CN1317535A - Photochromatic benzopyran compound, its preparing process and products containing it - Google Patents
Photochromatic benzopyran compound, its preparing process and products containing it Download PDFInfo
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- CN1317535A CN1317535A CN 01104403 CN01104403A CN1317535A CN 1317535 A CN1317535 A CN 1317535A CN 01104403 CN01104403 CN 01104403 CN 01104403 A CN01104403 A CN 01104403A CN 1317535 A CN1317535 A CN 1317535A
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Abstract
The present invention relates to a photochromatic benzopyran compound, its preparing process and the photochromatic products containing it. Said photochromatic compound has high comprehensive performance and better anti-fatigue nature.
Description
The present invention relates to the preparation method of a kind of photochromatic benzopyran compound and this compound, also relate to the photochromic article that contains this compound.
In recent years, photochromic material more and more is subjected to people's attention, photochromic resin ophthalmic lens particularly, and this is that glass lens has lightweight advantage owing to compare with glass mirror.In addition, because the security of photochromic transparent material potential, the application on the vehicles such as automobile and receiving set has also caused people's extensive attention.
Describe multiple naphthopyran compounds in USP3567605 and the US5106998 patent, also described some naphthopyran compounds among CN1120335A and the CN1129446A.
But, although these compounds have desired one or more fundamental propertys really, as high light transmittance in the dark, high tint permanence under solar radiation, the fast colorizing and the kinetics of fading, but all these compounds do not have the over-all properties that the energy industrially scalable is made satisfactory goods, and the fatigue resistance of these compounds is relatively poor.
Therefore the purpose of this invention is to provide a kind of photochromatic benzopyran compound, it is colour solid and has very high maximum absorption, fatigue resistance is better than known pyrylium compound, and has good comprehensive performances.
Another object of the present invention provides the method for the above-mentioned photochromatic benzopyran compound of preparation.
Another purpose of the present invention provides the photochromic article with above-mentioned photochromatic benzopyran compound.
To achieve these goals, the invention provides a kind of photochromatic benzopyran compound with following logical formula I:
Wherein R1 represents H, C1-C5 alkyl, C3-C6 cycloalkyl, halogen.R4 represents the H atom, C1-C6 alkyl, C1-C6 alkoxyl group, aryl, aryloxy, and R4 also can represent to be fused to carbocyclic ring or the heterocycle on the A ring in addition.R2, R3 can be identical or different, each represents to get or unsubstituting aromatic yl independently, described aryl substituent is C1-C6 alkyl, C3-C6 cycloalkyl, halo C1-C6 alkyl, hydroxyl, C1-C6 alkoxyl group, C1-C6 alkoxyl group, C1-C8 alkyl, halogen, and wherein said halogen group refers to fluorine, chlorine or bromine.
R2, the structure of preferred following logical formula II (III) representative of R3
R5 wherein, R5 ' can be identical or different, each represents H, C1-C6 alkyl, C1-C6 alkoxyl group, fluorine, chlorine or bromine independently, R6, R6 ' can be identical or different, represents C1-C6 alkyl, C1-C6 alkoxyl group, C3-C6 cycloalkyl, hydroxyl, chlorine, fluorine or bromine respectively, and a, b can be identical or different, is respectively 0 to 2 integer.
Photochromic naphtho-of the present invention is given a tongue-lashing the compound of muttering and can be synthesized by the method that may further comprise the steps:
The beta naphthal that a. will lead to formula IV
Wherein R4 represents the H atom, the C1-C6 alkyl, the C1-C6 alkoxyl group, aryl, aryloxy, R4 also can represent to be fused to carbocyclic ring or the heterocycle on the A ring, chlorination in organic solvent, there is chlorination generation chlorination naphthols down in the amine with general formula R 1 at organic bases (generally being tertiary amine, as triethylamine) again, the chlorination naphthols is further hydrodehalogenation reaction again, makes the substituted naphthol of general formula (V):
B. the benzene or derivatives thereof is reacted under acidic conditions, makes R2, the R3 compound with logical formula VI (VII) structure:
R5 wherein, R5 ' can be identical or different, each represents H, C1-C6 alkyl, C1-C6 alkoxyl group, chlorine, fluorine or bromine independently, R6 or R6 ' can be identical or different, represent C1-C6 alkyl, C1-C6 alkoxyl group, C3-C6 cycloalkyl, hydroxyl, fluorine, chlorine or bromine respectively, and a, b can be identical or different, are respectively 0 to 2 integer;
C. allow the organism of general formula VI, VII exist Louis acid as AlCl
3Condition under react, form corresponding ketone compounds, with resulting ketone compounds and sodium carbide, in suitable organic solvent, react, generate the propargyl alcohol of general formula (VIII):
D. with the substituted naphthol of general formula (V) and the propargyl alcohol of general formula (VIII), at acidic alumina, trichoroacetic acid(TCA) or other an acidic catalyst carry out condensation under existing, and make the naphthopyran compounds with logical formula I.
