CN1300146C - Photochromic compound of spiro [indolerin-phenanthroline oxazine and its preparation and use - Google Patents
Photochromic compound of spiro [indolerin-phenanthroline oxazine and its preparation and use Download PDFInfo
- Publication number
- CN1300146C CN1300146C CNB2004100091609A CN200410009160A CN1300146C CN 1300146 C CN1300146 C CN 1300146C CN B2004100091609 A CNB2004100091609 A CN B2004100091609A CN 200410009160 A CN200410009160 A CN 200410009160A CN 1300146 C CN1300146 C CN 1300146C
- Authority
- CN
- China
- Prior art keywords
- phenanthroline
- replacement
- hydrochloride
- indoline
- diketone
- 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
Abstract
The present invention belongs to the technical field of preparation and application of spirobenzoxazine photochromic materials, which particularly relates to an indoline spirophenanthroline photochromic compound, a preparing method thereof and an application thereof. Substituted 1, 10-phenanthroline is used as raw materials to prepare substituted 1, 10-phenanthroline-5, 6-diketone monooxime hydrochloride by oxidation and oximation, and the substituted 1, 10-phenanthroline-5, 6-diketone monooxime hydrochloride can be condensed with substituted indole iodide in the presence of organic alkali to prepare indoline spirophenanthroline by purification. The structure of the indoline spirophenanthroline is shown as the specification. The indoline spirophenanthroline photochromic compound of the present invention has the characteristics of high thermal stability, good anti-fatigue performance, good application prospects, etc.
Description
Technical field
The invention belongs to the preparation and the applied technical field of spirooxazine photochromic material, particularly relate to spiral shell [indoline-phenanthroline Bing oxazine] photochromic compound and preparation method thereof and purposes.
Background technology
Organic photochromic material has wide development and application prospect, is widely used in aspects such as the storage of optical storage and holographic optical, photochromic glasses, protection, false proof and camouflage.Compare advantages such as response speed is fast, easily processing, low cost that it has with inorganic materials.
The indoline spirooxazine compounds is the photochromics with certain using value, is widely studied.They have good anti-fatigue performance and weather resistance really.
Photochromic principle can be described below:
Photochromic material A is the indoline spirooxazine compounds herein, at the light (hv of certain wavelength
1) shine down, can change its molecular structure and form compd B, be a part cyanine compound herein, and colour-change takes place.Compd B can be at the light (hv of another wavelength
2) or the effect of heat (Δ) recover down original color, this reversing process just is called photochromism.
Spirooxazine compounds is a very important class in numerous photochromic compoundses, and its biggest advantage is exactly that anti-fatigue performance is good, can pass through quality-colour killing circulation and repeatedly not have tangible photolysis phenomenon.
The photochromism of Luo oxazine is to be in the news first in 1961, structure is the simplest, indoline spironaphthooxazine-1,3-dihydro-1,3,3-trimethylammonium spiral shell [2H-indoles-2,3 '-[3H] naphtho-[2,1-b] derivative that [1,4] oxazine] and its 5-chlorine replace, the toluene solution of these two compounds becomes blueness under the irradiation of UV-light.After this, the people such as Ono of the U.S. have synthesized some spiro oxazone derivatives again.After 10 years, the Chu of the U.S. and Hovey recognize that at first the optical loss speed of this compounds is very low, thereby very big application prospect is arranged.They have expanded the synthetic of this compounds, and having prepared has substituent derivative on some naphthalene nucleus.Nineteen eighty-three, the Chu of the U.S. at first studied its photophysical property.1992, the two laser of humans such as Fan Meigong substep of China were studied the mechanism of spiral shell oxazine photochromic reactions.But these researchs mainly all concentrate on naphtho-spiral shell oxazine and quino-spiral shell oxazine aspect, yet there are no report for spiral shell [indoline-Fei hello quinoline oxazine] compound.
