CN102633708A - Synthesizing and purifying method of midbody 9-(2-ethoxy) carbazole - Google Patents
Synthesizing and purifying method of midbody 9-(2-ethoxy) carbazole Download PDFInfo
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Abstract
The invention relates to a preparing and purifying method of midbody 9-(2-ethoxy) carbazole, comprising the following steps of: carrying out a reaction on carbazole and halogenated ethanol as raw materials under the effect of a phase transfer catalyst, stopping reacting when the reaction is carried out to a certain degree, selecting solvent, adequately using the solubility difference between the raw material carbazole and the 9-(2-ethoxy) carbazole, selecting the proper solvent to separate the carbazole from the midbody 9-(2-ethoxy) carbazole by means of dissolving and filtering, and simply recrystallizing, so that a product with required purity can be obtained, and the unreacted raw material carbazole can be recovered. The method is good in selectivity, high in product purity, wide in raw material source, low in price, and simple, reasonable and feasible in technology.
Description
Technical field
The invention belongs to resource and pharmaceutical chemistry technical field, particularly relate to the synthetic and purification process of a kind of midbody 9-(2-hydroxyethyl) carbazole.
Background technology
Carbazole and verivate thereof are one type of important nitrogenous heteroaromatic compounds; Intramolecularly contains bigger conjugated system; Strong intramolecularly transfer transport takes place easily, its special rigidity condensed ring structure in addition, this all makes carbazole compound show many particular performances and biological activity; Has a widespread use in that photovaltaic material, dyestuff, Supramolecular Recognition etc. are multi-field, especially with 9-(2-hydroxyethyl) carbazole typical case the most.Simultaneously, 9-(2-hydroxyethyl) carbazole also is a very important medicine intermediate, and market demand is huge, and good market outlook are arranged.
Up to the present, the method that is used to produce 9-(2-hydroxyethyl) carbazole is a lot, all is to be raw material with the carbazole, with glycol chlorohydrin, bromoethanol, oxyethane or ethylene carbonate as hydroxyethylation reagent.Because two the phenyl ring conjugation of N atom lone-pair electron and next door on the carbazole, the cloud density on the N atom reduces, and activity reduces, and it is extremely low to cause N to go up H acidity, all is to use highly basic to carry out catalysis to peel off hydrogen when carrying out the N-hydroxyethylation.Wherein maximum as the hydroxyethylated research of N-that hydroxyethylation reagent carries out carbazole with ethylene carbonate.Usually with sodium hydroxide or Pottasium Hydroxide as catalyzer (
J. Phys. Chem., 1993,
97: 11164 – 11167;
J. Phys. Chem., 1995,
99: 16047 – 16051), but because carbazole N goes up a little less than the Wasserstoffatoms acidity, and the alkalescence of sodium hydroxide and Pottasium Hydroxide is not enough strong, so when reacting, high temperature that need be more than 100 ℃; For solubleness and the reactive behavior that increases carbazole, all adopt high boiling non-protonic solvent DMF usually, and DMF decomposes easily under highly basic and high temperature, cause solvent to be difficult to reclaim, increased production cost.If the alkali in will reacting replaces the stronger sodium hydride of alkalescence of equivalent, can peel off the H on the N, thereby can reduce temperature of reaction and can use more lower boiling solvent, the convenient recovery (
J. Mol. Liq,2003,105:185-190).But in actually operating, find that this kind method productive rate is still lower, explain that sodium hydride is still limited for the stripping ability that carbazole N goes up the H atom.Also have the certain methods method be when carrying out hydroxyethylation with oxyethane (
Chem. Mater.,1995,7:1237-1242;
Macromolecules, 1997,
30: 7821 – 7827;
Polymer, 2001,42:1101-1107), because reacting ethylene oxide is active high, so yield is better, and raw materials cost is low.But oxyethane is gaseous matter, and blast easily, and this has just caused the production unit higher requirement has been increased production cost greatly.Use in addition in addition glycol chlorohydrin (
Macromol.,1996,
29:4613-4618), bromoethanol (
Synthetic Metals,2009,159:1512 – 1516) report all need make alkali with sodium hydride, and reaction yield is all very low; For promoting reaction to carry out, also use microwave method (J. Mol. Liq., 2003,105:185 – 190), but also not too big improvement.
