CN117865879A - Synthesis of N-aminoaryl carbazole derivatives from aryl diamines and application thereof - Google Patents
Synthesis of N-aminoaryl carbazole derivatives from aryl diamines and application thereof Download PDFInfo
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- -1 aryl diamines Chemical class 0.000 title claims abstract description 38
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 title claims description 5
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 8
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000007810 chemical reaction solvent Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 4
- 238000004440 column chromatography Methods 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- YFOOEYJGMMJJLS-UHFFFAOYSA-N 1,8-diaminonaphthalene Chemical compound C1=CC(N)=C2C(N)=CC=CC2=C1 YFOOEYJGMMJJLS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000012955 diaryliodonium Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims 3
- ZAPYLSLVQJQGEY-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalen-2-amine Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3N)=CC=CC2=C1 ZAPYLSLVQJQGEY-UHFFFAOYSA-N 0.000 claims 1
- RONZMCPXGUADIF-UHFFFAOYSA-N 2-(3-aminophenoxy)aniline Chemical compound NC1=CC=CC(OC=2C(=CC=CC=2)N)=C1 RONZMCPXGUADIF-UHFFFAOYSA-N 0.000 claims 1
- XSZYBMMYQCYIPC-UHFFFAOYSA-N 4,5-dimethyl-1,2-phenylenediamine Chemical compound CC1=CC(N)=C(N)C=C1C XSZYBMMYQCYIPC-UHFFFAOYSA-N 0.000 claims 1
- 150000001716 carbazoles Chemical class 0.000 claims 1
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 125000004433 nitrogen atom Chemical group N* 0.000 claims 1
- 125000001424 substituent group Chemical group 0.000 claims 1
- 238000001308 synthesis method Methods 0.000 abstract description 14
- 238000006254 arylation reaction Methods 0.000 abstract description 3
- 238000013459 approach Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 125000003277 amino group Chemical group 0.000 abstract 1
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000005481 NMR spectroscopy Methods 0.000 description 31
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 238000004896 high resolution mass spectrometry Methods 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 238000001228 spectrum Methods 0.000 description 12
- UZVGSSNIUNSOFA-UHFFFAOYSA-N dibenzofuran-1-carboxylic acid Chemical compound O1C2=CC=CC=C2C2=C1C=CC=C2C(=O)O UZVGSSNIUNSOFA-UHFFFAOYSA-N 0.000 description 10
- 239000000654 additive Substances 0.000 description 9
- 230000000996 additive effect Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 9
- CUAPXNXBWGCQBG-UHFFFAOYSA-N 2-carbazol-9-ylaniline Chemical compound NC1=CC=CC=C1N1C2=CC=CC=C2C2=CC=CC=C21 CUAPXNXBWGCQBG-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- CNPURSDMOWDNOQ-UHFFFAOYSA-N 4-methoxy-7h-pyrrolo[2,3-d]pyrimidin-2-amine Chemical compound COC1=NC(N)=NC2=C1C=CN2 CNPURSDMOWDNOQ-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 4
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000006193 diazotization reaction Methods 0.000 description 4
- 238000007363 ring formation reaction Methods 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalene Chemical group C1=CC=C2C(C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- MYKQKWIPLZEVOW-UHFFFAOYSA-N 11h-benzo[a]carbazole Chemical compound C1=CC2=CC=CC=C2C2=C1C1=CC=CC=C1N2 MYKQKWIPLZEVOW-UHFFFAOYSA-N 0.000 description 2
- BBOJZBYSEFRINK-UHFFFAOYSA-N 2-(2,7-dichlorocarbazol-9-yl)aniline Chemical compound NC1=CC=CC=C1N1C2=CC(Cl)=CC=C2C2=CC=C(Cl)C=C21 BBOJZBYSEFRINK-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 235000019439 ethyl acetate Nutrition 0.000 description 2
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
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- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 125000003003 spiro group Chemical group 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 150000001538 azepines Chemical class 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- WCZVZNOTHYJIEI-UHFFFAOYSA-N cinnoline Chemical compound N1=NC=CC2=CC=CC=C21 WCZVZNOTHYJIEI-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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- Indole Compounds (AREA)
Abstract
The invention relates to an N-aminoaryl carbazole compound constructed by double N-arylation reaction of copper-catalyzed aryl diamine and cyclic diaryl iodonium salt, wherein the residual amino group can further undergo intramolecular cyclization reaction to obtain fused ring carbazole and spiro carbazole derivatives, belonging to the field of organic chemical synthesis, and being a method with simple operation and excellent yield. The invention provides a more economic and simple synthesis method for constructing the N-aminoaryl carbazole with good yield, high selectivity and narrow half-peak width, and simultaneously adds a modularized approach for assembling 5/7-membered fused carbazole on an N site. The method and the application have the advantages of simple steps, excellent yield, easy separation of products and the like, and are expected to realize industrialized mass production.
Description
Technical Field
The invention belongs to the field of organic chemical synthesis, and relates to a method for synthesizing N-aminoaryl carbazole by N-arylation reaction of copper-catalyzed aryl diamine and cyclic diaryl iodonium salt, and a modularized approach for obtaining five-membered ring, seven-membered ring and spiro ring after diazotization/cyclization of N-aminoaryl carbazole.
Background
Wen a And Nachtsheim b See: (a) D.Zhu, Q.Liu, B.Luo, M.Chen, R.Pi, P.Huang and S.Wen, adv.Synth.Catal.,2013,355,2172-2178, (b) S.RiedmUller and B.J.Nachtsheim,Beilstein J.Org.Chem.,2013,9,1202–1209][4+1 ] of catalyzing aniline and cyclic diaryliodonium salts by using Cu and Pd, respectively, is reported]Cyclic double C-N coupling, wherein the reaction of ortho-substituted anilines is not yet documented. Aryl diamine as bidentate ligand with two coordination atoms, N-aminoaryl can be used as a potential C-N axial chiral diaryl to give five membered cyclic carbazole by diazotisation/cyclisation [ see: Y.Hiraga, R.Kuwahara and T.Hatta, tetrahedron,2021,94,132317]. Six-membered and seven-membered ring fusions have been rarely reported heretofore. In this respect, dong a And Zeng b See: s. -S.Li, Y. -Q.Xia, F. -Z.Hu, C. -F.Liu, F.Su and L.Dong, chem. -Asian J, 2016,11,3165-3168, Z.Zhang, K.Liu, X.Chen, S. -J.Su, Y.Deng and W.Zeng, RSC adv, 2017,7,30554-30585]The synthesis of five-membered ring fused carbazole and 1, 2-benzocarbazole by Ir (III) and Rh (III), respectively, is reported. Despite these pioneering efforts for pi-augmented carbazole, few general, inexpensive and modular tools for assembling 5/6/7-membered ring fused carbazole at the N-site should be developed. And in the last decade, cyclic diaryliodonium salts have rapidly evolved as a useful diarylating agent. See: X.Peng, A.Rahim, W.Peng, F.Jiang, Z.Gu and S.Wen, chem.Rev.,2023,123,1364-1416]. Recently, li reported the synthesis of benzo [ c ] using cyclic diaryliodonium]Cinnoline [ see: R.Xie, Y.Xiao, Y.Wang, Z. -W.Xu, N.Tian, S.Li and M. -H.Zeng, org.Lett.,2023,14,2415-2419]Tricolo [ b, d, f]Azepines [ see: huang, y. -N.Tian, S.Ren, J.Wang, Y.Xiao, Q.Zhu and S.Li, org.Chem.Front.,2022,9,6259-6264]And triphenylene [ see: L.Huang, R.Xie, C.Wen, Y.Yang, Y.Wang, S.Ren, B.Huang and S.Li, org.Biomol.Chem.,2022,20,3913-3916]. Thus, it is necessary and significant to explore new strategies and develop efficient methods for constructing N-aminoaryl carbazole from cyclic diaryliodonium salts with bidentate diamines by one-pot reaction in chemical grade solvents.
Disclosure of Invention
The invention aims to provide a preparation method for industrially producing N-aminoaryl carbazole derivatives in large scale and diazotization/cyclization application of N-aminoaryl carbazole, which has the advantages of mild reaction conditions, simple process, convenient operation, low cost and small environmental pollution, and provides a more economic and simple synthesis method for constructing N-aminoaryl carbazole with good yield, high selectivity and narrow half-peak width.
The invention has the following thought: the aryl diamine is used as a substrate 1, the cyclic diaryl iodonium salt is used as a substrate 5, a catalyst, an additive and a solvent are added into a reactor, a reaction is started, and after the reaction is finished, the product 6-9 can be obtained through column chromatography or recrystallization.
The reaction chemistry equation:
wherein:
(1) The molar feed ratio of the aryl diamine to the cyclic diaryl iodonium salt in the reaction system is 1:1.
(2) The catalyst is preferably CuBr.
(3) The metal catalyst may be used in an amount of 10 to 20mol% equivalent (relative to the aryl diamine), preferably 10mol%.
(4) The reaction additive base and the ligand can be Na 2 CO 3 、NEt 3 2,2' -bipyridine, cs 2 CO 3 、K 3 PO 4 The method comprises the steps of carrying out a first treatment on the surface of the Preferably NEt 3 。
(5) The amount of base used as the reaction additive may be 0.1 to 3 equivalents (relative to the aryl diamine), preferably 2 equivalents.
(6) The reaction temperature may be from 0℃to 200℃and preferably 120 ℃.
(7) The reaction time may be 1 to 48 hours, preferably 20 hours.
(8) The reaction solvent may be isopropanol, acetonitrile, ethylene glycol, N-dimethylformamide, methanol, 1, 4-dioxane, 1, 2-dichloroethane, preferably 1, 2-dichloroethane.
(9) The concentration of the reaction solvent was 0.2M (relative to the aryl diamine)
Compared with the prior art, the invention has the advantages that the novel synthesis method is related to N-arylation reaction of aryl diamine and cyclic diaryl iodonium salt, the operation is simple and convenient, the environment is protected, and a more economic and simple synthesis method is provided for constructing the N-amino aryl carbazole with good yield, high selectivity and narrow half-peak width. The application is also wider, and the N-amino aryl can be used as potential C-N axial chiral diaryl, and five-, six-and seven-membered ring fused carbazole is obtained through diazotization/cyclization. There have been few reports of synthesizing five-membered ring fused carbazole, and despite these pioneering efforts on pi-extended carbazole, there are few general, inexpensive and modular tools for assembling 5/6/7-membered ring fused carbazole at the N-site, and thus our development and application have been innovated.
Drawings
FIG. 1 is a synthetic reaction scheme for the preparation of N-aminoaryl carbazole in accordance with the present invention.
FIG. 2 is a diazotization/cyclization application of N-aminoaryl carbazole according to the invention.
FIG. 3 shows the nuclear magnetic resonance hydrogen spectrum of 2- (9H-carbazol-9-yl) aniline (6 a) as a product of the present invention.
FIG. 4 is a fluorescence emission spectrum of the present invention for products 6a-d, 7a-b, 8a-b and 9.
FIG. 5 is a fluorescence excitation spectrum and an emission spectrum of the product 10.11.12 according to the present invention
Detailed Description
Example 1: synthesis method 1 of 2- (9H-carbazol-9-yl) aniline (6 a): o-phenylenediamine (0.2 mmol, 21.6 mg), 5H-5λ, was weighed out 3 Dibenzo [ b, d ]]Iodine-5-yl triflate (0.25 mmol, mg) at a feed ratio of 1:1.25, cu (OAc) 2 ·H 2 O (8 mg, 20mol% relative to the amount of O-phenylenediamine) was used as a catalyst, na 2 CO 3 (61.8 mg, 3 equivalents to the amount of o-phenylenediamine) as a base, N-dimethylformamide (1 ml) was added as a reaction solvent, and the reaction was carried out under a nitrogen atmosphere at 120℃for 24 hours. Removing solvent after reaction, separating and purifying by column chromatography to obtain white solid, and dryingThe pure product 2- (9H-carbazole-9-yl) aniline (6 a) is obtained with the yield of 90 percent. Nuclear magnetic resonance hydrogen spectrum: (deuterated chloroform as solvent, BRUER Assnd-500 type nuclear magnetic resonance apparatus) 1 HNMR (500 mhz, cdcl 3): δ=8.16 (d, j=7.5 hz, 2H), 7.42 (t, j=7.5 hz, 2H), 7.35-7.26 (m, 4H), 7.19 (d, j=8.0 hz, 2H), 6.97 (d, j=8.0 hz, 1H), 6.92 (t, j=7.5 hz, 1H), 3.55 (s, 2H) ppm. High resolution mass spectrometry (ESI) ([ M+H)] + )C 18 H 15 N 2 Calculated 259.1230, found 259.1229.
Example 2: the synthesis method of 2- (2, 7-dichloro-9H-carbazole-9-yl) aniline (6 b) comprises the following steps: the procedure is as in example 1, with the substrate 5H-5 lambda 3 Dibenzo [ b, d ]]Substitution of iodo-5-yl triflate with 3, 7-dichloro-5H-5λ 3 Dibenzo [ b, d ]]Iodine-5-yl trifluoro methane sulfonate with 88% yield. Nuclear magnetic resonance hydrogen spectrum: (deuterated chloroform as solvent, BRUER Assnd-400 nuclear magnetic resonance spectrometer) 1 H NMR (500 mhz, cdcl 3): δ=7.98 (d, j=7.0 hz, 2H), 7.34 (t, j=7.8 hz, 1H), 7.25-7.24 (m, 2H), 7.19 (d, j=8.0 hz, 1H), 7.13 (s, 2H), 6.96 (d, j=8 hz, 1H), 6.91 (t, j= 7.5,1H), 3.55 (s, 2H) ppm. High resolution mass spectrometry (ESI) ([ M+H)] + )C 18 H 13 N 2 Cl 2 Calculated 327.0450, found 327.0453.
Example 3: the synthesis method of 2- (2-methyl-7- (trifluoromethyl) -9H-carbazole-9-yl) aniline (6 c) comprises the following steps: the procedure is as in example 1, with the substrate 5H-5 lambda 3 Dibenzo [ b, d ]]Substitution of iodo-5-yl triflate with 3-methyl-7- (trifluoromethyl) -5H-5 lambda 3 Dibenzo [ b, d ]]Iodine-5-yl trifluoro mesylate with 54% yield. (deuterated chloroform as solvent, BRUKER Assnd 500 type nuclear magnetic resonance apparatus) 1 H NMR(500MHz,CDCl3):δ＝8.16(d,J＝8.0Hz,1H),8.05(d,J＝8.0Hz,1H),7.50(d,J＝8.0Hz,1H),7.38–7.35(m,2H),7.23(d,J＝8.0Hz,1H),7.16(d,J＝8.0Hz,1H),7.00–6.98 (m, 2H), 6.94 (t, j=7.5 hz, 1H), 3.53 (s, 2H), 2.49 (s, 3H) ppm. High resolution mass spectrometry (ESI) ([ M+H)] + )C 20 H 16 F 3 N 2 Calculated 341.1260, found 341.1270.
Example 4: the synthesis method of 2- (9H-carbazole-9-yl) -4, 5-dimethylaniline (6 d) comprises the following steps: the procedure is as in example 1, substituting 4, 5-dimethyl-phenyl-1, 2-diamine for the substrate o-phenylenediamine in 35% yield. Nuclear magnetic resonance hydrogen spectrum: (deuterated chloroform as solvent, BRUER Assnd-500 type nuclear magnetic resonance apparatus) 1 H NMR (500 mhz, cdcl 3): δ=8.14 (d, j=7.5 hz, 2H), 7.40 (t, j=7.8 hz, 2H), 7.28-7.26 (m, 2H), 7.19 (d, j=8.0 hz, 2H), 7.02 (s, 1H), 6.81 (s, 1H), 2.99 (br s, 2H), 2.31 (s, 3H), 2.21 (s, 3H) ppm. High resolution mass spectrometry (ESI) ([ M+H)] + )C 20 H 19 N 2 Calculated 287.1543, found 287.1542.
Example 5: synthesis method 2 of 8- (9H-carbazol-9-yl) naphthalen-1-amine (7 a): 1, 8-diaminonaphthalene (0.2 mmol, 31.6 mg), 5H-5λ, was weighed out 3 Dibenzo [ b, d ]]Iodine-5-yl triflate (0.25 mmol, 107 mg) at a feed ratio of 1:1.25, cu (OAc) 2 ·H 2 O (8 mg, 20mol% relative to the amount of O-phenylenediamine) was used as a catalyst, na 2 CO 3 (42.4 mg, 2 equivalents to the amount of o-phenylenediamine) as a base, N-dimethylformamide (1 ml) was added as a reaction solvent, and the reaction was carried out in an air atmosphere at 120℃for 24 hours. After the reaction is finished, the solvent is removed, and the white solid is obtained through column chromatography separation and purification, and is dried to obtain the pure product 8- (9H-carbazole-9-yl) naphthalene-1-amine (7 a), and the yield is 96%. Nuclear magnetic resonance hydrogen spectrum: (deuterated chloroform as solvent, BRUER Assnd-500 type nuclear magnetic resonance apparatus) 1 H NMR(500MHz,CDCl3):δ＝8.19(d,J＝8.0Hz,2H),7.98(d,J＝8.5Hz,1H),7.52(t,J＝7.8Hz,1H),7.44–7.31(m,6H),7.25(d,J＝8.5hz, 1H), 7.07 (d, j=8.5 hz, 2H), 6.60 (d, j=7.5 hz, 1H), 3.60 (s, 2H) ppm. High resolution mass spectrometry (ESI) ([ M+H)] + )C 22 H 17 N 2 Calculated 309.1386, found 309.1388.
Example 6: the synthesis method of 8- (2-methoxy-9H-carbazole-9-yl) naphthalene-1-amine (7 b) comprises the following steps: the procedure is as in example 2, with the substrate 5H-5 lambda 3 Dibenzo [ b, d ]]Substitution of iodo-5-yl triflate with 3-methoxy-5H-5λ 3 Dibenzo [ b, d ]]Iodine-5-yl trifluoro methane sulfonate with 65% yield. Nuclear magnetic resonance hydrogen spectrum: (deuterated chloroform as solvent, BRUER Assnd-500 type nuclear magnetic resonance apparatus) 1 H NMR (500 mhz, cdcl 3): δ=8.08-8.06 (m, 1H), 8.03 (d, j=8.5 hz, 1H), 7.97 (d, j=8.5 hz, 1H), 7.52 (t, j=7.5 hz, 1H), 7.42 (d, j=8.0 hz, 1H), 7.34 (t, j=7.8 hz, 1H), 7.29-7.28 (m, 2H), 7.24 (d, j=7.0 hz, 1H), 6.97 (d, j=6.5 hz, 1H), 6.92 (d, j=9.0 hz, 1H), 6.60 (d, j=7.5 hz, 1H), 6.51 (s, 1H), 3.74 (s, 3H), 3.49 (s, 2H) ppm. High resolution mass spectrometry (ESI) ([ M+H)] + )C 23 H 19 N 2 O calculated 339.1492, found 339.1499.
Example 7:2'- (9H-carbazol-9-yl) - [1,1' -binaphthyl ]]-synthesis of 2-amine (8 a): the procedure is as in example 1, substituting o-phenylenediamine with (R) - (+) -1,1' -bi-2-naphthylamine in 48% yield. Nuclear magnetic resonance hydrogen spectrum: (deuterated chloroform as solvent, BRUER Assnd-500 type nuclear magnetic resonance apparatus) 1 HNMR (500 mhz, cdcl 3): δ=8.17 (d, j=9.0 hz, 1H), 8.09 (d, j=8.0 hz, 1H), 7.92 (d, j=8.0 hz, 1H), 7.85 (d, j=7.5 hz, 1H), 7.69 (d, j=7.5 hz, 1H), 7.64 (t, j=7.5 hz, 1H), 7.58 (d, j=7.5 hz, 1H), 7.47-7.43 (m, 2H), 7.40 (d, j=8.5 hz, 1H), 7.35 (d, j=8.0 hz, 1H), 7.24 (d, j=8.0 hz, 1H), 7.18-7.12 (m, 2H), 7.08 (d, j=7.5 hz, 1H), 7.04-6.96 (m, 4H), 6.71 (d, 9.0hz, 1H), 3 ppm (2H). High resolution mass spectrometry (ESI) ([ M+H)] + )C 32 H 23 N 2 Calculated 435.1856, found 435.1864.
Example 8:2'- (2, 7-di-tert-butyl-9H-carbazol-9-yl) - [1,1' -binaphthyl ]]-synthesis of 2-amine (8 b): the procedure is as in example 1, substituting o-phenylenediamine with (R) - (+) -1,1' -bi-2-naphthylamine, and converting the substrate 5H-5 lambda 3 Dibenzo [ b, d ]]Substitution of iodo-5-yl triflate with 3- (tert-butyl) -7-isopropyl-5H-5 lambda 3 Dibenzo [ b, d ]]Iodine-5-yl trifluoro methane sulfonate with the yield of 52 percent. Nuclear magnetic resonance hydrogen spectrum: (deuterated chloroform as solvent, BRUER Assnd-500 type nuclear magnetic resonance apparatus) 1 HNMR (500 mhz, cdcl 3): δ=8.17 (d, j=8.5 hz, 1H), 8.11 (d, j=8.5 hz, 1H), 7.78 (d, j=8.0 hz, 1H), 7.69 (d, j=8.0 hz, 1H), 7.65-7.62 (m, 2H), 7.54 (d, j=8.5 hz, 1H), 7.48-7.42 (m, 3H), 7.24 (s, 1H), 7.20 (d, j=8.5 hz, 1H), 7.17 (d, j=8.5 hz, 1H), 7.10 (d, j=8.5 hz, 1H), 7.03 (s, 1H), 6.98 (t, j=7.93 (t, j=7.5 hz, 1H), 6.75 (d, j=8.5 hz, 1H), 3.48-7.42 (s, 1H), 7.20 (d, j=8.5 hz, 1H), 7.32 (s, 1H), 32 ppm (s, 32H). High resolution mass spectrometry (ESI) ([ M+H)] + )C 40 H 39 N 2 Calculated 547.3108, found 547.3118.
Example 9: the synthesis method of the 2- (2- (9H-carbazole-9-yl) phenoxy) aniline (9) comprises the following steps: the procedure is as in example 1, substituting o-phenylenediamine with (R) - (+) -1,1' -bi-2-naphthylamine in 32% yield. Nuclear magnetic resonance hydrogen spectrum: (deuterated chloroform as solvent, BRUER Assnd-500 type nuclear magnetic resonance apparatus) 1 HNMR (500 mhz, cdcl 3) delta=8.12 (d, j=8.0 hz, 2H), 7.57 (d, j=7.5 hz, 1H), 7.46-7.39 (M, 3H), 7.30-7.25 (M, 5H), 7.13 (d, j=8.0 hz, 1H), 6.82-6.76 (M, 2H), 6.59-6.54 (M, 2H), 3.36 (s, 2H) ppm high resolution mass spectrometry (ESI) ([ m+h)] + )C 18 H 13 F 2 N 2 Calculated 351.1492, found 351.1490.
Example 10: indole [3,21-jk ]]The synthesis method of carbazole (10) comprises the following steps: method of implementation to 0 ℃ to 9- (2-amino phenyl) -9H-carbazole 6a in acetic acid and sulfuric acid mixture solution dropwise NaNO 2 Is a solution of (a) and (b). After 10 minutes, the mixture was heated to 130 ℃ for 30 minutes. The reaction mixture was cooled to room temperature and poured into water, extracted, distilled under reduced pressure to give crude product, which was purified on a silica gel (200-300 mesh) column and eluted with petroleum ether/EtOAc (100/1, v/v) to give product 10 as a white solid in 60% yield. Nuclear magnetic resonance hydrogen spectrum: (deuterated chloroform as solvent, BRUER Assnd-500 type nuclear magnetic resonance apparatus) 1 HNMR (500 mhz, cdcl 3): δ=8.15 (d, j=8.0 hz, 2H), 8.06 (d, j=7.5 hz, 2H), 7.92 (d, j=8.0 hz, 2H), 7.61-7.55 (m, 3H), 7.37 (t, j=7.8 hz, 2H) ppm. High resolution mass spectrometry (ESI) ([ M+H)] + )C 18 H 11 Calculated N242.0960, found 242.0961.
Example 11: naphtho [2',1':4,5;1',2':6,7]Azaplam [3,21-jk ]]The synthesis method of carbazole (11) comprises the following steps: method of the embodiment 2'- (9H-carbazol-9-yl) - [1,1' -binaphthyl ]]Dropwise adding NaNO into solution of-2-amine in acetic acid 2 The temperature of the mixture was maintained at 0 c and stirred for 10 minutes. Urea was added and the tube was then heated to 40 ℃ for 30 minutes. After cooling to room temperature, extraction, distillation under reduced pressure, purification of the crude product on a column of silica gel (200-300 mesh) and elution with petroleum ether/EtOAc afforded the product as a white solid in 40% yield. Nuclear magnetic resonance hydrogen spectrum: (deuterated chloroform as solvent, BRUER Assend-500 Nuclear magnetic resonance spectrometer): 1 H NMR(500MHz,CDCl 3 ) δ=8.01 (d, j=7.5 hz, 1H), 7.97 (d, j=8.5 hz, 1H), 7.91 (t, j=8.5 hz, 2H), 7.87-7.31 (m, 2H), 7.78 (d, j=8.0 hz, 1H), 7.74 (d, j=9.0 hz, 1H), 7.64 (d, j=9.0 hz, 2H), 7.51 (t, j=7.8 hz, 1H), 7.46 (t, j=7.5 hz, 1H), 7.42-7.31 (m, 4H), 7.25-7.23 (m, 1H), 7.12 (t, j=7.8 hz, 1H), 6.97 (d, j=9.0 hz, 1H) ppm. High resolution mass spectrometry (ESI) ([ M+H)] + )C 32 H 20 Calculated N418.1590, found 418.1589.
Example 12: spiro [ carbazole-9, 7' -dibenzo [ c, g ]]Carbazole derivative]-9-onium (12) synthesis method: the procedure is as in example 11, with products 11 and 12 being obtained in one-pot reaction in a yield of 56%. Nuclear magnetic resonance hydrogen spectrum: (deuterated chloroform as solvent, BRUER Assend-500 Nuclear magnetic resonance spectrometer): 1 H NMR(500MHz,CDCl 3 ) δ=9.04 (d, j=8.5 hz,2 h), 8.49 (d, j=7.5 hz,2 h), 8.12 (q, j=8.2 hz,4 h), 7.96 (t, j=7.8 hz,2 h), 7.85 (q, j=8.5 hz,4 h), 7.46 (t, j=7.8 hz,2 h), 7.08 (d, j=9.5 hz,2 h), 6.89 (d, j=8.5 hz,2 h) ppm. High resolution mass spectrometry (ESI) ([ M+H)] + )C 32 H 21 N + Calculated 418.1590, found 418.1589.
Example 10: the procedure was as in example 1, except that the additive was changed from CuBr to CuOAc, with a yield of 48%.
Example 11: the procedure was as in example 1, except that the additive was changed from CuBr to CuI, with a yield of 53%.
Example 12: the procedure is as in example 1, except that the additive is changed from CuBr to CuBr 2 The yield thereof was found to be 74%.
Example 13: the procedure was as in example 1, except that the additive was changed from CuBr to CuO, with a yield of 34%. Example 14: the procedure is as in example 1, except that the additive is composed of Net 3 Change to K 2 CO 3 The yield thereof was found to be 58%.
Example 15: the procedure is as in example 1, except that the additive is composed of Net 3 Change into Na 2 CO 3 The yield thereof was found to be 67%.
Example 16: the procedure is as in example 1, except that the solvent 1, 2-dichloroethane is replaced by isopropanol with a yield of 60%.
The liquid fluorescence test was performed at room temperature for each of the compounds 6a-12, with a slit width of 2.5/2.5nm. As can be seen from fig. 4,5, the half-widths of 6a-d and 10 are relatively narrow, with half-widths of 25-46nm;9 is also very narrow at 42nm, and exhibits narrow emission properties. As can be seen from FIG. 5, the indole [3,21-jk ] carbazole excitation wavelength is 307nm, and the emission wavelength is 375 nm; naphtho [2',1':4,5;1',2':6,7] aza-flat [3,21-jk ] carbazole excitation wavelength 277nm, emission wavelength 503nm, showing blue greenish luminescence (cyan); as can be seen from FIG. 5, spiro [ carbazole-9, 7' -dibenzo [ c, g ] carbazole ] -9-ium excitation wavelength was 371nm, emission wavelength was 408nm, showing violet luminescence.
The foregoing descriptions of specific exemplary embodiments of the present invention are presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application to thereby enable one skilled in the art to make and utilize the invention in various exemplary embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (3)
1. A method for synthesizing an N-aminoaryl carbazole derivative from an aryl diamine (1-4) and a cyclic diaryliodonium salt (5), characterized by the following chemical reaction formula:wherein, the aryl diamine substrate can be o-phenylenediamine 1a, 4, 5-dimethyl o-phenylenediamine 1b, 1, 8-diaminonaphthalene 2, binaphthyl amine 3, 2' -oxydianiline 4; substituent R of cyclic diaryl iodonium triflate 1 And R is 2 Can be H, methoxy, chloro, tert-butyl, trifluoromethyl, R 1 And R is 2 May be the same or different.
2. A process for the synthesis of N-aminoaryl carbazole from aryl diamines (1-4) and cyclic diaryliodonium salts (5), characterized by the steps of:
aryl diamine 1-4 (0.5 mmol), cyclic diaryl iodonium salt 5 (0.5 mmol), the feed ratio was 1:1, cuprous bromide (7.2 mg, 10mol% relative to the amount of aryl diamine) was used as a catalyst, triethylamine (139 μl, 2 equivalents relative to the amount of aryl diamine) was used as a base, 1, 2-dichloroethane (1 ml) was added as a reaction solvent, and the reaction was carried out in an air atmosphere at 120 ℃ for 20 hours; after the reaction is finished, removing the solvent, separating and purifying by column chromatography to obtain solid, and drying to obtain the pure product N-amino aryl carbazole compound 6-9.
3. The product N-aminoaryl carbazole compound as claimed in claim 2, which is applicable to further intramolecular diazotisation cyclisation reactions to produce carbazole derivatives 10-12 fused at the nitrogen atom; the N-aminoaryl carbazole compounds are furthermore characterized by compounds 6a to 6d and 10, with half-widths of 25 to 46 nm.
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