CN106045899B - A kind of compound 3- nitros -9- xenyls carbazole and its synthetic method - Google Patents
A kind of compound 3- nitros -9- xenyls carbazole and its synthetic method Download PDFInfo
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- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
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Abstract
A kind of 3 nitro of noval chemical compound, 9 xenyl carbazole and its synthetic method, and accurate structural characterization has been done to noval chemical compound；The synthetic method of noval chemical compound of the present invention is as follows：Using 3 nitrocarbazoles as starting material, 3 nitro, 9 xenyl carbazole is made through coupling reaction with 4 halogenated biphenyls, reaction temperature is 70 ~ 180oC, the reaction time was at 12 ~ 48 hours.Reaction process is easy to operate, 80% or more yield.3 nitro, the 9 xenyl carbazole of synthesis can be applied to organic photoelectrical material field, be the important intermediate of potential carbazoles photoelectric material.
Description
Technical field
The invention belongs to field of fine chemical, specially a kind of noval chemical compound 3- nitros -9- xenyls carbazole and its synthesis
Method.
Background technology
Organic electroluminescent LED（OLED）Compared to traditional liquid crystal material, there is ultralight, ultra-thin, brightness height, sound
Answer speed fast, visible angle is big, it is flexible and low in energy consumption the advantages that, be popular in recent years research field.And restrict Organic Electricity
The main problem of electroluminescent material development is service life and the efficiency of luminous organic material, therefore, research synthesis high heat stability
Property, the luminous organic material for being easy to carrier transport is the Main way studied at present.
Carbazole is typical electron rich group, have good cavity transmission ability, the structure derived from carbazole have compared with
Big rigid planar structure and good cavity transmission ability and high luminous power, can significantly improve OLED luminous organic materials
Thermal stability, service life and luminous efficiency, thus have broader market prospects.
The synthetic method of 3- nitro -9- xenyl carbazoles, at present there has been no pertinent literature report, patent of the present invention passes through one
Step coupling method has obtained 3- nitro -9- xenyl carbazoles, and the product of high-quality is obtained by corresponding purification process.
Invention content
The purpose of the present invention is to provide a kind of higher noval chemical compound 3- nitros -9- xenyls carbazole of purity and its synthesis
Method, the synthetic method are easy to operate.
3- nitros -9- xenyls carbazole of the present invention and its technical solution of synthesis are：
Pass through following steps synthesising target compound：By 3- nitrocarbazoles, 4- halogenated biphenyls, metallic catalyst, alkali and match
Body is added in reaction unit, after inert gas replacement, organic solvent is added, is warming up to 70 ~ 180oC, the reaction time 12 ~ 48 is small
When.After reaction through distilling water washing extraction, organic phase drying concentration crystallizes to obtain 3- nitro -9- biphenyl after column chromatography purification
Base carbazole, target compound structural formula are as follows：
The 4- halogenated biphenyls are 4- chlordiphenyls, and 4- bromo biphenyls are any in 4- iodine biphenyl, and dosage is 3- nitro clicks
1 ~ 2 times of azoles mole；The metallic catalyst be Cu (powder), CuCl, CuBr, CuI, (CuOTf) 2,
CuSCN, CuNO3, CuCl2, Cu2O, Cu(OAc)2, Cu(acac)2, CuSO4•5H2O, PdCl2(dppf), Pd
(PPh3) any in 4, Pd (OAc) 2, catalyst amount is the 0.1%-50% of 3- nitrocarbazole moles；The alkali is uncle
Sodium butoxide, potassium tert-butoxide, sodium methoxide, sodium ethoxide, potassium ethoxide, 1,8- diazabicylo, 11 carbon -7- alkene（DBU）, tetrabutylammonium hydrogen
Any in amine-oxides, base amount is 1 ~ 10 times of 3- nitrocarbazole moles；The ligand be 1,10- phenanthrolines, N, N,
N', N'- tetramethylethylenediamine, 1,2- cyclohexanediamine, N, N'- dimethyleyelohexane diamines, 2,2'- bipyridyls, L-PROLINE, N,
N'- dimethylglycines, triphenylphosphine, tricyclohexyl phosphine, dinaphthalene hexichol phosphorus（BINAP）In it is any, ligand dosage be 3- nitre
The 0.5%-50% of base carbazole mole；The organic solvent be acetonitrile, ethyl acetate, dioxane, toluene, dimethylbenzene, two
Chloromethanes, chloroform, 1,2- dichloroethanes, 1,2- dichloro-benzenes, pyridine, n,N-Dimethylformamide（DMF）, N- methylpyrroles
Alkanone, dimethyl sulfoxide (DMSO)（DMSO）In it is any.
3- nitrocarbazoles, 4- halogenated biphenyls, metallic catalyst, alkali and ligand are added in reaction unit, through inert gas
After displacement, organic solvent is added, is warming up to 70 ~ 180oC, 12 ~ 48 hours reaction time.After reaction through distilling water washing extraction
Take, organic phase drying concentration, column chromatography purification after crystallize 3- nitro -9- xenyl carbazoles, target compound structural formula are as follows
It is shown：
The 4- halogenated biphenyls are 4- chlordiphenyls, and 4- bromo biphenyls are any in 4- iodine biphenyl, and dosage is 3- nitro clicks
1 ~ 2 times of azoles mole.
5, according to the synthetic method of the 3- nitro -9- xenyl carbazoles described in claim 3, which is characterized in that the gold
Metal catalyst is Cu (powder), CuCl, CuBr, CuI, (CuOTf) 2, CuSCN, CuNO3, CuCl2, Cu2O, Cu
(OAc) any in 2, Cu (acac) 2, CuSO4 5H2O, PdCl2 (dppf), Pd (PPh3) 4, Pd (OAc) 2, catalysis
Agent dosage is the 0.1%-50% of 3- nitrocarbazole moles.
The alkali is sodium tert-butoxide, potassium tert-butoxide, sodium methoxide, sodium ethoxide, potassium ethoxide, 1,8- diazabicylo 11
Carbon -7- alkene（DBU）, any in tetrabutylammonium hydroxide, base amount is 1 ~ 10 times of 3- nitrocarbazole moles.
The ligand is 1,10- phenanthrolines, N, N, N', N'- tetramethylethylenediamines, 1,2- cyclohexanediamine, N, N'- diformazans
Basic ring hexamethylene diamine, 2,2'- bipyridyls, L-PROLINE, N, N'- dimethylglycines, triphenylphosphine, tricyclohexyl phosphine, dinaphthalene two
Benzene phosphorus（BINAP）In it is any, ligand dosage be 3- nitrocarbazole moles 0.5%-50%.
The organic solvent be acetonitrile, ethyl acetate, dioxane, toluene, dimethylbenzene, dichloromethane, chloroform,
1,2- dichloroethanes, 1,2- dichloro-benzenes, pyridine, n,N-Dimethylformamide（DMF）, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO)
（DMSO）In it is any.
Using 3- nitrocarbazoles and 4- halogenated biphenyls as raw material, the coupling reaction through metal catalytic synthesizes 3- nitro -9- biphenyl
Base carbazole, synthetic route are as follows：
Reaction step is：3- nitrocarbazoles, 4- halogenated biphenyls, metallic catalyst, alkali and ligand are added in reaction bulb, it is lazy
After property gas displacement reaction system, the organic solvent of degasification is added, is warming up to 70 ~ 180oC, the reaction time was at 12 ~ 48 hours.Instead
Organic solvent diluting after answering, after distilling water washing, organic layer drying concentration is crystallized after column chromatography purification, is obtained yellowish
The powdered 3- nitros -9- xenyl carbazoles of color；
The wherein described 4- halogenated biphenyls are 4- chlordiphenyls, 4- bromo biphenyls, and any in 4- iodine biphenyl, dosage is 3- nitre
1 ~ 2 times of base carbazole mole；The metallic catalyst be Cu (powder), CuCl, CuBr, CuI, (CuOTf) 2,
CuSCN, CuNO3, CuCl2, Cu2O, Cu(OAc)2, Cu(acac)2, CuSO4•5H2O, PdCl2(dppf), Pd
(PPh3) any in 4, Pd (OAc) 2, catalyst amount is the 0.1%-50% of 3- nitrocarbazole moles；The alkali is uncle
Sodium butoxide, potassium tert-butoxide, sodium methoxide, sodium ethoxide, potassium ethoxide, 1,8- diazabicylo, 11 carbon -7- alkene（DBU）, tetrabutylammonium hydrogen
Any in amine-oxides, base amount is 1 ~ 10 times of 3- nitrocarbazole moles；The ligand be 1,10- phenanthrolines, N, N,
N', N'- tetramethylethylenediamine, 1,2- cyclohexanediamine, N, N'- dimethyleyelohexane diamines, 2,2'- bipyridyls, L-PROLINE, N,
N'- dimethylglycines, triphenylphosphine, tricyclohexyl phosphine, dinaphthalene hexichol phosphorus（BINAP）In it is any, ligand dosage be 3- nitre
The 0.5%-50% of base carbazole mole；The organic solvent be acetonitrile, ethyl acetate, dioxane, toluene, dimethylbenzene, two
Chloromethanes, chloroform, 1,2- dichloroethanes, 1,2- dichloro-benzenes, pyridine, n,N-Dimethylformamide（DMF）, N- methylpyrroles
Alkanone（NMP）, dimethyl sulfoxide (DMSO)（DMSO）In it is any.
3- nitrocarbazoles are added in 25 milliliters of reaction tubes（0.30 g, 1.41 mmol）, 4- iodine biphenyl（0.59 g,
2.12 mmol）, Cu powder（44.8 mg, 0.71 mmol）, 1,10- phenanthrolines（0.25 g, 1.41 mmol）And potassium tert-butoxide
（0.79 g, 7.05 mmol）, after replacing argon gas, it is added and removes 10 ml of oxygen DMF.Mixture stirs 24 hours at 145 DEG C,
TLC tracking reaction converts completely until raw material.After the completion of reaction, solvent is removed under reduced pressure.Ethyl acetate dissolving, distillation washing is added
After washing, revolving removes solvent after dry organic phase, and it is pure to obtain pale yellow powder shape by column chromatography, recrystallization purification for crude product
Product, yield 81.5%.1H-NMR (CDCl3, 400 MHz): δ= 9.10 (s, 1H), 8.36 (d, 1H, J = 8
Hz), 8.24 (d, 1H, J = 8 Hz,), 7.88 (d, 2H, J = 8 Hz), 7.71 (d, 2H, J = 8 Hz),
7.63 (d, 2H, J = 8 Hz), 7.53 (m, 7H); 13C-NMR (CDCl3, 100 MHz): δ= 143.91,
142.31, 141.59, 141.41, 139.85, 135.37, 129.07, 128.87, 128.00, 127.69,
127.35, 127.19, 123.15, 123.05, 121.84, 121.65, 120.94, 117.30, 110.76,
109.59. TOF-HRMS (m/z), Calcd. for C24H16N2O2 (M) 364.1212, Found 363.1139 [(M-
H)-]。
Using 3- nitrocarbazoles and 4- halogenated biphenyls as raw material, the coupling reaction through metal catalytic synthesizes 3- nitro -9- biphenyl
Base carbazole, synthetic route are as follows：
Specifically reaction step is：Reaction bulb is added in 3- nitrocarbazoles, 4- halogenated biphenyls, metallic catalyst, alkali and ligand
In, after inert gas replacement reaction system, the organic solvent of degasification is added, is warming up to 70 ~ 180oC, reaction time are small 12 ~ 48
When.Organic solvent diluting after reaction, after distilling water washing, organic layer drying concentration is crystallized after column chromatography purification, is obtained
Pale yellow powder shape 3- nitro -9- xenyl carbazoles.
The wherein described 4- halogenated biphenyls are 4- chlordiphenyls, 4- bromo biphenyls, and any in 4- iodine biphenyl, dosage is 3- nitre
1 ~ 2 times of base carbazole mole；The metallic catalyst is Cu (powder), CuCl, CuBr, CuI, (CuOTf)2,
CuSCN, CuNO3, CuCl2, Cu2O, Cu(OAc)2, Cu(acac)2, CuSO4•5H2O, PdCl2(dppf), Pd
(PPh3)4, Pd(OAc)2In it is any, catalyst amount be 3- nitrocarbazole moles 0.1%-50%；The alkali is uncle
Sodium butoxide, potassium tert-butoxide, sodium methoxide, sodium ethoxide, potassium ethoxide, 1,8- diazabicylo, 11 carbon -7- alkene（DBU）, tetrabutylammonium hydrogen
Any in amine-oxides, base amount is 1 ~ 10 times of 3- nitrocarbazole moles；The ligand be 1,10- phenanthrolines, N, N,
N', N'- tetramethylethylenediamine, 1,2- cyclohexanediamine, N, N'- dimethyleyelohexane diamines, 2,2'- bipyridyls, L-PROLINE, N,
N'- dimethylglycines, triphenylphosphine, tricyclohexyl phosphine, dinaphthalene hexichol phosphorus（BINAP）In it is any, ligand dosage be 3- nitre
The 0.5%-50% of base carbazole mole；The organic solvent be acetonitrile, ethyl acetate, dioxane, toluene, dimethylbenzene, two
Chloromethanes, chloroform, 1,2- dichloroethanes, 1,2- dichloro-benzenes, pyridine, n,N-Dimethylformamide（DMF）, N- methylpyrroles
Alkanone（NMP）, dimethyl sulfoxide (DMSO)（DMSO）In it is any.
The present invention realizes one-step synthesis method 3- nitro -9- xenyl carbazoles, through column chromatography purification, recrystallization etc. techniques,
The product of high-purity can be obtained, operation is simple.
Description of the drawings
Fig. 1 is 3- nitro -9- xenyl carbazoles1H-NMR spectrum；
Fig. 2 is 3- nitro -9- xenyl carbazoles13C-NMR spectrograms.
Specific implementation mode
Technical scheme of the present invention is made below by Figure of description and embodiment and further being illustrated.
Example 1
3- nitrocarbazoles are added in 25 milliliters of reaction tubes（0.30 g, 1.41 mmol）, 4- iodine biphenyl（0.59 g,
2.12 mmol）, Cu powder（44.8 mg, 0.71 mmol）, 1,10- phenanthrolines（0.25 g, 1.41 mmol）And potassium tert-butoxide
（0.79 g, 7.05 mmol）, after replacing argon gas, it is added and removes 10 ml of oxygen DMF.Mixture stirs 24 hours at 145 DEG C,
TLC tracking reaction converts completely until raw material.After the completion of reaction, solvent is removed under reduced pressure.Ethyl acetate dissolving, distillation washing is added
After washing, revolving removes solvent after dry organic phase, and it is pure to obtain pale yellow powder shape by column chromatography, recrystallization purification for crude product
Product, yield 81.5%.1H-NMR (CDCl3, 400 MHz): δ= 9.10 (s, 1H), 8.36 (d, 1H, J = 8
Hz), 8.24 (d, 1H, J = 8 Hz,), 7.88 (d, 2H, J = 8 Hz), 7.71 (d, 2H, J = 8 Hz),
7.63 (d, 2H, J = 8 Hz), 7.53 (m, 7H); 13C-NMR (CDCl3, 100 MHz): δ= 143.91,
142.31, 141.59, 141.41, 139.85, 135.37, 129.07, 128.87, 128.00, 127.69,
127.35, 127.19, 123.15, 123.05, 121.84, 121.65, 120.94, 117.30, 110.76,
109.59. TOF-HRMS (m/z), Calcd. for C24H16N2O2 (M) 364.1212, Found 363.1139 [(M-
H)-]。
Example 2
3- nitrocarbazoles are added in 25 milliliters of reaction tubes（1.50 g, 7.07 mmol）, 4- bromo biphenyls（1.98 g,
8.48 mmol）、CuCl（0.21 g, 2.12 mmol）, 1,2- cyclohexanediamine（0.24 g, 2.12 mmol）And sodium tert-butoxide
（1.70 g, 17.68 mmol）, after replacing argon gas, it is added and removes 25 ml of oxygen NMP.It is small that mixture stirs 24 at 140 DEG C
When, TLC tracking is removed under reduced pressure solvent, is dissolved in ethyl acetate after the reaction was complete, distills water washing, is rotated after dry organic phase
Solvent is removed, crude product obtains pale yellow powder shape sterling, yield 86.1% by column chromatography, recrystallization purification.1H-NMR
(CDCl3, 400 MHz): δ= 9.10 (s, 1H), 8.36 (d, 1H, J = 8 Hz), 8.24 (d, 1H, J = 8
Hz,), 7.88 (d, 2H, J = 8 Hz), 7.71 (d, 2H, J = 8 Hz), 7.63 (d, 2H, J = 8 Hz),
7.53 (m, 7H); 13C-NMR (CDCl3, 100 MHz): δ= 143.91, 142.31, 141.59, 141.41,
139.85, 135.37, 129.07, 128.87, 128.00, 127.69, 127.35, 127.19, 123.15,
123.05, 121.84, 121.65, 120.94, 117.30, 110.76, 109.59. TOF-HRMS (m/z),
Calcd. for C24H16N2O2 (M) 364.1212, Found 363.1139 [(M-H)-]。
Example 3
3- nitrocarbazoles are added in 25 milliliters of reaction tubes（0.22 g, 1.04 mmol）, 4- iodine biphenyl（0.31 g,
1.09 mmol）、Pd(PPh3)4（60.1 mg, 0.05 mmol）, sodium tert-butoxide（0.15 g, 1.56 mmol）, replace argon gas
Afterwards, 5 ml of DMF except oxygen are added.Mixture stirs 12 hours at 110 DEG C, and TLC tracking reactions are complete to consumption of raw materials.
After solvent is fallen in vacuum distillation, water washing is distilled, organic phase is dried with anhydrous sodium sulfate, rotates organic phase, and crude product passes through column
Chromatography, recrystallization purification, obtain pale yellow powder shape sterling, yield 89.7%.1H-NMR (CDCl3, 400 MHz): δ=
9.10 (s, 1H), 8.36 (d, 1H, J = 8 Hz), 8.24 (d, 1H, J = 8 Hz,), 7.88 (d, 2H, J
= 8 Hz), 7.71 (d, 2H, J = 8 Hz), 7.63 (d, 2H, J = 8 Hz), 7.53 (m, 7H); 13C-NMR
(CDCl3, 100 MHz): δ= 143.91, 142.31, 141.59, 141.41, 139.85, 135.37, 129.07,
128.87, 128.00, 127.69, 127.35, 127.19, 123.15, 123.05, 121.84, 121.65,
120.94, 117.30, 110.76, 109.59. TOF-HRMS (m/z), Calcd. for C24H16N2O2 (M)
364.1212, Found 363.1139 [(M-H)-]。
Claims (1)
1. a kind of synthetic method of 3- nitros -9- xenyl carbazoles, which is characterized in that be added 0.22 in 25 milliliters of reaction tubes
G, the 3- nitrocarbazoles of 1.04 mmol, 0.31 g, 1.09 mmol 4- iodine biphenyl, 60.1 mg, 0.05mmol Pd
(PPh3)4, after replacing argon gas, 5 ml of DMF except oxygen are added in 0.15 g, 1.56 mmol sodium tert-butoxides；
Mixture stirs 12 hours at 110 DEG C, and TLC tracking reactions are complete to consumption of raw materials；
After solvent is fallen in vacuum distillation, water washing is distilled, organic phase is dried with anhydrous sodium sulfate, rotates organic phase, crude product warp
Column chromatography, recrystallization purification are crossed, pale yellow powder shape sterling, yield 89.7% are obtained.
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| CN101282931A (en) * | 2005-10-07 | 2008-10-08 | 东洋油墨制造株式会社 | Tanaka Hiroaki |
Non-Patent Citations (2)
| Title |
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| One-pot two-step synthesis of N-arylcarbazolebased skeleton;Sheng Tao et al.;《RSC Adv.》;20160413;第6卷;第43250-43260页 * |
| Templateffekte bei neuartigen selbstreplizierenden Molekulen;M. Morgan Conn et al.;《Angew.Chem.》;19941231;第106卷;第1665-1167页 * |
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