CN102993211B - Azacyclo-substituted benzo spirooxazine photochromic compound and preparation method thereof - Google Patents
Azacyclo-substituted benzo spirooxazine photochromic compound and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an azacyclo-substituted benzo spirooxazine photochromic compound and a preparation method of the azacyclo-substituted benzo spirooxazine photochromic compound, which relates to an organic photochromic material. The compound has the chemical structural formula, in which R1 is H, CH3 or Cl, R2 is shown in the description. The preparation method comprises the following steps: firstly, synthesizing R1-substituted-1,3,3-trimethyl-2-methylene indoline; secondly, synthesizing azacyclo-substituted-2-nitrosophenol; and thirdly, synthesizing the azacyclo-substituted benzo spirooxazine photochromic compound. The compound is fast in color changing speed and decoloration speed, and bright in color. Most compounds are red photochromic compounds which are wider in application and applicability. The preparation method has the advantages of simple synthesizing process, easily obtained materials, low cost and higher yield.
Description
Technical field
Technical scheme of the present invention relates to organic photochromic material, and specifically nitrogen heterocyclic replaces benzo spirooxazine photochromic compound and preparation method thereof.
Background technology
The high-technology fields such as photochromic compound may be used for optical storage material, photochromic computer, pretends hidden material, protection and finishing material.CN 201110058251.1 discloses quino-spirooxazine photochromic compound and preparation method thereof; CN1629249 discloses 6 '-heterocyclic substituted naphtho-Luo oxazine photochromic compound and preparation method thereof.Along with the fast development of above-mentioned high-technology field, more, that there is new feature performance novel photochromic compound must be researched and developed, with satisfied society and scientific and technological demand.
Summary of the invention
Technical problem to be solved by this invention is: provide nitrogen heterocyclic to replace benzo spirooxazine photochromic compound and preparation method thereof, this compounds color change, colour killing speed are all fast and bright in colour, majority is red photochromic compound, and purposes is more extensive, and suitability is wider.
The present invention solves this technical problem adopted technical scheme: nitrogen heterocyclic replaces benzo spirooxazine photochromic compound, has following chemical structure of general formula:
In formula:
R
1=H, CH
3or Cl,
Above-mentioned nitrogen heterocyclic replaces the preparation method of benzo spirooxazine photochromic compound, and step is as follows:
The first step, R
1replace the synthesis of-1,3,3-trimethylammonium 2-methylene radical indoline
In above formula, R
1=H, CH
3or Cl,
I.R
1the synthesis of substituted phenylhydrazines hydrochloride
In 250ml there-necked flask, add R shown in 0.1mol above formula
1substituted aniline and 1. 125ml mass percent concentration are the hydrochloric acid of 30%, stir, are cooled to 0 ~ 5 DEG C, drip 0.12mol NaNO
2be dissolved in NaNO obtained in 60ml water
2the aqueous solution, drips off rear maintenance 0 ~ 5 DEG C reaction 2 hours, obtains R
1substituted-phenyl diazonium salt solution, then under the condition passing into nitrogen, by this R
1substituted-phenyl diazonium salt solution joins 2. 90gSnCl
23. 200ml mass percent concentration is in the mixed solution of the hydrochloric acid of 30%, keeps 0 ~ 5 DEG C to react 1 hour, obtains R
1substituted phenylhydrazines HCl, solid, productive rate is 88 ~ 92%;
II.R
1replace the synthesis of-2,3,3-tri-methyl indole
In 500ml there-necked flask, add 0.2mol and walk obtained R by above-mentioned I
1substituted phenylhydrazines hydrochloride and 300ml Glacial acetic acid, after heating for dissolving, add 44ml methyl isopropyl Ketone, refluxes 8 hours, and distillation, except desolventizing, adds saturated sodium bicarbonate aqueous solution, regulates pH to 7, with chloroform extraction, use anhydrous MgSO
4drying, through distillation, removing chloroform, obtains product R
1replace 2,3,3-tri-methyl indole, productive rate is 58 ~ 62%;
III.R
1replace the synthesis of-1,3,3-trimethylammonium-2-methylene radical indoline
Under nitrogen protection condition, in 100ml flask, add 0.025mol walk obtained R by above-mentioned II
1replacement-2,3,3-tri-methyl indole and 1. 0.03mol methyl iodide are dissolved in the solution formed in 30ml chloroform, reflux 3 hours, and adularescent solid is separated out, then adds 2. 0.04mol triethylamine, continue backflow 1 hour, and cooling, washes with water, use anhydrous MgSO
4drying, boils off solvent, obtains product R
1replace-1,3,3-trimethylammonium-2-methylene radical indoline, productive rate is 76 ~ 82%;
Second step, nitrogen heterocyclic R
2replace the synthesis of-2-nitrosophenol
Above-mentioned R
2=5-pyrrolidyl or above-mentioned R
2=5-morpholinyl,
A.5-the synthesis of pyrrolidyl-2-nitrosophenol
I.3-the synthesis of pyrrolidyl phenol
