CN103086952B - Preparation method of 4,4'-[(9-butyl-9H-carbazole-3-)methylene]bis[N-methyl-N-phenyl]aniline - Google Patents
Preparation method of 4,4'-[(9-butyl-9H-carbazole-3-)methylene]bis[N-methyl-N-phenyl]aniline Download PDFInfo
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Abstract
The invention relates to a preparation method of 4,4'-[(9-butyl-9H-carbazole-3-)methylene]bis[N-methyl-N-phenyl]aniline, which comprises the following steps: adding tetrabutyl ammonium bromide and carbazole in a sodium hydroxide solution, dissolving while heating, dropwisely adding chlorobutane, extracting while keeping the temperature after the reaction is completed, and stratifying to obtain a BC methylbenzene solution; adding N,N-dimethylformamide and phosphorus oxychloride, and reacting to obtain a BCA intermediate compound; adding a proper amount of process water for washing, stirring, standing, stratifying, removing the underlayer acidic water, and then distilling to remove all the methylbenzene and water; and adding methanol and N-methyl diphenylamine, reacting, and then refining to obtain the finished product. According to the invention, the method is more reasonable in design; and a catalyst is added in the method, so that the conversion rate and use rate of carbazole are increased, the production cost is lowered, the yields of the intermediate compound and the final product are improved, and the quality of the final product is enhanced.
Description
Technical field
The present invention relates to a kind of preparation method of pressure sensitive dye, especially relate to the preparation method of 4,4'-[(9-butyl-9 hydrogen-carbazole-3-) methylene radical] two [N-Methyl-N-phenyl] aniline.
Background technology
In prior art, application number is that the Chinese patent application of CN93105523.7 discloses a kind of azo dispersion dyes containing carbazolyl heterocyclic ring and preparation method thereof.In the method, the Ar in Dyes structural formulae is arylamine parent, and arylamine is 2,5-dichlorphenamide bulk powder, 5-nitro-7-amino-benzene a pair of horses going side by side isothiazole, and R is alkyl, hydroxyalkyl, cyanoalkyl or various ester group.First by the nitrosyl sulfuric acid of preparation during preparation, arylamine is added wherein, diazotization in 0-65 DEG C, add in the solution such as coupling component carbazole after adjustment acidity, in 0-60 DEG C, carry out even summation reaction, then filter, be washed to neutrality, drying, former dyestuff yield 95%.The defect of this technical scheme is: the rough technique that carbazole utilization ratio is low, this technology is this serial reaction, is not accurate to single product.
Summary of the invention
Technical problem to be solved by this invention is for the deficiencies in the prior art, there is provided a kind of technological design more reasonable, effectively improve the transformation efficiency of carbazole, improve the preparation method of the yield of product and 4,4'-[(9-butyl-9 hydrogen-carbazole-3-) methylene radical] two [N-Methyl-N-phenyl] aniline of quality.
Technical problem to be solved by this invention is realized by following technical scheme.The present invention is a kind of preparation method of 4,4'-[(9-butyl-9 hydrogen-carbazole-3-) methylene radical] two [N-Methyl-N-phenyl] aniline, and be characterized in, its step is as follows:
(1) in sodium hydroxide solution, Tetrabutyl amonium bromide and carbazole is added, heat temperature raising dissolves, then slowly chlorobutane is dripped, then backflow 3 ~ 10 hours are incubated, toluene or other organic solvents insulation extraction of 2 ~ 5 times of weight of reaction mass is added after having reacted, after stirring stratification, point sub-cloud water layer, again all moisture and part toluene are steamed, obtain the toluene solution of BC; The weight ratio of NaOH solution, Tetrabutyl amonium bromide, carbazole and chlorobutane is preferably 60 ~ 70:1.5 ~ 2.5:25 ~ 35:15 ~ 25;
(2) in the toluene solution of BC, add appropriate DMF, then drip N, the phosphorus oxychloride of 1 ~ 2 times of weight of dinethylformamide, controls temperature of reaction at 55 ~ 100 DEG C, drips after terminating, continue insulation 5 ~ 12 hours, after having reacted, obtain BCA intermediate;
(3) appropriate technique washing material is added again, after stirring stratification, point sub-cloud sour water, then the distillation all toluene of removing and water; Add 3 ~ 10 times of methyl alcohol of material and the N-methyldiphenylamine of 2 ~ 7 times again, control temperature of reaction between 30 ~ 120 DEG C, then add appropriate hydrochloric acid; Keep temperature in the kettle to stir more than 5 hours at 30 ~ 120 DEG C, cooling leaves standstill and removes upper strata methyl alcohol; Again add material 1 ~ 5 times of methyl alcohol and a small amount of ammoniacal liquor or alkali lye, temperature rising reflux, again lowers the temperature and removes upper strata methyl alcohol, repeats 1 ~ 3 time until obtain finished product.
