Allyl chloroformate → prop-2-en-1-yl 7-(4-amino-3-nitrophenyl)-2,3-dihydro-1,4-benzoxazepine-4(5H)-carboxylate

HRID 473873Notes

Reaction equation

HRID 473873 reaction equation
Cl.[N+:2]([C:5]1[CH:11]=[C:10]([C:12]2[CH:13]=[CH:14][C:15]3[O:21][CH2:20][CH2:19][NH:18][CH2:17][C:16]=3[CH:22]=2)[CH:9]=[CH:8][C:6]=1[NH2:7])([O-:4])=[O:3].CCN(C(C)C)C(C)C.Cl[C:33]([O:35][CH2:36][CH:37]=[CH2:38])=[O:34]>ClCCl>[NH2:7][C:6]1[CH:8]=[CH:9][C:10]([C:12]2[CH:13]=[CH:14][C:15]3[O:21][CH2:20][CH2:19][N:18]([C:33]([O:35][CH2:36][CH:37]=[CH2:38])=[O:34])[CH2:17][C:16]=3[CH:22]=2)=[CH:11][C:5]=1[N+:2]([O-:4])=[O:3]

Participants

5

Reactant 3

HCID 18052Allyl chloroformateHCID 81531DiisopropylethylamineHCID 675138822-Nitro-4-(2,3,4,5-tetrahydro-1,4-benzoxazepin-7-yl)aniline hydrochloride salt

Product 1

HCID 67513766prop-2-en-1-yl 7-(4-amino-3-nitrophenyl)-2,3-dihydro-1,4-benzoxazepine-4(5H)-carboxylateYield 101.5%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

2-nitro-4-(2,3,4,5-tetrahydro-1,4-benzoxazepin-7-yl)aniline hydrochloride salt (3.61 g, 11.2 mmol) and DIPEA (5.2 mL, 30 mmol) were taken into dichloromethane (50 mL) followed by dropwise addition of allyl chloroformate (1.23 mL, 11.2 mmol) over 5 minutes. The mixture was allowed to stir 30 minutes at room temperature then concentrated. The residue was partitioned with ethyl acetate and 10% aqueous citric acid and the organic solution washed with brine then dried over anhydrous sodium sulfate, filtered and concentrated to give prop-2-en-1-yl 7-(4-amino-3-nitrophenyl)-2,3-dihydro-1,4-benzoxazepine-4(5H)-carboxylate (4.2 g, 100% yield) as a red amorphous residue. MS (EI) for C19H19N3O5: 370 (MH1).

Workup

  1. concentrationthen concentrated
  2. customThe residue was partitioned with ethyl acetate and 10% aqueous citric acid
  3. washthe organic solution washed with brine
  4. dry with materialthen dried over anhydrous sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-52787454aaa542028c9e1a5802aa7f3f
Source dataset
uspto-grants-2014_01
Patent number
US08637499B2

Reaction notes

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