1-(3, 4-disubstituted phenyl) piperazine skeleton derivative and application thereof in medicine preparation
A halogenated, pharmaceutical technology, applied in the field of organic synthetic drugs, to achieve the effect of lowering blood sugar levels, excellent inhibitory effect, and regulating sugar metabolism
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Embodiment 1
[0082] Embodiment 1, the preparation of compound 1-methyl-4-phenylpiperazine (6a)
[0083]
[0084] Weigh compound N-methylpiperazine (3, 20mg, 0.2mmol), iodobenzene (4a, 44mg, 0.22mmol), palladium (II) acetate (ie Pd(OAc) 2 , 2.24mg, 0.01mmol), 4,5-bisdiphenylphosphine-9,9-dimethylxanthene (ie Xant-phos, 29mg, 0.05mmol) and cesium carbonate (ie Cs 2 CO 3 , 97.5mg, 0.3mmol) was added to a 25mL double-necked round bottom flask, and then 6mL of anhydrous 1,4-dioxane solution was added. Under the condition of nitrogen protection, stir and heat to 100°C, and react for 12h. The reaction process was monitored by thin-layer chromatography, and the reaction solution was concentrated by a rotary evaporator after the reaction. The concentrated solution was purified by column chromatography to obtain compound 1-methyl-4-phenylpiperazine (6a) with a yield of 21%. 1 H NMR (400MHz, DMSO-d 6 )δ7.20(dd, J=8.6,7.3Hz,2H),6.92(d,J=7.8Hz,2H),6.76(t,J=7.2Hz,1H),3.15-3.07(m,4H), 2.48-2.40(...
Embodiment 2
[0085] Embodiment 2, the preparation of compound N-phenyl-5-(4-methylpiperazin-1-yl)-2-nitrobenzamide (6b)
[0086]
[0087] N-methylpiperazine (3, 20mg, 0.2mmol) intermediate compound N-phenyl-5-fluoro-2-nitrobenzamide (4b, 70mg, 0.2mmol), Pd(OAc) 2 (2.24mg, 0.01mmol), Xant-phos (29mg, 0.05mmol) and Cs 2 CO 3 (97.5mg, 0.3mmol) was weighed into a 25mL double-necked round bottom flask, and 6mL of 1,4-dioxane solvent was added to dissolve it. Under the condition of nitrogen protection, the reaction was heated to 100° C., and the reaction was stirred for 12 h. The reaction process was monitored by thin-layer chromatography, and the reaction solution was concentrated by a rotary evaporator after the reaction. Then, the product was purified by column chromatography. The compound N-phenyl-5-(4-methylpiperazin-1-yl)-2-nitrobenzamide (6b) was obtained with a yield of 31%. 1 H NMR (400MHz, DMSO-d 6 )δ9.35(d,J=8.5Hz,1H),7.99(d,J=9.3Hz,1H),7.41-7.30(m,8H),7.29-7.21(m,2H),7.04(dd...
Embodiment 3
[0088] Embodiment 3, the preparation of compound 5-(4-methylpiperazin-1-yl)-N-(naphthalene-1-yl)-2-nitrobenzamide (6c)
[0089]
[0090] Using the corresponding raw materials I-a and I-b shown in Table 1, according to the same synthesis method as compound 6b, compound 6c was prepared with a yield of 39%. 1 H NMR (400MHz, DMSO-d 6 )δ10.43(s,1H),8.23-8.16(m,1H),8.10(d,J=9.4Hz,1H),8.00-7.91(m,1H),7.83(d,J=7.8Hz,2H ),7.61-7.52(m,3H),7.18(d,J=2.8Hz,1H),7.11(dd,J=9.5,2.9Hz,1H),3.54(t,J=5.1Hz,4H),2.45 (t,J=5.1Hz,4H),2.24(s,3H). 13 C NMR(101MHz,DMSO)δ166.64,154.43,136.92,134.63,134.19,133.80,128.74,128.43,127.36,126.52,126.28,126.18,126.00,123.70,122.77,113.27,112.74,54.68,46.80,46.10.HRMS m / z(ESI)calcd for C 22 h 23 N 4 o 3 [M+H] + 391.1765 found: 391.1772, calcd for C 22 h 22 N4 o 3 Na[M+Na] + 413.1584found: 413.1593.
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