CN106117117B - A kind of preparation method of the fluorenyl benzindole derivative containing halogen - Google Patents
A kind of preparation method of the fluorenyl benzindole derivative containing halogen Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of the fluorenyl benzindole derivative containing halogen, belong to technical field of organic synthesis.It includes the following steps：(1) bromo-reaction；(2) C C coupling reactions；(3) ether solution is reacted；(4) intramolecular cyclization reaction.Present invention firstly provides a kind of new method for preparing fluorenyl benzindole compound, this method is safe and environment-friendly efficiently；Method using the present invention, the reaction yield for the fluorenyl benzindole derivative containing halogen prepared is high, total recovery can reach 55 65%, without largely using precious metals palladium catalyst, cost is greatly reduced, purity is high, and HPLC purity is single miscellaneous less than 100ppm up to 99.9%, without dihalo object and isomers, meet the application of the organic photoelectrical materials such as OLED.
Description
Technical field
The present invention relates to a kind of preparation methods of the fluorenyl benzindole derivative containing halogen, belong to organic synthesis technology
Field.
Background technology
In recent years, with the development and application of organic photoelectrical material, fluorenyl benzindole class compound becomes a kind of important
It is organic to can be applied to electroluminescent organic material, organic effect pipe and organic non linear optical material etc. for photoelectric material intermediate
Person in electronics.More for the preparation method of such compound, traditional preparation method is predominantly following several：
(1) South Korea bucket mountain chemical patent WO 2011025282 using 9,9- dialkyl group bromos fluorenes be raw material, through with 2- nitros
Phenyl boric acid pinacol ester C-C couplings, Cadogan are cyclized to obtain fluorenyl benzindole, due to there is selectivity in the cyclization process
There is 50% or so isomers in problem, products therefrom, and it is larger to isolate and purify difficulty, at the same obtained fluorenyl benzindole into
There are bromo isomer and two bromination products during row bromo-reaction, purifying difficulty is equally increased, the more difficult satisfaction of products therefrom has
The requirement of machine photoelectric material.Reaction scheme is as follows：
(2) Merck KGaA house journal WO 2010136109 using 9,9- dialkyl group bromos fluorenes be raw material, through with aniline C-
N couplings, palladium C-H activation cyclisation obtain fluorenyl benzindole, due to equally existing selective problems in the cyclization process, and
It needs, using substantial amounts of noble metal catalyst palladium (mole 0.1-0.2), to considerably increase raw material during cyclization
Cost, at the same obtained fluorenyl benzindole when carrying out bromo-reaction also there are bromo isomer and two bromination products, it is pure
It is big to change difficulty, the more difficult requirement for meeting organic photoelectrical material of products therefrom.Reaction scheme is as follows：
(3) Chinese patent CN 104892487, Japanese light extraction patent WO 2014208698 and Rhom and Hass patent WO
2015046916 use 9,9- dialkyl group bromos fluorenes as raw material, through being cyclized with o-chloraniline C-N couplings, palladium C-H activation
Fluorenyl benzindole is obtained, due to equally existing selective problems, while obtained fluorenyl benzindole in the cyclization process
When carrying out bromo-reaction also there are bromo isomer and two bromination products, not easy purification, products therefrom is more difficult to meet organic light
The requirement of electric material.Reaction scheme is as follows：
With the development of organic photoelectrical material, the purity requirement of raw material is gradually stepped up, traditional preparation side above-mentioned at present
Two bromo-derivative contents are higher in product obtained by method, seriously affect finished-product material performance.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of preparation of the fluorenyl benzindole derivative containing halogen
Method.Method using the present invention, the reaction yield height for the fluorenyl benzindole derivative containing halogen prepared, cost
It is low, purity is high, no dihalo object and isomers.
The technical solution that the present invention solves above-mentioned technical problem is as follows：A kind of fluorenyl benzindole derivative containing halogen
Preparation method, include the following steps：
(1) bromo-reaction：Using dichloromethane, chloroform or dichloroethanes as solvent, NBS and 9,9- dimethyl -2- aminofluorenes
Or 9,9- diphenyl -2- aminofluorenes, 0.95-1.05 in molar ratio:1, -5-50 DEG C of reaction temperature, when reaction time 1-6 is small, into
Row bromo-reaction after processing is quenched in sodium hydrogensulfite, obtains bromo- 9, the 9- dimethyl -2- aminofluorenes of 3- or bromo- 9, the 9- hexichol of 3-
Base -2- aminofluorenes；
(2) C-C coupling reactions：Using toluene or glycol dimethyl ether as solvent, bromo- 9, the 9- bis- of 3- that are obtained with step (1)
Methyl-2-amino fluorenes or bromo- 9, the 9- diphenyl -2- aminofluorenes of 3-, and halogenated phenyl boric acids of 2- methoxyl groups -5-, in molar ratio 1.0-
1.2:1, under palladium catalyst, organophosphorus ligand catalysis and under inorganic salts co-catalysis, 60-90 DEG C of reaction temperature, the reaction time
When 4-12 is small, C-C coupling reactions obtain C-C coupled products；
(3) ether solution is reacted：Using dichloromethane, chloroform or dichloroethanes as solvent, with alchlor, boron trifluoride ether or
Boron tribromide is catalyst, the C-C coupled products that the catalyst is obtained with step (2), in molar ratio 0.4-2.0:1, reaction
- 10-60 DEG C of temperature, when reaction time 0.5-6 is small, the reaction of ether solution obtains ether solution reaction product；
(4) intramolecular cyclization reaction：Using toluene or xylene as solvent, with p-methyl benzenesulfonic acid, benzene sulfonic acid, sulfuric acid or salt
Acid is catalyst, ether solution reaction product that the catalyst is obtained with step (3), in molar ratio 0.1-1.0:1, reaction temperature
80-130 DEG C, when reaction time 3-12 is small, intramolecular cyclization reaction derives to get to the fluorenyl benzindole containing halogen
Object.
