CN102391088B - (1R, 5R)-(-)-3-arylmethylene nopinone ultraviolet absorbent and preparation method thereof - Google Patents
(1R, 5R)-(-)-3-arylmethylene nopinone ultraviolet absorbent and preparation method thereof Download PDFInfo
- Publication number
- CN102391088B CN102391088B CN201110261873.4A CN201110261873A CN102391088B CN 102391088 B CN102391088 B CN 102391088B CN 201110261873 A CN201110261873 A CN 201110261873A CN 102391088 B CN102391088 B CN 102391088B
- Authority
- CN
- China
- Prior art keywords
- nopinone
- ultraviolet absorbent
- ultraviolet
- arylmethylene
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Cosmetics (AREA)
Abstract
The invention discloses a (1R, 5R)-(-)-3-arylmethylene nopinone ultraviolet absorbent and a preparation method thereof. The ultraviolet absorbent is (1R, 5R)-(-)-3-(4'-hydroxylbenzylidene) nopinone, (1R, 5R)-(-)-3-(4'-hydroxyl-3'-methoxylbenzylidene) nopinone, (1R, 5R)-(-)-3-(2'-hydroxyl-3'-methoxylbenzylidene) nopinone, (1R, 5R)-(-)-3-(4'-chlorobenzylidene) nopinone or (1R, 5R)-(-)-3-(furan-2'-ylbenzylidene) nopinone. The preparation method of the ultraviolet absorbent comprises the following steps: beta-pinene which is cheap and easy to get is taken as a raw material; nopinone with a bicyclic structure similar with that of camphor is obtained through selective oxidation; and the aldol condensation is carried out on the nopinone and aromatic aldehyde with a different structure so as to synthesize the ultraviolet absorbent. The preparation method has the advantages of simple synthetic route, simplicity and convenience, and economy for operating, high yield, little pollution and the like, and the defect that the camphor has long synthetic route, and high cost and the like is overcome. The synthesized ultraviolet absorbent has the advantages of good ultraviolet absorption effect, wide range of ultraviolet absorption spectrum and good stability and the like, and thus, the ultraviolet absorbent can have an excellent application prospect in ultraviolet absorption.
Description
Technical field
The present invention relates to UV light absorber and preparation method thereof, be specifically related to a kind of (1R, 5R)-(-)-3-arylmethylene nopinone ultraviolet absorbent and preparation method thereof.
Background technology
Amount of ultraviolet irradiation is along with the destruction of ozonosphere constantly increases, and the impact bringing to the mankind is familiar with by world wide.Contained ultraviolet ray in sunlight is divided into the short wave ultraviolet (UVC) of 200～280nm to educational circles of Dermatology Department, the long wave ultraviolet (UVA) of the medium wavelength of 280～320nm ultraviolet ray (UVB) and 320～400nm, and wherein the ultraviolet ray below 280nm is absorbed by ozonosphere and can not arrive ground.The ultraviolet ray meeting on arrival ground brings various impacts to people's skin, and UVB can cause that skin produces erythema or blister, promotes melanochrome to form, and makes skin chromogenesis calm, causes the formation of foxiness, is main strick precaution object.Once thought in the past that UVA can not produce large impact to skin, but all proved that by electron microscope or histochemical method accepting excessive UVA irradiation meeting brings certain impact to skin, UVA section UV-light is different from UVB, its energy can reach dermal layer of the skin, bring variation slowly to the spandex fiber in vessel wall or conjunctive tissue, thereby cause that the brown of skin, skin elasticity decline, promote the generation of wrinkle, make people sharply aging, can also promote in addition erythematous response even to cause phototoxicity or photosensitized reaction.Sensitive skin can also make immunity degradation by damage dna through the radiation of UVB and UVA continuously under daylight, even brings out skin carcinoma.So defend excessive UVA, UVB to irradiate that protection human body escapes injury, delaying senility seems particularly important.The desirable UV light absorber of used for cosmetic should possess following character: the UV-light that can absorb 280～360nm; Optical extinction coefficient is high, and consumption is few; Be not subject to the impact of solvent in makeup; Water-soluble little; Nontoxic without phototoxicity; Discord skin and components of cosmetics react, and intermiscibility is good; Do not cause xerosis cutis, free from extraneous odour, lower-price characteristic.