In the step (1) of preparation method of the present invention: the weight ratio of NaOH solution, Tetrabutyl amonium bromide, carbazole and chlorobutane is preferably 65:2:30:20.
In the step (1) of preparation method of the present invention: drip chlorobutane again after heating to 85 ~ 90 DEG C of dissolvings.
In the step (2) of preparation method of the present invention: control temperature of reaction at 60 ~ 65 DEG C, be incubated at 65 ~ 70 DEG C after dripping phosphorus oxychloride.
The concrete technology route of the inventive method is as follows, wherein, the structural formula of BC, the BCA described in the present invention is also see shown in following operational path, and BC4 is 4,4'-[(9-butyl-9 hydrogen-carbazole-3-) methylene radical] two [N-Methyl-N-phenyl] aniline:
Compared with prior art, the inventive method design is more reasonable, and the method is owing to adding catalyzer, improve transformation efficiency and the rate of utilization of carbazole, reduce production cost, improve the yield of intermediate and the finished product, also improve the quality of the finished product simultaneously.
Embodiment
Below further describe concrete technical scheme of the present invention, so that those skilled in the art understands the present invention further, and do not form the restriction to its right.
Embodiment 1, a kind of preparation method of 4,4'-[(9-butyl-9 hydrogen-carbazole-3-) methylene radical] two [N-Methyl-N-phenyl] aniline, its step is as follows:
(1) in sodium hydroxide solution, Tetrabutyl amonium bromide and carbazole is added, heat temperature raising dissolves, then slowly chlorobutane is dripped, then backflow 3 hours are incubated, toluene or other organic solvents insulation extraction of 2 times of weight of reaction mass is added after having reacted, after stirring stratification, point sub-cloud water layer, again all moisture and part toluene are steamed, obtain the toluene solution of BC; The weight ratio of NaOH solution, Tetrabutyl amonium bromide, carbazole and chlorobutane is 60:1.5:25:15.
(2) in the toluene solution of BC, add appropriate DMF, then drip N, the phosphorus oxychloride of 1 times of weight of dinethylformamide, controls temperature of reaction at 55 DEG C, drips after terminating, continue insulation 5 hours, after having reacted, obtain BCA intermediate;
(3) appropriate technique washing material is added again, after stirring stratification, point sub-cloud sour water, then the distillation all toluene of removing and water; Add 3 times of methyl alcohol of material and the N-methyldiphenylamine of 2 times again, control temperature of reaction between 30 DEG C, then add appropriate hydrochloric acid; Keep temperature in the kettle to stir more than 5 hours at 30 DEG C, cooling leaves standstill and removes upper strata methyl alcohol; Again add material 1 times of methyl alcohol and a small amount of ammoniacal liquor or alkali lye, temperature rising reflux, again lowers the temperature and removes upper strata methyl alcohol, repeats 1 ~ 3 time until obtain finished product.
