JPH03188041A - Novel benzoylketone derivative, ultraviolet ray absorbing agent containing same derivative and cosmetic containing same absorbing agent - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention provides a novel benzoyl ketone derivative that has an ultraviolet absorbing effect and excellent photostability, and a novel benzoyl ketone derivative containing the same that has a sunburn prevention effect. This invention relates to excellent ultraviolet absorbers and cosmetics.

[Conventional technology]

Ultraviolet rays are known to cause various changes in the skin. Dermatologically, the working wavelength is 400 to 320n.
Ultraviolet rays are divided into long-wavelength ultraviolet rays of m, medium-wavelength ultraviolet rays of 320 to 290 nI11, and short-wavelength ultraviolet rays of 290 t++n or less, and are called UV-^, [IV-8, and ■v-C, respectively. The ultraviolet rays in sunlight are uv-^ and UV-8,
UV-C is absorbed in the ozone layer and almost never reaches the ground.

When the skin is irradiated with a certain amount of light, tlV-8 causes changes in the skin, such as the formation of erythema and chickenpox, as well as accelerated melanin formation and pigmentation.

On the other hand, UV-^ causes a blackening effect on the skin (immediate blackening) immediately after irradiation, and since the energy reaches the dermis, it causes changes in the elastic fibers in blood vessel walls and connective tissues. It is believed that the effects of both UV-^ and UV-B accelerate skin aging and are a factor in the appearance of age spots, wrinkles, and freckles.

As the effects of ultraviolet rays on human skin become clearer, compounds that absorb UV-^ and UV-8 have been developed. It is said that it is desirable that such ultraviolet absorbers satisfy all of the following conditions.

■ Absorbing UV-8 or UV- light as completely as possible.

■ Stable against light and heat.

■ No toxicity, irritation or other adverse effects on the skin.

■　Effects should last.

■ Excellent compatibility with cosmetic bases.

Conventionally, dibenzoylmethane derivatives have been used as the υV-^ absorbent, and derivatives of cinnamic acid ester, benzophenone, p-aminobenzoic acid, salicylic acid, etc. have been used as the IV-8 absorbent.

[Problem to be solved by the invention]

However, these conventional ultraviolet absorbers do not necessarily fully satisfy the above conditions, particularly their stability against light is insufficient, and it is known that they decompose or react with ultraviolet light (Int, J.

Cos+netic 5science, 10.53
(1988) ] o The decomposition of these ultraviolet absorbers is
Not only does this lead to a decrease in the duration of the effect, but the effects on the skin of the decomposition products themselves or products generated by reactions with the compound cannot be ignored [Fragrance Journal, 84
．． 34 (1987)).

Therefore, there has been a desire for an ultraviolet absorber that satisfies the above conditions, particularly an ultraviolet absorber that has excellent stability against light.

[Means to solve the problem]

In view of these circumstances, the present inventors have synthesized a number of benzoyl ketone derivatives and studied their properties, and found that
A novel benzoyl ketone derivative represented by the general formula (I) below has excellent UV-^ and tlV-8 absorption effects,
The present invention was completed based on the discovery that it is extremely stable against light, and that by blending it, a cosmetic with excellent sunburn prevention effects can be obtained.

That is, the present invention is based on the following general formula (1) % formula % (1) [wherein Ar is substituted with 1 to 2 C 1 to 24 linear or branched alkoxy groups or alkenyloxy groups] represents a phenyl group which may be
The n groups -COCH and C0RI may be the same or different, R' is a saturated or unsaturated alkenyloxyalkyl group or group having 2 to 24 carbon atoms, and 1 carbon number.
-24 hydroxyalkyl group, C1-24 alkoxyalkyl group, C1-24 (R' and R4 each represent an alkenyloxyalkyl group or group having 1 to 24 carbon atoms, and R3 and R4 together represent may form a 5- to 7-membered ring that may contain an oxygen atom) (however,
Ar is a phenyl group, n=2 is a group -CDCI(,COR'
is bonded to the 1st and 3rd positions on the benzene nucleus, then R
1 is not an ethyl group or a 3-butenyl group)], an ultraviolet absorber containing the same, and a cosmetic containing the same.

In the above general formula (I), Ar is a phenyl group or 1
A phenyl group substituted with ~2 straight-chain or branched alkoxy or alkenyloxy groups having 1 to 24 carbon atoms, preferably a phenyl group or a phenyl group substituted with one substituent .

