CN106117117A - A kind of preparation method of the fluorenyl benzindole derivant containing halogen - Google Patents
A kind of preparation method of the fluorenyl benzindole derivant containing halogen Download PDFInfo
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Abstract
The invention discloses the preparation method of a kind of fluorenyl benzindole derivant containing halogen, belong to technical field of organic synthesis.It comprises the steps: (1) bromo-reaction；(2) C C coupling reaction；(3) ether solution reaction；(4) intramolecular cyclization reaction.Present invention firstly provides a kind of new method preparing fluorenyl benzindole compound, this method is safe and environment-friendly efficiently；The method using the present invention, the reaction yield of the fluorenyl benzindole derivant containing halogen prepared is high, total recovery can reach 55 65%, without using precious metals palladium catalyst in a large number, cost is greatly reduced, purity high, and HPLC purity is up to 99.9%, single miscellaneous less than 100ppm, thing without dihalo and isomer, meet the application of the organic photoelectrical materials such as OLED.
Description
Technical field
The present invention relates to the preparation method of a kind of fluorenyl benzindole derivant containing halogen, belong to organic synthesis technology
Field.
Background technology
In recent years, along with the exploitation of organic photoelectrical material is applied, fluorenyl benzindole compounds becomes a kind of important
Photoelectric material intermediate, can be applicable to electroluminescent organic material, organic effect pipe and organic non linear optical material etc. organic
Person in electronics.Preparation method for this compounds is more, and traditional preparation method is mainly the most several:
(1) Korea S's bucket mountain chemical patent WO 2011025282 uses 9, and 9-dialkyl group bromo fluorenes is raw material, warp and 2-nitro
Phenylboric acid pinacol ester C-C coupling, Cadogan cyclisation obtain fluorenyl benzindole, owing to there is selectivity in this cyclization process
Problem, there is about 50% isomer in products therefrom, and isolated and purified difficulty is relatively big, simultaneously obtained by fluorenyl benzindole entering
There are bromo isomer and two bromination products during row bromo-reaction, increase purification difficulty equally, products therefrom more difficult meet have
The requirement of machine photoelectric material.Reaction scheme is as follows:
(2) Merck KGaA house journal WO 2010136109 uses 9, and 9-dialkyl group bromo fluorenes is raw material, warp and aniline C-
N coupling, the activation cyclisation of palladium C-H obtain fluorenyl benzindole, owing to this cyclization process equally existing selective problems, and
Need during cyclization to use substantial amounts of noble metal catalyst palladium (mole 0.1-0.2), considerably increase raw material
Cost, simultaneously obtained by fluorenyl benzindole also there are bromo isomer and two bromination products when carrying out bromo-reaction, pure
Change difficulty big, the more difficult requirement meeting organic photoelectrical material of products therefrom.Reaction scheme is as follows:
(3) Chinese patent CN 104892487, Japan go out light patent WO 2014208698 and Rhom and Hass's patent WO
2015046916 all use 9, and 9-dialkyl group bromo fluorenes is raw material, through being cyclized with o-chloraniline C-N coupling, the activation of palladium C-H
Obtain fluorenyl benzindole, owing to this cyclization process equally existing selective problems, simultaneously obtained by fluorenyl benzindole
Also there is bromo isomer and two bromination products, not easy purification when carrying out bromo-reaction, products therefrom is more difficult meets organic light
The requirement of electric material.Reaction scheme is as follows:
Along with the development of organic photoelectrical material, raw-material purity requirement is gradually stepped up, current above-mentioned tradition preparation side
In product obtained by method, two bromo-derivative content are higher, have a strong impact on finished-product material performance.
Summary of the invention
The technical problem to be solved is to provide the preparation of a kind of fluorenyl benzindole derivant containing halogen
Method.The method using the present invention, the reaction yield of the fluorenyl benzindole derivant containing halogen prepared is high, cost
Low, purity is high, without dihalo thing and isomer.
The technical scheme is that a kind of fluorenyl benzindole derivant containing halogen
Preparation method, comprise the steps:
(1) bromo-reaction: with dichloromethane, chloroform or dichloroethanes as solvent, NBS and 9,9-dimethyl-2-aminofluorene
Or 9,9-diphenyl-2-aminofluorene, 0.95-1.05:1 in molar ratio, reaction temperature-5-50 DEG C, in 1-6 hour response time, enter
Row bromo-reaction, after sodium sulfite cancellation processes, obtains 3-bromo-9,9-dimethyl-2-aminofluorene or 3-bromo-9,9-hexichol
Base-2-aminofluorene；
(2) C-C coupling reaction: with toluene or glycol dimethyl ether as solvent, the 3-bromo-9 obtained with step (1), 9-bis-
Methyl-2-amino fluorenes or 3-bromo-9,9-diphenyl-2-aminofluorene, with 2-methoxyl group-5-halogeno-benzene boric acid, 1.0-in molar ratio
1.2:1, under palladium catalyst, organophosphorus ligand catalysis, and under inorganic salt co-catalysis, reaction temperature 60-90 DEG C, the response time
4-12 hour, C-C coupling reaction, obtain C-C coupled product；
(3) ether solution reaction: with dichloromethane, chloroform or dichloroethanes as solvent, with aluminum chloride, boron trifluoride diethyl etherate or
Boron tribromide is catalyst, the C-C coupled product that described catalyst and step (2) obtain, 0.4-2.0:1 in molar ratio, reaction
Temperature-10-60 DEG C, in 0.5-6 hour response time, ether solution is reacted, is obtained ether solution product；
(4) intramolecular cyclization reaction: with toluene or xylene as solvent, with p-methyl benzenesulfonic acid, benzenesulfonic acid, sulphuric acid or salt
Acid is catalyst, the ether solution product that described catalyst and step (3) obtain, 0.1-1.0:1 in molar ratio, reaction temperature
80-130 DEG C, 3-12 hour response time, intramolecular cyclization reaction, i.e. obtain the described fluorenyl benzindole containing halogen and derive
Thing.