Method using the present invention, the reaction yield for the fluorenyl benzindole derivative containing halogen prepared is high, always
Yield can reach 55-65%, and at low cost, purity is high (HPLC purity is more than 99.9%, single miscellaneous be less than 100ppm), through HPLC-MS
Detection, no dihalo object and isomers.
Based on the above technical solutions, the present invention can also be improved as follows.
Further, in step (1), the NBS and 9,9- dimethyl -2- aminofluorenes or 9,9- diphenyl -2- aminofluorenes
Molar ratio is 1:1,0 DEG C of the reaction temperature, when the reaction time is 4 small.
Further, in step (2), bromo- 9, the 9- dimethyl -2- aminofluorenes of the 3- or bromo- 9, the 9- diphenyl -2- amino of 3-
Fluorenes, the molar ratio with the halogenated phenyl boric acids of 2- methoxyl groups -5- are 1.1:1,75 DEG C of the reaction temperature, the reaction time is 8 small
When.
Further, in step (2), the palladium catalyst is Pd (OAc)2、Pd(dba)2、Pd2(dba)3、PdCl2In one
Kind.
Further, in step (2), the organophosphorus ligand is triphenylphosphine, DPPP, Xantphos, Sphos, P (t-
Bu)3·HBF4In one kind.
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), the inorganic salts are potassium carbonate, one kind in sodium carbonate, potassium hydroxide.
Further, in step (3), the molar ratio for the C-C coupled products that the catalyst is obtained with step (2) is 1.2:1,
The reaction temperature is 25 DEG C, when the reaction time is 3 small.
Further, in step (4), the molar ratio for the ether solution reaction product that the catalyst is obtained with step (3) is
0.5:1, the reaction temperature is 105 DEG C, when the reaction time is 7.5 small
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-succinimides, also known as N- bromo ambers
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：It is double that (two is sub-
Benzyl benzylacetones) palladium.
Pd2(dba)3, English name：Tris (dibenzylideneacetone) dipalladium, Chinese：Three
(dibenzalacetone) two palladium.
PdCl2, English name：Palladium chloride, Chinese：Palladium bichloride, also known as palladium chloride.
DPPP, English name：3-bis (diphenylphosphino) propane, Chinese：Double (the diphenyl of 1,3-
Phosphine) propane.
Xantphos, English name：Dimethylbisdiphenylphosphinoxanthene, Chinese：4,5-
Double diphenylphosphine -9,9- xanthphos.
Sphos, English name：Dicyclohexyl(2',6'-dimethoxy-[1,1'-biphenyl]-2-yl)
Phosphane, Chinese：2- dicyclohexyl phosphine -2', 6'- dimethoxy-biphenyls.
P(t-Bu)3·HBF4, English name：Tri-t-butylphosphonium tetrafluoroborate, Chinese
Title：Tri-tert-butylphosphine tetrafluoroborate.
The beneficial effects of the invention are as follows：
(1) present invention firstly provides a kind of new method for preparing fluorenyl benzindole compound, this method is safe and environment-friendly
Efficiently.
(2) method using the present invention, the reaction yield for the fluorenyl benzindole derivative containing halogen prepared is high,
Total recovery can reach 55-65%, and without largely using precious metals palladium catalyst, cost is greatly reduced, purity is high, and HPLC purity can
Up to 99.9%, list is miscellaneous to be less than 100ppm, is detected through HPLC-MS, no dihalo object and isomers meet the organic photoelectrics material such as OLED
The application of material.
(3) preparation method of the invention is simple, and raw material is cheap and easy to get, wide market, is suitble to large-scale production.
Specific embodiment
The principle of the present invention and feature are described below in conjunction with specific embodiment, example is served only for explaining this hair
It is bright, it is not intended to limit the scope of the present invention.
Embodiment 1：Prepare chloro- 7,7- dimethyl -5,7- dihydros indeno [2,1-b] carbazoles of 2-
The preparation of the bromo- 2- amino -9,9- dimethyl fluorenes of 3-：20.9g (100mmol) 2- amino -9,9- dimethyl fluorenes is molten
In 250mL chloroformic solutions, 0-5 DEG C of temperature, is added portionwise NBS 17.8g (100mmol), reaction mixture is in 0-5 DEG C in control
2.0hrs is reacted, adding in 100g2.5% aqueous solution of sodium bisulfite to reaction system is quenched reaction, is layered, 100mL washings are organic
Phase, anhydrous sodium sulfate drying, vacuum desolvation agent obtains bromo- 2- amino -9, the 9- dimethyl fluorene crude product 29.1g of 3-, then using 8g/
G recrystallizing methanols obtain white solid powder 24.3g, yield 84.37%.
