CN100434430C - Indolinospirobenzoxazine compound, and synthesis method and use thereof - Google Patents
Indolinospirobenzoxazine compound, and synthesis method and use thereof Download PDFInfo
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Abstract
The present invention belongs to the technical field of preparation and application of indoline spirobenzoxazine photochromic materials, which particularly relates to an indoline spirobenzoxazine compound, a synthesizing method thereof and applications thereof. The indoline spirobenzoxazine compound is obtained by the following steps: dissolving 1-(R1)-2, 3, 3-trimethyl-pseudoindole iodine salts in anhydrous alcohol solution under the protection of nitrogen; adding hexahydropyridine whose concentration is 0.5 wt% to 10 wt% of that of a catalyst; dripping anhydrous alcohol solution of 2-nitroso-3-R3-5-R2-phenol equimolar to 1-(R1)-2, 3, 3-trimethyl-pseudoindole iodine salts under a reflux condition while distilling; continuously carrying out reflux after the dripping process is finished; concentrating obtained products; making the products pass through silicon gel columns. The compound of the present invention can be used for preparing photochromic materials, such as resin eyeglasses, anti-counterfeiting materials and reusable timely optical storage and optical switch materials with low power.
Description
Technical field
The invention belongs to the preparation and the applied technical field of indoline spirooxazine photochromic material, particularly Indolinospirobenzoxacompound compound and preparation method and use thereof.
Background technology
Organic photochromic material has broad application prospects, and compares with inorganic materials, advantages such as speed of response is fast, easily processing, low cost that it has.
The indoline spirooxazine compounds is owing to have anti-fatigue performance and weather resistance preferably, and it is the class photochromics with certain using value, is studied widely.
Photochromicly roughly 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, part blue or green compounds, thus 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.
In this field, study maximum be indoline spironaphthooxazine compounds (M.Richwoodet al, Mo1.Cryst.Liq.Cryst., 1994,246,17-24).But this type compound is under UV-irradiation, and great majority can only produce blue one-tenth colour solid.The one class benzindole quinoline Luo benzo oxazinyl compound that has been 4,936,995 patent report as U.S. Patent number, blue but the tone after their quality remains.This shows that the one-tenth colour solid of design, synthesizing indoline spirooxazine compounds is red material, the tone that further enriches this compounds will be researchist's difficult problem anxious to be captured.
Summary of the invention
One of purpose of the present invention is the synthetic new Indolinospirobenzoxacompound compound of a class.Mostly be red after this class Indolinospirobenzoxacompound compound is photochromic greatly.Make the red tone of indoline spirooxazine compounds be able to perfect.
Two of purpose of the present invention provides the synthetic method of indoline Luo benzoxazine compound.
Three of purpose of the present invention provides the purposes of indoline Luo benzoxazine compound.
Four of purpose of the present invention provides a compounds, as the main intermediate of synthesizing indoline spirooxazine photochromic material---2-nitrosobenzene amphyl synthetic method.
Indolinospirobenzoxacompound compound of the present invention has following structure:
Wherein: R
1=C
1-C
18Alkyl, alkene, hydroxyalkyl, ether or ester group etc.R
2, R
3And R
4Can be respectively hydrogen, C
1 -C
8Alkyl, alkoxyl group, halogen, nitro, alkene, hydroxyl, carboxyl, amido, pyrrolidyl, morpholine or hexahydropyridine base etc.
This compounds is characterised in that the absorption spectrum of their one-tenth colour solid compares with the one-tenth colour solid of most of indoline spironaphthooxazine compounds, and orchid moves absorption peak.Institute of the present invention synthetic compound is at UV-light (hv
1) irradiation under become redness.See Fig. 1.
The synthetic general formula of Indolinospirobenzoxacompound compound of the present invention is as follows:
Wherein: R
1=C
1-C
18Alkyl, alkene, hydroxyalkyl, ether or ester group etc.R
2, R
3And R
4Can be respectively hydrogen, C
1 -C
8Alkyl, alkoxyl group, halogen, nitro, alkene, hydroxyl, carboxyl, amido, pyrrolidyl, morpholine or hexahydropyridine base etc.
