3-ureidoisoquinolin-8-yl derivatives
A technology of dimethylamino and alkyl, applied in the field of novel 3-ureidoisoquinolin-8-yl derivatives
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[0968] Preparation of synthetic intermediates
[0969] Preparation A: 1-[8-(Aminomethyl)isoquinolin-3-yl]-3-ethyl-urea:
[0970] A.1. N-(2-bromo-benzyl)-2,2-diethoxy-acetamidine:
[0971] Starting from 2-bromobenzylamine (20.00 g; commercially available) and methyl 2,2-diethoxy-acetimidate (24.46 g; 85% pure) and proceeding in a similar manner to Procedure A , and the title compound (39.31 g) was obtained as yellow oil.
[0972] MS (ESI, m / z): 315.2 and 317.2 [M+H of the two main isotopes + ].
[0973] A.2.8-Bromo-isoquinolin-3-yl-amine:
[0974] Starting from intermediate A.1 (39.31 g) and proceeding in an analogous manner to procedure B without additional purification, the title compound was obtained as a yellow solid (19.66 g; 82% yield over 2 steps).
[0975] 1 H NMR(d6-DMSO)δ: 8.92(s, 1H); 7.53(d, J=8.3Hz, 1H); 7.41-7.37(m, 1H); 7.33-7.26(m, 1H); 6.61(s, 1H); 6.18(br.s, 2H).
[0976] MS (ESI, m / z): 223.2 and 225.2 [M+H of the two main isotopes + ].
[0977] A.3....
example 1
[1068] Example 1: But-3-ynoic acid [3-(3-ethyl-ureido)-isoquinolin-8-ylmethyl]-amide:
[1069] Starting from the compound of Preparation A and 3-butynoic acid and proceeding in an analogous manner to Procedure G, the title compound was obtained as a white solid (31% yield) after purification by preparative HPLC (basic conditions). ).
[1070] 1 H NMR(d6-DMSO)δ: 9.18(s,1H); 9.01(s,1H); 8.47(t,J=5.7Hz,1H); 8.00(s,1H);7.70-7.64(m,1H) ;7.55(dd,J=8.3,6.9Hz,1H);7.28(d,J=6.4Hz,1H);7.09(t,J=5.4Hz,1H);5.79(t,J=6.6Hz,1H) ; 5.31(d, J=6.6Hz, 2H); 4.79(d, J=5.7Hz, 2H); 3.21-3.11(m, 2H); 1.08(t, J=7.2Hz, 3H).
[1071] LC-MS (01): MS (ESI, m / z): 311.2 [M+H + ];t R =0.58min.
example 2
[1072] Example 2: N-[3-(3-Ethyl-ureido)-isoquinolin-8-ylmethyl]-isonicotine:
[1073] Starting from the compound of Preparation A and isonicotinic acid and proceeding in an analogous manner to Procedure H, the title compound was obtained as an amorphous solid after purification by preparative HPLC (basic conditions) (55% yield) .
[1074] LC-MS (01): MS (ESI, m / z): 350.2 [M+H + ];t R =0.53min.
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