By the 20ml ethanol solution of 0.01mol Metha Amino Phenon and 0.01mol sodium carbonate, put into 100ml there-necked flask, drip 0.012mol 1, the 20ml ethanolic soln of 4-dibromobutane, refluxes 8 hours, pours in frozen water by the reaction solution obtained thus, separate out white precipitate, filter, obtain product 3-pyrrolidyl phenol, productive rate is 90%;
The synthesis of II.5-pyrrolidyl-2-nitrosophenol
By walked by above-mentioned I obtained 0.1mol 3-pyrrolidyl phenol be dissolved into 35ml mass percent concentration be 30% hydrochloric acid and 20ml water in, be cooled to 0 DEG C, then drip 0.1mol NaNO
2be dissolved in NaNO obtained in 50ml water
2the aqueous solution, stirs half an hour at 0 ~ 5 DEG C, suction filtration, to be dissolved in 200ml ethanol by gained intermediate product thus, reflux 1 hour, be cooled to 35 DEG C, add 100ml ether, crystallize out, suction filtration, dry, gained intermediate product is thus joined in 150ml water and is dissolved with in sodium bicarbonate aqueous solution that 2.75g sodium bicarbonate formed, crystallize out, suction filtration, obtain product 5-pyrrolidyl-2-nitrosophenol, productive rate 88%;
B.5-the synthesis of morpholinyl-2-nitrosophenol
I.3-the synthesis of morpholinyl phenol
By 0.01mol Metha Amino Phenon and 0.01mol Na
2cO
320ml ethanol solution, put into 100ml there-necked flask, drip the ethanolic soln of the 20ml of 0.012mol dibromo ether, reflux 8 hours, the reaction solution obtained thus is poured in frozen water, separate out white precipitate, filter to obtain product morpholinyl phenol, productive rate is 86%.
The synthesis of II.5-morpholinyl-2-nitrosophenol
By 0.1mol by above-mentioned I walk obtained morpholinyl phenol be dissolved into 35ml mass percent concentration be 30% hydrochloric acid and 30ml water in, be cooled to 0 ~ 5 DEG C, then drip 0.1mol NaNO
2be dissolved in NaNO obtained in 50ml water
2the aqueous solution, stirs half an hour at 0 ~ 5 DEG C, suction filtration, to be dissolved in 200ml ethanol by gained intermediate product thus, reflux 1 hour, is cooled to 35 DEG C, adds in 100ml ether, separate out solid, suction filtration, joins gained intermediate product thus in 150ml water and is dissolved with in sodium bicarbonate aqueous solution that 2.75g sodium bicarbonate formed, suction filtration, obtain 5-morpholinyl-2-nitrosophenol, productive rate is 80%.
3rd step, nitrogen heterocyclic replaces the synthesis of benzo spirooxazine photochromic compound
In 100ml round-bottomed flask, under nitrogen protection condition, the nitrogen heterocyclic obtained by above-mentioned second step by 0.01mol replaces-2-nitrosophenol and is dissolved in 20ml dehydrated alcohol, drips the R that 0.012mol is obtained by the above-mentioned the first step
1replace-1,3,3-trimethylammonium-2-methylene radical indoline is dissolved in the solution that 20ml dehydrated alcohol is formed, reflux 6 ~ 10 hours, and TLC monitors, after having reacted, through distillation and concentration, be sherwood oil by volume ratio: ethyl acetate=3 ~ 7: the sherwood oil of 1 and ethyl acetate as eluent, use column chromatography, the above-mentioned nitrogen heterocyclic of obtained final product replaces benzo spirooxazine photochromic compound, and productive rate is 27 ~ 33%.
Above-mentioned nitrogen heterocyclic replaces the preparation method of benzo spirooxazine photochromic compound, and wherein the amount of reactant used expands by equal proportion or reduces obtained coming to the same thing.
Above-mentioned nitrogen heterocyclic replaces the preparation method of benzo spirooxazine photochromic compound, and raw material wherein used and solvent are all by commercially available.
Above-mentioned nitrogen heterocyclic replaces the preparation method of benzo spirooxazine photochromic compound, and the apparatus adopted and operating procedure are all known by those skilled in the art.
The invention has the beneficial effects as follows:
Azepine of the present invention cyclosubstituted benzo spirooxazine photochromic compound is the same with naphtho-spiral shell oxazine compounds or quino-spiral shell oxazine compounds, can be used for optical storage material, photochromic computer, pretends hidden material, protection and the high-technology field such as finishing material.The feature that azepine of the present invention cyclosubstituted benzo spirooxazine photochromic material has that lovely luster, variable color and colour killing speed are all fast, majority is bright-coloured redness, preparation method is fairly simple and have wide range of applications, for providing a kind of novel material in above-mentioned high-technology field.The preparation method of azepine of the present invention cyclosubstituted benzo spirooxazine photochromic compound has the advantage that synthesis technique is simple, raw material is easy to get, cost is low and productive rate is higher.
In the prior art that relevant photochromic compound has been reported, seldom see that nitrogen heterocyclic replaces the report, particularly Pyrrolidine ring of benzo spirooxazine photochromic compound and synthetic method thereof, morpholine ring not yet finds relevant information reports.