Under nitrogen protection, according to document (E.Fischer; Schmitt, Ber.21, the 1-(R of 1072 (1888) methods preparation
1)-2,3,3-trimethylammonium-pseudo-indole salt compounded of iodine is dissolved in the ethanol solution, and adding concentration is the hexahydropyridine of 0.5wt%-10wt% catalytic amount, under refluxad, drips and 1-(R
1)-2,3, the equimolar 2-nitroso-group-phenol derivatives of 3-trimethylammonium-pseudo-indole salt compounded of iodine or 2-nitroso-group-3-R
3-5-R
2The ethanol solution of-phenol, the distillation while dripping, and make rate of addition equal the speed that distillates of solvent; After being added dropwise to complete, continue backflow 1-6 hour; After concentrating, cross silicagel column, get target compound of the present invention, Indolinospirobenzoxacompound class photochromic material.
Wherein: R
1=C
1-C
18Alkyl, alkene, hydroxyalkyl, ether or ester group etc.R
2And R
3Can be respectively hydrogen, C
1 -C
8Alkyl, alkoxyl group, halogen, nitro, alkene, hydroxyl, carboxyl, amido, pyrrolidyl, morpholine or hexahydropyridine base etc.
Photochromic Indolinospirobenzoxacompound compound of the present invention has increased the spectral range and the tone of spirooxazine photochromic material, has increased the selectivity of using, and has increased the stability that becomes colour solid.This compounds can be used for preparing photochromic resin lens one class off-color material, anti-fake material, in good time optical storage of reusable low power and photoswitch material.
Description of drawings
Fig. 1. the compound of the embodiment of the invention 2 becomes the visible absorption spectra synoptic diagram of colour solid generative process under UV-irradiation.
Embodiment
One, 2-nitrosobenzene amphyl synthetic
Synthesizing of (1) 3,5-two octyloxies-phenol:
The synthetic method of pressing chemical reagent 1999,21 (2) 68-70 is synthetic.
(2) .1-Pyrrolidine-3,5-dihydroxy-benzene synthetic:
1,3,5-trihydroxy-phenol 27g, 4-dimethylamino pyridine 0.5g, Pyrrolidine 12g, in 90ml methyl alcohol, stirring at room 6 hours.The light green precipitation forms, and filters.Precipitation is washed with the methanol solution of 30wt%, and drying gets target product 21g.Mother liquor adds salt solution, stirs 10 minutes, forms partly precipitated again, filter, 6g, common product 27g, productive rate 90%.
1HNMR(CDCl
3)，δ(ppm)：7.8(s，2H，)，5.78(s，1H，)，5.6(s，2H，)，3.2(t，4H，N-CH2)，2.0(t，4H，-CH2)。
(3) .3-n-butoxy-5-Pyrrolidine base-phenol is synthetic:
In the 30ml acetonitrile, add the 1-Pyrrolidine, 3, the 5-dihydroxy-benzene (1.8g, 0.01mol), K
2CO
3(0.6g), be heated to 60 ℃, stirred 10 minutes, add 0.5g phenylbenzene-18-and be preced with-6 crown ethers, iodo-n-butane (0.01mol) reaction 3 hours.Remove and desolvate.Use hcl acidifying, chloroform extraction, MgSO
4Drying is removed and is desolvated, and crosses silicagel column, gets target product.Mp：182-184℃。
1HNMR(CDCl
3)，δ(ppm)：5.70，5.75，5.80(3s，3H)，3.9(t，2H，O-CH
2)，3.25(t，4H，N-CH
2)，2.0(t，4H，-CH
2)，1.75(p，2H，-CH
2)，1.5(p，2H，-CH
2)，1.0(t，3H，-CH
3)。
(4) 2-nitroso-group-3-n-butoxy-5-Pyrrolidine base-phenol is synthetic:
The acetic acid of 3-normal-butyl-5-Pyrrolidine base-phenol: in the solution of water=10: 1,0-5 ℃, drip the aqueous solution of Ya Xiao Suan Na.After adding, continue to stir 2 hours.Red precipitate forms, and filters washing.Use DMF/H
2O forms sediment.Productive rate 60%, mp:136-139 ℃,
1HNMR (CDCl
3), δ (ppm): 6.8 (s, 1H, Ar-H), 5.3 (s, 1H, Ar-H), 4.0 (t, 2H ,-OCH
2), 3.25 (t, 4H, N-CH
2), 2.0 (p, 4H ,-CH
2), 1.75 (p, 2H ,-CH
2), 1.5 (h, 2H, CH
2), 1.0 (t, 3H, CH
3).