The method using the present invention, the reaction yield of the fluorenyl benzindole derivant containing halogen prepared is high, always
Yield can reach 55-65%, and low cost, purity high (HPLC purity is more than 99.9%, and list is miscellaneous less than 100ppm), through HPLC-MS
Detection, without dihalo thing and isomer.
On the basis of technique scheme, the present invention can also do following improvement.
Further, in step (1), described NBS and 9,9-dimethyl-2-aminofluorene or 9,9-diphenyl-2-aminofluorene
Mol ratio is 1:1, described reaction temperature 0 DEG C, and the response time is 4 hours.
Further, in step (2), described 3-bromo-9,9-dimethyl-2-aminofluorene or 3-bromo-9,9-diphenyl-2-amino
Fluorenes, is 1.1:1 with the mol ratio of 2-methoxyl group-5-halogeno-benzene boric acid, described reaction temperature 75 DEG C, and the described response time is 8 little
Time.
Further, in step (2), described palladium catalyst is Pd (OAc)2、Pd(dba)2、Pd2(dba)3、PdCl2In one
Kind.
Further, in step (2), described organophosphorus ligand is triphenylphosphine, DPPP, Xantphos, Sphos, P (t-
Bu)3·HBF4In one.
Wherein, No. CAS of DPPP: No. CAS of 6737-42-4, Xantphos: No. CAS of 161265-03-8, Sphos:
657408-07-6, P (t-Bu)3·HBF4No. CAS: 113978-91-9.
Further, in step (2), described inorganic salt is the one in potassium carbonate, sodium carbonate, potassium hydroxide.
Further, in step (3), the mol ratio of the C-C coupled product that described catalyst and step (2) obtain is 1.2:1,
Described reaction temperature is 25 DEG C, and the described response time is 3 hours.
Further, in step (4), the mol ratio of the ether solution product that described catalyst and step (3) obtain is
0.5:1, described reaction temperature is 105 DEG C, and the described response time is 7.5 hours
The reaction scheme of this method is as follows:
In above-mentioned reaction scheme, R represents methyl or phenyl；X represents bromine or chlorine.
Name Resolution:
NBS, English name: N-bromobutanimide, Chinese: N-bromo-succinimide, also known as N-bromo amber
Amber acid imide.
Pd(OAc)2, English name: Palladium acetate, Chinese: palladium, also known as acid chloride.
Pd(dba)2, English name: Bis (dibenzylideneacetone) palladium, Chinese: double (two is sub-
Benzylacetone) palladium.
Pd2(dba)3, English name: Tris (dibenzylideneacetone) dipalladium, Chinese: three
(dibenzalacetone) two palladium.
PdCl2, English name: Palladium chloride, Chinese: Palladous chloride., also known as palladium chloride.
DPPP, English name: 3-bis (diphenylphosphino) propane, Chinese: 1,3-double (diphenyl
Phosphine) propane.
Xantphos, English name: Dimethylbisdiphenylphosphinoxanthene, Chinese: 4,5-
Double diphenylphosphine-9,9-dimethyl xanthenes.
Sphos, English name: Dicyclohexyl (2', 6'-dimethoxy-[1,1'-biphenyl]-2-yl)
Phosphane, Chinese: 2-dicyclohexyl phosphine-2', 6'-dimethoxy-biphenyl.
P(t-Bu)3·HBF4, English name: Tri-t-butylphosphonium tetrafluoroborate, Chinese
Title: tri-butyl phosphine tetrafluoroborate.
The invention has the beneficial effects as follows:
(1) present invention firstly provides a kind of new method preparing fluorenyl benzindole compound, this method is safe and environment-friendly
Efficiently.
(2) method using the present invention, the reaction yield of the fluorenyl benzindole derivant containing halogen prepared is high,
Total recovery can reach 55-65%, it is not necessary to use precious metals palladium catalyst, cost to be greatly reduced in a large number, purity high, HPLC purity can
Reaching 99.9%, list is miscellaneous less than 100ppm, detects through HPLC-MS, without dihalo thing and isomer, meets the organic photoelectric materials such as OLED
The application of material.
(3) preparation method of the present invention is simple, and cheaper starting materials is easy to get, wide market, is suitable for large-scale production.
Detailed description of the invention
Being described principle and the feature of the present invention below in conjunction with specific embodiment, example is served only for explaining this
Bright, it is not intended to limit the scope of the present invention.
Embodiment 1: preparation 2-chloro-7,7-dimethyl-5,7-dihydro indeno [2,1-b] carbazole
The preparation of 3-bromo-2-amino-9,9-dimethyl fluorene: by molten for 20.9g (100mmol) 2-amino-9,9-dimethyl fluorene
In 250mL chloroformic solution, in controlling, temperature 0-5 DEG C, is dividedly in some parts NBS 17.8g (100mmol), and reactant mixture is in 0-5 DEG C
Reaction 2.0hrs, adds 100g2.5% aqueous solution of sodium bisulfite cancellation reaction, layering to reaction system, and 100mL washing is organic
Phase, anhydrous sodium sulfate is dried, and vacuum desolvation agent obtains 3-bromo-2-amino-9,9-dimethyl fluorene crude product 29.1g, then uses 8g/
G recrystallizing methanol obtains white solid powder 24.3g, yield 84.37%.