Summary of the invention
Spiral shell oxazine compound-spiral shell [indoline-Fei hello quinoline oxazine] photochromic compound of providing a class to have novel texture is provided one of purpose of the present invention.
Two of purpose of the present invention is to provide the synthetic method of a kind of spiral shell [indoline-Fei hello quinoline oxazine] photochromic compound.
Three of purpose of the present invention be to study different substituents on the indole ring and the nitrogen-atoms in heterocycle, introduced to the influence of the photochromic property of spiral shell [indoline-Fei hello quinoline oxazine] photochromic compound.
Four of purpose of the present invention is to provide the purposes of spiral shell [indoline-Fei hello quinoline oxazine] photochromic compound.
The structure of institute of the present invention synthetic spiral shell [indoline-phenanthroline Bing oxazine] has following general formula:
Wherein: R
1Can be C
1-C
18Alkyl, alkene, hydroxyalkyl, carboxyalkyl, alkoxyl group or ester group etc.R
2Can be hydrogen, C
1-C
8Alkyl, alkoxyl group, alkene, carbalkoxy, hydroxyl, halogen, nitro, carboxyl, amino, amido, amide group, pyrrolidyl, morpholinyl, hexahydropyridine base or fused benzene rings etc.R
3Can be hydrogen, C
1-C
4Alkyl, alkoxy or halogen etc.
The photochromic reactions of this compounds can be represented with following general formula:
Photochromic compound A becomes compd B under UV-irradiation, the B visible light absorbing.When B is subjected to visible radiation or is heated, then can turn back to A.This working cycle can come and go repeatedly.
The synthetic route of spiral shell of the present invention [indoline-phenanthroline Bing oxazine] photochromic compound is as follows:
Wherein: R
1Can be C
1-C
18Alkyl, alkene, hydroxyalkyl, carboxyalkyl, alkoxyl group or ester group etc.R
2Can be hydrogen, C
1-C
8Alkyl, alkoxyl group, alkene, carbalkoxy, hydroxyl, halogen, nitro, carboxyl, amino, amido, amide group, pyrrolidyl, morpholinyl, hexahydropyridine base or fused benzene rings etc.R
3Can be hydrogen, C
1-C
4Alkyl, alkoxy or halogen etc.
With 1 of replacement, 10-phenanthroline-5,6-diketone monoxime hydrochloride and an amount of solvent are in reactor, after being heated to backflow, slowly drip mol ratio and be 1: 1～1: 10 the indoles salt compounded of iodine of replacement and the mixing solutions of organic bases, (1 of the indoles salt compounded of iodine of replacement and replacement, 10-phenanthroline-5, the mol ratio of 6-diketone monoxime hydrochloride is 1: 1～1: 1.5, preferred 1: 1.2), under 80～100 degree, refluxed 15～24 hours.Reaction mixture obtains spiral shell [indoline-phenanthroline Bing oxazine] through separation, purifying.
Described organic bases can be triethylamine, Pyrrolidine, hexahydropyridine, pyridine, morpholine or their any mixture etc.
Described solvent is alcohols, toluene, benzene, sherwood oil or their any mixed solvent etc. of 1～4 carbon atom.
The separation of described reaction mixture, purifying are directly to filter out precipitation from reaction mixture, use lower boiling alcohols (as dehydrated alcohol) recrystallization then; Perhaps, separate, use lower boiling alcohols recrystallization at last with silica gel column chromatography with the reaction mixture removal of solvent under reduced pressure.
Desired raw material replaces among the present invention 1,10-phenanthroline-5, and the synthetic route and the method for 6-diketone monoxime hydrochloride are as follows:
Wherein: R
3Can be hydrogen, C
1-C
4Alkyl, alkoxy or halogen etc.
