Oxalyl chloride → HCID 86628356, compound

HRID 1093934Notes

Reaction equation

HRID 1093934 reaction equation
[C:1](Cl)(=[O:5])[C:2](Cl)=O.[F:7][C:8]([F:33])([F:32])[C:9]([NH:11][C@H:12]1[CH2:31][CH2:30][N:15]2[C:16]3[CH:29]=[CH:28]C=[CH:26][C:17]=3[N:18]([CH3:25])[C:19]3[CH:24]=[CH:23][CH:22]=[CH:21][C:20]=3[C@@H:14]2[CH2:13]1)=[O:10]>CN(C=O)C>[F:33][C:8]([F:7])([F:32])[C:9]([NH:11][C@H:12]1[CH2:31][CH2:30][N:15]2[C:16]3[CH:29]=[CH:28][C:2]([CH:1]=[O:5])=[CH:26][C:17]=3[N:18]([CH3:25])[C:19]3[CH:24]=[CH:23][CH:22]=[CH:21][C:20]=3[C@@H:14]2[CH2:13]1)=[O:10]

Participants

4

Reactant 2

HCID 65578Oxalyl chlorideHCID 86628357HCID 86628357, compound

Product 1

HCID 86628356HCID 86628356, compound

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Conditions

Temperature
80 °C

Procedure

Oxalyl chloride (436 μL, 5 mmol) was carefully added dropwise, with stirring, to DMF (0.5 ml) at 0° C. then held for 25 minutes. A solution of cis-2,2,2-trifluoro-N-(1,2,3,4,10,14b-hexahydro-10-methyldibenzo[b,f]pyrido[1,2-d][1,4]diazepin-2-yl)acetamide (9: R2=COCF3) (400 mg, 1.07 mmol) in DMF (2 ml) was added dropwise to the resulting suspension and the reaction mixture heated to 80° C. and held for 1.5 hours. The reaction was cooled to ambient temperature and quenched by dropwise addition of NaHCO3 solution in H2O. The product was extracted into EtOAc, dried (Na2SO4) and concentrated under reduced pressure. Then the crude product was purified by column chromatography on silica to afford cis-2,2,2-trifluoro-N-(8-formyl-1,2,3,4,10,14b-hexahydro-10-methyldibenzo[b,f]pyrido[1,2-d][1,4]diazepin-2-yl)acetamide (9: R2=COCF3; R8=CHO) (130 mg, 30%). Data: (m/z)=404 (M+H)+. [Column chromatography also afforded cis-2,2,2-trifluoro-N-(6-formyl-1,2,3,4,10,14b-hexahydro-10-methyldibenzo[b,f]pyrido[1,2-d][1,4]diazepin-2-yl)acetamide (9: R2=COCF3; R6=CHO) (45 mg, 10%). Data: (m/z)=404 (M+H)+.]

Workup

  1. waitheld for 1.5 hours
  2. temperatureThe reaction was cooled to ambient temperature
  3. customquenched by dropwise addition of NaHCO3 solution in H2O
  4. extractionThe product was extracted into EtOAc
  5. dry with materialdried (Na2SO4)
  6. concentrationconcentrated under reduced pressure
  7. customThen the crude product was purified by column chromatography on silica

Sources & evidence

ORD record
ord-29373f18cd5645bf9a5fe25787826e67
Source dataset
uspto-grants-2012_03
Patent number
US08133885B2

Reaction notes

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