The UV light absorber that can be used for makeup has kind more than 60, but for the consideration of security, all there is strict restriction various countries to the use of UV light absorber.Wherein, what U.S. FDA ratified in 1993 that spendable UV light absorber You16Zhong， European Union allows to use in approval in 2000 has 24 kinds, and what Japan allowed to use calendar year 2001 has 27 kinds.China stipulates in < < cosmetics health standard > > for 2007, and in makeup group, available chemical sun-screening agent comprises camphor class, cinnamic acid ester class, salicylic acid, benzoic acids, benzophenone class, triazines, benzene azole etc.
Terpene compound as UV light absorber is mainly camphor derivatives at present, comprises the derivatives such as Unisol S-22,4-methyl benzyl subunit camphor, benzylidene camphor sulfonic acid, Terephthalidene Dicamphor Sulfonic Acid.(tertiary butyl) benzylidene camphor derivative not only can be used as UV light absorber, also can make oxidation inhibitor and medicine simultaneously and be used for the treatment of allergic, anti-inflammatory etc., and Terephthalidene Dicamphor Sulfonic Acid is a kind of wide spectrum UV light absorber, extinction scope, between 290～390nm, and has the highest absorption peak at 345nm place.Artificial camphor is as terpene compound, and its building-up process exists the shortcomings such as synthetic route is long, environmental pollution is large, and natural camphor exists the weak points such as price is high, source is few.For this reason, the terpenes UV light absorber of development of new is especially aobvious urgent.
Summary of the invention
Goal of the invention: for the deficiencies in the prior art, the object of this invention is to provide a kind of (1R, 5R)-(-)-3-arylmethylene nopinone ultraviolet absorbent, makes it have and absorbs that ultraviolet line spectrum is wide, stability strong, prepare the advantages such as simple.Another object of the present invention is to provide a kind of method of preparing above-mentioned a kind of (1R, 5R)-(-)-3-arylmethylene nopinone ultraviolet absorbent.
Technical scheme: in order to realize foregoing invention object, the technical solution used in the present invention is:
(1R, 5R)-(-)-3-arylmethylene nopinone ultraviolet absorbent, general structure is:
In formula, Ar is
or
or
or
or
(1R, 5R)-(-)-3-arylmethylene nopinone ultraviolet absorbent, concrete structure and title are as follows:
(1R, 5R)-(-)-3-(furans-2 '-methylene) nopinone, (5);
A method for prepare (1R, 5R)-(-)-3-arylmethylene nopinone ultraviolet absorbent, detailed process is: beta-pinene, through the oxidation of peracidity potassium manganate, changes into nopinone; Under base catalysis, nopinone and aromatic aldehyde carry out aldol condensation and generate serial nopinone derivative.Nopinone is colorless oil nopinone liquid, and yield is 83.9%, and purity is 95.04%, specific rotatory power [a]=+ 27.3 ° (c=1.0, CCl
3).
The application of above-mentioned (1R, 5R)-(-)-3-arylmethylene nopinone ultraviolet absorbent in absorbing ultraviolet ray.
The application of above-mentioned (1R, 5R)-(-)-3-arylmethylene nopinone ultraviolet absorbent in absorbing ultraviolet ray; Wherein, (1R, 5R)-(-)-3-arylmethylene nopinone ultraviolet absorbent is (1R, 5R)-(-)-3-(4 '-hydroxyl benzylidene) nopinone, (1R, 5R)-(-)-3-(4 '-hydroxyl-3 '-methoxyl group benzylidene) nopinone, (1R, 5R)-(-)-3-(2 '-hydroxyl-3 '-methoxyl group benzylidene) nopinone, (1R, 5R)-(-)-3-(4 '-chlorine benzylidene) nopinone, (1R, 5R)-(-)-3-(furans-2 '-methylene) nopinone or their mixture.