With 1 of replacement, the 10-phenanthroline mixes (mole ratio is 1: 1～1: 20) with Sodium Bromide or Potassium Bromide, be dissolved in then (as reaction medium) in the vitriol oil.Drip concentrated nitric acid again, with 1 of replacement, the 10-phenanthroline is oxidized to 1 of replacement, 10-phenanthroline-5, and the 6-diketone, adjust pH 6～8, preferred pH value 7 is separated, and uses recrystallizing methanol, obtains yellow needle-like crystal; With replace 1,10-phenanthroline-5,6-diketone and oxammonium hydrochloride (mole ratio is 1: 1) react generation pale yellow powder shape solid in solvent, promptly get replace 1,10-phenanthroline-5,6-diketone monoxime hydrochloride.
Described adjust pH can be used mineral alkali, as sodium hydroxide, sodium bicarbonate, yellow soda ash etc.
1 of described replacement, 10-phenanthroline-5, the substituting group of 6-diketone monoxime hydrochloride can be hydrogen, C
1-C
4Alkyl, alkoxy or halogen etc.
The indoles salt compounded of iodine of described replacement is 2,3 of replacement, 3-tri-methyl indole salt compounded of iodine.
Desired raw material replaces among the present invention 2,3, and 3-tri-methyl indole salt compounded of iodine can be bought from the market, or by following synthetic route and method preparation:
Wherein: R
1Can be C
1-C
18Alkyl, alkene, hydroxyalkyl, carboxyalkyl, alkoxyl group or ester group etc.R
2Can be hydrogen, C
1-C
8Alkyl, alkoxyl group, alkene, carbalkoxy, hydroxyl, halogen, nitro, carboxyl, amino, amido, amide group, pyrrolidyl, morpholinyl, hexahydropyridine base or fused benzene rings etc.
The aniline and the NaNO that replace
2Take place after the diazotization reaction by SnCl
2Or Na
2SO
3Be reduced to the hydrazinobenzene hydrochloride salt of replacement, adopt the Fischer indole synthesis with the hydrazinobenzene hydrochloride salt that replaces and isopropyl methyl reactive ketone synthetic replace 2,3, the 3-tri-methyl indole, at last with the idoalkane salify obtain replacing 2,3,3-tri-methyl indole salt compounded of iodine.
1 of the replacement of using as starting raw material, the aniline of 10-phenanthroline and replacement is can buy on the market.
Compare with the synthetic method of traditional De Luo oxazine compound, simple and easy to do with the synthetic of the inventive method synthesizing new spiral shell [indoline-phenanthroline Bing oxazine] and method of purification, productive rate is higher, has more practical value.Its productive rate and fusing point see Table 1.
Table 1: the productive rate and the fusing point (R of spiral shell [indoline-phenanthroline Bing oxazine]
1=CH
3, R
3=H)
| Compound | SP1 | SP2 | SP3 | SP4 | SP5 | SP6 | SP7 |
| Substituent R 2 | H | CH 3 | CH 3O | F | Cl | Br | 4，5-Benzo |
| Productive rate | 37％ | 68％ | 61％ | 31％ | 39％ | 52％ | 96％ |
| Fusing point | 125～126℃ | 241℃ | 244℃ | 128～130℃ | 234℃ | 235℃ | 239℃ |
The spiral shell that the present invention synthesized [indoline-phenanthroline Bing oxazine] compound can be used for the following aspects:
1. protect and finishing material
Utilize the susceptibility of photochromic material, make radiating material against sunshine optical radiation.Variable color forms protective layer when rayed, thereby cuts off the injury that causes because of direct irradiation, as light-sensitive sunglasses, sunscreen, photo chromic glass etc.At present, the organic photochromic glasses have accounted for more than 90 percent of light-sensitive glasses market in the international market.
2. photochromic films and photochromic coating
This compounds is dissolved in the polymer, is coated in glass, paper substrate or metallic surface, treat promptly to form stable variable color film after solvent volatilizees naturally.Use UV-irradiation, become colouredly from colourless, then can be returned to initial colourless state with radiation of visible light, this phenomenon can be repeatedly repeatedly.Also can make photochromic coating and be used to prepare anti-fake material such as anti-false trademark etc. and camouflage material such as net defence, camouflage paint etc.
