CN102633708B - 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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- CN102633708B CN102633708B CN201210037795.4A CN201210037795A CN102633708B CN 102633708 B CN102633708 B CN 102633708B CN 201210037795 A CN201210037795 A CN 201210037795A CN 102633708 B CN102633708 B CN 102633708B
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- TXCZYRHNBULEQZ-UHFFFAOYSA-N CC1(C)C(C2)C2CC1 Chemical compound CC1(C)C(C2)C2CC1 TXCZYRHNBULEQZ-UHFFFAOYSA-N 0.000 description 1
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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 a kind of intermediate 9-(2-hydroxyethyl) the synthetic and purification process of carbazole.
Background technology
Carbazole and derivative thereof are the important azaaromatics of a class, molecule contains larger conjugated system, easily there is transfer transport in strong molecule, in addition its special rigidity condensed ring structure, this all makes carbazole compound show performance and the biological activity of many uniquenesses, there is widespread use photoelectric material, dyestuff, Supramolecular Recognition etc. are multi-field, especially with 9-(2-hydroxyethyl) carbazole typical case the most.Meanwhile, 9-(2-hydroxyethyl) carbazole is also a very important medicine intermediate, market demand is huge, has good market outlook.
Up to the present, for the production of 9-(2-hydroxyethyl) method of carbazole is a lot, is all taking carbazole as raw material, using chloroethanol, bromoethanol, oxyethane or ethylene carbonate as hydroxyethylation reagent.Due to the N atom lone-pair electron on carbazole and two, side phenyl ring conjugation, the cloud density on N atom reduces, and activity reduces, and causes the upper H acidity of N extremely low, is all to use highly basic to carry out catalysis to peel off hydrogen while carrying out N-hydroxyethylation.Wherein carry out the hydroxyethylated most study of N-of carbazole as hydroxyethylation reagent with ethylene carbonate.Conventionally using sodium hydroxide or potassium hydroxide as catalyzer (
j. Phys. Chem., 1993,
97: 11164 – 11167;
j. Phys. Chem., 1995,
99: 16047 – 16051), but due to a little less than the upper hydrogen atom acidity of carbazole N, and the alkalescence of sodium hydroxide and potassium hydroxide is not enough strong, therefore, in the time reacting, needs 100 DEG C of above high temperature; In order to increase solubleness and the reactive behavior of carbazole, conventionally all adopt high boiling non-protonic solvent DMF, and DMF easily decomposes under highly basic and high temperature, cause solvent to be difficult to reclaim, increase production cost.If the alkali in reaction is replaced to the stronger sodium hydride of alkalescence of equivalent, can peel off the H on N, thereby can reduce temperature of reaction and can use more lower boiling solvent, convenient recovery (
j. Mol. Liq,2003,105:185-190).But in actually operating, find that this kind of method productive rate is still lower, illustrate that sodium hydride is still limited for the stripping ability of the upper H atom of carbazole N.Also have certain methods method be while 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 activity is high, therefore yield is better, and raw materials cost is low.But oxyethane is gaseous matter, and easily blast, this has just caused the requirement higher to production unit, has greatly increased production cost.In addition use in addition chloroethanol (
macromol.,1996,
29:4613-4618), bromoethanol (
synthetic Metals,2009,159:1512 – 1516) report, all need to 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 large improvement.
In addition, current all 9-(2-hydroxyethyls) carbazole preparation method also has a very large shortcoming, and that is exactly the problem that product generation cascade reaction causes.Because the upper H acidity of carbazole N is extremely low, the 9-(2-hydroxyethyl generating) activity of alcoholic extract hydroxyl group of carbazole is close with it, therefore product 9-(2-hydroxyethyl) H of hydroxyl easily competes with the upper H of raw material carbazole N in carbazole, there are a series of cascade reactions with hydroxyethylation reagent, generate a large amount of 9-(2-hydroxyethyls) carbazole derivative
Reaction equation:
Product by product
The reason that side reaction occurs:
These impurity are all product 9-(2-hydroxyethyls) carbazole analogue, difference is only the number difference that oxyethyl group replaces, therefore they and 9-(2-hydroxyethyl) carbazole character approaches, be difficult to separation and purification, literature method often needs repeatedly recrystallization or column chromatography to carry out purifying for obtaining sterling, thereby make productive rate very low, complex operation, does not have the extensive value of preparing.Therefore need the succinct 9-(2-hydroxyethyl efficiently of exploitation) preparation method of carbazole.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of intermediate 9-(2-hydroxyethyl for above-mentioned prior art) the synthetic and purification process of carbazole, its selectivity is good, yield improves, easy and simple to handle, cost is low, reduced to greatest extent the generation of cascade reaction side reaction.