In addition, when Ar is a substituted phenyl group, the substituent is particularly preferably a linear or branched alkoxy group having 1 to 4 carbon atoms, and specific examples thereof include a methoxy group, an ethoxy group, an n- propoxy group, isopropoxy group,
Examples include n-butoxy group and tert-butoxy group.

In addition, in the above general formula (I), R' has 2 to 2 carbon atoms.
Specific examples of the saturated or unsaturated alkenyloxyalkyl group or group of 24 include ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, 1-
Butyl group, butenyl group, n-pentyl group, n-hexyl group, n-heptyl group, heptenyl group, n-octyl group,
octenyl group, n-nonyl group, nonenyl group, n-decyl group, decenyl group, n-undecyl group, undecenyl group,
n-dodecyl group, dodecenyl group, n-tridecyl group, tridecenyl group, n-tetradecyl group, tetradecenyl group, n-bentatecyl group, pentadecenyl group, inventatecyl group, n-hexadecyl group, hexadecenyl group, isohexadecyl group, Examples include n-heptadecyl group, heptadecenyl group, inheptadecyl group, octadecyl group, octadecenyl group, inoctadecyl group, cyclohexyl group, adamantyl group, and the like.

Further, as the hydroxyalkyl group having 1 to 24 carbon atoms represented by R', hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, hydroxybutyl group, hydroxypentyl group, hydroxyhexyl group, hydroxyhebutyl group, hydroxyoctyl group group, hydroxynonyl group, hydroxydecyl group, hydroxyundecyl group,
Examples include hydroxydodecyl group, hydroxytetradecyl group, hydroxyhexadecyl group, hydroxyoctadecyl group, and the like.

Examples of the alkoxyalkyl group having 1 to 24 carbon atoms represented by R1 include methoxymethyl group, ethoxymethyl group, propoxymethyl group, isopropoxymethyl group, butyloxymethyl group, pentyloxymethyl group, hexyloxymethyl group, octyloxy Methyl group, decyloxymethyl group, undecyloxymethyl group, tetradecyloxymethyl group, hexadecyloxymethyl group, octadecyloxymethyl group, methoxyethyl group, ethoxyethyl group,
Propoxyethyl group, methoxypropyl group, ethoxypropyl group, propoxypropyl group, methoxybutyl group,
Ethoxybutyl group, propoxybutyl group, methoxyethyl group, ethoxypentyl group, propoxypentyl group, methoxidedodecyl group, ethoxidedodecyl group, propoxidedodecyl group, methoxyhexadecyl group, ethoxyhexadecyl group, propoxyhexadecyl group, methoxyoctadecyl group , ethoxyoctadecyl group, propoxyoctadecyl group, and the like.

Examples of the alkenyloxyalkyl group having 1 to 24 carbon atoms represented by R' include a troxymethyl group, a butenyloxymethyl group, a hexenyloxymethyl group, an undecenyloxymethyl group, an octadecenyloxymethyl group, and an allyl group. Examples include oxyethyl group, allyloxypropyl group, allyloxybutyl group, allyloxypentyl group, allyloxydodecyl group, allyloxyhexadecyl group, and allyloxyoctadecyl group.

Dimethylamino group, ethylmethylamino group, diethylamino group, methylpropylamino group, methylisopropylamino group, methylbutylamino group, methyl-t-butylamino group, diisopropylamino group, dipropylamino group, ethylbutylamino group, methyl hexylamino group,
Di-5ec-butylamino group, diisobutylamino group,
Examples include diethylamino group, diethylamino group, bis(2-ethylhexyl)amino group, dioctylamino group, methyloctadecylamino group, pyrrolidyl group, piperidyl group, and morpholyl group.

Further, in the above general formula (I), n is an integer of 2 to 4, but 2 is particularly preferable.

The benzoyl ketone derivative (1) of the present invention can be prepared, for example, by a known method CJ, ^tn, Chem, Sac, 80.
, 4891 (195B); J, Chromat
ogr,, 312.109 (1984); J, P
olym, Sci, Polym, Chem, Bd,
, 20.3079 (1982)), as shown below (
a), (c) or It (c) (D).