Embodiment
Embodiment 1
1,3,3-trimethylammonium-6 ' [the preparation of Isosorbide-5-Nitrae] oxazine of-pyrrolidyl spiral shell indoline-2,3 '-[3H] benzo [2,1-b].
The first step, the synthesis of 1,3,3-trimethylammonium 2-methylene radical indoline
I. the synthesis of hydrazinobenzene hydrochloride salt
In 250ml there-necked flask, add 0.1mol aniline and 1. 125ml mass percent concentration be the hydrochloric acid of 30%, stir, be cooled to 0 DEG C, drip 0.12mol NaNO
2be dissolved in NaNO obtained in 60ml water
2the aqueous solution, drips off maintenance 0 DEG C reaction 2 hours, obtains phenyldiazonium salts solution, then under the condition passing into nitrogen, above-mentioned phenyldiazonium salts solution is joined 2. 90gSnCl
23. 200ml mass percent concentration is in the mixed solution of the hydrochloric acid of 30%, and keep 0 DEG C to react 1 hour, obtain hydrazinobenzene hydrochloride salt solid, productive rate is 92%.
The synthesis of II.2,3,3-tri-methyl indole
In 500ml there-necked flask, add 0.2mol and walk obtained hydrazinobenzene hydrochloride salt and 300ml Glacial acetic acid by above-mentioned I, after heating for dissolving, add 44ml methyl isopropyl Ketone, reflux 8 hours, distillation, except desolventizing, adds saturated sodium bicarbonate aqueous solution, regulate pH to 7, with chloroform extraction, use anhydrous MgSO
4drying, through distillation, removing chloroform, obtain product 2,3,3-tri-methyl indole, productive rate is 62%.
The synthesis of III.1,3,3-trimethylammonium-2-methylene radical indoline
Under nitrogen protection condition; in 100ml flask, add 0.025mol walk obtain 2 by above-mentioned II; 3,3-tri-methyl indole and 1. 0.03mol methyl iodide are dissolved in the solution formed in 30ml chloroform, reflux 3 hours; adularescent solid is separated out; add 2. 0.04mol triethylamine again, continue backflow 1 hour, cooling; wash with water, use anhydrous MgSO
4drying, boils off solvent, and obtain product 1,3,3-trimethylammonium-2-methylene radical indoline, productive rate is 82%.
Second step, the synthesis of 5-pyrrolidyl-2-nitrosophenol
I.3-the synthesis of pyrrolidyl phenol
By the 20ml ethanol solution of 0.01mol Metha Amino Phenon and 0.01mol sodium carbonate, put into 100ml there-necked flask, drip 0.012mol 1, the 20ml ethanolic soln of 4-dibromobutane, refluxes 8 hours, pours in frozen water by the reaction solution obtained thus, separate out white precipitate, filter, obtain product 3-pyrrolidyl phenol, productive rate is 90%.
The synthesis of II.5-pyrrolidyl-2-nitrosophenol
By walked by above-mentioned I obtained 0.1mol 3-pyrrolidyl phenol be dissolved into 35ml mass percent concentration be 30% hydrochloric acid and 20ml water in, be cooled to 0 DEG C, then drip 0.1mol NaNO
2be dissolved in the aqueous solution obtained in 50ml water, stir half an hour at 0 DEG C, suction filtration, to be dissolved in 200ml ethanol by gained intermediate product thus, reflux 1 hour, be cooled to 35 DEG C, add 100ml ether, crystallize out, suction filtration, dry, gained intermediate product is thus joined in 150ml water and is dissolved with in sodium bicarbonate aqueous solution that 2.75g sodium bicarbonate formed, crystallize out, suction filtration, obtain product 5-pyrrolidyl-2-nitrosophenol, productive rate is 88%.
3rd step, 1,3,3-trimethylammonium-6 ' [the preparation of Isosorbide-5-Nitrae] oxazine of-pyrrolidyl spiral shell indoline-2,3 '-[3H] benzo [2,1-b]
In 100ml round-bottomed flask, under the condition of nitrogen protection, 5-pyrrolidyl-2-the nitrosophenol obtained by above-mentioned second step by 0.01mol is dissolved in 20ml dehydrated alcohol, drip 0.012mol obtained by the above-mentioned the first step 1, 3, 3-trimethylammonium 2-methylene radical indoline is dissolved in the solution that 20ml dehydrated alcohol is formed, reflux 6 hours, TLC monitors, after having reacted, through distillation and concentration, be sherwood oil by volume ratio: ethyl acetate=7: the sherwood oil of 1 and ethyl acetate as eluent carry out silica gel column chromatography, obtained final product 1, 3, 3-trimethylammonium-6 '-pyrrolidyl spiral shell indoline-2, 3 '-[3H] benzo [2, 1-b] [1, 4] oxazines, productive rate is 29%.This obtained compound obtains after tested: m.p117-118 DEG C,
1HNMR(400MHz，CDCl
3)：δ＝7.37(s，1H)，7.23(d，J＝7.6Hz，1H)，7.08(s，1H)，6.88(d，J＝7.2Hz，1H)，6.58(s，1H)，6.15(s，1H)，5.96(s，1H)，3.26(s，4H)，2.77(s，3H)，1.99(s，4H)，1.36(s，3H)，1.30(s，3H)
MS(ES1)m/z：348.2[M+H]
+。
Embodiment 2
1,3,3,5-tetramethyl--6 ' [the preparation of Isosorbide-5-Nitrae] oxazine of-pyrrolidyl spiral shell indoline-2,3 '-[3H] benzo [2,1-b].
