CN108997298B - Synthetic method of naphtho [1,8-bc ] pyran compound - Google Patents
Synthetic method of naphtho [1,8-bc ] pyran compound Download PDFInfo
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Abstract
The invention discloses a naphtho [1,8-bc]The synthesis method of pyran compounds uses alpha-substituted acetophenone compounds and diazo compounds as raw materials, and directly obtains naphtho [1,8-bc]The pyran compound, namely the naphthalene ring and the pyran ring are simultaneously constructed in one-pot reaction, has the advantages of simple and convenient operation process, mild conditions, wide substrate application range and the like, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a synthetic method of a naphtho [1,8-bc ] pyran compound.
Background
The naphtho [1,8-bc ] pyran is an important oxygen-containing fused heterocycle, and has important development and application values in the research fields of biology, medicine, materials and the like due to the special structure, physicochemical property and obvious biological activity of the naphtho [1,8-bc ] pyran. In addition, naphtho [1,8-bc ] pyrans are core structural skeletons of many natural products. In view of its importance, several methods have been developed to construct the structural skeleton of naphtho [1,8-bc ] pyran. Although most of the existing synthetic methods are effective and reliable, the defects of expensive raw materials, complex operation, harsh conditions, low atom economy and the like exist, so that the existing synthetic methods cannot be widely applied to actual production. Therefore, research and development of the naphtho [1,8-bc ] pyran compound which is synthesized by taking cheap and easily available reagents as raw materials through simple and convenient operation steps have important theoretical significance and application value.
Disclosure of Invention
The technical problem solved by the invention is to provide a synthetic method of a naphtho [1,8-bc ] pyran compound, which takes an alpha-substituted acetophenone compound and a diazo compound as raw materials, directly obtains the naphtho [1,8-bc ] pyran compound through C-H bond activation and series reaction, namely simultaneously constructs a naphthalene ring and a pyran ring in a one-pot reaction, has the advantages of simple and convenient operation process, mild conditions, wide substrate application range and the like, and is suitable for industrial production.
The invention adopts the following technical scheme for solving the technical problems, and the synthetic method of the naphtho [1,8-bc ] pyran compound is characterized in that: dissolving an alpha-substituted acetophenone compound 1 and a diazo compound 2 in a solvent, then adding a catalyst and an additive, and reacting at 60-100 ℃ in an air atmosphere to obtain a naphtho [1,8-bc ] pyran compound 3, wherein the reaction equation in the synthesis method is as follows:
wherein R is1Is hydrogen, C1-6Straight or branched chain alkyl, alkoxy, trifluoromethyl, fluorine, chlorine, alkoxycarbonyl, alkyl formyl, phenyl or substituted phenyl, wherein the alkyl in the alkoxy is C1-6Alkyl, alkoxy in alkoxycarbonyl being C1-6Alkoxy, the alkyl group in the alkylcarboxyl group being C1-6Alkyl, the substituent in the substituted phenyl being C1-4Alkyl or halogen, R2Is cyano, benzenesulfonyl, substituted benzenesulfonyl or alkoxycarbonyl, the substituent in substituted benzenesulfonyl is C1-4Alkyl or halogen, alkoxy in alkoxycarbonyl being C1-4Alkoxy radical, R3Is hydrogen, C1-4Straight-chain or branched alkyl, phenyl or substituted phenyl, the substituent in the substituted phenyl being C1-4Alkyl or halogen, R4Is hydrogen, C1-4Straight-chain or branched alkyl, phenyl or substituted phenyl, the substituent in the substituted phenyl being C1-4Alkyl or halogen, N is 1 or 2, the solvent is N, N-dimethylformamide, 1, 2-dichloroethane, tetrahydrofuran, acetonitrile, toluene or dioxane, and the catalyst is dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer ([ RhCp Cl [ ]2]2) The additive is one or more of copper acetate monohydrate, silver hexafluoroantimonate, sodium acetate, cesium acetate, copper acetylacetonate or silver acetate.
Further preferably, the amount ratio of the alpha-substituted acetophenone compound 1, the diazo compound 2, the catalyst and the additive is 1:2-3:0.05: 0.5-3.
Compared with the prior art, the invention has the following advantages: (1) the synthetic process is simple and efficient, the naphtho [1,8-bc ] pyran compounds are directly synthesized by utilizing one-pot series reaction of the alpha-substituted acetophenone compounds and the diazo compounds, namely, a naphthalene ring and a pyran ring are simultaneously constructed through one-pot reaction, the synthetic efficiency is high, and the requirements of green chemistry are met; (2) the raw materials are cheap and easy to obtain or the raw materials are easy to prepare; (3) the reaction condition is mild, and the operation is simple and convenient; (4) the application range of the substrate is wide. Therefore, the invention provides an economical and practical new method for synthesizing the naphtho [1,8-bc ] pyran compound.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Example 1
1a (0.5mmol,73mg), 2a (1.25mmol,173mg), dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer (0.025mmol,15mg), copper acetate monohydrate (1mmol,200mg) and N, N-dimethylformamide (2mL) were added to a 15mL pressure resistant tube, the reaction tube was sealed under an air atmosphere, and then placed in an 80 ℃ oil bath to stir for reaction for 14 hours. The reaction mixture was quenched with 10mL of water, extracted with ethyl acetate (10 mL. times.3), and the organic phase was washed with water and saturated brine, and dried over anhydrous sodium sulfate. Filtration, spin-drying and separation on silica gel column (petroleum ether/ethyl acetate 5/1) gave the product 3aa (25mg, 14%) as a yellow solid. The characterization data for this compound are as follows:1H NMR(600MHz,CDCl3)δ:2.18-2.22(m,4H),2.66(t,J＝7.2Hz,2H),2.73(t,J＝6.6Hz,2H),2.90(t,J＝6.6Hz,2H),3.16(t,J＝6.0Hz,2H),7.62-7.65(m,1H),8.66(d,J＝7.2Hz,1H),9.11(d,J＝8.4Hz,1H).13C NMR(100MHz,CDCl3)δ:19.8,22.0,28.4,29.7,38.8,40.3,92.8,113.1,114.1,120.37,120.45,122.4,124.5,125.0,134.0,134.3,148.4,157.1,168.0,196.4,197.5.HRMS calcd forC21H15NNaO3:352.0944[M+Na]+,found:352.0944。
example 2
As described in example 1, 1a (0.5mmol,73mg), 2a (1.25mmol,173mg), dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer (0.025mmol,15mg), copper acetate monohydrate (1mmol,200mg), silver hexafluoroantimonate (0.25mmol,86mg) and N, N-dimethylformamide (2mL) were charged into a 15mL pressure-resistant tube, the reaction tube was sealed under an air atmosphere, and then placed in an oil bath at 80 ℃ and stirred for reaction for 14 hours. The reaction mixture was quenched with 10mL of water, extracted with ethyl acetate (10 mL. times.3), and the organic phase was washed with water and saturated brine, and dried over anhydrous sodium sulfate. Filtration, spin-drying and separation on silica gel column (petroleum ether/ethyl acetate 5/1) gave the product 3aa (26mg, 16%) as a yellow solid.
