CN109879759A - A kind of sun-proof molecule of methyl cinnamate type and its application and suncream - Google Patents
A kind of sun-proof molecule of methyl cinnamate type and its application and suncream Download PDFInfo
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- CN109879759A CN109879759A CN201711276095.XA CN201711276095A CN109879759A CN 109879759 A CN109879759 A CN 109879759A CN 201711276095 A CN201711276095 A CN 201711276095A CN 109879759 A CN109879759 A CN 109879759A
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Abstract
The present invention relates to one kind when introducing different substituent groups on methyl cinnamate phenyl ring, and obtained compound molecule, such molecule can be used for suncream field, use as sun-proof molecule.The structure of the sun-proof molecule isWherein R1、R2、R3For hydrogen atom, alkyl or contain heteroatomic substituent group.The present invention obtains a series of compound molecule by the meta position of change methyl cinnamate and the substituent group of contraposition, such molecule can be used as the main component of suncream.The synthesis material of this compound molecule is easy to get, synthesis step is simple, there is good absorption in ultraviolet B ray (UVB) and A ray (UVA) wave band, lifetime of excited state with picosecond (being lower than 30ps), and there is the SPF (sun protection factor, SPF) not less than 5.
Description
Technical field:
The present invention relates to organic synthesis, ultraviolet protection and suncream fields, and in particular to a kind of methyl cinnamate chemical combination
The synthetic method of object molecule.
Background technique:
It is found in the atmosphere of the south pole of the earth overhead for the first time ozone content since nineteen seventies British scientist
It gradually decreases, since determining that this phenomenon is Antarctic ozone hole to scientists in 1985, global atmosphere elsewhere
Middle ozone content is also gradually decreasing.And in ozone layer ozone concentration reduction so that ultraviolet radioactive of the sun to earth surface
Amount increases, and will generate destruction to ecological environment, and influence the normal existence of the mankind and other biological organism.In order to reduce skin
The risk of skin carcinogenesis, various sunscreen products come out.
Ultraviolet light in solar radiation can be divided into three wave bands, respectively UVC (190~280nm), UVB (280~
315nm) and UVA (315~400nm), wherein the ultraviolet light of UVC wave band is absorbed by ozone layer completely, UVB wave band it is ultraviolet wide
It is partly absorbed, and the ultraviolet light of UVA wave band is not absorbed completely.Some researches show that the ultraviolet radiations of UVB and UVA wave band
The damage that can result in human skin cell leads to various skin diseases (Wang S.Q., Balagula Y., Osterwalder
U., Dermatol.Ther., 2010,23,31 and Duthie M.S., Kimber I., Norval M., Br.J.Dermatol.,
1999,140,995).So a kind of good sun-proof molecule should have good absorption to the ultraviolet light of UVB and UVA wave band, and
And ground state can be quickly returned to after reaching excitation state, by the energy dissipation of ultraviolet light into environment.However, approval uses at present
Sun-proof molecular amounts it is few, and its biocompatibility and energy dissipation mechanism are all unofficial.
There are the danger that Sinapoyl Malate (SM, structure are shown in Fig. 1 a) is used to resist ultraviolet light in the leaf epidermis of plant
Evil, SM is a kind of ester derivant of sinapic acid (SA, structure are shown in Fig. 1 b).SA is widely distributed in plant kingdom, and is easy to extract, and
SM then needs to synthesize to obtain by multistep reaction.This patent is the molecular structure from SA or similar SA, has synthesized a kind of cortex cinnamomi
Sour methyl compound.Obviously, this is the compound close to plant extracts, will have good biocompatibility.Therefore, this is special
Methyl cinnamate compound molecule described in benefit by be SM in a kind of similar plants antiultraviolet molecule, while again can be with
It is readily synthesized to obtain.
Summary of the invention:
The methyl cinnamate type that UVB and UVA wave band ultraviolet light can be absorbed the purpose of the present invention is to provide one kind is sun-proof
Molecule, the sun-proof molecule are the cinnamic acid replaced using meta position and/or contraposition and methanol as a kind of methyl cinnamate of Material synthesis
The sun-proof molecule of type.