Beneficial effect: compared with prior art, (1R of the present invention, the outstanding advantages that 5R)-(-)-3-arylmethylene nopinone ultraviolet absorbent has is: the present invention be take beta-pinene cheap and easy to get as raw material, through selective oxidation, make the nopinone with the twin nuclei similar to camphor, carry out aldol reaction with the aromatic aldehyde of different structure again, synthetic UV light absorber, the advantage such as have simple, the easy and simple to handle economy of synthetic route, yield is high, pollution is few, has overcome that camphor synthetic route is long, the high deficiency of price.The UV light absorber of synthesized has the advantages such as ultraviolet absorption effect is good, ultra-violet absorption spectrum scope is wide, in absorbing ultraviolet ray, can have good application prospect.
Accompanying drawing explanation
Fig. 1 is the photodegradation measurement result figure of (1R, 5R)-(-)-3-aryl methylene nopinone derivative;
Fig. 2 is the absorbance result of variations figure of (1R, 5R)-(-)-3-aryl methylene nopinone derivative.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further explained.
Embodiment 1: the preparation of nopinone
The preparation method of nopinone, can reference literature in [research of the synthetic dextrorotation nopinone of left-handed beta-pinene selective oxidation, Nanjing Forestry University's journal: natural science edition, 2010,34 (2), 89-94] disclosed method carry out.Also can use following methods:
In the 100mL four-hole boiling flask of being furnished with agitator, thermometer, constant voltage feed hopper and reflux condensing tube, add acetone, sulfuric acid and beta-pinene, ice bath is cooled to 15 ℃ of left and right, adds fully fine ground KMnO in batches
4, in 1～1.5h, add.Remove ice bath, at room temperature continue reaction 5～6h.After reaction finishes, with sand core funnel, remove by filter MnO
2, then use washing with acetone solid residue.With rotation concentrating instrument, reclaim acetone, in residuum, add hexanaphthene, with saturated common salt water washing, to neutrality, use anhydrous Na
2sO
4dry organic layer, boils off after hexanaphthene under normal pressure, then rectification under vacuum, collects 100～102 ℃/2.7kPa cut, obtains the intermediate product nopinone of colourless oil liquid, and purity is 95.3%, and specific rotatory power is
Embodiment 2:(1R, 5R) preparation of-(-)-3-arylmethylene nopinone ultraviolet absorbent
Under base catalysis, get (the 1R of embodiment 1 preparation, 5S)-(+)-nopinone, respectively with p-Hydroxybenzaldehyde, vanillin food grade,1000.000000ine mesh, O-VANILLIN, 4-chloro-benzaldehyde, furfural carries out aldol reaction, further after dehydration, obtain (1R, 5R)-(-)-3-(4 '-hydroxyl benzylidene) nopinone (1), (1R, 5R)-(-)-3-(4 '-hydroxyl-3 '-methoxyl group benzylidene) nopinone (2), (1R, 5R)-(-)-3-(2 '-hydroxyl-3 '-methoxyl group benzylidene) nopinone (3), (1R, 5R)-(-)-3-(4 '-chlorine benzylidene) nopinone (4), (1R, 5R)-(-)-3-(furans-2 '-methylene) nopinone (5).
The preparation of (1R, 5R)-(-)-3-(4 '-hydroxyl benzylidene) nopinone (1):
The potassium tert.-butoxide t-butanol solution 30ml that is 10% by 1.38g (0.01mol) nopinone, concentration and 1.83g (0.015mol) p-Hydroxybenzaldehyde add be furnished with agitator, in the 100mL there-necked flask of thermometer and reflux exchanger, under nitrogen protection, back flow reaction 7～8h reaches more than 95% (GC follows the tracks of detection) to nopinone transformation efficiency.Reaction solution is through ethyl acetate extraction 3 times, and organic phase water and the saturated common salt of merging are washed to neutrality, through anhydrous Na
2sO
4after being dried, filtering, concentrating, obtain yellow solid crude product, use again acetone solution, be back to that solution is transparent, filtrate is placed a couple of days and carried out recrystallization after filtering, obtain water white (1R, 5R)-(-)-3-(4-hydroxyl benzylidene) nopinone crystal, yield is 38.8%, GC purity 97.4%; M.p.199.6～200.6 ℃;
(c=0.6, CCl
3); FT-IR (KBr) n (cm
-1): 3378 (n
o-H), 2962～2911 (n
c-H), 1669 (n
c=O), 1607～1469 (phenyl ring, n
asC=C), 987～647 (monosubstituted phenyl ring, t
c-H); EI-MS m/z (%): 242 (M
+, 100), 227 (M
+-15,31), 199 (227-C
2h
4, 42), 186 (22), 171 (47), 132 (56), 107 (54), 83 (35), 55 (53), 41 (34).