In addition, current all 9-(2-hydroxyethyl) carbazole preparation method also has a very big shortcoming, and that is exactly the problem that product generation cascade reaction causes.Because it is extremely low that carbazole N goes up H acidity; The activity of the alcoholic extract hydroxyl group of 9-(2-hydroxyethyl) carbazole that generates is close with it; Therefore the easy and upward H competition of raw material carbazole N of the H of hydroxyl in product 9-(2-hydroxyethyl) carbazole; With hydroxyethylation reagent a series of cascade reactions taking place, generates a large amount of 9-(2-hydroxyethyl) carbazole derivative
Reaction equation:
The product by product
The reason that side reaction takes place:
These impurity all are product 9-(2-hydroxyethyl) carbazole analogues; Difference only is that the substituted number of oxyethyl group is different, so they are approaching with 9-(2-hydroxyethyl) carbazole character, very difficult separation and purification; Literature method often needs repeatedly recrystallization or column chromatography to carry out purifying for obtaining pure article; Thereby make productive rate very low, complex operation does not have the value of mass preparation.Therefore the preparation method who needs exploitation simple and high-efficient 9-(2-hydroxyethyl) carbazole.
Summary of the invention
Technical problem to be solved by this invention is to provide to above-mentioned prior art the synthetic and purification process of a kind of midbody 9-(2-hydroxyethyl) carbazole; Its selectivity is good, yield improves, easy and simple to handle, cost is low, has reduced the generation of cascade reaction side reaction to greatest extent.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: the synthetic and purification process of a kind of midbody 9-(2-hydroxyethyl) carbazole is characterized in that including following steps:
1) preparation of 9-(2-hydroxyethyl) carbazole bullion
Carbazole is dissolved in the solvent orange 2 A that mass volume ratio is 1:8-30; Add mineral alkali, ethylene halohydrin, phase-transfer catalyst and inorganic iodine then for thing; Be heated to 40-100 ℃ of reaction under the vigorous stirring, reaction removes by filter insolubles after accomplishing; Removal of solvent under reduced pressure obtains white solid 9-(2-hydroxyethyl) carbazole bullion;
Wherein the quality of mineral alkali be the carbazole quality 0.2-1 doubly, the quality of ethylene halohydrin be the carbazole quality 0.5-5 doubly, the quality of phase-transfer catalyst be the carbazole quality 0.01-0.1 doubly, inorganic iodine for the quality of thing be the carbazole quality 0.01-0.05 doubly;
2) purifying of 9-(2-hydroxyethyl) carbazole
Step 1) gained 9-(2-hydroxyethyl) carbazole bullion is added in the high polarity solvent that mass volume ratio is 1:1-10; Remove by filter insolubles and reclaim, reclaim the raw material carbazole, add activated carbon decolorizing in the gained solution; The quality of gac is 0.01-0.1 a times of carbazole bullion quality; The decolouring after-filtration that finishes is removed gac, and surplus solution adds the low polar solvent recrystallization, and the white, needle-shaped crystals that obtains is 9-(2-hydroxyethyl) carbazole.
Press such scheme; The described solvent orange 2 A of step 1) is an organic solvent dichloromethane, 1; 2-ethylene dichloride, chloroform, THF, methyltetrahydrofuran, ether, sherwood oil (60 ℃-90 ℃ of boiling ranges), methyl ethyl ether, isopropyl ether, MTBE, 1; 3-dioxane, 1, any one in 4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, ethylene glycol diethyl ether, benzene,toluene,xylene and the chlorobenzene or multiple mixing;
Press such scheme, the described solvent orange 2 A of step 1) also includes water, and wherein the volume ratio of organic solvent and water is 1:0.3-2.
Press such scheme, the described mineral alkali of step 1) is any one or the multiple mixing in sodium hydroxide, Pottasium Hydroxide, calcium hydroxide, salt of wormwood, yellow soda ash, sodium hydrogencarbonate and the saleratus.
Press such scheme, the described ethylene halohydrin of step 1) is β-glycol chlorohydrin or β-bromoethanol.
