CN109232383A - A method of synthesis 4- bromine carbazole - Google Patents
A method of synthesis 4- bromine carbazole Download PDFInfo
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- CN109232383A CN109232383A CN201811470191.2A CN201811470191A CN109232383A CN 109232383 A CN109232383 A CN 109232383A CN 201811470191 A CN201811470191 A CN 201811470191A CN 109232383 A CN109232383 A CN 109232383A
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- 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
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Abstract
The invention discloses a kind of synthetic methods of 4- bromine carbazole, belong to organic synthesis field.This method is using o-chloronitrobenzene as starting material, the high temperature coupling reaction synthesis 2 under copper powder catalysis, 2 '-dinitro biphenyl, 4- nitrocarbazole is obtained by triethyl phosphite cyclization later, diazonium salt is obtained by zinc powder reduction, diazo-reaction under 4- nitrocarbazole acid condition, and then reacts synthetic product 4- bromine carbazole with cuprous bromide.This method raw material is easy to get, production cost is low, and yield is easy to industrialized production up to 70% or more, provides the foundation for 4- bromine carbazole and its subsequent derivation object industrialization.
Description
Technical field
The present invention relates to a kind of carbazole compound production method more particularly to the synthetic methods of 4- bromine carbazole, and belonging to has
Machine synthesizes field.
Background technique
Organic Light-Emitting Display is a kind of electric energy conversion film for the electric energy of application being converted into luminous energy.Organic electroluminescent
Film has the advantages that following prominent, and low in energy consumption, flexible, fast response time, visual angle be wide, can large-area displays, luminous color
It is complete etc., it is that luminescent device at low cost is made in a kind of existing multiple standards, technical compatibility, thus is realizing that coloured plate is aobvious
Show that aspect shows powerful vitality.Currently, organic electroluminescence device is towards practical, commercialized development, but
The brightness of device, efficiency and there is still a need for further increase on the service life.For existing charge transport compound major part mobility
Low, this poor status of stability develops the organic macromolecule with strong electron-withdrawing group group and continuous pi-conjugated system, and will be more
The molecule of kind of functional group is assembled, and collection carries out transmission using hole charge and has become one kind together in same molecule
New research direction.Carbazole and its derivative belong to electron rich system, not only have biggish pi-conjugated system, while also having
Stronger cyclic voltammetry method characteristic.From the point of view of in structure, the electrophilic N atom of carbazole attracts pi-conjugated system by inductive effect
Electronics make pi-conjugated system electron rich, therefore click since the lone pair electrons of the pi-conjugated effect N atom of P- supply pi-conjugated system again
Azole compounds have very strong cavity transmission ability.Carbazole ring substituents position is different, and electronic effect is entirely different, into
And its cavity transmission ability also differs widely.The polymer of the segment containing carbazole is in field of photoelectric devices increasingly by weight in recent years
Depending on.
Currently, the synthesis about bromo carbazole class compound, 3- bromine carbazole, 3,6- dibromo carbazole are all by the straight of carbazole
Bromination synthesis is connect, and it is relatively large to synthesize difficulty due to its special structure for 4- bromo carbazole.Current existing two kinds of 4-
The synthetic method of bromine carbazole is as follows:
1. preparing adjacent nitre by the lithium halogen exchange of butyl lithium, boronation reaction under low temperature using o-bromonitrobenzene as starting material
Base phenyl boric acid, then ortho-nitrophenyl boric acid and adjacent bromo-iodobenzene are coupled, pass through triethyl phosphite Cyclization 4- bromine carbazole again.
2. reacting synthesis ortho-nitrophenyl pinacol borate by Miyaura boronation, then using o-bromonitrobenzene as raw material
It is coupled again with adjacent bromo-iodobenzene, eventually by triethyl phosphite Cyclization 4- bromine carbazole.
Both the above synthetic method is required to use boronation reaction and Suzuki coupling reaction, and used expensive starting materials close
At condition harshness, therefore lead to its higher cost, it can not mass production.
Summary of the invention
It is an object of that present invention to provide a kind of raw materials to be easy to get, production cost is low, and can apply to industrialized 4- bromine click
Azoles new synthetic method.
To achieve the purpose of the present invention, technical solution of the present invention is as follows:
Using o-chloronitrobenzene as starting material, high temperature coupling reaction synthesizes 2,2 '-dinitro biphenyl under copper powder catalysis, it
4- nitrocarbazole is obtained by triethyl phosphite cyclization afterwards, passes through zinc powder reduction, diazotising under 4- nitrocarbazole acid condition
Reaction obtains diazonium salt, and then synthetic product 4- bromine carbazole is reacted with cuprous bromide.