The preparation of 3- (the chloro- 2- methoxyphenyls of 5-) -9,9- dimethyl -9H- fluorenes -2- amine：By 23.0g (80mmol) 3-
Bromo- 2- amino -9,9- dimethyl fluorenes, the chloro- 2- methoxyphenylboronic acids of 14.9g (80mmol) 5- and 200mL toluene add in tri- mouthfuls of 1L
In flask, nitrogen is sufficiently displaced from, and adds in catalyst 90mg (0.4mmol) Pd (OAc)2With 232mg (0.8mmol) P (t-Bu)3·
HBF4And the aqueous sodium carbonate of 100g12%, be heated to reflux 80-85 DEG C, reaction 4-6.0 it is small when, TLC tracking react into
Journey.After completion of the reaction, static layering, washing, the drying of organic phase anhydrous sodium sulfate, desolventizing obtain 3- (the chloro- 2- methoxybenzenes of 5-
Base) -9,9- dimethyl -9H- fluorenes -2- amine crude product 28.3g, without purifying, yield is in terms of 100%.
The preparation of 2- (2- amino -9,9- dimethyl -9H- fluorenes -3- bases) -4- chlorophenols：By 28.3g (80mmol) 3- (5-
Chloro- 2- methoxyphenyls) -9,9- dimethyl -9H- fluorenes -2- amine and 20.0g (80mmol) Boron tribromide be added to 200mL dichloros
In ethane solution, 12.0hrs is stirred in 10 DEG C, pours into 300ml ice water and is quenched, is layered, washing, organic phase is by anhydrous slufuric acid
Sodium is dried, and desolventizing obtains 2- (2- amino -9,9- dimethyl -9H- fluorenes -3- bases) -4- chlorophenol crude product 27.1g, without purifying,
Yield is in terms of 100%.
The preparation of chloro- 7,7- dimethyl -5,7- dihydros indeno [2,1-b] carbazoles of 2-：By 27.1g (80mmol) 2- (2- ammonia
Base -9,9- dimethyl -9H- fluorenes -3- bases) to be added to 200mL toluene molten for -4- chlorophenols and 15.3g (80mmol) p-methyl benzenesulfonic acid
In liquid, in 105-110 DEG C be stirred to react 3-6 it is small when, TLC tracking reaction process.After completion of the reaction, cool down, add in 200ml water
It is quenched, is layered, washing, organic phase is dried by anhydrous sodium sulfate, and desolventizing obtains chloro- 7,7- dimethyl -5, the 7- dihydro indenos of 2-
[2,1-b] carbazole crude product, toluene alcohol mixed solvent recrystallize twice, HPLC purity 99.95%, yield 77.09%.
MS(ESI)：318.41([M+1]+), calculated value 317.10.
1H NMR(400MHz,CDCl3)δ：10.84 (s, 1H) be carbazole nitrogen on active hydrogen, 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：Prepare bromo- 7,7- dimethyl -5,7- dihydros indeno [2,1-b] carbazoles of 2-
The preparation of the bromo- 2- amino -9,9- dimethyl fluorenes of 3-：20.9g (100mmol) 2- amino -9,9- dimethyl fluorenes is molten
In 200mL dichloroethane solutions, -5-0 DEG C of Nei Wen is controlled, NBS 16.9g (95mmol) are added portionwise, reaction mixture is in 0-
5 DEG C of reaction 4.0hrs add in 100g2.5% aqueous solution of sodium bisulfite to reaction system and reaction are quenched, are layered, 100mL washings
Organic phase, anhydrous sodium sulfate drying, vacuum desolvation agent obtain bromo- 2- amino -9, the 9- dimethyl fluorene crude product 28.8g of 3-, then make
White solid powder 23.4g, yield 81.19% are recrystallized to give with toluene alcohol mixed solvent.
The preparation of 3- (the bromo- 2- methoxyphenyls of 5-) -9,9- dimethyl -9H- fluorenes -2- amine：By 23.0g (80mmol) 3-
Bromo- 2- amino -9,9- dimethyl fluorenes, the bromo- 2- methoxyphenylboronic acids of 17.3g (75mmol) 5- and 250mL toluene add in tri- mouthfuls of 1L
In flask, nitrogen is sufficiently displaced from, and adds in catalyst 90mg (0.4mmol) Pd (OAc)2With 463mg (0.8mmol) Xantphos with
And 140g, 12% wet chemical, 80-85 DEG C of reflux is heated to, when reaction 4-6.0 is small, TLC tracking reaction process.Instead
Should after, static layering, washing, organic phase anhydrous sodium sulfate drying, desolventizing obtain 3- (the bromo- 2- methoxyphenyls of 5-)-
9,9- dimethyl -9H- fluorenes -2- amine crude product 29.6g, without purifying, yield is in terms of 100%.
The preparation of 2- (2- amino -9,9- dimethyl -9H- fluorenes -3- bases) -4- bromophenols：By 29.6g (75mmol) 3- (5-
Bromo- 2- methoxyphenyls) -9,9- dimethyl -9H- fluorenes -2- amine and 12.5g (50mmol) Boron tribromide be added to 240mL chloroforms
In solution, 8.0hrs is stirred in 0 DEG C, pours into 300ml ice water and is quenched, is layered, washing, organic phase is done by anhydrous sodium sulfate
Dry, desolventizing obtains 2- (2- amino -9,9- dimethyl -9H- fluorenes -3- bases) -4- bromophenol crude product 28.4g, without purifying, yield
In terms of 100%.
The preparation of bromo- 7,7- dimethyl -5,7- dihydros indeno [2,1-b] carbazoles of 2-：By 28.4g (75mmol) 2- (2- ammonia
Base -9,9- dimethyl -9H- fluorenes -3- bases) -4- bromophenols and 1.4g (8mmol) benzene sulfonic acid be added in 200mL xylene solutions,
In 125-130 DEG C be stirred to react 3-6 it is small when, TLC tracking reaction process.After completion of the reaction, cool down, add in 200ml water and be quenched,
Layering, washing, organic phase are dried by anhydrous sodium sulfate, and desolventizing obtains bromo- 7,7- dimethyl -5, the 7- dihydro indenos [2,1- of 2-
B] carbazole crude product, toluene alcohol mixed solvent recrystallization obtain 20.2g, HPLC purity 99.91%, yield 74.36% twice.