The preparation of 3-(5-chloro-2-methoxyphenyl)-9,9-dimethyl-9H-fluorenes-2-amine: by 23.0g (80mmol) 3-
Bromo-2-amino-9,9-dimethyl fluorene, 14.9g (80mmol) 5-chloro-2-methoxyphenylboronic acid and 200mL toluene add 1L tri-mouthfuls
In flask, nitrogen is sufficiently displaced from, and adds catalyst 90mg (0.4mmol) Pd (OAc)2With 232mg (0.8mmol) P (t-Bu)3·
HBF4And the aqueous sodium carbonate of 100g12%, be heated to backflow 80-85 DEG C, react 4-6.0 hour, TLC tracking react into
Journey.After completion of the reaction, static layering, washing, organic facies anhydrous sodium sulfate are dried, and desolventizing obtains 3-(5-chloro-2-methoxybenzene
Base)-9,9-dimethyl-9H-fluorenes-2-amine crude product 28.3g, it is not necessary to purification, yield is in terms of 100%.
The preparation of 2-(2-amino-9,9-dimethyl-9H-fluorenes-3-base)-4-chlorophenol: by 28.3g (80mmol) 3-(5-
Chloro-2-methoxyphenyl)-9,9-dimethyl-9H-fluorenes-2-amine and 20.0g (80mmol) Boron tribromide join 200mL dichloro
In ethane solution, stirring 12.0hrs in 10 DEG C, pour into cancellation in 300ml frozen water, layering, washing, organic facies is by anhydrous slufuric acid
Sodium is dried, and desolventizing obtains 2-(2-amino-9,9-dimethyl-9H-fluorenes-3-base)-4-chlorophenol crude product 27.1g, it is not necessary to purification,
Yield is in terms of 100%.
The preparation of 2-chloro-7,7-dimethyl-5,7-dihydro indeno [2,1-b] carbazole: by 27.1g (80mmol) 2-(2-ammonia
Base-9,9-dimethyl-9H-fluorenes-3-base) to join 200mL toluene molten for-4-chlorophenol and 15.3g (80mmol) p-methyl benzenesulfonic acid
In liquid, in 105-110 DEG C of stirring reaction 3-6 hour, TLC followed the tracks of reaction process.After completion of the reaction, cooling, add in 200ml water
Cancellation, layering, washing, organic facies is dried by anhydrous sodium sulfate, and desolventizing obtains 2-chloro-7,7-dimethyl-5,7-dihydro indeno
[2,1-b] carbazole crude product, twice of toluene alcohol mixed solvent recrystallization, HPLC purity 99.95%, yield 77.09%.
MS (ESI): 318.41 ([M+1]+), value of calculation 317.10.
1H NMR(400MHz,CDCl3) δ: 10.84 (s, 1H) are the active hydrogen on carbazole nitrogen, 8.24 (d, 1H), 7.88 (s,
1H), 7.74 (d, 1H), 7.57-7.52 (m, 3H), 7.38-7.29 (m, 3H) and 1.71 (s, 6H).
Embodiment 2: preparation 2-bromo-7,7-dimethyl-5,7-dihydro indeno [2,1-b] carbazole
The preparation of 3-bromo-2-amino-9,9-dimethyl fluorene: by molten for 20.9g (100mmol) 2-amino-9,9-dimethyl fluorene
In 200mL dichloroethane solution, controlling Nei Wen-5-0 DEG C, be dividedly in some parts NBS 16.9g (95mmol), reactant mixture is in 0-
5 DEG C of reaction 4.0hrs, add 100g2.5% aqueous solution of sodium bisulfite cancellation reaction, layering to reaction system, and 100mL washes
Organic facies, anhydrous sodium sulfate is dried, and vacuum desolvation agent obtains 3-bromo-2-amino-9,9-dimethyl fluorene crude product 28.8g, then makes
It is recrystallized to give white solid powder 23.4g, yield 81.19% with toluene alcohol mixed solvent.
The preparation of 3-(5-bromo-2-methoxyphenyl)-9,9-dimethyl-9H-fluorenes-2-amine: by 23.0g (80mmol) 3-
Bromo-2-amino-9,9-dimethyl fluorene, 17.3g (75mmol) 5-bromo-2-methoxyphenylboronic acid and 250mL toluene add 1L tri-mouthfuls
In flask, nitrogen is sufficiently displaced from, and adds catalyst 90mg (0.4mmol) Pd (OAc)2With 463mg (0.8mmol) Xantphos with
And 140g, the wet chemical of 12%, it being heated to backflow 80-85 DEG C, react 4-6.0 hour, TLC follows the tracks of reaction process.Instead
After Ying, static layering, washing, organic facies anhydrous sodium sulfate be dried, desolventizing obtain 3-(5-bromo-2-methoxyphenyl)-
9,9-dimethyl-9H-fluorenes-2-amine crude product 29.6g, it is not necessary to purification, yield is in terms of 100%.
The preparation of 2-(2-amino-9,9-dimethyl-9H-fluorenes-3-base)-4-bromophenol: by 29.6g (75mmol) 3-(5-
Bromo-2-methoxyphenyl)-9,9-dimethyl-9H-fluorenes-2-amine and 12.5g (50mmol) Boron tribromide join 240mL chloroform
In solution, stirring 8.0hrs in 0 DEG C, pour into cancellation in 300ml frozen water, layering, washing, organic facies is done by anhydrous sodium sulfate
Dry, desolventizing obtains 2-(2-amino-9,9-dimethyl-9H-fluorenes-3-base)-4-bromophenol crude product 28.4g, it is not necessary to purification, yield
In terms of 100%.
The preparation of 2-bromo-7,7-dimethyl-5,7-dihydro indeno [2,1-b] carbazole: by 28.4g (75mmol) 2-(2-ammonia
Base-9,9-dimethyl-9H-fluorenes-3-base)-4-bromophenol and 1.4g (8mmol) benzenesulfonic acid join in 200mL xylene solution,
In 125-130 DEG C of stirring reaction 3-6 hour, TLC followed the tracks of reaction process.After completion of the reaction, cooling, add cancellation in 200ml water,
Layering, washing, organic facies is dried by anhydrous sodium sulfate, and desolventizing obtains 2-bromo-7,7-dimethyl-5,7-dihydro indeno [2,1-
B] carbazole crude product, toluene alcohol mixed solvent recrystallization obtains 20.2g, HPLC purity 99.91%, yield 74.36% for twice.
