesis Example 8 5.6054 g of the ester obtained in Synthesis Example 7 and 4.4713 g of siloxane (M HM ) were poured into a Hein 100 container, and a few drops of H, PtC16 isopropyl alcohol were added, and the mixture was stirred at reflux temperature for 4 hours to dissolve hydrosilyl. A chemical reaction was carried out. The product was isolated by silica gel column chromatography using toluene as a solvent, and 2,7846'g (27.6
%)Obtained.

This substance was identified by the following analytical values.

(3-bis(trimethylsiloxy)methylsilylpropyl) -3.4.5- ) Rimethoxycinname-1.G
C-MS N” 500H-NM
R(CDCI+)7.55(LH,d(J=16.12
f(z)), 6.31(IH d(J=15.63Hz
)), 6.70 (2H, s), 4.11 (2H, t),
3.82 (9H, s), 1.69 (2H, m), 0
．． 51 (2H, t), 0.06 (18H, s).

The UV spectrum of this substance at a concentration of 10 ppm (ethanol solvent) is that of the compound obtained in Synthesis Example 2 (
There was almost no difference from Figure 1).

Synthesis Example 9 Ester obtained in Synthesis Example 75. OOOg and 35.500g of siloxane HSi (OSiMe3) in Hensen 10
0 ml, and then add H2PtC1. Add a few drops of isopropyl alcohol and stir at reflux temperature for 4 hours.
A hydrosilylation reaction was performed. The product was isolated by silica gel column chromatography using toluene as a solvent, and 2.0
77 g (20.1%) were obtained.

This substance was identified by the following analytical values.

[3-tris(trimethylsiloxy)silylpropyl]
-3,4,5-trimethoxycinnamate GC-MS
N""574' H-NMR (CDC
I:l)7.61 (IH,d (J=15.87H
z) ), 6.36(IH, d(J=15.87t
(z) ) , 6.77 (2H,s) , 4.17
(2H, t), 3.90 (9H, s) 1.7
4 (28 m), 0.53 (21 (, t), 0.13 (1
8H,s).

However, the chemical shift is CHCl, hydrogen (7.27 ppm
) was set as the standard.

Second? a UV spectra of 4 bodies (ethanol 10pp
m concentration) was almost the same as that of the compound obtained in Synthesis Example 2 (FIG. 1).

Synthesis Example 10 3.4.5-1-rimethoxycinnamic acid 11.960 g,
Thionyl chloride 11 was stirred in 80% benzene at reflux salinity for 3 hours to form acid chloride, and after desolvation, 3.64
80 ml of toluene containing 0 g of ■-buten-4-ol
was added, the reaction system was cooled in a water bath, and 40 d of toluene containing 5.340 g of triethylamine was slowly added.
Stirred for 4 hours. After filtering, washing the toluene layer with water and removing the water, 10.0342 g (68.4%) of 3,4.5-1-rimethoxycinnamic acid ester was obtained by silica gel gel chromatography using toluene as a solvent. .

It is a white crystal with a melting point of 61L8-63.8°C, and is GC-
MS (M”292).

Synthesis Example 11 2.9303 g of the ester obtained in Synthesis Example 10 and 2.2289 g of siloxane (M HM ) were mixed with 100 g of benzene.
d, and several drops of HzPtC16 isopropyl alcohol solution were added thereto, followed by stirring at reflux temperature for 2 hours to carry out a hydrosilylation reaction. The product was isolated by silica gel column chromatography using toluene as a solvent, and 3.1488 g of the oily silicone derivative of the present invention was obtained (
61.0%) was obtained.

This substance was identified by the following analytical values.

(3-bis(trimethylsiloxy)methylsilylbutyl) -3,4,5-trimethoxycinnamate Synthesis Example 1
2 According to Synthesis Example 11, siloxane H5i (O5iMez)
A hydrosilylation reaction was carried out using s. An oily silicone derivative of the present invention was obtained by silica gel column chromatography.

This substance was identified by the following analytical values.

[3-tris(trimethylsiloxy)silylbutyl)
-3,4,5-trimethoxycinnamate GC-MS
M"514'H-NMR (CD
CI, ) 7.59 (IH, d (J= 15.62H
z) ), 6.35 (LH, d(J=16.LL
Hz)), 6.74(2H,s), 4.21(2F(,
t), 3.87 (9H, s), 1.75 (2H, m),
1.47 (2H, m), 0.51 (2H, m), 0.1
0 (18H.

s), 0.01 (3H, s).

The UV spectrum of this derivative (ethanol concentration: 10 ppm) was almost the same as that of the compound obtained in Synthesis Example 2 (FIG. 1).

GC-MS N"588') I-NMR (CDCI 3) 7.59 (IH, d
(J=15.62Hz)), 6.35(LH, d(
J=16.11Hz)), 6.74(2H,s), 4.
21 (2H, t), 3.87 (98, s), 1.75 (
2H, m), 1.47 (2H, m), 0.51 (2H,
m), 0.10 (27H.

S).

The UV spectrum of this derivative (ethanol concentration: 10 ppm) was almost the same as that of the compound obtained in Synthesis Example 2 (FIG. 1).