3. can wipe rewriting type optical disk
Spirooxazine photochromic compound is applied to CD storage technique, is used to prepare photochromic CD, have that storage density height, storage life are long, speed soon, advantage such as processing and low price easily.
Other
Can be used as the material of preparation photoswitch molecular device etc.
Of the present invention synthetic and method of purification is simple and easy to do, productivity ratio is higher.
Spiral shell of the present invention [indoline-phenanthroline Bing oxazine] photochromic compound has characteristics such as Heat stability is good, fatigue resistance be good, has Application Prospect preferably.
The present invention has the characteristics of following several respects:
1. raw material is easy to get, and is synthetic and method of purification is simple and easy to do, the productive rate height, and as the data that table 1 provided, the productive rate of SP7 is near quantitatively.
2. the anti-fatigue performance of institute's synthetic spiral shell [indoline-phenanthroline Bing oxazine] compound is good.
3. institute's synthetic spiral shell [indoline-phenanthroline and oxazine] compound has the significantly molten discoloration effect that causes, and need not ultraviolet lighting in polar solvent also has and be colour solid in a large number and exist, and the character and the application thereof that are colour solid for research spiral shell oxazine provide convenience.
Embodiment
Embodiment 1
1,10-phenanthroline-5,6-diketone synthetic
Add the 140mL vitriol oil in the reaction flask, the slow down 10.0g 1 of adding is stirred in the ice bath cooling, and 10-two water phenanthrolines keep reactant below 5 ℃, add Sodium Bromide 17.3g, concentrated nitric acid 70mL successively.Add back stirring at room 20min, heated and stirred refluxes, and temperature slowly is raised to 120 ℃, is incubated 1 hour.Cooling gets brown clear solution, and in the impouring 600g trash ice, transferring pH with 30% (w/v) NaOH solution was 7, obtains the muddy aqueous solution under it was stirred.Suction filtration, solid is used the water hot extraction, filtered while hot, merging filtrate, cooling, CHCl
3Extraction, the organic phase anhydrous sodium sulfate drying revolves and boils off solvent, must 9.7g (91%) orange solids.Use recrystallizing methanol, obtain yellow needle-like crystal.mp.257～258℃。
Embodiment 2
1,10-phenanthroline-5,6-diketone monoxime hydrochloride synthetic
Put 4.2g1,10-phenanthroline-5,6-diketone, 1.53g oxammonium hydrochloride and 100mL ethanol were warmed up to 50 ℃ in 1 hour in flask, stirring and refluxing 3 hours, and cooling is filtered, washing with alcohol, drying gets pale yellow powder shape solid 4.2g; Filtrate is concentrated the 0.9g product of getting back, overall yield 97%, mp.221～222 ℃ (decomposition).
Embodiment 3
1,3,3-trimethylammonium-1,3-dihydro spiral shell [2H-indoles-2,2 '-[2H] two pyridos [3,2-f] [2,3-h] [1,4] benzoxazine] (being called SP1) synthetic
Make solvent with about 100mL dehydrated alcohol, add 1,10-phenanthroline-5,6-diketone monoxime hydrochloride 1.1g (5mmol) is heated to backflow.With 1,2,3,3-tetramethyl-indoles salt compounded of iodine 1.8g (6mmol), triethylamine 3.0g (30mmol) and about 20mL dehydrated alcohol mix, dissolving, slowly be added drop-wise to above-mentionedly 1,10-phenanthroline-5 is in the ethanol solution of 6-diketone monoxime hydrochloride, added in 1 hour, refluxed 20 hours down at 80～100 ℃, remove by filter minute quantity impurity, rotary evaporation removes and desolvates, silicagel column separates 5～8 times, chloroform is as eluent, and the dehydrated alcohol recrystallization obtains light brown crystal 0.7g, yield 37%, M.P.125～126 ℃.