(a) Ar(C[]0R)B+n-R'C(]C)+3 →A
r(COCH*C[]R1)-(Il)
(IIr) (1) [In the formula, R represents a methyl group, ethyl group, n-propyl group, or n-butyl group, and ^r, R1 and n represent the same as above] That is, benzoate (II) and ketone (III)
Compound (I) of the present invention is produced by condensing these. Ketones (III) used in this reaction include methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, 2-hydroxy-2-propyl methyl ketone, binacolon, 2-butanone, 2-pentanone, 3-methyl-2-butanone, -hexanone, 5-hexen-2-one, 2-octanone, cyclohexylmethylketone, adamantylmethylketone, methoxyacetone, ethoxyacetone, propoxyacetone, allyloxyacetone, methylmethoxyacetone, dimethylmethoxyacetone and the like. The reaction in method (a) is carried out in a solvent such as anhydrous tetrahydrofuran, toluene, or xylene using a base as a catalyst at 20 to 150°C for several tens of minutes to 10 minutes.
It is preferable to carry out the test for 0 hours. Examples of bases used here include metal hydrides such as sodium hydride; metal alkylated compounds such as butyllithium; amines such as triethylamine; metal amides such as sodium amide; and metal alkoxide compounds such as sodium methoxide. It will be done.

(c) Ar(COCHJ,,+n-R'CO[lR-Ar(C
OCH2CORI2C'OR').

(IV) (V) (r)
[In the formula, R1^r, R1 and n are the same as described above] That is, the compound (1) of the present invention is produced by condensing the acetylbenzene derivative (IV) and the ester (V). Examples of the ester (V) used in this reaction include methyl acetate, ethyl acetate, methyl piperate, ethyl pivalate, methyl propionate, methyl butyrate, methyl isobutyrate, methyl valerate, ethyl isovalerate, methyl caproate, Methyl caprylate, ethyl caprate,
Examples thereof include methyl 2-ethylbosunate, methyl octoate, methyl decanoate, methyl undecanoate, methyl myristate, methyl valmitate, methyl stearate, methyl isostearate, and methyl oleate.

The reaction in method (a) is carried out under the same conditions as in method (a) above.

(C) (II) (Vl) (T)' [In the formula, R5Ar5R2, R5 and n are the same as above] That is, condensation of benzoate (■) and N,N-disubstituted acetamide (VI) Compound (I)' of the present invention is produced by doing this. N used in this reaction, N
-Disubstituted acetamide (VI) includes N,N-dimethylacetamide, N-ethyl-N-methylacetamide, N,N-bis(2-ethylhexyl)acetamide, N-methyl-N-octadedylacetamide, acetylpyrrolidine , acetylpiperidine, acetylmorpholine, and the like. The reaction in method (C) is carried out under the same conditions as in method (a) above.

The ultraviolet absorber of the present invention containing the benzoyl ketone derivative (I) thus obtained may use one or more of these benzoyl ketone derivatives (I) as is, or may be prepared by adding it to a carrier and mixing it. Preferably, it is in the form of The carrier may be any carrier as long as it is inert to the benzoyl ketone derivative (I), and may be solid, liquid, emulsion, foam, gel, or the like. Typical examples include water, alcohol, fats and oils (e.g. alkenyloxyalkyl groups or oils, fatty acid esters,
Examples include long-chain alcohols, silicone oils), fine powders such as starch or talc, and low-boiling alkenyloxyalkyl groups or halogenated alkenyloxyalkyl groups used as aerosol propellants. The ultraviolet absorber of the present invention further includes the benzoyl ketone derivative (I) of the present invention.
Other ingredients, as long as they do not impair the ultraviolet absorption effect of
For example, preservatives, fragrances, colorants, surfactants, etc. can be added and blended.

Cosmetics containing benzoyl ketone derivative (1) (hereinafter referred to as "cosmetics of the present invention") contain benzoyl ketone derivative (I) having an affinity for the cosmetic base.
It is prepared by appropriately selecting a species or two or more species, blending it into a known cosmetic base by a conventional method, and making it into a dosage form such as a cream, solution, oil, spray, stick, milky lotion, foundation, or ointment. Ru.

That is, by selectively using the benzoyl ketone derivative (1) according to the cosmetic base, oil-based cosmetic oils, oil-based creams and oil-based emulsions containing a large amount of oil,
From basic cosmetics such as weak oil-based creams, weak oil-based emulsions, and water-based lotions that contain large amounts of water to makeup cosmetics such as oil-based foundations and lipsticks, all products that have UV-absorbing properties can be used. It is possible to produce cosmetics in the form of Suitable bases and solvents for this include solid or liquid paraffin, crystal oil, alkenyloxyalkyl groups or the like, such as ceresin, osikelite or montan wax; vegetable oils, such as olive, earth wax, carnauba wax, lanolin or spermaceti. or animal fats and waxes; and also stearic acid, valmitic acid, oleic acid, glycerin monostearate, glycerin distearate, glycerin monooleate, isopropyl myristate, isopropyl stearate, or butyl stearate, etc. Fatty acids and esters thereof; alcohols such as ethyl alcohol, isopropyl alcohol, cetyl alcohol, stearyl alcohol, palmityl alcohol, or hexyldodecyl alcohol; and the like. Further, polyhydric alcohols having a moisturizing effect such as glycol, glycerin or sorbitol can also be used.