The present invention solves the problems of the technologies described above adopted technical scheme: a kind of intermediate 9-(2-hydroxyethyl) the synthetic and purification process of carbazole, it is characterized in that including following steps:
1) 9-(2-hydroxyethyl) preparation of carbazole crude product
Carbazole is dissolved in the solvent orange 2 A that mass volume ratio is 1:8-30, then add mineral alkali, ethylene halohydrin, phase-transfer catalyst and inorganic iodine for thing, under vigorous stirring, be heated to 40-100 DEG C of reaction, after having reacted, remove by filter insolubles, removal of solvent under reduced pressure, obtains white solid 9-(2-hydroxyethyl) carbazole crude product;
Wherein the quality of mineral alkali be carbazole quality 0.2-1 doubly, the quality of ethylene halohydrin be carbazole quality 0.5-5 doubly, the quality of phase-transfer catalyst be carbazole quality 0.01-0.1 doubly, inorganic iodine for the quality of thing be carbazole quality 0.01-0.05 doubly;
2) 9-(2-hydroxyethyl) purifying of carbazole
By step 1) gained 9-(2-hydroxyethyl) carbazole crude product is added in the large polar solvent that mass volume ratio is 1:1-10, remove by filter insolubles and reclaim, reclaim to obtain raw material carbazole, in gained solution, add activated carbon decolorizing, the quality of gac is 0.01-0.1 times of carbazole crude product quality, after decolouring, remove by filter gac, surplus solution adds low polar solvent recrystallization, and the white, needle-shaped crystals obtaining is 9-(2-hydroxyethyl) carbazole.
Press such scheme, step 1) described solvent orange 2 A is organic solvent dichloromethane, 1,2-ethylene dichloride, chloroform, tetrahydrofuran (THF), methyltetrahydrofuran, ether, sherwood oil (60 DEG C-90 DEG C of boiling ranges), methyl ethyl ether, isopropyl ether, methyl tertiary butyl ether, 1, any one in 3-dioxane, Isosorbide-5-Nitrae-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, ethylene glycol diethyl ether, benzene,toluene,xylene and chlorobenzene or multiple mixing;
Press such scheme, step 1) described solvent orange 2 A also includes water, and wherein the volume ratio of organic solvent and water is 1:0.3-2.
Press such scheme, step 1) described mineral alkali is any one or the multiple mixing in sodium hydroxide, potassium hydroxide, calcium hydroxide, salt of wormwood, sodium carbonate, sodium bicarbonate and saleratus.
Press such scheme, step 1) described ethylene halohydrin is β-chloroethanol or β-bromoethanol.
Press such scheme, step 1) described phase-transfer catalyst is 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, Dodecyl trimethyl ammonium chloride, 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, any one in PEG1000 and PEG2000 or multiple mixing.
Press such scheme, step 1) described inorganic iodide is sodium iodide, potassiumiodide, lithium iodide, magnesium iodide, zinc iodide, calcium iodide, cadmium iodide, cesium iodide or iron iodide.
Press such scheme, step 2) described large polar solvent is any one or the multiple mixing in methyl alcohol, ethanol, n-propyl alcohol, Virahol, acetone, butanone, 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, methyl tertiary butyl ether, 1,3-dioxane, Isosorbide-5-Nitrae-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, ethylene glycol diethyl ether, benzene, toluene or dimethylbenzene.
The reaction equation the present invention relates to and popular response mechanism are:
This reaction mechanism is taking β-chloroethanol as hydroxyethylation reagent, and sodium hydroxide is that mineral alkali is example.