Embodiment 2, a kind of preparation method of 4,4'-[(9-butyl-9 hydrogen-carbazole-3-) methylene radical] two [N-Methyl-N-phenyl] aniline, its step is as follows:
(1) in sodium hydroxide solution, Tetrabutyl amonium bromide and carbazole is added, heat temperature raising dissolves, then slowly chlorobutane is dripped, then backflow 10 hours are incubated, toluene or other organic solvents insulation extraction of 5 times of weight of reaction mass is added after having reacted, after stirring stratification, point sub-cloud water layer, again all moisture and part toluene are steamed, obtain the toluene solution of BC; The weight ratio of NaOH solution, Tetrabutyl amonium bromide, carbazole and chlorobutane is 70:2.5:35:25;
(2) in the toluene solution of BC, add appropriate DMF, then drip N, the phosphorus oxychloride of 2 times of weight of dinethylformamide, controls temperature of reaction at 100 DEG C, drips after terminating, continue insulation 12 hours, after having reacted, obtain BCA intermediate;
(3) appropriate technique washing material is added again, after stirring stratification, point sub-cloud sour water, then the distillation all toluene of removing and water; Add 10 times of methyl alcohol of material and the N-methyldiphenylamine of 7 times again, control temperature of reaction between 120 DEG C, then add appropriate hydrochloric acid; Keep temperature in the kettle to stir more than 5 hours at 120 DEG C, cooling leaves standstill and removes upper strata methyl alcohol; Again add material 5 times of methyl alcohol and a small amount of ammoniacal liquor or alkali lye, temperature rising reflux, again lowers the temperature and removes upper strata methyl alcohol, repeats 3 times until obtain finished product.
Embodiment 3, a kind of preparation method of 4,4'-[(9-butyl-9 hydrogen-carbazole-3-) methylene radical] two [N-Methyl-N-phenyl] aniline, its step is as follows:
(1) in sodium hydroxide solution, Tetrabutyl amonium bromide and carbazole is added, heat temperature raising dissolves, then slowly chlorobutane is dripped, then backflow 6 hours are incubated, toluene or other organic solvents insulation extraction of 3 times of weight of reaction mass is added after having reacted, after stirring stratification, point sub-cloud water layer, again all moisture and part toluene are steamed, obtain the toluene solution of BC; The weight ratio of NaOH solution, Tetrabutyl amonium bromide, carbazole and chlorobutane is 65:2:30:20;
(2) in the toluene solution of BC, add appropriate DMF, then drip N, the phosphorus oxychloride of 1.5 times of weight of dinethylformamide, controls temperature of reaction at 65 DEG C, drips after terminating, continue insulation 10 hours, after having reacted, obtain BCA intermediate;
(3) appropriate technique washing material is added again, after stirring stratification, point sub-cloud sour water, then the distillation all toluene of removing and water; Add 7 times of methyl alcohol of material and the N-methyldiphenylamine of 5 times again, control temperature of reaction between 70 DEG C, then add appropriate hydrochloric acid; Keep temperature in the kettle to stir more than 5 hours at 75 DEG C, cooling leaves standstill and removes upper strata methyl alcohol; Again add material 3 times of methyl alcohol and a small amount of ammoniacal liquor or alkali lye, temperature rising reflux, again lowers the temperature and removes upper strata methyl alcohol, repeats 2 times until obtain finished product.
Embodiment 4, in the step (1) of the preparation method of embodiment 1-3 described in any one: heat to 85-90 DEG C dissolve after drip chlorobutane again.
Embodiment 5, in the step (2) of the preparation method of embodiment 1-4 described in any one: control temperature of reaction at 60-65 DEG C, is incubated after dripping phosphorus oxychloride at 65-70 DEG C; All the other are identical.
Preparation method's experiment of embodiment 6,4,4'-[(9-butyl-9 hydrogen-carbazole-3-) methylene radical] two [N-Methyl-N-phenyl] aniline, step is as follows:
To in 250ml flask, add 64g32%NaOH solution, 1.8g catalyzer Tetrabutyl amonium bromide, 28.5g carbazole, is warmed up to 85 ~ 90 DEG C, stirs 30 minutes, dripped the chlorobutane of 18g with 3 hours, and 85 DEG C of insulations 5 hours, sampling detected carbazole < 05%, add toluene 90g and water 35g, 85 DEG C of insulations 30 minutes, branch vibration layer, with 50g water washing toluene layer 2 times, steam 36g toluene, take away the moisture in system.
To in system, add 15.5gDNF, dripped 32g phosphorus oxychloride with 4 hours, control temperature, at 60-65 DEG C, after dripping, is incubated 7 hours at 65 ~ 70 DEG C.
