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Method for manufacturing 1,9-diazaphenalene derivative

A technology of derivatives and diazepam, applied in the field of preparation of 1,9-diazepine derivatives, can solve problems such as unseen synthesis

Inactive Publication Date: 2016-10-05
郑建鸿
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0005] Although the existing technology can synthesize heterocyclic compounds with multiple merging aromatic rings through metal-catalyzed reactions involving C-H bond activation, however, there is no synthesis of 1,9-diazo with high substitution or even multiple merging aromatic rings. method of derivatives

Method used

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  • Method for manufacturing 1,9-diazaphenalene derivative
  • Method for manufacturing 1,9-diazaphenalene derivative
  • Method for manufacturing 1,9-diazaphenalene derivative

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1～23

[0035] 0.25mmol benzamidine (benzamidine) derivative (I), 0.80mmol alkyne compound (II), 6.0mol% [Cp*Rh(CH 3 EN) 3 ](SbF 6 ) 2 (Cp* represents pentamethylcyclopentadienyl, as a catalyst) and 1.12 mmol (4.5 equivalents) of copper (II) acetate (as an oxidant) are placed in a sealed tube, vacuum pumped and nitrogen purge (purge) 3 times , and then injected 3.5mL 2-methyl-2-butanol (2-methyl-2-butanol, t-amylOH, tert-amyl alcohol) (as a solvent) with a syringe under a nitrogen atmosphere, and reacted at 130°C with stirring 18 hours. After the reaction, it was cooled and diluted with 10 mL of dichloromethane, then filtered with a Celite pad and washed with 50 mL of dichloromethane, and finally the filtrate was collected and concentrated in vacuo, and then filtered with a silica gel column The product (Ⅲ) was purified by chromatography [the eluent was hexane-ethyl acetate (5-15%)]. Its reaction formula is as follows:

[0036]

[0037] In the following Examples 1-23, R in th...

Embodiment 1

[0042] 83% yield, scarlet solid, m.p.265-268°C, 1 H NMR (500MHz, CDCl 3 ):δ7.52-7.50(m,5H),7.47-7.38(m,2H),7.28-7.19(m,10H),7.12-7.06(m,5H),7.05-6.96(m,5H),6.92 -6.88(m,2H),6.80(td,J=8.0,2.0Hz,1H),6.50-6.49(m,2H), 13 C NMR (125MHz, CDCl 3 ): δ150.0, 149.3, 140.5, 138.6, 137.8, 137.6, 136.9, 136.8, 135.6, 135.2, 134.6, 131.8, 131.7, 131.2, 130.9, 130.2, 130.0, 129.7, 128.5, 128.9.2, 126 126.5, 125.9, 125.5, 124.9, 123.2, 121.8, 118.9, 117.5, HRMS (FAB + )m / z:MH + C 49 h 32 N 2 Calculated value: 648.2565, found value 648.2563, IR(KBr): 3054, 2929, 2337, 1342cm -1 .

Embodiment 2

[0044] Yield 78%, orange solid, m.p.294-297°C, 1 H NMR (400MHz, CDCl 3 ):δ7.51-7.45(m,5H),7.26-7.17(m,8H),7.07-6.95(m,11H),6.93-6.86(m,3H),6.77(td,J=7.2,1.2Hz ,1H),6.71(s,1H),6.45(d,J=7.2Hz,2H),2.27(s,3H), 13 C NMR (125MHz, CDCl 3 ): δ150.2,149.3,141.4,140.7,138.8,138.0,137.9,137.4,137.1,136.9,135.8,135.2,134.6,131.9,131.8,131.3,130.2,130.1,129.8,129.3,181.127 127.5, 127.0, 126.7, 126.6, 126.5, 125.8, 125.4, 124.9, 122.8, 120.4, 119.0, 118.8, 22.6, HRMS (EI + )C 50 h 34 N 2 Calculated: 662.2722, Found: 662.2724, IR(KBr): 3054, 2931, 2337, 1342cm -1 .

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Abstract

The present invention relates to a preparation method of 1,9-diazepine derivatives. A method for preparing 1,9-diazepine derivatives shown in the following formula (III), comprising: making benzonitrile compounds shown in the following formula (IV), amines shown in the following formula (V) The compound and the alkyne compound shown in the following formula (II) carry out a catalytic reaction in the presence of an oxidizing agent and a rhodium-containing metal salt or a ruthenium-containing metal salt; R 1 ~R 3 , R, Y 1 , Y 2 and X are defined as described in the specification. The preparation method of the 1,9-diazepine derivative of the present invention can synthesize diversified highly substituted products with high yield through a simple one-pot reaction.

Description

technical field [0001] The invention relates to a preparation method of 1,9-diazaphenalene derivatives, in particular to a preparation method of highly substituted 1,9-diazaphenalene derivatives. Background technique [0002] In the past, the diazoaromatic heterocyclic compound with three merging aromatic rings was benzo[b][1,8]diazine (benzo[b][1,8]diazanaphthalene), for example, Taiwan Patent Publication No. 263510, Its three aromatic rings merge in a straight line in an anthracene-like manner and are used as an antimicrobial agent. [0003] J.Org.Chem.1990,55,6140-6147 discloses a kind of lH-2,3-dihydro-1,9-diazepine (lH-2,3-dihydro-1,9- diazaphenalene) derivatives (where Ar represents phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-chlorophenyl or 4-fluorophenyl, R represents hydrogen or benzyl), the three Two rings merge with each other, but not all of them are aromatic rings. Not only the synthesis steps are complicated, but also it is difficult to synthesize highly subst...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D471/06C07D495/16C09K11/06
CPCC07D471/06
Inventor 郑建鸿贾亚库马陈旻贤
Owner 郑建鸿
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