Synthesis Example 13 According to Synthesis Example 6, siloxane H5i was prepared using the same ester.
A hydrosilylation reaction was performed using (O5iMe:+)z. An oily silicone derivative of the present invention was obtained by silica gel column chromatography.

This substance was identified by the following analytical values.

[3-tris(trimethylsiloxy)silyl-1-methylpropyl, l-3,4-dimethoxycinnamate GC
-MS N''' 558H-NMR (CD
C13) 7.63 (IH, d (J=15.62Hz
) ) , 6.32 (IH, d(J= 15.62
Hz)), 6.85(LH, d(J=8.30
Hz)), 7.05 (it(,s), 7.10(
LH, d(J=8.30Hz)), 4.95((LH,
q), 3.90 (6H, s) 1.65 (2H, m)
, 1.29 (3H, d(J=6.83Hz))
;0.54 (2H, m).

0.10 (27t(,s).

The UV spectrum of this derivative (ethanol concentration: 10 ppm) was almost the same as that of the compound obtained in Synthesis Example 6 (FIG. 2).

Synthesis Example 14 3.4.5-1-rimethoxycinnamic acid 23.912g 1
, 22 ml of thionyl chloride in 700 mdl of benzene
After stirring at reflux temperature for an hour to form an acid chloride, after removing the solvent, 160 ml of toluene containing IO, 332 g of ethylene glycol monoallyl ether (CH2CHCH20CH, CH20H) was added, and the reaction system was cooled in a water bath.10. Toluene 8 containing 233g triethylamine
0ml was slowly added and stirred for 24 hours. After filtering, washing the toluene layer with water and removing water, 3, 4.
5-trimethoxycinnamic acid ester 23.189g (7
17%). This ester is in the form of an oil.

GC-, Il, s M” 322H-NMR
(CDCI 3) 7.62 (IH, d (J= 15.
63Hz) ), 6.39 (LH, d(J=16
．． 12Hz)), 6.76(2H,s), 5.
92(1,)l,m), 5.31(LH,d(
J=17.09Hz) ), 5.21 (18, d
(J=10.74Hz) ), 4-37 (2H
, L), 4.06(2)1, d(J=5.37
Hz)), 3.88 (9H,s), 3.72
(2H, t) Synthesis Example 15 The ester obtained in Synthesis Example 14 (3,2329g) was mixed with siloxane MHM (2,2896g) toluene? The mixture was refluxed in J medium (50 ml) for 2 hours to carry out a hydrosilylation reaction. The silicone derivative of the present invention in the form of an oil was obtained by silica gel column chromatography at a concentration of 3.92%.
51 g (71.8%) were obtained.

This substance was identified by the following analytical values.

GC-Kari S A 544 The UV spectrum of this derivative (ethanol concentration: 10 ppm) was almost the same as that of the compound obtained in Synthesis Example 2 (FIG. 1).

Synthesis example 2.3.4.6.8.9.11.12.13.1
The silicone-based cinnamic acid derivative (dimethoxy,
Regarding the solubility of the trimethoxy-substituted product) in a silicone base, a solubility test in dimethylpolysiloxane and methylphenylbolyxane was conducted at 25°C. In either case, 10% by weight or more is dissolved,
It showed excellent solubility. Note that the ester as a precursor showed almost no solubility.

In addition, for water resistance and oil resistance, the silicone-based cinnamic acid derivative (dimethoxy, trimethoxy substituted product) of the present invention was mixed with 50% water in ethanol, mixed with oil such as liquid paraffin, and stirred and mixed at 50'C. After being left for 60 days, no hydrolysis occurred, confirming that the product had excellent water resistance and water resistance.

Next, examples as ultraviolet absorbers will be shown.

It can be seen from the UV spectra in Figures 1 and 2 that it has an ultraviolet absorption effect that is particularly excellent in UV-B absorption.

The electronic spectrum of the ultraviolet absorber may shift by about 10 to 20 mm depending on the base (or solvent) in which it is blended. For example, N,N-dimethyl 2-ethylhexyl cinnamate shifts by 1Qnm in ethanol and dimethylpolysiloxane. Ultraviolet absorbers are required to have little solvent dependence. The silicone-based cinnamic acid derivative of the present invention has little solvent dependence.

Furthermore, safety as an ultraviolet absorber and stability against heat and light are required.

The silicone-based cinnamic acid derivative of the present invention has no safety problems such as sensitization, mutagenicity, photosensitization, and phototoxicity, and has good stability against heat (including hydrolysis).

In terms of stability against light, it is completely stable under normal sunlight irradiation, and photoisomerization (trans-cis) reaction occurs for the first time when irradiated with an ultra-high pressure mercury lamp, but absorption is observed in the UV-B SF4 region. It can be said to be an excellent UV absorber.

The ultraviolet absorption effect when dissolved in a silicone base will be shown below.