Above-mentioned photochromatic benzopyran compound, it is 3-phenyl-3 (to cyclopropyl) phenyl-3H-naphtho-[2,1-b] pyrans;
3-phenyl-3 (to cyclobutyl) phenyl-3H-naphtho-[2,1-b] pyrans;
3-phenyl-3 (to cyclopentyl) phenyl-3H-naphtho-[2,1-b] pyrans;
3-phenyl-3 (to cyclohexyl) phenyl-3H-naphtho-[2,1-b] pyrans;
3-(to methoxyl group) phenyl-3 (to cyclobutyl) phenyl-3H-naphtho-[2,1-b] pyrans;
3-(to methoxyl group) phenyl-3 (to cyclopentyl) phenyl-3H-naphtho-[2,1-b] pyrans;
3-(to methoxyl group) phenyl-3 (to cyclohexyl) phenyl-3H-naphtho-[2,1-b] pyrans.
In the above-mentioned manufacture method, in those skilled in the art's such as the reaction principle of each step and reaction conditions the ken.
Institute of the present invention synthetic naphthopyran compounds can have many-sided application, as making optical mirror slip, automotive windshield, aircraft and automobile transparent substance, plastic film, parasols, sunshade, textiles and coating.
Obviously, those skilled in the art can utilize the photochromic article manufacture method of various routines, in conjunction with various organic substrate materials and various additive, dyestuff for example, antioxidant, stablizer, dispersion agent, coupling agents etc. are used to naphthopyran compounds of the present invention to make the photochromic article that contains this compound.
According to naphthopyran compounds of the present invention, but its have than existing known similar compound with comparison structure significantly high bring out optical density(OD), therefore producing the required photochromic amount of equal effect significantly reduces, cost reduces, and while naphtho-of the present invention is given a tongue-lashing muttering thing and had good fatigue resistance.
Naphthopyran compounds of the present invention is used in combination with other suitable complementary photochromic compounds, can produce grey or dark brown tone with muted color.Can comprise with the photochromic compounds of naphthopyran compounds generation complementary color of the present invention: US4637698,3562172,3578602,4816584, spiral shell described in 4215010 and 4342668 (indolinyl) Nai Bing oxazine, (indoline) Nai Bing oxazine, all these patent documentations are whole as a reference to be contained in this for spiral shell (indoline) Kui Lin Bing oxazine and spiral shell.
The photochromic compound introducing amount of naphthopyran compounds of the present invention and complementary color thereof is 0.001～0.1% (based on the weight percent of matrix material), and preferable amount is 0.05%～0.08%.
The organic substrate material that can use naphthopyran compounds of the present invention comprises: the polymkeric substance of allyl carbonate polyol ester polymer of monomers such as glycol ether two (allyl carbonate), polyacrylate(s) such as polymethylmethacrylate, cellulose acetate, the triacetate fibre element, cellulose acetate propionate, cellulose acetate butyrate, Vinyl Acetate Copolymer, polyvinyl alcohol, urethane, polycarbonate-based, the diol ester of poly terephthalic acid second, polystyrene, the styrene/methacrylic acid methyl terpolymer, ethylene, vinylbenzene/acrylonitrile multipolymer and polyvinyl butyral acetal.The joining thing of transparent multipolymer and transparent polymer also is fit to do substrate material.Preferred substrate material: polymethylmethacrylate, glycol ether two (allyl carbonate), rhodias, cellulose propionate, polystyrene and/vinyl acetate copolymer and polyvinyl butyral acetal.
Can understand the present invention better by following examples.
Embodiment 1
3-phenyl-3 (to cyclopropyl) phenyl-34-naphtho-[2,1-b] is given a tongue-lashing mutter synthetic
Step 1:
A. cyclopropyl-phenyl is synthetic
With benzene (39g 0.5mol), cyclopropylene (28.4g, 0.71mol) addition reaction under acidic conditions, synthetic cyclopropyl-phenyl 76.9g.
