CN108619119A - The purposes of benzyl phenyl ketone derivative - Google Patents
The purposes of benzyl phenyl ketone derivative Download PDFInfo
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- CN108619119A CN108619119A CN201810581092.5A CN201810581092A CN108619119A CN 108619119 A CN108619119 A CN 108619119A CN 201810581092 A CN201810581092 A CN 201810581092A CN 108619119 A CN108619119 A CN 108619119A
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Abstract
The invention discloses the purposes of benzyl phenyl ketone derivative or its salt, solvate in preparing ultra-violet absorber shown in formula (I)：Wherein, R1、R2、R3、R4、R5Separately it is selected from hydrogen, C1‑C6Alkyl, C3‑C6Naphthenic base, phenyl.The experimental results showed that, there is absorption maximum in benzyl phenyl ketone derivative and its Yan UVB of the present invention area (280~320nm), it is a kind of effective ultra-violet absorber, by having absorption to contact of the shielding ultraviolet rays to human skin ultraviolet light, ultraviolet light is blocked, achieve the purpose that prevent it from encroaching on skin, can be used for preparing the drug or cosmetics for preventing dermal photodamage.
Description
Technical field
The present invention relates to the purposes of benzyl phenyl ketone derivative.
Background technology
Ultraviolet spectrogram in sunlight is can be divided into 3 wave bands, i.e. short wave ultraviolet in 200~400nm wave-length coverages
UVC200~280nm, ultraviolet B radiation 280~320nm of UVB, long wave ultraviolet UVA320~400nm.Different wave length it is ultraviolet
Line, the depth for penetrating skin are different.Wherein UVB is most of, and by epidermal absorption, fraction reaches high dermis, is skin damage
The main wave band of wound.
Ultraviolet light has following aspects the injury of skin：1, so that B16 cell is increased, color can be caused calm, it is such as black
The various color spots such as spot, freckle, chloasma increase, increase, deepening；2, keratinocyte hyperplasia, dermal collagen fiber and bullet
Property fiber destruction.It can lead to pachyderma, relaxation, coarse and wrinkle；3, telangiectasis can generate erythema；4, skin is exempted from
Epidemic disease function reduction can form cutaneum carcinoma or precancerous lesion, such as light keratosis, squamous cell carcinoma, melanoma.
It is more to chemical ultraviolet absorbers research both at home and abroad at present, such as cinnamic acid, salicylic acid, diphenyl alkanes, benzene
Ketone etc..- 4 methoxy benzophenone of 2- hydroxyls (oxybenzone), also known as UV-9, benzophenone-3, BP-3 or sun-screening agent 2
Number, belong to benzene ketone compounds, be a kind of extensive ultra-violet absorber, be I class sun-screening agent of U.S. FDA approval, in the U.S. and
European frequency of use is higher, is widely used in the sun care preparations such as suntan lotion, frost, honey, lotion, oil.
Have no the report that can be used as ultraviolet absorber about the compounds of this invention at present.
Invention content
The purpose of the present invention is to provide benzyl phenyl ketone derivative shown in formula (I) or its salt, solvate prepare it is ultraviolet
Purposes in light absorbers：
Wherein, R1、R2、R3、R4、R5Separately it is selected from hydrogen, C1-C6Alkyl, C3-C6Naphthenic base, phenyl.
Further, the R1、R2、R3、R4、R5Separately it is selected from hydrogen, methyl, ethyl.
Further, shown in the salt such as formula (II) of benzyl phenyl ketone derivative shown in the formula (I)：
Wherein, M is selected from Li, Na, K, Rb, Cs, Ca, Mg, Al, Fe, Cu, Mn or Zn.
Further, the benzyl phenyl ketone derivative or its salt are one of following compound：
Further, benzyl phenyl ketone derivative shown in the formula (I) is prepared by following methods：
Take blackberry lily aglycon, alkyl blackberry lily aglycon obtained after alkylation, then under alkaline condition demethylation up to formula (I) institute
Show benzyl phenyl ketone derivative；
Or blackberry lily aglycon is taken, the mixing of alkylation blackberry lily aglycon and benzyl phenyl ketone derivative is obtained after alkylated reaction
Object, up to benzyl phenyl ketone derivative shown in formula (I) after separation.