(Formulation example) Ultraviolet absorber combination example (oil type)■ Decamethylcyclopentasiloxane 48.0%■ Dimethylpolysiloxane (10cs/25'C) 20.0
■ Methylphenylpolysiloxane (20cs/25°C) 20.0 ■ Silicone resin 10.0 ■
Silicone-based cinnamic acid derivative of the present invention 2.0 These are mixed, sufficiently dissolved, and then filtered to obtain a product.

(Comparative Example) A product was obtained in the same manner as in the Formulation Example except for excluding ■ in the formulation of the Formulation Example.

The UV protection effects of the formulation examples and comparative examples obtained as described above were measured.

The ultraviolet ray prevention effect was measured using the ultraviolet sensitive composition described in JP-A-62-112020.

The method for producing this composition will be described below.

Leuco crystal violet 1.0g, tetrabromodimethylsulfone 0.1g, ethylene-vinyl acetate copolymer 10g, I-luene 1. A solution consisting of OOml is prepared and designated as solution I. Separately, 7 g of N,N-dimethylpara-dannobenzoic acid-2-ethylhexyl ester,
Ethylene-vinyl acetate combination 10 g, toluene
Prepare a liquid consisting of 100 square meters, first apply Liquid I to a photographic base paper to be used as liquid at a solid content of 1 g/m, and after drying, apply liquid ■ on top of it at a solid content of 5 g/m. n? A UV-sensitive composition is obtained.

This ultraviolet-sensitive composition is a paper whose color changes from white to pale purple to purple to deep purple when irradiated with ultraviolet rays as the amount of ultraviolet irradiation increases.

40 cm of the sample to be measured is mixed in 12 g of castor oil and treated with a roller to uniformly disperse it. A transparent PET film was placed on top of the above-mentioned ultraviolet sensitive composition on a 5 cm diameter film, 1.5 g was applied on top of it to a uniform thickness, and the PET film was irradiated with an ultraviolet lamp for 8 minutes. Using a Hitachi 607 spectrophotometer, the color difference was calculated using the LAB coordinate system based on the color of the UV-sensitive composition when the amount of UV irradiation was zero.

The results are shown below.

Color difference of blending example (Synthesis example 2; 21 〃 (〃 3; 21 〃 (〃 4; 21 〃 (〃 6; 21 (〃 8; 20 〃 (〃 9; 21 〃(〃11; 20 〃(〃12: 20 〃(〃13; 22 〃(〃15); 20 Color difference of comparative example; 58 The color difference of the formulation example is smaller than the color difference of the corresponding comparative example, and it can be seen that the UV protection effect is high. That is, the present invention It can be seen that an excellent ultraviolet protection effect can be obtained by blending the silicone-based cinnamic acid derivative.

(Effects of the Invention) The silicone-based cinnamic acid derivative of claim 1 is an extremely useful new compound that absorbs the UV-B wavelength region, exhibits excellent solubility in noricone oil, and has excellent water resistance and oil resistance. .

The manufacturing method of claim 2 can produce this compound extremely efficiently, and the ultraviolet absorber of claim 3 is extremely suitable for formulation in external preparations such as cosmetics and quasi-drugs. It is an excellent UV absorber. That is, u v −8
It sufficiently protects wavelengths in the 61 range and has excellent solubility in silicone oil, so it can be blended in any amount according to the purpose without impairing the properties of the silicone base, and has water resistance and oil resistance. It is also an excellent UV absorber.

[Brief explanation of the drawing]

Figure 1 shows the UV radiation of the silicone-based cinnamic acid derivative obtained in Synthesis Example 2 at a concentration of 10 ppm (solvent, ethanol).
The spectrum is shown. Figure 2 shows silicone-based cinnamic acid BX obtained in Synthesis Example 6.
The UV spectra of 4 compounds at a concentration of 10 ppm (solvent, ethanol) are shown. Figure 3 shows 10p of unsubstituted silicone, which is a known compound.
Figure 2 shows the U■ spectrum at a concentration of pm (solvent, ethanol).

Claims (3)

[Claims] (1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Siloxanes having at least one unit represented by (I), in which other units that may exist in the siloxane are general A silicone-based cinnamic acid derivative represented by the formula O_(_4_-_m_)_/_2SiR^3_m. [In the above general formula, R^1 is an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a trimethylsiloxy group, and R^2 is a divalent hydrocarbon group having at least 2 carbon atoms (
(including those having multiple atoms O), X is an alkoxy group,
n is an integer of 0 to 3, a is an integer of 2 or 3, R^3 is an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a trimethylsiloxy group, and m is an integer of 0 to 3. ] (2) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [Y is a monovalent hydrocarbon group having at least 2 carbon atoms and an olefinically unsaturated bond (multiple atoms O
), X represents an alkoxy group, and a represents 2 or 3. ] and ▲There are mathematical formulas, chemical formulas, tables, etc.▼Units and R^3_m
Siloxane having SiO_(_4_-_m_)_/_2 units [R^1 and R^3 represent an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a trimethylsiloxy group, and n and m represent integers of 0 to 3. ] The method for producing a silicone-based citric acid derivative according to claim 1, characterized in that the reaction is carried out in an organic solvent in the presence of a catalyst. (3) A UV absorber comprising the silicone-based cinnamic acid derivative according to claim 1.