CN103992261B - 2-bromine carbazole industrial preparation process - Google Patents
2-bromine carbazole industrial preparation process Download PDFInfo
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- CN103992261B CN103992261B CN201410242683.1A CN201410242683A CN103992261B CN 103992261 B CN103992261 B CN 103992261B CN 201410242683 A CN201410242683 A CN 201410242683A CN 103992261 B CN103992261 B CN 103992261B
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- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
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Abstract
The invention discloses a kind of industrialized process for preparing of 2-bromo carbazole, belong to fine chemistry industry or organic molecule photoelectric functional material production field.Its synthesis technique comprises the following steps: (1) with 4-bromo biphenyl for starting raw material, by nitrated obtained intermediate (I); (2) with three (2-pyridyl) phosphine, to be reductor slough Hou Guanhuan by the oxygen on nitro in intermediate (I) obtains finalization compound 2-bromine carbazole (II).Preparation process condition gentleness of the present invention is controlled, and preparation method is simple, and yield is high; And not needing post, suitability for industrialized is produced.Obtained 2-bromine carbazole not only may be used for synthesized micromolecule photoelectric functional material, as medicine intermediate etc., can also have a good application prospect.
Description
Technical field
The invention belongs to fine chemistry industry or organic molecule photoelectric functional material production field, the synthesis technique of the particularly a kind of new suitability for industrialized amplification of 2-bromine carbazole.
Background technology
2-bromine carbazole (2-Bromocarbazole, CASNo:3652-90-2), its structural formula is:
Carbazole compound structure has following characteristics: (1) carbazole ring is easy to form metastable positive ion; (2) there is in molecule larger conjugated system and strong cyclic voltammetry method ability; (3) generally there is good hole transport performance, photochemical stability, in ultraviolet light range, have very strong absorption and energy gap is high.2 2-bromine carbazoles replaced have larger conjugated system compared with other carbazole compounds, there is stronger photosensitization performance and lower fusing point and much can launch valuable blue light, be more suitable for making OLED, its application in nearly 20 years is more and more extensive, so its easy, economic industrialization synthesis just seems particularly important.
According to the document of open report, the synthetic method of 2-bromine carbazole mainly contains four kinds:
First method (AngewandteChemie, InternationalEdition2013,52 (10): 2968-2971) with adjacent bromine nitrosobenzene and o-trimethyl silicon based phenol trifluoromethane sulfonic acid ester for starting raw material, through cyclization, driffractive ring under the existence of cesium fluoride (CsF), obtained 2-bromine carbazole after the substitution reaction of Intramolecular electricity.
The defect of this method is:
(1) raw material should not obtain, and photo-labile is shown in by adjacent bromine nitrosobenzene; (2) single step reaction comprises multiple pilot process in fact, is unfavorable for middle control analysis; (3) product by purification by silica gel column chromatography, need be only suitable for the preparation in a small amount in laboratory, is difficult to carry out industrialization.
Second method (JournalOfHeterocyclicChemistry.2001,38 (11): 11-23; WO201216248) take 2 nitro biphenyl as raw material, under iron(ic) chloride and bromine effect, obtain the bromo-2 '-nitrobiphenyl of 4-, then with the bromo-2 '-nitrobiphenyl of 4-and triethyl-phosphite backflow 12h, obtained 2-bromine carbazole.
The defect of this method is:
(1) the first step reaction, easily obtains single bromo nitryl biphenyl product of polybromide and other positions, causes yield lower, and purifying needs the method adopting pillar; (2) second step temperature of reaction is high, long reaction time, is not suitable for industrialization and amplifies.
The third synthetic method (WO2012169821; WO2012039561; US20130168656) be with 2-nitro iodobenzene and to bromobenzeneboronic acid for raw material, Suzuki linked reaction obtains 2-nitro-4 '-bromo biphenyl, as substrate and triethyl-phosphite back flow reaction, obtain 2-bromine carbazole.
The defect of this method is:
(1) the first step reaction, raw materials used 2-nitro iodobenzene, on the high side to bromobenzeneboronic acid, palladium catalyst, considerably increase process costs, be not suitable as industrialized production process; (2) second step temperature of reaction is high, long reaction time, is not suitable for industrialization and amplifies.
4th kind of synthetic method (WO2013084885; WO2013084881; WO2012165256; WO201204399; Synthesis.2005,10:1619-1624) the first step be with 2,5-bis-bromo nitrobenzene and phenylo boric acid for raw material, obtain 2-nitro-4-bromo biphenyl through coupling; Second step refluxes under orthodichlorobenzene solvent with obtained 2-nitro-4-bromo biphenyl and triphenylphosphine to be obtained by reacting 2-bromine carbazole.
The defect of this method is:
(1) intermediate of the first step synthesis needs to be removed by by product 2,5-phenylbenzene oil of mirbane by crossing pillar, otherwise closes and have the 2-phenyl carbazole being difficult to remove after ring and generate, therefore this technique is not suitable for industrialization amplifies; (2) raw materials cost is high, is not suitable as industrialized production process; (3) high, the long reaction time of temperature of reaction and total recovery is on the low side.
This shows, be badly in need of at present improving its technique, adopt raw material to be easy to get, aftertreatment did not need post and the simple preparation method of technique could meet the needs that industrial scale is produced.
Summary of the invention
For the deficiency of the synthetic method of current existing 2-bromine carbazole, the object of the present invention is to provide that a kind of cost is low, mild condition is controlled, and the preparation technology of 2-bromine carbazole that suitability for industrialized is amplified.
For realizing the object of the invention, technical scheme is as follows: the present invention adopts 4-bromo biphenyl to be raw material, the vitriol oil is solvent, be that nitrating agent carries out nitrated obtained intermediate product (I) with cupric nitrate, again with three (2-pyridyl) phosphine for reductor, sloughed by oxygen on nitro in intermediate product (I), Guan Huan obtains ultimate aim thing 2-bromine carbazole (II).
Its synthetic route is as follows:
The main component of intermediate product (I) has compound a, compound b and compound c, be shown below, wherein first two is product Intermediate, and deoxidation ring closure reaction can not occur compound c, the selection of the application's condition by experiment, effectively controls compound c content to promote the yield of target product.
This synthesis technique comprises following concrete steps:
(1) 4-bromo biphenyl is dropped in the vitriol oil, control temperature of reaction 0 ~ 30 DEG C, add cupric nitrate, stirring reaction under constant temperature, after then adding NaOH or KOH solution to neutrality in reaction solution, with dichloromethane extraction, after dry, underpressure distillation concentrates, and reclaims methylene dichloride, obtains intermediate product (I).
(2) under noble gas protection, add intermediate product (I) and three (2-pyridyl) phosphine reductor in a kettle. successively, stirring reaction at 90 ~ 110 DEG C, after purified, dry and obtain solid 2-bromine carbazole (II).
In the first step nitration reaction, the mol ratio of 4-bromo biphenyl and the vitriol oil is: 1: 2; The mol ratio of 4-bromo biphenyl and cupric nitrate is: 1: 1.0 ~ 1.5.
Second step ring-closure reaction, intermediate product (I) and reductor mol ratio are: 1: 2.0 ~ 3.5.
The present invention has the following advantages:
(1) the first step is nitrated, and described nitrating agent is cupric nitrate and vitriol oil mixture, be conducive to intermediate product a, b generate, preparation process condition gentleness is controlled, temperature of reaction and the time moderate, improve nitrated selectivity.
(2) second step cyclization, selects reductor to be three (2-pyridyl) phosphine, cyclization is more easily carried out, and shortens the reaction times, reduce process costs, improve reaction yield.
(3) intermediate product a, b and c is generated in reaction, wherein intermediate product a, b generates target compound in the presence of an oxidizer, for solid, and deoxidation ring closure reaction can not be there is in compound c, be dissolved in methylene dichloride, well by product and target compound are separated, are convenient to aftertreatment and purifying products, economical and convenient.
(4) nitrated and cyclization aftertreatment did not all need pillar, and be more suitable for suitability for industrialized production, yield is higher, and two step total recoverys can reach more than 72%.
Embodiment
For better illustrating the present invention, as follows for embodiment:
embodiment 1
With in the 500mL there-necked flask of mechanical stirring, thermometer and constant pressure funnel, add 46.6g(0.20mol) 4-bromo biphenyl and 40g(0.40mol) vitriol oil, stirs 5min, adds Cu (NO in batches
3)
237.6g(0.20mol), control temperature of reaction 0 ~ 10 DEG C, add rear constant temperature stirring reaction 5h.200mL methylene dichloride is added after reaction terminates, stir abundant extracted products, liquid in reaction flask is carefully proceeded in separating funnel, separate lower floor's nitration mixture layer, nitration mixture layer 20mL dichloromethane extraction, merge organic layer, and the NaOH solution slowly adding mass percent 10% in organic layer is extremely neutral, leave standstill and separate organic layer, 25mL × 2 saturated common salt water washing, anhydrous Na
2sO
4dry, vacuum concentration obtains dark reddish-brown oil liquid 50.6g.
Under noble gas protection; in 250mL be with churned mechanically three-necked bottle, add 50.6g(be about 0.18mol) concentrated solution of previous step; 122.1g(0.46mol) three (2-pyridyl) phosphine; be heated with stirring to 90 ~ 100 DEG C of reactions; HPLC detects 2-nitro-4-bromo biphenyl in raw material and 2-nitro-4 '-bromo biphenyl all reacts completely, stops stirring.Add 200mL sherwood oil, filter, the solid obtained adds 250mL methylene dichloride reflux again and stirs 1h, and cooling suction filtration, a small amount of washed with dichloromethane filter cake, obtains 35.6g off-white color solid 2-bromine carbazole (II), total recovery: 72.1% after vacuum-drying.MS(FAB):m/z246(M
+);
1HNMR(CDCl
3):δ11.39(s,1H,N-H),8.14–8.11(dd,
J=8.0Hz,2H,Ar-H),7.67(d,
J=1.7Hz,1H,Ar-H),7.53–7.16(m,4H,Ar-H)。
embodiment 2
With in the 500mL there-necked flask of mechanical stirring, thermometer and constant pressure funnel, add 46.6g(0.20mol) 4-bromo biphenyl and 40g(0.40mol) vitriol oil, stirs 5min, adds Cu (NO in batches
3)
248.9g(0.26mol), control temperature of reaction 20 ~ 30 DEG C, add rear constant temperature stirring reaction 5h.200mL methylene dichloride is added after reaction terminates, stir abundant extracted products, liquid in reaction flask is carefully proceeded in separating funnel, separate lower floor's nitration mixture layer, nitration mixture layer 20mL dichloromethane extraction, merge organic layer, and the NaOH solution slowly adding mass percent 10% in organic layer is extremely neutral, leave standstill and separate organic layer, 25mL × 2 saturated common salt water washing, anhydrous Na
2sO
4dry, vacuum concentration obtains dark reddish-brown oil liquid 52.8g.
Under noble gas protection; in 250mL be with churned mechanically three-necked bottle, add 52.8g(be about 0.19mol) concentrated solution of previous step; 148.8g(0.57mol) three (2-pyridyl) phosphine; be heated with stirring to 100 ~ 110 DEG C of reactions; HPLC detects 2-nitro-4-bromo biphenyl in raw material and 2-nitro-4 '-bromo biphenyl all reacts completely, stops stirring.Add 200mL sherwood oil, filter, the solid obtained adds 250mL methylene dichloride reflux again and stirs 1h, and cooling suction filtration, a small amount of washed with dichloromethane filter cake, obtains 39.1g off-white color solid 2-bromine carbazole (II), total recovery: 78.5% after vacuum-drying.