(5), 2-nitroso-group-3,5-dimorpholine base-phenol synthetic:
3, the acetic acid of 5-dimorpholine base-phenol (according to document Angrew.Chem.Internat.Edit., 1967, Vol.6,1067 method is synthetic): in the solution of water=10: 1,0-5 ℃, drip the aqueous solution of Ya Xiao Suan Na.After adding, continue to stir 2 hours.Red precipitate forms, and filters washing.Use the DMF recrystallization, get the scarlet precipitation, target product, productive rate 62%.
Mp：238-240℃。
1HNMR(CDCl
3)，δ(ppm)：5.65(s，1H，Ar-H，)，5.55(s，1H，Ar-H，)，3.9(t，4H，OCH
2)，3.85(t，4H，OCH
2)，3.6(t，4H，NCH
2)，3.4(t，4H，NCH
2)。
(6), 2-nitroso-group-3, the two hexahydropyridine base-phenol of 5-:
3, the acetic acid of the two hexahydropyridine base-phenol of 5-(according to document Angrew.Chem.Internat.Edit., 1967, Vol.6,1067 method is synthetic): in the solution of water=10: 1,0-5 ℃, drip the aqueous solution of Ya Xiao Suan Na.After adding, continue to stir 2 hours.Red precipitate forms, and filters washing.Use the DMF recrystallization, get the scarlet precipitation.Productive rate 58%.MP：166-168℃。
1HNMR(CDCl
3)，δ(ppm)：5.55(s，1H，Ar-H，)，5.45(s，1H，Ar-H，)，3.56(t，4H，-NCH
2)，3.33(t，4H，-NCH
2)，1.7(m，12H，(CH
2)
3)。
(7), 2-nitroso-group-3,5-two octyloxies-phenol:
3, the acetic acid of 5-two octyloxies-phenol: in the solution of water=10: 1,0-5 ℃, drip the aqueous solution of Ya Xiao Suan Na.After adding, continue to stir 2 hours.Red precipitate forms, and filters washing.Use the DMF recrystallization, get the scarlet product.mp：44-46℃，NMR(CDCl
3)，δ(ppm)：10.35(s，1H，Ar-OH)，6.01(m，3H，Ar-H)，3.98(t，4H，OCH
2)，1.75(p，4H，CH
2)，1.45(m，4H，CH
2)，1.29-0.89(m，22H，-(CH
2)
4-CH
3)。
Two, the synthetic and purposes of Indolinospirobenzoxacompound compound
Embodiment 1.
1,3.3-trimethylammonium-7 '-normal butane base, 5 '-pyrrolidyl-indoline [2,3 '] spiral shell benzo [synthesizing of 1,4] oxazine:
Under nitrogen protection, according to document [E.FICHER; SCHMITT, BER, 21,1,2,3 of 1072 (1888) methods preparation, 3-tetramethyl--pseudo-indole salt compounded of iodine is dissolved in the ethanol solution, adds 5wt% catalyzer hexahydropyridine, under refluxad, drip and 1,2,3, the ethanol solution of the equimolar 2-nitroso-group of 3-tetramethyl--pseudo-indole salt compounded of iodine-3-n-butoxy-5-Pyrrolidine base-phenol, the distillation while dripping, and make rate of addition equal solvent to distill out speed.After being added dropwise to complete.Continue backflow 1-2 hour.Retort solution after concentrating, is crossed silicagel column, gets product indoles Luo benzoxazine compound.