MS(ESI)：362.71([M+1]+), calculated value 361.05.
1H NMR(400MHz,CDCl3)δ：10.61 (s, 1H) be carbazole nitrogen on active hydrogen, 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：Prepare bromo- 7,7- diphenyl -5,7- dihydros indeno [2,1-b] carbazoles of 2-
The preparation of the bromo- 2- amino -9,9- diphenylfluorenes of 3-：33.3g (100mmol) 2- amino -9,9- diphenylfluorenes is molten
In 300mL dichloromethane solutions, 10-15 DEG C of temperature, is added portionwise NBS 18.2g (102mmol) in control, reaction mixture in
10-15 DEG C of reaction 8.0hrs, 100g is added in reaction system, and reaction is quenched in 2.5% aqueous solution of sodium bisulfite, is layered, 100mL
Organic phase, anhydrous sodium sulfate drying are washed, vacuum desolvation agent obtains bromo- 2- amino -9, the 9- diphenylfluorene crude product 41.3g of 3-, and
Afterwards white solid powder 33.6g, yield 81.55% are recrystallized to give using toluene alcohol mixed solvent.
The preparation of 3- (the bromo- 2- methoxyphenyls of 5-) -9,9- diphenyl -9H- fluorenes -2- amine：By 33.0g (80mmol) 3-
Bromo- 2- amino -9,9- diphenylfluorenes, the bromo- 2- methoxyphenylboronic acids of 17.3g (75mmol) 5- and 250mL toluene add in tri- mouthfuls of 1L
In flask, nitrogen is sufficiently displaced from, and adds in catalyst 90mg (0.4mmol) Pd (OAc)2With 463mg (0.8mmol) Xantphos with
And the wet chemical of 140g 12%, 80-85 DEG C of reflux is heated to, when reaction 8.0 is small, TLC tracking reaction process.Reaction
After, static layering, washing, the drying of organic phase anhydrous sodium sulfate, desolventizing obtain 3- (the bromo- 2- methoxyphenyls of 5-) -9,
9- diphenyl -9H- fluorenes -2- amine crude product 38.9g, without purifying, yield is in terms of 100%.
The preparation of 2- (2- amino -9,9- diphenyl -9H- fluorenes -3- bases) -4- bromophenols：By 38.9g (75mmol) 3- (5-
Bromo- 2- methoxyphenyls) -9,9- diphenyl -9H- fluorenes -2- amine and 37.6g (150mmol) Boron tribromide be added to 400mL dichloros
In dichloromethane, 8.0hrs is stirred in 15 DEG C, pours into 300ml ice water and is quenched, is layered, washing, organic phase is by anhydrous slufuric acid
Sodium is dried, and desolventizing obtains 2- (2- amino -9,9- diphenyl -9H- fluorenes -3- bases) -4- bromophenol crude product 37.9g, without purifying,
Yield is in terms of 100%.
The preparation of bromo- 7,7- diphenyl -5,7- dihydros indeno [2,1-b] carbazoles of 2-：By 37.9g (75mmol) 2- (2- ammonia
Base -9,9- diphenyl -9H- fluorenes -3- bases) -4- bromophenols and 2.9g (15mmol) p-methyl benzenesulfonic acid be added to 300mL toluene solutions
In, in 105-110 DEG C be stirred to react 3.0 it is small when, TLC tracking reaction process.After completion of the reaction, cool down, add in 200ml water and quench
Go out, be layered, washing, organic phase dried by anhydrous sodium sulfate, desolventizing obtain bromo- 7,7- diphenyl -5, the 7- dihydro indenos of 2- [2,
1-b] carbazole crude product, toluene alcohol mixed solvent recrystallize twice, HPLC purity 99.93%, yield 78.63%.
LC-MS：486.07([M+1]+), calculated value 485.08.
1H NMR(400MHz,CDCl3)δ：11.16 (s, 1H) be carbazole nitrogen on active hydrogen, 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：Prepare chloro- 7,7- diphenyl -5,7- dihydros indeno [2,1-b] carbazoles of 2-
The preparation of the bromo- 2- amino -9,9- diphenylfluorenes of 3-：33.3g (100mmol) 2- amino -9,9- diphenylfluorenes is molten
In 300mL dichloroethane solutions, 15-20 DEG C of temperature, is added portionwise NBS 17.8g (100mmol) in control, reaction mixture in
15-20 DEG C of reaction 12.0hrs, 100g is added in reaction system, and reaction is quenched in 2.5% aqueous solution of sodium bisulfite, is layered,
100mL washes organic phase, anhydrous sodium sulfate drying, and vacuum desolvation agent obtains bromo- 2- amino -9, the 9- diphenylfluorene crude products of 3-
41.4g is then recrystallized to give white solid powder 33.0g, yield 80.12% using toluene alcohol mixed solvent.
