7-aminocarbazolesulfonamide derivatives as well as preparation method and application thereof
A technology of aminocarbazole sulfonamide and carbazole sulfonamide, which is applied in the field of medicine and can solve the problems of poor tumor cell inhibitory effect and low antitumor activity
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Embodiment 1
[0100] N-(4-Methoxyphenyl)-7-amino-9-methyl-3-carbazole sulfonamide (9a)
[0101] Step 1. Synthesis of intermediate 9-methyl-7-nitrocarbazole
[0102]
[0103] Reaction a: Under anhydrous and oxygen-free conditions, dissolve 2'-bromoacetanilide and 4-nitrophenylboronic acid pinacol ester in the solvent toluene, then add anhydrous potassium phosphate and Pd(OAc) in sequence 2 And SPhOS, sealed, oil bath to control the reaction temperature around 90 ℃, after 24 hours of reaction, the reaction solution was extracted, washed with water, dried, spin-dried, and passed through the column (PE:EA=4:1) to obtain a yellow solid product. Namely compound 5.
[0104] Among them, the mass of anhydrous potassium phosphate is about twice the mass of 2’-bromoacetanilide, the catalyst Pd(OAc) 2 The amount of SPhOS is about 8% of 2'-bromoacetanilide, and the amount of SPhOS is about 16% of 2'-bromoacetanilide.
[0105] Reaction b: Under anhydrous conditions, dissolve compound 5 in DMSO, and then add mol...
Embodiment 2
[0122] N-(2,4-Dimethoxyphenyl)-7-amino-9-methyl-3-carbazole sulfonamide (9b)
[0123] See Example 1 for the synthesis process, and the specific conditions are as follows:
[0124] Step 3: Compound 1 (60mg, 0.18mmol), Compound 2 (34mg, 0.22mmol) (R 1 = 2,4-OMe), anhydrous K 2 CO 3 (49mg, 0.36mmol), DMF (3mL), room temperature: 8h, column chromatography (PE:EA=1:1).
[0125] The product (denoted as 3b) is a yellow solid, yield: 50%
[0126] 1 H NMR(500MHz, DMSO-d 6 )δppm 9.18(s,1H), 8.64(d,J=7.0Hz,2H), 8.52(d,J=8.5Hz,1H), 8.12(d,J=8.5Hz,1H), 7.86(m,2H ), 7.09(d,J=8.5Hz,1H), 6.43(d,J=8.5Hz,1H), 6.36(s,1H),4.05(s,3H),3.66(s,3H), 3.29(s ,3H). 13 C NMR(101MHz, DMSO-d 6 )δppm 158.6,154.4,145.9,144.3,140.4,132.2,127.9,126.4,121.4,121.3,119.7,117.9,114.6,110.102,106.2,104.6,98.9,55.3,55.2,29.8.MS m / z(%)440( M-1,100).
[0127] Step 4: Reactant 3b (40mg, 0.091mmol), Pd / C (5%) (20% equiv), H 2 : 40Psi, methanol / THF (1:1) 30mL, room temperature: 3-4h, column chromatography (PE:EA=2:3).
[0128] T...
Embodiment 3
[0131] N-(2,5-Dimethoxyphenyl)-7-amino-9-methyl-3-carbazole sulfonamide (9c)
[0132] See Example 1 for the synthesis process, and the specific conditions are as follows:
[0133] Step 3: Compound 1 (110mg, 0.34mmol), Compound 2 (60mg, 0.41mmol) (R 1 = 2,5-OMe), anhydrous K 2 CO 3 (94mg, 0.68mmol), DMF (3mL), room temperature: 4h, column chromatography (PE:EA=2:1)
[0134] The product (denoted as 3c) is a yellow solid, yield: 60.1%, melting point: 208.0-210.2°C.
[0135] 1 H NMR(500MHz, DMSO-d 6 )δppm 9.42(s,1H),8.79(s,1H),8.63(s,1H),8.55(d,J=9.0Hz,1H), 8.14(d,J=9.0Hz,1H),7.98(d ,J=9.0Hz,1H), 7.87(d,J=9.0Hz,1H), 6.86(d,J=2.5Hz,1H), 6.78(d,J=9.0Hz,1H), 6.60(dd,J =9.0,2.5Hz,1H),4.04(s,3H),3.62(s,3H),3.42(s,3H). 13 C NMR(101MHz, DMSO-d 6 )δppm 152.8, 146.0, 145.6, 144.4, 1405, 131.7, 126.7, 126.6, 126.2, 121.6, 119.9, 114.7, 112.6, 110.5, 110.0, 109.8, 106.2, 56.1, 55.3, 29.8.
[0136] Step 4: Reactant 3c (90mg, 0.20mmol), Pd / C (5%) (20% equiv), H 2 : 40Psi, methanol / THF (1:1) 50mL, roo...
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