The amount of the benzoyl ketone derivative in the ultraviolet absorber and cosmetics of the present invention is not particularly limited as it may vary depending on the form of use, as long as it is present in an effective amount, but generally 0.1-20 It is advisable to mix it in an amount of 0.5 to 10% by weight, preferably 0.5 to 10% by weight.

The ultraviolet absorbers and cosmetics of the present invention may contain only benzoyl ketone derivatives, but they may also be used in combination with other 11V-B absorbers or UV-^ absorbers as ordinary sunscreen cosmetics. is more preferable. Such [IV-8 absorbents include, for example, p-methylbenzylidene-D, L-camphor or its sulfonic acid sodium salt; 2-phenylbenzimidazole-5-sulfonic acid sodium salt, 3.4-dimethylphenylglyoxyl. acid sodium salt, 4-phenylbenzophenone,
Examples include 4-phenylbenzophenone-2'-carboxylic acid isooctyl ester, p-methoxycinnamic acid ester, 2-phenyl-5-methylbenzoxazole, and p-dimethylaminobenzoic acid ester. UV-
As the A absorbent, 4-methoxy-2'-carboxydibenzoylmethane, 4-methoxy-4'-t-butyldibenzoylmethane, 4-isopropyldibenzoylmethane, 2-hydroxy-4-methoxybenzophenone or dibenzylidene camphor Examples include the following.

In addition to the above-mentioned components, various additives can be added to the cosmetic composition of the present invention. Suitable additives include, for example, W2
Examples include O-type and 0/W-type emulsifiers. As the emulsifier, commercially available emulsifiers can be used. Also methylcellulose, ethylcellulose or carboxymethylcellulose,
Thickening agents such as polyacrylic acid, tragacanth, agar or gelatin can also be added as additives. Furthermore, fragrances, preservatives, humectants, emulsion stabilizers, medicinal ingredients, and/or physiologically acceptable colorants may be added as necessary.

〔Example〕

The present invention will be explained in more detail by giving test examples and examples.

Example 1 1,4-bis(4,4-dimethyl-3-oxopentanoyl)benzene [Formula (I) 1,1 and R'=t-Bu,
n==2. m = O] Synthesis of (Ia): 32 g (0.8 mol!> , Vina Colon 7
9 g (0.79 moj) and 700 ml of anhydrous tetrahydrofuran were mixed under a nitrogen stream, and a solution of 70 g (0.3 button o1) of dimethyl terephthalate in tetrahydrofuran (300 mt') was added dropwise over 1 hour while stirring at room temperature. After completion of the reaction, the reaction mixture was heated under reflux for 6 hours.After the reaction was completed, it was cooled to room temperature, and 180% of a 2N aqueous hydrochloric acid solution was added dropwise.

Next, the mixture was extracted with chloroform, dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain a crude product. This was recrystallized using hexane to obtain 78 g of colorless scaly crystals of the target compound (yield: 66%).

Melting point + 125.5-126.5°C IR (Ilr, C11-'): 2974.28
72.1584.1563゜1485, 1268.1
290. 1140.840,792.741')I-
NMR (CDCI!, δ): 1.27 (18H,s
), 6J4(2H,s), 7.95(4H,s
) Elemental analysis calculation value (%) C; 72,70. H: 7.93 Actual value (%) C: 72.61. ) I; 7.96 Example 2 1.3-bis(4,4-dimethyl-3-oxopentanoyl)benzene [In formula (I), R'=t-Bu,
n=2. Synthesis of (Tb): 1.5 g (38 mmol) of 60% sodium hydride, 1.5 g (38 mmol) of 60% sodium hydride, and 1.5 g (38 mmol) of 60% sodium hydride in a 100-length three-tube flask equipped with a stirring device, a dropping funnel, a reflux condenser, and a nitrogen inlet tube. 3
, 6g (36mm) dimethyl isophthalate 3
．． 0 g (15.5 mmol) and 30 ml of anhydrous tetrahydrofuran were mixed with stirring under a nitrogen stream, and heated under reflux for 6 hours. After the reaction was completed, the mixture was allowed to cool, 10 rnl of 2N hydrochloric acid was added thereto, extracted with chloroform, dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain a crude product. This was recrystallized using hexane and colorless crystals of the target compound 3.1
g (yield 61%).