The preparation of (1R, 5R)-(-)-3-(4 '-hydroxyl-3 '-methoxyl group benzylidene) nopinone (2):
The potassium tert.-butoxide toluene solution 30ml that is 10% by 1.38g (0.01mol) nopinone, concentration and 1.824g (0.012mol) vanillin food grade,1000.000000ine mesh (Vanillin) add be furnished with agitator, in the 100mL there-necked flask of thermometer and reflux exchanger; back flow reaction 10～12h under nitrogen protection; nopinone transformation efficiency reaches 70～80%, wherein have an appointment 10～15% by product and 70～75% principal product.Reaction solution is through ethyl acetate extraction 3 times, and organic phase water and the saturated common salt of merging are washed to neutrality, through anhydrous Na
2sO
4after being dried, filtering, concentrating, obtain yellow solid crude product, use again acetone solution, add a little ethanol and be back to that solution is transparent, filtrate is placed a couple of days and carried out recrystallization after filtering, obtain water white (1R, 5R)-(-)-3-(4-hydroxy-3-methoxy benzylidene) nopinone crystal, yield is 19.2%, GC purity 95.3%, m.p.173.5～1742 ℃
(c=0.32, CCl3).FT-IR (KBr) v (cm
-1): 3238 (v
o-H), 2966～2901 (v
c-H), 1674 (v
c=O), 1593～1440 (phenyl ring, v
asC=C), 1307～1130 (v
o-CH3), 856～619 (τ
c-H); EI-MS m/z (%): 272 (M
+, 100), 257 (19), 229 (18), 203 (30), 162 (26), 137 (24), 115 (21), 91 (20), 83 (16), 55 (33), 41 (19).
The preparation of (1R, 5R)-(-)-3-(2 '-hydroxyl-3 '-methoxyl group benzylidene) nopinone (3):
The potassium tert.-butoxide toluene solution 30ml that is 20% by 2.76g (0.02mol) nopinone, concentration and 3.65g (0.024mol) O-VANILLIN (3-methoxyl group-Benzaldehyde,2-hydroxy) add be furnished with agitator, in the 100mL there-necked flask of thermometer and reflux exchanger; back flow reaction 20～22h under nitrogen protection, nopinone transformation efficiency is 50%.Reaction solution is through toluene extraction 3 times, and organic phase water and the saturated common salt of merging are washed to neutrality, through anhydrous Na
2sO
4after being dried, filtering, concentrating, obtain yellow solid crude product, use again acetone solution, add a little ethanol and be back to that solution is transparent, filtrate is placed a couple of days and carried out recrystallization after filtering, obtain water white (1R, 5R)-(-)-3-(2-hydroxy-3-methoxy benzylidene) nopinone crystal, yield is 47.1%, GC purity 96.8%, m.p.195.2～195.6 ℃
(c=0.24, CCl
3); FT-IR (KBr) v (cm
-1): 3246 (v
o-H), 2959～2935 (v
c-H), 1673 (v
c=O), 1597～1440 (phenyl ring, v
asC=C), 1301～1201 (v
o-CH3), 795～726 (τ
c-H); EI-MS m/z (%): 272 (M
+, 30), 231 (100), 213 (14), 197 (13), 161 (24), 137 (21), 128 (12), 115 (21), 91 (21), 55 (33), 41 (19).
