Triethyl phosphite → HCID 90643554, compound

HRID 1056928Notes

Reaction equation

HRID 1056928 reaction equation
P(OCC)(OCC)OCC.[N:11]([CH2:14][CH2:15][CH2:16][O:17][C:18]1[CH:19]=[C:20]2[C:25](=[CH:26][C:27]=1[O:28][CH3:29])[C:24](=[O:30])[N:23]([CH2:31][CH2:32][CH2:33][N:34]1[CH2:39][CH2:38][O:37][CH2:36][CH2:35]1)[C:22]1[C:40]3[CH:41]=[C:42]4[O:50][CH2:49][O:48][C:43]4=[CH:44][C:45]=3[C:46](=[O:47])[C:21]2=1)=[N+]=[N-]>C1C=CC=CC=1.C(Cl)(Cl)Cl>[NH2:11][CH2:14][CH2:15][CH2:16][O:17][C:18]1[CH:19]=[C:20]2[C:25](=[CH:26][C:27]=1[O:28][CH3:29])[C:24](=[O:30])[N:23]([CH2:31][CH2:32][CH2:33][N:34]1[CH2:35][CH2:36][O:37][CH2:38][CH2:39]1)[C:22]1[C:40]3[CH:41]=[C:42]4[O:50][CH2:49][O:48][C:43]4=[CH:44][C:45]=3[C:46](=[O:47])[C:21]2=1

Participants

5

Reactant 2

HCID 31215Triethyl phosphiteHCID 118453386HCID 118453386, compound

Product 1

HCID 90643554HCID 90643554, compound

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 6212ChloroformSolvent

Procedure

Triethyl phosphite (0.022 mL, 0.183 mmol) was added to a solution of the compound 21 (0.040 g, 0.073 mmol) in benzene (4 mL), and the mixture was heated at reflux for 24 h. The mixture was diluted to a volume of 200 mL with CHCl3, washed with H2O (2×50 mL) and saturated aq NaCl (50 mL), dried over anhydrous sodium sulfate, and concentrated. The resulting residue was purified by flash column chromatography (SiO2, ˜40 g), eluting with a gradient of 0.5% MeOH in CHCl3, to yield the title compound as a solid. The solid (0.015 g, 0.023 mmol) was diluted with benzene (4 mL), and 2 M HCl in methanol (6 mL) was added to the solution. The mixture was heated at reflux for 3 h. The reaction mixture was allowed to cool to room temperature and the precipitate was filtered to provide the desired compound 22 as a solid (0.007 g, 58%): mp>350° C. IR (film) 3413, 2346, 1751, 1651, 1559, 1437, 1309, 737 cm−1; 1H NMR (D2O) δ 6.77 (s, 1H), 6.62 (s, 1H), 6.56 (s, 1H), 6.16 (s, 1H), 5.96 (s, 2H), 4.86-4.82 (m, 2H), 4.01 (s, 6H), 3.78 (s, 2H), 3.67 (s, 3H), 3.32 (s, 4H), 3.24-3.19 (t, J=7.5 Hz, 2H), 2.19-2.17 (m, 4H); ESIMS m/z 522 (MH+); HRESIMS m/z 522.2249 (MH+), called for C28H32N3O7 522.2246; HPLC purity: 95.23% (C-18 reverse phase, MeOH—H2O, 85:15).

Workup

  1. temperaturethe mixture was heated
  2. temperatureat reflux for 24 h
  3. washwashed with H2O (2×50 mL) and saturated aq NaCl (50 mL)
  4. dry with materialdried over anhydrous sodium sulfate
  5. concentrationconcentrated
  6. customThe resulting residue was purified by flash column chromatography (SiO2, ˜40 g)
  7. washeluting with a gradient of 0.5% MeOH in CHCl3

Sources & evidence

ORD record
ord-a9e17506618c48db955ca66ad8e725b2
Source dataset
uspto-grants-2016_07
Patent number
US09399660B2

Reaction notes

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