The first step, the synthesis of 1,3,3,5-tetramethyl-2-methylene radical indoline
I. to the synthesis of tolylhydrazine hydrochloride
In 250ml there-necked flask, add 0.1mol open-chain crown ether, add the hydrochloric acid that 125ml mass percent concentration is 30%, stir and be cooled to 2 DEG C, drip 0.12mol NaNO
2be dissolved in NaNO obtained in 60ml water
2the aqueous solution, drips off maintenance 2 DEG C reaction 2 hours, obtains p-methylphenyl diazonium salt solution, then under the condition passing into nitrogen, above-mentioned p-methylphenyl diazonium salt solution is joined 90g SnCl
2be in the mixed solution of the hydrochloric acid of 30% with 200ml mass percent concentration, keep 2 DEG C to react 1 hour, obtain hydrazinobenzoic acid hydrochloride solid, productive rate is 90%.
The synthesis of II.2,3,3,5-tetramethyl-indoles
In 500ml there-necked flask, adding 0.2mol is walked obtained to hydrazinobenzoic acid hydrochloride and 300ml Glacial acetic acid by above-mentioned I, after heating is all dissolved, add 44ml methyl isopropyl Ketone, reflux 8 hours, distillation is except desolventizing, add saturated sodium bicarbonate aqueous solution, regulate pH to 7, with chloroform extraction, anhydrous MgSO
4drying, through distillation, removing chloroform, obtains product 2,3,3,5-tetramethyl-indoles, productive rate 60%.
The synthesis of III.1,3,3,5-tetramethyl-2-methylene radical indoline
Under the condition of nitrogen protection; in 100ml flask, add 0.025mol walk obtain 2,3,3 by above-mentioned II; 5-tetramethyl-indoles and 0.03mol methyl iodide are dissolved in the solution formed in 30ml chloroform; reflux 3 hours, adularescent solid is separated out, then adds 0.04mol triethylamine; continue backflow 1 hour; cooling, washes with water, uses anhydrous MgSO
4drying, boils off solvent, obtains product l, and 3,3-trimethylammonium-2-methylene radical indoline, productive rate is 80%.
Second step, the synthesis of 5-pyrrolidyl-2-nitrosophenol
Except being stir except half an hour at 2 DEG C in the operation of II step wherein, other are all with the second step of embodiment 1, and obtain product 5-pyrrolidyl-2-nitrosophenol, productive rate is 88%.
3rd step, 1,3,3,5-tetramethyl--6 ' [the preparation of Isosorbide-5-Nitrae] oxazine of-pyrrolidyl spiral shell indoline-2,3 '-[3H] benzo [2,1-b]
In 100ml round-bottomed flask, under the condition of nitrogen protection, 5-pyrrolidyl-2-the nitrosophenol obtained by above-mentioned second step by 0.01mol is dissolved in 20ml dehydrated alcohol, drip 0.012mol obtained by the above-mentioned the first step 1, 3, 3, 5-tetramethyl-2-methylene radical indoline be dissolved in the solution formed in 20ml dehydrated alcohol, reflux 8 hours, TLC monitors, after having reacted, through distillation and concentration, be sherwood oil by volume ratio: ethyl acetate=6: the sherwood oil of 1 and ethyl acetate as eluent carry out silica gel column chromatography, obtained final product 1, 3, 3, 5-tetramethyl--6 '-pyrrolidyl spiral shell indoline-2, 3 '-[3H] benzo [2, 1-b] [1, 4] oxazines, productive rate is 36%.This obtained compound obtains after tested: mp.104-106 DEG C,
1HNMR(400MHz CDCl
3)：δ＝7.38(d，J＝2.0Hz，1H)，7.24(d，J＝8.5Hz，1H)，7.01(d，J＝7.9Hz，1H)，6.91(s，1H)，6.49(d，J＝7.9Hz，1H)，6.15(d，J＝8.6Hz，1H)，5.98(s，1H)，3.25(m，4H)，2.75(s，3H)，2.34(s，3H)，1.98(m，4H)，1.36(s，3H)，1.31(s，3H)
MS(ES1)m/z：362[M+H]
+。
Embodiment 3
[the preparation of 2,1-b] oxazine of 1,3,3-trimethylammonium-5-chloro-6 '-pyrrolidyl spiral shell indoline-2,3 '-[3H] benzo.