Step 2
B.1-phenyl-1 '-cyclobutyl benzophenone is synthetic
With Benzoyl chloride (14.6g 0.1mol), cyclopropyl-phenyl (11.8g 0.1mol) and AlCl3, the stirring heating reaction is to there not being the HCl gas evolution.After the cooling reaction solution poured in 3% the HCl solution and filter, be washed to neutral product 7.5g.
Step 3
C.1-phenyl-1 '-cyclobutyl phenylpropyl alcohol-2-alkynes-1-alcohol is synthetic
With 1-phenyl-1 '-cyclopropyl-phenyl ketone (75.g 0.05mol) and sodium carbide (2.4g 0.05mol), organic solvent 250ml, magnetic agitation, heating, the TCL monitoring reaction is after reaction is finished, tell organic layer with separating funnel, remove organic solvent under reduced pressure, get xanchromatic oily product.
Step 4
D.3-phenyl-3-(to cyclopropyl) phenyl-3H-benzo pyrrole [2,1-b] pyrans is synthetic
Product 1-phenyl-1 '-cyclopropyl third-2-alkynes-1-alcohol (0.05ml), 2-Naphthol (7.18g with step 3,0.05mol), the mixture heating up of acid Al2O3 (5g) and toluene (50.0ml) stirs, the TCL monitoring reaction, cooling, filter, and use the toluene wash solids, evaporimeter boils off solvent, and column chromatography separates, and boils off eluent again and gets brown solid, petroleum ether, white solid 3-phenyl-(to cyclopropyl) phenyl-3H-naphtho-[2,1-b] be given a tongue-lashing the compound 3.27g productive rate 17.50% of muttering, mp142～145 ℃.
Embodiment 2
Synthesizing of 3-phenyl-3-(to cyclobutyl) phenyl-3H-naphtho-[2,1-b] pyrylium compound
Change the cyclopropylene among the embodiment 1 into cyclobutene, other step is with embodiment 1.
Embodiment 3
Synthesizing of 3-phenyl-3-(to cyclopentyl) phenyl-3H-naphtho-[2,1-b] pyrylium compound
Change the cyclopropylene among the embodiment 1 into cyclopentenes, other step is with embodiment 1.
Embodiment 4
Synthesizing of 3-phenyl-3-(to cyclohexyl) phenyl-3H-naphtho-[2,1-b] pyrylium compound
Change the cyclopropylene among the embodiment 1 into cyclopentenes, other step is with embodiment 1.
Embodiment 5
Synthesizing of 3-(to methoxyl group) phenyl-3-(to cyclobutyl) phenyl-3H-naphthopyran compounds
Change the Benzoyl chloride among the embodiment 2 into anisoyl chloride, other step is with embodiment 2.
Implement 6
Synthesizing of 3-(to methoxyl group) phenyl-3-(to cyclopentyl) phenyl-3H-naphthopyran compounds
Change the Benzoyl chloride among the embodiment 3 into anisoyl chloride, other step is with embodiment 3.
Embodiment 7
Synthesizing of 3-(to methoxyl group) phenyl-3-(to cyclohexyl) phenyl-3H-naphthalene [2.1-b] and pyrylium compound
Change the Benzoyl chloride among the embodiment 4 into anisoyl chloride, other step is with embodiment 4.
The comparative example 1
3-methoxyphenyl-3-(to a trichloromethyl) phenyl-6-methoxyl group-3H-naphthalene [2,1-b] pyrans
With 4-methoxyl group-beta naphthal (0.19g, 0.0011mol), 1-methoxyphenyl-1-(to a trifluoromethyl) phenyl alkynes third-2-base-1-alcohol (0.33g, 0.0011mol) mixture heating up of acid A1203 Brockmaun 1 (3.5g) and toluene (40.0ml) and stir 1h, cooled and filtered.Use Zu NaOH, wash filtrate then with water, dry and evaporation obtains thick orange.Grind with hexane, use the hexane recrystallization subsequently, obtain 3-methoxyphenyl-3-(to a trichloromethyl) phenyl-6-methoxyl group-3H-naphtho-[2,1-b] pyrans white solid (productive rate 20%) of following formula, 149～151 ℃ of fusing points.
