Pyrrolobenzodiazepine compound as well as preparation method and application thereof
A compound, diazepine technology, applied in the field of medicine, can solve problems such as limiting the scope of clinical applications
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Embodiment 1
[0061] Example 1(S)-10-(N-hydroxy-p-toluamide)-1,5,10,11a-tetrahydro-3H-benzo[e]pyrrolo[1,2-][1, 4] Diaza -3,11(2H)-dione (A1)
[0062] The o-nitrobenzyl bromide was dropped into DMF, and NaH was added in batches in an ice-water bath. After one hour of reaction, L-pyroglutamic acid methyl ester was added, and the reaction was continued for two hours at room temperature. post-processing. The solid powder was dissolved in acetic acid, and reduced iron powder was added, and the temperature was raised to reflux for 2 hours. The solution was then concentrated in vacuo and the resulting black viscous material was diluted with ethyl acetate and most of the insoluble material was removed by filtration. The filtrate was purified by flash chromatography on silica gel using ethyl acetate-petroleum ether (10:1 v / v) to give an off-white solid. Anhydrous DMF was added to the solid, sodium hydride was added in portions, and methyl p-bromomethylbenzoate was added after stirring for half ...
Embodiment 2
[0064] Example 2 (S)-10-(N-hydroxy-p-methylphenylacetamide)-1,5,10,11a-tetrahydro-3H-benzo[e]pyrrolo[1,2-][1, 4] Diaza -3,11(2H)-dione (A2)
[0065] The compound preparation method of embodiment 2 is the same as that of embodiment 1, except that methyl p-bromomethyl phenylacetate is used instead of methyl p-bromomethyl benzoate in the third step. A white solid powder was obtained with a yield of 25.9%. mp: 180.1-182.6°C.
[0066] 1 H NMR (600MHz, DMSO) δ 10.61(s, 1H), 8.79(s, 1H), 7.52(d, J=8.0Hz, 1H), 7.46–7.42(m, 1H), 7.39(d, J= 7.4Hz, 1H), 7.24 (t, J=7.3Hz, 1H), 7.16–7.10 (m, 4H), 5.36 (d, J=15.2Hz, 1H), 4.85 (d, J=15.1Hz, 1H) ,4.61(d,J=13.6Hz,1H),4.03(t,J=7.0Hz,1H),3.69(d,J=13.5Hz,1H),3.20(s,2H),2.49–2.42(m, 1H), 2.34–2.28 (m, 2H), 1.95–1.88 (m, 1H).
Embodiment 3
[0067] Example 3 (S)-10-(N-hydroxybutyramide)-1,5,10,11a-tetrahydro-3H-benzo[e]pyrrolo[1,2-][1,4]diazepine miscellaneous -3,11(2H)-dione (A3)
[0068] The compound preparation method of embodiment 3 is the same as that of embodiment 1, except that methyl 4-bromobutyrate is used instead of methyl p-bromomethylbenzoate in the third step. A white solid powder was obtained with a yield of 25.9%. mp: 180.1-182.6°C. The yield was 21.1%. mp: 178.3-179.6°C.
[0069] 1 H NMR(600MHz, DMSO)δ10.34(s,1H),8.66(s,1H),7.48(d,J=9.9Hz,3H),7.31(s,1H),4.70(d,J=13.7Hz ,1H),4.26–4.15(m,1H),3.93(d,J=11.4Hz,2H),3.66–3.56(m,1H),2.41(s,1H),2.29(d,J=7.4Hz, 2H), 1.91(d, J=6.8Hz, 2H), 1.87(d, J=7.3Hz, 1H), 1.18(t, J=6.8Hz, 2H).
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