The first step, the synthesis of 1,3,3-trimethylammonium-5 chlorine methylene radical indoline
I. the synthesis of p-chlorophenylhydxazine hydrochloride
In 250ml there-necked flask, add 0.1mol p-Chlorobenzoic acid amide, add the hydrochloric acid that 125ml mass percent concentration is 30%, stir and be cooled to 5 DEG C, drip 0.12mol NaNO
2be dissolved in NaNO obtained in 60ml water
2the aqueous solution, drips off maintenance 5 DEG C reaction 2 hours, obtains rubigan diazonium salt solution, then under the condition passing into nitrogen, above-mentioned rubigan diazonium salt solution is joined 90g SnCl
2be in the mixed solution of the hydrochloric acid of 30% with 200ml mass percent concentration, keep 5 DEG C to react 1 hour, obtain p-hydrochloride solid, productive rate is 88%.
The synthesis of II.2,3,3-trimethylammonium-5 chloro-indole
In 500ml there-necked flask, add 0.2mol and walk obtained p-hydrochloride and 300ml Glacial acetic acid by above-mentioned I, after heating is all dissolved, add 44ml methyl isopropyl Ketone, reflux 8 hours, distillation is except desolventizing, add saturated sodium bicarbonate aqueous solution, regulate PH to 7, with chloroform extraction, anhydrous MgSO
4drying, through distillation, removing chloroform, obtain product 2,3,3-trimethylammonium-5-chloro-indole, productive rate is 58%.
The synthesis of III.1,3,3-trimethylammonium 5-chlorine methylene radical indoline
Under the condition of nitrogen protection; in 100ml flask, add 0.025mol and walk obtain 2,3 by above-mentioned II; 3-trimethylammonium-5-chloro-indole and 0.03mol methyl iodide are dissolved in the solution formed in 30ml chloroform; reflux 3 hours, adularescent solid is separated out, then adds 0.04mol triethylamine; continue backflow 1 hour; cooling, washes with water, uses anhydrous MgSO
4drying, boils off solvent, and obtain product 1,3,3-trimethylammonium 5-chlorine methylene radical indoline, productive rate is 76%.
Second step, the synthesis of 5-pyrrolidyl-2-nitrosophenol
Except being stir except half an hour at 5 DEG C in the operation of II step wherein, other are all with the second step of embodiment 1, and obtain product 5-pyrrolidyl-2-nitrosophenol, productive rate is 88%.
3rd step, [the preparation of Isosorbide-5-Nitrae] oxazine of 1,3,3-trimethylammonium-5-chloro-6 '-pyrrolidyl spiral shell indoline-2,3 '-[3H] benzo [2,1-b]
In 100ml round-bottomed flask, under the condition of nitrogen protection, 5-pyrrolidyl-2-the nitrosophenol obtained by above-mentioned second step by 0.01mol is dissolved in 20ml dehydrated alcohol, drip 0.012mol obtained by the above-mentioned the first step 1, 3, 3-trimethylammonium-5-chlorine methylene radical indoline be dissolved in the solution formed in 20ml dehydrated alcohol, reflux 9 hours, TLC monitors, after having reacted, through distillation and concentration, be sherwood oil by volume ratio: ethyl acetate=5: the sherwood oil of 1 and ethyl acetate as eluent carry out silica gel column chromatography, obtained final product 1, 3, 3-trimethylammonium-5-chloro-6 '-pyrrolidyl spiral shell indoline-2, 3 '-[3H] benzo [2, 1-b] [1, 4] oxazines, productive rate is 29%.
This obtained compound obtains after tested: m.p138-139 DEG C,
1HNMR(400MHz CDCl
3)：δ＝7.33(s，1H)，7.22(d，J＝8.5Hz，1H)，7.13(dd，J＝8.2，16HE，1H)，7.00(s，1H)，6.46(d，J＝8.2Hz，1H)，6.14(dd，J＝8.6，2.1HE，1H)，5.94(d，J＝1.94Hz，1H)，3.24(t，J＝6.3Hz，4H)，2.74(s，1H)，1.97(t，J＝6.3Hz，4H)，1.33(s，3H)，1.29(s，3H)
MS(ES1)m/z：382[M+H]
+。
Embodiment 4
1,3,3-trimethylammonium-6 ' [the preparation of Isosorbide-5-Nitrae] oxazine of-morpholinyl spiral shell indoline-2,3 '-[3H] benzo [2,1-b].
The first step, the synthesis of 1,3,3-trimethylammonium-2-methylene radical indoline
With the first step of embodiment 1, obtain product 1,3,3-trimethylammonium-2-methylene radical indoline, productive rate is 82%.
Second step, the synthesis of 5-morpholinyl-2-nitrosophenol
I.3-the synthesis of morpholinyl phenol
By 0.01mol Metha Amino Phenon and 0.01mol Na
2cO
320ml ethanol solution, put into 100ml there-necked flask, drip the ethanolic soln of the 20ml of 0.012mol dibromo ether, reflux 8 hours, the reaction solution obtained thus is poured in frozen water, separate out white precipitate, filter to obtain product morpholinyl phenol, productive rate is 86%.