1HNMR(CDCl
3)，δ(ppm)：7.45-6.5(m，4H，)，5.66(s，1H，)，5.57(s，1H，Ar-H)，4.1(t，2H，OCH
2，)，3.32(t，4H，CH
2-N-CH
2)，2.8(s，3H，N-CH
3)2.0(t，4H，N-CH
2-)，1.8(p，2H，-CH
2-)，1.5(p，2H，-CH
2-CH
3)，1.35(s，6H，CH
3)1.0(t，3H，-CH
3)。Has good photochromic properties and stability.
Embodiment 2.
1,3,3-trimethylammonium-5 ', 7 '-dimorpholine base indoline-[2,3 '], the spiral shell benzo [synthesizing of 1,4] oxazine:
Under nitrogen protection, according to document E.FICHER; SCHMITT, BER, 21,1,2,3 of 1072 (1888) methods preparation, 3-tetramethyl--pseudo-indole salt compounded of iodine is dissolved in the ethanol solution, adds 5wt% catalyzer hexahydropyridine, under refluxad, drip and 1,2,3, the equimolar 2-nitroso-group-3 of 3-tetramethyl--pseudo-indole salt compounded of iodine, the ethanol solution of 5-dimorpholine base-phenol, the distillation while dripping, and make rate of addition equal solvent to distill out speed.After being added dropwise to complete.Continue backflow 1-2 hour.After concentrating, cross silicagel column, get principal product indoles spiral shell benzoxazine compound, recrystallization in ethanol.
1H NMR, (CDCl
3), δ (ppm): 7.4-6.4 (m,, 4H), 5.85 (s,, 1H), 5.95 (s, 1H), 3.85 (t, O-CH
2, 8H), 3.6 (t-N-CH
2, 8H), 3.2 (s, 3H, N-CH
3) 0.95 (s, 6H, CH
3) have good photochromic properties and stability.
The second eyeball solution of gained compound under UV-irradiation visible absorption spectra figure such as Fig. 1 institute not.
Embodiment 3.
1-propenyl-3,3-dimethyl-5 ', 7 '-dimorpholine base indoline [2,3 ']-spiral shell benzo [synthesizing of 1,4] oxazine:
Under nitrogen protection, according to document E.FICHER; SCHMITT, BER, 21, the 1-propenyl-2,3 of 1072 (1888) methods preparation, 3-trimethylammonium-pseudo-indole salt compounded of iodine is dissolved in the ethanol solution, add 5% catalyzer hexahydropyridine, under refluxad, drip and 1-propenyl-2,3, the equimolar 2-nitroso-group-3 of 3-trimethylammonium-pseudo-indole salt compounded of iodine, the dehydrated alcohol of 5-dimorpholine base-phenol, the distillation while dripping, and make rate of addition equal the speed of distilling out.After being added dropwise to complete.Continue backflow 1-2 hour.After concentrating, cross silicagel column, get target compound.Mp：59-60℃
1HNMR(CDCl
3)，δ(ppm)：1.33(s，6H，CH
3)，3.15(t，8H，N-CH
2，)，3.25(t，2H，N-CH
2-)，3.82(t，O-CH
2，8H，)，5.16(d，2H，-CH＝CH
2，)，5.76(d，1H，-CH＝CH
2)，6.0(2s，2H，Ar-H)，6.58-7.46(m，，5H，)。Has good photochromic properties and stability.
Embodiment 4.
