1,1'-Carbonyldiimidazole → HCID 66752712, compound

HRID 1785410Notes

Reaction equation

HRID 1785410 reaction equation
[CH3:1][C:2]1[C:7]2=[N:8][C:9]3[C:10]([C:32]([OH:34])=O)=[CH:11][N:12]([C:17]4[CH:22]=[CH:21][C:20]([B:23]5[O:27][C:26]([CH3:29])([CH3:28])[C:25]([CH3:31])([CH3:30])[O:24]5)=[CH:19][CH:18]=4)[C:13](=[O:16])[C:14]=3[CH:15]=[C:6]2[CH:5]=[CH:4][CH:3]=1.[CH:35]1[N:39]=[CH:38][N:37]([C:40](N2C=NC=C2)=O)[CH:36]=1>>[CH3:38][N:37]([CH3:40])[CH2:36][CH2:35][NH:39][C:32]([C:10]1[C:9]2[N:8]=[C:7]3[C:2]([CH3:1])=[CH:3][CH:4]=[CH:5][C:6]3=[CH:15][C:14]=2[C:13](=[O:16])[N:12]([C:17]2[CH:22]=[CH:21][C:20]([B:23]3[O:27][C:26]([CH3:29])([CH3:28])[C:25]([CH3:31])([CH3:30])[O:24]3)=[CH:19][CH:18]=2)[CH:11]=1)=[O:34]

Participants

3

Reactant 2

HCID 682631,1'-CarbonyldiimidazoleHCID 66752865HCID 66752865, compound

Product 1

HCID 66752712HCID 66752712, compoundYield 74%

Conditions

Temperature
100 °C

Procedure

From acid 18p, carried out under nitrogen, with a reflux time of 48 h and a recharge with an equal amount of CDI after 24 h. When the amination reaction was complete, the volatiles were removed at reduced pressure with heat (−0.3 mmHg, 100° C., 20 min) and residual N,N-dimethylethylenediamine was removed by azeotropic distillation with toluene (×3). The residue was then boiled in toluene and, while hot, decanted from a brown oil. The toluene was removed at reduced pressure, and the residue was recrystallized from acetonitrile to give the intermediate N-[2-(dimethylamino)ethyl]-6-methyl-1-oxo-2-[4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)phenyl]1,2-dihydrobenzo[b][1,6]naphthyridine-4-carboxamide as a yellow solid (74%), mp 139-141° C. 1H NMR (CDCl3): δ 1.34 (s, 12H, 4×CH3), 2.31 [s, 6H, N(CH3)2], 2.64 (t, J=6.5 Hz, 2H, CH2CH2NMe2), 2.81 (s, 3H, ArCH3), 3.72 (q, J=6.1 Hz, 2H, CH2CH2NMe2), 7.42-7.48 (m, 3H, H-8,2′,6′), 7.69 (d, J=6.9 Hz, 1H, H-7), 7.80 (d, J=8.1 Hz, 1H, H-9), 7.95 (d, J=8.3 Hz, 2H, H-3′, 5′), 8.68 (s, 1H, H-3), 9.23 (s, 1H, H-10), 10.98 (br t, J=5.4 Hz, 1H, CONH). 13C NMR (CDCl3): δ 18.2 (ArCH3), 24.5 (4×CH3)1 37.2 (CH2CH2NMe2), 45.0 [N(CH3) 2], 58.3 (CH2CH2NMe2), 83.8 (2×C), 109.7 (C-4), 119.4 (C-10a), 125.5 (2×CH, C-2′, 6′), 125.7 (C-9a), 126.4 (CH, C-8), 127.0 (CH, C-9), 132.7 (CH, C-7), 135.6 (2×CH, C-3′, 5′), 140.1 (CH, C-10), 142.0 (C-1′), 142.8 (CH, C-3), 147.8 (C-5a), 148.4 (C-4a), 161.7 (C-1), 164.1 (CONH). C-6 and C-4′ were not observed.

Workup

  1. customcarried out under nitrogen, with a reflux time of 48 h
  2. customWhen the amination reaction
  3. customthe volatiles were removed at reduced pressure
  4. customwas removed by azeotropic distillation with toluene (×3)
  5. customwhile hot, decanted from a brown oil
  6. customThe toluene was removed at reduced pressure
  7. customthe residue was recrystallized from acetonitrile

Sources & evidence

ORD record
ord-81d125d897ad43d9b4a7e449f8ee8a48
Source dataset
uspto-grants-2009_03
Patent number
US07504507B2

Reaction notes

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