Further, salt shown in the formula (II) is prepared by following methods：
Blackberry lily aglycon is taken, alkyl blackberry lily aglycon is obtained after alkylation；After the sulfonated reaction of alkyl blackberry lily aglycon again with normal salt
Saturated aqueous solution reacts up to alkyl blackberry lily aglycon -5 '-sulfonate；Last demethylation under alkaline condition is up to shown in formula (II)
Benzyl phenyl ketone sulfonate derivatives；
Alternatively, taking blackberry lily aglycon, reacted up to blackberry lily aglycon -5 '-sulfonate with normal salt saturated aqueous solution after sulfonating reaction；
Blackberry lily aglycon -5 '-sulfonate is after alkylated reaction up to alkyl blackberry lily aglycon -5 '-sulfonate；Finally take off under alkaline condition
Methyl is up to benzyl phenyl ketone sulfonate derivatives shown in formula (II).
Further, sulfuric acid, oleum, chlorosulfonic acid or three oxygen that the sulfonated reagent of the sulfonating reaction is 85~98%
Change sulphur；The normal salt is hydrochloride, hydrobromate, hydriodate or nitrate.
The present invention also provides benzyl phenyl ketone derivatives shown in formula (I) or its salt, solvate to prepare prevention skin light
The drug of damage or the purposes in cosmetics：
Wherein, R1、R2、R3、R4、R5Separately it is selected from hydrogen, C1-C6Alkyl, C3-C6Naphthenic base, phenyl.
The present invention also provides a kind of sun care preparations, it is with benzyl phenyl ketone derivative or its salt, solvent shown in formula (I)
Conjunction object is active constituent, along with acceptable auxiliary material is prepared in cosmetics：
Wherein, R1、R2、R3、R4、R5Separately it is selected from hydrogen, C1-C6Alkyl, C3-C6Naphthenic base, phenyl.
The present invention also provides benzyl phenyl ketone derivative or its salt：
The experimental results showed that there is absorption maximum in benzyl phenyl ketone derivative of the present invention and its areas Yan UVB (280~320nm),
It is a kind of effective ultra-violet absorber, by having absorption to contact of the shielding ultraviolet rays to human skin ultraviolet light,
Ultraviolet light blocks, and achievees the purpose that prevent it from encroaching on skin, can be used for preparing the drug or cosmetics for preventing dermal photodamage.
Obviously, the above according to the present invention is not being departed from according to the ordinary technical knowledge and customary means of this field
Under the premise of the above-mentioned basic fundamental thought of the present invention, the modification, replacement or change of other diversified forms can also be made.
The specific implementation mode of form by the following examples remakes further specifically the above of the present invention
It is bright.But the range that this should not be interpreted as to the above-mentioned theme of the present invention is only limitted to example below.It is all to be based on the above of the present invention
The technology realized all belongs to the scope of the present invention.
Description of the drawings
Fig. 1 is the infrared spectrogram of compound 3.
Fig. 2 is the mass spectrogram of compound 3.
Fig. 3 is the hydrogen spectrogram of compound 3.
Fig. 4 is the carbon spectrogram of compound 3.
Fig. 5 is the infrared spectrogram of compound 4.
Fig. 6 is the mass spectrogram of compound 4.
Fig. 7 is the hydrogen spectrogram of compound 4.
Fig. 8 is the infrared spectrogram of compound 5.
Fig. 9 is the mass spectrogram of compound 5.
Figure 10 is the hydrogen spectrogram of compound 5.
Figure 11 is the ultra-violet absorption spectrum of compound 1.
Figure 12 is the ultra-violet absorption spectrum of compound 2.
Figure 13 is the ultra-violet absorption spectrum of compound 3.
Figure 14 is the ultra-violet absorption spectrum of compound 4.
Figure 15 is the ultra-violet absorption spectrum of compound 5.
Figure 16 is the ultra-violet absorption spectrum of control compound.
