CN103992261A - Industrial process for preparing 2-bromo-carbazole - Google Patents

Industrial process for preparing 2-bromo-carbazole Download PDF

Info

Publication number
CN103992261A
CN103992261A CN201410242683.1A CN201410242683A CN103992261A CN 103992261 A CN103992261 A CN 103992261A CN 201410242683 A CN201410242683 A CN 201410242683A CN 103992261 A CN103992261 A CN 103992261A
Authority
CN
China
Prior art keywords
carbazole
bromo
reaction
intermediate product
add
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201410242683.1A
Other languages
Chinese (zh)
Other versions
CN103992261B (en
Inventor
刘睿
周铎
崔富民
杨振强
杨瑞娜
安小龙
王艳超
韩兆海
王中锋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
PUYANG HUICHENG ELECTRONIC MATERIAL CO Ltd
Original Assignee
PUYANG HUICHENG ELECTRONIC MATERIAL CO Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by PUYANG HUICHENG ELECTRONIC MATERIAL CO Ltd filed Critical PUYANG HUICHENG ELECTRONIC MATERIAL CO Ltd
Priority to CN201410242683.1A priority Critical patent/CN103992261B/en
Publication of CN103992261A publication Critical patent/CN103992261A/en
Application granted granted Critical
Publication of CN103992261B publication Critical patent/CN103992261B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Indole Compounds (AREA)

Abstract

The invention discloses an industrial method for preparing 2-bromo-carbazole and belongs to the field of fine chemical industry or the production of organic small molecular optoelectronic functional materials. The synthetic process comprises the following steps: (1) nitrating 4-bromobiphenyl serving as a starting material to prepare an intermediate (I); and (2) removing oxygen from the nitro group of the intermediate (I) in the presence of tri(2-pyridyl) phosphine serving as a deoxidizer and carrying ring closing to obtain the final compound, namely, 2-bromo-carbazole (II). The method disclosed by the invention has the advantages of mild and controlled preparation process conditions, simple preparation method, high yield and no need of column chromatography and is suitable for industrial production. The obtained 2-bromo-carbazole can be used for synthesizing organic small molecular optoelectronic functional materials, and can be used as pharmaceutical intermediates and the like and has good application prospects.

