CN108003165B - A kind of synthetic method of 5,11- dihydro -5- Phenylindole simultaneously [3,2-b] carbazole - Google Patents
A kind of synthetic method of 5,11- dihydro -5- Phenylindole simultaneously [3,2-b] carbazole Download PDFInfo
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- CN108003165B CN108003165B CN201711393499.7A CN201711393499A CN108003165B CN 108003165 B CN108003165 B CN 108003165B CN 201711393499 A CN201711393499 A CN 201711393499A CN 108003165 B CN108003165 B CN 108003165B
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Abstract
The invention discloses the production methods of one kind 5,11- dihydro -5- Phenylindole simultaneously [3,2-b] carbazole, belong to organic chemical synthesis field.Realize by the following method: 3- amino-N- phenyl carbazole is starting material, has synthesized 5,11- dihydro -5- Phenylindole simultaneously [3,2-b] carbazole through bromination, Suzuki coupling and Buchwald coupling reaction.Reaction process side reaction is few, easy to operate and high income.Simultaneously [3,2-b] carbazole can be used for organic photoelectrical material, medicine and other fields to 5, the 11- dihydro -5- Phenylindole of synthesis, be the important intermediate of carbazoles photoelectric material, medicine and pesticide.
Description
Technical field
The present invention relates to the preparation methods of a kind of indoles simultaneously [3,2-b] carbazole derivates, more particularly to one kind 5,11- bis-
The synthetic method of hydrogen -5- Phenylindole simultaneously [3,2-b] carbazole belongs to organic chemical synthesis field.
Background technique
Carbazole is a kind of important heterocyclic compound, is widely present in natural products and pharmaceutical chemistry molecule, is had bright
Aobvious biology and pharmacological activity.In addition, carbazole and its derivative have excellent luminous point performance, it is total with biggish pi-electron
Yoke system and stronger cyclic voltammetry method characteristic, from the point of view of structure, the electrophilic N atom of carbazole is absorbed double by inductive effect
Electronics on key；On the other hand, since the unshared electronics of the pi-conjugated effect N atom of p- supplies double bond again, make double bond electron rich.
Therefore, carbazole derivates generally have very strong cavity transmission ability, and carbazole polymer or small molecule compound can be in Organic Electricities
Hole transmission layer is used as in electroluminescence device, which reduce the crystallizations of small molecule material, improve device lifetime, increase simultaneously
The chance of electron-hole recombinations improves the luminous efficiency of device.
Simultaneously [3,2-b] carbazole derivates have excellent optically and electrically performance to indoles, extensive concern and are ground in recent years
Study carefully.Simultaneously [3,2-b] carbazole derivates and its polymer are proved to can be used as excellent optics and electricity material and are applied to indoles
In Organic Light Emitting Diode, organic field effect tube, Organic Thin Film Transistors and photovoltaic device, the study found that indoles simultaneously [3,
2-b] substituting group position difference such as will affect its electronic effect, and then influence its cavity transmission ability and thermal stability at the property on carbazole
Energy.The synthetic method of current 5,11- dihydro -5- Phenylindole simultaneously [3,2-b] carbazole is reported by US20150228911 etc., is answered
For the hole mobile material in electroluminescent organic material.It, which is synthesized, mainly passes through indoles simultaneously [3,2-b] carbazole and iodobenzene
Reaction synthesis, this method deficiency is indoles, and simultaneously [3,2-b] carbazole synthesis step is more, and price is higher.
WO2012169821 report it is a kind of using 2- bromine-N-phenylcarbazole be starting material synthesize 5,11- dihydro -5- Phenylindole simultaneously
The method of [3,2-b] carbazole, this method yield is lower, and is easy to produce isomers 5,12- dihydro -5- phenyl-indole simultaneously [3,
2-a] carbazole, it is difficult to it separates, production cost is higher, need to explore and be suitble to industrial new method.
Summary of the invention
The purpose of the present invention is to provide a kind of reaction process is simple, high income, at low cost and suitable industrialized production 5,
The method of 11- dihydro -5- Phenylindole simultaneously [3,2-b] carbazole.
To achieve the purpose of the present invention, the present invention is synthesized using 3- amino-N- phenyl carbazole as starting material through bromination reaction
The bromo- 3- amino-N- phenyl carbazole of 2-, then synthesizes 5,11- dihydro -5- under palladium acetate catalytic action with bromophenyl acid reaction
Phenylindole simultaneously [3,2-b] carbazole.
