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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
ノート
印刷プレビュー

反応式

HRID 476394 の反応式
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]
参加物実験手順後処理出典と根拠反応ノート

参加物

9

反応物 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

生成物 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-carboxylate収率 54%

試薬・触媒・溶媒 2

HCID 142844-(Dimethylamino)pyridine触媒HCID 8857Ethyl Acetate溶媒

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-073921034ef443feb5f55690e81d5537
出典データセット
uspto-grants-2014_01
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US08637664B2

反応ノート

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