MS (ESI): 362.71 ([M+1]+), value of calculation 361.05.
1H NMR(400MHz,CDCl3) δ: 10.61 (s, 1H) are the active hydrogen on carbazole nitrogen, 8.24 (d, 1H), 8.10 (s,
1H), 7.91 (s, 1H), 7.82-7.42 (m, 6H) and 1.83 (s, 6H).
Embodiment 3: preparation 2-bromo-7,7-diphenyl-5,7-dihydro indeno [2,1-b] carbazole
The preparation of 3-bromo-2-amino-9,9-diphenylfluorene: by molten for 33.3g (100mmol) 2-amino-9,9-diphenylfluorene
In 300mL dichloromethane solution, control in temperature 10-15 DEG C, be dividedly in some parts NBS 18.2g (102mmol), reactant mixture in
10-15 DEG C of reaction 8.0hrs, adds 100g, 2.5% aqueous solution of sodium bisulfite cancellation reaction, layering, 100mL to reaction system
Washing organic facies, anhydrous sodium sulfate is dried, and vacuum desolvation agent obtains 3-bromo-2-amino-9,9-diphenylfluorene crude product 41.3g, and
Rear use toluene alcohol mixed solvent is recrystallized to give white solid powder 33.6g, yield 81.55%.
The preparation of 3-(5-bromo-2-methoxyphenyl)-9,9-diphenyl-9H-fluorenes-2-amine: by 33.0g (80mmol) 3-
Bromo-2-amino-9,9-diphenylfluorene, 17.3g (75mmol) 5-bromo-2-methoxyphenylboronic acid and 250mL toluene add 1L tri-mouthfuls
In flask, nitrogen is sufficiently displaced from, and adds catalyst 90mg (0.4mmol) Pd (OAc)2With 463mg (0.8mmol) Xantphos with
And the wet chemical of 140g 12%, it being heated to backflow 80-85 DEG C, react 8.0 hours, TLC follows the tracks of reaction process.Reaction
After, static layering, washing, organic facies anhydrous sodium sulfate are dried, and desolventizing obtains 3-(5-bromo-2-methoxyphenyl)-9,
9-diphenyl-9H-fluorenes-2-amine crude product 38.9g, it is not necessary to purification, yield is in terms of 100%.
The preparation of 2-(2-amino-9,9-diphenyl-9H-fluorenes-3-base)-4-bromophenol: by 38.9g (75mmol) 3-(5-
Bromo-2-methoxyphenyl)-9,9-diphenyl-9H-fluorenes-2-amine and 37.6g (150mmol) Boron tribromide join 400mL dichloro
In dichloromethane, stirring 8.0hrs in 15 DEG C, pour into cancellation in 300ml frozen water, layering, washing, organic facies is by anhydrous slufuric acid
Sodium is dried, and desolventizing obtains 2-(2-amino-9,9-diphenyl-9H-fluorenes-3-base)-4-bromophenol crude product 37.9g, it is not necessary to purification,
Yield is in terms of 100%.
The preparation of 2-bromo-7,7-diphenyl-5,7-dihydro indeno [2,1-b] carbazole: by 37.9g (75mmol) 2-(2-ammonia
Base-9,9-diphenyl-9H-fluorenes-3-base)-4-bromophenol and 2.9g (15mmol) p-methyl benzenesulfonic acid join 300mL toluene solution
In, in 105-110 DEG C of stirring reaction 3.0 hours, TLC followed the tracks of reaction process.After completion of the reaction, cooling, add in 200ml water and quench
Go out, layering, washing, organic facies is dried by anhydrous sodium sulfate, and desolventizing obtains 2-bromo-7,7-diphenyl-5,7-dihydro indeno [2,
1-b] carbazole crude product, twice of toluene alcohol mixed solvent recrystallization, HPLC purity 99.93%, yield 78.63%.
LC-MS:486.07 ([M+1]+), value of calculation 485.08.
1H NMR(400MHz,CDCl3) δ: 11.16 (s, 1H) are the active hydrogen on carbazole nitrogen, 8.17 (s, 1H), 8.10 (d,
1H),8.00(s,1H),7.93(s,1H)7.49-7.45(m,2H),7.40-7.33(m,3H,)7.30-7.19(m,10H),
7.13-7.11(t,1H)。
Embodiment 4: preparation 2-chloro-7,7-diphenyl-5,7-dihydro indeno [2,1-b] carbazole
The preparation of 3-bromo-2-amino-9,9-diphenylfluorene: by molten for 33.3g (100mmol) 2-amino-9,9-diphenylfluorene
In 300mL dichloroethane solution, control in temperature 15-20 DEG C, be dividedly in some parts NBS 17.8g (100mmol), reactant mixture in
15-20 DEG C of reaction 12.0hrs, adds 100g, 2.5% aqueous solution of sodium bisulfite cancellation reaction to reaction system, is layered,
100mL washes organic facies, and anhydrous sodium sulfate is dried, and vacuum desolvation agent obtains 3-bromo-2-amino-9,9-diphenylfluorene crude product
41.4g, then uses toluene alcohol mixed solvent to be recrystallized to give white solid powder 33.0g, yield 80.12%.