1,3,3-trimethylammonium-5 '-morpholinyl-7 '-skatole quinoline [2,3] benzo [synthesizing of 1,4] oxazine:
Under nitrogen protection, according to document E.FICHER; SCHMITT, BER, 21,1,2,3 of 1072 (1888) methods preparation, 3-tetramethyl--pseudo-indole salt compounded of iodine is dissolved in the ethanol solution, adds 5wt% catalyzer hexahydropyridine, under refluxad, drip and 1,2,3, the dehydrated alcohol of the equimolar 2-nitroso-group of 3-tetramethyl--pseudo-indole salt compounded of iodine-3 methyl-5-morpholinyl phenol, the distillation while dripping, and make rate of addition equal the speed that solvent distills out.After being added dropwise to complete.Continue backflow 1-2 hour.After concentrating, cross silicagel column, get target compound.
1HNMR(CDCl
3)，δ(ppm)：1.33(s，6H，CH
3)，3.15(s，3H，N-CH
3，)，3.25(t，4H，N-CH
2-)，3.82(t，O-CH
2-，4H，)，5.6(s，1H，)，5.99(s，1H，)，6.5-7.2(m，5H，)。Has good photochromic properties and stability.
Embodiment 5.
1-octadecyl-3,3-dimethyl-5 ', 7 '-dimorpholine base indoline [2,3 '] spiral shell benzo [synthesizing of 1,4] oxazine:
Under nitrogen protection, according to document E.FICHER; SCHMITT, BER, 21, the 1-octadecyl-2,3 of 1072 (1888) methods preparation, 3-trimethylammonium-pseudo-indole salt compounded of iodine is dissolved in the ethanol solution, add 5wt% catalyzer hexahydropyridine, under refluxad, drip and 1-octadecyl-2,3, the equimolar 2-nitroso-group-3 of 3-trimethylammonium-pseudo-indole salt compounded of iodine, in the dehydrated alcohol of 5-dimorpholine base phenol, the distillation while dripping, and make rate of addition equal solvent to distill out speed.After being added dropwise to complete.Continue backflow 1-2 hour.Concentrate the back and cross silicagel column, get target product.MP：6℃。
1HNMR(CDCl
3)，δ(ppm)：0.933-1.3(m，35H，-(CH
2)
16-CH
3)，2.05(s，3H，CH
3)，2.2(s，3H，CH
3)，3.15(t，2H，N-CH
2，)，3.25(t，4H，N-CH
2-)，3.95(t，4H，O-CH
2)，5.9(s，1H，)，6.05(s，1H，)，6.5-7.2(m，5H，，)。Has good photochromic properties and stability.
Embodiment 6.
1,3,3-trimethylammonium-5 ', 7 '-two octyloxy indoline [2,3 '] spiral shell benzos [synthesizing of 1,4] oxazine:
Under nitrogen protection, according to document E.FICHER; SCHMITT, BER, 21,1,2,3 of 1072 (1888) methods preparation, 3-tetramethyl--pseudo-indole salt compounded of iodine is dissolved in the ethanol solution, adds 5wt% catalyzer hexahydropyridine, under refluxad, drip and 1,2,3, the equimolar 2-nitroso-group-3 of 3-tetramethyl--pseudo-indole salt compounded of iodine, the ethanol solution of 5-two octyloxies-phenol, the distillation while dripping, and make rate of addition equal the speed that solvent distills out.After being added dropwise to complete.Continue backflow 1-2 hour.After concentrating, cross silicagel column, get the 0.9g target product.Productive rate 19%.
1HNMR(CDCl
3)，δ(ppm)：0.933-1.36(m，36H，(-(CH
2)
6CH
3，2CH
3)，3.15(s，3H，N-CH3，)，3.8(t，4H，O-CH
2)，5.98(s，1H)，6.0(s，1H，)，6.5-7.2(m，5H，，)。Has good photochromic properties and stability.
Claims (3)
1. Indolinospirobenzoxacompound compound, it is characterized in that: this compound has following structure:
Wherein: R
1=C
1-C
18Alkyl; R
2, R
3With 4
3Be respectively hydrogen, C
1-C
8Alkyl, octyloxy, pyrrolidyl, morpholine or hexahydropyridine base.