To in 500ml flask, add 200g water, and drip reaction solution above, control temperature < 80 DEG C, and stir 30 minutes at 80 DEG C, branch vibration layer, add 200g water and 2g ammonia scrubbing toluene layer, branch vibration layer, evaporated under reduced pressure toluene obtains BCA.
To in the 500nl flask containing BCA, add 180g methyl alcohol, 55gN-methyl-diphenylamine, 4.5g concentrated hydrochloric acid, be warmed up to 65 DEG C, and reflux 9 hours.
Divide and remove upper strata methanol mother liquor, with 40g methyl alcohol and 6g ammonia scrubbing product, when product becomes golden yellow sticky solid, divide and remove methyl alcohol, add 80g methyl alcohol and wash 1 time again, be warmed up to 130 DEG C, solvent evaporated, product melting, discharging, in shallow bottom tray, obtains block bright yellow solid after cooling; 92g, yield 90%.
Claims (1)
1. the preparation method of one kind 4,4'-[(9-butyl-9 hydrogen-carbazole-3-) methylene radical] two [N-Methyl-N-phenyl] aniline, it is characterized in that, its step is as follows:
To in 250ml flask, add 64g32%NaOH solution, 1.8g catalyzer Tetrabutyl amonium bromide, 28.5g carbazole, is warmed up to 85 ~ 90 DEG C, stirs 30 minutes, dripped the chlorobutane of 18g with 3 hours, and 85 DEG C of insulations 5 hours, sampling detected carbazole < 05%, add toluene 90g and water 35g, 85 DEG C of insulations 30 minutes, branch vibration layer, with 50g water washing toluene layer 2 times, steam 36g toluene, take away the moisture in system;
To in system, add 15.5gDNF, dripped 32g phosphorus oxychloride with 4 hours, control temperature, at 60-65 DEG C, after dripping, is incubated 7 hours at 65 ~ 70 DEG C;
To in 500ml flask, add 200g water, and drip reaction solution above, control temperature < 80 DEG C, and stir 30 minutes at 80 DEG C, branch vibration layer, add 200g water and 2g ammonia scrubbing toluene layer, branch vibration layer, evaporated under reduced pressure toluene obtains BCA;
To in the 500ml flask containing BCA, add 180g methyl alcohol, 55gN-methyl-diphenylamine, 4.5g concentrated hydrochloric acid, be warmed up to 65 DEG C, and reflux 9 hours;
Divide and remove upper strata methanol mother liquor, with 40g methyl alcohol and 6g ammonia scrubbing product, when product becomes golden yellow sticky solid, divide and remove methyl alcohol, add 80g methyl alcohol and wash 1 time again, be warmed up to 130 DEG C, solvent evaporated, product melting, discharging is in shallow bottom tray, block bright yellow solid 92g is obtained, yield 90% after cooling.
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| CN201310069140.XA CN103086952B (en) | 2013-02-19 | 2013-02-19 | Preparation method of 4,4'-[(9-butyl-9H-carbazole-3-)methylene]bis[N-methyl-N-phenyl]aniline |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4202820A (en) * | 1976-10-26 | 1980-05-13 | Ciba-Geigy Corporation | Pressure-sensitive or heat-sensitive recording material containing a carbazolyl methane compound |
| CN1081697A (en) * | 1993-05-08 | 1994-02-09 | 武汉染料厂 | Contain azo dispersion dyes of carbazolyl heterocyclic ring and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08259825A (en) * | 1995-01-23 | 1996-10-08 | Mitsubishi Paper Mills Ltd | Improved acid color developing-type achromatic dye |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4202820A (en) * | 1976-10-26 | 1980-05-13 | Ciba-Geigy Corporation | Pressure-sensitive or heat-sensitive recording material containing a carbazolyl methane compound |
| CN1081697A (en) * | 1993-05-08 | 1994-02-09 | 武汉染料厂 | Contain azo dispersion dyes of carbazolyl heterocyclic ring and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 《9-乙基-3-咔唑亚甲基-α-苯基-苯腙的合成》;李笃信;《精细化工·功能材料》;20000731;第391-392页的1.2.1和1.2.2 * |
| 《基于N-苯基咔唑的红色有机电致发光材料》;付慧英;《功能材料与器件学报》;20060831;280-284 * |
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