The purpose of the present invention is to achieve the following:
A kind of synthesis step of the sun-proof molecule of methyl cinnamate type is as follows:
For cinnamic acid, methanol and the concentrated sulfuric acid replaced using meta position and/or contraposition as raw material, synthesis obtains corresponding cinnamic acid first
Ester compounds, i.e., required sun-proof molecule, general structure I are as follows:
In general formula I, R1、R2、R3For hydrogen atom, alkyl or contain heteroatomic substituent group；R1、R2、R3It is C when for alkyl1~
C10Alkyl, preferably C1The alkyl of~C5；R1、R2、R3It can be hydroxyl or alkoxy for when containing hetero atom substituents.
The synthetic method of the above-mentioned sun-proof molecule of methyl cinnamate type, the reaction condition in the step are in round-bottomed flask
Middle that cinnamic acid, methanol and the concentrated sulfuric acid replaced is added, wherein methanol should at least be added and not have completely as reactant and reaction dissolvent
The amount of reactant cinnamic acid is crossed, and the concentrated sulfuric acid need to only be added a little as catalyst；
Blender is started, 4~10h is heated to reflux, after reaction is cooled to room temperature, rotates reaction solution；Suitable second is added
Acetoacetic ester dissolution, and extracted with saturated sodium bicarbonate solution；Upper layer organic solution is dry with anhydrous sodium sulfate, then revolve
It steams；Utilize column chromatography methods (SiO2；7%~50%EtOAc/PE) purified reaction product, it then rotates, and use vacuum oven
Required sun-proof molecule is obtained after being dried.
A kind of sun-proof molecule of methyl cinnamate type prepared according to above-mentioned synthetic method.
It can be used for absorbing UVB and UVA wave band according to the sun-proof molecule of methyl cinnamate type prepared by above-mentioned synthetic method
Ultraviolet light after reaching excitation state, can return to ground state in the time scale of picosecond (being lower than 30ps), effectively by ultraviolet light
Energy dissipation into environment, and have not less than 5 spf value, so as to be used for suncream field.
Beneficial effects of the present invention:
The present invention is reacted using the cinnamic acid for replacing meta position and/or contraposition with methanol to prepare required sun-proof molecule,
The sun-proof molecule has good absorption to the ultraviolet light of UVB and UVA wave band, the excitation state longevity with picosecond (being lower than 30ps)
Life, and there is the spf value not less than 5.Chemical structure of the invention is similar to the naturally occurring sun-proof molecule SM of nature, tool
There is preferable biocompatibility, so as to be used for suncream field.And the sun-proof molecule synthesis raw material compared to SM, in the present invention
It is easy to get, synthesis step is simple, convenient post-treatment.
Detailed description of the invention:
Naturally occurring sun-proof molecule in the nature lifted in Fig. 1 background technique；
The chemical equation of synthesized sun-proof molecule in Fig. 2 embodiment 1；
The ultraviolet-visible absorption spectroscopy of sun-proof creams in Fig. 3 embodiment 2；
The femtosecond transient absorption attenuation curve of sun-proof molecule in Fig. 4 embodiment 3.
Specific embodiment:
Embodiment is for further illustrating the present invention, but the present invention is not limited to embodiments.
The synthesis of 1 3,5- dimethoxy-4 ' of embodiment-hydroxy-methyl cinnamate (Methyl Sinapate, MS):
Major experimental drug 3 used in embodiment, 5- dimethoxy-4 '-hydroxycinnamic acid (SA, purity >=98%) purchase
It buys from Beijing lark prestige Science and Technology Ltd..
It is 98% that 500mg (2.23mmol) SA, 15mL methanol and 2 drop mass fractions are added in 100mL round-bottomed flask
The concentrated sulfuric acid.Blender is started, 8h is heated to reflux, after reaction is cooled to room temperature, rotates reaction solution；It is molten that suitable ethyl acetate is added
Solution, and extracted with saturated sodium bicarbonate solution；Upper layer organic solution is dry with anhydrous sodium sulfate, then rotate；It utilizes
Column chromatography methods (SiO2；7%~50%EtOAc/PE) purified reaction product, it then rotates, and done with vacuum oven
387mg solid product, yield 72.6% are finally obtained after dry.Pass through measurement1H and13C nuclear magnetic resoance spectrum learns synthesized production
Object is required sun-proof molecule MS.