Specific implementation mode
The preparation of embodiment 1,2- hydroxy-3-methoxies -4,6,4 '-triethoxy benzyl phenyl ketone (compound 3)
(2,6- dihydroxy -3- methoxyl groups -4,4 '-diethoxy benzyl phenyl ketone) 10g of compound 2 is taken to be burnt in 500ml round bottoms
In bottle, adds 2g NaOH, 95% ethyl alcohol 50ml, ebuillition of heated 5 minutes in water-bath, then add 2ml dithyl sulfates, react 10 points
Clock takes out, immediately with hydrochloric acid tune PH to 1~2, water is added to stir, and puts to room temperature, and precipitation, filtering, water washing and precipitating to efflux is precipitated
PH 6~7, obtains pale yellow powder, is recrystallized with absolute ethyl alcohol, filtering, 60 DEG C are dried under reduced pressure, obtain compound 3 (faint yellow platelet,
8.0g must be measured).
The preparation of embodiment 2,2- hydroxy-3-methoxies -4,6,4 '-triethoxy benzyl phenyl ketone (compound 3)
It takes blackberry lily aglycon 10g in 500ml round-bottomed flasks, adds 2g NaOH, 95% ethyl alcohol 50ml, boiling is heated in water-bath
Rise 5 minutes, then add 2ml dithyl sulfates, react 45 minutes, take out, immediately with hydrochloric acid tune PH to 1~2, water is added to stir, put to
Precipitation, filtering is precipitated in room temperature, and water washing and precipitating is dried under reduced pressure for 6~7,60 DEG C to efflux PH, obtains brownish-yellow powder 12g.Take this
Powder 5.0g adds 95% ethyl alcohol of 50ml to dissolve, and filtering, filtrate is concentrated into 10ml, absorption is mixed thoroughly with 80 mesh silica gel of 10g, dry,
It is finely ground, as upper prop sample, 200~300 mesh silica gel dry chromatography (column specifications of sample：Diameter 5cm × length 70cm), chloroform
For solvent, expansion finishes, and segmentation cutting silicagel column silica gel, TLC combining data detections, isolated compound 3, the amount of obtaining is 1.2g.
Structure determination：Compound 3, white platelet (absolute ethyl alcohol), mp.107~109 DEG C；UVλmaxnm:283；ESI-MS
m/z 375[M+H]+；IR、MS、1H-NMR、13C-NMR is shown in Fig. 1~4, is identified as 2- hydroxy-3-methoxies -4,6,4 '-three second
Oxygroup benzyl phenyl ketone.
The preparation of embodiment 3,2,6- dihydroxy -3,4,4 '-trimethoxy benzyl phenyl ketone -5 '-sodium sulfonate
It takes blackberry lily aglycon 10g in 500ml round-bottomed flasks, adds 2g NaOH, 95% ethyl alcohol 50ml, boiling is heated in water-bath
Rise 5 minutes, then add 2ml dimethyl suflfates, react 15 minutes, take out, immediately with hydrochloric acid tune PH to 1~2, water is added to stir, put to
Precipitation, filtering is precipitated in room temperature, and water washing and precipitating is dried under reduced pressure for 6~7,60 DEG C to efflux PH, obtains pale powder.With chloroform weight
Crystallization, filtering, 60 DEG C are dried under reduced pressure, and obtain 5- hydroxyls -6,7,4 '-trimethoxy isoflavones 10.0g (white crystalline powder).
It takes above-mentioned powder 10g in 100ml round-bottomed flasks, 40ml sulfuric acid is added, stirring, will be anti-to entirely molten, placement 2 hours
Liquid is answered to be added in 400ml saturated aqueous sodium chlorides, it is stirring while adding, a large amount of pale precipitations are precipitated, place, water is used in filtering
Recrystallization, filtering, 60 DEG C are dried under reduced pressure to get 5- hydroxyls -6,7,4 '--5 '-sodium sulfonates of trimethoxy isoflavones, the amount of obtaining 10g.
