1-Butanol → HCID 67195717, compound

HRID 2366865Notes

Reaction equation

HRID 2366865 reaction equation
[CH3:1][CH:2]([O:4][C:5](=[O:22])[NH:6][C@H:7]1[C:16]2[C:11](=[CH:12][CH:13]=[C:14](Br)[CH:15]=2)[N:10]([C:18](=[O:20])[CH3:19])[C@@H:9]([CH3:21])[CH2:8]1)[CH3:3].[CH2:23]([OH:27])[CH2:24][CH2:25][CH3:26].CCN(C(C)C)C(C)C.[O:37]1CCOC[CH2:38]1>CN(C)C1C=CN=CC=1.CCOC(C)=O.CC1C(P(C2C([CH2-])=CC=CC=2)C2C(C)=CC=CC=2)=CC=CC=1.CC1C(P(C2C([CH2-])=CC=CC=2)C2C(C)=CC=CC=2)=CC=CC=1.CC(O)=O.CC(O)=O.[Pd].[Pd].[C-]#[O+].[C-]#[O+].[C-]#[O+].[C-]#[O+].[C-]#[O+].[C-]#[O+].[Mo].O>[C:18]([N:10]1[C:11]2[C:16](=[CH:15][C:14]([C:38]([O:27][CH2:23][CH2:24][CH2:25][CH3:26])=[O:37])=[CH:13][CH:12]=2)[C@H:7]([NH:6][C:5]([O:4][CH:2]([CH3:3])[CH3:1])=[O:22])[CH2:8][C@@H:9]1[CH3:21])(=[O:20])[CH3:19]

Participants

10

Reactant 4

HCID 2631-ButanolHCID 312751,4-DioxaneHCID 81531DiisopropylethylamineHCID 529350201-Methylethyl((cis)-1-acetyl-6-bromo-2-methyl-1,2,3,4-tetrahydro-4-quinolinyl)carbamate

Product 1

HCID 67195717HCID 67195717, compoundYield 71.8%

Reagents, catalysts & solvents 5

HCID 142844-(Dimethylamino)pyridineCatalystHCID 98885Molybdenum carbonyl (Mo(CO)6)CatalystHCID 11104995trans-Bis(acetato)bis[2-[bis(2-methylphenyl)phosphino]benzyl]dipalladium(II)CatalystHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
180 °C

Procedure

1-Methylethyl[(2S,4R)-1-acetyl-6-bromo-2-methyl-1,2,3,4-tetrahydro-4-quinolinyl]carbamate (for a preparation, see Example 4) (2.4 g, 6.50 mmol), N,N-dimethyl-4-pyridinamine (1.588 g, 13.00 mmol), trans-di-mu(m)-acetatobis[2-(di-o-tolylphosphino)benzyl]dipalladium(II) (Hermann's catalyst) (0.305 g, 0.325 mmol), 1-butanol (7.23 g, 97 mmol), molybdenum hexacarbonyl (0.858 g, 3.25 mmol), DIPEA (1.680 g, 13.00 mmol) were combined with 1,4-dioxane (2 mL) in 2 sealed 20 mL vials and the mixture was stirred at 180° C. for 30 min under microwave irradiation, then cooled to room temperature. The microwave seals were distinctly raised on completion of the reaction and the pressure was released by use of a 20 mL syringe and needle. The vials were opened and the black reaction mixtures were combined in a 250 mL conical flask, diluted with EtOAc (40 mL) and treated with water. The layers were separated and the organic phase was dried over MgSO4 then concentrated in vacuo. Purification of the residue using SP4 on a 50 G silica cartridge (gradient: 0-100% AcOEt in Hexanes) gave butyl (2S,4R)-1-acetyl-2-methyl-4-({[(1-methylethyl)oxy]carbonyl}amino)-1,2,3,4-tetrahydro-6-quinolinecarboxylate (1.822 g, 4.67 mmol, 71.8% yield)

Workup

  1. customsealed 20 mL vials
  2. temperaturecooled to room temperature
  3. temperatureThe microwave seals were distinctly raised on completion of the reaction
  4. customthe pressure was released by use of a 20 mL syringe
  5. customthe black reaction mixtures
  6. customwere combined in a 250 mL conical flask
  7. customThe layers were separated
  8. dry with materialthe organic phase was dried over MgSO4
  9. concentrationthen concentrated in vacuo
  10. customPurification of the residue

Sources & evidence

ORD record
ord-44f70875ef034defa263d14943eb6637
Source dataset
uspto-grants-2014_04
Patent number
US08697725B2

Reaction notes

Loading…