The measurement of the ultraviolet-visible absorption spectroscopy and spf value of the sun-proof molecule of embodiment 2:
In the creams that the sun-proof molecule MS incorporation of synthesis is bought, wherein the mass fraction of sun-proof molecule is 10%, keeping away
It is used magnetic stirrer 24 hours in light situation.Creams mixture is applied to the stone for posting one layer of 3M adhesive tape after mixing evenly
On English glass plate (4cm*4cm), applying amount 2mg/cm2.After being protected from light dry half an hour, inhaled with the UV, visible light with integrating sphere
The measurement that spectrometer carries out absorption spectrum is received, absorption spectrum is as shown in figure 3, be 10.0 by calculating its spf value.And pass through phase
With method measure and be usually used in the Homosalate of commercial suncream (Homosalate, purchase is from the limited public affairs of Beijing Yi Nuokai science and technology
Department) absorption spectrum also as shown in figure 3, calculate its spf value be 3.2.
The measurement of the sun-proof molecule femtosecond transient absorption spectra of embodiment 3:
The phosphate buffer solution solution for preparing certain density sun-proof molecule MS makes its trap on 1.00 left sides by adjusting
Right (quartz cell of 1mm*1cm).It is excited with maximum absorption wavelength, measures femtosecond transient absorption light using the flow cell of 1mm*1cm
Spectrum, attenuation curve as shown in figure 4, be fitted its service life be 7.69ps.
Conclusion: by the figures above and embodiment as it can be seen that methyl cinnamate compound molecule of the present invention is because it is to UVB
There is good absorption with the ultraviolet light of UVA wave band, the lifetime of excited state with picosecond (being lower than 30ps), and have and be not less than
5 spf value uses so as to be used for suncream field as sun-proof molecule.
Claims (6)
1. a kind of sun-proof molecule of methyl cinnamate type, it is characterised in that: the structure of the compound molecule is as shown in general formula I:
In general formula I, R1、R2、R3For hydrogen atom, alkyl or contain heteroatomic substituent group.
2. sun-proof molecule according to claim 1, it is characterised in that: R in the general formula I1、R2、R3It is C when for alkyl1
~C10Alkyl, preferably C1~C5Alkyl；
R1、R2、R3It can be hydroxyl or alkoxy when for containing heteroatomic substituent group.
3. a kind of application of sun-proof molecule of any of claims 1 or 2, it is characterised in that: the sun-proof molecule is preparing skin
Application in sun-proof externally applied drug.
4. application according to claim 3, it is characterised in that: the sun-proof molecule can be, but not limited to purple as protection
The compound of outside line uses, specifically, I compound represented molecule of general formula has good suction to the ultraviolet light of UVB and UVA wave band
It receives, and after absorbing ultraviolet light and reaching excitation state, ground state can be returned in the time scale of picosecond (being lower than 30ps), had
Ground is imitated by the energy dissipation of ultraviolet light into environment, to prevent the destruction of ultraviolet light.
5. application according to claim 3 or 4, it is characterised in that: the sun-proof molecule can with but be not exclusively for sun-proof
White field, specially SPF SPF are not less than 5.
6. a kind of suncream containing sun-proof molecule as claimed in claim 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201711276095.XA CN109879759A (en) | 2017-12-06 | 2017-12-06 | A kind of sun-proof molecule of methyl cinnamate type and its application and suncream |
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| CN201711276095.XA CN109879759A (en) | 2017-12-06 | 2017-12-06 | A kind of sun-proof molecule of methyl cinnamate type and its application and suncream |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6413017A (en) * | 1987-07-03 | 1989-01-17 | Pola Chem Ind Inc | Skin-beautifying cosmetic |
| CN105408301A (en) * | 2013-07-17 | 2016-03-16 | 北京北沃乐基生物医药科技有限公司 | Ultraviolet absorbent having better ultraviolet protection effect, and combination thereof |
| CN105434188A (en) * | 2015-12-29 | 2016-03-30 | 广州市科能化妆品科研有限公司 | Sunscreen cream and preparation method thereof |
-
2017
- 2017-12-06 CN CN201711276095.XA patent/CN109879759A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6413017A (en) * | 1987-07-03 | 1989-01-17 | Pola Chem Ind Inc | Skin-beautifying cosmetic |
| CN105408301A (en) * | 2013-07-17 | 2016-03-16 | 北京北沃乐基生物医药科技有限公司 | Ultraviolet absorbent having better ultraviolet protection effect, and combination thereof |
| CN105434188A (en) * | 2015-12-29 | 2016-03-30 | 广州市科能化妆品科研有限公司 | Sunscreen cream and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| JACOB C. DEAN ET AL.: "Plant Sunscreens in the UV-B: Ultraviolet Spectroscopy of Jet-Cooled Sinapoyl Malate, Sinapic Acid, and Sinapate Ester Derivatives", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
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Application publication date: 20190614 |