CN108610278A - A kind of synthetic method of 6- amino -5- acyl groups benzo [a] carbazole compound - Google Patents

A kind of synthetic method of 6- amino -5- acyl groups benzo [a] carbazole compound Download PDF

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CN108610278A
CN108610278A CN201810733102.2A CN201810733102A CN108610278A CN 108610278 A CN108610278 A CN 108610278A CN 201810733102 A CN201810733102 A CN 201810733102A CN 108610278 A CN108610278 A CN 108610278A
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reaction
amino
acyl groups
synthetic method
carbazole compound
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CN108610278B (en
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范学森
贾瑞雪
陈�光
张新迎
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Henan Normal University
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Henan Normal University
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
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    • C07D209/80—[b, c]- or [b, d]-condensed

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Abstract

The invention discloses a kind of 6 amino, 5 acyl group benzo [a] carbazole compound synthetic method, which passes through Rh using 2 aryl, 3 cyanogen radical indole compounds and sulfur ylide as raw material（III）A series of 6 amino, 5 acyl group benzos of catalysis cascade reaction synthesis [a] carbazole compound, have many advantages, such as easy to operate, mild condition, wide application range of substrates, is suitable for industrialized production.

Description

A kind of synthetic method of 6- amino -5- acyl groups benzo [a] carbazole compound
Technical field
The invention belongs to technical field of organic synthesis, and in particular to a kind of 6- amino -5- acyl groups benzo [a] carbazoles chemical combination The synthetic method of object.
Background technology
Benzo [a] carbazole and its derivative are not only widespread in nature, but also are the dominance structures of new drug research Unit and important compound library source.In addition, realizing luminous, hole in benzo [a] carbazole or many organic luminescent devices The core skeleton of the functions such as transmission, material of main part has important application value in organic functional material exploitation etc..In benzene And the functional groups such as amino and acyl group are introduced on the original structure skeleton of [a] carbazole, it not only may be implemented to benzo [a] carbazoles The bioactivity and other performance for closing object are regulated and controled, and various reactivity worth of amino and acyl group etc. can be utilized further Build increasingly complex organic functional molecular.It is worth noting that, 6- amino -5- acyl groups benzo [a] carbazole compound is Have that synthetic method is not only very limited, and still have raw material be difficult to obtain, severe reaction conditions, complex for operation step, atom The problems such as economy is relatively low, to make its application in actual production be restricted.Therefore, it studies and develops with cheap and easy to get Reagent be raw material, via easy operating procedure and synthesis 6- amino -5- acyl groups benzo [a] click under mild reaction conditions The method of azole compounds not only has important theory significance, but also has certain application value.
Invention content
The technical problem to be solved by the present invention is to provide a kind of conjunctions of 6- amino -5- acyl groups benzo [a] carbazole compound At method, which is catalyzed using 2- aryl -3- cyanogen radical indole compounds and sulfur ylide as raw material by Rh (III) Cascade reaction synthesizes a series of 6- amino -5- acyl groups benzo [a] carbazole compounds, has easy to operate, mild condition, substrate The advantages that applied widely, is suitable for industrialized production.
The present invention adopts the following technical scheme that solve above-mentioned technical problem, a kind of 6- amino -5- acyl groups benzo [a] carbazole The synthetic method of class compound, it is characterised in that：2- aryl -3- cyanogen radical indole compounds 1 are dissolved in solvent, then successively Sulfur ylide 2, catalyst and additive is added, 6- amino -5- acyl groups benzo [a] carbazoles chemical combination is made in 80-120 DEG C of reaction Object 3, the reaction equation in the synthetic method are：
Wherein R1For hydrogen, chlorine, fluorine, C1-4Linear or branched alkyl group or alkoxy, the alkyl in the alkoxy are C1-4Alkyl, R2For hydrogen, trifluoromethyl, fluorine, chlorine, C1-4Linear or branched alkyl group or alkoxy, the alkyl in the alkoxy are C1-4Alkyl, R3For Phenyl or substituted-phenyl, the substituent group on the substituted-phenyl phenyl ring are chlorine, fluorine, trifluoromethyl, C1-6Linear or branched alkyl group or first Oxygroup, solvent are tetrahydrofuran, 1,2- dichloroethanes, dichloromethane, acetonitrile or chlorobenzene, and catalyst is dichloro (pentamethyl ring penta Dialkylene) close rhodium (III) dimer ([RhCp*Cl2]2), additive is the mixing of cesium acetate or silver hexafluoroantimonate and cesium acetate Object.