The preparation of 3-(5-chloro-2-methoxyphenyl)-9,9-diphenyl-9H-fluorenes-2-amine: by 33.0g (80mmol) 3-
Bromo-2-amino-9,9-diphenylfluorene, 14.9g (80mmol) 5-chloro-2-methoxyphenylboronic acid and 300mL toluene add 1L tri-mouthfuls
In flask, nitrogen is sufficiently displaced from, and adds catalyst 90mg (0.4mmol) Pd (OAc)2With 232mg (0.8mmol) P (t-Bu)3·
HBF4And 200g, the wet chemical of 10%, be heated to backflow 80-85 DEG C, react 6.0 hours, TLC tracking react into
Journey.After completion of the reaction, static layering, washing, organic facies anhydrous sodium sulfate are dried, and desolventizing obtains 3-(5-chloro-2-methoxybenzene
Base)-9,9-diphenyl-9H-fluorenes-2-amine crude product 37.8g, it is not necessary to purification, yield is in terms of 100%.
The preparation of 2-(2-amino-9,9-diphenyl-9H-fluorenes-3-base)-4-chlorophenol: by 37.8g (80mmol) 3-(5-
Chloro-2-methoxyphenyl)-9,9-diphenyl-9H-fluorenes-2-amine and 22.5g (90mmol) Boron tribromide join 500mL dichloro
In ethane solution, stirring 12.0hrs in 0-5 DEG C, pour into cancellation in 300ml frozen water, layering, washing, organic facies is by anhydrous sulfur
Acid sodium is dried, and desolventizing obtains 2-(2-amino-9,9-diphenyl-9H-fluorenes-3-base)-4-chlorophenol crude product 37.0g, it is not necessary to pure
Changing, yield is in terms of 100%.
The preparation of 2-chloro-7,7-diphenyl-5,7-dihydro indeno [2,1-b] carbazole: by 37.0g (80mmol) 2-(2-ammonia
Base-9,9-diphenyl-9H-fluorenes-3-base)-4-chlorophenol and 7.7g (40mmol) p-methyl benzenesulfonic acid join 500mL toluene solution
In, in 105-110 DEG C of stirring reaction 6.0 hours, TLC followed the tracks of reaction process.After completion of the reaction, cooling, add in 200ml water and quench
Go out, layering, washing, organic facies is dried by anhydrous sodium sulfate, and desolventizing obtains 2-chloro-7,7-diphenyl-5,7-dihydro indeno [2,
1-b] carbazole crude product, toluene alcohol mixed solvent recrystallization obtains 24.8g, HPLC purity 99.92%, yield 70.09% for twice.
LC-MS:442.16 ([M+1]+), value of calculation 441.13.
1H NMR(400MHz,CDCl3) δ: 11.03 (s, 1H) are the active hydrogen on carbazole nitrogen, 8.15 (s, 1H), 8.04 (d,
1H),7.92(s,1H),7.76(s,1H)7.42-7.40(m,2H),7.32-7.7.29(m,3H,)7.23-7.12(m,10H),
7.10-7.08(t,1H)。
Embodiment 5: preparation 2-chloro-7,7-dimethyl-5,7-dihydro indeno [2,1-b] carbazole
The preparation of 3-bromo-2-amino-9,9-dimethyl fluorene: by molten for 20.9g (100mmol) 2-amino-9,9-dimethyl fluorene
In 250mL chloroformic solution, in controlling, temperature 0 DEG C, is dividedly in some parts NBS 17.8g (100mmol), and reactant mixture is in 0 DEG C of reaction
4.0hrs, adds 100g 2.5% aqueous solution of sodium bisulfite cancellation reaction, layering to reaction system, and 100mL washes organic facies,
Anhydrous sodium sulfate is dried, and vacuum desolvation agent obtains 3-bromo-2-amino-9,9-dimethyl fluorene crude product 29.0g, then uses 8g/g first
Alcohol is recrystallized to give white solid powder 23.5g, yield 81.63%.
The preparation of 3-(5-chloro-2-methoxyphenyl)-9,9-dimethyl-9H-fluorenes-2-amine: by 25.4g (88mmol) 3-
Bromo-2-amino-9,9-dimethyl fluorene, 14.9g (80mmol) 5-chloro-2-methoxyphenylboronic acid and 200mL toluene add 1L tri-mouthfuls
In flask, nitrogen is sufficiently displaced from, and adds catalyst 90mg (0.4mmol) Pd (OAc)2With 232mg (0.8mmol) P (t-Bu)3·
HBF4And the aqueous sodium carbonate of 100g 12%, it being heated to 75 DEG C, react 8 hours, TLC follows the tracks of reaction process.React complete
After, static layering, washing, organic facies anhydrous sodium sulfate are dried, and desolventizing obtains 3-(5-chloro-2-methoxyphenyl)-9,9-bis-
Methyl-9 H-fluorene-2-amine crude product 28.0g, it is not necessary to purification, yield is in terms of 100%.
The preparation of 2-(2-amino-9,9-dimethyl-9H-fluorenes-3-base)-4-chlorophenol: by 28.0g (80mmol) 3-(5-
Chloro-2-methoxyphenyl)-9,9-dimethyl-9H-fluorenes-2-amine and 24.0g (96mmol) Boron tribromide join 200mL dichloro
In ethane solution, stirring 3.0hrs in 25 DEG C, pour into cancellation in 300ml frozen water, layering, washing, organic facies is by anhydrous slufuric acid
Sodium is dried, and desolventizing obtains 2-(2-amino-9,9-dimethyl-9H-fluorenes-3-base)-4-chlorophenol crude product 26.9g, it is not necessary to purification,
Yield is in terms of 100%.
The preparation of 2-chloro-7,7-dimethyl-5,7-dihydro indeno [2,1-b] carbazole: by 26.9g (80mmol) 2-(2-ammonia
Base-9,9-dimethyl-9H-fluorenes-3-base)-4-chlorophenol and 7.7g (40mmol) p-methyl benzenesulfonic acid join 200mL toluene solution
In, in 105 DEG C of stirring reactions 3-6 hour, TLC followed the tracks of reaction process.After completion of the reaction, cooling, add cancellation in 200ml water,
Layering, washing, organic facies is dried by anhydrous sodium sulfate, and desolventizing obtains 2-chloro-7,7-dimethyl-5,7-dihydro indeno [2,1-
B] carbazole crude product, toluene twice 20.1g of alcohol mixed solvent recrystallization, HPLC purity 99.97%, yield 79.09%, list is miscellaneous all
Isomer and dichloro-thing is not found less than 100ppm, HPLC-MS detection.