The synthesis of II.5-morpholinyl-2-nitrosophenol
By 0.1mol by above-mentioned I walk obtained morpholinyl phenol be dissolved into 35ml mass percent concentration be 30% hydrochloric acid and 30ml water in, be cooled to 0 DEG C, then drip 0.1mol NaNO
2be dissolved in the aqueous solution obtained in 50ml water, stir half an hour at 0 DEG C, suction filtration, to be dissolved in 200ml ethanol by gained intermediate product thus, reflux 1 hour, is cooled to 35 DEG C, adds in 100ml ether, separate out solid, suction filtration, joins gained intermediate product thus in 150ml water and is dissolved with in sodium bicarbonate aqueous solution that 2.75g sodium bicarbonate formed, suction filtration, obtain product 5-morpholinyl-2-nitrosophenol, productive rate is 80%.
3rd step, 1,3,3-trimethylammonium-6 ' [the preparation of Isosorbide-5-Nitrae] oxazine of-morpholinyl spiral shell indoline-2,3 '-[3H] benzo [2,1-b]
In 100ml round-bottomed flask, under the condition of nitrogen protection, 5-morpholinyl-2-the nitrosophenol obtained by above-mentioned second step by 0.01mol is dissolved in 20ml dehydrated alcohol, drip 0.012mol obtained by the above-mentioned the first step 1, 3, 3-trimethylammonium 2-methylene radical indoline be dissolved in the solution formed in 20ml dehydrated alcohol, reflux 7 hours, TLC monitors, after having reacted, through distillation and concentration, silica gel column chromatography is carried out with the sherwood oil of volume ratio 3: 1 and ethyl acetate as eluent, obtained final product 1, 3, 3-trimethylammonium-6 '-morpholinyl spiral shell indoline-2, 3 '-[3H] benzo [2, 1-b] [1, 4] oxazines, productive rate is 27%.
This obtained compound obtains after tested: m.p149-151 DEG C,
1HNMR(400MHz CDCl
3)：δ＝7.50(s，1H)，7.31(d，J＝8.1Hz，1H)，7.20(t，J＝7.7Hz，1H)，7.07(d，J＝6.7Hz，1H)，6.88(t，J＝7.5HE，1H)，6.56(d，J＝8.3Hz，1H)，6.48(s，1H)，6.35(s，1H)，3.84(t，4H)，3.16(t，4H)，2.75(s，3H)，1.32(d，J＝13.9Hz，6H)
MS(ES1)m/z：364.1[M+H]
+。
Embodiment 5
1,3,3,5-tetramethyl--6 ' [the preparation of Isosorbide-5-Nitrae] oxazine of-morpholinyl spiral shell indoline-2,3 '-[3H] benzo [2,1-b].
The first step, the synthesis of 1,3,3,5-tetramethyl-2-methylene radical indoline
With the first step of embodiment 2, obtain product 1,3,3-trimethylammonium-2-methylene radical indoline, productive rate is 80%;
Second step, the synthesis of 5-morpholinyl-2-nitrosophenol
Except wherein II step operation in be cooled to 2 DEG C and 2 DEG C stir half an hour, other are all with the second step of embodiment 4, and obtain product 5-morpholinyl-2-nitrosophenol, productive rate is 80%;
3rd step, 1,3,3,5-tetramethyl--6 ' [the preparation of Isosorbide-5-Nitrae] oxazine of-morpholinyl spiral shell indoline-2,3 '-[3H] benzo [2,1-b]
In 100ml round-bottomed flask, under the condition of nitrogen protection, 5-morpholinyl-2-the nitrosophenol obtained by above-mentioned second step by 0.01mol is dissolved in 20ml dehydrated alcohol, drip 0.012mol by above-mentioned the-step obtained 1, 3, 3, the vlil that being dissolved in of 5-tetramethyl-2-methylene radical indoline is formed in 20ml dehydrated alcohol 8 hours, TLC monitors, after having reacted, through distillation and concentration, be sherwood oil by volume ratio: ethyl acetate=6: the sherwood oil of 1 and ethyl acetate as eluent carry out silica gel column chromatography, obtained final product 1, 3, 3, 5-tetramethyl--6 '-morpholinyl spiral shell indoline-2, 3 '-[3H] benzo [2, 1-b] [1, 4] oxazines, productive rate is 33%.
This obtained compound obtains after measured: m.p.159-161 DEG C,
1HNMR(400MHz CDCl
3)：δ＝7.51(s，1H)，7.31(s，1H)，7.03(d，J＝7.7Hz，1H)，6.92(s，1H)，6.50(d，J＝3.0Hz，1H)，6.48(d，J＝4.0Hz，1H)，6.33(d，J＝2.6Hz，1H)，3.87(m，3H)，3.22(m，3H)，2.75(s，3H)，1.36(s，3H)，1.33(s，3H)
MS(ESI)m/z：377[M+H]
+。
Embodiment 6
[the preparation of 2,1-b] oxazine of 1,3,3-trimethylammonium-5-chloro-6 '-morpholinyl spiral shell indoline-2,3 '-[3H] benzo.
