Phosphorus oxychloride → 3-Chloro-5,6,8,9-tetrahydro-1,2,7-triaza-benzocycloheptene-7-carboxylic acid tert-butyl ester

HRID 239164Notes

Reaction equation

HRID 239164 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH2:14][CH2:13][C:12]2=[N:15][NH:16][C:17](=O)[CH:18]=[C:11]2[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].O=P(Cl)(Cl)[Cl:22]>>[C:1]([O:5][C:6]([N:8]1[CH2:14][CH2:13][C:12]2[N:15]=[N:16][C:17]([Cl:22])=[CH:18][C:11]=2[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

3

Reactant 2

HCID 24813Phosphorus oxychlorideHCID 86686513tert-Butyl 3-oxo-2,3,5,6,8,9-hexahydro-7H-pyridazino[3,4-d]azepine-7-carboxylate

Product 1

HCID 866860553-Chloro-5,6,8,9-tetrahydro-1,2,7-triaza-benzocycloheptene-7-carboxylic acid tert-butyl ester

Procedure

11 g 3-oxo-2,3,5,6,8,9-hexahydro-1,2,7-triaza-benzocycloheptene-7-carboxylic acid tert-butyl ester in 90 ml phosphor oxychloride was refluxed overnight. The phosphor oxychloride was quenched with 8.7 g sodium carbonate to pH 8 and 100 mL water was added to the reaction mixture. Di-tert.butyl-dicarbonate was added to the reaction mixture and stirred over night. The solution was extracted with 50% ethyl acetate in hexane. The extracted organic layer was dried, concentrated under reduced pressure and purified by column chromatography to afford 8.0 g of the desired product. (M+H)+=284

Workup

  1. customThe phosphor oxychloride was quenched with 8.7 g sodium carbonate to pH 8 and 100 mL water
  2. additionwas added to the reaction mixture
  3. additionDi-tert.butyl-dicarbonate was added to the reaction mixture
  4. extractionThe solution was extracted with 50% ethyl acetate in hexane
  5. customThe extracted organic layer was dried
  6. concentrationconcentrated under reduced pressure
  7. custompurified by column chromatography

Sources & evidence

ORD record
ord-0da00b326e9d4cd097d2cef098a55893
Source dataset
uspto-grants-2014_02
Patent number
US08642774B2

Reaction notes

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