Press such scheme, the described phase-transfer catalyst of step 1) is any one or the multiple mixing among benzyltriethylammoinium chloride, tetrabutylammonium chloride, Tetrabutyl amonium bromide, tetrabutylammonium iodide, 4-butyl ammonium hydrogen sulfate, tetrabutyl ammonium sulfate, triethylbenzene ammonium chloride, triethyl phenyl brometo de amonio, tributyl phenyl brometo de amonio, three heptyl phenyl brometo de amonios, three (dodecyl) phenyl brometo de amonio, tri-n-octyl methyl ammonium chloride, DTAC, tetradecyl trimethyl ammonium chloride, triethyl hexyl brometo de amonio, triethyl octyl group brometo de amonio, triethyl decyl brometo de amonio, triethyl dodecyl bromination ammonium, triethyl hexadecyl brometo de amonio, PEG400, PEG600, PEG800, PEG1000 and the PEG2000.
Press such scheme, the described inorganic iodide of step 1) is Soiodin, potassiumiodide, lithium iodide, magnesium iodide, zinc iodide, calcium iodide, cadmium iodide, cesium iodide or iron iodide.
Press such scheme, step 2) described high polarity solvent is any one or the multiple mixing in methyl alcohol, ethanol, n-propyl alcohol, Virahol, acetone, butanone, the water.
Press such scheme; Step 2) described low polar solvent is sherwood oil, normal hexane, hexanaphthene, Skellysolve A, normal heptane, methylene dichloride, 1; 2-ethylene dichloride, chloroform, ether, methyl ethyl ether, isopropyl ether, MTBE, 1; 3-dioxane, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, ethylene glycol diethyl ether, benzene, toluene or YLENE.
Reaction equation that the present invention relates to and popular response mechanism are:
This reaction mechanism is a hydroxyethylation reagent with β-glycol chlorohydrin, and sodium hydroxide is that mineral alkali is an example.
Beneficial effect of the present invention is: when reaction; The last H atom of N and the O on the product hydroxyl that make full use of raw material go up H for the minute differences of halogen replacement ethanol in substitution reaction; And the method that adopts phase-transfer catalysis enlarges this difference, suppresses simultaneously that O-is alkylating to carry out.And timely termination reaction, farthest avoided the generation of cascade reaction.Thereby can control reaction process, its basic no coupling product is generated; When separation and purification, through utilizing the dissolubility difference of raw material and product, use suitable solvent, realize that unreacted intact raw material and the easy of product separate, and can finely carry out the intact raw material of unreacted and reclaim, reduced production cost; This preparing method's reaction conditions is gentle, do not contain anhydrous with oxygen free operation, do not need special devices, temperature of reaction to be easy to control, the reaction times is short, solvent is easy to reclaim, and is fit to plant produced.
Description of drawings
Fig. 1 is 9-(2-hydroxyethyl) carbazole
1H-NMR collection of illustrative plates (CDCl
3, 600MHz).
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to following embodiment.
Embodiment 1:
1) preparation of 9-(2-hydroxyethyl) carbazole bullion:
5.00g carbazole dissolves in 1 of 50ml, in the 4-dioxane, vigorous stirring adds 3.00g sodium hydroxide; 0.50g Tetrabutyl amonium bromide is warming up to reflux state, adds the 0.1g potassiumiodide, adds β-bromoethanol 3.00g; Behind the reaction 3h, suction filtration is removed the solid matter in the solution, and removal of solvent under reduced pressure obtains white solid; With the rinse of white solid water, obtain the bullion 7.00g of 9-(2-hydroxyethyl) carbazole, this bullion comprises part material carbazole, 9-(2-hydroxyethyl) carbazole and minor by-products;
2) purifying of 9-(2-hydroxyethyl) carbazole:
Above-mentioned 9-(2-hydroxyethyl) carbazole bullion is not carried out drying, directly be dissolved in the 20ml ethanol, fully stir back filtering insolubles, insolubles is the carbazole raw material, and vacuum-drying gets the 1.92g carbazole, and the recovery is 38.4%.In ethanol liquid, add 0.20g gac, reflux decolour.After decolouring finishes, remove by filter gac.Then in 60 ℃ of hot soln, add the sherwood oil recrystallization.Filter the back solid and in vacuum, carry out drying, obtain recrystallized product white, needle-shaped crystals 3.20g, yield is 50.7%.Like Fig. 1:
Fusing point: 82.4-83.4 ℃;
1H NMR (400 MHz, CDCl
3, δ ppm): δ 1.63 (s, 1H, OH); 3.98 (t, 2H, NCH2); 4.42 (t, 2H, OCH2); 7.23 (d, 2H, 1,8-H); 7.426 (t, 4H, 2,3,6,7-H); 8.08 (d, 2H, 4,5-H).