MS (ESI): 318.41 ([M+1]+), value of calculation 317.10.
1H NMR(400MHz,CDCl3) δ: 10.84 (s, 1H) are the active hydrogen on carbazole nitrogen, 8.24 (d, 1H), 7.88 (s,
1H), 7.74 (d, 1H), 7.57-7.52 (m, 3H), 7.38-7.29 (m, 3H) and 1.71 (s, 6H).
Embodiment 6: preparation 2-bromo-7,7-dimethyl-5,7-dihydro indeno [2,1-b] carbazole
The preparation of 3-bromo-2-amino-9,9-dimethyl fluorene: by molten for 20.9g (100mmol) 2-amino-9,9-dimethyl fluorene
In 250mL chloroformic solution, in controlling, temperature 0 DEG C, is dividedly in some parts NBS 17.8g (100mmol), and reactant mixture is in 0 DEG C of reaction
4.0hrs, adds 100g2.5% aqueous solution of sodium bisulfite cancellation reaction, layering to reaction system, and 100mL washes organic facies,
Anhydrous sodium sulfate is dried, and vacuum desolvation agent obtains 3-bromo-2-amino-9,9-dimethyl fluorene crude product 29.0g, then uses 8g/g first
Alcohol is recrystallized to give white solid powder 23.5g, yield 81.63%.
The preparation of 3-(5-bromo-2-methoxyphenyl)-9,9-dimethyl-9H-fluorenes-2-amine: by 23.8g (82.5mmol) 3-
Bromo-2-amino-9,9-dimethyl fluorene, 17.3g (75mmol) 5-bromo-2-methoxyphenylboronic acid and 250mL toluene add 1L tri-mouthfuls
In flask, nitrogen is sufficiently displaced from, and adds catalyst 90mg (0.4mmol) Pd (OAc)2With 463mg (0.8mmol) Xantphos with
And the wet chemical of 140g 12%, it being heated to 75 DEG C, react 8.0 hours, TLC follows the tracks of reaction process.After completion of the reaction,
Static layering, washing, organic facies anhydrous sodium sulfate are dried, and desolventizing obtains 3-(5-bromo-2-methoxyphenyl)-9,9-diformazan
Base-9H-fluorenes-2-amine crude product 29.6g, it is not necessary to purification, yield is in terms of 100%.
The preparation of 2-(2-amino-9,9-dimethyl-9H-fluorenes-3-base)-4-bromophenol: by 29.6g (75mmol) 3-(5-
Bromo-2-methoxyphenyl)-9,9-dimethyl-9H-fluorenes-2-amine and 22.5g (90mmol) Boron tribromide join 240mL chloroform
In solution, stirring 3.0hrs in 25 DEG C, pour into cancellation in 300ml frozen water, layering, washing, organic facies is done by anhydrous sodium sulfate
Dry, desolventizing obtains 2-(2-amino-9,9-dimethyl-9H-fluorenes-3-base)-4-bromophenol crude product 28.6g, it is not necessary to purification, yield
In terms of 100%.
The preparation of 2-bromo-7,7-dimethyl-5,7-dihydro indeno [2,1-b] carbazole: by 28.6g (75mmol) 2-(2-ammonia
Base-9,9-dimethyl-9H-fluorenes-3-base)-4-bromophenol and 7.2g (37.5mmol) benzenesulfonic acid join 200mL xylene solution
In, in 105 DEG C of stirring reactions 7.5 hours, TLC followed the tracks of reaction process.After completion of the reaction, cooling, add cancellation in 200ml water,
Layering, washing, organic facies is dried by anhydrous sodium sulfate, and desolventizing obtains 2-bromo-7,7-dimethyl-5,7-dihydro indeno [2,1-
B] carbazole crude product, toluene alcohol mixed solvent recrystallization obtains 21.6g, HPLC purity 99.96%, yield 79.63%, list for twice
Miscellaneous respectively less than 100ppm, HPLC-MS detection does not finds isomer and two bromo-derivatives.
MS (ESI): 362.71 ([M+1]+), value of calculation 361.05.
1H NMR(400MHz,CDCl3) δ: 10.61 (s, 1H) are the active hydrogen on carbazole nitrogen, 8.24 (d, 1H), 8.10 (s,
1H), 7.91 (s, 1H), 7.82-7.42 (m, 6H) and 1.83 (s, 6H).
Embodiment 7: preparation 2-bromo-7,7-diphenyl-5,7-dihydro indeno [2,1-b] carbazole
The preparation of 3-bromo-2-amino-9,9-diphenylfluorene: by molten for 33.3g (100mmol) 2-amino-9,9-diphenylfluorene
In 300mL dichloromethane solution, in controlling, temperature 0 DEG C, is dividedly in some parts NBS 18.0g (100mmol), and reactant mixture is in 0 DEG C
Reaction 4.0hrs, adds 100g 2.5% aqueous solution of sodium bisulfite cancellation reaction, layering to reaction system, and 100mL washing has
Machine phase, anhydrous sodium sulfate is dried, and vacuum desolvation agent obtains 3-bromo-2-amino-9,9-diphenylfluorene crude product 41.3g, then uses
Toluene alcohol mixed solvent is recrystallized to give white solid powder 36.5g, yield 88.62%.