Specific technical solution is as follows:
Simultaneously [3,2-b] carbazole has following structural to 5,11- dihydro -5- Phenylindole prepared by the present invention:
Its synthetic route is as follows:
Specific reaction step is as follows:
3- amino-N- phenyl carbazole is dissolved in acetonitrile, hydrobromic acid is added, dioxygen is slowly added dropwise in control reaction temperature
Water, natural temperature reaction is stayed overnight after being added dropwise completely, and reaction solution aqueous solution of sodium bisulfite is washed, and separates organic layer, and hydrochloric acid is added, obtains
It is dry to white solid, obtain the bromo- 3- amino-N- phenyl carbazole hydrochloride of 2-；
Under argon gas protection, by the bromo- 3- amino-N- phenyl carbazole hydrochloride of 2-, bromophenyl boric acid, cesium carbonate, N- methyl pyrrole
Pyrrolidone solvent is added to reaction system, and after replacing system air, catalyst acetic acid palladium and bis- [(the 2- first of (R, R) -1,2- are added
Phenyl) phenyl phosphino-] ethane, back flow reaction, after reaction plus water terminates reaction, is extracted, separates organic layer, dry
Overnight, it is concentrated to give crude product, 1,2- Bromofume-alcohol mixed solvent is recrystallized to give product 5, and 11- dihydro -5- Phenylindole is simultaneously
[3,2-b] carbazole.
3- amino-N- phenyl carbazole and hydrobromic acid molar ratio are 1: 0.85-0.95,3- ammonia in the bromination reaction
Base-N- phenyl carbazole and hydrogen peroxide molar ratio are 1: 0.9-1.1；- 20-0 DEG C of bromination reaction temperature.
The bromo- 3- amino-N- phenyl carbazole hydrochloride of the 2- and bromophenyl boric acid molar ratio are 1: 1；
The cesium carbonate and bromophenyl boric acid molar ratio is 1: 2.2-3；
The palladium acetate and bromophenyl boric acid molar ratio is 0.001-0.01:1；
Bis- [(2- methoxyphenyl) phenyl phosphino-] ethane of described organophosphorus ligand (R, the R) -1,2- and palladium acetate mole
Than being 2: 1.
The present invention uses 3- amino-N- phenyl carbazole for starting material, through bromination, Suzuki coupling reaction and Buchwald
Coupling reaction has synthesized 5,11- dihydro -5- Phenylindole simultaneously [3,2-b] carbazole.The present invention uses hydrobromic acid method for oxidation bromination,
Double bromine contents are effectively controlled, the waste in bromine source is avoided, this method effectively controls the generation of the bromo- 3- amino-N- phenyl carbazole of 4-,
It is set to synthesize the generation for avoiding impurity 5,12- dihydro -5- phenyl-indole simultaneously [3,2-a] carbazole in subsequent products；The present invention makes
Organophosphorus ligand (R, R) -1,2- bis- [(2- methoxyphenyls) is used with the bromo- 3- amino-N- phenyl carbazole of 2- and bromophenyl boric acid
Phenyl phosphino-] Suzuki coupling reaction is realized under palladium acetate catalytic action for ethane and Buchwald coupling reaction one kettle way closes
At 5,11- dihydro -5- Phenylindole simultaneously [3,2-b] carbazole, high income, up to 76% or more, easily separated, by-product is few, purity
Height, up to 99% or more, operating process is simple, is suitably applied industrialized production.
Specific embodiment
For preferably the present invention will be described, an example is as follows: raw materials used is commercially available product.
Example 1
103.3 g(0.4 mol) 3- amino-N- phenyl carbazole is dissolved in 400 mL acetonitriles in 2 L there-necked flasks, is added
Enter 68.7 g(0.34 mol) 40% hydrobromic acid aqueous solution of mass percent, it is slowly added dropwise 44.9 at -20 DEG C of reaction temperature of control
ML(0.44 mol) 30% hydrogen peroxide, natural temperature reaction is stayed overnight after being added dropwise completely, and reaction solution aqueous solution of sodium bisulfite is washed
It washs, separates organic layer, hydrochloric acid is added and obtains the bromo- 3- amino-N- phenyl carbazole hydrochloride of 2-, 137.5 g after drying；It is protected in argon gas
Under shield, by the bromo- 3- amino-N- phenyl carbazole hydrochloride of 137.5 g (0.36 mol) 2-, 72.3 g bromophenyl boric acid, 53.1
G cesium carbonate, 300 mLN- methyl pyrrolidone solvents are added in 2 L there-necked flasks, then 0.08 g vinegar is added in displaced air system
Sour palladium and bis- [(2- methoxyphenyl) phenyl phosphino-] ethane of 0.33 g (R, R) -1,2-, back flow reaction, liquid chromatograph inspection
Survey, after plus 500 mL ice water terminate reaction, 500 mL methylene chloride extraction, organic layer sodium hydrate aqueous solution is washed, anhydrous
Sodium sulphate is dried overnight, and is concentrated to give crude product, 500 mL1, and -350 mL alcohol mixed solvent of 2- Bromofume recrystallization obtains twice
Product 5,11- dihydro -5- Phenylindole simultaneously 101.7 g of [3,2-b] carbazole, content 99.5%, total recovery 76.5%.
1H NMR ( 400 MHz, DMSO-d6), δ/ppm:11.209(s, 1H; N-H), 8.349(d, 1H; J
=7.48Hz; ArH), 8.279(s, 1H; ArH), 8.155 (d, 1H;J=7.56Hz; ArH), 8.077(s,
1H; ArH), 7.728-7.489(m, 6H; ArH), 7.439-7.381(m, 3H; ArH), 7.269(t, 1H;J=
7.12Hz; ArH), 7.099(t, 1H;J=7.2Hz; ArH).
13C NMR (100 MHz, DMSO-d6), δ/ppm: 141.2, 141.1, 137.7, 135.8, 135.6,
130.2, 127.3, 126.8, 126.1, 125.7, 123.0, 122.8, 122.6, 122.4, 120.5, 120.4,
119.2, 117.9, 110.6, 109.1, 100.9, 99.4。
Example 2
258.3 g(1.0 mol) 3- amino-N- phenyl carbazole is dissolved in 2000 mL acetonitriles in 5 L there-necked flasks,
182.0 g(0.9 mol are added) it 40% hydrobromic acid aqueous solution of mass percent, is slowly added dropwise at -20 DEG C of reaction temperature of control
102.0 mL(1.0 mol) 30% hydrogen peroxide, natural temperature reaction is stayed overnight after being added dropwise completely, and reaction solution sodium hydrogensulfite is water-soluble
Liquid washing, separates organic layer, and hydrochloric acid is added and obtains the bromo- 3- amino-N- phenyl carbazole hydrochloride of 2-, 331.4 g after drying；In argon
Under gas shielded, by the bromo- 3- amino-N- phenyl carbazole hydrochloride of 331.4 g(0.88 mol) 2-, 174.7 g bromophenyl boric acid,
113.1 g cesium carbonates, 2000 mLN- methyl pyrrolidone solvents are added in 5 L there-necked flasks, then displaced air system is added
1.0 g palladium acetates and bis- [(2- methoxyphenyl) phenyl phosphino-] ethane of 4.0 g (R, R) -1,2-, back flow reaction, liquid chromatogram
Instrument detection, after plus 2000 mL ice water terminate reaction, 2000 mL methylene chloride extraction, organic layer sodium hydrate aqueous solution
It washes, anhydrous sodium sulfate is dried overnight, and is concentrated to give crude product, 2000 mL1,2- Bromofume -1400mL alcohol mixed solvent recrystallization
Obtain product 5 twice, 11- dihydro -5- Phenylindole simultaneously 267.8 g of [3,2-b] carbazole, content 99.3%, total recovery 80%.
Example 3
258.3 g(1.0 mol) 3- amino-N- phenyl carbazole is dissolved in 2000 mL acetonitriles in 5 L there-necked flasks,
192.1 g(0.95 mol are added) it 40% hydrobromic acid aqueous solution of mass percent, is slowly added dropwise at 0 DEG C of reaction temperature of control
112.3 mL(1.1 mol) 30% hydrogen peroxide, natural temperature reaction is stayed overnight after being added dropwise completely, and reaction solution sodium hydrogensulfite is water-soluble
Liquid washing, separates organic layer, and hydrochloric acid is added and obtains the bromo- 3- amino-N- phenyl carbazole hydrochloride of 2-, 302.6 g after drying；In argon
Under gas shielded, by the bromo- 3- amino-N- phenyl carbazole hydrochloride of 302.6 g(0.81 mol) 2-, 162.7 g bromophenyl boric acid,
87.7 g cesium carbonates, 2000 mL N-Methyl pyrrolidone solvents are added in 5 L there-necked flasks, are added 1.8 after displaced air system
G palladium acetate and bis- [(2- methoxyphenyl) phenyl phosphino-] ethane of 7.4 g (R, R) -1,2-, back flow reaction, liquid chromatograph inspection
Survey, after plus 2000 mL ice water terminate reaction, the extraction of 2000 mL methylene chloride, organic layer sodium hydrate aqueous solution washes, nothing
Aqueous sodium persulfate is dried overnight, and is concentrated to give crude product, 2000 mL1, and 2- Bromofume -1400mL alcohol mixed solvent recrystallizes twice
Obtain product 5,11- dihydro -5- Phenylindole simultaneously 261.0 g of [3,2-b] carbazole, content 99.2%, total recovery 78.1%.
Simultaneously [3,2-b] carbazole content reaches 99.0% or more to above-described 5,11- dihydro -5- Phenylindole, is important
Fine-chemical intermediate has expanded application of the carbazole analog derivative as intermediate in organic photoelectrical material design synthesis,
The fields such as medicine and pesticide are also with a wide range of applications.
Claims (6)
1. one kind 5, the production method of 11- dihydro -5- Phenylindole simultaneously [3,2-b] carbazole, which is characterized in that as follows
Synthesis: 3- amino-N- phenyl carbazole is dissolved in acetonitrile, hydrobromic acid is added, hydrogen peroxide is slowly added dropwise in control reaction temperature, drop
It adds complete rear natural temperature reaction to stay overnight, reaction solution is washed through aqueous solution of sodium bisulfite, separates organic layer, and hydrochloric acid is added, obtains
Solid, it is dry, obtain the bromo- 3- amino-N- phenyl carbazole hydrochloride of 2-；Under argon gas protection, by the bromo- 3- amino-N- phenyl click of 2-
Triazole hydrochloride, bromophenyl boric acid, cesium carbonate, N-Methyl pyrrolidone solvent are added to reaction system, after replacing system air, add
Enter catalyst acetic acid palladium and bis- [(2- methoxyphenyl) phenyl phosphino-] ethane of (R, R) -1,2-, back flow reaction, after reaction
Add water to terminate reaction, is extracted, separate organic layer, be dried overnight, be concentrated to give crude product, 1,2- Bromofume-alcohol mixed solvent
It is recrystallized to give product 5,11- dihydro -5- Phenylindole simultaneously [3,2-b] carbazole.
2. the production method of 5,11- dihydro -5- Phenylindole as described in claim 1 simultaneously [3,2-b] carbazole, feature exist
In the 3- amino-N- phenyl carbazole and hydrobromic acid molar ratio are 1: 0.85-0.95,3- amino-N- phenyl carbazole and dioxygen
Water molar ratio is 1: 0.9-1.1；- 20-0 DEG C of bromination reaction temperature.
3. the production method of 5,11- dihydro -5- Phenylindole as described in claim 1 simultaneously [3,2-b] carbazole, feature exist
In the bromo- 3- amino-N- phenyl carbazole hydrochloride of 2- and bromophenyl boric acid molar ratio are 1: 1.
4. the production method of 5,11- dihydro -5- Phenylindole as described in claim 1 simultaneously [3,2-b] carbazole, feature exist
In the cesium carbonate and bromophenyl boric acid molar ratio are 1: 2.2-3.
5. the production method of 5,11- dihydro -5- Phenylindole as described in claim 1 simultaneously [3,2-b] carbazole, feature exist
In the palladium acetate and bromophenyl boric acid molar ratio are 0.001-0.01:1.
6. the production method of 5,11- dihydro -5- Phenylindole as described in claim 1 simultaneously [3,2-b] carbazole, feature exist
In bis- [(2- methoxyphenyl) phenyl phosphino-] ethane of (R, R) -1,2- and palladium acetate molar ratio are 2: 1.
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