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Synthetic method of pyrazolidinone-fused benzo 1,3-oxazepine compound

A technology of pyrazolidone and oxazepine, which is applied in the field of organic synthesis, can solve the problems of low atom economy, generation of by-products, and difficulty in obtaining, and achieves the effects of high atom economy, simple operation and mild reaction conditions.

Active Publication Date: 2021-07-30
HENAN NORMAL UNIV
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  • Application Information

AI Technical Summary

Problems solved by technology

Although these methods are relatively reliable, the raw materials used need to be prepared through multi-step reactions, which are costly and difficult to obtain.
In addition, the loss of atoms such as halogen after the reaction also makes the atom economy of the reaction low and produces a large number of by-products

Method used

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  • Synthetic method of pyrazolidinone-fused benzo 1,3-oxazepine compound
  • Synthetic method of pyrazolidinone-fused benzo 1,3-oxazepine compound
  • Synthetic method of pyrazolidinone-fused benzo 1,3-oxazepine compound

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] Under an argon atmosphere, 1a, 2a, an organic solvent, an oxidizing agent, an additive and a catalyst were sequentially added into a 15mL reaction bottle, the stopper was covered and sealed, and it was placed in an oil bath to raise the temperature and stir for reaction. After the reaction was completed, it was cooled to room temperature, extracted, dried, spin-dried, and separated through a silica gel column (petroleum ether / ethyl acetate=3 / 1) to obtain the white solid product 3a. The reaction equation is expressed as:

[0024]

[0025] By changing the reaction conditions such as reaction solvent, oxidant, additive, catalyst, reaction temperature and equivalent ratio between reactants, the experimental results are shown in Table 1.

[0026] Synthesis of 3a under different reaction conditions in table 1 a

[0027]

[0028]

Embodiment 2

[0030]

[0031] Under argon atmosphere, 1a (57.0mg, 0.3mmol), 2a (76.5mg, 0.45mmol), acetonitrile (3mL), [RhCp*Cl 2 ] 2 (4.7mg, 0.0075mmol), silver acetate (100.1mg, 0.6mmol) and 2,4,6-trimethylbenzoic acid (98.5mg, 0.6mmol), cover the stopper and place it in an oil bath at 100°C The reaction was stirred for 12 hours. After the reaction was completed, it was cooled to room temperature, extracted, dried, spin-dried, and separated through a silica gel column (petroleum ether / ethyl acetate=3 / 1) to obtain a white solid product 3a (74.3mg, 75%) . The X-ray single crystal diffraction pattern is figure 1 . mp 244.8-245.7℃. 1 H NMR (600MHz, CDCl 3 ):δ8.13-8.12(m,1H),8.10(s,1H),7.91-7.89(m,1H),7.86(d,J=9.0Hz,1H),7.57(dd,J 1 =7.8Hz,J 2 =1.8Hz,1H),7.50-7.47(m,3H),7.42-7.39(m,1H),7.28(d,J=9.0Hz,1H),7.23(td,J 1 =7.8Hz,J 2 =1.2Hz,1H),5.52(s,1H),1.29(s,3H),1.13(s,3H). 13 C{ 1 H}NMR (150MHz, CDCl 3 ): δ178.3, 151.2, 146.5, 132.6, 132.0, 131.5, 130.2, 128.8, 128.6, 128.4, 126.9, ...

Embodiment 3

[0033] According to the method and steps of Example 2, by changing the reactants 1 and 2, various pyrazolidinone-benzo-1,3-oxazepine compounds 3 were synthesized, and the specific results are shown in Table 2.

[0034] Table 2 Synthesis of various pyrazolidinone-benzo-1,3-oxazepine compounds 3 a,b

[0035]

[0036] Representative product characterization data are as follows:

[0037] 8,8,14-Trimethyl-7a,8-dihydrobenzo[d]naphtho[1,2-f]pyrazolo[5,1-b][1,3]oxazepin-9(10H)-one(3b)

[0038] White solid (68.1mg, 66%), mp 241.2-242.2℃. 1 H NMR (400MHz, CDCl 3 ):δ8.14-8.12(m,1H),8.08(s,1H),7.89-7.86(m,1H),7.82(d,J=8.8Hz,1H),7.51-7.45(m,2H), 7.37(d,J=1.2Hz,1H),7.34(d,J=8.4Hz,1H),7.25(s,1H),7.19(dd,J 1 =8.4Hz,J 2 =1.6Hz,1H),5.45(s,1H),2.39(s,3H),1.27(s,3H),1.12(s,3H). 13 C{ 1 H}NMR (100MHz, CDCl 3): δ178.3, 151.2, 144.1, 132.6, 132.5, 132.2, 131.5, 130.1, 129.4, 128.6, 128.5, 126.8, 125.7, 125.4, 124.4, 119.8, 115.9, 108.9, 43.5, 21.5, 208.8 m / z:[M+Na] + Calcd for C 22 h ...

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Abstract

The invention discloses a synthesis method of a pyrazolidinone-fused benzo 1,3-oxazepine compound, and belongs to the technical field of organic synthesis. 1-aryl pyrazolidinone 1 and a diazonaphthalene ketone compound 2 are used as raw materials, and in the presence of a catalyst, an oxidizing agent and an additive, a heating reaction is performed in an organic solvent to obtain the pyrazolidinone-fused benzo 1,3-oxazepine compound 3. According to the method, the pyrazolidinone-fused benzo 1,3-oxazepine compound is efficiently and regioselectively synthesized through cascade reaction between the 1-aryl pyrazolidinone compound and the diazonaphthalene ketone compound, and the method has the advantages that the raw materials are simple and easy to obtain, the operation is simple and convenient, the condition is mild, the selectivity is good, the substrate application range is wide, and the like.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a method for synthesizing pyrazolidinone-benzo-1,3-oxazepine compounds. Background technique [0002] Benzoxazepines are an important class of condensed heterocyclic compounds containing both nitrogen and oxygen heteroatoms. This type of compound not only exists widely in nature, but many of them have anticonvulsant, antitumor, antidepressant, anti Anxiety, antibacterial and other physiological and pharmacological activities. [0003] At present, such compounds are mainly synthesized by condensation reaction of difunctional benzene (especially dihalogenated benzene or monohalogenated benzene, etc.) with other component compounds. Although these methods are relatively reliable, the raw materials used need to be prepared through multi-step reactions, which are costly and difficult to obtain. In addition, the loss of atoms such as halogen after the reaction a...

Claims

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Application Information

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IPC IPC(8): C07D498/04C07D231/22
CPCC07D498/04C07D231/22
Inventor 范学森王慕华张凌华张新迎陈茜
Owner HENAN NORMAL UNIV
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