The photochromic material of gained is dissolved in the ethoxylated bisphenol a diacrylate forms the thick sample panel of 2mm through polymerization, following table is the test result of each sample panel of obtaining:
Wherein
-λ max is the xenon lamp of 2min sample board at 6000lux, the result of test gained under the room temperature
-T0
Before aging-initial the transmittance that under λ max, records
-TD15
Before aging-transmittance behind the irradiation 15min that records under the λ max
-TOD-induces optical density(OD)
-T0
After aging-under the 6000lux xenon lamp, illumination after 200 hours under 25～34 ℃ of conditions, the initial transmission that under λ max, records
-TD15
After aging-under the 6000lux xenon lamp, illumination after 200 hours under 25～34 ℃ of conditions, the transmittance embodiment introducing amount λ max T0 behind the irradiation 15min that records under the λ max
Before agingTD15
Before agingTOD T0
After agingTD15
After aging
% nm % % % %1 0.1 450 89 4.8 1.27 89 5.02 0.1 450 89 1.8 1.69 89 1.93 0.1 450 89 2.4 1.56 89 2.44 0.1 450 89 3.0 1.47 89 3.25 0.1 450 89 3.0 1.47 89 3.06 0.1 450 92 2.1 1.64 92 2.17 0.1 450 90 2.8 1.51 90 3.0 Comparative Examples 0.1 425 87.3 70.0 0.12 87.3 80.0
As seen from the above table, obtain higher TOD value (between 1.27～1.93) with naphthopyran compounds of the present invention, this shows that can to obtain high-density with photochromic material of the present invention painted.The low TOD value (0.12) of these results and comparative sample forms sharp contrast.
Photochromatic benzopyran compound of the present invention in addition shows very strong resistance to fatigue, without any the obviously degraded of degree, can keep good photochromic performance and the strong dark color under the deepening state in a long time.
Above-mentioned explanation should be understood that just to illustrate of the present invention, and should not be understood that limitation of the present invention.Under the situation that does not break away from the spirit and scope of the present invention, those skilled in the art can make various modifications and variations.
Claims (17)
1, the photochromatic benzopyran compound of following logical formula I
Wherein R1 represents alkyl, the cycloalkyl of C3-C6, the halogen of H, C1-C5, R2, R3 can be identical or different, each represents to replace or unsubstituted aryl independently, described aryl substituent is C1-C6 alkyl, C3-C6 cycloalkyl, halo (C1-C6) alkyl, hydroxyl, C1-C6 alkoxyl group, C1-C6 alkoxyl group (C1-C8) alkyl, halogen, described halogen group refers to fluorine, chlorine or bromine, R4 represents H atom, C1-C6 alkyl, C1-C6 alkoxyl group, aryl, aryloxy, and R4 also can represent to be fused to carbocyclic ring or the heterocycle on the A ring in addition.
2, according to the photochromatic benzopyran compound of claim 1, wherein R2, R3 can be represented by following structural formula (II), (III) respectively:
Wherein R5, R5 ' can be identical or different, each represents H, C1-C6 alkyl, C1-C6 alkoxyl group, fluorine, chlorine or bromine independently, R6, R6 ' can be identical or different, represent C1-C6 alkyl, C1-C6 alkoxyl group, C3-C6 cycloalkyl, hydroxyl, fluorine, chlorine or bromine respectively, and a, b can be identical or different, is respectively 0 to 2 integer.
3, according to the photochromatic benzopyran compound of claim 1 or 2, it is 3-phenyl-3 (to cyclopropyl) phenyl-3H-naphtho-[2,1-b] pyrans.
4, according to the photochromatic benzopyran compound of claim 1 or 2, it is 3-phenyl-3 (to cyclobutyl) phenyl-3H-naphtho-[2,1-b] pyrans.
5, according to the photochromatic benzopyran compound of claim 1 or 2, it is 3-phenyl-3 (to cyclopentyl) phenyl-3H-naphtho-[2,1-b] pyrans.
6, according to the photochromatic benzopyran compound of claim 1 or 2, it is 3-phenyl-3 (to cyclohexyl) phenyl-3H-naphtho-[2,1-b] pyrans.
7, according to the photochromatic benzopyran compound of claim 1 or 2, it is 3-(to methoxyl group) phenyl-3 (to cyclobutyl) phenyl-3H-naphtho-[2,1-b] pyrans.
8, according to the photochromatic benzopyran compound of claim 1 or 2, it is 3-(to methoxyl group) phenyl-3 (to cyclopentyl) phenyl-3H-naphtho-[2,1-b] pyrans.
9, according to the photochromatic benzopyran compound of claim 1 or 2, it is 3-(to methoxyl group) phenyl-3 (to cyclohexyl) phenyl-3H-naphtho-[2,1-b] pyrans.