Example 3
As described in example 1, 1a (0.5mmol,73mg), 2a (1.25mmol,173mg), dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer (0.025mmol,15mg), copper acetate monohydrate (1mmol,200mg), sodium acetate (0.25mmol,21mg) and N, N-dimethylformamide (2mL) were charged into a 15mL pressure-resistant tube, the reaction tube was sealed under an air atmosphere, and then placed in an oil bath at 80 ℃ and stirred for reaction for 14 hours. The reaction mixture was quenched with 10mL of water, extracted with ethyl acetate (10 mL. times.3), and the organic phase was washed with water and saturated brine, and dried over anhydrous sodium sulfate. Filtration, spin-drying and separation on silica gel column (petroleum ether/ethyl acetate 5/1) gave the product 3aa (66mg, 40%) as a yellow solid.
Example 4
As described in example 1, 1a (0.5mmol,73mg), 2a (1.25mmol,173mg), dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer (0.025mmol,15mg), copper acetate monohydrate (1mmol,200mg), cesium acetate (0.25mmol,48mg) and N, N-dimethylformamide (2mL) were charged into a 15mL pressure-resistant tube, and the reaction tube was sealed under an air atmosphere and then placed in an oil bath at 80 ℃ to be stirred for reaction for 14 hours. The reaction mixture was quenched with 10mL of water, extracted with ethyl acetate (10 mL. times.3), and the organic phase was washed with water and saturated brine, and dried over anhydrous sodium sulfate. Filtration, spin-drying and separation on silica gel column (petroleum ether/ethyl acetate 5/1) gave the product 3aa (81mg, 49%) as a yellow solid.
Example 5
As described in example 1, 1a (0.5mmol,73mg), 2a (1.25mmol,173mg), dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer (0.025mmol,15mg), copper acetate monohydrate (1mmol,200mg), cesium acetate (0.25mmol,48mg) and 1, 2-dichloroethane (2mL) were charged into a 15mL pressure-resistant tube, the reaction tube was sealed under an air atmosphere, and then placed in an oil bath at 80 ℃ and stirred for reaction for 14 hours. The reaction mixture was quenched with 10mL of water, extracted with ethyl acetate (10 mL. times.3), and the organic phase was washed with water and saturated brine, and dried over anhydrous sodium sulfate. Filtration, spin-drying and separation on silica gel column (petroleum ether/ethyl acetate 5/1) gave the product 3aa (145mg, 88%) as a yellow solid.
Example 6
As described in example 1, 1a (0.5mmol,73mg), 2a (1.25mmol,173mg), dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer (0.025mmol,15mg), copper acetate monohydrate (1mmol,200mg), cesium acetate (0.25mmol,48mg) and tetrahydrofuran (2mL) were charged into a 15mL pressure-resistant tube, the reaction tube was sealed under an air atmosphere, and then placed in an 80 ℃ oil bath and stirred for reaction for 14 hours. The reaction mixture was quenched with 10mL of water, extracted with ethyl acetate (10 mL. times.3), and the organic phase was washed with water and saturated brine, and dried over anhydrous sodium sulfate. Filtration, spin-drying and separation on silica gel column (petroleum ether/ethyl acetate 5/1) gave the product 3aa (117mg, 71%) as a yellow solid.
Example 7
As described in example 1, 1a (0.5mmol,73mg), 2a (1.25mmol,173mg), dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer (0.025mmol,15mg), copper acetate monohydrate (1mmol,200mg), cesium acetate (0.25mmol,48mg) and dioxane (2mL) were charged into a 15mL pressure resistant tube, the reaction tube was sealed under an air atmosphere, and then placed in an 80 ℃ oil bath to stir for reaction for 14 hours. The reaction mixture was quenched with 10mL of water, extracted with ethyl acetate (10 mL. times.3), and the organic phase was washed with water and saturated brine, and dried over anhydrous sodium sulfate. Filtration, spin-drying and separation on silica gel column (petroleum ether/ethyl acetate 5/1) gave the product 3aa (125mg, 76%) as a yellow solid.
Example 8
As described in example 1, 1a (0.5mmol,73mg), 2a (1.25mmol,173mg), dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer (0.025mmol,15mg), copper acetate monohydrate (1mmol,200mg), cesium acetate (0.25mmol,48mg) and acetonitrile (2mL) were charged into a 15mL pressure resistant tube, the reaction tube was sealed under an air atmosphere, and then placed in an 80 ℃ oil bath and stirred for reaction for 14 hours. The reaction mixture was quenched with 10mL of water, extracted with ethyl acetate (10 mL. times.3), and the organic phase was washed with water and saturated brine, and dried over anhydrous sodium sulfate. Filtration, spin-drying and separation on silica gel column (petroleum ether/ethyl acetate 5/1) gave the product 3aa (119mg, 72%) as a yellow solid.
Example 9
As described in example 1, 1a (0.5mmol,73mg), 2a (1.25mmol,173mg), dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer (0.025mmol,15mg), copper acetate monohydrate (1mmol,200mg), cesium acetate (0.25mmol,48mg) and toluene (2mL) were charged into a 15mL pressure-resistant tube, the reaction tube was sealed under an air atmosphere, and then placed in an 80 ℃ oil bath and stirred for reaction for 14 hours. The reaction mixture was quenched with 10mL of water, extracted with ethyl acetate (10 mL. times.3), and the organic phase was washed with water and saturated brine, and dried over anhydrous sodium sulfate. Filtration, spin-drying and separation on silica gel column (petroleum ether/ethyl acetate 5/1) gave the product 3aa (120mg, 73%) as a yellow solid.
Example 10
As described in example 1, 1a (0.5mmol,73mg), 2a (1.25mmol,173mg), dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer (0.025mmol,15mg), copper acetate (1mmol,182mg), cesium acetate (0.25mmol,48mg) and 1, 2-dichloroethane (2mL) were charged into a 15mL pressure-resistant tube, the reaction tube was sealed under an air atmosphere, and then placed in an 80 ℃ oil bath and stirred for reaction for 14 hours. The reaction mixture was quenched with 10mL of water, extracted with ethyl acetate (10 mL. times.3), and the organic phase was washed with water and saturated brine, and dried over anhydrous sodium sulfate. Filtration, spin-drying and separation on silica gel column (petroleum ether/ethyl acetate 5/1) gave the product 3aa (100mg, 61%) as a yellow solid.
