1,1-Spironorbornane-pyrano[4,3-b]chromones and their preparation methods and applications
A technology for chromone compounds and spironorbornane, which is applied in the field of medicinal chemistry and can solve the problems of inability to obtain anti-tumor drugs and few types of compound sources.
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[0027] The present invention also provides a preparation method of 1,1-spironorbornane-pyrano[4,3-b]chromones, comprising the following steps: 3-iodochromones, α- Bromoacetophenone compounds, norbornene, base compounds, palladium catalysts, phosphine ligands and organic solvents are mixed for a series cyclization reaction to obtain 1,1-spironorbornane-pyrano[4,3 -b] chromones;
[0028] The 3-iodochromone compound has a structure shown in formula II, and the α-bromoacetophenone compound has a structure shown in formula III,
[0029]
[0030] Among them, R 1 , R 2 , R 3 , R 4 , R 5 independently H, halogen, nitro, cyano, C 1 ~C 10 Alkyl, C 1 ~C 10 Alkoxy, aldehyde, ester, amino, heteroaryl, phenyl, alkyl-substituted phenyl or alkoxy-substituted phenyl. The reaction formula of above-mentioned series cyclization reaction is as shown in formula (1):
[0031]
[0032] Wherein, compound 1 is 3-iodochromone compound, compound 2 is α-bromoacetophenone compound, compoun...
Embodiment 1
[0048] 3-iodochromone (0.4mmol), α-bromoacetophenone (0.4mmol), norbornene (0.8mmol, 150.6mg), Pd (OPiv) 2 (Palladium pivalate) (0.04mmol, 12.3mg), P(4-F-C 6 h 4 ) 3 (Tris(4-fluorophenyl)phosphine) (0.08mmol, 25.3mg), K 3 PO 4 (0.8mmol, 169.8mg) and 2.5mL of mesitylene were added to a 4mL reaction flask, reacted at 100°C for 24h, after the reaction was completed, cooled to room temperature, and the resulting reaction solution was subjected to column chromatography (the eluent was acetic acid Ethyl ester and petroleum ether are mixed according to the ratio of 10:1 by volume), and the solution obtained by column chromatography is removed from the solvent to obtain a yellow solid with a yield of 118.5mg and a yield of 83%. After testing, its diastereoselective The sex ratio is 88:12, and the melting point is 163.2~165.0℃.
[0049] The above-mentioned yellow solid was characterized by single crystal-X-ray diffraction, and the results were as follows: figure 1 shown. Depend ...
Embodiment 2
[0056] The 3-iodochromone in Example 1 was replaced by 3-iodo-5-methoxychromone, and the other conditions were the same as in Example 1 to finally obtain a yellow solid with a yield of 80.4 mg and a yield of 52%. Its diastereoselectivity was detected to be 90:10, and its melting point was 170.8-171.2°C.
[0057] The above-mentioned yellow solid was subjected to NMR characterization, and the specific result data are as follows:
[0058] 1 H NMR (400MHz, CDCl 3 )δ(major+minor)7.83-7.81(m, 0.20H), 7.78-7.76(m, 1.80H), 7.48-7.47(m, 0.4H), 7.46-7.42(m, 3.60H), 6.94(dd , J=8.4, 0.92Hz, 1H), 6.75(d, J=8.0Hz, 1H), 6.28(s, 0.10H), 6.23(s, 0.90H), 3.96(s, 3H), 3.77(dd, J=13.4, 2.0Hz, 1H), 2.86(d, J=4.4Hz, 0.90H), 2.75(d, J=3.8Hz, 0.10H), 2.48-2.44(m, 1H), 2.29(d, J =10.8Hz, 0.20H), 1.95-1.90(t, J=11.4Hz, 1.80H), 1.76(d, J=13.2Hz, 1H), 1.51-1.42(m, 1H), 1.29-1.24(m, 2H), 1.14(d, J=9.8Hz, 1H);
[0059] 13 C NMR (100MHz, CDCl 3 )δ(major+minor) 176.0, 161.5, 160.1, 159.9, 156.9, 133...
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