Pyridine → HCID 131726469, compound

HRID 1354871Notes

Reaction equation

HRID 1354871 reaction equation
[NH:1]([C:33]([O:35][CH2:36][CH:37]=[CH2:38])=[O:34])[C@@H:2]([C:4]([NH:6][C@H:7]([C:15]([NH:17][C@H:18]([C:30]([OH:32])=[O:31])[CH2:19][CH2:20][CH2:21][CH2:22][NH:23][C:24]([O:26][CH2:27][CH:28]=[CH2:29])=[O:25])=[O:16])[CH2:8][C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1)=[O:5])[CH3:3].[CH3:39][C:40]([NH:51][CH2:52][CH:53]([OH:69])[CH2:54][O:55][C:56]1[C:61]2[C:62]3[C:67]([NH:68][C:60]=2[CH:59]=[CH:58][CH:57]=1)=[CH:66][CH:65]=[CH:64][CH:63]=3)([C:42]1[CH:47]=[CH:46][C:45]([N:48]=[N+:49]=[N-:50])=[CH:44][CH:43]=1)[CH3:41].C1C(C(O)=O)=CC=C(N)C=1.N1C=CC=CC=1.ClC(OC1C=CC([N+]([O-])=O)=CC=1)=O>O1CCCC1.ClCCl>[NH:1]([C:33]([O:35][CH2:36][CH:37]=[CH2:38])=[O:34])[C@@H:2]([C:4]([NH:6][C@H:7]([C:15]([NH:17][C@H:18]([C:30]([OH:32])=[O:31])[CH2:19][CH2:20][CH2:21][CH2:22][NH:23][C:24]([O:26][CH2:27][CH:28]=[CH2:29])=[O:25])=[O:16])[CH2:8][C:9]1[CH:10]=[CH:11][CH:12]=[CH:13][CH:14]=1)=[O:5])[CH3:3].[CH3:41][C:40]([NH:51][CH2:52][CH:53]([OH:69])[CH2:54][O:55][C:56]1[C:61]2[C:62]3[C:67]([NH:68][C:60]=2[CH:59]=[CH:58][CH:57]=1)=[CH:66][CH:65]=[CH:64][CH:63]=3)([C:42]1[CH:47]=[CH:46][C:45]([N:48]=[N+:49]=[N-:50])=[CH:44][CH:43]=1)[CH3:39].[CH3:41][C:40]([NH:51][CH2:52][CH:53]([OH:69])[CH2:54][O:55][C:56]1[C:61]2[C:62]3[C:67]([NH:68][C:60]=2[CH:59]=[CH:58][CH:57]=1)=[CH:66][CH:65]=[CH:64][CH:63]=3)([C:42]1[CH:47]=[CH:46][C:45]([N:48]=[N+:49]=[N-:50])=[CH:44][CH:43]=1)[CH3:39]

Participants

5

Reactant 3

HCID 1049PyridineHCID 821294-Nitrophenyl chloroformateHCID 131726467HCID 131726467, compound

Product 1

HCID 131726469HCID 131726469, compoundYield 89%

Reagents, catalysts & solvents 1

HCID 21919333Tetrahydrofurane dichloromethaneSolvent

Procedure

A solution of 80.2 mg (102 μmol) of compound 17, pyridine (25 μl, 3.0 eq.) and 4-nitrophenyl chloroformate (44.3 mg, 220 μmol) in dry tetrahydrofuran/dichloromethane was stirred under an Argon atmosphere at 0° C. for two hours and overnight at room temperature. The solution was evaporated in vacuo and the residual product was dissolved in dichloromethane. After washing the organic layer with brine and 0.5 N potassium bisulfate, the organic layer was dried over anhydrous sodium sulfate and concentrated to dryness. The resulting crude product was subjected to column chromatography (SiO2—CHCl3/MeOH 20/1) to obtain 61.9 mg (84%) of compound 18. M.P. 69–70° C.; 1H-NMR (300 MHz, CDCl3/CD3OD): δ 1.23 (d, 3H, 3J=7.0 Hz, CH3-Ala), 1.10–2.08 (m, 6H, 3 CH2-Lys), 3.04 (m, 1H, benzylic), 3.13 (m, 2H, N—CH2-Lys), 3.27 (bd, 1H, benzylic), 4.06 (m, 1H, Hα), 4.26 (m, 1H, Hα), 4.35–4.70 (m, 5H, Hα and Aloc), 5.04–5.47 (m, 4H, Aloc), 5.14 (s, 2H, benzylic-spacer), 5.24 (s, 2H, benzylic-spacer), 5.72 (m, 1H, Aloc), 5.90 (m, 1H, Aloc), 7.10–7.46 (m, 13H, aromatic), 7.65 (d, 2H, 3J=8.3 Hz, aromatic), 8.27 (d, 2H, 3J=9.1 Hz, aromatic-PNP) ppm; MS (FAB) m/e 952 (M+H)+, 974 (M+Na)+; C40H46O12 (.¼H2O) calculated C, 59.51%; H, 5.81%; N, 10.41%; measured C 59.52%; H, 5.54%; N, 10.12%.

Workup

  1. customThe solution was evaporated in vacuo
  2. dissolutionthe residual product was dissolved in dichloromethane
  3. washAfter washing the organic layer with brine and 0.5 N potassium bisulfate
  4. dry with materialthe organic layer was dried over anhydrous sodium sulfate
  5. concentrationconcentrated to dryness

Sources & evidence

ORD record
ord-bc5ad02019af49ffacd22a222c690f69
Source dataset
uspto-grants-2007_05
Patent number
US07223837B2

Reaction notes

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