Beneficial effect of the present invention is: in the time of reaction, the N that makes full use of raw material goes up H on the O on H atom and product hydroxyl and replaces the minute differences of ethanol in substitution reaction for halogen, and adopt the method for phase-transfer catalysis that this difference is expanded, suppress that O-is alkylating to carry out simultaneously.And timely termination reaction, farthest avoid the generation of cascade reaction.Thereby can control reaction process, its basic no coupling product is generated; In the time of separation and purification, by utilizing the dissolubility difference of raw material and product, use suitable solvent, realize the complete raw material of unreacted and the easy of product and separate, and can finely carry out the complete raw materials recovery of unreacted, reduce production cost; This preparation method's reaction conditions gentleness, containing anhydrous and oxygen free operation, do not need special equipment, temperature of reaction to be easy to control, the reaction times is short, and solvent is easy to reclaim, and is applicable to plant produced.
Brief description of the drawings
Fig. 1 is 9-(2-hydroxyethyl) carbazole
1h-NMR collection of illustrative plates (CDCl
3, 600MHz).
Embodiment
In order to understand better the present invention, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
Embodiment 1:
1) 9-(2-hydroxyethyl) preparation of carbazole crude product:
5.00g carbazole dissolves in Isosorbide-5-Nitrae-dioxane of 50ml, vigorous stirring, add 3.00g sodium hydroxide, 0.50g Tetrabutyl amonium bromide, is warming up to reflux state, add 0.1g potassiumiodide, add β-bromoethanol 3.00g, after reaction 3h, suction filtration is removed the solid matter in solution, removal of solvent under reduced pressure, obtains white solid, by the rinse of white solid water, obtain 9-(2-hydroxyethyl) the crude product 7.00g of carbazole, this crude product comprises part material carbazole, 9-(2-hydroxyethyl) carbazole and a small amount of by product;
2) 9-(2-hydroxyethyl) purifying of carbazole:
By above-mentioned 9-(2-hydroxyethyl) carbazole crude product is not dried, is directly dissolved in 20ml ethanol, filtering insolubles after fully stirring, insolubles is carbazole raw material, and vacuum-drying obtains 1.92g carbazole, and the rate of recovery is 38.4%.In ethanol, add 0.20g gac, reflux decolour.After decolouring, remove by filter gac.Then in 60 DEG C of hot solution, add sherwood oil recrystallization.After filtering, solid is dried in vacuum, obtains recrystallized product white, needle-shaped crystals 3.20g, and yield is 50.7%.As Fig. 1:
Fusing point: 82.4-83.4 DEG C;
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)
As shown in Table 1, first, in the situation that other condition is identical, the less productive rate of moieties of catalyzer is higher, this may be the too late catalyzer that has larger alkyl chain of catalytic effect because of this part catalyzer, thereby has reduced the activity that side reaction occurs, second, add in right amount the catalyzer that has larger alkyl chain, contribute to improve productive rate.This may be because a small amount of catalyzer that has large alkyl has the effect that causes catalysis.
Embodiment 2:
1) 9-(2-hydroxyethyl) preparation of carbazole crude product:
5.00g carbazole is dissolved in the tetrahydrofuran (THF) of 40ml, vigorous stirring, adds 3.00g potassium hydroxide, and 0.50g PEG400, is warming up to reflux state, adds 0.1g sodium iodide, adds β-chloroethanol 3.00g.After reaction 3h, reaction completes substantially.Suction filtration is removed the solid matter in solution.Removal of solvent under reduced pressure.The white solid obtaining.By the rinse of white solid water, obtain 9-(2-hydroxyethyl) the crude product 6.90g of carbazole.
2) 9-(2-hydroxyethyl) purifying of carbazole:
By above-mentioned 9-(2-hydroxyethyl) carbazole crude product is not dried, is directly dissolved in 30ml Virahol, filtering insolubles after fully stirring, insolubles is carbazole raw material, and vacuum-drying obtains 2.01g carbazole, and the rate of recovery is 40.2%.0.20g gac, reflux decolour will be added in isopropyl alcohol liquid.After decolouring, remove by filter gac.Then in 60 DEG C of solution, add normal hexane recrystallization.After filtering, solid is dried in vacuum, obtains recrystallized product white, needle-shaped crystals 3.11g, and yield is 49.2%.
Fusing point: 82.1-83.5 DEG C.