Synthetic route of the invention is as follows:
Specific reaction step is as follows:
(1) addition o-chloronitrobenzene and copper powder catalyst in reaction flask, 200-220 DEG C of system temperature of holding, insulation reaction,
After reaction, it is cooled to room temperature, extracts organic layer, filter out solid residue, residual washing-out merges organic layer, solvent is evaporated off
Sticky solid is obtained, 2,2 '-dinitro biphenyl of solid is recrystallized to give.
(2) under inert gas shielding, 2,2 '-dinitro biphenyl is added in another reaction flask, are warming up to 140-160
DEG C, stirring is lower to be added dropwise cyclization reagent triethyl phosphite by dropping funel, continues that the temperature is kept to be stirred to react, reacts
Terminate to add alkali neutralization aqueous solution, separates organic layer, cold filtration obtains brown ceramic powder 4- nitrocarbazole, is recrystallized to give 4- nitro
Carbazole sterling.
(3) under inert gas shielding, 4- nitrocarbazole in acid condition, is added zinc powder reduction and obtains 4- aminocarbazole,
Hydrobromic acid is added later, sodium nitrite in aqueous solution is gradually added dropwise under the conditions of ice-water bath, diazonium salt is made, bromine is added dropwise again later
Change cuprous aqueous solution, after fully reacting, sodium hydrogensulfite is added and removes extra bromine, washing obtains crude product, later by tying again
Crystalline substance obtains the 4- bromine carbazole product of off-white color.
Copper powder catalyst and o-chloronitrobenzene molar ratio are 1:1.1-1.3 in step (1)；2,2 '-dinitros in step (2)
Biphenyl and triethyl phosphite molar ratio are 1:4-5；4- nitrocarbazole and zinc powder reduction agent molar ratio are 1 in step (3):
3-5。
The innovative point and advantage of 4- bromine carbazole new synthetic method of the present invention are: raw material is easy to get, production cost is low, produces
Rate is readily applied to industrialized production up to 70% or more, provides the foundation for 4- bromine carbazole and its subsequent derivation object industrialization.
Specific embodiment
For preferably the present invention is described in detail, an example is as follows:
Example one
1) adjacent chlorine nitro is added in the 500mL three neck round bottom flask that blender, thermometer, reflux condensing tube are housed at one
Benzene 44.1g (0.28mol), copper powder 19.7g (0.31mol).Mixture is heated to 200 DEG C, and keeps the temperature 12h.
It is detected by chromatogram tracking, raw material o-chloronitrobenzene content stops reaction after being lower than 2%, is cooled to room temperature, to anti-
Addition 150mL methylene chloride in system is answered to be extracted.450mL*3 washed reaction liquid is used again, stirs to get thick solid,
Pass through 200mL recrystallizing methanol later.Obtain faint yellow solid 2,2- dinitro biphenyl 52.6g, yield 77%.
2) under inert gas shielding, faint yellow 2, the 2- dinitro biphenyl investment of 48.8g (0.20mol) is had into mechanical stirring
In tri- mouthfuls of reaction flasks of 500mL of thermometer, 160 DEG C are heated to, 150g triethyl phosphite is slowly added dropwise, is added dropwise complete
After keep the temperature 2h, stop heating, sodium hydrate aqueous solution be added and neutralizes, cools and 4- nitrocarbazole crude product, methanol is obtained by filtration
It is recrystallized to give 4- nitrocarbazole sterling 32.2g, yield 71%.
3) under inert gas shielding, by 30g zinc powder, 100mL ethyl alcohol, 100mL water, 10mL glacial acetic acid, 22.6g (0.1mol)
4- nitrocarbazole is put into 500mL reaction flask, and heating is kept for 40 DEG C.2h is kept the temperature, stops reaction when reaction solution is in canescence, adds
Enter a small amount of sodium hydroxide, it is organic that the extraction of 150mL methylene chloride is added after reaction system is cooling to 8-9 in the Ph value of regulation system
Layer extracts organic layer out, methylene chloride is evaporated off, and 40% hydrobromic acid 150mL of mass percentage is added when product will be precipitated, in addition
150mL water, the cooling 30min of ice-water bath is added.It is added dropwise sodium nitrite in aqueous solution 50mL (sodium nitrite 13.7g, 0.2mol), is added dropwise
After the completion, 30min is kept the temperature, continues that cuprous bromide aqueous solution 200mL (cuprous bromide 21.5g, 0.15mol) is added dropwise later.Reaction
10g sodium hydrogensulfite is added after 2h and removes extra bromine, water phase is added the extraction of 150mL methylene chloride, methylene chloride is evaporated off, then
150mL recrystallizing methanol is added, light yellow solid 4- bromine carbazole 17.7g, content 99%+, yield 72% is obtained by filtration.MS
(FAB):m/z 246(M+).1H NMR (DMSO): δ [ppm] 11.66 (s, 1H, NH), 8.57-8.59 (d, 1H, Ar), 7.47-
7.58 (m, 2H, Ar), 7.24-7.39 (m, 4H, Ar).