Description

2-bromine carbazole industrial preparation process
Technical field
The invention belongs to fine chemistry industry or organic molecule photoelectric functional material production field, the synthesis technique that particularly a kind of new suitability for industrialized of 2-bromine carbazole is amplified.
Background technology
2-bromine carbazole (2-Bromocarbazole, CAS No:3652-90-2), its structural formula is:
Carbazole compound structure has following characteristics: (1) carbazole ring is easy to form metastable positive ion; (2) in molecule, there is larger conjugated system and the strong interior electron transfer capacity of molecule; (3) generally there is good hole transport performance, photochemical stability, in ultraviolet light range, have very strong absorption and energy gap high.The 2-bromine carbazole of 2 replacements is compared and is had larger conjugated system 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 device, its application in nearly 20 years is more and more extensive, so its easy, economic industrialization is synthetic, 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, International Edition 2013,52 (10): 2968-2971) take adjacent bromine nitrosobenzene and o-trimethyl silicon based phenol trifluoromethane sulfonic acid ester is starting raw material, under the existence of cesium fluoride (CsF), through cyclization, driffractive ring, in molecule, after electrophilic substitution reaction, make 2-bromine carbazole.
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 a plurality of pilot processs in fact, is unfavorable for middle control analysis; (3) product need pass through purification by silica gel column chromatography, is only suitable for preparing in a small amount in laboratory, is difficult to carry out industrialization.
Second method (Journal Of Heterocyclic Chemistry. 2001,38 (11): 11-23; WO201216248) take 2 nitro biphenyl as raw material, under iron(ic) chloride and bromine effect, make the bromo-2 '-nitrobiphenyl of 4-, then with the bromo-2 '-nitrobiphenyl of 4-and triethyl-phosphite backflow 12h, make 2-bromine carbazole.
The defect of this method is:
(1) the first step is reacted, and easily obtains single bromo nitryl biphenyl product of polybromide and other positions, cause yield lower, and purifying need to adopt the method for pillar; (2) second step temperature of reaction is high, and long reaction time is not suitable for industrialization and amplifies.
The third synthetic method (WO2012169821; WO2012039561; US20130168656) be to take 2-nitro iodobenzene and be raw material to bromobenzene boric acid, Suzuki linked reaction makes 2-nitro-4 '-bromo biphenyl, as substrate and triethyl-phosphite back flow reaction, obtains 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 bromobenzene boric acid, palladium catalyst, has increased process costs greatly, is not suitable as industrialized production process; (2) second step temperature of reaction is high, and long reaction time is not suitable for industrialization and amplifies.
The 4th kind of synthetic method (WO2013084885; WO2013084881; WO2012165256; WO201204399; Synthesis.2005,10:1619-1624) the first step be with 2,5-, bis-bromo nitrobenzenes and phenylo boric acid for raw material, through coupling, make 2-nitro-4-bromo biphenyl; Second step is that the 2-nitro-4-bromo biphenyl and the triphenylphosphine back flow reaction under orthodichlorobenzene solvent that make obtain 2-bromine carbazole.
The defect of this method is:
(1) the synthetic intermediate of the first step need to pass through pillar by by product 2, and 5-phenylbenzene oil of mirbane is removed, otherwise had the 2-phenyl carbazole generation that is difficult to remove after closing ring, therefore this technique is not suitable for industrialization, amplified; (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 are on the low side.
This shows, be badly in need of at present its technique to improve, 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 the 2-bromine carbazole that amplifies of suitability for industrialized.
For realizing the object of the invention, technical scheme is as follows: it is raw material that the present invention adopts 4-bromo biphenyl, the vitriol oil is solvent, with cupric nitrate, be that nitrating agent carries out the nitrated intermediate product (I) that makes, three (2-pyridyl) phosphine of take is again reductor, oxygen on nitro in intermediate product (I) is sloughed, closed ring and make 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 compound c deoxidation ring closure reaction can not occur, the application is the selection of 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 0 ~ 30 ℃ of temperature of reaction, add cupric nitrate, stirring reaction under constant temperature then adds 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, in reactor, add successively intermediate product (I) and three (2-pyridyl) phosphine reductor, stirring reaction at 90 ~ 110 ℃, purified after, oven dry obtains 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) with reductor mol ratio is: 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, is conducive to intermediate product a, b and generates, and preparation process condition gentleness is controlled, and temperature of reaction and time are moderate, have improved nitrated selectivity.
(2) second step cyclization, selecting reductor is three (2-pyridyl) phosphine, cyclization is more easily carried out, and shortened the reaction times, has reduced process costs, has improved reaction yield.