embodiment 3
With in the 500mL there-necked flask of mechanical stirring, thermometer and constant pressure funnel, add 46.6g(0.20mol) 4-bromo biphenyl and 40g(0.40mol) vitriol oil, stirs 5min, adds Cu (NO in batches
3)
252.5g(0.28mol), control temperature of reaction 10 ~ 20 DEG C, add rear constant temperature stirring reaction 5h.200mL methylene dichloride is added after reaction terminates, stir abundant extracted products, liquid in reaction flask is carefully proceeded in separating funnel, separate lower floor's nitration mixture layer, nitration mixture layer 20mL dichloromethane extraction, merge organic layer, and the KOH solution slowly adding mass percent 10% in organic layer is extremely neutral, leave standstill and separate organic layer, 25mL × 2 saturated common salt water washing, anhydrous Na
2sO
4dry, vacuum concentration obtains dark reddish-brown oil liquid 53.4g.
Under noble gas protection; in 250mL be with churned mechanically three-necked bottle, add 53.4g(be about 0.19mol) concentrated solution of previous step; 165.5g(0.63mol) three (2-pyridyl) phosphine; be heated with stirring to 90 ~ 100 DEG C of reactions; HPLC detects 2-nitro-4-bromo biphenyl in raw material and 2-nitro-4 '-bromo biphenyl all reacts completely, stops stirring.Add 200mL sherwood oil, filter, the solid obtained adds 250mL methylene dichloride reflux again and stirs 1h, and cooling suction filtration, a small amount of washed with dichloromethane filter cake, obtains 36.5g off-white color solid 2-bromine carbazole (II), total recovery: 74.2% after vacuum-drying.
Claims (3)
1. a preparation technology for 2-bromine carbazole, is characterized in that, comprises the following steps:
(1) 4-bromo biphenyl is dropped in the vitriol oil, control temperature of reaction 0 ~ 30 DEG C, add cupric nitrate, stirring reaction under constant temperature, after then adding basic solution to neutrality in reaction solution, with dichloromethane extraction, after dry, underpressure distillation concentrates, and reclaims methylene dichloride, obtains intermediate product (I);
(2) under noble gas protection, add intermediate product (I) and three (2-pyridyl) phosphine reductor in a kettle. successively, stirring reaction at 90 ~ 110 DEG C, after purified, dry and obtain 2-bromine carbazole;
Wherein intermediate product (I) main component is as follows:
。
2. the preparation technology of 2-bromine carbazole according to claim 1, is characterized in that: in step (1), the mol ratio of 4-bromo biphenyl and the vitriol oil is: 1: 2; The mol ratio of 4-bromo biphenyl and cupric nitrate is: 1: 1.0 ~ 1.5.
3. the preparation technology of 2-bromine carbazole according to claim 1, is characterized in that: in step (2), intermediate product (I) and reductor mol ratio are: 1: 2.0 ~ 3.5.
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| CN108299284A (en) * | 2018-01-18 | 2018-07-20 | 河南省科学院化学研究所有限公司 | A kind of bromo- 6,9- diphenyl carbazole industrialized producing technologies of 2- |
| CN111534458B (en) * | 2020-04-13 | 2022-01-14 | 浙江工业大学 | Achromobacter TBC-1 and application thereof in degradation of 1,3,6,8-tetrabromocarbazole |
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| CN103232385A (en) * | 2013-04-23 | 2013-08-07 | 苏州谷力生物科技有限公司 | 2,7-dibromo-N-perfluoro-butylethylcarbazole and preparation method thereof |
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| "Diversification of Carbazoles by LiCl-mediated Catalytic CuI Reaction";Joong Hyun Cho等;《Bull. Korean Chem. Soc.》;20111231;第32卷(第7期);第2461页Scheme 1 * |
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