CN1161359C - Biindolelinenaphtho-spiroxazine compound, its preparing process and products containing it - Google Patents
Biindolelinenaphtho-spiroxazine compound, its preparing process and products containing it Download PDFInfo
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- CN1161359C CN1161359C CNB011044047A CN01104404A CN1161359C CN 1161359 C CN1161359 C CN 1161359C CN B011044047 A CNB011044047 A CN B011044047A CN 01104404 A CN01104404 A CN 01104404A CN 1161359 C CN1161359 C CN 1161359C
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- indoline
- photochromic
- compound
- naphtho
- oxazine
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Abstract
The present invention relates to a photochromic benzindolium spironaphthooxazine compound and a preparation method thereof. The general formula of the compound is shown as a formula (I), wherein R1 represents C3 to C10 alkyl, alkenyl or alkynyl, R2 and R2' are identical and represent hydrogen, alkyl, aryl or pyridyl, and R3 and R3', R4 and R4', R5 and R5', R6 and R6' are respectively identical and represent hydrogen or methyl. The benzindolium spironaphthooxazine compound can be used to prepare photochromic eyeglasses and other photochromic products. The photochromic benzindolium spironaphthooxazine compound has the advantages of excellent comprehensive performance and good fatigue resistance.
Description
The present invention relates to photochromic pair of indoline naphtho-spiral shell oxazine compound, its preparation method, and the photochromic article that contains this compounds.
Photochromic compound can hard to bear polychromatic light or the influence of monochromatic ray (as ultraviolet radiation) and changes colour, and when stopping photoirradiation, can reply its original color again, perhaps under polychromatic light that is different from first kind of light or monochromatic influence, perhaps temperature and/or be different from the polychrome of first kind of light or monochromatic influence under also can be like this.
These photochromic compounds can be used for different fields, for example can be used for making optical system, panelling, ornament, the display element of eye-use lens, contact lens, screening sunglasses, optical filtering, photographic camera or photographic apparatus or other optics and optical viewer, perhaps be used for optics mint-mark (coding) and come storage information.
Use in the optics eyewear art at eye, the photochromic lens that comprises one or more photochromic compounds must have:
-in the dark or in the high transmissivity that does not have under the situation of sunlight
-low transmissivity under similar irradiation
-suitable colour developing or variable color kinetics
The acceptable tone of-user
-in 0～40 ℃ temperature range, can keep its serviceability
-weather resistance
In fact, the characteristic of these lens is determined that by active photochromic compound these active photochromic compounds also must be compatible with organic substance or the inorganic substance of forming lens.
In the various photochromic compounds described in the prior art, can be referring to United States Patent (USP) 3578602,3562172,4215010, European patent 0171909,0313941, French Patent 2647789, European patent 0600669 described indoline Luo Nai oxazine (indolinospironspironaphtoxazines), these compounds are considered to satisfy the requirement of afore mentioned rules.
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.
The object of the present invention is to provide a kind of photochromic pair of new indoline naphtho-Luo oxazine compound, these compounds have good especially photochromic properties, and these compounds still are stable, no matter sneak into the form in the matrix or the form of coating, and the matrix that forms with organic polymer or inorganics is compatible.
Another object of the present invention provides the preparation method of this type of photochromic pair of indoline naphtho-Luo oxazine compound.
Another purpose of the present invention provides the photochromic article that contains this type of photochromic pair of indoline naphtho-Luo oxazine compound.
In order to realize the foregoing invention purpose, the invention provides a kind of photochromic compound, it has following chemical general formula (I)
Wherein, R1 represents C3-C10 alkyl, alkenyl or alkynyl; R2, R2 ' are identical, represent hydrogen, alkyl, aryl or pyridyl; R3 is identical respectively with R6 ' with R5 ', R6 with R3 ', R4 and R4 ', R5, can be hydrogen or methyl.
Photochromic compound of the present invention prepares in order to the below method:
Postcooling of enough time of ketone solution reaction with indoline and halogenated alkane, haloolefin or acetylenic halide hydro carbons is placed, and separates out solid product 1.
1. the solid product of step 1 is reacted at certain temperature range with bases again, and cooling is also got dried recovered with organic solvent-benzene and is obtained product 2.
With the alcoholic solution of 1-Nitroso-2-naphthol and the product alcoholic solution reaction 2. of step 2, cooling, filtration, washing, drying get target compound crude product 3., through recrystallization, get the crystal target thing 3. again.