Melting point +106.0~107.5℃ IRCv, cm-'): 3124.29
74.2B72.1611゜1563, 1482.14
31.1290.1227.1134.1095°87
9, 804.705'H-NMR (CDIJ!,, δ): 1.27 (18) 1. s), 6J4(2)1. s),
7.55 (lfl, t.

J=7.8Hz), 8.02 (2H, dd, J=7.
8Ftz, J=1.5)1z).

8, 38 (IH, br, s) Elemental analysis calculation value (%) C; 72.70. )l; 7.93 Actual value (%) ['; 72.5B, )l; 7.95 Example 3 4-Methoxy-1,3-bis(4,4-dimethyl-3-
Synthesis of oxopentanoyl)benzene (with formula % formula % = 1) (Ic): 60% sodium hydride in a 100 Id three-bottle flask equipped with a stirrer, dropping funnel, reflux condenser and nitrogen inlet tube. 1.5g (38mm), Vinacologne 3
．． 6 g (36 mmall>), 4-methoxyisophthallll dimethyl 3.0 g (13.4 mmol) and anhydrous tetrahedral 07 run 30- were mixed with stirring under a nitrogen atmosphere, and heated under reflux for 5 hours. After the reaction was completed, the mixture was allowed to cool and 2N −
After adding 10 ml of hydrochloric acid, the mixture was extracted with chloroform. After drying the extract over anhydrous sodium sulfate, the solvent was distilled off to obtain a crude product. This was recrystallized using hexane to obtain 3.2 g of colorless crystals of the target compound (yield: 66%).

Melting point: 69.4-70.8°C IR (v xlr, CI-'): 296B, 1
620.1584.1506゜1467, 1368.1
275.1263.11 & 2.1131.1071゜1
011,795'l(-NMR(CDCj!3.6):1.24(9H
,s), 1.25(9H,s), 3.99(3H,s
), 6.29 (IH, s), 13.52 (1) 1.
s), 7.04 (IH, d, J=8.8Hz).

8,04 (LH, dd, J=8.8.2.3Hz),
8.35 (IH, d, J=2, 3Hz) Elemental analysis calculation value (%) C; 69,98. tl; 7.83 Actual value (%) C; 69,92. H; 7.85 Example 4 1.4-bis(4-methyl-3-oxopentanoyl)
Benzene [1ll--CH(C)I3 in formula (I)
)2. m=0, n=2] (Id)
Synthesis: The same procedure as in Example 1 was performed except that 68 g of isopropyl methyl ketone (0,7 button ol) was used instead of binacolon, to obtain 76 g of the target compound in the form of pale yellow needles. (Yield 72%).

Melting point: 97. O~97.5℃ IR (!'.-, cm-'): 2980.29
32.1608.1437゜1284, 1188.10
9B, 939.807'H-NMR (CDfJ3.δ
): 1, 25 (12H, d), 2.55-2.77 (
2H, m), 6.25 (2H, s).

7,95 (4t(,s), 14.7(2H,b
s) Example 5 1.4-bis(3-oxopentanoyl)benzene [in formula (I), R'=CJs, m = 0, n
= 2) Synthesis of (Ie): Methyl ketone 57 instead of binacolon in Example 1
The same operation as in Example 1 was carried out except that g (0.79 mol) was used to obtain 54 g of the target compound in the form of pale yellow crystals (yield 56%).

Melting point: 122.5-123.5°C IR (am-'): 2980.295
0.161? , 1293°1161, 1119.10
83.813.774'H-NMR (CDC13, δ)
: 1.25 (6H, t), 2.50 (4H, q), 6
．． 22 (2H, s), 7.95 (4H, s), 15
．． 2(2H, bs) Example 6 1.4-(3-oxododecanoyl)benzene [Formula (1
), R'=C*Ls, m=0. n = 2] (If): In a 100-capacity three-bottle flask equipped with a stirrer, a dropping funnel, a reflux condenser, and a nitrogen inlet tube, 1.1 g of 60% sodium hydride (28 mmoJ, 2.0 g (12.3 mmol) of p-diacetylbenzene, 4.8 g (25.7 mmol) of methyl caprate, and 20 g of anhydrous tetrahydrofuran were mixed with stirring under a nitrogen stream,
The mixture was heated under reflux for an hour. After the reaction was completed, it was left to cool, and 15 ml of 2N hydrochloric acid was added. was added, and then extracted with chloroform. After drying the extract over anhydrous sodium sulfate, the solvent was distilled off to obtain a crude product. This was recrystallized using hexane to obtain 3.6 g (yield: 63%) of pale yellow scale-like crystals of the target compound.