Further preferably, 2- aryl -3- cyanogen radical indole compounds 1, sulfur ylide 2, catalyst and the additive The ratio between the amount for the substance that feeds intake be 1:1-2:0.025-0.06:0.5-1.
Compared with the prior art, the present invention has the following advantages：(1) raw material is cheap and easy to get or raw material is easy to prepare；(2) Building-up process is simple, efficient, directly by the cascade reaction between 2- aryl -3- cyanogen radical indole compounds and sulfur ylide To 6- amino -5- acyl groups benzo [a] carbazole compound, combined coefficient is high, need to be intermediate to reaction when avoiding multi-step synthesis Body carries out the wasting of resources and environmental pollution caused by isolated or purified processing；(3) reaction condition is mild, easy to operate；(4) bottom Object it is applied widely.Therefore, the present invention provides one kind for the synthesis of 6- amino -5- acyl groups benzo [a] carbazole compound Efficient and practical new method.
Specific implementation mode
The above of the present invention is described in further details by the following examples, but this should not be interpreted as to this The range for inventing above-mentioned theme is only limitted to embodiment below, and all technologies realized based on the above of the present invention belong to this hair Bright range.
Embodiment 1
Sequentially added in 15mL reaction tubes 1a (0.5mmol, 109.1mg), tetrahydrofuran (3mL), 2a (0.75mmol, 147.2mg), dichloro (pentamethylcyclopentadiene base) closes rhodium (III) dimer ([RhCp*Cl2]2, 0.025mmol, 15.4mg) and Cesium acetate (0.25mmol, 48.0mg), will react the seal of tube under air conditions, be subsequently placed in 80 DEG C of oil baths and be stirred to react 12h.After reaction, it waits for that reaction tube is cooled to room temperature, 10mL water is added, (10mL × 3) are then extracted with ethyl acetate, later Organic phase water and saturated salt solution wash successively, anhydrous sodium sulfate drying.Filtering, is spin-dried for, mistake silica gel post separation (petroleum ether/ Ethyl acetate=20/1) obtain yellow solid product 3a (63.9mg, 38%).The characterize data of the compound is as follows：1H NMR (400MHz,CDCl3):δ 6.91 (s, 2H), 7.12 (t, J=7.6Hz, 1H), 7.20-7.31 (m, 3H), 7.39-7.47 (m, 3H), 7.51-7.56 (m, 3H), 7.70 (d, J=8.0Hz, 1H), 8.37 (d, J=8.0Hz, 1H), 8.43 (d, J=8.0Hz, 1H),12.56(s,1H).13C NMR(100MHz,CDCl3):δ105.8,107.0,111.5,116.0,120.0,121.0, 121.6,122.0,122.7,124.1,125.6,126.2,128.5,129.1,131.8,132.5,138.5,138.7, 141.6,146.0,197.1.HRMS calcd for C23H16N2ONa:359.1155[M+Na]+,found:359.1154。
Embodiment 2
Sequentially added in 15mL reaction tubes 1a (0.5mmol, 109.1mg), tetrahydrofuran (3mL), 2a (0.75mmol, 147.2mg)、[RhCp*Cl2]2(0.025mmol, 15.4mg), cesium acetate (0.25mmol, 48.0mg) and silver hexafluoroantimonate (0.25mmol, 85.9mg) will react the seal of tube under air conditions, be subsequently placed in 80 DEG C of oil baths and be stirred to react 12h.Reaction After, it waits for that reaction tube is cooled to room temperature, 10mL water is added, (10mL × 3) are then extracted with ethyl acetate, organic phase is used later Water and saturated salt solution wash successively, anhydrous sodium sulfate drying.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate =20/1) yellow solid product 3a (59.0mg, 35%) is obtained.
Embodiment 3
Sequentially added in 15mL reaction tubes 1a (0.5mmol, 109.1mg), acetonitrile (3mL), 2a (0.75mmol, 147.2mg)、[RhCp*Cl2]2(0.025mmol, 15.4mg), cesium acetate (0.25mmol, 48.0mg) and silver hexafluoroantimonate (0.25mmol, 85.9mg) will react the seal of tube under air conditions, be subsequently placed in 80 DEG C of oil baths and be stirred to react 12h.Reaction After, it waits for that reaction tube is cooled to room temperature, 10mL water is added, (10mL × 3) are then extracted with ethyl acetate, organic phase is used later Water and saturated salt solution wash successively, anhydrous sodium sulfate drying.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate =20/1) yellow solid product 3a (55.5mg, 33%) is obtained.
Embodiment 4
Sequentially added in 15mL reaction tubes 1a (0.5mmol, 109.1mg), dichloromethane (3mL), 2a (0.75mmol, 147.2mg)、[RhCp*Cl2]2(0.025mmol, 15.4mg) and cesium acetate (0.25mmol, 48.0mg), will under air conditions The seal of tube is reacted, is subsequently placed in 80 DEG C of oil baths and is stirred to react 12h.After reaction, it waits for that reaction tube is cooled to room temperature, is added Then (10mL × 3) are extracted with ethyl acetate in 10mL water, organic phase water and saturated salt solution wash successively later, anhydrous sulphur Sour sodium drying.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20/1) and obtains yellow solid product 3a (45.4mg, 27%).
Embodiment 5
Sequentially added in 15mL reaction tubes 1a (0.5mmol, 109.1mg), dichloroethanes (3mL), 2a (0.75mmol, 147.2mg)、[RhCp*Cl2]2(0.025mmol, 15.4mg) and cesium acetate (0.25mmol, 48.0mg), will under air conditions The seal of tube is reacted, is subsequently placed in 80 DEG C of oil baths and is stirred to react 12h.After reaction, it waits for that reaction tube is cooled to room temperature, is added Then (10mL × 3) are extracted with ethyl acetate in 10mL water, organic phase water and saturated salt solution wash successively later, anhydrous sulphur Sour sodium drying.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20/1) and obtains yellow solid product 3a (57.2mg, 34%).
Embodiment 6
Sequentially added in 15mL reaction tubes 1a (0.5mmol, 109.1mg), tetrahydrofuran (3mL), 2a (0.75mmol, 147.2mg)、[RhCp*Cl2]2(0.025mmol, 15.4mg) and cesium acetate (0.25mmol, 48.0mg), will under air conditions The seal of tube is reacted, is subsequently placed in 100 DEG C of oil baths and is stirred to react 12h.After reaction, it waits for that reaction tube is cooled to room temperature, is added Then (10mL × 3) are extracted with ethyl acetate in 10mL water, organic phase water and saturated salt solution wash successively later, anhydrous sulphur Sour sodium drying.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20/1) and obtains yellow solid product 3a (70.6mg, 42%).
Embodiment 7
Sequentially added in 15mL reaction tubes 1a (0.5mmol, 109.1mg), tetrahydrofuran (3mL), 2a (0.75mmol, 147.2mg)、[RhCp*Cl2]2(0.025mmol, 15.4mg) and cesium acetate (0.25mmol, 48.0mg), will under air conditions The seal of tube is reacted, is subsequently placed in 120 DEG C of oil baths and is stirred to react 12h.After reaction, it waits for that reaction tube is cooled to room temperature, is added Then (10mL × 3) are extracted with ethyl acetate in 10mL water, organic phase water and saturated salt solution wash successively later, anhydrous sulphur Sour sodium drying.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20/1) and obtains yellow solid product 3a (65.6mg, 39%).
Embodiment 8
Sequentially added in 15mL reaction tubes 1a (0.5mmol, 109.1mg), tetrahydrofuran (3mL), 2a (0.5mmol, 98.1mg)、[RhCp*Cl2]2(0.03mmol, 18.5mg) and cesium acetate (0.5mmol, 96.0mg), will be anti-under air conditions The seal of tube is answered, is subsequently placed in 100 DEG C of oil baths and is stirred to react 12h.After reaction, it waits for that reaction tube is cooled to room temperature, is added Then (10mL × 3) are extracted with ethyl acetate in 10mL water, organic phase water and saturated salt solution wash successively later, anhydrous sulphur Sour sodium drying.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20/1) and obtains yellow solid product 3a (62.2mg, 37%).