The first step, the synthesis of 1,3,3-trimethylammonium-5-chlorine methylene radical indoline
With the first step of embodiment 3, obtain product 1,3,3-trimethylammonium 5-chlorine methylene radical indoline, productive rate is 76%.
Second step, the synthesis of 5-morpholinyl-2-nitrosophenol
Except wherein II step operation in be cooled to 5 DEG C and 5 DEG C stir half an hour, other are all with the second step of embodiment 4, and obtain product 5-morpholinyl-2-nitrosophenol, productive rate is 80%;
3rd step, [the preparation of 2,1-b] oxazine of 1,3,3-trimethylammonium-5-chloro-6 '-morpholinyl spiral shell indoline-2,3 '-[3H] benzo
In 100ml round-bottomed flask, under the condition of nitrogen protection, 5-morpholinyl-2-the nitrosophenol obtained by above-mentioned second step by 0.01mol is dissolved in the dehydrated alcohol of 20ml, drip 0.012mol obtained by the above-mentioned the first step 1, 3, the chloro-methylene radical indoline of 3-trimethylammonium-5-be dissolved in the solution formed in 20ml dehydrated alcohol, reflux 10 hours, TLC monitors, after having reacted, through distillation and concentration, be sherwood oil by volume ratio: ethyl acetate=4: the sherwood oil of 1 and ethyl acetate as eluent carry out silica gel column chromatography, obtained final product 1, 3, 3-trimethylammonium-5-chloro-6 '-morpholinyl spiral shell indoline-2, 3 '-[3H] benzo [2, 1-b] oxazine, productive rate is 27%.This obtained compound obtains after tested: m.p.158 ~ 159 DEG C,
1HNMR(400MHz CDCl
3)：δ＝7.46(s，1H)，7.29(d，J＝8.7Hz，1H)，7.15(dd，J＝8.2，1.9Hz，1H)，7.02(s，1H)，6.50(d，J＝8.6Hz，1H)，6.46(d，J＝8.2Hz，1H)，6.31(s，1H)，3.91(m，4H)，3.20(m，4H)，2.73(s，3H)，1.31(s，3H)，1.30(s，3H)，
MS(ESI)m/z：398[M+H]
+。
In above-mentioned all embodiments, used raw material reaction thing and solvent are all by commercially available.
In above-mentioned all embodiments, the apparatus adopted and operating procedure are all known by those skilled in the art.
Claims (1)
1. nitrogen heterocyclic replaces the preparation method of benzo spirooxazine photochromic compound, it is characterized in that step is as follows:
The first step, R
1replace the synthesis of-1,3,3-trimethylammonium 2-methylene radical indoline
In above formula, R
1=H, CH
3or Cl,
I.R
1the synthesis of substituted phenylhydrazines hydrochloride
In 250ml there-necked flask, add R shown in 0.1mol above formula
1substituted aniline and 1. 125ml mass percent concentration are the hydrochloric acid of 30%, stir, are cooled to 0 ~ 5 DEG C, drip 0.12mol NaNO
2be dissolved in NaNO obtained in 60ml water
2the aqueous solution, drips off rear maintenance 0 ~ 5 DEG C reaction 2 hours, obtains R
1substituted-phenyl diazonium salt solution, then under the condition passing into nitrogen, by this R
1substituted-phenyl diazonium salt solution joins 2. 90gSnCl
23. 200ml mass percent concentration is in the mixed solution of the hydrochloric acid of 30%, keeps 0 ~ 5 DEG C to react 1 hour, obtains R
1substituted phenylhydrazines HCl, solid, productive rate is 88 ~ 92%;
II.R
1replace the synthesis of-2,3,3-tri-methyl indole
In 500ml there-necked flask, add 0.2mol and walk obtained R by above-mentioned I
1substituted phenylhydrazines hydrochloride and 300ml Glacial acetic acid, after heating for dissolving, add 44ml methyl isopropyl Ketone, refluxes 8 hours, and distillation, except desolventizing, adds saturated sodium bicarbonate aqueous solution, regulates pH to 7, with chloroform extraction, use anhydrous MgSO
4drying, through distillation, removing chloroform, obtains product R
1replace 2,3,3-tri-methyl indole, productive rate is 58 ~ 62%;
III.R
1replace the synthesis of-1,3,3-trimethylammonium-2-methylene radical indoline
Under nitrogen protection condition, in 100ml flask, add 0.025mol walk obtained R by above-mentioned II
1replacement-2,3,3-tri-methyl indole and 1. 0.03mol methyl iodide are dissolved in the solution formed in 30ml chloroform, reflux 3 hours, and adularescent solid is separated out, then adds 2. 0.04mol triethylamine, continue backflow 1 hour, and cooling, washes with water, use anhydrous MgSO
4drying, boils off solvent, obtains product R
1replace-1,3,3-trimethylammonium-2-methylene radical indoline, productive rate is 76 ~ 82%;
Second step, nitrogen heterocyclic R
2replace the synthesis of-2-nitrosophenol
Above-mentioned R
2=5-pyrrolidyl or above-mentioned R
2=5-morpholinyl,
A.5-the synthesis of pyrrolidyl-2-nitrosophenol
I.3-the synthesis of pyrrolidyl phenol