Melting point: 122.5-123.0°C IR (!'*mr, Cm-'): 2920.28
54.1617.1473°1293, 1155.78
6'H-NMR (CDC/!, δ): 1.90 (6) 1. t), 1.12-1.43 (20
H, m), 1.56 (4H, bs), 1.60-1
．． 80 (4H, m), 2.47 (4) 1. t).

6.20 (2H, s), 7.95 (4H, s), 1
4.6(2)1. bs) Example 7 1.3.5-) Lis(4,4-dimethyl-3-oxopentanoyl)benzene [R'-C(C
Hs)s, m=0, n=3) (I
Synthesis of g): 2.29 g (57 aonol) of 60% sodium hydride, 5.24 g (52 mmol) of binacolon, in a 100 d three-bottle flask equipped with a stirrer, a dropping funnel, a reflux condenser and a nitrogen inlet tube. Riftyl 1.3.5
-benzenetricarboxylate 4.0 g (15,8
+++mol) and anhydrous tetrahydrofuran (40-mol) were mixed with stirring under a nitrogen stream, and the mixture was heated under reflux for 7 hours. After the reaction was completed, the mixture was allowed to cool, 2N salt W130- was added thereto, extracted with chloroform, and then dried over anhydrous sodium sulfate.
The solvent was distilled off to obtain a crude product. This was recrystallized using acetone, and 3.8 g of yellow crystals of the target compound (yield 52%)
) was obtained.

') I-NMR (CDC1,, δ): IJO (27H
,s), 6.403H,s), 8.49(3H
,s).

15,6 (3H, bs) Example 8 1.4-bis(4-hydroxy-4-methyl-3-oxopentanoyl)benzene [: In formula (1), R'=
C(CHs)2DH, m=0, n=3]
Synthesis of (I h): 3-methyl-3
-Hydroxy-2-butanone 15 g (147 mmoj, p-) pyridinium luenesulfonate 500 mg
(2, OmmolIt) and anhydrous methylene chloride O'Jl'
100- were mixed with stirring under a nitrogen stream, and 11.7 g (162 mmol) of ethyl vinyl ether was slowly added dropwise.
The mixture was stirred at room temperature for 3 hours. After the reaction was completed, the mixture was washed with a 5% aqueous sodium bicarbonate solution, extracted with chloroform, and the extract was dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain a crude product. Furthermore, 17.0 g of 3(1-ethoxyethoxy)-3-methyl-butan-2-one (b,
p, 38-40℃/l mmHg, yield 66%)
I got it.

3-(1-ethoxyethoxy)-3- thus obtained
Methyl-butan-2-one 9.9g (57mmo!)
In a 100-capacity three-meter flask equipped with a stirrer, a dropping funnel, a reflux condenser, and a nitrogen inlet tube, 2 Jg (57 mmof) of 60% sodium hydride, 5.0 g (25 mmol) of dimethyl terephthalate, and 50 IrLI of anhydrous tetrahydrofuran were added. ! Mix with stirring under nitrogen stream, 7
The mixture was heated under reflux for an hour. After the reaction was completed, it was left to cool, and 30 ml of 2N hydrochloric acid was added. is added, extracted with chloroform, dried over anhydrous sodium sulfate, and then distilled off. Add 30-methanol to this and make 2N-salt! Add 10 drops and stir at room temperature for 30 minutes. The precipitate that had separated out was collected by filtration and recrystallized from chloroform-acetone to obtain 4.1 g (yield: 48%) of the target compound as pale yellow crystals.

Melting point: 276.5-277, 5°C IR<v 1ilr+cIII-'): 3112
,2980.1690,15B3゜1425,1356
．． 1173.1056.825') I-NMR (CDI
j! ,,δ): 1.52(12H,s), 6.09(
2t(,s), 7.95(4H,s).

14, 8 (2)1. bs) Example 9 1.4-bis(4-methyl-3-year-old xo-4-azapentanoyl)benzene [R'=N(CH
s) a, m = O, n = 2: ] (
Synthesis of Ii): In a 200-volume three-bottle flask equipped with a stirrer, dropping funnel, reflux condenser and nitrogen inlet, 5.0 g (125 mmol) of 60% sodium hydride, 6 g (122 mmol) of dimethylacetamide 1O. , dimethyl terephthalate Log (51 ma+ol) and anhydrous tetrahydrofuran 100 ml! Stir and mix under nitrogen stream,
The mixture was heated under reflux for 4 hours. After the reaction was completed, it was left to cool, and 65 ml of 2N hydrochloric acid was added. The extract was then dried over anhydrous sulfuric acid (sulfuric acid) + 7 um, and the solvent was distilled off to obtain a crude product. This was recrystallized using chloroform-ethanol to obtain 10.0 g (yield: 64%) of the target compound as pale yellow crystals.