Table 1
Table 1 (identical) with embodiment 1
Can know by table 1, the first, under the identical situation of other condition; The more little productive rate of the moieties of catalyzer is high more; This possibly be to have the catalyzer of alkyl chain greatly because the catalytic effect of this part catalyzer is too late, thereby has reduced the activity that side reaction takes place, second; An amount of catalyzer that has big alkyl chain that adds helps to improve productive rate.This possibly be because a spot of catalyzer that has big alkyl has the catalytic effect of initiation.
Embodiment 2:
1) preparation of 9-(2-hydroxyethyl) carbazole bullion:
The 5.00g carbazole is dissolved in the THF of 40ml, vigorous stirring adds 3.00g Pottasium Hydroxide, and 0.50g PEG400 is warming up to reflux state, adds the 0.1g Soiodin, adds β-glycol chlorohydrin 3.00g.Behind the reaction 3h, reaction is accomplished basically.Suction filtration is removed the solid matter in the solution.Removal of solvent under reduced pressure.The white solid that obtains.With the rinse of white solid water, obtain the bullion 6.90g of 9-(2-hydroxyethyl) carbazole.
2) purifying of 9-(2-hydroxyethyl) carbazole:
Above-mentioned 9-(2-hydroxyethyl) carbazole bullion is not carried out drying, directly be dissolved in the 30ml Virahol, fully stir back filtering insolubles, insolubles is the carbazole raw material, and vacuum-drying gets the 2.01g carbazole, and the recovery is 40.2%.With adding 0.20g gac, reflux decolour in the isopropyl alcohol liquid.After decolouring finishes, remove by filter gac.Then in 60 ℃ of solution, add the normal hexane recrystallization.Filter the back solid and in vacuum, carry out drying, obtain recrystallized product white, needle-shaped crystals 3.11g, yield is 49.2%.
Fusing point: 82.1-83.5 ℃.
Table 2
Table 2 (with embodiment 2 same operation)
Can know by table 2: the first, the catalytic effect of PEG400 is similar with the catalytic effect of the quaternary ammonium salt that has less alkyl chain, and these quaternary ammonium salts comprise Tetrabutyl amonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide, triethylbenzene ammonium chloride etc.; The second, under the identical condition of other conditions, the yield that adopts mixed base is obviously greater than single alkali; The 3rd, use sodium hydroxide or Pottasium Hydroxide to make alkali, its yield is starkly lower than identical carbonate.
Embodiment 3:
1) preparation of 9-(2-hydroxyethyl) carbazole bullion:
The 5.00g carbazole is dissolved in the sherwood oil (60 ℃-90 ℃ of boiling ranges) of 40ml, vigorous stirring adds 3.00g Pottasium Hydroxide, and 0.50g PEG2000 is warming up to reflux state, adds the 0.1g Soiodin, adds glycol chlorohydrin 3.00g.Behind the reaction 3h, reaction is accomplished basically.Suction filtration is removed the solid matter in the solution.Removal of solvent under reduced pressure.The white solid that obtains with the rinse of white solid water, obtains the bullion 7.00g of 9-(2-hydroxyethyl) carbazole.
2) purifying of 9-(2-hydroxyethyl) carbazole:
Above-mentioned 9-(2-hydroxyethyl) carbazole bullion is not carried out drying, directly be dissolved in the 30ml Virahol, fully stir back filtering insolubles, insolubles is the carbazole raw material, and vacuum-drying gets the 1.93g carbazole, and the recovery is 38.6%.With adding 0.20g gac, reflux decolour in the isopropyl alcohol liquid.After decolouring finishes, remove by filter gac.Then in 60 ℃ of solution, add the normal hexane recrystallization.Filter the back solid and in vacuum, carry out drying, obtain recrystallized product white, needle-shaped crystals 3.11g, yield is 49.2%.
Table 3
Table 3 (with embodiment 3 same operation)
Can know by table 3: the first, from PEG400-PEG800, molecular weight is big more, and the yield of product is high more.The second, when the PEG molecular weight greater than 1000 the time, the yield of product obviously reduces, this is because the macromolecular stronger katalysis of PEG, causes the activity that side reaction takes place and increases.The 3rd, with embodiment 1, an amount of catalyzer that adds a small amount of strong katalysis helps the raising of reaction yield.