It takes above-mentioned crystallization 10g in 100ml round-bottomed flasks, adds 5%NaOH aqueous solution 50ml, heated 4 hours in water-bath,
With hydrochloric acid tune PH 6~7, put to room temperature, crystallization, filtering is recrystallized with water, is filtered, 60 DEG C are dried under reduced pressure to get 2,6- dihydroxies
Base -3,4,4 '--5 '-sodium sulfonates of trimethoxy benzyl phenyl ketone are white crystalline powder, the amount of obtaining 8.0g.
The preparation of embodiment 4,2,6- dihydroxy -3,4,4 '-trimethoxy benzyl phenyl ketone -5 '-sodium sulfonate
It takes blackberry lily aglycon 10g in 100ml round-bottomed flasks, 40ml sulfuric acid, stirring to complete molten, placement 2 hours, reaction is added
Liquid is slowly poured into 400ml saturated aqueous sodium chlorides, stirring while adding, and a large amount of pale precipitations are precipitated, and is placed, and is filtered, and is used
Water recrystallizes, and filtering, 60 DEG C are dried under reduced pressure to get blackberry lily aglycon -5 '-sodium sulfonate.Light yellow crystalline powder, the amount of obtaining 12g.
It takes this crystalline powder 10g in 500ml round-bottomed flasks, adds 2g NaOH, 95% ethyl alcohol 50ml, add in water-bath
Heat boiling 5 minutes, then add 2ml dimethyl suflfates, it reacts 15 minutes, takes out, immediately with hydrochloric acid tune PH to 1~2, water is added to stir,
It puts to room temperature, precipitation, filtering is precipitated, water washing and precipitating is dried under reduced pressure for 6~7,60 DEG C to efflux PH, obtains pale powder.Use water
Recrystallization, filtering, 60 DEG C are dried under reduced pressure, and obtain 5- hydroxyls -6,7,4 '--5 '-sodium sulfonates of trimethoxy isoflavones.Pale yellow crystals
Property powder, the amount of obtaining 12g.
It takes above-mentioned crystallization 10g in 100ml round-bottomed flasks, adds 5%NaOH aqueous solution 50ml, heated 4 hours in water-bath,
With hydrochloric acid tune PH 6~7, put to room temperature, crystallization, filtering is recrystallized with water, is filtered, 60 DEG C are dried under reduced pressure to get 2,6- dihydroxies
Base -3,4,4 '--5 '-sodium sulfonates of trimethoxy benzyl phenyl ketone are white crystalline powder, the amount of obtaining 8.0g.
Structure determination：Compound 4, white crystalline powder (water), UV λmaxnm:291；ESI-MS m/z 443[M+Na]
(M：420)；IR、MS、1H-NMR is shown in Fig. 5~7, is identified as 2,6- dihydroxy -3,4,4 '--5 '-sulphurs of trimethoxy benzyl phenyl ketone
Sour sodium.
The preparation of embodiment 5,2,6- dihydroxy -3- methoxyl groups -4,4 '-diethoxy benzyl phenyl ketone -5 '-sodium sulfonate
It takes blackberry lily aglycon 10g in 500ml round-bottomed flasks, adds NaOH2g, 95% ethyl alcohol 50ml, the ebuillition of heated in water-bath
5 minutes, then add 2ml dithyl sulfates, it reacts 15 minutes, takes out, immediately with hydrochloric acid tune PH to 1~2, water is added to stir, put to room
Precipitation, filtering is precipitated in temperature, and water washing and precipitating is dried under reduced pressure for 6~7,60 DEG C to efflux PH, obtains pale powder.It is tied again with chloroform
Crystalline substance, filtering, 60 DEG C are dried under reduced pressure, and obtain -6 methoxyl group of 5- hydroxyls -, 7,4 '-diethoxy isoflavones 11.0g (pale yellow crystals
Powder).
It takes above-mentioned powder 10g in 100ml round-bottomed flasks, 40ml sulfuric acid is added, stirring, will be anti-to entirely molten, placement 2 hours
Liquid is answered to be added in 400ml saturated aqueous sodium chlorides, it is stirring while adding, a large amount of pale precipitations are precipitated, place, water is used in filtering
Recrystallization, filtering, 60 DEG C are dried under reduced pressure to get -6 methoxyl group of 5- hydroxyls -, 7,4 '--5 '-sodium sulfonates of diethoxy, the amount of obtaining 10g
(light yellow crystalline powder).