Embodiment 4
The 5-methyl isophthalic acid, 3,3-trimethylammonium-1,3-dihydro spiral shell [2H-indoles-2,2 '-[2H] two pyridos [3,2-f] [2,3-h] [1,4] benzoxazine] (being called SP2) synthetic
Make solvent with about 200mL dehydrated alcohol, add 1,10-phenanthroline-5,6-diketone monoxime hydrochloride 2.3g (10mmol) is heated to backflow.With 1,2,3,3-tetramethyl--5-skatole salt compounded of iodine 3.8g (12mmol), hexahydropyridine 60mmol and about 20mL dehydrated alcohol mix, dissolving, slowly are added drop-wise to above-mentioned 1,10-phenanthroline-5 in the ethanol solution of 6-diketone monoxime hydrochloride, added in 1 hour, refluxed 15 hours down at 80～100 ℃, remove by filter minute quantity impurity, rotary evaporation removes to desolvate and obtains green solid, twice in dehydrated alcohol recrystallization, obtain green crystal 2.7g, yield 68%, M.P.241 ℃.
Embodiment 5
5-methoxyl group-1,3,3-trimethylammonium-1,3-dihydro spiral shell [2H-indoles-2,2 '-[2H] two pyridos [3,2-f] [2,3-h] [1,4] benzoxazine] (being called SP3) synthetic
Make solvent with about 200mL dehydrated alcohol, add 1,10-phenanthroline-5,6-diketone monoxime hydrochloride 2.3g (10mmol) is heated to backflow.With 1,2,3,3-tetramethyl--5-methoxyl group indoles salt compounded of iodine 4.0g (12mmol), triethylamine 6.1g (60mmol) and about 20mL dehydrated alcohol mix, dissolving, slowly are added drop-wise to above-mentioned 1,10-phenanthroline-5 in the ethanol solution of 6-diketone monoxime hydrochloride, added in 1 hour, refluxed 20 hours down at 80～100 ℃, filtration obtains green solid, and dehydrated alcohol recrystallization twice obtains green crystal 2.5g, yield 61%, M.P.244 ℃.
Embodiment 6
5-fluoro-1,3,3-trimethylammonium-1,3-dihydro spiral shell [2H-indoles-2,2 '-[2H] two pyridos [3,2-f] [2,3-h] [1,4] benzoxazine] (being called SP4) synthetic
Make solvent with about 200mL dehydrated alcohol, add dried 1,10-phenanthroline-5,6-diketone monoxime hydrochloride 1.8g (8mmol) is heated to backflow.With 1,2,3,3-tetramethyl--5-fluoro indole salt compounded of iodine 3.2g (10mmol), triethylamine 5.0g (50mmol) and about 20mL dehydrated alcohol mix, dissolving, slowly are added drop-wise to above-mentioned 1,10-phenanthroline-5, in the ethanol solution of 6-diketone monoxime hydrochloride, added in 1 hour, refluxed 24 hours down at 80～100 ℃, remove by filter minute quantity impurity, rotary evaporation removes and desolvates, and silicagel column separates 6～8 times, and chloroform is as eluent, the dehydrated alcohol recrystallization, obtain blue colored crystal 1.0g, yield 31%, M.P.128～130 ℃.
Embodiment 7
5-chloro-1,3,3-trimethylammonium-1,3-dihydro spiral shell [2H-indoles-2,2 '-[2H] two pyridos [3,2-f] [2,3-h] [1,4] benzoxazine] (being called SP5) synthetic
Make solvent with about 200mL dehydrated alcohol, add 1,10-phenanthroline-5,6-diketone monoxime hydrochloride 2.3g (10mmol) is heated to backflow.With 1,2,3,3-tetramethyl--5-chloro-indole salt compounded of iodine 4.0g (12mmol), hexahydropyridine 60mmol and about 20mL dehydrated alcohol mix, dissolving, slowly are added drop-wise to above-mentioned 1,10-phenanthroline-5 in the ethanol solution of 6-diketone monoxime hydrochloride, added in 1 hour, refluxed 20 hours down at 80～100 ℃, remove by filter minute quantity impurity, rotary evaporation removes and desolvates, silicagel column separates 5～8 times, and chloroform is as eluent, the dehydrated alcohol recrystallization, obtain green crystal 1.6g, yield 39%, M.P.234 ℃.