Example 11
As described in example 1, 1a (0.5mmol,73mg), 2a (1.25mmol,173mg), dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer (0.025mmol,15mg), copper acetylacetonate (1mmol,262mg), cesium acetate (0.25mmol,48mg) and 1, 2-dichloroethane (2mL) were charged into a 15mL pressure-resistant tube, and the reaction tube was sealed under an air atmosphere and then placed in an oil bath at 80 ℃ to be stirred for reaction for 14 hours. The reaction mixture was quenched with 10mL of water, extracted with ethyl acetate (10 mL. times.3), and the organic phase was washed with water and saturated brine, and dried over anhydrous sodium sulfate. Filtration, spin-drying and separation on silica gel column (petroleum ether/ethyl acetate 5/1) gave the product 3aa (110mg, 67%) as a yellow solid.
Example 12
As described in example 1, 1a (0.5mmol,73mg), 2a (1.25mmol,173mg), dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer (0.025mmol,15mg), silver acetate (1mmol,167mg), cesium acetate (0.25mmol,48mg) and 1, 2-dichloroethane (2mL) were charged into a 15mL pressure-resistant tube, the reaction tube was sealed under an air atmosphere, and then placed in an 80 ℃ oil bath and stirred for reaction for 14 hours. The reaction mixture was quenched with 10mL of water, extracted with ethyl acetate (10 mL. times.3), and the organic phase was washed with water and saturated brine, and dried over anhydrous sodium sulfate. Filtration, spin-drying and separation on silica gel column (petroleum ether/ethyl acetate 5/1) gave the product 3aa (114mg, 69%) as a yellow solid.
Example 13
As described in example 1, 1a (0.5mmol,73mg), 2a (1.25mmol,173mg), dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer (0.025mmol,15mg), cesium acetate (0.25mmol,48mg) and 1, 2-dichloroethane (2mL) were charged into a 15mL pressure-resistant tube, the reaction tube was sealed under an air atmosphere, and then placed in an oil bath at 100 ℃ to be stirred for reaction for 14 hours. The reaction mixture was quenched with 10mL of water, extracted with ethyl acetate (10 mL. times.3), and the organic phase was washed with water and saturated brine, and dried over anhydrous sodium sulfate. Filtration, spin-drying and separation on silica gel column (petroleum ether/ethyl acetate 5/1) gave the product 3aa (12mg, 7%) as a yellow solid.
Example 14
As described in example 1, 1a (0.5mmol,73mg), 2a (1.25mmol,173mg), dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer (0.025mmol,15mg), cesium acetate (1mmol,192mg) and 1, 2-dichloroethane (2mL) were charged into a 15mL pressure resistant tube, the reaction tube was sealed under an air atmosphere, and then placed in an oil bath at 100 ℃ and stirred for reaction for 14 hours. The reaction mixture was quenched with 10mL of water, extracted with ethyl acetate (10 mL. times.3), and the organic phase was washed with water and saturated brine, and dried over anhydrous sodium sulfate. Filtration, spin-drying and separation on silica gel column (petroleum ether/ethyl acetate 5/1) gave the product 3aa (48mg, 29%) as a yellow solid.
Example 15
As described in example 1, 1a (0.5mmol,73mg), 2a (1mmol,138mg), dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer (0.025mmol,15mg), copper acetate monohydrate (1mmol,200mg), cesium acetate (0.25mmol,48mg) and 1, 2-dichloroethane (2mL) were charged into a 15mL pressure-resistant tube, the reaction tube was sealed under an air atmosphere, and then placed in a 60 ℃ oil bath to stir for reaction for 14 hours. The reaction mixture was quenched with 10mL of water, extracted with ethyl acetate (10 mL. times.3), and the organic phase was washed with water and saturated brine, and dried over anhydrous sodium sulfate. Filtration, spin-drying and separation on silica gel column (petroleum ether/ethyl acetate 5/1) gave the product 3aa (92mg, 56%) as a yellow solid.
Example 16
As described in example 1, 1a (0.5mmol,73mg), 2a (1.5mmol,207mg), dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer (0.025mmol,15mg), copper acetate monohydrate (1mmol,200mg), cesium acetate (0.25mmol,48mg) and 1, 2-dichloroethane (2mL) were charged into a 15mL pressure-resistant tube, the reaction tube was sealed under an air atmosphere, and then placed in an oil bath at 100 ℃ and stirred for reaction for 14 hours. The reaction mixture was quenched with 10mL of water, extracted with ethyl acetate (10 mL. times.3), and the organic phase was washed with water and saturated brine, and dried over anhydrous sodium sulfate. Filtration, spin-drying and separation on silica gel column (petroleum ether/ethyl acetate 5/1) gave the product 3aa (134mg, 81%) as a yellow solid.
