Dimethylformamide → HCID 66673896, compound

HRID 424148Notes

Reaction equation

HRID 424148 reaction equation
[C:1]([O:5][C:6]([NH:8][CH:9]1[C:18]([CH2:21][CH3:22])([CH2:19][CH3:20])[C:17]2[CH:16]=[C:15](OS(C(F)(F)F)(=O)=O)[CH:14]=[CH:13][C:12]=2[CH2:11][CH:10]1[O:31][CH3:32])=[O:7])([CH3:4])([CH3:3])[CH3:2].[CH3:33][N:34](C)C=O>[C-]#N.[Zn+2].[C-]#N.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2].O>[C:1]([O:5][C:6](=[O:7])[NH:8][C@H:9]1[C@H:10]([O:31][CH3:32])[CH2:11][C:12]2[C:17](=[CH:16][C:15]([C:33]#[N:34])=[CH:14][CH:13]=2)[C:18]1([CH2:19][CH3:20])[CH2:21][CH3:22])([CH3:3])([CH3:4])[CH3:2]

Participants

7

Reactant 2

HCID 6228DimethylformamideHCID 86631097HCID 86631097, compound

Product 1

HCID 66673896HCID 66673896, compoundYield 96%

Reagents, catalysts & solvents 4

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 962WaterSolvent2×

Conditions

Temperature
110 °C

Procedure

Trifluoro-methanesulfonic acid 7-tert-butoxycarbonylamino-8,8-diethyl-6-methoxy-5,6,7,8-tetrahydro-naphthalen-2-yl ester (236.6 g, 0.49 mol) was dissolved in N,N-dimethylformamide (851 mL, 10.99 mol) and water (23.8 mL, 1.32 mol) at room temperature. The solution was purged with nitrogen for 5 min, and then connected to house vacuum for 5 min. Nitrogen purging and exposure to vacuum was repeated twice. To the reaction mixture was added zinc cyanide (34.2 g, 0.29 mol), tris(dibenzylideneacetone)dipalladium(0) (4.4 g, 4.8 mmol) and 1,1′-bis(diphenylphosphino)ferrocene (5.4 g, 9.7 mmol) with stirring. The reaction mixture was purged with nitrogen for 5 min, heated under nitrogen at 110° C. for 1 h, cooled to room temperature and then filtered through celite. The filtered reaction mixture was added slowly to water (3 L), cooled to 0° C. with stirring, stirred for 30 min at 0° C., and then filtered. The filter cake was washed with water (500 mL) and dried in air for 2 h, slurried in ethanol (1 L) with stirring over 1 h, and then filtered to give the title compound (165.0 g, >96% purity). The filtrate was dried (21.6 g) and dissolved in ethanol (110 mL) with stirring over 1 h, and the resulting slurry was filtered and dried under vacuum to give additional product (10.2 g, >98% purity).

Workup

  1. customat room temperature
  2. customThe solution was purged with nitrogen for 5 min
  3. customfor 5 min
  4. customThe reaction mixture was purged with nitrogen for 5 min
  5. temperaturecooled to room temperature
  6. filtrationfiltered through celite
  7. customThe filtered reaction mixture
  8. temperaturecooled to 0° C.
  9. stirringwith stirring
  10. stirringstirred for 30 min at 0° C.
  11. filtrationfiltered
  12. washThe filter cake was washed with water (500 mL)
  13. customdried in air for 2 h
  14. stirringwith stirring over 1 h
  15. filtrationfiltered

Sources & evidence

ORD record
ord-e066a55eb3344ed8b80362443eb1c92e
Source dataset
uspto-grants-2012_01
Patent number
US08101791B2

Reaction notes

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