Embodiment 8
5-bromo-1,3,3-trimethylammonium-1,3-dihydro spiral shell [2H-indoles-2,2 '-[2H] two pyridos [3,2-f] [2,3-h] [1,4] benzoxazine] (being called SP6) synthetic
Make solvent with about 200mL dehydrated alcohol, add 1,10-phenanthroline-5,6-diketone monoxime hydrochloride 1.8g (8mmol) is heated to backflow.With 1,2,3,3-tetramethyl--5-bromo indole salt compounded of iodine 3.7g (9.7mmol), triethylamine 5.0g (50mmol) and about 20mL dehydrated alcohol mix, dissolving, slowly are added drop-wise to above-mentioned 1,10-phenanthroline-5, in the ethanol solution of 6-diketone monoxime hydrochloride, added in 1 hour, refluxed 24 hours down at 80～100 ℃, remove by filter small amount of impurities, rotary evaporation removes and desolvates, and silicagel column separates 5～8 times, and chloroform is as eluent, the dehydrated alcohol recrystallization, obtain green crystal 1.9g, yield 52%, M.P.235 ℃.
Embodiment 9
1,3,3-trimethylammonium-1,3-dihydro spiral shell [2H-benzo [4,5] indoles-2,2 '-[2H] two pyridos [3,2-f] [2,3-h] [1,4] benzoxazine] (being called SP7) synthetic
Make solvent with about 180mL dehydrated alcohol, add 1,10-phenanthroline-5,6-diketone monoxime hydrochloride 1.8g (8mmol) is heated to backflow.With 1,2,3,3-tetramethyl--benzo [4,5] indoles salt compounded of iodine 3.4g (9.7mmol), triethylamine 5.0g (50mmol) and about 20mL dehydrated alcohol mix, dissolving, slowly be added drop-wise to above-mentionedly 1,10-phenanthroline-5 is in the ethanol solution of 6-diketone monoxime hydrochloride, added in 1 hour, and refluxed 15 hours down, filter and obtain green solid at 80～100 ℃, twice in dehydrated alcohol recrystallization, obtain green crystal 3.3g, yield 96%, M.P.239 ℃.
Embodiment 10
SP1～SP7 is dissolved in chloroform and the methyl alcohol respectively, sky-blue is used ultra violet lamp, color burn, avy blue; Lucifuge is placed, and color shoals.This illustrates that they have photochromic action, and open loop body and closed loop body exist balance in solution.They are distributed to (as methyl methacrylate) in the macromolecular solution, are applied to surfaces such as object such as paper, cotton, metal, equally also have photochromic action, and can repeat repeatedly, therefore can be used as camouflage material such as net defence, camouflage paint.
Claims (8)
1. a spiral shell [indoline-phenanthroline and oxazine] photochromic compound, it is characterized in that: described spiral shell [indoline-phenanthroline and oxazine] has following structure:
Wherein: R
1Be C
1-C
18Alkyl; R
2Be C
1-C
8Alkyl, halogen or with the phenyl ring of indoles condensed phenyl ring mutually; R
3Be hydrogen.