(3) in reaction, generate intermediate product a, b and c, wherein intermediate product a, b generate target compound under oxygenant exists, for solid, and can there is not deoxidation ring closure reaction in compound c, be dissolved in methylene dichloride, well that by product and target compound is separated, be convenient to aftertreatment and purifying products, economical and convenient.
(4) nitrated and cyclization aftertreatment did not all need pillar, was more suitable for suitability for industrialized production, and yield is higher, and two step total recoverys can reach more than 72%.
Embodiment
For the present invention is better illustrated, as follows for embodiment:
embodiment 1
In the 500mL there-necked flask with mechanical stirring, thermometer and constant pressure funnel, add 46.6g(0.20mol) 4-bromo biphenyl and 40 g(0.40mol) vitriol oil, stir 5min, add Cu (NO in batches 3) 237.6 g(0.20mol), control 0 ~ 10 ℃ of temperature of reaction, add rear constant temperature stirring reaction 5h.After finishing, reaction adds 200 mL methylene dichloride, 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, merges organic layer, and slowly add the NaOH solution of mass percent 10% to neutral in organic layer, the standing organic layer that separates, 25mL * 2 saturated common salt water washing, anhydrous Na 2sO 4dry, vacuum concentration obtains reddish brown oily liquids 50.6g.
Under noble gas protection; at 250mL, add the about 0.18mol of 50.6g(in churned mechanically three-necked bottle) concentrated solution of previous step; 122.1g(0.46mol) three (2-pyridyl) phosphine; be heated with stirring to 90 ~ 100 ℃ of reactions; 2-nitro-4-bromo biphenyl and 2-nitro-4 '-bromo biphenyl that HPLC detects in raw material all react completely, and stop stirring.Add 200mL sherwood oil, filter, the solid obtaining adds 250mL methylene dichloride reflux to stir 1h again, cooling suction filtration, and a small amount of washed with dichloromethane filter cake, obtains 35.6 g off-white color solid 2-bromine carbazoles (II), total recovery: 72.1% after vacuum-drying.MS(FAB):?m/z?246?(M +);? 1H?NMR?(CDCl 3):?δ?11.39?(s,?1H,?N-H),?8.14–8.11?(dd,? J=8.0?Hz,?2H,?Ar-H),?7.67?(d,? J=1.7?Hz,?1H,?Ar-H),?7.53–7.16?(m,?4H,?Ar-H)。
embodiment 2
In the 500 mL there-necked flasks with mechanical stirring, thermometer and constant pressure funnel, add 46.6g(0.20mol) 4-bromo biphenyl and 40 g(0.40mol) vitriol oil, stir 5min, add Cu (NO in batches 3) 248.9 g(0.26mol), control 20 ~ 30 ℃ of temperature of reaction, add rear constant temperature stirring reaction 5h.After finishing, reaction adds 200 mL methylene dichloride, 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, merges organic layer, and slowly add the NaOH solution of mass percent 10% to neutral in organic layer, the standing organic layer that separates, 25 mL * 2 saturated common salt water washings, anhydrous Na 2sO 4dry, vacuum concentration obtains reddish brown oily liquids 52.8g.
Under noble gas protection; at 250 mL, add the about 0.19mol of 52.8g(in churned mechanically three-necked bottle) concentrated solution of previous step; 148.8g(0.57mol) three (2-pyridyl) phosphine; be heated with stirring to 100 ~ 110 ℃ of reactions; 2-nitro-4-bromo biphenyl and 2-nitro-4 '-bromo biphenyl that HPLC detects in raw material all react completely, and stop stirring.Add 200mL sherwood oil, filter, the solid obtaining adds 250mL methylene dichloride reflux to stir 1h again, cooling suction filtration, and 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
In the 500 mL there-necked flasks with mechanical stirring, thermometer and constant pressure funnel, add 46.6g(0.20mol) 4-bromo biphenyl and 40 g(0.40mol) vitriol oil, stir 5min, add Cu (NO in batches 3) 252.5 g(0.28mol), control 10 ~ 20 ℃ of temperature of reaction, add rear constant temperature stirring reaction 5h.After finishing, reaction adds 200 mL methylene dichloride, 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, merges organic layer, and slowly add the KOH solution of mass percent 10% to neutral in organic layer, the standing organic layer that separates, 25 mL * 2 saturated common salt water washings, anhydrous Na 2sO 4dry, vacuum concentration obtains reddish brown oily liquids 53.4g.
Under noble gas protection; at 250 mL, add the about 0.19mol of 53.4g(in churned mechanically three-necked bottle) concentrated solution of previous step; 165.5g(0.63mol) three (2-pyridyl) phosphine; be heated with stirring to 90 ~ 100 ℃ of reactions; 2-nitro-4-bromo biphenyl and 2-nitro-4 '-bromo biphenyl that HPLC detects in raw material all react completely, and stop stirring.Add 200mL sherwood oil, filter, the solid obtaining adds 250mL methylene dichloride reflux to stir 1h again, cooling suction filtration, and 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 0 ~ 30 ℃ of temperature of reaction, add cupric nitrate, stirring reaction under constant temperature then adds 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, in reactor, add successively intermediate product (I) and three (2-pyridyl) phosphine reductor, stirring reaction at 90 ~ 110 ℃, purified after, oven dry obtains 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) with reductor mol ratio is: 1: 2.0 ~ 3.5.
CN201410242683.1A 2014-06-04 2014-06-04 2-bromine carbazole industrial preparation process Active CN103992261B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410242683.1A CN103992261B (en) 2014-06-04 2014-06-04 2-bromine carbazole industrial preparation process

