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Hydrochloric Acid → Methyl 4-({4-[(4-{[4-({4-[(4-tert-butoxycarbonylamino-1-methyl-1H-pyrrole-2-carbonyl)-amino]-1-methyl-1H-pyrrole-2-carbonyl}-amino)-1-methyl-1H-pyrrole-2-carbonyl]-amino}-1-methyl-1H-pyrrole-2-carbonyl)-amino]-1-methyl-1H-pyrrole-2-carbonyl}-amino)-1-methyl-1H-pyrrole-2-carboxylate

HRID 476394
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 476394
C(C1NC=CC=1)(OC(C)(C)C)=[O:2].[C:13]([O:17][C:18]([NH:20][C:21]1[CH:22]=[C:23]([C:27]([NH:29][C:30]2[CH:31]=[C:32]([C:36]([NH:38][C:39]3[CH:40]=[C:41]([C:45](OC)=[O:46])[N:42]([CH3:44])[CH:43]=3)=[O:37])[N:33]([CH3:35])[CH:34]=2)=[O:28])[N:24]([CH3:26])[CH:25]=1)=[O:19])([CH3:16])([CH3:15])[CH3:14].Cl.C(OC([NH:57][C:58]1[CH:59]=[C:60]([C:64]([NH:66][C:67]2[CH:68]=[C:69]([C:73]([NH:75][C:76]3[CH:77]=[C:78](C(O)=O)[N:79](C)[CH:80]=3)=[O:74])[N:70]([CH3:72])[CH:71]=2)=[O:65])[N:61]([CH3:63])[CH:62]=1)=O)(C)(C)C.CCN=C=NCCCN(C)C.O1[CH2:101][CH2:100][O:99][CH2:98]C1>CN(C1C=CN=CC=1)C.CCOC(C)=O>[C:13]([O:17][C:18]([NH:20][C:21]1[CH:22]=[C:23]([C:27]([NH:29][C:30]2[CH:31]=[C:32]([C:36]([NH:38][C:39]3[CH:40]=[C:41]([C:45]([NH:57][C:58]4[CH:59]=[C:60]([C:64]([NH:66][C:67]5[CH:68]=[C:69]([C:73]([NH:75][C:76]6[CH:77]=[C:101]([C:100]([O:99][CH3:98])=[O:2])[N:79]([CH3:78])[CH:80]=6)=[O:74])[N:70]([CH3:72])[CH:71]=5)=[O:65])[N:61]([CH3:63])[CH:62]=4)=[O:46])[N:42]([CH3:44])[CH:43]=3)=[O:37])[N:33]([CH3:35])[CH:34]=2)=[O:28])[N:24]([CH3:26])[CH:25]=1)=[O:19])([CH3:16])([CH3:14])[CH3:15]
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Komponenten

9

Edukt 6

HCID 313Hydrochloric AcidHCID 159081-Ethyl-3-(3'-dimethylaminopropyl)carbodiimideHCID 312751,4-DioxaneHCID 10553378Methyl 4-({4-[(4-tert-butoxycarbonylamino-1-methyl-1H-pyrrole-2-carbonyl)-amino]-1-methyl-1H-pyrrole-2-carbonyl}-amino)-1-methyl-1H-pyrrole-2-carboxylateHCID 114316714-({4-[(4-tert-butoxycarbonylamino-1-methyl-1H-pyrrole-2-carbonyl)-amino]-1-methyl-1H-pyrrole-2-carbonyl}-amino)-1-methyl-1H-pyrrole-2-carboxylic acid
HCID 1545894776369-00-1

Produkt 1

HCID 16082635Methyl 4-({4-[(4-{[4-({4-[(4-tert-butoxycarbonylamino-1-methyl-1H-pyrrole-2-carbonyl)-amino]-1-methyl-1H-pyrrole-2-carbonyl}-amino)-1-methyl-1H-pyrrole-2-carbonyl]-amino}-1-methyl-1H-pyrrole-2-carbonyl)-amino]-1-methyl-1H-pyrrole-2-carbonyl}-amino)-1-methyl-1H-pyrrole-2-carboxylateAusbeute 54 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 142844-(Dimethylamino)pyridineKatalysatorHCID 8857Ethyl AcetateLösungsmittel

Versuchsvorschrift

The Boc pyrrole trimer (5) (0.2 g, 0.40 mmol) in a dry round bottomed flask was treated with 4M HCl in dioxane (2.5 mL). The reaction mixture was stirred at room temperature for 30 minutes during which time a precipitate (5′) formed. The solvent was removed and the residue dried under vacuum. The residue was dissolved in dry DMF (2.5 mL) and the Boc pyrrole trimer acid (6) (0.194 g, 0.40 mmol, 1 equiv.) was added followed by EDCI (0.115 g, 0.6 mmol, 1.5 equiv.) and DMAP (0.058 g, 0.47 mmol, 1.2 equiv.). The reaction mixture was stirred for 48 hours then diluted with EtOAc (50 mL) and washed with 10% HCl solution (3×30 mL) and saturated NaHCO3 solution (3×30 mL). The organic layer was dried over MgSO4 then concentrated in vacuo to give an orange solid 0.185 g (54%). 1H NMR d6-DMSO δ 9.95 (2H, s, N—H), 9.93 (2H, s, N—H), 9.86 (1H, s, N—H), 9.08 (1H, s, Boc-N—H), 7.47 (1H, d, J=1.8 Hz, Py-H), 7.25 (1H, d, J=2.2 Hz, Py-H), 7.24 (2H, d, J=2.0 Hz, Py-H), 7.22 (1H, d, J=1.6 Hz, Py-H), 7.07 (2H, d, J=1.6 Hz, Py-H), 7.07 (1H, d, J=2.0 Hz, Py-H), 6.91 (2H, d, J=1.9 Hz, Py-H), 6.89 (1H, s, Py-H), 6.84 (1H, s, Py-H), 3.86 (3H, s, N—CH3), 3.86 (6H, s, N—CH3), 3.85 (3H, s, N—CH3), 3.84 (3H, s, N—CH3), 3.81 (3H, s, N—CH3), 3.74 (3H, s, O—CH3), 1.46 (9H, s, Boc-H).

Aufarbeitung

  1. customformed
  2. customThe solvent was removed
  3. customthe residue dried under vacuum
  4. dissolutionThe residue was dissolved in dry DMF (2.5 mL)
  5. stirringThe reaction mixture was stirred for 48 hours
  6. washwashed with 10% HCl solution (3×30 mL) and saturated NaHCO3 solution (3×30 mL)
  7. dry with materialThe organic layer was dried over MgSO4
  8. concentrationthen concentrated in vacuo

Quellen und Nachweise

ORD-Eintrag
ord-073921034ef443feb5f55690e81d5537
Quelldatensatz
uspto-grants-2014_01
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US08637664B2

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