Embodiment 9
Sequentially added in 15mL reaction tubes 1a (0.5mmol, 109.1mg), tetrahydrofuran (3mL), 2a (1mmol, 196.2mg)、[RhCp*Cl2]2(0.0125mmol, 7.7mg) and cesium acetate (0.5mmol, 96.0mg), will under air conditions The seal of tube is reacted, is subsequently placed in 100 DEG C of oil baths and is stirred to react 12h.After reaction, it waits for that reaction tube is cooled to room temperature, is added Then (10mL × 3) are extracted with ethyl acetate in 10mL water, organic phase water and saturated salt solution wash successively later, anhydrous sulphur Sour sodium drying.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20/1) and obtains yellow solid product 3a (52.1mg, 31%).
Embodiment 10
Sequentially added in 15mL reaction tubes 1b (0.5mmol, 116.1mg), tetrahydrofuran (3mL), 2a (0.75mmol, 147.2mg)、[RhCp*Cl2]2(0.025mmol, 15.4mg) and cesium acetate (0.25mmol, 48.0mg), will under air conditions The seal of tube is reacted, is subsequently placed in 100 DEG C of oil baths and is stirred to react 12h.After reaction, it waits for that reaction tube is cooled to room temperature, is added Then (10mL × 3) are extracted with ethyl acetate in 10mL water, organic phase water and saturated salt solution wash successively later, anhydrous sulphur Sour sodium drying.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20/1) and obtains yellow solid product 3b (71.8mg, 41%).The characterize data of the compound is as follows：1H NMR(600MHz,DMSO-d6):δ2.53(s,3H),6.88 (s, 2H), 7.09-7.11 (m, 1H), 7.19 (d, J=8.4Hz, 1H), 7.22-7.25 (m, 1H), 7.27 (d, J=8.4Hz, 1H), 7.40 (t, J=7.8Hz, 2H), 7.51-7.55 (m, 3H), 7.58 (d, J=8.4Hz, 1H), 8.23 (s, 1H), 8.33 (d, J=7.8Hz, 1H), 12.39 (s, 1H)13C NMR(150MHz,DMSO-d6):δ21.8,106.1,107.2,111.7, 116.6,121.3,122.0,122.4,123.5,125.9,126.0,126.7,129.0,129.3,129.6,132.2, 133.0,137.2,139.3,142.2,146.7,197.5.HRMS calcd for C24H18N2ONa:373.1311[M+Na]+, found:373.1319。
Embodiment 11
Sequentially added in 15mL reaction tubes 1c (0.5mmol, 118.1mg), tetrahydrofuran (3mL), 2a (0.75mmol, 147.2mg)、[RhCp*Cl2]2(0.025mmol, 15.4mg) and cesium acetate (0.25mmol, 48.0mg), will under air conditions The seal of tube is reacted, is subsequently placed in 100 DEG C of oil baths and is stirred to react 12h.After reaction, it waits for that reaction tube is cooled to room temperature, is added Then (10mL × 3) are extracted with ethyl acetate in 10mL water, organic phase water and saturated salt solution wash successively later, anhydrous sulphur Sour sodium drying.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20/1) and obtains yellow solid product 3c (77.8mg, 44%).The characterize data of the compound is as follows：1H NMR(600MHz,DMSO-d6):δ6.84(dd,J1= 8.4Hz,J2=2.4Hz, 1H), 7.06 (s, 2H), 7.16 (td, J1=8.4Hz, J2=2.4Hz, 1H), 7.31 (t, J= 7.8Hz, 1H), 7.44-7.46 (m, 3H), 7.56-7.58 (m, 3H), 7.70 (d, J=8.4Hz, 1H), 8.41-8.43 (m, 2H),12.57(s,1H).13C NMR(150MHz,DMSO-d6):δ105.7(d,3JC-F=3.3Hz), 107.0,110.8, 111.0(d,3JC-F=3.3Hz), 112.0,113.5,120.7,121.4,123.2,124.7,125.1 (d,2JC-F=9.8Hz), 129.1,129.6,132.4,134.6(d,2JC-F=9.8Hz), 138.9,139.2,141.9,118.0,160.5 (d,1JC-F= 239.6Hz),197.3.19F NMR(377MHz,DMSO)δ:-113.7.HRMS calcd for C23H15FN2ONa: 377.1061[M+Na]+,found:377.1063。
Embodiment 12