Example 17
As described in example 1, 1b (0.5mmol,80mg), 2a (1.25mmol,173mg), dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer (0.025mmol,15mg), copper acetate monohydrate (1mmol,200mg), cesium acetate (0.25mmol,48mg) and 1, 2-dichloroethane (2mL) were charged into a 15mL pressure-resistant tube, the reaction tube was sealed under an air atmosphere, and then placed in an oil bath at 80 ℃ and stirred for reaction for 14 hours. The reaction mixture was quenched with 10mL of water, extracted with ethyl acetate (10 mL. times.3), and the organic phase was washed with water and saturated brine, and dried over anhydrous sodium sulfate. Filtration, spin-drying and separation on silica gel (petrol ether/ethyl acetate 5/1) gave the product 3ba (160mg, 92%) as a yellow solid. The characterization data for this compound are as follows:1H NMR(400MHz,CDCl3)δ:2.17-2.23(m,4H),2.49(s,3H),2.65(t,J＝6.8Hz,2H),2.72(t,J＝6.8Hz,2H),2.89(t,J＝6.4Hz,2H),3.16(t,J＝6.0Hz,2H),8.50(s,1H),8.94(s,1H).13C NMR(100MHz,CDCl3)δ:19.9,22.0,23.4,28.5,29.8,38.9,40.4,91.8,112.9,114.3,118.7,121.8,122.0,124.1,124.7,134.2,145.7,148.7,157.0,168.1,196.6,197.6.HRMS calcd for C22H18NO3:344.1281[M+H]+,found:344.1282。
example 18
1c (0.5mmol,101mg), 2a (1.25mmol,173mg), dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer (0.025mmol,15mg), copper acetate monohydrate (1mmol,200mg), cesium acetate (0.25mmol,48mg) and 1, 2-dichloroethane (2mL) were charged into a 15mL pressure-resistant tube as described in example 1, the reaction tube was sealed under an air atmosphere, and then placed in an oil bath at 80 ℃ and stirred for reaction for 14 hours. The reaction mixture was quenched with 10mL of water, extracted with ethyl acetate (10 mL. times.3), and the organic phase was washed with water and saturated brine, and dried over anhydrous sodium sulfate. Filtration, spin-drying and separation on silica gel (petrol ether/ethyl acetate 5/1) gave the product 3ca as a yellow solid (181mg, 94%). The characterization data for this compound are as follows:1H NMR(400MHz,CDCl3)δ:1.36(s,9H),2.09-2.15(m,4H),2.60(t,J＝6.8Hz,2H),2.68(t,J＝6.8Hz,2H),2.85(t,J＝6.4Hz,2H),3.10(t,J＝6.0Hz,2H),8.93(d,J＝1.2Hz,1H),9.29(d,J＝1.2Hz,1H).13C NMR(150MHz,CDCl3)δ:19.9,22.0,28.5,29.8,31.1,36.2,39.0,40.5,91.9,113.3,114.3,118.8,119.1,120.6,122.3,124.7,134.3,148.6,157.0,158.4,168.0,196.7,197.8.HRMS calcd for C25H24NO3:386.1751[M+H]+,found:386.1751。
example 19
As described in example 1, 1d (0.5mmol,88mg), 2a (1.25mmol,173mg), dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer (0.025mmol,15mg), copper acetate monohydrate (1mmol,200mg), cesium acetate (0.25mmol,48mg) and 1, 2-dichloroethane (2mL) were charged into a 15mL pressure-resistant tube, the reaction tube was sealed under an air atmosphere, and then placed in an oil bath at 80 ℃ and stirred for reaction for 14 hours. The reaction mixture was quenched with 10mL of water, extracted with ethyl acetate (10 mL. times.3), and the organic phase was washed with water and saturated brine, and dried over anhydrous sodium sulfate. Filtration, spin-drying and separation on silica gel (petrol ether/ethyl acetate 3/1) gave the product 3da as a yellow solid (162mg, 90%). The characterization data for this compound are as follows:1H NMR(400MHz,CDCl3)δ:2.18-2.22(m,4H),2.67(t,J＝6.4Hz,2H),2.73(t,J＝6.8Hz,2H),2.94(t,J＝6.4Hz,2H),3.19(t,J＝6.0Hz,2H),3.95(s,3H),8.43(d,J＝2.0Hz,1H),8.80(d,J＝2.0Hz,1H).13C NMR(150MHz,CDCl3)δ:19.8,22.0,28.5,29.9,38.8,40.5,55.6,90.5,105.1,111.3,112.6,114.5,115.8,120.8,126.6,136.4,149.8,156.5,164.8,168.5,196.4,197.8.HRMS calcd for C22H18NO4:360.1230[M+H]+,found:360.1243。
example 20
As described in example 1, 1e (0.5mmol,107mg), 2a (1.25mmol,173mg), dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer (0.025mmol,15mg), copper acetate monohydrate (1mmol,200mg), cesium acetate (0.25mmol,48mg) and 1, 2-dichloroethane (2mL) were charged into a 15mL pressure-resistant tube, the reaction tube was sealed under an air atmosphere, and then placed in an oil bath at 80 ℃ and stirred for reaction for 14 hours. The reaction mixture was quenched with 10mL of water, extracted with ethyl acetate (10 mL. times.3), and the organic phase was washed with water and saturated brine, and dried over anhydrous sodium sulfate. Filtration, spin-drying and separation on silica gel (petrol ether/ethyl acetate 5/1) gave the product 3ea as a yellow solid (151mg, 76%). The characterization data for this compound are as follows:1H NMR(400MHz,CDCl3)δ:2.15-2.20(m,4H),2.61(t,J＝6.8Hz,2H),2.70(t,J＝6.8Hz,2H),2.89(t,J＝6.4Hz,2H),3.17(t,J＝6.4Hz,2H),8.86(d,J＝1.2Hz,1H),9.41(s,1H).13C NMR(150MHz,CDCl3)δ:19.7,21.8,28.4,29.7,38.7,40.2,95.0,112.3,113.3,116.1(q,3JC-F＝3.3Hz),121.4,121.7(q,3JC-F＝5.4Hz),122.8,123.7(q,1JC-F＝271.35Hz),126.3,133.3,135.1(q,2JC-F＝31.7Hz),149.4,156.4,168.9,196.0,197.3.HRMScalcd for C22H14F3NNaO3:420.0818[M+Na]+,found:420.0818。
example 21
