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Polysubstituted benzo bicyclo[2.2.2]octane derivative and preparation method thereof

A multi-substitution and derivative technology, applied in organic chemistry and other fields, can solve the problems of cumbersome steps, low yield, environmental pollution, etc., and achieve the effects of mild reaction conditions, simple operation, and low cost

Active Publication Date: 2018-01-16
ZHEJIANG SHENGXIAO CHEM
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  • Abstract
  • Description
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AI Technical Summary

Problems solved by technology

[0004] At present, there are not many reports on the synthesis of multi-substituted benzobicyclo[2.2.2]octane derivatives, and most of the existing synthesis methods use Lewis acid or transition metal catalyst system, which will inevitably cause great pollution to the environment and damage, and the yield is low, or the steps are cumbersome

Method used

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  • Polysubstituted benzo bicyclo[2.2.2]octane derivative and preparation method thereof
  • Polysubstituted benzo bicyclo[2.2.2]octane derivative and preparation method thereof
  • Polysubstituted benzo bicyclo[2.2.2]octane derivative and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] Into a 50mL quartz tube, add 100mg (0.41mmol) of dimethyl ester-substituted o-phthalene, 92mg (0.82mmol) of N-methylmaleimide and 20mL of acetonitrile, stir well, pass nitrogen gas for 30 minutes, and place in Under ultraviolet light, light reaction was carried out at room temperature for 4 h. After the reaction was completed, the reaction solvent was concentrated and spin-dried by a rotary evaporator, and then a mixed solution of petroleum ether: ethyl acetate with a volume ratio of 4:1 was used as an eluent to carry out purification and separation by silica gel column chromatography to obtain the corresponding poly Substituted benzobicyclo[2.2.2]octane derivatives, the reaction formula is:

[0027]

[0028] Product purity is 99%, and productive rate is 84%, and its nuclear magnetic data analysis is: 1 H NMR (400MHz, CDCl 3 )δ7.26–7.14(m,3H),7.14–6.99(m,1H),4.06(t,J=2.7Hz,1H),3.93(t,J=3.0Hz,1H),3.82(s,3H ),3.59(s,3H),3.47(dd,J=5.5,2.2Hz,1H),3.23(dd,J=8.5,3.2Hz,1H...

Embodiment 2

[0031] Into a 50mL quartz tube, add 90mg (0.37mmol) of dimethyl ester substituted ortho-phthalene, 137mg (0.78mmol) of N-benzylmaleimide and 20mL of acetonitrile, stir well and put nitrogen into it for 30 minutes Placed under ultraviolet light, light reaction at room temperature for 6h. After the reaction was completed, the reaction solution was concentrated and spin-dried by a rotary evaporator, and then a mixed solution of petroleum ether: ethyl acetate with a volume ratio of 6:1 was used as an eluent for purification and separation by silica gel column chromatography to obtain the corresponding poly Substituted benzobicyclo[2.2.2]octane derivatives, the reaction formula is:

[0032]

[0033] The purity of the product was 99.2%, and the yield was 83%. The NMR data analysis is as follows: 1 H NMR (400MHz, CDCl 3 )δ7.25–7.01(m,7H),6.57(d,J=7.1Hz,2H),4.27(s,2H),4.09(t,J=2.7Hz,1H),3.96(t,J=3.0 Hz,1H),3.83(s,3H),3.60(s,3H),3.49(dd,J=5.4,2.2Hz,1H),3.26(dd,J=8.6,3.2Hz,1H),3....

Embodiment 3

[0036] In the 50mL quartz tube, add 60mg (0.22mmol) diethyl ester-substituted o-phthalene, 48mg (0.43mmol) N-methylmaleimide and 15mL acetonitrile, stir well and place under a UV lamp, Light reaction at room temperature for 7h. After the reaction was completed, the reaction solution was concentrated and spin-dried by a rotary evaporator, and then a mixed solution of petroleum ether: ethyl acetate with a volume ratio of 8:1 was used as an eluent for purification and separation by silica gel column chromatography to obtain the corresponding poly Substituted benzobicyclo[2.2.2]octane derivatives, the chemical reaction formula is:

[0037]

[0038] The product had a purity of 99% and a yield of 71%. The NMR data analysis is as follows: 1 H NMR (400MHz, CDCl 3)δ7.28–7.15(m,3H),7.14–7.03(m,1H),4.34–4.17(m,2H),4.12–3.98(m,3H),3.94(t,J=3.1Hz,1H) ,3.46(dd,J=5.4,2.4Hz,1H),3.24(dd,J=8.5,3.2Hz,1H),3.20(dd,J=5.4,2.9Hz,1H),3.12(dd,J=8.5 ,3.3Hz,1H),2.48(d,J=4.1Hz,3H),1.36(t,J=7.1Hz,3...

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Abstract

The invention provides a polysubstituted benzo bicyclo[2.2.2]octane derivative with a structural formula shown as (I). The preparation method of the derivative includes: at room temperature or in airor nitrogen atmosphere, dissolving o-benzene diene derivative and a compound containing olefin structure in an organic solvent, mixing the substances evenly, subjecting the mixture to illumination under UV light, after complete reaction, conducting rotary evaporation of the solvent, and then carrying out silica gel column chromatography for separation and purification. The polysubstituted benzo bicyclo[2.2.2]octane derivative provided by the invention has a lot of biological activity and enormous research value, the preparation method can be carried out under normal temperature and pressure, the reaction conditions are mild, transition metal catalysis is unnecessary, and the method has the advantages of simple operation, no pollution, safety and environmental protection, low cost and the like. Specifically, R1 and R2 ester group, acyl or nitrile group, R3 is hydrogen, alkoxy, halogen or alkyl; and X is O, NH, N-CH3, N-C2H5, N-phenyl, N-tert-butyl or N-benzyl.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and in particular relates to a multi-substituted benzobicyclo[2.2.2]octane derivative and a preparation method thereof. Background technique [0002] The bicyclo[2.2.2]octane carbon skeleton widely exists in biologically active natural products and non-natural products. Due to the inherent stereostructure of bicyclo, it is an important raw material for the synthesis of other natural products. For example, cutting bicyclo Any carbon-carbon bond can be added to obtain cis-1,4-disubstituted cyclohexane. According to literature reports, a series of benzobicyclo[2.2.2]octane derivatives have a variety of biological activities, the structure of which is shown in the following compounds 1-3, wherein compound 1 is a calcium ion channel blocker, compound 2 is A cannabinoid receptor ligand, compound 3 is a tumor necrosis factor-α inhibitor, so the synthesis of multi-substituted benzobicyclo[2.2.2]octane d...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D209/58C07D307/00
Inventor 夏吾炯刘强郭小忠冯永胜徐景祥章丽袁鹏
Owner ZHEJIANG SHENGXIAO CHEM
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