The preparation of (1R, 5R)-(-)-3-(4 '-chlorine benzylidene) nopinone (4):
The sodium methylate t-butanol solution 30ml that is 10% by 1.38g (0.01mol) nopinone, concentration and 1.68g (0.012mol) 4-chloro-benzaldehyde add be furnished with agitator, in the 100mL there-necked flask of thermometer and reflux exchanger; back flow reaction 5～8h under nitrogen protection, nopinone transformation efficiency reaches 100%.Reaction solution adds saturated aqueous common salt and is extracted with ethyl acetate 3 times, and organic phase water and the saturated common salt of merging are washed to neutrality, through anhydrous Na
2sO
4after being dried, filtering, concentrating, obtain yellow solid crude product, use again acetone solution, add a little ethanol and be back to that solution is transparent, filtrate is placed a couple of days and carried out recrystallization after filtering, obtain (the 1R of yellow transparent, 5R)-(-)-3-(4-chlorine benzylidene) nopinone crystal, yield is 85.5%, GC purity 97.8%, m.p.109.7～110.7 ℃
(c=0.31, CCl
3); FT-IR (KBr) v (cm
-1): 2984～2874 (v
c-H), 1686 (v
c=O), 1686～1407 (phenyl ring, v
asC=C), 979～686 (phenyl ring is to replacing); EI-MSm/z (%): 260 (M
+, 97), 245 (54), 217 (54), 204 (21), 189 (39), 165 (31), 150 (48), 141 (47), 125 (48), 115 (100), 83 (78), 55 (89).
The preparation of (1R, 5R)-(-)-3-(furans-2 '-methylene) nopinone (5):
The NaOH ethanolic soln 30ml that is 10% by 1.38g (0.01mol) nopinone, concentration and 1152g (0.012mol) furfural add be furnished with agitator, in the 100mL there-necked flask of thermometer and reflux exchanger; back flow reaction 4～4.5h under nitrogen protection, nopinone transformation efficiency reaches 93.6%.Reaction solution adds saturated aqueous common salt and is extracted with ethyl acetate 3 times, and organic phase water and the saturated common salt of merging are washed to neutrality, through anhydrous Na
2sO
4after being dried, filtering, concentrating, obtain yellow solid crude product, [V after silica gel column chromatography separation
sherwood oil: V
ethyl acetate=6: 1], obtain yellow liquid (1R, 5R)-(-)-3-(furans-2-methylene) nopinone, yield is 85.5%, GC purity 97.1%,
(c=0.5, CCl
3); FT-IR (KBr) v (cm
-1): 3435 (v=
c-H), 2935 (v
c-H), 1691 (v
c=O), 1610～1548 (furan nucleus, v
c=C), 1297～1195 (v
c-O-C), 744 (δ
c=cout-of-plane deformation vibration); EI-MS m/z (%): 216 (M
+, 86), 201 (27), 173 (100), 145 (35), 131 (15), 115 (21), 106 (37), 91 (31), 78 (24), 65 (14), 55 (38), 41 (16), 39 (18).
The physical properties of 5 kinds (1R, 5R)-(-)-3-aryl methylene nopinone derivative of relatively preparing, result is as shown in table 1.
The physical properties of table 1 (1R, 5R)-(-)-3-aryl methylene nopinone derivative
As known from Table 1: synthetic 5 kinds of (1R of gained, 5R)-(-)-3-aryl methylene nopinone derivative all has higher optical activity, but aryl structure is different and identical aryl with the opticity of different substituents products therefrom, have nothing in common with each other, (1R wherein, the specific rotatory power of 5R)-(-)-3-(2-hydroxy-3-methoxy benzylidene) nopinone is the highest, next is (1R, 5R)-(-)-3-(4-hydroxyl benzylidene) nopinone, and (1R, 5R)-(-)-3-(furans-2-methylene) nopinone is minimum.
The extinction ability of embodiment 3 (1R, 5R)-(-)-3-aryl methylene nopinone derivative is measured
5 kinds of compounds of embodiment 2 synthesizeds are dissolved in 55% ethanol, are configured to the solution that massfraction is about 0.0015% left and right, within the scope of 200～700nm, carry out full UV scanning, measure its range of absorbency and maximum absorption wavelength.And calculating each compound molar absorptivity ε according to following formula, result is as shown in table 2.