Sequentially added in 15mL reaction tubes 1d (0.5mmol, 124.1mg), tetrahydrofuran (3mL), 2a (0.75mmol, 147.2mg)、[RhCp*Cl2]2(0.025mmol, 15.4mg) and cesium acetate (0.25mmol, 48.0mg), will under air conditions The seal of tube is reacted, is subsequently placed in 100 DEG C of oil baths and is stirred to react 12h.After reaction, it waits for that reaction tube is cooled to room temperature, is added Then (10mL × 3) are extracted with ethyl acetate in 10mL water, organic phase water and saturated salt solution wash successively later, anhydrous sulphur Sour sodium drying.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20/1) and obtains yellow solid product 3d (91.4mg, 50%).The characterize data of the compound is as follows：1H NMR(600MHz,DMSO-d6):δ3.30(s,3H),6.61 (d, J=2.4Hz, 1H), 6.91 (dd, J1=8.4Hz, J2=2.4Hz, 1H), 7.23 (s, 2H), 7.29 (t, J=7.8Hz, 1H), 7.40-7.44 (m, 3H), 7.51-7.54 (m, 3H), 7.67 (d, J=7.8Hz, 1H), 8.27 (d, J=9.0Hz, 1H), 8.39 (d, J=7.8Hz, 1H), 12.42 (s, 1H)13C NMR(150MHz,DMSO-d6):δ54.7,105.7,105.9, 108.8,111.3,111.9,112.7,120.5,121.1,123.5,124.0,124.2,129.0,129.3,131.7, 135.0,138.9,140.0,143.1,148.2,157.4,197.4.HRMS calcd for C24H18N2NaO2:389.1260 [M+Na]+,found:389.1260。
Embodiment 13
Sequentially added in 15mL reaction tubes 1e (0.5mmol, 126.4mg), tetrahydrofuran (3mL), 2a (0.75mmol, 147.2mg)、[RhCp*Cl2]2(0.025mmol, 15.4mg) and cesium acetate (0.25mmol, 48.0mg), will under air conditions The seal of tube is reacted, is subsequently placed in 100 DEG C of oil baths and is stirred to react 12h.After reaction, it waits for that reaction tube is cooled to room temperature, is added Then (10mL × 3) are extracted with ethyl acetate in 10mL water, organic phase water and saturated salt solution wash successively later, anhydrous sulphur Sour sodium drying.Filtering, is spin-dried for, and crosses the isolated target product 3e of silicagel column.
Embodiment 14
Sequentially added in 15mL reaction tubes 1f (0.5mmol, 124.1mg), tetrahydrofuran (3mL), 2a (0.75mmol, 147.2mg)、[RhCp*Cl2]2(0.025mmol, 15.4mg) and cesium acetate (0.25mmol, 48.0mg), will under air conditions The seal of tube is reacted, is subsequently placed in 100 DEG C of oil baths and is stirred to react 12h.After reaction, it waits for that reaction tube is cooled to room temperature, is added Then (10mL × 3) are extracted with ethyl acetate in 10mL water, organic phase water and saturated salt solution wash successively later, anhydrous sulphur Sour sodium drying.Filtering, is spin-dried for, and crosses the isolated target product 3f of silicagel column.
Embodiment 15
Sequentially added in 15mL reaction tubes 1a (0.5mmol, 109.1mg), tetrahydrofuran (3mL), 2b (0.75mmol, 173.0mg)、[RhCp*Cl2]2(0.025mmol, 15.4mg) and cesium acetate (0.25mmol, 48.0mg), will under air conditions The seal of tube is reacted, is subsequently placed in 100 DEG C of oil baths and is stirred to react 12h.After reaction, it waits for that reaction tube is cooled to room temperature, is added Then (10mL × 3) are extracted with ethyl acetate in 10mL water, organic phase water and saturated salt solution wash successively later, anhydrous sulphur Sour sodium drying.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20/1) and obtains yellow solid product 3g (83.2mg, 45%).The characterize data of the compound is as follows：1H NMR(400MHz,DMSO-d6):δ6.99(s,2H),7.16 (t, J=7.6Hz, 1H), 7.22 (d, J=8.4Hz, 1H), 7.27 (d, J=8.4Hz, 1H), 7.31 (d, J=7.6Hz, 1H), 7.45 (t, J=8.8Hz, 3H), 7.55 (d, J=8.0Hz, 2H), 7.71 (d, J=8.0Hz, 1H), 8.38 (d, J=8.0Hz, 1H), 8.43 (d, J=8.4Hz, 1H), 12.55 (s, 1H)13C NMR(100MHz,DMSO-d6):δ105.4,106.9, 111.6,116.1,120.1,121.0,121.7,122.1,122.7,124.2,125.7,126.3,128.6,131.0, 132.4,136.4,138.5,138.9,140.4,146.4,195.5.HRMS calcd for C23H16ClN2O:371.0946[M +H]+,found:371.0950。
