Chloroacetyl chloride → HCID 67264695, compound

HRID 1688020Notes

Reaction equation

HRID 1688020 reaction equation
Cl[CH2:2][C:3](Cl)=[O:4].[N+:6]([C:9]1[CH:10]=[CH:11][C:12]2[O:18][CH2:17][CH2:16][CH2:15][NH:14][C:13]=2[CH:19]=1)([O-:8])=[O:7].[CH2:20]([N:22](CC)[CH2:23][CH3:24])[CH3:21].N1CCCC1>CN(C)C1C=CN=CC=1.C(#N)C.C(Cl)Cl.O>[N+:6]([C:9]1[CH:10]=[CH:11][C:12]2[O:18][CH2:17][CH2:16][CH2:15][N:14]([C:3](=[O:4])[CH2:2][N:22]3[CH2:23][CH2:24][CH2:21][CH2:20]3)[C:13]=2[CH:19]=1)([O-:8])=[O:7]

Participants

9

Reactant 4

HCID 6577Chloroacetyl chlorideHCID 8471TriethylamineHCID 31268PyrrolidineHCID 109871302,3,4,5-Tetrahydro-7-nitro-1,5-benzoxazepine

Product 1

HCID 67264695HCID 67264695, compoundYield 88.1%

Reagents, catalysts & solvents 4

HCID 142844-(Dimethylamino)pyridineCatalystHCID 962WaterSolventHCID 6342AcetonitrileSolventHCID 6344DichloromethaneSolvent

Procedure

Chloroacetyl chloride (0.50 mL, 6.3 mmol; Acros) was added to a solution of 2-Nitro-6,7,8,9-tetrahydro-5-oxa-9-aza-benzocycloheptene (0.58 g, 3.0 mmol;), Triethylamine (1.0 mL, 7.2 mmol), and 4-Dimethylaminopyridine (20 mg, 0.1 mmol; Acros) in Acetonitrile (10 mL) (Exothermic-immediate color change to a dark mixture). The reaction was stirred under an atmosphere of Nitrogen. After 1 h, Pyrrolidine (2.0 mL, 24 mmol) was added, as HPLC had shown the first acylation to be complete. After overnight stirring, the mixture was diluted with DCM (30 mL) and water (30 mL), the layers separated and the aq. extracted with 10 mL DCM. The combined organics were washed with brine (20 mL) and dried, then conc. The residue was chromatographed (ISCO, 40 g, 0-5% MeOH:DCM) to afford 1-(2-Nitro-7,8-dihydro-6H-5-oxa-9-aza-benzocyclohepten-9-yl)-2-pyrrolidin-1-yl-ethanone as a yellow oil (807 mg, 88%). 1H-NMR (CDCl3): rotamers, broad spectrum; 13C-NMR (CDCl3): 169.8, 160.3, 142.5, 133.6, 124.8, 124.2, 122.1, 70.9, 57.6, 54.0, 45.3, 28.0, 23.7

Workup

  1. stirringAfter overnight stirring
  2. customthe layers separated
  3. extractionthe aq. extracted with 10 mL DCM
  4. washThe combined organics were washed with brine (20 mL)
  5. customdried
  6. customconc. The residue was chromatographed (ISCO, 40 g, 0-5% MeOH:DCM)

Sources & evidence

ORD record
ord-557db2a3a8d249a0ac5c33b9e27c75ce
Source dataset
uspto-grants-2012_04
Patent number
US08148391B2

Reaction notes

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