10, a kind of method for preparing the photochromatic benzopyran compound of claim 1, this method comprises the steps:
The beta naphthal that a. will lead to formula IV
Wherein R4 represents the H atom, the C1-C6 alkyl, the C1-C6 alkoxyl group, aryl, aryloxy, R4 also can represent to be fused to carbocyclic ring or the heterocycle on the A ring, chlorination in organic solvent, amine chlorination in the presence of organic bases with general formula R 1 generates the chlorination naphthols again, and the chlorination naphthols is further hydrodehalogenation reaction again, makes the substituted naphthol of general formula (V):
B. the benzene or derivatives thereof is reacted under acidic conditions, makes R2, the R3 compound with logical formula VI (VII) structure:
R5 wherein, R5 ' can be identical or different, each represents H, C1-C6 alkyl, C1-C6 alkoxyl group, chlorine, fluorine or bromine independently, R6 or R6 ' can be identical or different, represent C1-C6 alkyl, C1-C6 alkoxyl group, C3-C6 cycloalkyl, hydroxyl, fluorine, chlorine or bromine respectively, and a, b can be identical or different, are respectively 0 to 2 integer;
C. the organism with general formula VI, VII reacts under the condition that has Louis acid, forms corresponding ketone compounds, with resulting ketone compounds and sodium carbide, reacts in suitable organic solvent, generates the propargyl alcohol of general formula (VIII):
D. with the substituted naphthol of general formula (V) and the propargyl alcohol of general formula (VIII), at acidic alumina, trichoroacetic acid(TCA) or other an acidic catalyst carry out condensation under existing, and make the naphthopyran compounds with logical formula I.
11, the photochromic article that comprises each described naphthopyran compounds among organic substrate material and the claim 1-9.
12, according to the photochromic article of claim 11, wherein said organic substrate material is selected from allyl carbonate polyvalent alcohol polymer of monomers, polyacrylate(s), cellulose acetate, cellulosetri-acetate, cellulose acetate propionate, cellulose acetate butyrate, polyvinyl acetate (PVA), polyvinyl alcohol, polyurethane kind, polycarbonate-based, polyethylene terephthalate, polystyrene, the styrene/methacrylic acid methyl terpolymer, ethylene, vinylbenzene/propylene ester copolymer and polyvinyl butyral acetal.
13, according to the photochromic article of claim 10 or 11, wherein the amount of naphthopyran compounds is 0.001～0.1% (weight percent), based on the weight of organic substrate material.
14, according to the photochromic article of claim 13, wherein the amount of naphthopyran compounds is 0.05～0.08% (weight percent), based on the weight of organic substrate material.
15, according to arbitrary described photochromic article in the right 11～14, it also comprises and is selected from spiral shell (indoline) Nai Bing oxazine class, other photochromic compound of spiral shell (indoline) Kui Lin Bing oxazine class.
16, according to each photochromic article in the right 12～15, it is that eyeglass forms.
17, photochromic article according to claim 16, wherein eyeglass is an ophthalmic lens.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016094602A (en) * | 2010-04-02 | 2016-05-26 | ノバルティス アーゲー | Adjustable chromophore compounds and materials incorporating such compounds |
| CN108250174A (en) * | 2018-02-07 | 2018-07-06 | 中国科学院兰州化学物理研究所苏州研究院 | Naphtho-pyrans compounds and preparation method thereof |
| CN110215009A (en) * | 2019-06-13 | 2019-09-10 | 钱立英 | A kind of rain-proof shoe sheath material and shoe cover becoming function with light |
-
2001
- 2001-02-23 CN CN 01104403 patent/CN1317535A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016094602A (en) * | 2010-04-02 | 2016-05-26 | ノバルティス アーゲー | Adjustable chromophore compounds and materials incorporating such compounds |
| US10029229B2 (en) | 2010-04-02 | 2018-07-24 | Novartis Ag | Adjustable chromophore compounds and materials incorporating such compounds |
| CN108250174A (en) * | 2018-02-07 | 2018-07-06 | 中国科学院兰州化学物理研究所苏州研究院 | Naphtho-pyrans compounds and preparation method thereof |
| CN108250174B (en) * | 2018-02-07 | 2021-09-10 | 中国科学院兰州化学物理研究所苏州研究院 | Naphthopyran compounds and preparation method thereof |
| CN110215009A (en) * | 2019-06-13 | 2019-09-10 | 钱立英 | A kind of rain-proof shoe sheath material and shoe cover becoming function with light |
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