The preparation of 3- (the chloro- 2- methoxyphenyls of 5-) -9,9- diphenyl -9H- fluorenes -2- amine：By 33.0g (80mmol) 3-
Bromo- 2- amino -9,9- diphenylfluorenes, the chloro- 2- methoxyphenylboronic acids of 14.9g (80mmol) 5- and 300mL toluene add in tri- mouthfuls of 1L
In flask, nitrogen is sufficiently displaced from, and adds in catalyst 90mg (0.4mmol) Pd (OAc)2With 232mg (0.8mmol) P (t-Bu)3·
HBF4And 200g, 10% wet chemical, be heated to reflux 80-85 DEG C, reaction 6.0 it is small when, TLC tracking react into
Journey.After completion of the reaction, static layering, washing, the drying of organic phase anhydrous sodium sulfate, desolventizing obtain 3- (the chloro- 2- methoxybenzenes of 5-
Base) -9,9- diphenyl -9H- fluorenes -2- amine crude product 37.8g, without purifying, yield is in terms of 100%.
The preparation of 2- (2- amino -9,9- diphenyl -9H- fluorenes -3- bases) -4- chlorophenols：By 37.8g (80mmol) 3- (5-
Chloro- 2- methoxyphenyls) -9,9- diphenyl -9H- fluorenes -2- amine and 22.5g (90mmol) Boron tribromide be added to 500mL dichloros
In ethane solution, 12.0hrs is stirred in 0-5 DEG C, pours into 300ml ice water and is quenched, is layered, washing, organic phase is by anhydrous sulphur
Sour sodium drying, desolventizing obtains 2- (2- amino -9,9- diphenyl -9H- fluorenes -3- bases) -4- chlorophenol crude product 37.0g, without pure
Change, yield is in terms of 100%.
The preparation of chloro- 7,7- diphenyl -5,7- dihydros indeno [2,1-b] carbazoles of 2-：By 37.0g (80mmol) 2- (2- ammonia
Base -9,9- diphenyl -9H- fluorenes -3- bases) -4- chlorophenols and 7.7g (40mmol) p-methyl benzenesulfonic acid be added to 500mL toluene solutions
In, in 105-110 DEG C be stirred to react 6.0 it is small when, TLC tracking reaction process.After completion of the reaction, cool down, add in 200ml water and quench
Go out, be layered, washing, organic phase dried by anhydrous sodium sulfate, desolventizing obtain chloro- 7,7- diphenyl -5, the 7- dihydro indenos of 2- [2,
1-b] carbazole crude product, toluene alcohol mixed solvent recrystallization obtain 24.8g, HPLC purity 99.92%, yield 70.09% twice.
LC-MS：442.16([M+1]+), calculated value 441.13.
1H NMR(400MHz,CDCl3)δ：11.03 (s, 1H) be carbazole nitrogen on active hydrogen, 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：Prepare chloro- 7,7- dimethyl -5,7- dihydros indeno [2,1-b] carbazoles of 2-
The preparation of the bromo- 2- amino -9,9- dimethyl fluorenes of 3-：20.9g (100mmol) 2- amino -9,9- dimethyl fluorenes is molten
In 250mL chloroformic solutions, NBS 17.8g (100mmol) are added portionwise in 0 DEG C of temperature in control, and reaction mixture is in 0 DEG C of reaction
4.0hrs adds in 2.5% aqueous solution of sodium bisulfite of 100g to reaction system and reaction is quenched, is layered, 100mL washing organic phases,
Anhydrous sodium sulfate is dried, and vacuum desolvation agent obtains bromo- 2- amino -9, the 9- dimethyl fluorene crude product 29.0g of 3-, then using 8g/g first
Alcohol is recrystallized to give white solid powder 23.5g, yield 81.63%.
The preparation of 3- (the chloro- 2- methoxyphenyls of 5-) -9,9- dimethyl -9H- fluorenes -2- amine：By 25.4g (88mmol) 3-
Bromo- 2- amino -9,9- dimethyl fluorenes, the chloro- 2- methoxyphenylboronic acids of 14.9g (80mmol) 5- and 200mL toluene add in tri- mouthfuls of 1L
In flask, nitrogen is sufficiently displaced from, and adds in catalyst 90mg (0.4mmol) Pd (OAc)2With 232mg (0.8mmol) P (t-Bu)3·
HBF4And the aqueous sodium carbonate of 100g 12%, 75 DEG C, when reaction 8 is small are heated to, TLC tracking reaction process.Reaction finishes
Afterwards, static layering, washing, the drying of organic phase anhydrous sodium sulfate, desolventizing obtain 3- (the chloro- 2- methoxyphenyls of 5-) -9,9- bis-
Methyl-9 H-fluorene -2- amine crude product 28.0g, without purifying, yield is in terms of 100%.
The preparation of 2- (2- amino -9,9- dimethyl -9H- fluorenes -3- bases) -4- chlorophenols：By 28.0g (80mmol) 3- (5-
Chloro- 2- methoxyphenyls) -9,9- dimethyl -9H- fluorenes -2- amine and 24.0g (96mmol) Boron tribromide be added to 200mL dichloros
In ethane solution, 3.0hrs is stirred in 25 DEG C, pours into 300ml ice water and is quenched, is layered, washing, organic phase is by anhydrous slufuric acid
Sodium is dried, and desolventizing obtains 2- (2- amino -9,9- dimethyl -9H- fluorenes -3- bases) -4- chlorophenol crude product 26.9g, without purifying,
Yield is in terms of 100%.