By the 20ml ethanol solution of 0.01mol Metha Amino Phenon and 0.01mol sodium carbonate, put into 100ml there-necked flask, drip 0.012mol 1, the 20ml ethanolic soln of 4-dibromobutane, refluxes 8 hours, pours in frozen water by the reaction solution obtained thus, separate out white precipitate, filter, obtain product 3-pyrrolidyl phenol, productive rate is 90%;
The synthesis of II.5-pyrrolidyl-2-nitrosophenol
By walked by above-mentioned I obtained 0.1mol 3-pyrrolidyl phenol be dissolved into 35ml mass percent concentration be 30% hydrochloric acid and 20ml water in, be cooled to 0 DEG C, then drip 0.1mol NaNO
2be dissolved in NaNO obtained in 50ml water
2the aqueous solution, stirs half an hour at 0 ~ 5 DEG C, suction filtration, to be dissolved in 200ml ethanol by gained intermediate product thus, reflux 1 hour, be cooled to 35 DEG C, add 100ml ether, crystallize out, suction filtration, dry, gained intermediate product is thus joined in 150ml water and is dissolved with in sodium bicarbonate aqueous solution that 2.75g sodium bicarbonate formed, crystallize out, suction filtration, obtain product 5-pyrrolidyl-2-nitrosophenol, productive rate 88%;
B.5-the synthesis of morpholinyl-2-nitrosophenol
I.3-the synthesis of morpholinyl phenol
By 0.01mol Metha Amino Phenon and 0.01mol Na
2cO
320ml ethanol solution, put into 100ml there-necked flask, drip the ethanolic soln of the 20ml of 0.012mol dibromo ether, reflux 8 hours, the reaction solution obtained thus is poured in frozen water, separate out white precipitate, filter to obtain product morpholinyl phenol, productive rate is 86%;
The synthesis of II.5-morpholinyl-2-nitrosophenol
By 0.1mol by above-mentioned I walk obtained morpholinyl phenol be dissolved into 35ml mass percent concentration be 30% hydrochloric acid and 30ml water in, be cooled to 0 ~ 5 DEG C, then drip 0.1mol NaNO
2be dissolved in NaNO obtained in 50ml water
2the aqueous solution, stirs half an hour at 0 ~ 5 DEG C, suction filtration, to be dissolved in 200ml ethanol by gained intermediate product thus, reflux 1 hour, is cooled to 35 DEG C, adds in 100ml ether, separate out solid, suction filtration, joins gained intermediate product thus in 150ml water and is dissolved with in sodium bicarbonate aqueous solution that 2.75g sodium bicarbonate formed, suction filtration, obtain 5-morpholinyl-2-nitrosophenol, productive rate is 80%;
3rd step, nitrogen heterocyclic replaces the synthesis of benzo spirooxazine photochromic compound
In 100ml round-bottomed flask, under nitrogen protection condition, the nitrogen heterocyclic obtained by above-mentioned second step by 0.01mol replaces-2-nitrosophenol and is dissolved in 20ml dehydrated alcohol, drips the R that 0.012mol is obtained by the above-mentioned the first step
1replace-1,3,3-trimethylammonium-2-methylene radical indoline is dissolved in the solution that 20ml dehydrated alcohol is formed, reflux 6 ~ 10 hours, and TLC monitors, after having reacted, through distillation and concentration, be sherwood oil by volume ratio: ethyl acetate=3 ~ 7: the sherwood oil of 1 and ethyl acetate as eluent, use column chromatography, obtained final product nitrogen heterocyclic replaces benzo spirooxazine photochromic compound, and its chemical structure of general formula is as follows:
In formula:
R
1=H, CH
3or Cl,
R
2＝
Productive rate is 27 ~ 33%,
Above-mentioned nitrogen heterocyclic replaces the preparation method of benzo spirooxazine photochromic compound, and wherein the amount of reactant used expands by equal proportion or reduces obtained coming to the same thing.
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| JPH03107839A (en) * | 1989-09-22 | 1991-05-08 | Hitachi Ltd | Organic compound having perfluoroalkyl group and monomolecular film formed by using the same and application thereof |
| JPH04117385A (en) * | 1990-09-04 | 1992-04-17 | Citizen Watch Co Ltd | Photochromic compound |
| JP2001051369A (en) * | 1999-08-16 | 2001-02-23 | Minolta Co Ltd | Image forming method |
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| US4816584A (en) * | 1986-11-12 | 1989-03-28 | Ppg Industries, Inc. | Photochromic spiro(indoline)benzoxazines |
| US4936995A (en) * | 1988-05-17 | 1990-06-26 | Ppg Industries, Inc. | Photochromic compound and articles containing the same |
| JP3175161B2 (en) * | 1990-09-27 | 2001-06-11 | 東レ株式会社 | Photochromic material |
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