2. the synthetic method of spiral shell according to claim 1 [indoline-phenanthroline Bing oxazine] photochromic compound is characterized in that:
With 1 of replacement, 10-phenanthroline-5,6-diketone monoxime hydrochloride and organic solvent are mixed in the reactor, after being heated to backflow, slowly drip mol ratio and be 1: 1～1: 10 the indoles salt compounded of iodine of replacement and the mixing solutions of organic bases, wherein, 1 of indoles salt compounded of iodine that replaces and replacement, 10-phenanthroline-5, the mol ratio of 6-diketone monoxime hydrochloride is 1: 1～1: 1.5, refluxes down at 80～100 ℃; Reaction mixture obtains spiral shell [indoline-phenanthroline Bing oxazine] photochromic compound through separation, purifying; Structure is:
Wherein: R
1Be C
1-C
18Alkyl; R
2Be C
1-C
8Alkyl, halogen or with the phenyl ring of indoles condensed phenyl ring mutually; R
3Be hydrogen;
1 of described replacement, 10-phenanthroline-5,6-diketone monoxime hydrochloride prepares by the following method:
With replace 1, the 10-phenanthroline mixes with Sodium Bromide or Potassium Bromide, wherein 1 of replacement, the mole ratio of 10-phenanthroline and Sodium Bromide or Potassium Bromide is 1: 1～1: 20, is dissolved in then in the vitriol oil, drips concentrated nitric acid again, with 1 of replacement, the 10-phenanthroline is oxidized to 1 of replacement, 10-phenanthroline-5,6-diketone, adjust pH 6～8, separate, use recrystallizing methanol, obtain yellow needle-like crystal; With replace 1,10-phenanthroline-5,6-diketone and oxammonium hydrochloride react generation pale yellow powder shape solid in organic solvent, promptly get replace 1,10-phenanthroline-5,6-diketone monoxime hydrochloride; Wherein, 1 of replacement, 10-phenanthroline-5, the mole ratio of 6-diketone and oxammonium hydrochloride is 1: 1;
1 of described replacement, 10-phenanthroline-5, the substituting group of 6-diketone monoxime hydrochloride is a hydrogen;
The indoles salt compounded of iodine of described replacement is 2,3 of replacement, 3-tri-methyl indole salt compounded of iodine, and structure is:
Wherein: R
1Be C
1-C
18Alkyl; R
2Be C
1-C
8Alkyl, halogen or with the phenyl ring of indoles condensed phenyl ring mutually.
3. method according to claim 2 is characterized in that: described organic bases is triethylamine, Pyrrolidine, hexahydropyridine, pyridine, morpholine or their any mixture.
4. method according to claim 2 is characterized in that: described solvent is alcohols, toluene, benzene, sherwood oil or their any mixed solvent of 1～4 carbon atom.
5. method according to claim 2 is characterized in that: described return time is 15～24 hours.
6. method according to claim 2 is characterized in that: the separation of described reaction mixture, purifying are directly to filter out precipitation from reaction mixture, use lower boiling alcohols recrystallization then; Perhaps, separate, use lower boiling alcohols recrystallization at last with silica gel column chromatography with the reaction mixture removal of solvent under reduced pressure.
7. the purposes of spiral shell according to claim 1 [indoline-phenanthroline Bing oxazine] photochromic compound, it is characterized in that: be used to prepare the material of photochromic CD, photoswitch molecular device, photochromic glasses or anti-false trademark, and the coating of the photochromic material that is used to pretend.