Example two
1) o-chloronitrobenzene is added in the 500mL three neck round bottom flask that blender, thermometer, reflux condensing tube are housed
44.1g (0.28mol), copper powder 22.8g (0.36mol).220 DEG C are first heated to, thermotonus 10h is then kept.Pass through color
Tracing detection is composed, after raw material o-chloronitrobenzene content is lower than 2%, cooling stops reaction, and cooling reaction solution to room temperature is anti-to this
Addition 150mL methylene chloride in system is answered to be extracted.450mL*3 washed reaction liquid is used again, stirs to get thick solid,
Pass through 200mL recrystallizing methanol later.Obtain faint yellow solid 2,2- dinitro biphenyl 51.2g, yield 75%.
2) under inert gas protection, 2, the 2- dinitro biphenyl investment that step on 48.8g (0.20mol) obtains is had
In tri- mouthfuls of reaction flasks of 500mL of mechanical stirring and thermometer, 140 DEG C are heated to, 133g (0.80mol) phosphorous is slowly added dropwise
Triethylenetetraminehexaacetic acid ester keeps the temperature 2h after being added dropwise to complete, and is cooled to 80 DEG C, and sodium hydrate aqueous solution is added and neutralizes, cools and is obtained by filtration
4- nitrocarbazole crude product, recrystallizing methanol obtain 4- nitrocarbazole sterling 31.7g, yield 70%.
3) under inert gas shielding, by 20g zinc powder, 100mL ethyl alcohol, 100mL water, 10mL glacial acetic acid, 22.6g (0.1mol)
4- nitrocarbazole is put into 500mL reaction flask, heats and keeps 40 DEG C.Insulation reaction 2h stops when reaction solution is in canescence
It only reacts, 150mL dichloromethane is added after reaction system is cooling to 8-9 in the Ph value that sodium hydrate aqueous solution regulation system is added
Alkane extracts organic layer, extracts organic layer out, methylene chloride is evaporated off, and 40% hydrobromic acid of mass percentage is added when product will be precipitated
150mL additionally incorporates 150mL water, the cooling 30min of ice-water bath.Dropwise addition sodium nitrite in aqueous solution 50mL (sodium nitrite 13.7g,
0.2mol), after being added dropwise to complete, keep the temperature 30min, continue later be added dropwise cuprous bromide aqueous solution 200mL (cuprous bromide 21.5g,
0.15mol).10g sodium hydrogensulfite is added after reaction 2h and removes extra bromine, stops reaction, with 150mL methylene chloride extraction water
Methylene chloride is evaporated off in phase, and 150mL recrystallizing methanol is then added, light yellow solid 4- bromine carbazole 17.2g, content is obtained by filtration
99%+, yield 70%.
Example three
1) equipped with blender, thermometer, reflux condensing tube 500mL three neck round bottom flask in o-chloronitrobenzene is added
44.1g (0.28mol), copper powder 19.7g (0.31mol).Mixture is heated to 200 DEG C, and keeps the temperature 10h.It is examined by chromatogram tracking
It surveys, raw material o-chloronitrobenzene content stops reaction after being lower than 2%, is cooled to room temperature, and 150mL dichloromethane is added into reaction system
Alkane is extracted.After hydrolysis, then with 450mL*3 washed reaction liquid, thick solid is stirred to get, passes through 200mL first later
Alcohol recrystallization.Obtain faint yellow solid 2,2- dinitro biphenyl 52.6g, yield 77%.
2) under inert gas shielding, 48.8g (0.20mol) 2,2- dinitro biphenyl investment be furnished with mechanical stirring and temperature
In tri- mouthfuls of reaction flasks of 500mL of meter, 150 DEG C are warming up to, 150g (0.9mol) triethyl phosphite is slowly added dropwise, after being added dropwise completely
2h is kept the temperature, after being cooled to 80 DEG C, sodium hydrate aqueous solution neutralization reaction liquid is slowly added to, cools to room temperature, be obtained by filtration
4- nitrocarbazole crude product obtains 4- nitrocarbazole sterling 32.7g, yield 72% with 100ml recrystallizing methanol.
3) under inert gas shielding, by 30g zinc powder, 100mL ethyl alcohol, 100mL water, 10mL glacial acetic acid, 22.6g (0.1mol)
4- nitrocarbazole is put into 500mL reaction flask, and heating reaction solution to 40 DEG C and keeps 2h, and reaction solution is gradually faded to by light yellow
Stop reaction when canescence, by the Ph value of sodium hydroxide solution regulation system to 8-9, is fully cooled reaction solution, 150mL is added
Methylene chloride extracts organic layer, merges organic layer, removes methylene chloride under reduced pressure, and quality percentage is added when product will be precipitated and contains
40% hydrobromic acid 150mL is measured, 150mL water, the cooling 30min of ice-water bath is added.It is water-soluble that sodium nitrite is slowly added dropwise into reaction solution
Liquid 50mL (sodium nitrite 13.7g, 0.2mol) after being added dropwise to complete, keeps the temperature 30min, continues that cuprous bromide aqueous solution is added dropwise later
200mL (cuprous bromide 21.5g, 0.15mol).10g sodium hydrogensulfite is added after reaction 2h and removes extra bromine, makes reaction eventually
Only, water phase is extracted by 150mL methylene chloride, is merged organic phase, is removed methylene chloride under reduced pressure, and tie again using 150mL methanol
Light yellow solid 4- bromine carbazole 17.7g, content 99%+, yield 72% is obtained by filtration in crystalline substance.
Claims (2)
1. a kind of 4- bromine Synthetic Method of Carbazole, which is characterized in that comprise the steps of:
(1) o-chloronitrobenzene and copper powder catalyst are added in reaction flask, is kept for 200-220 DEG C of system temperature, insulation reaction is reacted
After, it is cooled to room temperature, extracts organic layer, filter out solid residue, merge organic layer, solvent is evaporated off and obtains sticky solid, pass through
It is recrystallized to give 2,2 '-dinitro biphenyl of solid；
(2) 2,2 '-dinitro biphenyl are added in another reaction flask, is warming up to 140-160 DEG C, passes through dropping funel under stirring
Triethyl phosphite is added dropwise, continues that the temperature is kept to be stirred to react, reaction terminates plus alkali neutralization aqueous solution, separates organic
Layer, cold filtration obtain 4- nitrocarbazole, are recrystallized to give 4- nitrocarbazole；
(3) in acid condition, zinc powder reduction obtains 4- aminocarbazole to 4- nitrocarbazole, hydrobromic acid is added later, in ice-water bath
Under the conditions of sodium nitrite in aqueous solution is gradually added dropwise diazonium salt is made, cuprous bromide aqueous solution is added dropwise again later, after fully reacting, adds
Enter sodium hydrogensulfite and remove extra bromine, washing obtains crude product, later by being recrystallized to give 4- bromine carbazole product.
2. 4- bromine Synthetic Method of Carbazole according to claim 1, it is characterised in that: copper powder catalyst and neighbour in step (1)
Chloronitrobenzene molar ratio is 1:1.1-1.3；2,2 '-dinitro biphenyl and triethyl phosphite molar ratio are 1 in step (2):
4-5；4- nitrocarbazole and zinc powder reduction agent molar ratio are 1:3-5 in step (3).
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| CN201811470191.2A CN109232383B (en) | 2018-12-04 | 2018-12-04 | Method for synthesizing 4-bromocarbazole |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1850800A (en) * | 2005-11-26 | 2006-10-25 | 山西大学 | N-bromo carbazole, and its preparing method |
| CN102060717A (en) * | 2011-01-07 | 2011-05-18 | 大连凯飞精细化工有限公司 | Method for synthesizing 3-amino-4-bromophenol |
| CN103936656A (en) * | 2014-04-11 | 2014-07-23 | 河南省科学院化学研究所有限公司 | Preparation method of 4-bromocarbazole |
| CN107108485A (en) * | 2014-10-24 | 2017-08-29 | 小野药品工业株式会社 | The channel activator of KCNQ2~5 |
-
2018
- 2018-12-04 CN CN201811470191.2A patent/CN109232383B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1850800A (en) * | 2005-11-26 | 2006-10-25 | 山西大学 | N-bromo carbazole, and its preparing method |
| CN102060717A (en) * | 2011-01-07 | 2011-05-18 | 大连凯飞精细化工有限公司 | Method for synthesizing 3-amino-4-bromophenol |
| CN103936656A (en) * | 2014-04-11 | 2014-07-23 | 河南省科学院化学研究所有限公司 | Preparation method of 4-bromocarbazole |
| CN107108485A (en) * | 2014-10-24 | 2017-08-29 | 小野药品工业株式会社 | The channel activator of KCNQ2~5 |
Non-Patent Citations (1)
| Title |
|---|
| IBUKI, EIICHI ET AL.: "Studies of Polyphenyls and polyphenylenes. I. Synthesis and infrared and electronic spectra of several sexiphenyls", 《BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN》 * |
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