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.
The two indoline naphtho-Luo oxazine compounds of institute of the present invention synthetic can have many-sided application, as being used as optical mirror slip, automotive windshield, receiving set and automobile transparent substance, plastic film, parasols, sunshade, the photochromic material of 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 make the photochromic article that contains this compound to of the present invention pair of indoline naphtho-Luo oxazine compound.
In practice, the modal goods that the present invention relates to are photochromic glasses eyeglass or sun glasses eyeglass etc.
Of the present invention pair of indoline naphtho-Luo oxazine compound comprises:
N, N '-trimethylene two (3,3-dimethyl naphtho-spiral shell oxazine indoline);
N, N '-tetramethylene two (3,3-dimethyl naphtho-spiral shell oxazine indoline);
N, N '-pentamethylene two (3,3-dimethyl naphtho-spiral shell oxazine indoline);
N, N '-hexamethylene two (3,3-dimethyl naphtho-spiral shell oxazine indoline);
N, N '-1, the inferior heptyl of 7-two (3,3-dimethyl naphtho-spiral shell oxazine indoline);
N, N '-octamethylene two (3,3-dimethyl naphtho-spiral shell oxazine indoline);
N, N '-nonamethylene two (3,3-dimethyl naphtho-spiral shell oxazine indoline);
N, N '-1, the inferior decyl of 10-two (3,3-dimethyl naphtho-spiral shell oxazine indoline);
N, N '-trimethylene two (3,3,5,6-tetramethyl-naphtho-Luo oxazine indoline);
N, N '-tetramethylene two (3,3,5,6-tetramethyl-naphtho-Luo oxazine indoline);
N, N '-pentamethylene two (3,3,5,6-tetramethyl-naphtho-Luo oxazine indoline);
N, N '-hexamethylene two (3,3,5,6-tetramethyl-naphtho-Luo oxazine indoline);
N, N '-1, the inferior heptyl of 7-two (3,3,5,6-tetramethyl-naphtho-Luo oxazine indoline);
N, N '-octamethylene two (3,3,5,6-tetramethyl-naphtho-Luo oxazine indoline);
N, N '-nonamethylene two (3,3,5,6-tetramethyl-naphtho-Luo oxazine indoline);
N, N '-1, the inferior decyl of 10-two (3,3,5,6-tetramethyl-naphtho-Luo oxazine indoline).
The organic substrate material that can use of the present invention pair of indoline naphtho-Luo oxazine compound is selected from: polyvalent alcohol (allyl carbonate) polymer of monomers, polyacrylic ester, rhodia, cellulose triacetate, polyvinylacetate, polyvinyl alcohol, urethane, polycarbonate, polyethylene terephthalate, polystyrene, vinylbenzene/methacrylic ester methyl ester multipolymer, vinylbenzene/acrylonitrile multipolymer, polyvinyl butyral acetal and above-mentioned two or more mixture of polymers arbitrarily.Preferred substrate material comprises: polymethylmethacrylate, glycol ether two (allyl carbonate), rhodia, cellulose propionate, polystyrene and ethylene and polyvinyl butyral acetal.
The consumption of photochromic compound depends on the deepening degree of requirement, and consumption is 0.001-0.1% (by weight) usually.
According to of the present invention pair of indoline naphtho-Luo oxazine compound, but it has than the existing known remarkable high saturating luminance of similar compound with comparison structure, therefore producing the required photochromic amount of equal effect significantly reduces, cost reduces, and of the present invention pair of indoline naphtho-Luo oxazine compound has good fatigue resistance simultaneously.
Photochromic compound of the present invention can use separately, also can with other suitable complementary photochromic compounds, other photochromic compounds that for example are selected from the aphthopyrans class are used, described aphthopyrans class photochromic compound comprises, Chinese patent CN1125985A for example, the naphthopyran compounds of describing among the CN1120335A, all these patent documentations can be used as reference.
Can understand the present invention better by the synthetic embodiment of following photochromic compound and the compound of acquisition thereof.
Embodiment 1
N, N '-trimethylene two (3,3-dimethyl naphtho-spiral shell oxazine indoline) synthetic
Step 1:
To 16g1-methyl-3,3-dimethyl indole quinoline C
11H
14Backflow drips 10.09g (0.05mol) 1 in following 1 hour in the butanone solution of N (0.1mol), and the butanone solution of 3-dibromopropane adds the back continuation and refluxed 20 hours, the cooling placement, and the solid that suction filtration is separated out, the dry mother liquor that also reclaims gets 1. C of product
25H
34N
2Br
217.0g, productive rate 65.2%.
Step 2:
With 2.5g (4.8mmol) product 1. with NaOH solution (5.6g alkali, 35ml water) 40～50 ℃ of fierce vibrations 15 minutes, cooling, with 3 * 20ml extracted with diethyl ether, the KOH drying, reclaim ether (later stage need reduce pressure), excess is oily, leaves standstill cooling, becomes solid very soon, with the ether washing, the dry 2. C of product that gets
25H
34N
21.70g productive rate～100%.
Step 3:
1.70g (9.6mmol) 1-Nitroso-2-naphthol is dissolved in the 60ml dehydrated alcohol under warm, add an amount of activated carbon, boiled 10 minutes, filtered while hot refluxes and drip the above-mentioned product that makes 1.73g (4.8mmol) ethanolic soln 2. down in gained filtrate, add the back and continue to reflux 3 hours, the cooling standing over night, the filter collection is separated out solid, with washing with alcohol 4 times, dry crude product target compound is C 3.
45H
42O
2N
41.55g, use re-crystallizing in ethyl acetate, get the two indoline naphtho-Luo oxazine xln 1.32g of target compound.
Embodiment 2
N, N '-tetramethylene two (3,3-dimethyl naphtho-spiral shell oxazine indoline) synthetic
According to synthetic this compound of the mode identical with embodiment 1, in synthesis step 1, with 1,4-dibromobutane replacement 1,3-dibromopropane.
Embodiment 3
N, N '-pentamethylene two (3,3-dimethyl naphtho-spiral shell oxazine indoline) synthetic
According to synthetic this compound of the mode identical, in synthesis step 1, replace 1 with pentamethylene bromide, the 3-dibromopropane with embodiment 1.
Embodiment 4
N, N '-trimethylene two (3,3,5,6-tetramethyl-naphtho-Luo oxazine indoline) synthetic
Step 1:
To 18.8g1-methyl-3,3,5,6-tetramethyl--indoline C
13H
18Backflow drips 10.09g (0.05mol) 1 in following 1 hour in (0.1mol) butanone solution of N, and the butanone solution of 3-dibromopropane continues after adding to reflux 20 hours, the cooling placement, and the solid that suction filtration is separated out through washing drying and reclaiming mother liquor, gets 1. C of product
29H
40N
2Br
218.9g, productive rate 65%.
Step 2:
With 2.76g (4.8mmol) product 1. with NaOH solution (5.6g alkali, 35ml water) 40～50 ℃ of fierce vibrations 15 minutes, cooling, with 3 * 20ml extracted with diethyl ether, the KOH drying, reclaim ether (later stage need reduce pressure), excess is oily, leaves standstill cooling, becomes solid very soon, with the ether washing, the dry 2. C of product that gets
29H
40N
21.96g productive rate～100%.
Step 3:
1.06g (6mmol) 1-Nitroso-2-naphthol is dissolved in the 60ml dehydrated alcohol under warm, add an amount of activated carbon, boiled 10 minutes, filtered while hot, refluxing drips the above-mentioned product that makes 1.25g (3mmol) ethanolic soln 2. down in gained solution, add the back and continue to reflux 3 hours, the cooling standing over night, the filter collection is separated out solid, uses washing with alcohol 4 times, the dry 3. C of crude product target compound that gets
49H
50O
2N
21.09g, use re-crystallizing in ethyl acetate, get xln 0.98g.
Embodiment 5
N, N '-tetramethylene two (3,3,5,6-tetramethyl-naphtho-Luo oxazine indoline) synthetic
According to synthetic this compound of the mode identical with embodiment 5, in synthesis step 1, with 1,4-dibromobutane replacement 1,3-dibromopropane.
Embodiment 6
N, N '-pentamethylene two (3,3,5,6-tetramethyl-naphtho-Luo oxazine indoline) synthetic
According to synthetic this compound of the mode identical, in synthesis step 1, replace 1 with pentamethylene bromide, the 3-dibromopropane with embodiment 5.
The comparative example 1
3-methoxyphenyl-3-(right-trichloromethyl) phenyl-6-methoxyl group-3H-naphthalene [2,1-b] pyrans
With 4-methoxyl group-beta naphthal (0.19g, 0.0011mol), 1-methoxyphenyl-1-(right-trifluoromethyl) phenyl alkynes third-2-base-1-alcohol (0.33g, 0.0011mol) mixture heating up of acid Al2O31 (3.5g) and toluene (40.0ml) and stir 1h, cooled and filtered.With NaOH and water washing, dry and evaporation obtains thick orange.Grind with hexane, use the hexane recrystallization subsequently, obtain 3-methoxyphenyl-3-(right-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 photochromic compound:
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 behind the irradiation 15min that records under the λ max
Embodiment introducing amount λ max T0
Before agingTD15
Before agingTOD T0
After agingTD15
After aging
％ nm ％ ％ ％ ％
1 0.1 450 89 4.8 1.27 89 5.0
2 0.1 450 89 1.8 1.69 89 1.9
3 0.1 450 89 2.4 1.56 89 2.4
4 0.1 450 89 3.0 1.47 89 3.2
5 0.1 450 89 3.0 1.47 89 3.0
6 0.1 450 92 2.1 1.64 92 2.1
Comparative Examples 0.1 425 85.3 70.0 0.12 87.3 80.0
As seen from the above table, obtain higher TOD value (between 1.27～1.93) with of the present invention pair of indoline naphtho-Luo oxazine compound, 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.
Photochromic pair of indoline naphtho-spiral shell oxazine 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 (6)
1. two indoline naphtho-Luo oxazine photochromic compounds of following general formula (I):
Wherein, R1 represents alkyl, the alkenyl or alkynyl of C3-C10; R2, R2 ' are identical, represent hydrogen, alkyl, aryl or pyridyl; R3 is identical respectively with R6 ' with R5 ', R6 with R3 ', R4 and R4 ', R5, can be hydrogen or methyl.
2. the preparation method of the described compound of claim 1 comprises the steps:
(1) place with the postcooling of enough time of ketone solution reaction of indoline and halogenated alkane, haloolefin, halo alkynes or halogenated aryl hydrocarbon, obtain following product:
(2) make product that step (1) obtains and bases at the certain temperature range internal reaction, cooling also obtains following product with the organic solvent extraction dried recovered:
(3) alcoholic solution of the alcoholic solution of the product that obtains of step (2) and 1-Nitroso-2-naphthol reaction through cooling, filtration, washing, drying, generates two indoline naphtho-Luo oxazine target compound crude products, through recrystallization
Obtain the crystal target thing.
3. photochromic article that contains organic substrate material and described photochromic pair of indoline of claim 1 and naphthalene spiral shell oxazine compound.
4. according to the photochromic article of claim 3, wherein the organic substrate material is selected from polyvalent alcohol (allyl carbonate) polymer of monomers, polyacrylic ester, rhodia, cellulose triacetate, polyvinylacetate, polyvinyl alcohol, urethane, polycarbonate, polyethylene terephthalate, polystyrene, vinylbenzene/methacrylic ester methyl ester multipolymer, vinylbenzene/acrylonitrile multipolymer, polyvinyl butyral acetal and above-mentioned two or more mixture of polymers.
5. according to claim 3 or 4 described photochromic articles, wherein the amount of two indoline naphtho-Luo oxazine compounds is 0.001～0.1% (weight percents), based on the weight of matrix material.
6. according to any one described photochromic article of claim 3-4, it also comprises other photochromic compounds that are selected from the aphthopyrans class.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011044047A CN1161359C (en) | 2001-02-23 | 2001-02-23 | Biindolelinenaphtho-spiroxazine compound, its preparing process and products containing it |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011044047A CN1161359C (en) | 2001-02-23 | 2001-02-23 | Biindolelinenaphtho-spiroxazine compound, its preparing process and products containing it |
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| Publication Number | Publication Date |
|---|---|
| CN1317487A CN1317487A (en) | 2001-10-17 |
| CN1161359C true CN1161359C (en) | 2004-08-11 |
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|---|---|---|---|
| CNB011044047A Expired - Fee Related CN1161359C (en) | 2001-02-23 | 2001-02-23 | Biindolelinenaphtho-spiroxazine compound, its preparing process and products containing it |
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2001
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