Table 2
Table 2(and embodiment 2 same operation)
As shown in Table 2: the catalytic effect of the first, PEG400 is similar to the catalytic effect of 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, adopt the yield of mixed base to be obviously greater than single alkali; The 3rd, use sodium hydroxide or potassium hydroxide to make alkali, its yield is starkly lower than identical carbonate.
Embodiment 3:
1) 9-(2-hydroxyethyl) preparation of carbazole crude product:
5.00g carbazole is dissolved in the sherwood oil (60 DEG C-90 DEG C of boiling ranges) of 40ml, vigorous stirring, adds 3.00g potassium hydroxide, and 0.50g PEG2000, is warming up to reflux state, adds 0.1g sodium iodide, adds chloroethanol 3.00g.After reaction 3h, reaction completes substantially.Suction filtration is removed the solid matter in solution.Removal of solvent under reduced pressure.The white solid obtaining, by the rinse of white solid water, obtains 9-(2-hydroxyethyl) the crude product 7.00g of carbazole.
2) 9-(2-hydroxyethyl) purifying of carbazole:
By above-mentioned 9-(2-hydroxyethyl) carbazole crude product is not dried, is directly dissolved in 30ml Virahol, filtering insolubles after fully stirring, insolubles is carbazole raw material, and vacuum-drying obtains 1.93g carbazole, and the rate of recovery is 38.6%.0.20g gac, reflux decolour will be added in isopropyl alcohol liquid.After decolouring, remove by filter gac.Then in 60 DEG C of solution, add normal hexane recrystallization.After filtering, solid is dried in vacuum, obtains recrystallized product white, needle-shaped crystals 3.11g, and yield is 49.2%.
Table 3
Table 3(and embodiment 3 same operation)
As shown in Table 3: the first, from PEG400-PEG800, molecular weight is larger, and the yield of product is higher.The second, in the time that PEG molecular weight is greater than 1000, the yield of product obviously reduces, and this is due to the macromolecular stronger katalysis of PEG, causes the activity increase that side reaction occurs.The 3rd, with embodiment 1, add in right amount the catalyzer of a small amount of strong katalysis, contribute to the raising of reaction yield.
Embodiment 4:
1) 9-(2-hydroxyethyl) preparation of carbazole crude product:
By 5.00g carbazole, heating for dissolving, in 100ml benzene, adds 50ml water, adds 3.00g sodium hydroxide, 0.1g PEG1000 and 0.3g tetrabutylammonium iodide, and reflux, vigorous stirring, adds 0.2g sodium iodide, adds chloroethanol 3.00g.After reaction 4h.Reaction completes substantially.Suction filtration is removed the solid matter in solution.Solvent is removed in decompression.Obtain white solid, by the rinse of white solid water.Obtain 9-(2-hydroxyethyl) the crude product 6.90g of carbazole.
2) 9-(2-hydroxyethyl) purifying of carbazole:
By above-mentioned 9-(2-hydroxyethyl) carbazole crude product is not dried, is directly dissolved in 30ml n-propyl alcohol, filtering insolubles after fully stirring, insolubles is carbazole raw material, and vacuum-drying obtains 1.85g carbazole, and the rate of recovery is 37.0%.0.20g gac, reflux decolour will be added in n-propyl alcohol liquid.After decolouring, remove by filter gac.Then in 60 DEG C of solution, add hexanaphthene recrystallization.After filtering, solid is dried in vacuum, obtains recrystallized product white, needle-shaped crystals 3.21g, and yield is 50.8%.
Fusing point: 81.8-82.7 DEG C.
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, in the identical situation of hydroxyethylation reagent, the derivative of the first benzene and benzene makees solvent, productive rate is without obvious difference, but than common solvent (tetrahydrofuran (THF), 1,4-dioxane) productive rate obviously raises, and possible cause is that this kind of non-polar solvent effectively suppressed the alkylating activity of O-; The second, use ethers to make solvent, productive rate obviously reduces, and possible cause is that hydrogen bond action has each other increased the alkylating activity of O-; The 3rd, at above-mentioned non-polar solvent (toluene, benzene, chlorobenzene etc.) in add a small amount of ether can effectively increase productive rate, possible cause is can effectively increase the solvability of carbazole in solvent adding of a small amount of ether, makes raw material in reaction in early stage, the status of having the advantage in solution.