Embodiment 4:
1) preparation of 9-(2-hydroxyethyl) carbazole bullion:
With the 5.00g carbazole, heating for dissolving adds 50ml water in 100ml benzene, add 3.00g sodium hydroxide, 0.1g PEG1000 and 0.3g tetrabutylammonium iodide, and reflux, vigorous stirring adds the 0.2g Soiodin, adds glycol chlorohydrin 3.00g.Behind the reaction 4h.Reaction is basic to be accomplished.Suction filtration is removed the solid matter in the solution.Solvent is removed in decompression.Obtain white solid, with the rinse of white solid water.Obtain the bullion 6.90g of 9-(2-hydroxyethyl) carbazole.
2) purifying of 9-(2-hydroxyethyl) carbazole:
Above-mentioned 9-(2-hydroxyethyl) carbazole bullion is not carried out drying, directly be dissolved in the 30ml n-propyl alcohol, fully stir back filtering insolubles, insolubles is the carbazole raw material, and vacuum-drying gets the 1.85g carbazole, and the recovery is 37.0%.With adding 0.20g gac, reflux decolour in the n-propyl alcohol liquid.After decolouring finishes, remove by filter gac.Then in 60 ℃ of solution, add the hexanaphthene recrystallization.Filter the back solid and in vacuum, carry out drying, obtain recrystallized product white, needle-shaped crystals 3.21g, yield is 50.8%.
Fusing point: 81.8-82.7 ℃.
Table 4 (inorganic solvent is 50ml water)
Table 4 (with embodiment 4 same operation)
Can be drawn to draw a conclusion by table 4: at catalyzer, alkali is under the identical situation of hydroxyethylation reagent; The verivate of first benzene and benzene is made solvent; Productive rate does not have obvious difference, but than common solvent (THF, 1; The 4-dioxane) productive rate obviously raises, and possible cause is that this kind non-polar solvent has effectively suppressed the alkylating activity of O-; The second, use ethers to make solvent, productive rate obviously reduces, and possible cause is that each other hydrogen bond action has increased the alkylating activity of O-; The 3rd, at above-mentioned non-polar solvent (toluene, benzene; Chlorobenzene etc.) add small amounts of ether in and can effectively increase productive rate; Possible cause is that the adding of small amounts of ether can effectively increase the solvability of carbazole in solvent, makes raw material in the reaction in early stage, the status of in solution, having the advantage.
Claims (9)
1. synthesizing and purification process of a midbody 9-(2-hydroxyethyl) carbazole, it is characterized in that including following steps:
1) preparation of 9-(2-hydroxyethyl) carbazole bullion
Carbazole is dissolved in the solvent orange 2 A that mass volume ratio is 1:8-30; Add mineral alkali, ethylene halohydrin, phase-transfer catalyst and inorganic iodine then for thing; Be heated to 40-100 ℃ of reaction under the vigorous stirring, reaction removes by filter insolubles after accomplishing; Removal of solvent under reduced pressure obtains white solid 9-(2-hydroxyethyl) carbazole bullion;
Wherein the quality of mineral alkali be the carbazole quality 0.2-1 doubly, the quality of ethylene halohydrin be the carbazole quality 0.5-5 doubly, the quality of phase-transfer catalyst be the carbazole quality 0.01-0.1 doubly, inorganic iodine for the quality of thing be the carbazole quality 0.01-0.05 doubly;
2) purifying of 9-(2-hydroxyethyl) carbazole
Step 1) gained 9-(2-hydroxyethyl) carbazole bullion is added in the high polarity solvent that mass volume ratio is 1:1-10; Remove by filter insolubles and reclaim, reclaim the raw material carbazole, add activated carbon decolorizing in the gained solution; The quality of gac is 0.01-0.1 a times of carbazole bullion quality; The decolouring after-filtration that finishes is removed gac, and surplus solution adds the low polar solvent recrystallization, and the white, needle-shaped crystals that obtains is 9-(2-hydroxyethyl) carbazole.
2. press the synthetic and purification process of the described 9-of claim 1 (2-hydroxyethyl) carbazole; It is characterized in that the described solvent orange 2 A of step 1) is an organic solvent dichloromethane, 1; 2-ethylene dichloride, chloroform, THF, methyltetrahydrofuran, ether, sherwood oil, methyl ethyl ether, isopropyl ether, MTBE, 1; 3-dioxane, 1, any one in 4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, ethylene glycol diethyl ether, benzene,toluene,xylene and the chlorobenzene or multiple mixing.
