Dichloromethane → (E)-7-(2-Carboxy-vinyl)-2-oxo-1,2,3,5-tetrahydro-pyrido[2,3-e][1,4]diazepine-4-carboxylic acid benzyl ester hydrochloride

HRID 1362093Notes

Reaction equation

HRID 1362093 reaction equation
[CH2:1]([O:8][C:9]([N:11]1[CH2:17][C:16]2[CH:18]=[C:19](/[CH:22]=[CH:23]/[C:24]([O:26]C(C)(C)C)=[O:25])[CH:20]=[N:21][C:15]=2[NH:14][C:13](=[O:31])[CH2:12]1)=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(O)(C(F)(F)F)=O.C(Cl)[Cl:40]>CCOCC>[ClH:40].[CH2:1]([O:8][C:9]([N:11]1[CH2:17][C:16]2[CH:18]=[C:19](/[CH:22]=[CH:23]/[C:24]([OH:26])=[O:25])[CH:20]=[N:21][C:15]=2[NH:14][C:13](=[O:31])[CH2:12]1)=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 6344DichloromethaneHCID 6422Trifluoroacetic acidHCID 59456961(E)-7-(2-tert-Butoxycarbonyl-vinyl)-2-oxo-1,2,3,5-tetrahydro-pyrido[2,3-e][1,4]diazepine-4-carboxylic acid benzyl ester

Product 1

HCID 66967367(E)-7-(2-Carboxy-vinyl)-2-oxo-1,2,3,5-tetrahydro-pyrido[2,3-e][1,4]diazepine-4-carboxylic acid benzyl ester hydrochlorideYield 91%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

A solution of (E)-7-(2-tert-butoxycarbonyl-vinyl)-2-oxo-1,2,3,5-tetrahydro-pyrido[2,3-e][1,4]diazepine-4-carboxylic acid benzyl ester (0.31 g, 0.73 mmol) in CH2Cl2 (5 mL) was treated with TFA (5 mL). After stirring at room temperature for 30 min, the clear tan solution was concentrated in vacuo. The resulting oil was treated with anhydrous HCl (10 mL of a 4.0 M solution in dioxane, 40 mmol) to give a cloudy mixture. The mixture was diluted with Et2O (200 mL) to give an off-white precipitate. After stirring for 15 min, the solid was isolated by filtration, washed with Et2O, and dried under vacuum for 1.5 h to give the title compound (0.27 g, 91%) as an off-white solid: 1H NMR (300 MHz, DMSO-d6) δ 10.50-10.47 (m, 1H), 8.49 (s, 1H), 8.09-8; 15 (m, 1H), 7.53-7.59 (m, 1H), 7.15-7.33 (m, 5H), 6.51-6.65 (m, 1H), 5.42 (bs, 2H), 5.05-5.08 (m, 2H), 4.63 (s, 2H), 4.43 (s, 2H); MS (ESI) m/e 368 (M+H)+.

Workup

  1. concentrationthe clear tan solution was concentrated in vacuo
  2. additionThe resulting oil was treated with anhydrous HCl (10 mL of a 4.0 M solution in dioxane, 40 mmol)
  3. customto give a cloudy mixture
  4. customto give an off-white precipitate
  5. stirringAfter stirring for 15 min
  6. customthe solid was isolated by filtration
  7. washwashed with Et2O
  8. customdried under vacuum for 1.5 h

Sources & evidence

ORD record
ord-978bf4dc62ad48438cc4955b184c6e6a
Source dataset
uspto-grants-2011_02
Patent number
US07879872B2

Reaction notes

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