The preparation of 3-(5-bromo-2-methoxyphenyl)-9,9-diphenyl-9H-fluorenes-2-amine: by 34.0g (82.5mmol) 3-
Bromo-2-amino-9,9-diphenylfluorene, 17.3g (75mmol) 5-bromo-2-methoxyphenylboronic acid and 250mL toluene add 1L tri-mouthfuls
In flask, nitrogen is sufficiently displaced from, and adds catalyst 90mg (0.4mmol) Pd (OAc)2With 463mg (0.8mmol) Xantphos with
And the wet chemical of 140g 12%, it being heated to 75 DEG C, react 8.0 hours, TLC follows the tracks of reaction process.After completion of the reaction,
Static layering, washing, organic facies anhydrous sodium sulfate are dried, and desolventizing obtains 3-(5-bromo-2-methoxyphenyl)-9,9-hexichol
Base-9H-fluorenes-2-amine crude product 38.9g, it is not necessary to purification, yield is in terms of 100%.
The preparation of 2-(2-amino-9,9-diphenyl-9H-fluorenes-3-base)-4-bromophenol: by 38.9g (75mmol) 3-(5-
Bromo-2-methoxyphenyl)-9,9-diphenyl-9H-fluorenes-2-amine and 22.5g (90mmol) Boron tribromide join 400mL dichloro
In dichloromethane, stirring 3.0hrs in 25 DEG C, pour into cancellation in 300ml frozen water, layering, washing, organic facies is by anhydrous slufuric acid
Sodium is dried, and desolventizing obtains 2-(2-amino-9,9-diphenyl-9H-fluorenes-3-base)-4-bromophenol crude product 37.9g, it is not necessary to purification,
Yield is in terms of 100%.
The preparation of 2-bromo-7,7-diphenyl-5,7-dihydro indeno [2,1-b] carbazole: by 37.9g (75mmol) 2-(2-ammonia
Base-9,9-diphenyl-9H-fluorenes-3-base) to join 300mL toluene molten for-4-bromophenol and 7.2g (37.5mmol) p-methyl benzenesulfonic acid
In liquid, in 105 DEG C of stirring reactions 7.5 hours, TLC followed the tracks of reaction process.After completion of the reaction, cooling, add in 200ml water and quench
Go out, layering, washing, organic facies is dried by anhydrous sodium sulfate, and desolventizing obtains 2-bromo-7,7-diphenyl-5,7-dihydro indeno [2,
1-b] carbazole crude product, toluene alcohol mixed solvent recrystallization obtains 26.3g, HPLC purity 99.96%, yield 72.09%, list for twice
Miscellaneous respectively less than 100ppm, HPLC-MS detection does not finds isomer and two bromo-derivatives.
LC-MS:486.07 ([M+1]+), value of calculation 485.08.
1H NMR(400MHz,CDCl3) δ: 11.16 (s, 1H) are the active hydrogen on carbazole nitrogen, 8.17 (s, 1H), 8.10 (d,
1H),8.00(s,1H),7.93(s,1H)7.49-7.45(m,2H),7.40-7.33(m,3H,)7.30-7.19(m,10H),
7.13-7.11(t,1H)。
Embodiment 8: preparation 2-chloro-7,7-diphenyl-5,7-dihydro indeno [2,1-b] carbazole
The preparation of 3-bromo-2-amino-9,9-diphenylfluorene: by molten for 33.3g (100mmol) 2-amino-9,9-diphenylfluorene
In 300mL dichloromethane solution, in controlling, temperature 0 DEG C, is dividedly in some parts NBS 18.0g (100mmol), and reactant mixture is in 0 DEG C
Reaction 4.0hrs, adds 100g 2.5% aqueous solution of sodium bisulfite cancellation reaction, layering to reaction system, and 100mL washing has
Machine phase, anhydrous sodium sulfate is dried, and vacuum desolvation agent obtains 3-bromo-2-amino-9,9-diphenylfluorene crude product 41.3g, then uses
Toluene alcohol mixed solvent is recrystallized to give white solid powder 36.5g, yield 88.62%.
The preparation of 3-(5-chloro-2-methoxyphenyl)-9,9-diphenyl-9H-fluorenes-2-amine: by 36.3g (88mmol) 3-
Bromo-2-amino-9,9-diphenylfluorene, 14.9g (80mmol) 5-chloro-2-methoxyphenylboronic acid and 300mL toluene add 1L tri-mouthfuls
In flask, nitrogen is sufficiently displaced from, and adds catalyst 90mg (0.4mmol) Pd (OAc)2With 232mg (0.8mmol) P (t-Bu)3·
HBF4And the wet chemical of 200g 10%, it being heated to 75 DEG C, react 8.0 hours, TLC follows the tracks of reaction process.React
Bi Hou, static layering, washing, organic facies anhydrous sodium sulfate be dried, and desolventizing obtains 3-(5-chloro-2-methoxyphenyl)-9,9-
Diphenyl-9H-fluorenes-2-amine crude product 37.8g, it is not necessary to purification, yield is in terms of 100%.
The preparation of 2-(2-amino-9,9-diphenyl-9H-fluorenes-3-base)-4-chlorophenol: by 37.9g (80mmol) 3-(5-
Chloro-2-methoxyphenyl)-9,9-diphenyl-9H-fluorenes-2-amine and 22.5g (90mmol) Boron tribromide join 500mL dichloro
In ethane solution, stirring 12.0hrs in 25 DEG C, pour into cancellation in 300ml frozen water, layering, washing, organic facies is by anhydrous slufuric acid
Sodium is dried, and desolventizing obtains 2-(2-amino-9,9-diphenyl-9H-fluorenes-3-base)-4-chlorophenol crude product 37.0g, it is not necessary to purification,
Yield is in terms of 100%.