It takes above-mentioned crystallization 10g in 100ml round-bottomed flasks, adds 5%NaOH aqueous solution 50ml, heated 4 hours in water-bath,
With hydrochloric acid tune PH 6~7, put to room temperature, crystallization, filtering is recrystallized with water, is filtered, 60 DEG C be dried under reduced pressure to get：2,6- dihydroxies
Methoxyl group -4 base -3-, 4 '--5 '-sodium sulfonates of diethoxy benzyl phenyl ketone are white crystalline powder, the amount of obtaining 8.0g.
The preparation of embodiment 6,2,6- dihydroxy -3- methoxyl groups -4,4 '-diethoxy benzyl phenyl ketone -5 '-sodium sulfonate
It takes blackberry lily aglycon 10g in 100ml round-bottomed flasks, 40ml sulfuric acid is added, stirring, will be anti-to entirely molten, placement 2 hours
Liquid is answered to be added in 400ml saturated aqueous sodium chlorides, it is stirring while adding, a large amount of pale precipitations are precipitated, place, water is used in filtering
Recrystallization, filtering, 60 DEG C are dried under reduced pressure to get blackberry lily aglycon -5 '-sodium sulfonate.Light yellow crystalline powder, the amount of obtaining 12g.
It takes this crystalline powder 10g in 500ml round-bottomed flasks, adds 2g NaOH, 95% ethyl alcohol 50ml, add in water-bath
Heat boiling 5 minutes, then add 2ml dithyl sulfates, it reacts 15 minutes, takes out, immediately with hydrochloric acid tune PH to 1~2, water is added to stir,
It puts to room temperature, precipitation, filtering is precipitated, water washing and precipitating is dried under reduced pressure for 6~7,60 DEG C to efflux PH, obtains pale powder.Use water
Recrystallization, filtering, 60 DEG C are dried under reduced pressure, and obtain -6 methoxyl group of 5- hydroxyls -, 7,4 '--5 '-sodium sulfonates of diethoxy.Pale yellow crystals
Property powder, the amount of obtaining 13g.
It takes above-mentioned crystallization 10g in 100ml round-bottomed flasks, adds 5%NaOH aqueous solution 50ml, heated 4 hours in water-bath,
With hydrochloric acid tune PH 6~7, put to room temperature, crystallization, filtering is recrystallized with water, is filtered, 60 DEG C are dried under reduced pressure to get 2,6- dihydroxies
Base -3- methoxyl groups -4,4 '-diethoxy benzyl phenyl ketone -5 '-sodium sulfonate.Light yellow crystalline powder, the amount of obtaining 8.0g.
Structure determination：Compound 5, light yellow crystalline powder (water), UV λmaxnm:290；ESI-MS m/z 471[M+
Na](M：448)；IR、MS、1H-NMR is shown in Fig. 8~10, is identified as methoxyl group -4 2,6- dihydroxy -3-, 4 '-diethoxies two
Acetophenone -5 '-sodium sulfonate.
Embodiment 7, ultraviolet spectroscopy
Experiment material：
Target compound：Compound 1~5：Wherein compound 1 and 2 is prepared with reference to CN201710425327.7, compound 3
~5 are prepared by the method described in Examples 1 to 6；
Control compound：ESCALOL 567.
Above compound 10mg is taken respectively, is placed in 50ml volumetric flasks, and scale is dissolved and be diluted to 70% ethyl alcohol, is shaken
Even, precision draws this liquid 1ml in 50ml volumetric flasks, dilute with 70% ethyl alcohol and is settled to scale and shakes up, and divides according to ultraviolet-visible
Light photometry (Chinese Pharmacopoeia 2015 editions four 0401), using 70% ethyl alcohol as blank, is scanned in 200~400nm wave-length coverages,
Recording light spectrogram.Collection of illustrative plates is shown in Figure 11~16.