The preparation of chloro- 7,7- dimethyl -5,7- dihydros indeno [2,1-b] carbazoles of 2-：By 26.9g (80mmol) 2- (2- ammonia
Base -9,9- dimethyl -9H- fluorenes -3- bases) -4- chlorophenols and 7.7g (40mmol) p-methyl benzenesulfonic acid be added to 200mL toluene solutions
In, in 105 DEG C be stirred to react 3-6 it is small when, TLC tracking reaction process.After completion of the reaction, cool down, add in 200ml water and be quenched,
Layering, washing, organic phase are dried by anhydrous sodium sulfate, and desolventizing obtains chloro- 7,7- dimethyl -5, the 7- dihydro indenos [2,1- of 2-
B] carbazole crude product, 20.1g, HPLC purity 99.97%, yield 79.09% are single miscellaneous equal twice for toluene alcohol mixed solvent recrystallization
Less than 100ppm, HPLC-MS detections do not find isomers and dichloro- object.
MS(ESI)：318.41([M+1]+), calculated value 317.10.
1H NMR(400MHz,CDCl3)δ：10.84 (s, 1H) be carbazole nitrogen on active hydrogen, 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：Prepare bromo- 7,7- dimethyl -5,7- dihydros indeno [2,1-b] carbazoles of 2-
The preparation of the bromo- 2- amino -9,9- dimethyl fluorenes of 3-：20.9g (100mmol) 2- amino -9,9- dimethyl fluorenes is molten
In 250mL chloroformic solutions, NBS 17.8g (100mmol) are added portionwise in 0 DEG C of temperature in control, and reaction mixture is in 0 DEG C of reaction
4.0hrs adds in 100g2.5% aqueous solution of sodium bisulfite to reaction system and reaction is quenched, is layered, 100mL washing organic phases,
Anhydrous sodium sulfate is dried, and vacuum desolvation agent obtains bromo- 2- amino -9, the 9- dimethyl fluorene crude product 29.0g of 3-, then using 8g/g first
Alcohol is recrystallized to give white solid powder 23.5g, yield 81.63%.
The preparation of 3- (the bromo- 2- methoxyphenyls of 5-) -9,9- dimethyl -9H- fluorenes -2- amine：By 23.8g (82.5mmol) 3-
Bromo- 2- amino -9,9- dimethyl fluorenes, the bromo- 2- methoxyphenylboronic acids of 17.3g (75mmol) 5- and 250mL toluene add in tri- mouthfuls of 1L
In flask, nitrogen is sufficiently displaced from, and adds in catalyst 90mg (0.4mmol) Pd (OAc)2With 463mg (0.8mmol) Xantphos with
And the wet chemical of 140g 12%, 75 DEG C, when reaction 8.0 is small are heated to, TLC tracking reaction process.After completion of the reaction,
Static layering, washing, the drying of organic phase anhydrous sodium sulfate, desolventizing obtain 3- (the bromo- 2- methoxyphenyls of 5-) -9,9- diformazans
Base -9H- fluorenes -2- amine crude product 29.6g, without purifying, yield is in terms of 100%.
The preparation of 2- (2- amino -9,9- dimethyl -9H- fluorenes -3- bases) -4- bromophenols：By 29.6g (75mmol) 3- (5-
Bromo- 2- methoxyphenyls) -9,9- dimethyl -9H- fluorenes -2- amine and 22.5g (90mmol) Boron tribromide be added to 240mL chloroforms
In solution, 3.0hrs is stirred in 25 DEG C, pours into 300ml ice water and is quenched, is layered, washing, organic phase is done by anhydrous sodium sulfate
Dry, desolventizing obtains 2- (2- amino -9,9- dimethyl -9H- fluorenes -3- bases) -4- bromophenol crude product 28.6g, without purifying, yield
In terms of 100%.
The preparation of bromo- 7,7- dimethyl -5,7- dihydros indeno [2,1-b] carbazoles of 2-：By 28.6g (75mmol) 2- (2- ammonia
Base -9,9- dimethyl -9H- fluorenes -3- bases) -4- bromophenols and 7.2g (37.5mmol) benzene sulfonic acid be added to 200mL xylene solutions
In, in 105 DEG C be stirred to react 7.5 it is small when, TLC tracking reaction process.After completion of the reaction, cool down, add in 200ml water and be quenched,
Layering, washing, organic phase are dried by anhydrous sodium sulfate, and desolventizing obtains bromo- 7,7- dimethyl -5, the 7- dihydro indenos [2,1- of 2-
B] carbazole crude product, toluene alcohol mixed solvent recrystallizes obtains 21.6g twice, HPLC purity 99.96%, and yield 79.63% is single
Miscellaneous to be respectively less than 100ppm, HPLC-MS detections do not find isomers and two bromo-derivatives.
MS(ESI)：362.71([M+1]+), calculated value 361.05.
1H NMR(400MHz,CDCl3)δ：10.61 (s, 1H) be carbazole nitrogen on active hydrogen, 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：Prepare bromo- 7,7- diphenyl -5,7- dihydros indeno [2,1-b] carbazoles of 2-
The preparation of the bromo- 2- amino -9,9- diphenylfluorenes of 3-：33.3g (100mmol) 2- amino -9,9- diphenylfluorenes is molten
In 300mL dichloromethane solutions, 0 DEG C of temperature, is added portionwise NBS 18.0g (100mmol), reaction mixture is in 0 DEG C in control
4.0hrs is reacted, adding in 2.5% aqueous solution of sodium bisulfite of 100g to reaction system is quenched reaction, is layered, and 100mL washings have
Machine phase, anhydrous sodium sulfate drying, vacuum desolvation agent obtain bromo- 2- amino -9, the 9- diphenylfluorene crude product 41.3g of 3-, then use
Toluene alcohol mixed solvent is recrystallized to give white solid powder 36.5g, yield 88.62%.