8. purposes according to claim 7 is characterized in that: described photochromic material is film or net defence.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100091609A CN1300146C (en) | 2004-05-31 | 2004-05-31 | Photochromic compound of spiro [indolerin-phenanthroline oxazine and its preparation and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100091609A CN1300146C (en) | 2004-05-31 | 2004-05-31 | Photochromic compound of spiro [indolerin-phenanthroline oxazine and its preparation and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1583755A CN1583755A (en) | 2005-02-23 |
| CN1300146C true CN1300146C (en) | 2007-02-14 |
Family
ID=34600218
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100091609A Expired - Fee Related CN1300146C (en) | 2004-05-31 | 2004-05-31 | Photochromic compound of spiro [indolerin-phenanthroline oxazine and its preparation and use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1300146C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8620275B2 (en) | 2002-08-30 | 2013-12-31 | Qualcomm Incorporated | Server processing in providing messages for a wireless device connecting to a server |
| US8630634B2 (en) | 2002-08-30 | 2014-01-14 | Qualcomm Incorporated | Processing of interactive screens for a wireless device |
| US8660613B2 (en) | 2002-01-31 | 2014-02-25 | Qualcomm Incorporated | System and method for providing messages on a wireless device connecting to an application server |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100532495C (en) * | 2007-02-08 | 2009-08-26 | 中国科学院理化技术研究所 | Double functional photochromism compound with stable nitrogen-oxygen free radical group and spiro oxazinyl and synthetic method and use thereof |
| CN109627267B (en) * | 2019-01-10 | 2020-08-28 | 南京工业大学 | Iridium complex, and synthesis method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1180708A (en) * | 1997-11-12 | 1998-05-06 | 南开大学戈德防伪技术公司 | Photochemistry gene recognition material and its preparing method and use |
-
2004
- 2004-05-31 CN CNB2004100091609A patent/CN1300146C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1180708A (en) * | 1997-11-12 | 1998-05-06 | 南开大学戈德防伪技术公司 | Photochemistry gene recognition material and its preparing method and use |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8660613B2 (en) | 2002-01-31 | 2014-02-25 | Qualcomm Incorporated | System and method for providing messages on a wireless device connecting to an application server |
| US8620275B2 (en) | 2002-08-30 | 2013-12-31 | Qualcomm Incorporated | Server processing in providing messages for a wireless device connecting to a server |
| US8630634B2 (en) | 2002-08-30 | 2014-01-14 | Qualcomm Incorporated | Processing of interactive screens for a wireless device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1583755A (en) | 2005-02-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS6347721A (en) | Light reaction lens | |
| JPH06502180A (en) | Photochromic naphthopyran | |
| CN1296371C (en) | Photochromic bis-naphthopyran compounds and methods for their manufacture | |
| JP3358749B2 (en) | Phototautomeric compounds | |
| CN1300146C (en) | Photochromic compound of spiro [indolerin-phenanthroline oxazine and its preparation and use | |
| CN1046284C (en) | Spiro (indolino) oxazine photochromic compounds | |
| CN1046282C (en) | Photockromic heterocyclochromenes | |
| EP3307817B1 (en) | Novel spiropyran based composition and application thereof as security tag | |
| EP0530369A1 (en) | Crystal comprising indolinospirobenzothiopyran derivative and ring-opening isomer thereof | |
| JP5803025B2 (en) | Photochromic molecule | |
| CN1049232C (en) | Fluorescent dye with double chromogens and preparing process thereof | |
| JP2759307B2 (en) | Coumarin derivatives | |
| US3796576A (en) | Photographic material comprising a quinoxaline as dye bleaching catalyst | |
| CN1634909A (en) | 3- or 4- carbonyl substituted coumarin connected with naphthenones and its synthesis method and use | |
| CN1635029A (en) | Coumarin dyestuff linked by naphthene ketones, method for synthesis and use thereof | |
| CN101134849B (en) | Photochromic reactive dyes compound and method for preparing the same | |
| CN1446815A (en) | Compound of benzoindole spiroxaxine as well as its synthetic method and usage | |
| CN101624519A (en) | Preparation and application of pyrazolone-shrinking phenyl semicarbazide photochromic compounds | |
| CN100532495C (en) | Double functional photochromism compound with stable nitrogen-oxygen free radical group and spiro oxazinyl and synthetic method and use thereof | |
| CN101215282A (en) | Photochromic naphtho-pyrans compounds and synthetic method thereof | |
| JPH03251587A (en) | Spiroxazine compound and production thereof | |
| CN100349869C (en) | Cyanine dye containing end alkynyl radical and its synthesis process | |
| CN104402903A (en) | Photochromic compound and preparation method and application thereof | |
| CN1583754A (en) | Indole oxazine compound and its synthesis and use | |
| JPH049943A (en) | Spirooxazine recording material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |