CN105111218A - Preparing method for 5H-indole[3,2-a]pyrrole[3,4-c]carbazole-6,8(7H,13H)-diketone compound - Google Patents
Preparing method for 5H-indole[3,2-a]pyrrole[3,4-c]carbazole-6,8(7H,13H)-diketone compound Download PDFInfo
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- CN105111218A CN105111218A CN201510573551.1A CN201510573551A CN105111218A CN 105111218 A CN105111218 A CN 105111218A CN 201510573551 A CN201510573551 A CN 201510573551A CN 105111218 A CN105111218 A CN 105111218A
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- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains three hetero rings
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Abstract
The invention relates to a preparing method for a 5H-indole[3,2-a]pyrrole[3,4-c]carbazole-6,8(7H,13H)-diketone compound. The preparing method includes the steps that indole and maleimide serve as reaction raw materials, catalysts and oxidizing agents are added, and reacting is carried out for 8 h to 24 h at the normal temperature to the temperature of 100 DEG C; after reacting is completed, water is added to be stirred, extracting is carried out, an organic phase is steamed to remove solvents, recrystallization is carried out, and the compound is obtained. According to the preparing method, operation is easy, the reaction route is short, the reaction time is saved, the yield is high, and the preparing method is suitable for industrial production.
Description
Technical field
The invention belongs to the preparation field of indole carbazole compound, particularly a kind of preparation method of 5H-indoles [3,2-a] pyrroles [3,4-c] carbazole-6,8 (7H, 13H)-dione compounds.
Background technology
Indole carbazole is that a class has extensive bioactive natural alkaloid, and its biological activity comprises sterilization, desinsection, antiviral, hypertension and anticancer etc.The representational natural product of most has Staurosporine (staurosporine) and Rebeccamycin (butterfly mycin).Since 1977 find staurosporine, the bioactive research about indole carbazole Alkaloid constantly has new progress (Hirofumi, N.; Satoshi, O.Chemicalbiologyofnaturalindolocarbazoleproducts:30year ssincethediscoveryofstaurosporine.JournalofAntibiotics, 2009,62,17-26.).Staurosporine has prospect widely in the suppression of protein kinase C (PKC), cell cycle protein dependent kinase (CDKs) etc.And the mould procatarxis of butterfly has good topoisomerase I inhibit activities and antitumour activity, for clinical trial Hepatoma therapy, leukemia etc.5H-indoles [3,2-a] pyrroles [3,4-c] carbazole-6,8 (7H, 13H)-diketone (I) and derivative thereof are that by a kind of indole carbazole Alkaloid with special construction of transforming and modifying, (seat is true from the structural framing of staurosporine and butterfly mycin, Chen Hongjun, Chen Wenbin. a kind of indole carbazole compound and its preparation method and application .CN103360395, on October 23rd, 2013; Voldoire, A.; Sancelme, M.; Prudhomme, M.; Colson, P.; Houssier, C.; Bailly, C.; Leonce, S.; Lambel, S..Rebeccamycinanaloguesfromindolo [2,3-c] carbazole.BioorganicMedicinalChemistry, 2001,9 (2): 357-365.; Animati, F.; Berettoni, M.; Bigioni, M.; Binaschi, M.; Cipollone, A.; Irrissuto, C.; Nardelli, F.; Olivieri, L..Synthesisandbiologicalevaluationofrebeccamycinanalogs modifiedattheimidemoiety.BioorganicMedicinalChemistryLet ters, 2012,22 (15): 5013-5017.).Bibliographical information 5H-indoles [3,2-a] pyrroles [3,4-c] carbazole-6,8 (7H, the synthetic method of 13H)-diketone (I) mainly contains three kinds: method one (as shown in Figure 1), 3-sulfydryl indole and dichloro maleimide, under nitrogen protection, in the methanol solution of sodium hydroxide, stirring at room temperature obtains two sulfur indoles maleimide compound for 1 hour, then under the effect of Palladous chloride, Hunigs alkali in benzyl cyanide 80 DEG C reaction 40 hours, finally use sodium borohydride reduction process, column chromatography obtains Compound I, productive rate 10% (Fonseca, A.P.; Lobo, A.M.; Prabhakar, S.Anovelsynthesisofarcyriaflavin-A.Tetrahedron.Lett., 1995,36 (15): 2689-2692.); Method two (as shown in Figure 2), indoles and maleimide in glacial acetic acid 95 DEG C heating 64 hours, column chromatography obtains Compound I, productive rate 22% (Henon, H.; Messaoudi, S.; Hugon, B.; Anizon, F.; Pfeiffer, B.; Prudhomme, M..Tetrahedron, 2005,61 (23): 5599-5614.); Method three (as shown in Figure 3), with 2,3`-di-indoles for initial feed, through step synthetic compound I (Janosik, T. such as Diels-Alder reaction, amidation; Bergman, J.Reactionof2,3`-biindolyl:synthesisofindolo [3,2-a] carbazoles.Tetrahedron, 1999,55 (8): 2371-2380.), the method starting raw material is not easy to obtain, total recovery about 20%.Above-mentioned three kinds of methods, method one and method three reactions steps is longer, productive rate is low, method two long reaction time, productive rate are low.Therefore, new synthetic method is researched and developed significant.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of 5H-indoles [3,2-a] pyrroles [3,4-c] carbazole-6,8 (7H, the preparation method of 13H)-dione compounds, the method technological operation is simple, reactions steps is short, and the reaction times is short, cost is low, environmental friendliness, purity and yield are high, be applicable to suitability for industrialized production.
The preparation method of a kind of 5H-indoles [3,2-a] pyrroles [3,4-c] carbazole-6,8 (7H, 13H)-dione compounds of the present invention, comprising:
(1) indoles, maleimide, catalyzer and oxygenant are added in solvent, react 8 ~ 24 hours; Wherein, the mol ratio of indoles and maleimide is 2.0 ~ 2.5:1.0, and temperature of reaction is room temperature ~ 100 DEG C;
(2) add water stirring, extraction, and dry, recrystallization obtains 5H-indoles [3,2-a] pyrroles [3,4-c] carbazole-6,8 (7H, 13H)-dione compounds.
In described step (1), the mol ratio of indoles and catalyzer is 2.0 ~ 2.5:0.05 ~ 0.2.
Described catalyzer is palladium.
In described step (1), the mol ratio of indoles and oxygenant is 2.0 ~ 2.5:1.0 ~ 3.0.
In described step (1), oxygenant is neutralized verdigris, DDQ or Silver Nitrate.
Described oxygenant is neutralized verdigris, and the mol ratio of neutralized verdigris and indoles is 1.0 ~ 3.0:2.0 ~ 2.5.
In described step (1), solvent is DMSO, DMF, NMP or DMF/DMSO.
Described solvent is the ratio of DMF/DMSO, DMF/DMSO and maleimide is 1 milliliter ~ 100 milliliters: 1 gram.
In described step (1), the temperature of heating is 80 DEG C.
The time of stirring in described step (2) is 5 minutes.
In described step (2), the solvent of extraction is ethyl acetate.
In described step (2), the structural formula of 5H-indoles [3,2-a] pyrroles [3,4-c] carbazole-6,8 (7H, 13H)-dione compounds is
In described step (2), 5H-indoles [3,2-a] pyrroles [3,4-c] carbazole-6,8 (7H, 13H)-dione compounds is brown solid.
beneficial effect
Preparation method's reactions steps of the present invention is few, and shorten the reaction times, raw material is easy to get, and cost is low, simple to operate, reduces three-protection design, and yield is higher and be easy to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the synthetic route chart of method one;
Fig. 2 is the synthetic route chart of method two;
Fig. 3 is the synthetic route chart of method three;
Fig. 4 is the synthetic route chart of preparation method of the present invention;
Fig. 5 is the proton nmr spectra of 5H-indoles [3,2-a] pyrroles [3,4-c] carbazole-6,8 (7H, 13H)-diketone in embodiment 1;
Fig. 6 is the carbon-13 nmr spectra of 5H-indoles [3,2-a] pyrroles [3,4-c] carbazole-6,8 (7H, 13H)-diketone in embodiment 1.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
Getting indoles 1.17g (0.01mol), maleimide 0.97g (0.01mol), palladium 0.11g (0.0005mol) and neutralized verdigris 2.72g (0.015mol) is added in 100mL round-bottomed flask, add DMSO20mL, be heated to 80 DEG C and stir 8h, reaction is finished, add water 50mL, stir 5 minutes, extraction into ethyl acetate, organic phase is dry, and ethyl alcohol recrystallization obtains brown solid 5H-indoles [3,2-a] pyrroles [3,4-c] carbazole-6,8 (7H, 13H)-diketone 0.89g, yield 54%, mp:370 ~ 373 DEG C.As shown in Figure 5, carbon-13 nmr spectra as shown in Figure 6 for proton nmr spectra.
1HNMR(400MHz,DMSO)δ7.63–7.22(m,4H),7.75(s,2H),8.79(s,1H),8.95(s,1H),11.06(s,1H),12.19(s,1H),12.32(s,1H).
13CNMR(101MHz,DMSO)δ107.52,110.88,111.60,111.96,112.30,120.15,120.20,120.39,121.31,121.85,123.80,124.76,126.27,126.32,132.54,135.32,138.31,141.15,170.30,171.10.MS(ESI):m/z＝326.1[M+H]
+。
Embodiment 2
Getting indoles 2.34g (0.02mol), maleimide 0.97g (0.01mol), palladium 0.11g (0.0005mol) and neutralized verdigris 2.72g (0.015mol) is added in 100mL round-bottomed flask, add DMSO20mL and DMF10mL, be heated to 80 DEG C and stir 18h, reaction is finished, add water 50mL, stir 5 minutes, extraction into ethyl acetate, organic phase is dry, and ethyl alcohol recrystallization obtains brown solid 5H-indoles [3,2-a] pyrroles [3,4-c] carbazole-6,8 (7H, 13H)-diketone 2.54g, yield 78%, mp:370 ~ 373 DEG C.
Embodiment 3
Getting indoles 2.34g (0.02mol), maleimide 0.97g (0.01mol), palladium 0.11g (0.0005mol) and neutralized verdigris 0.91g (0.005mol) is added in 100mL round-bottomed flask, add DMSO20mL, be heated to 80 DEG C and stir 18h, reaction is finished, add water 50mL, stir 5 minutes, extraction into ethyl acetate, organic phase is dry, and ethyl alcohol recrystallization obtains brown solid 5H-indoles [3,2-a] pyrroles [3,4-c] carbazole-6,8 (7H, 13H)-diketone 1.07g, yield 33%, mp:370 ~ 373 DEG C.
Embodiment 4
Getting indoles 2.34g (0.02mol), maleimide 0.97g (0.01mol), palladium 0.11g (0.0005mol) and neutralized verdigris 2.72g (0.015mol) is added in 100mL round-bottomed flask, add DMSO20mL, be heated to 100 DEG C and stir 18h, reaction is finished, add water 50mL, stir 5 minutes, extraction into ethyl acetate, organic phase is dry, and ethyl alcohol recrystallization obtains brown solid 5H-indoles [3,2-a] pyrroles [3,4-c] carbazole-6,8 (7H, 13H)-diketone 2.21g, yield 68%, mp:370 ~ 373 DEG C.
Embodiment 5
Getting indoles 4.68g (0.04mol), maleimide 1.94g (0.02mol), palladium 0.44g (0.002mol) and neutralized verdigris 5.44g (0.015mol) is added in 100mL round-bottomed flask, add DMSO20mL and DMF10mL, be heated to 80 DEG C and stir 18h, reaction is finished, add water 70mL, stir 5 minutes, extraction into ethyl acetate, organic phase is dry, and ethyl alcohol recrystallization obtains brown solid 5H-indoles [3,2-a] pyrroles [3,4-c] carbazole-6,8 (7H, 13H)-diketone 5.54g, yield 70%, mp:370 ~ 373 DEG C.
Embodiment 6
Getting indoles 2.34g (0.02mol), maleimide 0.97g (0.01mol), palladium 0.11g (0.0005mol) and neutralized verdigris 0.91g (0.005mol) is added in 100mL round-bottomed flask, add DMF30mL, be heated to 80 DEG C and stir 18h, reaction is finished, add water 50mL, stir 5 minutes, extraction into ethyl acetate, organic phase is dry, and ethyl alcohol recrystallization obtains brown solid 5H-indoles [3,2-a] pyrroles [3,4-c] carbazole-6,8 (7H, 13H)-diketone 1.62g, yield 50%, mp:370 ~ 373 DEG C.
Embodiment 7
Getting indoles 3.51g (0.03mol), maleimide 1.45g (0.015mol), palladium 0.11g (0.0005mol) and neutralized verdigris 4.08g (0.022mol) is added in 100mL round-bottomed flask, add NMP30mL, be heated to 100 DEG C and stir 12h, reaction is finished, add water 50mL, stir 5 minutes, extraction into ethyl acetate, organic phase is dry, and ethyl alcohol recrystallization obtains brown solid 5H-indoles [3,2-a] pyrroles [3,4-c] carbazole-6,8 (7H, 13H)-diketone 2.08g, yield 43%, mp:370 ~ 373 DEG C.
Embodiment 8
Get indoles 1.17g (0.01mol), maleimide 0.49g (0.005mol), palladium 0.06g (0.25mmol) and 2, 3-bis-chloro-5, 6-dicyano-1, 4-benzoquinones (DDQ) 1.70g (0.015mol) is added in 100mL round-bottomed flask, add DMSO10mL and DMF5mL, be heated to 80 DEG C and stir 18h, reaction is finished, add water 50mL, stir 5 minutes, extraction into ethyl acetate, organic phase is dry, ethyl alcohol recrystallization obtains brown solid 5H-indoles [3, 2-a] pyrroles [3, 4-c] carbazole-6, 8 (7H, 13H)-diketone 0.65g, yield 20%, mp:370 ~ 373 DEG C.
Embodiment 9
Getting indoles 2.34g (0.02mol), maleimide 0.97g (0.01mol), palladium 0.11g (0.0005mol) and Silver Nitrate 2.5g (0.015mol) is added in 100mL round-bottomed flask, add DMF15mL, be heated to 80 DEG C and stir 18h, reaction is finished, add water 50mL, stir 5 minutes, extraction into ethyl acetate, organic phase is dry, and ethyl alcohol recrystallization obtains brown solid 5H-indoles [3,2-a] pyrroles [3,4-c] carbazole-6,8 (7H, 13H)-diketone 1.17g, yield 36%, mp:370 ~ 373 DEG C.
Claims (8)
1. the preparation method of 5H-indoles [3,2-a] pyrroles [3,4-c] carbazole-6,8 (7H, 13H)-dione compounds, comprising:
(1) indoles, maleimide, catalyzer and oxygenant are added in solvent, react 8 ~ 24 hours; Wherein, the mol ratio of indoles and maleimide is 2.0 ~ 2.5:1.0, and temperature of reaction is room temperature ~ 100 DEG C;
(2) add water stirring, extraction, and dry, recrystallization obtains 5H-indoles [3,2-a] pyrroles [3,4-c] carbazole-6,8 (7H, 13H)-dione compounds.
2. a kind of 5H-indoles [3 according to claim 1,2-a] pyrroles [3,4-c] carbazole-6,8 (7H, the preparation method of 13H)-dione compounds, it is characterized in that, in described step (1), the mol ratio of indoles and catalyzer is 2.0 ~ 2.5:0.05 ~ 0.2.
3. the preparation method of a kind of 5H-indoles [3,2-a] pyrroles [3,4-c] carbazole-6,8 (7H, the 13H)-dione compounds according to claims 1 or 2, it is characterized in that, described catalyzer is palladium.
4. a kind of 5H-indoles [3 according to claim 1,2-a] pyrroles [3,4-c] carbazole-6,8 (7H, the preparation method of 13H)-dione compounds, it is characterized in that, in described step (1), the mol ratio of indoles and oxygenant is 2.0 ~ 2.5:1.0 ~ 3.0.
5. a kind of 5H-indoles [3,2-a] pyrroles [3,4-c] carbazole-6 according to claim 1,8 (7H, the preparation method of 13H)-dione compounds, is characterized in that, in described step (1), oxygenant is neutralized verdigris, DDQ or Silver Nitrate.
6. a kind of 5H-indoles [3,2-a] pyrroles [3,4-c] carbazole-6 according to claim 1,8 (7H, the preparation method of 13H)-dione compounds, is characterized in that, in described step (1), solvent is DMSO, DMF, NMP or DMF/DMSO.
7. the preparation method of a kind of 5H-indoles [3,2-a] pyrroles [3,4-c] carbazole-6,8 (7H, 13H)-dione compounds according to claim 1, is characterized in that, in described step (1), the temperature of heating is 80 DEG C.
8. a kind of 5H-indoles [3 according to claim 1,2-a] pyrroles [3,4-c] preparation method of carbazole-6,8 (7H, 13H)-dione compounds, it is characterized in that, 5H-indoles [3,2-a] pyrroles [3,4-c] carbazole-6 in described step (2), the structural formula of 8 (7H, 13H)-dione compounds is
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110041338A (en) * | 2018-10-30 | 2019-07-23 | 贵州省中国科学院天然产物化学重点实验室 | One kind double indoles maleic amide class compounds with anti-tumor activity and its application |
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| CN103360395A (en) * | 2012-04-11 | 2013-10-23 | 南开大学 | Indole carbazole compound as well as preparation method and application thereof |
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| CN103360395A (en) * | 2012-04-11 | 2013-10-23 | 南开大学 | Indole carbazole compound as well as preparation method and application thereof |
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| A. PAULO FONSECA，等: "A Novel Synthesis of Arcyriaflavin-A", 《TETRAHEDRON LETTERS》 * |
| JAN BERGMAN，等: "Synthesis of Indolo[3,2-a]pyrrolo[3,4-c]carbazole in one Step from Indole and Maleimide", 《TETRAHEDRON》 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110041338A (en) * | 2018-10-30 | 2019-07-23 | 贵州省中国科学院天然产物化学重点实验室 | One kind double indoles maleic amide class compounds with anti-tumor activity and its application |
| CN110041338B (en) * | 2018-10-30 | 2021-11-30 | 贵州省中国科学院天然产物化学重点实验室 | Bis-indole maleimide compound with anti-tumor activity and application thereof |
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