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410242683.1A CN103992261B (en) 2014-06-04 2014-06-04 2-bromine carbazole industrial preparation process

Publications (2)

Publication Number Publication Date
CN103992261A true CN103992261A (en) 2014-08-20
CN103992261B CN103992261B (en) 2015-12-30

Family

ID=51306629

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410242683.1A Active CN103992261B (en) 2014-06-04 2014-06-04 2-bromine carbazole industrial preparation process

Country Status (1)

Country Link
CN (1) CN103992261B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105061296A (en) * 2015-08-10 2015-11-18 张家港江苏科技大学产业技术研究院 Preparation method for 2-substituted carbazole compounds
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-
CN111534458A (en) * 2020-04-13 2020-08-14 浙江工业大学 Achromobacter TBC-1 and application thereof in degradation of 1,3,6,8-tetrabromocarbazole

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JOONG HYUN CHO等: ""Diversification of Carbazoles by LiCl-mediated Catalytic CuI Reaction"", 《BULL. KOREAN CHEM. SOC.》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105061296A (en) * 2015-08-10 2015-11-18 张家港江苏科技大学产业技术研究院 Preparation method for 2-substituted carbazole compounds
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-
CN111534458A (en) * 2020-04-13 2020-08-14 浙江工业大学 Achromobacter TBC-1 and application thereof in degradation of 1,3,6,8-tetrabromocarbazole
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

Also Published As

Publication number Publication date
CN103992261B (en) 2015-12-30

Similar Documents

Publication Publication Date Title
CN106800493B (en) Method for reducing aromatic nitro group into aromatic amine
CN103992225B (en) A kind of salicylaldehyde derivatives and preparation method thereof
CN103232365B (en) Schiff base compound, and synthesis method and application thereof
CN104327008A (en) Synthesis method of benzoxazole compound
CN105968023A (en) Method for preparing bupropion hydrochloride
CN103641722A (en) Production method for 2-nitrobenzyl bromide
CN103992261B (en) 2-bromine carbazole industrial preparation process
CN101367736A (en) Synthesis of 2-aminobiphenyl compounds
CN107235891B (en) Preparation method of 4-bromocarbazole
CN108147972B (en) Preparation method of vipatavir intermediate and analogue thereof
CN107445886B (en) Preparation method of high-purity 3-bromo-9-phenylcarbazole
CN109651367B (en) Method for preparing 1, 4-dihydroquinoline and pyrrolo [1,2-a ] quinoline compounds
CN112358443A (en) Pyridine compound and preparation method thereof
CN105294415A (en) Preparation method of 3-halogenated fluorenone compound
CN102382051A (en) Method for preparing isoquinoline ketone and derivatives thereof
CN109232381B (en) 9- ([1,1' -biphenyl ] -3-yl) -2' -bromo-2, 9' -bicarbazole and synthesis method thereof
CN106905133B (en) Spiro-fluorene-indene diketone compound and preparation method and application thereof
CN107446590B (en) Process for synthesizing fluorine-containing dicyclohexyl alkene liquid crystal at tail end
CN110028409A (en) A kind of polysubstituted naphthalene derivatives and preparation method thereof
CN109836383A (en) A method of preparing 3,4- dihydroquinoline -2 (1H) -one class compound
CN111704548B (en) Method for preparing nitroolefin from aryl ethane and nitrate
CN110343047B (en) Preparation method of aminopyrene compound
CN108329262A (en) The synthetic method of N- (2- quinolyls) benzamide compound
CN109796372B (en) Method for preparing polysubstituted alkenyl amidine
CN108314649A (en) The synthetic method of 6- phenylphenanthridinewiths

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant