tert-Butyl carbazate → HCID 86722589, compound

HRID 1503066Notes

Reaction equation

HRID 1503066 reaction equation
[Br:1][C:2]1[CH:10]=[C:9](/[CH:11]=[CH:12]/[CH:13]([C:18]2[CH:23]=[C:22]([Cl:24])[C:21]([Cl:25])=[C:20]([Cl:26])[CH:19]=2)[C:14]([F:17])([F:16])[F:15])[CH:8]=[CH:7][C:3]=1[C:4](O)=[O:5].[NH:27]([C:29]([O:31][C:32]([CH3:35])([CH3:34])[CH3:33])=[O:30])[NH2:28].[CH3:36]CN=C=NCCCN(C)C.Cl.CCN(C(C)C)C(C)C>ClCCCl.CN(C1C=CN=CC=1)C.O>[Br:1][C:2]1[CH:10]=[C:9](/[CH:11]=[CH:12]/[CH:13]([C:18]2[CH:23]=[C:22]([Cl:24])[C:21]([Cl:25])=[C:20]([Cl:26])[CH:19]=2)[C:14]([F:17])([F:16])[F:15])[CH:8]=[CH:7][C:3]=1[C:4]([NH:28][N:27]([CH3:36])[C:29]([O:31][C:32]([CH3:35])([CH3:34])[CH3:33])=[O:30])=[O:5]

Participants

8

Reactant 4

HCID 70091tert-Butyl carbazateHCID 81531DiisopropylethylamineHCID 27239391,3-Propanediamine, N'-(ethylcarbonimidoyl)-N,N-dimethyl-, monohydrochlorideHCID 86722549(E)-2-bromo-4-(4,4,4-trifluoro-3-(3,4,5-trichlorophenyl)but-1-enyl)benzoic acid

Product 1

HCID 86722589HCID 86722589, compoundYield 79.6%

Reagents, catalysts & solvents 3

HCID 142844-(Dimethylamino)pyridineCatalystHCID 111,2-DichloroethaneSolventHCID 962WaterSolvent

Conditions

Temperature
25 °C

Procedure

To a stirred solution of (E)-2-bromo-4-(4,4,4-trifluoro-3-(3,4,5-trichlorophenyl)but-1-enyl)benzoic acid (800 mg, 1.63 mmol) in DCE (15 mL) was added tert-butyl hydrazinecarboxylate (290 mg, 1.96 mmol), DMAP (218 mg, 1.86 mmol), EDC.HCl (279 mg, 1.86 mmol) and DIPEA (0.8 mL, 4.89 mmol). The reaction mixture was stirred at 25° C. for 12 h, then diluted with water and extracted with EtOAc. The combined organic layers were washed with brine, dried over Na2SO4 and concentrated under reduced pressure. Purification by flash column chromatography (SiO2, 100-200 mesh; eluting with 30% hexane:EtOAc) afforded the title compound as a brown gum (800 mg, 72%): 1H NMR (300 MHz, DMSO-d6) δ 10.5 (bs, 1H), 7.96 (s, 1H), 7.91 (s, 2H), 7.66 (d, J=7.8 Hz, 1H), 7.37 (s, 1H), 7.03 (dd, J=15.3, 8.7 Hz, 1H), 6.78 (d, J=15.9 Hz, 1H), 4.87-4.81 (m, 1H), 3.08 (s, 3H), 1.43 (s, 9H).

Workup

  1. extractionextracted with EtOAc
  2. washThe combined organic layers were washed with brine
  3. dry with materialdried over Na2SO4
  4. concentrationconcentrated under reduced pressure
  5. customPurification
  6. washby flash column chromatography (SiO2, 100-200 mesh; eluting with 30% hexane:EtOAc)

Sources & evidence

ORD record
ord-8aeee932a44c401fa3c088a032d7227f
Source dataset
uspto-grants-2015_12
Patent number
US09211281B2

Reaction notes

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