As described in example 1, 1f (0.5mmol,82mg), 2a (1.25mmol,173mg), dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer (0.025mmol,15mg), copper acetate monohydrate (1mmol,200mg), cesium acetate (0.25mmol,48mg) and 1, 2-dichloroethane (2mL) were charged into a 15mL pressure-resistant tube, the reaction tube was sealed under an air atmosphere, and then placed in an oil bath at 80 ℃ and stirred for reaction for 14 hours. The reaction mixture was quenched with 10mL of water, extracted with ethyl acetate (10 mL. times.3), and the organic phase was washed with water and saturated brine, and dried over anhydrous sodium sulfate. Filtering, spin-drying, separating with silica gel column (petroleum ether/ethyl acetate)Ester 5/1) to yield the product 3fa as a yellow solid (141mg, 81%). The characterization data for this compound are as follows:1H NMR(600MHz,CDCl3)δ:2.20-2.24(m,4H),2.69(t,J＝6.6Hz,2H),2.76(t,J＝6.6Hz,2H),2.97(t,J＝6.6Hz,2H),3.23(t,J＝6.6Hz,2H),8.62(dd,J1＝10.2Hz,J2＝2.4Hz,1H),9.01(dd,J1＝12.0Hz,J2＝2.4Hz,1H).13C NMR(150MHz,CDCl3)δ:19.7,21.9,28.4,29.8,38.6,40.2,92.4,109.8(d,2JC-F＝27.45Hz),110.3(d,2JC-F＝30.75Hz),112.4(d,4JC-F＝3.3Hz),113.8,117.7,121.7(d,4JC-F＝5.4Hz),127.9(d,3JC-F＝13.2Hz),136.0(d,3JC-F＝13.05Hz),149.8,156.7,166.6(d,1JC-F＝249.45Hz),168.9,196.1,197.3.HRMScalcd for C21H14FNNaO3:370.0850[M+Na]+,found:370.0850。
example 22
As described in example 1, 1g (0.5mmol,90mg), 2a (1.25mmol,173mg), dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer (0.025mmol,15mg), copper acetate monohydrate (1mmol,200mg), cesium acetate (0.25mmol,48mg) and 1, 2-dichloroethane (2mL) were charged into a 15mL pressure-resistant tube, the reaction tube was sealed under an air atmosphere, and then placed in an oil bath at 80 ℃ and stirred for reaction for 14 hours. The reaction mixture was quenched with 10mL of water, extracted with ethyl acetate (10 mL. times.3), and the organic phase was washed with water and saturated brine, and dried over anhydrous sodium sulfate. Filtration, spin-drying and separation on silica gel (petrol ether/ethyl acetate 5/1) gave product 3ga (146mg, 80%) as a yellow solid. The characterization data for this compound are as follows:1H NMR(400MHz,CDCl3)δ:2.20-2.25(m,4H),2.67(t,J＝6.8Hz,2H),2.73(t,J＝6.8Hz,2H),2.94(t,J＝6.4Hz,2H),3.20(t,J＝6.0Hz,2H),8.56(d,J＝1.6Hz,1H),9.08(d,J＝1.6Hz,1H).13C NMR(100MHz,CDCl3)δ:19.6,21.8,28.4,29.8,38.6,40.2,93.2,111.8,113.7,118.3,120.5,121.1,123.3,126.2,134.1,141.5,149.7,156.3,169.0,196.1,197.3.HRMS calcd for C21H14ClNNaO3:386.0554[M+Na]+,found:386.0554。
example 23
As described in example 1, 1h (0.5mmol,102mg), 2a (1.25mmol,173mg), dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer (0.025mmol,15mg), copper acetate monohydrate (1mmol,200mg), cesium acetate (0.25mmol,48mg) and 1, 2-dichloroethane (2mL) were charged into a 15mL pressure-resistant tube, the reaction tube was sealed under an air atmosphere, and then placed in an oil bath at 80 ℃ and stirred for reaction for 14 h. The reaction mixture was quenched with 10mL of water, extracted with ethyl acetate (10 mL. times.3), and the organic phase was washed with water and saturated brine, and dried over anhydrous sodium sulfate. Filtration, spin-drying and separation on silica gel (petrol ether/ethyl acetate 5/1) gave the product 3ha (139mg, 72%) as a yellow solid. The characterization data for this compound are as follows:1H NMR(600MHz,CDCl3)δ:2.20-2.28(m,4H),2.68(t,J＝6.6Hz,2H),2.76(t,J＝6.6Hz,2H),2.95(t,J＝6.0Hz,2H),3.23(t,J＝6.0Hz,2H),4.03(s,3H),9.16(s,1H),9.71(s,1H).13C NMR(150MHz,CDCl3)δ:19.7,21.8(d,J＝13.2Hz),28.4,29.7(d,J＝3.3Hz),38.7,40.3,52.9,94.7,112.6,113.6,119.5,121.8,123.0,125.3,126.1,133.1,134.3,149.0,156.4,166.4,168.5,196.1,197.4.HRMS calcd for C23H17NNaO5:410.0999[M+Na]+,found:410.0999。
example 24
1i (0.5mmol,94mg), 2a (1.25mmol,173mg), dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer (0.025mmol,15mg), copper acetate monohydrate (1mmol,200mg), cesium acetate (0.25mmol,48mg) and 1, 2-dichloroethane (2mL), the reaction tube was sealed under an air atmosphere, and then placed in an oil bath at 80 ℃ to stir the reaction for 14 hours. The reaction mixture was quenched with 10mL of water, extracted with ethyl acetate (10 mL. times.3), and the organic phase was washed with water and saturated brine, and dried over anhydrous sodium sulfate. Filtration, spin-drying and separation on silica gel (petroleum ether/ethyl acetate 5/1) gave the product 3ia (132mg, 71%) as a yellow solid. The characterization data for this compound are as follows:1H NMR(400MHz,CDCl3)δ:2.22-2.25(m,4H),2.67-2.69(m,5H),2.75(t,J＝6.8Hz,2H),2.93(t,J＝6.4Hz,2H),3.20(t,J＝6.0Hz,2H),9.11(s,1H),9.64(s,1H).13C NMR(100MHz,CDCl3)δ:19.7,21.8,27.0,28.4,29.7,38.7,40.3,94.7,112.7,113.6,118.3,121.7,123.1,125.2,125.5,133.5,140.5,149.0,156.4,168.4,196.2,197.5,198.1.HRMScalcd for C23H17NNaO4:394.1050[M+Na]+,found:394.1045。
example 25
1j (0.5mmol,130mg), 2a (1.25mmol,173mg), dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer (0.025mmol,15mg), copper acetate monohydrate (1mmol,200mg), cesium acetate (0.25mmol,48mg) and 1, 2-dichloroethane (2mL) were charged into a 15mL pressure-resistant tube as described in example 1, the reaction tube was sealed under an air atmosphere, and then placed in an oil bath at 80 ℃ and stirred for reaction for 14 hours. The reaction mixture was quenched with 10mL of water, extracted with ethyl acetate (10 mL. times.3), and the organic phase was washed with water and saturated brine, and dried over anhydrous sodium sulfate. Filtration, spin-drying and separation on silica gel (petrol ether/ethyl acetate 5/1) gave the product 3ja as a yellow solid (144mg, 65%). The characterization data for this compound are as follows:1H NMR(400MHz,CDCl3)δ:2.04-2.17(m,4H),2.54-2.60(m,4H),2.77(t,J＝6.8Hz,2H),3.70(t,J＝6.0Hz,2H),7.53-7.65(m,3H),7.71(t,J＝8.0Hz,1H),7.97(d,J＝7.6Hz,2H),8.75(d,J＝7.6Hz,1H),9.04(d,J＝8.8Hz,1H).13C NMR(100MHz,CDCl3)δ:19.7,22.2,27.9,28.8,38.7,40.0,112.7,118.8,120.2,120.8,124.1,124.5,125.3,126.8,129.0,133.2,133.7,134.4,143.6,147.1,152.9,167.3,196.2,198.6.HRMS calcd forC26H21O5S:445.1104[M+H]+,found:445.1104。
