A kind of preparation method of novel anti-tumor IDO inhibitor
A technology of intermediates and compounds, applied in the field of preparation of novel anti-tumor IDO inhibitors, can solve the problems of toxic and side effects, poor biological activity of NLG919, limited clinical data, etc.
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Embodiment 1
[0068] Example 1: Compound 1
[0069]
[0070] Compound 1 was prepared from intermediate F (20 mg) and 4-chloro-1,2-phenylenediamine via general route 1 and general route 3. Compound 1 (10.05 mg) was obtained as a white solid with a yield of 37%. MS(ESI):m / z 408.3(M+H) + . 1 HNMR (500MHz, d 6 -DMSO)δ12.40(s,1H),8.79(d,J=4.5Hz,1H),8.11–8.04(m,1H),7.97(d,J=10.5Hz,1H),7.65(t,J =8.5Hz,1H),7.60–7.45(m,2H),7.42(d,J=4.0Hz,1H),7.15(d,J=8.5Hz,1H),3.30–3.24(m,1H),2.95 –2.88(m,1H),1.95(t,J=10.5Hz,2H),1.90–1.79(m,2H),1.61–1.47(m,3H),1.45–1.32(m,5H).
Embodiment 2
[0071] Example 2: Compound 17 and Compound 18
[0072]
[0073] Compound 17 (trans, rac) and Compound 18 (cis, rac) proceed from intermediate F (40 mg) and 4-fluoro-1,2-phenylenediamine via general route 1 and general route 3 prepared.
[0074] Compound 17 (8.49 mg), the first eluting isomer, was obtained as a white solid in 16% yield. MS(ESI):m / z392.5(M+H) + . 1 H NMR (500MHz, d 6 -DMSO)δ12.28(s,1H),8.79(s,1H),8.11–8.04(m,1H),7.97(d,J=10.5Hz,1H),7.65(t,J=8.5Hz,1H ),7.45–7.39(m,2H),7.34(d,J=10.0Hz,1H),7.02–6.92(m,1H),3.29–3.23(m,1H),2.93–2.87(m,1H), 2.00–1.91(m,2H),1.89–1.79(m,2H),1.61–1.46(m,3H),1.45–1.33(m,5H).
[0075] Compound 18 was obtained (9.24 mg), the second eluting isomer, as a white solid in 18% yield. MS(ESI):m / z392.5(M+H) + . 1 H NMR (500MHz, d 6 -DMSO)δ12.31(s,1H),8.86(s,1H),8.13–8.06(m,1H),7.97(d,J=11.0Hz,1H),7.66(t,J=8.5Hz,1H ),7.58(s,1H),7.44–7.39(m,1H),7.23(d,J=9.0Hz,1H),7.01–6.92(m,1H),3.45–3.35(m,2H),2.15– 2.09(m,1H),2.06–1.99(m,1H),1.93–1.8...
Embodiment 3
[0076] Embodiment 3: Compound 21 and Compound 22
[0077]
[0078] Compound 21 (trans, rac) and Compound 22 (cis, rac) starting from intermediate F (40 mg) and 4-methyl-1,2-phenylenediamine via general route 1 and general route Three prepared.
[0079] Compound 21 (11.40 mg), the first eluting isomer, was obtained as a white solid in 22% yield. MS(ESI):m / z 388.5(M+H) + . 1 H NMR (500MHz, d 6 -DMSO)δ11.98(s,1H),8.79(s,1H),8.11–8.04(m,1H),7.97(d,J=10.5Hz,1H),7.65(t,J=8.5Hz,1H ),7.44–7.38(m,2H),7.20(s,1H),6.93(t,J=9.5Hz,1H),3.30–3.23(m,1H),2.91–2.83(m,1H),2.39( s,3H),2.00–1.91(m,2H),1.89–1.78(m,2H),1.61–1.46(m,3H),1.44–1.33(m,5H).
[0080] Compound 22 (13.51 mg), the second eluting isomer, was obtained as a white solid in 26% yield. MS(ESI):m / z 388.5(M+H) + . 1 H NMR (500MHz, d 6 -DMSO)δ12.02(s,1H),8.86(s,1H),8.13–8.06(m,1H),7.97(d,J=11.0Hz,1H),7.66(t,J=9.0Hz,1H ),7.58(s,1H),7.39(d,J=8.5Hz,1H),7.20(s,1H),6.93(t,J=10.0Hz,1H),3.46–3.34(m,2H),2.38 (s,3H),2.16–2.09(m,1...
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