The preparation of 2-chloro-7,7-diphenyl-5,7-dihydro indeno [2,1-b] carbazole: by 37.0g (80mmol) 2-(2-ammonia
Base-9,9-diphenyl-9H-fluorenes-3-base)-4-chlorophenol and 7.7g (40mmol) p-methyl benzenesulfonic acid join 500mL toluene solution
In, in 105 DEG C of stirring reactions 7.5 hours, TLC followed the tracks of reaction process.After completion of the reaction, cooling, add cancellation in 200ml water,
Layering, washing, organic facies is dried by anhydrous sodium sulfate, and desolventizing obtains 2-chloro-7,7-diphenyl-5,7-dihydro indeno [2,1-
B] carbazole crude product, toluene alcohol mixed solvent recrystallization obtains 25.9g, HPLC purity 99.97%, yield 73.35%, list for twice
Miscellaneous respectively less than 100ppm, HPLC-MS detection does not finds isomer and dichloro-thing.
LC-MS:442.16 ([M+1]+), value of calculation 441.13.
1H NMR(400MHz,CDCl3) δ: 11.03 (s, 1H) are the active hydrogen on carbazole nitrogen, 8.15 (s, 1H), 8.04 (d,
1H),7.92(s,1H),7.76(s,1H)7.42-7.40(m,2H),7.32-7.7.29(m,3H,)7.23-7.12(m,10H),
7.10-7.08(t,1H)。
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all spirit in the present invention and
Within principle, any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.
Claims (8)
1. the preparation method of the fluorenyl benzindole derivant containing halogen, it is characterised in that comprise the steps:
(1) bromo-reaction: with dichloromethane, chloroform or dichloroethanes as solvent, NBS and 9,9-dimethyl-2-aminofluorene or 9,
9-diphenyl-2-aminofluorene, 0.95-1.05:1 in molar ratio, reaction temperature-5-50 DEG C, in 1-6 hour response time, carry out bromine
Generation reaction, after sodium sulfite cancellation processes, obtains 3-bromo-9,9-dimethyl-2-aminofluorene or 3-bromo-9,9-diphenyl-2-
Aminofluorene；
(2) C-C coupling reaction: with toluene or glycol dimethyl ether as solvent, the 3-bromo-9 obtained with step (1), 9-dimethyl-
2-aminofluorene or 3-bromo-9,9-diphenyl-2-aminofluorene, and 2-methoxyl group-5-halogeno-benzene boric acid, 1.0-1.2:1 in molar ratio,
Under palladium catalyst, organophosphorus ligand catalysis, and under inorganic salt co-catalysis, reaction temperature 60-90 DEG C, the response time, 4-12 was little
Time, C-C coupling reaction, obtain C-C coupled product；
(3) ether solution reaction: with dichloromethane, chloroform or dichloroethanes as solvent, with aluminum chloride, boron trifluoride diethyl etherate or tribromo
Change boron is catalyst, the C-C coupled product that described catalyst and step (2) obtain, 0.4-2.0:1 in molar ratio, reaction temperature-
10-60 DEG C, in 0.5-6 hour response time, ether solution is reacted, is obtained ether solution product；
(4) intramolecular cyclization reaction: with toluene or xylene as solvent, with p-methyl benzenesulfonic acid, benzenesulfonic acid, sulphuric acid or hydrochloric acid be
Catalyst, the ether solution product that described catalyst and step (3) obtain, 0.1-1.0:1 in molar ratio, reaction temperature 80-130
DEG C, 3-12 hour response time, intramolecular cyclization reaction, i.e. obtain the described fluorenyl benzindole derivant containing halogen.
The preparation method of a kind of fluorenyl benzindole derivant containing halogen the most according to claim 1, its feature exists
In, in step (1), described NBS and 9,9-dimethyl-2-aminofluorene or 9, the mol ratio of 9-diphenyl-2-aminofluorene is 1:1,
Described reaction temperature 0 DEG C, the response time is 4 hours.
The preparation method of a kind of fluorenyl benzindole derivant containing halogen the most according to claim 1, its feature exists
In, in step (2), described 3-bromo-9,9-dimethyl-2-aminofluorene or 3-bromo-9,9-diphenyl-2-aminofluorene, with 2-methoxy
The mol ratio of base-5-halogeno-benzene boric acid is 1.1:1, described reaction temperature 75 DEG C, and the described response time is 8 hours.
The preparation method of a kind of fluorenyl benzindole derivant containing halogen the most according to claim 1, its feature exists
In, in step (2), described palladium catalyst is Pd (OAc)2、Pd(dba)2、Pd2(dba)3、PdCl2In one.
The preparation method of a kind of fluorenyl benzindole derivant containing halogen the most according to claim 1, its feature exists
In, in step (2), described organophosphorus ligand is triphenylphosphine, DPPP, Xantphos, Sphos, P (t-Bu)3·HBF4In one
Kind.
The preparation method of a kind of fluorenyl benzindole derivant containing halogen the most according to claim 1, its feature exists
In, in step (2), described inorganic salt is the one in potassium carbonate, sodium carbonate, potassium hydroxide.
The preparation method of a kind of fluorenyl benzindole derivant containing halogen the most according to claim 1, its feature exists
In, in step (3), the mol ratio of the C-C coupled product that described catalyst and step (2) obtain is 1.2:1, described reaction temperature
Being 25 DEG C, the described response time is 3 hours.
The preparation method of a kind of fluorenyl benzindole derivant containing halogen the most according to claim 1, its feature exists
In, in step (4), the mol ratio of the ether solution product that described catalyst and step (3) obtain is 0.5:1, described instead
Answering temperature is 105 DEG C, and the described response time is 7.5 hours.
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Denomination of invention: Method for preparing fluorenyl benzoindole derivative containing halogen Effective date of registration: 20211202 Granted publication date: 20180518 Pledgee: Yantai Branch of China Merchants Bank Co.,Ltd. Pledgor: VALIANT Co.,Ltd. Registration number: Y2021980013807 |
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Date of cancellation: 20220823 Granted publication date: 20180518 Pledgee: Yantai Branch of China Merchants Bank Co.,Ltd. Pledgor: VALIANT Co.,Ltd. Registration number: Y2021980013807 |