2. the synthetic method of an Indolinospirobenzoxacompound compound as claimed in claim 1, it is characterized in that: described synthetic method is under nitrogen protection, with 1-(R
1)-2,3,3-trimethylammonium-pseudo-indole salt compounded of iodine is dissolved in the ethanol solution, and adding concentration is the hexahydropyridine of 0.5wt%-10wt% catalytic amount, under refluxad, drips and 1-(R
1)-2,3, the equimolar 2-nitroso-group-phenol derivatives of 3-trimethylammonium-pseudo-indole salt compounded of iodine or 2-nitroso-group-3-R
3-5-R
2The ethanol solution of-phenol, return time are 1-6 hour, and the distillation while dripping drips 2-nitroso-group-phenol derivatives or 2-nitroso-group-3-R
3-5-R
2The ethanol solution speed of-phenol equals the speed that distillates of solvent; After being added dropwise to complete, continue backflow 1-6 hour; After concentrating, cross silicagel column, obtain Indolinospirobenzoxacompound compound;
Wherein: R
1=C
1-C
18Alkyl; R
2, R
3With 4
3Be respectively hydrogen, C
1-C
8Alkyl, octyloxy, pyrrolidyl, morpholine or hexahydropyridine base.
3. the purposes of an Indolinospirobenzoxacompound compound as claimed in claim 1, it is characterized in that: described compound is used to prepare photochromic resin lens, anti-fake material, in good time optical storage of reusable low power and photoswitch material.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100430404C (en) * | 2005-10-28 | 2008-11-05 | 华东理工大学 | Spiro oxazone derivative containing naphthalimide unit |
| 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 |
| CN102993211B (en) * | 2011-09-19 | 2015-04-01 | 天津孚信科技有限公司 | Azacyclo-substituted benzo spirooxazine photochromic compound and preparation method thereof |
| CN102702226A (en) * | 2011-09-20 | 2012-10-03 | 湖南中医药大学 | Preparation of novel spirooxazine compound and photochromic property improvement thereof |
| CN105623239B (en) * | 2014-10-30 | 2019-02-15 | 中国中化股份有限公司 | A kind of photochromic composition and its application |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3578602A (en) * | 1967-08-30 | 1971-05-11 | Fuji Photo Film Co Ltd | Photochromic compound |
| US4785097A (en) * | 1986-09-26 | 1988-11-15 | Ppg Industries, Inc. | Method for synthesizing spiro-oxazines |
| JPS6452783A (en) * | 1987-03-20 | 1989-02-28 | Toray Industries | Novel spirobenzoxazine compound |
| US4816584A (en) * | 1986-11-12 | 1989-03-28 | Ppg Industries, Inc. | Photochromic spiro(indoline)benzoxazines |
| US4909963A (en) * | 1986-09-26 | 1990-03-20 | Ppg Industries, Inc. | Photochromic article |
| US4936995A (en) * | 1988-05-17 | 1990-06-26 | Ppg Industries, Inc. | Photochromic compound and articles containing the same |
-
2002
- 2002-07-02 CN CNB021234868A patent/CN100434430C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3578602A (en) * | 1967-08-30 | 1971-05-11 | Fuji Photo Film Co Ltd | Photochromic compound |
| US4785097A (en) * | 1986-09-26 | 1988-11-15 | Ppg Industries, Inc. | Method for synthesizing spiro-oxazines |
| US4909963A (en) * | 1986-09-26 | 1990-03-20 | Ppg Industries, Inc. | Photochromic article |
| US4816584A (en) * | 1986-11-12 | 1989-03-28 | Ppg Industries, Inc. | Photochromic spiro(indoline)benzoxazines |
| JPS6452783A (en) * | 1987-03-20 | 1989-02-28 | Toray Industries | Novel spirobenzoxazine compound |
| US4936995A (en) * | 1988-05-17 | 1990-06-26 | Ppg Industries, Inc. | Photochromic compound and articles containing the same |
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| CN1465578A (en) | 2004-01-07 |
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