ε＝A/CL
A-absorbancy
ε-molar absorptivity, L/mol.cm
The concentration of C-sample, mol/L,
The length of L-light path, cm
Uv-absorbing scope and the maximum absorption wavelength of table 2 (1R, 5R)-(-)-3-aryl methylene nopinone derivative
| Compound | Uv-absorbing scope | Maximum absorption wavelength λ max(nm) | Molar absorptivity ε (L/molcm) |
| 1 | 240～360 | 322.5 | 29400 |
| 2 | 200～390 | 335.0 | 23430 |
| 3 | 280～390 | 306.0 | 24780 |
| 4 | 240～350 | 295.0 | 34110 |
| 5 | 270～370 | 322.5 | 22290 |
As shown in Table 2: compound 1-5 all has stronger uv-absorbing. Compound 3 and 5 uv-absorbing scope are respectively 280～390nm and 270～370nm, maximum absorption wavelength λ
maxbe respectively 306nm, 24780L/molcm and 322.5nm, 22290L/molcm with light absorption value, possessed the condition as UV-A type uv-absorbing agent; 2 of compounds have the widest uv-absorbing scope, and maximum absorption wavelength λ
maxreach 335nm, there is the function that can absorb UV-A and UV-B simultaneously; From molar absorptivity, each compound to absorbing ultraviolet ability is sequentially: (4) > (1) > (3) > (2) > (5).
The photodegradation of embodiment 4 (1R, 5R)-(-)-3-aryl methylene nopinone derivative is measured
Respectively get the tool plug Erlenmeyer flask that 5 kinds of solution 50ml that embodiment 3 joins inject respectively 3 same sizes, 1 keeps in Dark Place, and 1 is placed in indoorly, and 1 is placed under sunlight.The aqueous solution of same ethanol massfraction of take is reference, measures it every day in the absorbancy of maximum absorption wave strong point, calculates the degradation rate of each compound under different condition, relatively the light stability of each uv-absorbing agent.
Test-results as shown in Figure 1,5 kinds of (1R that embodiment 2 is prepared, the variation of its absorbancy of 5R)-(-)-3-aryl methylene nopinone derivative under illumination is had nothing in common with each other, compound 1 and 2 absorbancy are obvious in variation a few days ago, second day is compared with first day, absorbancy has declined respectively 6.2% and 7.0%, and their absorbancy does not change substantially after two days, all in 0.35%; Compound 3 and 4 absorbancy are a few days ago changing littlely, and being respectively is 1.7% and 1.0%; And the absorbancy of compound 5 does not almost change, second day only declines 0.1% than first day.The absorbancy of all 5 kinds of compounds after the 3rd day nearly all do not change.Show thus: the stability of compound is sequentially 5 > 4 > 3 > 1 > 2, totally it seems, these 5 kinds of compounds all there is good light stability.
With same method, absorbancy to 5 of synthesized kinds of aryl methylene nopinone derivatives under indoor and lucifuge condition changes also to be measured, and compares, with direct solar light irradiation under indoor and lucifuge condition, the photodegradation phenomenon of these compounds weakens, and light stability strengthens.Under indoor and lucifuge condition, the photodegradation trend of uv-absorbing agent slows down, and uv-absorbing agent p-tolyl aldehyde also shows the trend that absorbancy increases to some extent.Visible under indoor and lucifuge condition, its light stability is better.Contrast the light stability under indoor and lucifuge condition, known, under lucifuge condition, light stability is better.
By synthetic 5 kinds (1R, 5R)-(-)-3-aryl methylene nopinone derivative, by waiting mass ratio to carry out composite, and make solvent solution-forming with 55% ethanol, under 200～400nm condition, carry out full scan, measure its uv-absorbing scope, determine its maximum absorption wavelength; Compound is placed on respectively under three kinds of conditions such as illumination, indoor and lucifuge, measure every day its under maximum absorption wavelength the variation of light absorption value, thereby measure the light stability of compound.