The preparation of 3- (the bromo- 2- methoxyphenyls of 5-) -9,9- diphenyl -9H- fluorenes -2- amine：By 34.0g (82.5mmol) 3-
Bromo- 2- amino -9,9- diphenylfluorenes, the bromo- 2- methoxyphenylboronic acids of 17.3g (75mmol) 5- and 250mL toluene add in tri- mouthfuls of 1L
In flask, nitrogen is sufficiently displaced from, and adds in catalyst 90mg (0.4mmol) Pd (OAc)2With 463mg (0.8mmol) Xantphos with
And the wet chemical of 140g 12%, 75 DEG C, when reaction 8.0 is small are heated to, TLC tracking reaction process.After completion of the reaction,
Static layering, washing, the drying of organic phase anhydrous sodium sulfate, desolventizing obtain 3- (the bromo- 2- methoxyphenyls of 5-) -9,9- hexichol
Base -9H- fluorenes -2- amine crude product 38.9g, without purifying, yield is in terms of 100%.
The preparation of 2- (2- amino -9,9- diphenyl -9H- fluorenes -3- bases) -4- bromophenols：By 38.9g (75mmol) 3- (5-
Bromo- 2- methoxyphenyls) -9,9- diphenyl -9H- fluorenes -2- amine and 22.5g (90mmol) Boron tribromide be added to 400mL dichloros
In dichloromethane, 3.0hrs is stirred in 25 DEG C, pours into 300ml ice water and is quenched, is layered, washing, organic phase is by anhydrous slufuric acid
Sodium is dried, and desolventizing obtains 2- (2- amino -9,9- diphenyl -9H- fluorenes -3- bases) -4- bromophenol crude product 37.9g, without purifying,
Yield is in terms of 100%.
The preparation of bromo- 7,7- diphenyl -5,7- dihydros indeno [2,1-b] carbazoles of 2-：By 37.9g (75mmol) 2- (2- ammonia
Base -9,9- diphenyl -9H- fluorenes -3- bases) to be added to 300mL toluene molten for -4- bromophenols and 7.2g (37.5mmol) p-methyl benzenesulfonic acid
In liquid, in 105 DEG C be stirred to react 7.5 it is small when, TLC tracking reaction process.After completion of the reaction, cool down, add in 200ml water and quench
Go out, be layered, washing, organic phase dried by anhydrous sodium sulfate, desolventizing obtain bromo- 7,7- diphenyl -5, the 7- dihydro indenos of 2- [2,
1-b] carbazole crude product, toluene alcohol mixed solvent recrystallization twice 26.3g, HPLC purity 99.96%, yield 72.09% are single
Miscellaneous to be respectively less than 100ppm, HPLC-MS detections do not find isomers and two bromo-derivatives.
LC-MS：486.07([M+1]+), calculated value 485.08.
1H NMR(400MHz,CDCl3)δ：11.16 (s, 1H) be carbazole nitrogen on active hydrogen, 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：Prepare chloro- 7,7- diphenyl -5,7- dihydros indeno [2,1-b] carbazoles of 2-
The preparation of the bromo- 2- amino -9,9- diphenylfluorenes of 3-：33.3g (100mmol) 2- amino -9,9- diphenylfluorenes is molten
In 300mL dichloromethane solutions, 0 DEG C of temperature, is added portionwise NBS 18.0g (100mmol), reaction mixture is in 0 DEG C in control
4.0hrs is reacted, adding in 2.5% aqueous solution of sodium bisulfite of 100g to reaction system is quenched reaction, is layered, and 100mL washings have
Machine phase, anhydrous sodium sulfate drying, vacuum desolvation agent obtain bromo- 2- amino -9, the 9- diphenylfluorene crude product 41.3g of 3-, then use
Toluene alcohol mixed solvent is recrystallized to give white solid powder 36.5g, yield 88.62%.
The preparation of 3- (the chloro- 2- methoxyphenyls of 5-) -9,9- diphenyl -9H- fluorenes -2- amine：By 36.3g (88mmol) 3-
Bromo- 2- amino -9,9- diphenylfluorenes, the chloro- 2- methoxyphenylboronic acids of 14.9g (80mmol) 5- and 300mL toluene add in tri- mouthfuls of 1L
In flask, nitrogen is sufficiently displaced from, and adds in catalyst 90mg (0.4mmol) Pd (OAc)2With 232mg (0.8mmol) P (t-Bu)3·
HBF4And the wet chemical of 200g 10%, 75 DEG C, when reaction 8.0 is small are heated to, TLC tracking reaction process.It has reacted
Bi Hou, static layering, washing, the drying of organic phase anhydrous sodium sulfate, desolventizing obtain 3- (the chloro- 2- methoxyphenyls of 5-) -9,9-
Diphenyl -9H- fluorenes -2- amine crude product 37.8g, without purifying, yield is in terms of 100%.
The preparation of 2- (2- amino -9,9- diphenyl -9H- fluorenes -3- bases) -4- chlorophenols：By 37.9g (80mmol) 3- (5-
Chloro- 2- methoxyphenyls) -9,9- diphenyl -9H- fluorenes -2- amine and 22.5g (90mmol) Boron tribromide be added to 500mL dichloros
In ethane solution, 12.0hrs is stirred in 25 DEG C, pours into 300ml ice water and is quenched, is layered, washing, organic phase is by anhydrous slufuric acid
Sodium is dried, and desolventizing obtains 2- (2- amino -9,9- diphenyl -9H- fluorenes -3- bases) -4- chlorophenol crude product 37.0g, without purifying,
Yield is in terms of 100%.
The preparation of chloro- 7,7- diphenyl -5,7- dihydros indeno [2,1-b] carbazoles of 2-：By 37.0g (80mmol) 2- (2- ammonia
Base -9,9- diphenyl -9H- fluorenes -3- bases) -4- chlorophenols and 7.7g (40mmol) p-methyl benzenesulfonic acid be added to 500mL toluene solutions
In, in 105 DEG C be stirred to react 7.5 it is small when, TLC tracking reaction process.After completion of the reaction, cool down, add in 200ml water and be quenched,
Layering, washing, organic phase are dried by anhydrous sodium sulfate, and desolventizing obtains chloro- 7,7- diphenyl -5, the 7- dihydro indenos [2,1- of 2-
B] carbazole crude product, toluene alcohol mixed solvent recrystallizes obtains 25.9g twice, HPLC purity 99.97%, and yield 73.35% is single
Miscellaneous to be respectively less than 100ppm, HPLC-MS detections do not find isomers and dichloro- object.
LC-MS：442.16([M+1]+), calculated value 441.13.
1H NMR(400MHz,CDCl3)δ：11.03 (s, 1H) be carbazole nitrogen on active hydrogen, 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 merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and
Within principle, any modifications, equivalent replacements and improvements are made should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of preparation method of the fluorenyl benzindole derivative containing halogen, which is characterized in that include the following steps：
(1) bromo-reaction：Using dichloromethane, chloroform or dichloroethanes as solvent, NBS and 9,9- dimethyl -2- aminofluorenes or 9,
9- diphenyl -2- aminofluorenes, in molar ratio 0.95-1.05:1, -5-50 DEG C of reaction temperature when reaction time 1-6 is small, carries out bromine
Generation reaction, after processing is quenched in sodium hydrogensulfite, obtains bromo- 9, the 9- dimethyl -2- aminofluorenes of 3- or bromo- 9, the 9- diphenyl -2- of 3-
Aminofluorene；
(2) C-C coupling reactions：Using toluene or glycol dimethyl ether as solvent, bromo- 9, the 9- dimethyl of 3- that is obtained with step (1)-
2- aminofluorenes or bromo- 9, the 9- diphenyl -2- aminofluorenes of 3-, and halogenated phenyl boric acids of 2- methoxyl groups -5-, in molar ratio 1.0-1.2:1,
Under palladium catalyst, organophosphorus ligand catalysis and under inorganic salts co-catalysis, 60-90 DEG C of reaction temperature, the reaction time, 4-12 was small
When, C-C coupling reactions obtain C-C coupled products；
(3) ether solution is reacted：Using dichloromethane, chloroform or dichloroethanes as solvent, with alchlor, boron trifluoride ether or tribromo
Change boron is catalyst, the C-C coupled products that the catalyst and step (2) obtain, in molar ratio 0.4-2.0:1, reaction temperature-
10-60 DEG C, when reaction time 0.5-6 is small, the reaction of ether solution obtains ether solution reaction product；
(4) intramolecular cyclization reaction：Using toluene or xylene as solvent, using p-methyl benzenesulfonic acid, benzene sulfonic acid, sulfuric acid or hydrochloric acid as
Catalyst, the ether solution reaction product that the catalyst and step (3) obtain, in molar ratio 0.1-1.0:1, reaction temperature 80-130
DEG C, when reaction time 3-12 is small, intramolecular cyclization reaction is to get to the fluorenyl benzindole derivative containing halogen.
2. a kind of preparation method of fluorenyl benzindole derivative containing halogen according to claim 1, feature exist
In in step (1), the NBS and the molar ratio of 9,9- dimethyl -2- aminofluorenes or 9,9- diphenyl -2- aminofluorenes are 1:1,
0 DEG C of the reaction temperature, when the reaction time is 4 small.
3. a kind of preparation method of fluorenyl benzindole derivative containing halogen according to claim 1, feature exist
In, in step (2), bromo- 9, the 9- dimethyl -2- aminofluorenes of the 3- or bromo- 9, the 9- diphenyl -2- aminofluorenes of 3-, with 2- methoxies
The molar ratio of the halogenated phenyl boric acids of base -5- is 1.1:1,75 DEG C of the reaction temperature, when the reaction time is 8 small.
4. a kind of preparation method of fluorenyl benzindole derivative containing halogen according to claim 1, feature exist
In in step (2), the palladium catalyst is Pd (OAc)2、Pd(dba)2、Pd2(dba)3、PdCl2In one kind.
5. a kind of preparation method of fluorenyl benzindole derivative containing halogen according to claim 1, feature exist
In in step (2), the organophosphorus ligand is triphenylphosphine, DPPP, Xantphos, Sphos, P (t-Bu)3·HBF4In one
Kind.
6. a kind of preparation method of fluorenyl benzindole derivative containing halogen according to claim 1, feature exist
In in step (2), the inorganic salts are potassium carbonate, one kind in sodium carbonate, potassium hydroxide.
7. a kind of preparation method of fluorenyl benzindole derivative containing halogen according to claim 1, feature exist
In in step (3), the molar ratio for the C-C coupled products that the catalyst is obtained with step (2) is 1.2:1, the reaction temperature
For 25 DEG C, when the reaction time is 3 small.
8. a kind of preparation method of fluorenyl benzindole derivative containing halogen according to claim 1, feature exist
In in step (4), the molar ratio for the ether solution reaction product that the catalyst is obtained with step (3) is 0.5:1, it is described anti-
Temperature is answered as 105 DEG C, when the reaction time is 7.5 small.
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