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Method for preparing disubstituted 4-aminocarbazole compound

A technology for aminocarbazoles and compounds, which is applied in the field of preparing disubstituted 4-aminocarbazoles, can solve the problems of severe reaction conditions, inability to obtain 4-aminocarbazoles, and difficulty in obtaining, and achieves the effect of an efficient synthesis method

Active Publication Date: 2018-12-07
TAIZHOU UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

In addition, these compounds are also intermediates in the synthesis of the natural product angiostatin (Chem. .HeterocyclicChem.,2004,41,1-6), catalytic reduction of 4-nitrocarbazole derivatives (Chem.Commun.2009,1467-1469), alkali-promoted ring closure reaction (Tetrahedron,2009,65,3592 -3602) and palladium-catalyzed intramolecular cyclization reaction of direct carbon-hydrogen bond to cyano addition (Org.Lett.2016,18,5002-5005), but these methods have some shortcomings, such as severe reaction conditions , It is difficult to obtain 4-nitrocarbazole compounds, 4-aminocarbazole derivatives that cannot be synthesized, etc.

Method used

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  • Method for preparing disubstituted 4-aminocarbazole compound
  • Method for preparing disubstituted 4-aminocarbazole compound
  • Method for preparing disubstituted 4-aminocarbazole compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0014] In a 20 mL dry reaction tube, under nitrogen protection, dissolve 1-p-toluenesulfonyl-3-nitroindole (0.1 mmol) and 2-(1-phenylethylidene) malononitrile (0.2 mmol) Add catalyst triethylamine (0.2mmol) to 2mL of acetonitrile, stir magnetically at 50°C for 24 hours, TLC detects that the raw material disappears, concentrates the organic solvent under reduced pressure, and then further purifies by column chromatography to obtain the product with a yield of 83%;

[0015] 2-Phenyl-3-cyano-4-amino-9-p-toluenesulfonylcarbazole

[0016] 1 H NMR (400MHz, CDCl 3 )δ8.40(d, J=8.4Hz, 1H), 7.88(s, 1H), 7.82(d, J=7.6Hz, 1H), 7.72(d, J=8.4Hz, 2H), 7.64(d, J=7.2Hz, 2H), 7.54-7.42(m, 5H), 7.16(d, J=8.0Hz, 2H); 5.16(brs, 2H), 2.30(s, 3H); 13 C NMR (100MHz, CDCl 3 )δ146.6, 145.5, 144.7, 141.6, 139.0, 138.0, 134.7, 129.9, 128.9, 128.7, 128.6, 126.8, 126.5, 124.5, 124.4, 120.4, 117.6, 115.0, 110.6, 106.3, 91.7: HR, 106.3, 91.7 calcd for[M+H] + (C 26 h 20 N 3 o 2 S) requires 438.1276,...

Embodiment 2

[0018] In a 20mL dry reaction tube, under nitrogen protection, 1-p-toluenesulfonyl-3-nitroindole (0.1mmol) and 2-(1-p-bromophenylethylene)malononitrile (0.2mmol ) was dissolved in 2 mL of acetonitrile, triethylamine (0.2 mmol) was added as a catalyst, magnetically stirred at 50° C. for 6 hours, detected by TLC, the raw material disappeared, the organic solvent was concentrated under reduced pressure, and then further purified by column chromatography to obtain the product with a yield of 68%;

[0019] 2-p-bromophenyl-3-cyano-4-amino-9-p-toluenesulfonylcarbazole

[0020] 1 H NMR (400MHz, CDCl 3 )δ8.41(d, J=8.4Hz, 1H), 7.84-7.82(m, 2H), 7.72(d, J=8.4Hz, 2H), 7.66(d, J=8.4Hz, 2H), 7.56- 7.50(m,3H),7.46(t,J=7.4Hz,1H),7.17(d,J=8.4Hz,2H),5.17(brs,2H),2.31(s,3H); 13 C NMR (100MHz, CDCl 3 )δ146.7, 145.6, 143.4, 141.5, 138.0, 137.9, 134.6, 131.9, 130.5, 130.0, 127.0, 126.5, 124.6, 123.2, 120.4, 117.4, 115.1, 110.8, 106.1, 91.3, 21.6 [M+H] + (C 26 h 19 BrN 3 o 2 S) requires 51...

Embodiment 3

[0022] In a 20mL dry reaction tube, under nitrogen protection, 1-p-toluenesulfonyl-3-nitroindole (0.1mmol) and 2-(1-p-chlorophenylethylidene)malononitrile (0.2mmol ) was dissolved in 2 mL of acetonitrile, added catalyst triethylamine (0.2 mmol), stirred magnetically at 50° C. for 6 hours, detected by TLC, the raw material disappeared, and the organic solvent was concentrated under reduced pressure, and then further purified by column chromatography to obtain the product with a yield of 73%;

[0023] 2-p-chlorophenyl-3-cyano-4-amino-9-p-toluenesulfonylcarbazole

[0024] 1 H NMR (400MHz, CDCl 3 )δ8.41(d,J=8.4Hz,1H),7.85-7.82(m,2H),7.72(d,J=8.4Hz,2H),7.59-7.44(m,6H),7.17(d,J =8.4Hz, 2H), 5.17(brs, 2H), 2.31(s, 3H); 13 C NMR (100MHz, CDCl 3 )δ146.7, 145.6, 143.4, 141.6, 138.0, 137.4, 134.9(3), 134.9(1), 134.6, 130.2, 130.0, 128.9, 127.0, 126.5, 124.6, 124.3, 120.4, 117.4, 115.1, 110.0 ,21.6; HRMS(ESI):calcd for[M+H] + (C 26 h 19 ClN 3 o 2 S) requires 472.0887, found 472....

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Abstract

The invention discloses a method for preparing a disubstituted 4-aminocarbazole compound. The method comprises the steps of with a 3-nitroguanidine compound and a 2-(1-arylethylidene)malononitrile compound as the raw materials and acetonitrile as a solvent, reacting at 50 DEG C for 6-24 hours in a nitrogen protection system, so as to synthesize a target compound. The synthetic method is simple, efficient, relatively high in yield and mild in conditions and has good application prospects.

Description

technical field [0001] The present invention relates to a kind of high-efficiency, simple and convenient chemical reaction, in relatively mild reaction system, through alkenyl Michael addition, cyclization reaction, isomerization reaction and elimination reaction series reaction, synthesize disubstituted 4-aminocarbazoles compound method. Background technique [0002] Among numerous carbazole derivatives, the 4-aminocarbazole skeleton exists in many drugs (Eur.J.Med.Chem.2012,56,225-236; U.S.Pat.Appl.Publ.(2010),US 20100160303 A1) and organic functional materials (Repub.Korean Kongkae Taeho Kongbo (2014), KR 2014130297 A). In addition, these compounds are also intermediates in the synthesis of the natural product angiostatin (Chem. .HeterocyclicChem.,2004,41,1-6), catalytic reduction of 4-nitrocarbazole derivatives (Chem.Commun.2009,1467-1469), alkali-promoted ring closure reaction (Tetrahedron,2009,65,3592 -3602) and palladium-catalyzed intramolecular cyclization reactio...

Claims

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Application Information

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IPC IPC(8): C07D209/88C07D409/04
CPCC07D209/88C07D409/04
Inventor 曹冬冬杨健国应安国莫寒劼陈定奔陈钢
Owner TAIZHOU UNIV
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