Embodiment 16
Sequentially added in 15mL reaction tubes 1a (0.5mmol, 109.1mg), tetrahydrofuran (3mL), 2c (0.75mmol, 157.7mg)、[RhCp*Cl2]2(0.025mmol, 15.4mg) and cesium acetate (0.25mmol, 48.0mg), will under air conditions The seal of tube is reacted, is subsequently placed in 100 DEG C of oil baths and is stirred to react 12h.After reaction, it waits for that reaction tube is cooled to room temperature, is added Then (10mL × 3) are extracted with ethyl acetate in 10mL water, organic phase water and saturated salt solution wash successively later, anhydrous sulphur Sour sodium drying.Filtering, is spin-dried for, and crosses silica gel post separation (petrol ether/ethyl acetate=20/1) and obtains yellow solid product 3h (66.6mg, 38%).The characterize data of the compound is as follows：1H NMR(600MHz,DMSO-d6):δ2.25(s,3H),7.04 (t, J=7.2Hz, 1H), 7.09 (d, J=6.6Hz, 1H), 7.13 (t, J=7.2Hz, 1H), 7.20-7.24 (m, 2H), 7.27 (d, J=7.8Hz, 1H), 7.31-7.34 (m, 2H), 7.46 (t, J=7.2Hz, 1H), 7.72 (d, J=8.4Hz, 1H), 7.78 (s, 2H), 8.35 (d, J=7.8Hz, 1H), 8.48 (d, J=7.8Hz, 1H), 12.59 (s, 1H)13C NMR(150MHz, DMSO-d6):δ20.2,106.7,107.2,112.2,117.0,120.8,121.4,122.3,122.5,123.4,124.7, 126.2,126.3,126.4,129.1,130.1,131.6,133.5,135.8,139.0,140.0,144.2,149.0, 198.1.HRMS calcd for C24H18N2ONa:373.1311[M+Na]+,found:373.1317。
Embodiment 17
Sequentially added in 15mL reaction tubes 1a (0.5mmol, 109.1mg), tetrahydrofuran (3mL), 2d (0.75mmol, 173.0mg)、[RhCp*Cl2]2(0.025mmol, 15.4mg) and cesium acetate (0.25mmol, 48.0mg), will under air conditions The seal of tube is reacted, is subsequently placed in 100 DEG C of oil baths and is stirred to react 12h.After reaction, it waits for that reaction tube is cooled to room temperature, is added Then (10mL × 3) are extracted with ethyl acetate in 10mL water, organic phase water and saturated salt solution wash successively later, anhydrous sulphur Sour sodium drying.Filtering, is spin-dried for, and crosses the isolated target product 3i of silicagel column.
Embodiment 18
Sequentially added in 15mL reaction tubes 1a (0.5mmol, 109.1mg), tetrahydrofuran (3mL), 2e (0.75mmol, 160.7mg)、[RhCp*Cl2]2(0.025mmol, 15.4mg) and cesium acetate (0.25mmol, 48.0mg), will under air conditions The seal of tube is reacted, is subsequently placed in 100 DEG C of oil baths and is stirred to react 12h.After reaction, it waits for that reaction tube is cooled to room temperature, is added Then (10mL × 3) are extracted with ethyl acetate in 10mL water, organic phase water and saturated salt solution wash successively later, anhydrous sulphur Sour sodium drying.Filtering, is spin-dried for, and crosses the isolated target product 3j of silicagel column.
Embodiment 19
Sequentially added in 15mL reaction tubes 1a (0.5mmol, 109.1mg), tetrahydrofuran (3mL), 2f (0.75mmol, 157.7mg)、[RhCp*Cl2]2(0.025mmol, 15.4mg) and cesium acetate (0.25mmol, 48.0mg), will under air conditions The seal of tube is reacted, is subsequently placed in 100 DEG C of oil baths and is stirred to react 12h.After reaction, it waits for that reaction tube is cooled to room temperature, is added Then (10mL × 3) are extracted with ethyl acetate in 10mL water, organic phase water and saturated salt solution wash successively later, anhydrous sulphur Sour sodium drying.Filtering, is spin-dried for, and crosses the isolated target product 3k of silicagel column.