Melting point: 188.0-189.0°C IRCv■,, Cm-'): 2932.162
0.1500.1440°1360, 1125.786
．． 640'H-NMR (C[]C/,, δ): 3.10 (12H, s), 4.13 (0,4t (, s
), 5°88 (1,6N, s).

7.82(3,21(,s), 7.75(0,4H,
d), 8.05 (0,4H,d) Example 10 1-(4-Methyl-3-oxo-4-azapentanoyl)-4-(4,4-dimethyl-3-oxopentanoyl)benzene [Formula In (I) R1=N(C)l-)*
and C(CHs)*, m = 0, n = 2] (Ij): In a 100-capacity three-bottle flask equipped with a stirrer, a dropping funnel, a reflux condenser, and a nitrogen inlet tube, 60 % Sodium hydride 5.0g (125mmol), Vinacolon 5
．． 1g (51mmol), dimethyl terephthalate 1
0 g (51+n+nojt) and 30 ml of anhydrous tetrahydrofuran were stirred and mixed under a nitrogen stream, and heated under reflux for 4 hours. Then, 4.4 g (5
1 mmof) was added dropwise thereto, and the mixture was further heated under reflux for 3 hours.

After the reaction was completed, the mixture was allowed to cool, 2N hydrochloric acid 65- was added thereto, extracted with chloroform, dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain a crude product. This was recrystallized using acetone, and 6.9 g of pale yellow crystals of the target compound (yield: 43
%) was obtained.

Melting point: 15g, 7-160.1t' LR (vcs+cts, cm-'): 3010
,1610,1503゜1368,1290.1164
．． 1116'H-NMR (ct+ces, δ): 1.29 (9H, s), 3.10 (6H, bs),
4.15 (0,3H,s).

5.88 (0,7)1. s), 6J5(LH,s)
, 7.78-8.10 (4) 1. m) Test Example 1 Ultraviolet absorption effect of the compound of the present invention: (Ia'
) to (Ij), and 2-hydroxy-4-methoxybenzophenone (UV-All collector) as a comparative compound.
and 2-ethylhexyl-p-methoxycinnamate (
The ultraviolet absorption effect (absorbance) was measured using [IV-8 absorbent] according to the following measurement method. The results are shown in Table 1.

(Measurement method) 2.5x 10-'mo of the present invention compound and comparative compound
l! /1 concentration of ethanol (99.5% reagent special grade) solution was prepared and placed in a quartz cell (1cIIX1cm),
Measurement was performed using a Hitachi model U-3410 self-recording spectrophotometer.

The following margin indicates that the compounds of the present invention are UV- to ultraviolet and UV-resistant.
For v-e ultraviolet light, the comparative compound 2-hydroxy-4
-methoxybenzophenone or 2-ethylhexyl-p
-It has a stronger absorption effect than methoxycinnamate, indicating that it has a high sun protection effect.

Test Example 2 Stability of the compound of the present invention against ultraviolet light = (experimental method) The compound of the present invention and the comparative compound were dissolved in a solvent of 99.5% ethanol/distilled water (3/2) to a volume of 2 ml of IIO1/1, and exposed to sunlight. Ultraviolet light was irradiated for 14 hours using a xenon stylus tester having a wavelength and intensity very similar to that of light. After distilling off the solvent, quantitative analysis was performed and stability was evaluated from the residual rate. The results are shown in Table 2.

Table 2 Photostability evaluation Below margin Ia: 1.4-bis(4,4-dimethyl-3-oxopentanoyl)benzene Ib: 1.3-bis(4,4-dimethyl-3-oxopentanoyl)benzene Ic: 4-methoxy-1,3-bis(4,4-dimethyl-3-oxopentanoyl)benzene Id: 1,4-bis(4-methyl-3-oxopentanoyl)benzene Ie: 1,4- Bis(3-oxopentanoyl)benzene If: 1.4-bis(3-oxododecanoyl)benzene Tg: 1,3.5-)lis(4,4-dimethyl-3-oxopentanoyl)benzene Ih: 1.4-bis(4-hydroxy-4-methyl-3
-oxopentanoyl)benzene 1i: 1,4-bis(
4-Methyl-3=oxo-4-azapentanoyl)benzene Ij: 1-(4-methyl-3-oxo-4-azapentanoyl)-4-(4,4-dimethyl-3-oxopentanoyl)benzene 2:4 -Methoxy-4'-t-butyldibenzoylmethane 3:2-Ethylhexyl-p-methoxycinnamate From the results in Table 2, 4-methoxy-4'-t-, which is commonly used as a t+V-^ absorbent, Butyldibenzoylmethane or [IV-Bll! ! , widely used as an acid agent 2
It is clear that compared to -ethylhexyl-p-methoxycinnamate, the compounds of the present invention have significantly better stability against ultraviolet light.