3. by the synthetic and purification process of the described 9-of claim 2 (2-hydroxyethyl) carbazole, it is characterized in that the described solvent orange 2 A of step 1) also includes water, wherein the volume ratio of organic solvent and water is 1:0.3-2.
4. by the synthetic and purification process of claim 1 or 2 or 3 described 9-(2-hydroxyethyl) carbazole, it is characterized in that the described mineral alkali of step 1) is any one or the multiple mixing in sodium hydroxide, Pottasium Hydroxide, calcium hydroxide, salt of wormwood, yellow soda ash, sodium hydrogencarbonate and the saleratus.
5. by the synthetic and purification process of claim 1 or 2 or 3 described 9-(2-hydroxyethyl) carbazole, it is characterized in that the described ethylene halohydrin of step 1) is β-glycol chlorohydrin or β-bromoethanol.
6. by the synthetic and purification process of claim 1 or 2 or 3 described 9-(2-hydroxyethyl) carbazole, it is characterized in that the described phase-transfer catalyst of step 1) is any one or the multiple mixing among benzyltriethylammoinium chloride, tetrabutylammonium chloride, Tetrabutyl amonium bromide, tetrabutylammonium iodide, 4-butyl ammonium hydrogen sulfate, tetrabutyl ammonium sulfate, triethylbenzene ammonium chloride, triethyl phenyl brometo de amonio, tributyl phenyl brometo de amonio, three heptyl phenyl brometo de amonios, three (dodecyl) phenyl brometo de amonio, tri-n-octyl methyl ammonium chloride, DTAC, tetradecyl trimethyl ammonium chloride, triethyl hexyl brometo de amonio, triethyl octyl group brometo de amonio, triethyl decyl brometo de amonio, triethyl dodecyl bromination ammonium, triethyl hexadecyl brometo de amonio, PEG400, PEG600, PEG800, PEG1000 and the PEG2000.
7. by the synthetic and purification process of claim 1 or 2 or 3 described 9-(2-hydroxyethyl) carbazole, it is characterized in that the described inorganic iodide of step 1) is Soiodin, potassiumiodide, lithium iodide, magnesium iodide, zinc iodide, calcium iodide, cadmium iodide, cesium iodide or iron iodide.
8. by the synthetic and purification process of claim 1 or 2 or 3 described 9-(2-hydroxyethyl) carbazole, it is characterized in that step 2) described high polarity solvent is any one or the multiple mixing in methyl alcohol, ethanol, n-propyl alcohol, Virahol, acetone, butanone, the water.
9. press the synthetic and purification process of claim 1 or 2 or 3 described 9-(2-hydroxyethyl) carbazole; It is characterized in that step 2) described low polar solvent is sherwood oil, normal hexane, hexanaphthene, Skellysolve A, normal heptane, methylene dichloride, 1; 2-ethylene dichloride, chloroform, ether, methyl ethyl ether, isopropyl ether, MTBE, 1; 3-dioxane, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, ethylene glycol diethyl ether, benzene, toluene or YLENE.
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| CN109369509A (en) * | 2018-11-13 | 2019-02-22 | 中国工程物理研究院激光聚变研究中心 | A kind of synthetic method of N- (6- hydroxyl hexyl) carbazole derivates and N- (6- hydroxyl hexyl) carbazole and its derivative |
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| EP1431350A1 (en) * | 2002-12-20 | 2004-06-23 | Nidek Co., Ltd. | Colorant for ocular lenses and colored ocular lens using the colorant |
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| EP1431350A1 (en) * | 2002-12-20 | 2004-06-23 | Nidek Co., Ltd. | Colorant for ocular lenses and colored ocular lens using the colorant |
Non-Patent Citations (2)
| Title |
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| K.DIDUCH ET AL: "Chromophoric Carbazole Methacrylates as Intermediates for Photorefractive Applications", 《POLISH J. CHEM.》 * |
| YONGXIN TAO ET AL: "Synthesis and photoluminescent property of star polymers with carbzole pendent and a zinc porphyrin core by ATRP", 《POLYMER》 * |
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| CN109369509A (en) * | 2018-11-13 | 2019-02-22 | 中国工程物理研究院激光聚变研究中心 | A kind of synthetic method of N- (6- hydroxyl hexyl) carbazole derivates and N- (6- hydroxyl hexyl) carbazole and its derivative |
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