Embodiment 20
Sequentially added in 15mL reaction tubes 1g (0.5mmol, 145.2mg), tetrahydrofuran (3mL), 2g (0.75mmol, 198.2mg)、[RhCp*Cl2]2(0.025mmol, 15.4mg) and cesium acetate (0.25mmol, 48.0mg), will under air conditions The seal of tube is reacted, is subsequently placed in 100 DEG C of oil baths and is stirred to react 12h.After reaction, it waits for that reaction tube is cooled to room temperature, is added Then (10mL × 3) are extracted with ethyl acetate in 10mL water, organic phase water and saturated salt solution wash successively later, anhydrous sulphur Sour sodium drying.Filtering, is spin-dried for, and crosses the isolated target product 3l of silicagel column.
Embodiment 21
Sequentially added in 15mL reaction tubes 1h (0.5mmol, 152.1mg), tetrahydrofuran (3mL), 2h (0.75mmol, 169.7mg)、[RhCp*Cl2]2(0.025mmol, 15.4mg) and cesium acetate (0.25mmol, 48.0mg), will under air conditions The seal of tube is reacted, is subsequently placed in 100 DEG C of oil baths and is stirred to react 12h.After reaction, it waits for that reaction tube is cooled to room temperature, is added Then (10mL × 3) are extracted with ethyl acetate in 10mL water, organic phase water and saturated salt solution wash successively later, anhydrous sulphur Sour sodium drying.Filtering, is spin-dried for, and crosses the isolated target product 3m of silicagel column.
Embodiment above describes the basic principles and main features and advantage of the present invention.The technical staff of the industry should Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe the originals of the present invention Reason, under the range for not departing from the principle of the invention, various changes and improvements may be made to the invention, these changes and improvements are each fallen within In the scope of protection of the invention.

Claims (2)

1. a kind of synthetic method of 6- amino -5- acyl groups benzo [a] carbazole compound, it is characterised in that：By 2- aryl -3- cyanogen Base Benzazole compounds 1 are dissolved in solvent, then sequentially add sulfur ylide 2, catalyst and additive, in 80-120 DEG C of reaction 6- amino -5- acyl groups benzo [a] carbazole compound 3 is made, the reaction equation in the synthetic method is：
Wherein R1For hydrogen, chlorine, fluorine, C1-4Linear or branched alkyl group or alkoxy, the alkyl in the alkoxy are C1-4Alkyl, R2For Hydrogen, trifluoromethyl, fluorine, chlorine, C1-4Linear or branched alkyl group or alkoxy, the alkyl in the alkoxy are C1-4Alkyl, R3For benzene Base or substituted-phenyl, the substituent group on the substituted-phenyl phenyl ring are chlorine, fluorine, trifluoromethyl, C1-6Linear or branched alkyl group or methoxy Base, solvent are tetrahydrofuran, 1,2- dichloroethanes, dichloromethane, acetonitrile or chlorobenzene, and catalyst is dichloro (pentamethyl ring penta 2 Alkenyl) rhodium (III) dimer is closed, additive is cesium acetate or the mixture of silver hexafluoroantimonate and cesium acetate.
2. the synthetic method of 6- amino -5- acyl groups benzo [a] carbazole compound according to claim 1, feature exist In：2- aryl -3- the cyanogen radical indole compounds 1, sulfur ylide 2, catalyst and additive the substance that feeds intake amount it Than being 1:1-2:0.025-0.06:0.5-1.
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CN109265386A (en) * 2018-11-15 2019-01-25 四川大学 It is a kind of to activate the new method that synthesis 3- is acylated indole derivatives by C-H
CN109467528A (en) * 2018-10-09 2019-03-15 佛山科学技术学院 A kind of synthetic method of 1- aminoindole derivatives
CN109867620A (en) * 2019-04-19 2019-06-11 苏州杉洋新材料有限公司 A kind of synthetic method of 5H- benzo [b] carbazole

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CN109467528A (en) * 2018-10-09 2019-03-15 佛山科学技术学院 A kind of synthetic method of 1- aminoindole derivatives
CN109467528B (en) * 2018-10-09 2020-11-06 佛山科学技术学院 Synthesis method of 1-aminoindole derivative
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