Example 11 O/W type cream: The following composition was blended according to a conventional method to produce an O/W type mulberry cream.

[Composition] (% by weight) Compound Ia of the present invention 2.0 Stearic acid 1.0 Lipophilic monostearic acid glyceride 2.0 Heptyl alcohol
1.0 stearyl alcohol
1.0 Squalane 10.
0 liquid paraffin 20.0 Vaseline 5.0 Butylparaben 0.1 Methylparaben 0.1 Triethanolamine 1.0 Glycerin
10.0 fragrance
Appropriate amount of water balance 1
00, 0 O/W type creams were prepared with the same composition except that each of the compounds Ib to Ij of the present invention was used instead of the compound Ia of the present invention.

Example 12 W10 type cream: The following composition was blended according to a conventional method to prepare W10 type cream.

[Composition] (% by weight) Compound Ia of the present invention 2.0 Sorbitan sesquioleate 4.0 Aluminum stearate 0.5 Hetyl alcohol 4.0 Liquid paraffin
16.0 Squalane
10.0 Isopropyl myristate
5.0 Sodium benzoate
0.3 Glycerin 10.0 Flavor Appropriate amount of water
Balance 100, 0 A W/○ type cream was prepared with the same composition except that each of the compounds Ib to Ij of the present invention was used instead of the compound 1a of the present invention.

Example 13 O/W type emulsion: The following composition was blended according to a conventional method to prepare an O/W type emulsion.

[Composition] (% by weight) Compound Ia of the present invention 3.0 Stearic acid 2.0 Sorbitan monostearate 1.5 Hetyl alcohol
0.4 stearyl alcohol
0.3 Isopropyl myristate
7.0 Squalane 5.0 Liquid paraffin 5.0 Solid paraffin 2.0 Ethylparaben 0.1 Methylparaben
0.1 carb ball
0.2 caustic potash
0.4 fragrance
Appropriate amount of water rose
'3100,0 O/W type emulsion was prepared with the same composition except that each of the present compounds Ib to Ij was used instead of the present compound IaO.

Example 14 Lotion: A lotion was prepared by blending the following composition according to a conventional method.

[Composition] (% by weight) Compound Ia of the present invention 2.0 Ethanol Glycerin Dipropylene glycol Lactate Sodium lactate Methyl paraben Flavor Color water 10.0 3.0 7.0 0.05 0.12 0.1 Appropriate amount Trace balance 100,0 A lotion was prepared with the same composition except that each of the compounds Ib to Ij of the present invention was used instead of the compound Ia of the present invention.

〔Effect of the invention〕

Since the benzoyl ketone derivative (1) of the present invention has excellent ultraviolet absorbing action and excellent stability, ultraviolet absorbers or cosmetics containing it have excellent sunburn prevention effects.

that's all

Claims (1)

[Claims] 1. The following general formula (I) Ar(COCH_2COR^1)_n(I) [in the formula,
Ar represents a phenyl group optionally substituted with a linear or branched alkoxy group having 1 to 2 carbon atoms or an alkenyloxy group, and n represents a number of 2 to 4; The groups -COCH_2COR^1 may be the same or different, and R^1 is a saturated or unsaturated hydrocarbon group having 2 to 24 carbon atoms, a hydroxyalkyl group having 1 to 24 carbon atoms, or a hydroxyalkyl group having 1 to 24 carbon atoms. alkoxyalkyl group, carbon number 1
~24 alkenyloxyalkyl groups or groups ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R^3 and R^4 each represent a hydrocarbon group of 1 to 24, and R^3 and R^4 together may further form a 5- to 7-membered ring which may further contain an oxygen atom (provided that Ar is a phenyl group, n
= 2 and the group -COCH_2COR^1 is 1 on the benzene nucleus
and 3-position, R^1 is not an ethyl group or a 3-butenyl group)]. 2. An ultraviolet absorber containing the benzoyl ketone derivative according to claim 1. 3. A cosmetic containing the benzoyl ketone derivative according to claim 1.