5 kinds of uv-absorbing agents are become to solvent according to impartial proportional arrangement, under 200～400nm condition, carry out full scan, find that the uv-absorbing wavelength region of this complex solvent becomes more extensive, and in different wavelength location, its uv-absorbing intensity is different.The maximum absorption band of single uv-absorbing agent is between 289.5～322.5, after composite, the demonstration of uv-absorbing full scan, its strongest ultraviolet absorption peak is at 307nm place, so select the light stability at 307nm place to investigate the light stability variation characteristic of compound.
By the combination solution configuring, according to identical method, be placed on respectively illumination, indoor, under lucifuge condition, detect the variation of its absorbance every day, result as shown in Figure 2, the absorbancy of the compound under different condition was since the 3rd day and the 4th day, and fall reduces step by step, starts to tend towards stability.Therefore the light stability of investigating compound was since comparison in the 4th day.The variation numerical value of choosing the absorbancy of latter four days, calculates its rate of descent, relatively the light stability of compound under different condition.By experimental data, can be obtained, under three kinds of conditions, the light stability of compound is higher than the stability of single product, and still meets and under illumination, degrade fastestly, and in closed environment, degradation speed is the slowest, and stability is best.
In sum, for different substituting groups, this series product all has uv-absorbing scope very widely, and Bees Wax is high, good stability, and the degradation rate of water-alcohol solution is lower, has good ultraviolet absorption curve.And this series product is under composite condition, and uv-absorbing is wider, and stability is better.Meanwhile, the material as uv-absorbing agent, should keep in Dark Place.
Claims (3)
1. (1R, 5R)-(-)-3-arylmethylene nopinone ultraviolet absorbent, is characterized in that, general structure is:
In formula, Ar is
.
2. a method of preparing (1R, 5R) claimed in claim 1-(-)-3-arylmethylene nopinone ultraviolet absorbent, is characterized in that, comprising: beta-pinene is oxidized through acid potassium permanganate, changes into nopinone; Under base catalysis, nopinone and aromatic aldehyde carry out aldol condensation generation (1R, 5R)-(-)-3-arylmethylene nopinone ultraviolet absorbent; Reaction formula is:
3. the application of (1R, 5R) claimed in claim 1-(-)-3-arylmethylene nopinone ultraviolet absorbent in absorbing ultraviolet ray.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110261873.4A CN102391088B (en) | 2011-09-06 | 2011-09-06 | (1R, 5R)-(-)-3-arylmethylene nopinone ultraviolet absorbent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110261873.4A CN102391088B (en) | 2011-09-06 | 2011-09-06 | (1R, 5R)-(-)-3-arylmethylene nopinone ultraviolet absorbent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102391088A CN102391088A (en) | 2012-03-28 |
| CN102391088B true CN102391088B (en) | 2014-03-05 |
Family
ID=45858498
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110261873.4A Expired - Fee Related CN102391088B (en) | 2011-09-06 | 2011-09-06 | (1R, 5R)-(-)-3-arylmethylene nopinone ultraviolet absorbent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102391088B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103086852B (en) * | 2013-02-21 | 2015-10-21 | 南京林业大学 | One prepares the novel method of 2,3-pinane diketone |
| CN103980217B (en) * | 2014-05-26 | 2015-12-30 | 南京林业大学 | One class pinane isoxazole compounds and synthetic method thereof and application |
| CN105503561B (en) * | 2015-12-24 | 2018-01-19 | 南京林业大学 | A kind of acid-base indicator and its synthetic method and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5178852A (en) * | 1989-03-31 | 1993-01-12 | L'oreal | Cosmetic and pharmaceutical compositions containing lipophilic derivatives of benzylidenecamphor and new lipophilic derivatives of benzylidenecamphor |