It can be seen that there is maximum in target compound and the areas control compound Jun UVB (280~320nm) from Figure 11~16
It absorbs.The areas UVB, also known as dongle promise line, it is most strong to skin ability to function, the nucleic acid in skin epidermal cells or albumen qualitative change can be made
Property, acute dermatitis --- daylight sunburn (erythema is burnt) occurs, therefore such compound is by having absorption to shield ultraviolet light
Contact of the ultraviolet light to human skin is covered, ultraviolet light is blocked, achievees the purpose that prevent it from encroaching on skin.
The ε values of 1 target compound of table and control compound
| Title | Molecular weight | It weighs (mg) | Concentration C (mg/ml) | λmaxnm | A | ε |
| Compound 1 | 318 | 21.96 | 0.00874 | 285.00 | 0.511 | 1.86×104 |
| Compound 2 | 346 | 35.72 | 0.014288 | 288.00 | 0.640 | 1.55×104 |
| Compound 3 | 374 | 37.28 | 0.014912 | 283.00 | 0.602 | 1.51×104 |
| Compound 4 | 420 | 10.49 | 0.004196 | 290.60 | 0.228 | 2.28×104 |
| Compound 5 | 448 | 10.20 | 0.00408 | 290.40 | 0.177 | 1.94×104 |
| Control compound | 228 | 12.27 | 0.004908 | 289.00 | 0.301 | 1.40×104 |
ε value calculation formula：ε=(A/C) × molecular weight
ε values refer to target compound in possessed λmaxMolar absorption coefficient under wavelength, it is considered that ε values are more than 104
To absorb by force, 103~104For middle absorption, it is less than 103For weak absorbing.A criterion of the ε values as antiultraviolet compound,
It is advisable with being more than 15000.As can be seen from the above table, the ε values of 5 target compounds are all higher than 15000, and more than control chemical combination
Object.
Illustrate beneficial effects of the present invention below by way of test example.
Test example 1, sunlight screening skin-protecting product safety research and pharmacodynamics test
(1) preparation of skin care item
Prescription：
| Target compound or control | 10g |
| Glycerine | 150g |
| Propylene glycol | 100g |
| Ethyl-para-hydroxybenzoate | 1g |
| Sodium pyrosulfite | 1g |
| Triethanolamine | 4g |
| Glycerin monostearate | 50g |
| Stearic acid | 100g |
| Atoleine | 100g |
| Albolene | 50g |
| Rosa Damascana | 2g |
| Distilled water adds to | 1000g |
Preparation method：Take stearic acid, glycerin monostearate, albolene, atoleine heating fusing, mixing, through thin
Cloth filters, and keeps the temperature 80 DEG C or so；Separately take target compound or control, glycerine, propylene glycol, triethanolamine, P-hydroxybenzoic acid second
Ester, sodium pyrosulfite are dissolved in hot distilled water, and are slowly added into oil phase in 80 DEG C or so, be stirred continuously.Wait for that lotion is cold
Rosa Damascana is added when but to 50 DEG C or less, continues to stir evenly, cooled to room temperature, bottles (50g/ bottles), capping,
Sunlight screening skin-protecting product.
In addition, removing main ingredient, i.e., target compound or control compound are not added with outer, prepare 100g blank lotions with method in proportion
(matrix), is for experiment.
(2) safety research
Adult healthy rabbit 36,2.5~3.0kg of weight is taken, it is random and be divided into 6 groups, it is every group 6, hard of hearing two
Respectively choose 2 × 2cm in portion2The symmetrical epidermis position of area cuts off the rabbit hair, and side applies sunlight screening skin-protecting product, and the other side applies blank
Matrix, whether there is or not redness, the generations such as papule for observation skin surface.As a result：The tested hard of hearing epidermis of rabbit does not generate irritative response,
Skin care item group is with matrix group without significant difference.
(3) pharmacodynamics test
42 rats are divided into 7 groups at random, every group 6, thorax abdomen loses hair or feathers 4cm2, respectively smear 6 kinds of skin care item of 1g and
Bare substrate covers rest part, to giving the ultraviolet light irradiation of 40 biological doses at coating (away from irradiation at ultraviolet lamp 50cm
20min).Skin care item are washed away according to after, are observed continuously one week.It the results are shown in Table 2.