example 26
1k (0.5mmol,137mg), 2a (1.25mmol,173mg), dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer (0.025mmol,15mg), copper acetate monohydrate (1mmol,200mg), cesium acetate (0.25mmol,48mg) and 1, 2-dichloroethane (2mL) were charged into a 15mL pressure-resistant tube as described in example 1, the reaction tube was sealed under an air atmosphere, and then placed in an oil bath at 80 ℃ and stirred for reaction for 14 hours. The reaction mixture was quenched with 10mL of water, extracted with ethyl acetate (10 mL. times.3), and the organic phase was washed with water and saturated brine, and dried over anhydrous sodium sulfate. Filtration, spin-drying and separation on silica gel (petrol ether/ethyl acetate 5/1) gave the product 3ka as a yellow solid (140mg, 61%). The characterization data for this compound are as follows:1H NMR(400MHz,CDCl3)δ:2.01-2.06(m,4H),2.37(s,3H),2.49(t,J＝6.8Hz,2H),2.58(t,J＝6.4Hz,2H),2.68(t,J＝6.8Hz,2H),3.61(t,J＝6.0Hz,2H),7.26(d,J＝8.0Hz,2H),7.57(t,J＝8.4Hz,1H),7.79(d,J＝8.0Hz,2H),8.63(d,J＝7.6Hz,1H),8.93(d,J＝8.8Hz,1H).13C NMR(100MHz,CDCl3)δ:19.7,21.7,22.2,28.0,28.8,38.7,40.0,112.7,119.2,120.0,120.8,124.0,124.4,125.3,127.0,129.5,133.5,134.2,140.5,144.2,147.1,152.9,167.4,196.3,198.6.HRMS calcd for C27H22NaO5S:481.1080[M+Na]+,found:481.1080。
example 27
1l (0.5mmol,147mg), 2a (1.25mmol,173mg), dichloro (pentamethylene) were introduced into a 15mL pressure-resistant tube as described in example 1Cyclopentadienyl) rhodium (III) dimer (0.025mmol,15mg), copper acetate monohydrate (1mmol,200mg), cesium acetate (0.25mmol,48mg) and 1, 2-dichloroethane (2mL), the reaction tube was sealed under an air atmosphere, and then placed in an oil bath at 80 ℃ and stirred for reaction for 14 hours. The reaction mixture was quenched with 10mL of water, extracted with ethyl acetate (10 mL. times.3), and the organic phase was washed with water and saturated brine, and dried over anhydrous sodium sulfate. Filtration, spin-drying and separation on silica gel (petrol ether/ethyl acetate 5/1) gave the product 3la as a yellow solid (158mg, 66%). The characterization data for this compound are as follows:1H NMR(400MHz,CDCl3)δ:2.02-2.09(m,4H),2.52(t,J＝6.8Hz,2H),2.57(t,J＝6.4Hz,2H),2.69(t,J＝6.8Hz,2H),3.59(t,J＝6.0Hz,2H),7.45(d,J＝8.4Hz,2H),7.65(t,J＝8.4Hz,1H),7.84(d,J＝8.4Hz,2H),8.69(d,J＝7.6Hz,1H),8.96(d,J＝8.8Hz,1H).13C NMR(150MHz,CDCl3)δ:19.7,22.2,28.0,28.8,38.7,40.0,112.8,118.3,120.3,120.8,124.2,124.5,125.3,128.4,129.3,133.9,134.4,139.8,141.9,146.9,153.1,167.1,196.2,198.5.HRMS calcd for C26H19ClNaO5S:501.0534[M+Na]+,found:501.0532。
example 28
As described in example 1, 1m (0.5mmol,147mg), 2a (1.25mmol,173mg), dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer (0.025mmol,15mg), copper acetate monohydrate (1mmol,200mg), cesium acetate (0.25mmol,48mg) and 1, 2-dichloroethane (2mL) were charged into a 15mL pressure-resistant tube, the reaction tube was sealed under an air atmosphere, and then placed in an oil bath at 80 ℃ and stirred for reaction for 14 hours. The reaction mixture was quenched with 10mL of water, extracted with ethyl acetate (10 mL. times.3), and the organic phase was washed with water and saturated brine, and dried over anhydrous sodium sulfate. Filtration, spin-drying and separation on silica gel (petrol ether/ethyl acetate 5/1) gave the product 3ma (144mg, 60%) as a yellow solid. The characterization data for this compound are as follows:1H NMR(600MHz,CDCl3)δ:2.01-2.08(m,4H),2.50(t,J＝6.6Hz,2H),2.54(t,J＝6.6Hz,2H),2.69(t,J＝6.6Hz,2H),3.62(t,J＝6.0Hz,2H),7.49(t,J＝7.8Hz,2H),7.57(t,J＝7.8Hz,1H),7.90(d,J＝7.8Hz,2H),8.68(s,1H),9.04(s,1H).13CNMR(150MHz,CDCl3)δ:19.6,22.1,28.0,28.9,38.5,39.9,111.8,119.1,119.2,120.7,123.1,123.7,126.80,126.84,129.1,133.4,134.9,141.2,143.3,148.3,152.6,168.1,195.8,198.2.HRMS calcd for C26H19ClNaO5S:501.0534[M+Na]+,found:501.0534。
example 29
1n (0.5mmol,168mg), 2a (1.25mmol,173mg), dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer (0.025mmol,15mg), copper acetate monohydrate (1mmol,200mg), cesium acetate (0.25mmol,48mg) and 1, 2-dichloroethane (2mL) were charged into a 15mL pressure-resistant tube as described in example 1, the reaction tube was sealed under an air atmosphere, and then placed in an oil bath at 80 ℃ and stirred for reaction for 14 hours. The reaction mixture was quenched with 10mL of water, extracted with ethyl acetate (10 mL. times.3), and the organic phase was washed with water and saturated brine, and dried over anhydrous sodium sulfate. Filtration, spin-drying and separation on silica gel (petrol ether/ethyl acetate 5/1) gave the product 3na as a yellow solid (159mg, 61%). The characterization data for this compound are as follows:1H NMR(400MHz,CDCl3)δ:1.99-2.08(m,4H),2.47-2.53(m,4H),2.70(t,J＝6.4Hz,2H),3.62(t,J＝5.6Hz,2H),7.31(t,J＝7.2Hz,1H),7.39(t,J＝7.6Hz,2H),7.47(t,J＝7.2Hz,2H),7.54(t,J＝6.8Hz,1H),7.69(d,J＝7.2Hz,2H),7.90(d,J＝7.6Hz,2H),9.03(s,1H),9.30(s,1H).13C NMR(150MHz,CDCl3)δ:19.7,22.3,28.0,28.9,38.7,40.1,112.7,118.5,119.3,119.8,122.6,124.1,125.9,126.8,127.9,128.4,128.9,129.0,133.2,134.7,140.3,143.6,146.0,147.7,152.8,167.6,196.3,198.6.HRMS calcd for C32H25O5S:521.1417[M+H]+,found:521.1417。
example 30
1o (0.5mmol,96mg), 2a (1.25mmol,173mg), dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer (0.025mmol,15mg), copper acetate monohydrate (1mmol,200mg), cesium acetate (0.25mmol,48mg) and 1, 2-dichloroethane (2mL) were charged into a 15mL pressure-resistant tube as described in example 1, the reaction tube was sealed under an air atmosphere, and then placed in an oil bath at 80 ℃ and stirred for reaction for 14 hours. The reaction mixture was quenched with 10mL of water, extracted with ethyl acetate (10 mL. times.3), and the organic phase was washed with water and saturated brine, and dried over anhydrous sodium sulfate. Filtration, spin-drying and separation on silica gel (petrol ether/ethyl acetate 5/1) gave the product 3oa as a yellow solid (68mg, 36%). The characterization data for this compound are as follows:1H NMR(400MHz,CDCl3)δ:1.45(t,J＝7.2Hz,3H),2.12-2.16(m,4H),2.62(t,J＝6.8Hz,2H),2.72(t,J＝6.8Hz,2H),2.78(t,J＝6.4Hz,2H),2.99(t,J＝6.0Hz,2H),4.47(q,J＝7.2Hz,2H),7.59-7.63(m,1H),8.67(d,J＝7.2Hz,1H),9.16(d,J＝8.4Hz,1H).13CNMR(150MHz,CDCl3)δ:14.4,19.9,22.3,28.5,28.6,38.9,40.6,61.7,112.7,114.7,119.5,120.8,122.0,124.1,124.8,132.2,133.2,145.1,150.6,166.3,168.2,196.6,198.4.HRMS calcdfor C23H21O5:377.1384[M+H]+,found:377.1374。
example 31
As described in example 1, 1a (0.5mmol,73mg), 2b (1.25mmol,190mg), dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer (0.025mmol,15mg), copper acetate monohydrate (1mmol,200mg), cesium acetate (0.25mmol,48mg) and 1, 2-dichloroethane (2mL) were charged into a 15mL pressure-resistant tube, the reaction tube was sealed under an air atmosphere, and then placed in an oil bath at 80 ℃ and stirred for reaction for 14 hours. The reaction mixture was quenched with 10mL of water, extracted with ethyl acetate (10 mL. times.3), and the organic phase was washed with water and saturated brine, and dried over anhydrous sodium sulfate. Filtering, spin-drying, separating with silica gel column (petroleum ether/ethyl ether)Ethyl acetate 5/1) to yield the product 3ab as a yellow solid (163mg, 91%). The characterization data for this compound are as follows: the product is a mixture of a pair of diastereomers.1H NMR(400MHz,CDCl3)δ:1.10-1.14(m,6H),2.23-2.34(m,4H),2.45-2.67(m,4H),2.77(d,J＝17.6Hz,1H),3.12(d,J＝17.6Hz,1H),7.47(t,J＝8.0Hz,1H),8.48(d,J＝7.6Hz,1H),8.96(d,J＝8.8Hz,1H).13C NMR(150MHz,CDCl3)δ:20.8,21.0,27.59,27.62,29.39,29.40,36.3,37.8,47.1,48.4,92.9,112.7,114.1,120.3,120.5,122.0,124.4,125.0,133.9,134.3,147.8,157.3,167.4,196.4,197.7.HRMS calcdfor C23H20NO3:358.1438[M+H]+,found:358.1439。
Example 32
As described in example 1, 1a (0.5mmol,73mg), 2c (1.25mmol,208mg), dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer (0.025mmol,15mg), copper acetate monohydrate (1mmol,200mg), cesium acetate (0.25mmol,48mg) and 1, 2-dichloroethane (2mL) were charged into a 15mL pressure-resistant tube, the reaction tube was sealed under an air atmosphere, and then placed in an oil bath at 80 ℃ and stirred for reaction for 14 hours. The reaction mixture was quenched with 10mL of water, extracted with ethyl acetate (10 mL. times.3), and the organic phase was washed with water and saturated brine, and dried over anhydrous sodium sulfate. Filtration, spin-drying and separation on silica gel (petrol ether/ethyl acetate 5/1) gave the product 3ac (172mg, 89%) as a yellow solid. The characterization data for this compound are as follows:1H NMR(600MHz,CDCl3)δ:1.15(s,6H),1.21(s,6H),2.53(s,2H),2.61(s,2H),2.81(s,2H),3.10(s,2H),7.77(t,J＝8.4Hz,1H),8.80(d,J＝7.2Hz,1H),9.28(d,J＝8.4Hz,1H).13C NMR(150MHz,CDCl3)δ:28.0,28.2,31.9,33.1,42.0,43.4,52.8,53.9,93.3,112.2,114.2,120.2,120.6,121.5,124.4,124.9,133.8,134.4,146.6,157.7,166.4,196.4,197.8.HRMS calcd for C25H23NNaO3:408.1570[M+Na]+,found:408.1565。
example 33
As described in example 1, 1a (0.5mmol,73mg), 2d (1.25mmol,225mg), dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer (0.025mmol,15mg), copper acetate monohydrate (1mmol,200mg), cesium acetate (0.25mmol,48mg) and 1, 2-dichloroethane (2mL) were charged into a 15mL pressure-resistant tube, the reaction tube was sealed under an air atmosphere, and then placed in an oil bath at 80 ℃ and stirred for reaction for 14 hours. The reaction mixture was quenched with 10mL of water, extracted with ethyl acetate (10 mL. times.3), and the organic phase was washed with water and saturated brine, and dried over anhydrous sodium sulfate. Filtration, spin-drying and separation on silica gel (petrol ether/ethyl acetate 5/1) gave the product 3ad (174mg, 84%) as a yellow solid. The characterization data for this compound are as follows: the product is a mixture of a pair of diastereomers.1H NMR(600MHz,CDCl3)δ:1.03-1.06(m,12H),1.71-1.76(m,2H),2.05-2.10(m,2H),2.39-2.47(m,2H),2.69-2.90(m,5H),3.27(d,J＝16.2Hz,1H),7.68-7.71(m,1H),8.72(d,J＝7.2Hz,1H),9.18(d,J＝8.4Hz,1H).13C NMR(150MHz,CDCl3)δ:20.8,21.0,27.59,27.62,29.39,29.40,36.3,37.8,47.1,48.4,92.9,112.7,114.1,120.3,120.5,122.0,124.4,125.0,133.9,134.3,147.8,157.3,167.4,196.4,197.7.HRMScalcd for C27H27NNaO3:436.1883[M+Na]+,found:436.1884。
Example 34
As described in example 1, 1a (0.5mmol,73mg), 2e (1.25mmol,173mg), dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer (0.025mmol,15mg), copper acetate monohydrate (1mmol,200mg), cesium acetate (0.25mmol,48mg) and 1, 2-dichloroethane (2mL) were charged into a 15mL pressure-resistant tube, the reaction tube was sealed under an air atmosphere, and then placed in an oil bath at 80 ℃ and stirred for reaction for 14 hours. The reaction was quenched with 10mL of water, extracted with ethyl acetate (10 mL. times.3), followed byThe organic phase was washed with water and saturated brine in this order, and dried over anhydrous sodium sulfate. Filtration, spin-drying and separation on silica gel (petrol ether/ethyl acetate 5/1) gave the product 3ae as a yellow solid (176mg, 73%). The characterization data for this compound are as follows: the product is a mixture of a pair of diastereomers.1H NMR(600MHz,CDCl3)δ:2.91-3.03(m,4H),3.14-3.16(m,2H),3.23-3.28(m,1H),3.50-3.52(m,2H),3.59-3.62(m,1H),7.30-7.41(m,10H),7.69-7.72(m,1H),8.76(dd,J1＝7.2Hz,J2＝3.0Hz,1H),9.23(d,J＝8.4Hz,1H).13C NMR(150MHz,CDCl3)δ:35.79,35.83,37.27,37.29,37.7,37.8,39.68,39.73,45.70,45.74,47.11,47.12,92.9,112.8,113.9,120.3,120.40,120.42,121.9,124.5,124.8,126.6,126.8,127.4,127.6,129.0,129.1,133.7,134.4,141.3,142.2,147.6,157.1,167.2,195.6,197.95,197.98.HRMS calcd for C33H23NNaO3:504.1570[M+Na]+,found:504.1568。
Example 35
As described in example 1, 1a (0.5mmol,73mg), 2f (1.25mmol,190mg), dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer (0.025mmol,15mg), copper acetate monohydrate (1mmol,200mg), cesium acetate (0.25mmol,48mg) and 1, 2-dichloroethane (2mL) were charged into a 15mL pressure-resistant tube, the reaction tube was sealed under an air atmosphere, and then placed in an oil bath at 80 ℃ and stirred for reaction for 14 hours. The reaction mixture was quenched with 10mL of water, extracted with ethyl acetate (10 mL. times.3), and the organic phase was washed with water and saturated brine, and dried over anhydrous sodium sulfate. Filtration, spin-drying and separation on silica gel (petrol ether/ethyl acetate 5/1) gave the product 3af (127mg, 71%) as a yellow solid. The characterization data for this compound are as follows:1H NMR(600MHz,CDCl3)δ:1.76-1.80(m,2H),1.89-1.93(m,2H),1.98-1.99(m,4H),2.69(t,J＝6.0Hz,2H),2.79(t,J＝6.6Hz,2H),2.93(t,J＝6.0Hz,2H),3.08(t,J＝7.2Hz,2H),7.54(t,J＝8.4Hz,1H),7.78(d,J＝8.4Hz,2H).13C NMR(100MHz,CDCl3)δ:21.0,22.4,23.0,23.7,29.8,31.8,41.6,42.9,92.3,114.5,117.6,117.8,120.8,121.8,126.4,129.5,132.67,132.74,139.1,156.7,162.9,201.9,207.2.HRMS calcd for C23H20NO3:358.1438[M+H]+,found:358.1427。
example 36
As described in example 1, 1d (0.5mmol,88mg), 2f (1.25mmol,190mg), dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer (0.025mmol,15mg), copper acetate monohydrate (1mmol,200mg), cesium acetate (0.25mmol,48mg) and 1, 2-dichloroethane (2mL) were charged into a 15mL pressure-resistant tube, the reaction tube was sealed under an air atmosphere, and then placed in an oil bath at 80 ℃ and stirred for reaction for 14 hours. The reaction mixture was quenched with 10mL of water, extracted with ethyl acetate (10 mL. times.3), and the organic phase was washed with water and saturated brine, and dried over anhydrous sodium sulfate. Filtration, spin-drying and separation on silica gel (petrol ether/ethyl acetate 5/1) gave the product 3df as a yellow solid (136mg, 70%). The characterization data for this compound are as follows:1H NMR(600MHz,CDCl3)δ:1.76-1.80(m,2H),1.90-1.94(m,2H),1.99-2.00(m,4H),2.70(t,J＝6.0Hz,2H),2.79(t,J＝6.6Hz,2H),2.95(t,J＝5.4Hz,2H),3.08(t,J＝6.6Hz,2H),3.89(s,3H),7.28(d,J＝1.8Hz,1H),7.50(d,J＝2.4Hz,1H).13C NMR(100MHz,CDCl3)δ:20.7,22.3,23.0,23.7,29.8,31.8,41.7,42.9,55.5,90.3,101.9,109.4,114.9,116.2,117.0,127.9,128.0,135.0,140.7,156.3,163.4,163.6,201.8,207.6.HRMS calcd forC24H21NNaO4:410.1363[M+Na]+,found:410.1363。
the foregoing embodiments have described the general principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the present invention, and that various changes and modifications may be made without departing from the scope of the principles of the present invention, and the invention is intended to be covered by the appended claims.
Claims (2)
1. A synthetic method of a naphtho [1,8-bc ] pyran compound is characterized in that: dissolving an alpha-substituted acetophenone compound 1 and a diazo compound 2 in a solvent, then adding a catalyst and an additive, and reacting at 60-100 ℃ in an air atmosphere to obtain a naphtho [1,8-bc ] pyran compound 3, wherein the reaction equation in the synthesis method is as follows:
wherein R is1Is hydrogen, C1-6Straight or branched chain alkyl, alkoxy, trifluoromethyl, fluorine, chlorine, alkoxycarbonyl, alkyl formyl, phenyl or substituted phenyl, wherein the alkyl in the alkoxy is C1-6Alkyl, alkoxy in alkoxycarbonyl being C1-6Alkoxy, the alkyl group in the alkylcarboxyl group being C1-6Alkyl, the substituent in the substituted phenyl being C1-4Alkyl or halogen, R2Is cyano, benzenesulfonyl, substituted benzenesulfonyl or alkoxycarbonyl, the substituent in substituted benzenesulfonyl is C1-4Alkyl or halogen, alkoxy in alkoxycarbonyl being C1-4Alkoxy radical, R3Is hydrogen, C1-4Straight-chain or branched alkyl, phenyl or substituted phenyl, the substituent in the substituted phenyl being C1-4Alkyl or halogen, R4Is hydrogen, C1-4Straight-chain or branched alkyl, phenyl or substituted phenyl, the substituent in the substituted phenyl being C1-4Alkyl or halogen, N is 1 or 2, the solvent is any one of N, N-dimethylformamide, 1, 2-dichloroethane, tetrahydrofuran, acetonitrile, toluene or dioxane, the catalyst is dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer, and the additive is one or more of copper acetate monohydrate, silver hexafluoroantimonate, sodium acetate, cesium acetate, copper acetylacetonate or silver acetate.
2. The method for synthesizing naphtho [1,8-bc ] pyran compounds according to claim 1, characterized in that: the dosage ratio of the alpha-substituted acetophenone compound 1, the diazo compound 2, the catalyst and the additive is 1:2-3:0.05: 0.5-3.
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