| US5730960A (en) * | 1994-07-23 | 1998-03-24 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Benzylidenenorcamphor derivatives |
-
2011
- 2011-09-06 CN CN201110261873.4A patent/CN102391088B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5178852A (en) * | 1989-03-31 | 1993-01-12 | L'oreal | Cosmetic and pharmaceutical compositions containing lipophilic derivatives of benzylidenecamphor and new lipophilic derivatives of benzylidenecamphor |
| US5730960A (en) * | 1994-07-23 | 1998-03-24 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Benzylidenenorcamphor derivatives |
Non-Patent Citations (2)
| Title |
|---|
| 刘兵等.左旋β-蒎烯选择性氧化合成右旋诺蒎酮的研究.《南京林业大学学报(自然科学版)》.2010,第34卷(第2期),第89-94页. |
| 左旋β-蒎烯选择性氧化合成右旋诺蒎酮的研究;刘兵等;《南京林业大学学报(自然科学版)》;20100331;第34卷(第2期);第89-94页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102391088A (en) | 2012-03-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Fu et al. | Natural deep eutectic solvent enhanced pulse-ultrasonication assisted extraction as a multi-stability protective and efficient green strategy to extract anthocyanin from blueberry pomace | |
| Hirohara et al. | Synthesis, photophysical properties and photocytotoxicity of mono-, di-, tri-and tetra-glucosylated fluorophenylporphyrins | |
| CN102391088B (en) | (1R, 5R)-(-)-3-arylmethylene nopinone ultraviolet absorbent and preparation method thereof | |
| CN105640842B (en) | A kind of preparation method of Purslane extract | |
| Hirohara et al. | Synthesis, photophysical properties and sugar-dependent in vitro photocytotoxicity of pyrrolidine-fused chlorins bearing S-glycosides | |
| Chaleix et al. | RGD‐porphyrin conjugates: synthesis and potential application in photodynamic therapy | |
| US20140193348A1 (en) | Molecules, compositions, and methods for light absorption | |
| CN108424393A (en) | A kind of hypochlorous acid fluorescence probe and its preparation method and application | |
| Eff et al. | In-vitro and in-vivo sunscreen activity of active compounds isolated from fruits of Phaleria marcocarpha (Scheff.) Boerl | |
| CN101606898B (en) | Application of schisandra extract in preparation of sunscreen skin care product | |
| Fu et al. | Acidified glycerol as a one-step efficient green extraction and preservation strategy for anthocyanin from blueberry pomace: New insights into extraction and stability protection mechanism with molecular dynamic simulation | |
| JP2011213699A (en) | Skin care external preparation having collagen production promotion action obtained from daisy inflorescence | |
| CN102105131A (en) | Cosmetic composition containing salt-fermented extract of natural materials | |
| KR20110125058A (en) | Cosmetic composition for blocking ultraviolet-a comprising extract of gracilariopsis chorda | |
| CN108078885B (en) | Dendrobium extract and application thereof in preparation of whitening sunscreen agent | |
| CN105693769A (en) | Rosmarinic acid derivative, preparation method and application | |
| CN105411926A (en) | Skin-tendering essence rich in anthocyanin and preparation method of skin-tendering essence | |
| WO2007098022A2 (en) | Ultraviolet absorber for cosmetics and polymeric materials | |
| CN104367486A (en) | Application of fraxinol glucosides in uvioresistant cosmetics | |
| Joo et al. | UV absorbent, marmesin, from the bark of Thanakha, Hesperethusa crenulata L. | |
| CN103304548B (en) | N'-(2-aminopyridine)-7-lignocaine-3-formamide-coumarin as well as preparation method and application thereof | |
| CN105732646A (en) | Sandwiched phthalocyanine rare-earth complex with two-photo absorption property and preparation method thereof | |
| Ngurah et al. | Synthesis and In Vitro Evaluation of C-methylcalix [4] resorcinaryl octacinnamate and C-methylcalix [4] resorcinaryl octabenzoate as the Sunscreen | |
| CN103980255A (en) | Dibenzimidazole derivative ultraviolet ray absorber and preparation method thereof | |
| CN102793648B (en) | Morse cymbidium root extract and applications thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140305 Termination date: 20150906 |
|
| EXPY | Termination of patent right or utility model |