The protective effect that 2 sunlight screening skin-protecting product of table tans severely to rat
From table 2 it can be seen that skin care item effect made of target compound (except compound 3) is better than or is equal to control
Skin care item.
To sum up, there is absorption maximum in benzyl phenyl ketone derivative and its Yan UVB of the present invention area (280~320nm), and being one kind has
The ultra-violet absorber of effect keeps off ultraviolet light by having absorption to contact of the shielding ultraviolet rays to human skin ultraviolet light
Firmly, achieve the purpose that prevent it from encroaching on skin, can be used for preparing the drug or cosmetics for preventing dermal photodamage.
Claims (10)
1. the purposes of benzyl phenyl ketone derivative or its salt, solvate in preparing ultra-violet absorber shown in formula (I)：
Wherein, R1、R2、R3、R4、R5Separately it is selected from hydrogen, C1-C6Alkyl, C3-C6Naphthenic base, phenyl.
2. purposes according to claim 1, it is characterised in that：The R1、R2、R3、R4、R5Separately it is selected from hydrogen, first
Base, ethyl.
3. purposes according to claim 1 or 2, it is characterised in that：The salt of benzyl phenyl ketone derivative shown in the formula (I) is such as
Shown in formula (II)：
Wherein, M is selected from Li, Na, K, Rb, Cs, Ca, Mg, Al, Fe, Cu, Mn or Zn.
4. according to claims 1 to 3 any one of them purposes, it is characterised in that：The benzyl phenyl ketone derivative or its salt are
One of following compound：
5. according to Claims 1 to 4 any one of them purposes, it is characterised in that：Benzyl phenyl ketone derivative shown in the formula (I)
It is to be prepared by following methods：
Take blackberry lily aglycon, alkyl blackberry lily aglycon obtained after alkylation, then under alkaline condition demethylation up to two shown in formula (I)
Acetophenone derivs；
Or blackberry lily aglycon is taken, the mixture of alkylation blackberry lily aglycon and benzyl phenyl ketone derivative is obtained after alkylated reaction, point
From rear up to benzyl phenyl ketone derivative shown in formula (I).
6. purposes according to claim 3 or 4, it is characterised in that：Salt is prepared by following methods shown in the formula (II)
It obtains：
Blackberry lily aglycon is taken, alkyl blackberry lily aglycon is obtained after alkylation；After the sulfonated reaction of alkyl blackberry lily aglycon again with positive salt loading
Reactant aqueous solution is up to alkyl blackberry lily aglycon -5 '-sulfonate；Last demethylation under alkaline condition is up to hexichol shown in formula (II)
Ethyl ketone sulfonate derivatives；
Alternatively, taking blackberry lily aglycon, reacted up to blackberry lily aglycon -5 '-sulfonate with normal salt saturated aqueous solution after sulfonating reaction；Blackberry lily
Aglycon -5 '-sulfonate is after alkylated reaction up to alkyl blackberry lily aglycon -5 '-sulfonate；Last demethylation under alkaline condition
Up to benzyl phenyl ketone sulfonate derivatives shown in formula (II).
7. purposes according to claim 6, it is characterised in that：The sulphur that the sulfonated reagent of the sulfonating reaction is 85~98%
Acid, oleum, chlorosulfonic acid or sulfur trioxide；The normal salt is hydrochloride, hydrobromate, hydriodate or nitrate.
8. benzyl phenyl ketone derivative or its salt, solvate shown in formula (I) are preparing the drug for preventing dermal photodamage or makeup
Purposes in product：
Wherein, R1、R2、R3、R4、R5Separately it is selected from hydrogen, C1-C6Alkyl, C3-C6Naphthenic base, phenyl.
9. a kind of sun care preparations, it is characterised in that：It is with benzyl phenyl ketone derivative or its salt, solvate shown in formula (I)
For active constituent, along with acceptable auxiliary material is prepared in cosmetics：
Wherein, R1、R2、R3、R4、R5Separately it is selected from hydrogen, C1-C6Alkyl, C3-C6Naphthenic base, phenyl.
10. benzyl phenyl ketone derivative or its salt：
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