Claims (4)
1. intermediate 9-(2-hydroxyethyl) the synthetic and purification process of carbazole, it is characterized in that including following steps:
1) 9-(2-hydroxyethyl) preparation of carbazole crude product
Carbazole is dissolved in the solvent orange 2 A that mass volume ratio is 1:8-30, then add mineral alkali, ethylene halohydrin, phase-transfer catalyst and inorganic iodine for thing, under vigorous stirring, be heated to 40-100 DEG C of reaction, after having reacted, remove by filter insolubles, removal of solvent under reduced pressure, obtains white solid 9-(2-hydroxyethyl) carbazole crude product;
Wherein the quality of mineral alkali be carbazole quality 0.2-1 doubly, the quality of ethylene halohydrin be carbazole quality 0.5-5 doubly, the quality of phase-transfer catalyst be carbazole quality 0.01-0.1 doubly, inorganic iodine for the quality of thing be carbazole quality 0.01-0.05 doubly;
Described solvent orange 2 A is methylene dichloride, 1,2-ethylene dichloride, chloroform, tetrahydrofuran (THF), methyltetrahydrofuran, ether, sherwood oil, methyl ethyl ether, isopropyl ether, methyl tertiary butyl ether, 1, any one in 3-dioxane, Isosorbide-5-Nitrae-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, ethylene glycol diethyl ether, benzene,toluene,xylene and chlorobenzene or multiple mixing;
Described phase-transfer catalyst is 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, Dodecyl trimethyl ammonium chloride, 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, any one in PEG1000 and PEG2000 or multiple mixing,
2) 9-(2-hydroxyethyl) purifying of carbazole
By step 1) gained 9-(2-hydroxyethyl) carbazole crude product is added in the large polar solvent that mass volume ratio is 1:1-10, remove by filter insolubles and reclaim, reclaim to obtain raw material carbazole, in gained solution, add activated carbon decolorizing, the quality of gac is 0.01-0.1 times of carbazole crude product quality, after decolouring, remove by filter gac, surplus solution adds low polar solvent recrystallization, the white, needle-shaped crystals obtaining is 9-(2-hydroxyethyl) carbazole, described large polar solvent is methyl alcohol, ethanol, n-propyl alcohol, Virahol, acetone, butanone, any one in water or multiple mixing, 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, methyl tertiary butyl ether, 1, 3-dioxane, 1, 4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, glycol dimethyl ether, ethylene glycol diethyl ether, benzene, toluene or dimethylbenzene.
2. by 9-(2-hydroxyethyl claimed in claim 1) the synthetic and purification process of carbazole, it is characterized in that step 1) described mineral alkali is any one or the multiple mixing in sodium hydroxide, potassium hydroxide, calcium hydroxide, salt of wormwood, sodium carbonate, sodium bicarbonate and saleratus.
3. by 9-(2-hydroxyethyl claimed in claim 1) the synthetic and purification process of carbazole, it is characterized in that step 1) described ethylene halohydrin is β-chloroethanol or β-bromoethanol.
4. by 9-(2-hydroxyethyl claimed in claim 1) the synthetic and purification process of carbazole, it is characterized in that step 1) described inorganic iodide is sodium iodide, potassiumiodide, lithium iodide, magnesium iodide, zinc iodide, calcium iodide, cadmium iodide, cesium iodide or iron iodide.
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| Chromophoric Carbazole Methacrylates as Intermediates for Photorefractive Applications;K.Diduch et al;《Polish J. Chem.》;20021231;第76卷;1495-1503 * |
| K.Diduch et al.Chromophoric Carbazole Methacrylates as Intermediates for Photorefractive Applications.《Polish J. Chem.》.2002,第76卷1495-1503. |
| Synthesis and photoluminescent property of star polymers with carbzole pendent and a zinc porphyrin core by ATRP;Yongxin Tao et al;《Polymer》;20110730;第52卷;4261-4267 * |
| Yongxin Tao et al.Synthesis and photoluminescent property of star polymers with carbzole pendent and a zinc porphyrin core by ATRP.《Polymer》.2011,第52卷4261-4267. |
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Granted publication date: 20141001 Termination date: 20160220 |