HCID 16659512, compound → HCID 16658990, compound

HRID 1350178Notes

Reaction equation

HRID 1350178 reaction equation
FC(F)(F)CC1C=NC2C=CC=CC=2O1.[CH2:16]([C@H:20]1[N:25]([CH2:26][C:27]([F:30])([F:29])[F:28])[C:24]2[CH:31]=[CH:32][C:33]([N+:35]([O-])=O)=[CH:34][C:23]=2[O:22][CH2:21]1)[CH:17]([CH3:19])[CH3:18]>C(OCC)(=O)C.[Pd]>[NH2:35][C:33]1[CH:32]=[CH:31][C:24]2[N:25]([CH2:26][C:27]([F:30])([F:29])[F:28])[C@H:20]([CH2:16][CH:17]([CH3:19])[CH3:18])[CH2:21][O:22][C:23]=2[CH:34]=1

Participants

5

Reactant 2

HCID 16659512HCID 16659512, compoundHCID 69473239HCID 69473239, compound

Product 1

HCID 16658990HCID 16658990, compoundYield 65.3%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 8857Ethyl AcetateSolvent

Procedure

(3R)-7-Amino-3,4-dihydro-3-isobutyl-4-(2,2,2-trifluoroethyl-2H-1,4-benzoxazine (Structure 16 of Scheme III, where R3, R4, R5, R7, R8=H, R=isobutyl, R13=CH2CF3) This compound was prepared by treatment of (3R)-3,4-dihydro-3-isobutyl-7-nitro-4-(2,2,2-trifluoroethyl)-2H-1,4-benzoxazine (0.22 g, 0.69 mmol) and 10% Pd/C (0.075 g) in 5 mL ethyl acetate under an H2 atmosphere for 16 h. The mixture was filtered through Celite and concentrated to an oil. Flash chromatography (3:1 hexanes:ethyl acetate) afforded 0.13 g (65%) of (3R)-7-amino-3,4-dihydro-3-isobutyl-4-trifluoroethyl-2H-1,4-benzoxazine. Data for (3R)-7-amino-3,4-dihydro-3-isobutyl-4-trifluoroethyl-2H-1,4-benzoxazine: Rf0.3 (3:1 hexanes:EtOAc); 1H NMR (400 MHz, CDCl3) δ 6.63 (d, 1H, J=8.5), 6.27 (dd, 1H, J=8.5, 2.6), 6.23 (d, 1H, J=2.5), 4.10 (dd, 1H, ABx, J=10.6, 1.8), 3.97 (dd, 1H, ABx, J=10.6, 2.3), 3.70–3.51 (m, 2H), 3.38 (broad s, 2H), 3.19–3.13 (m, 1H), 1.75–1.63 (m, 1H), 1.47–1.25 (m, 2H), 0.93 (d, 3H, J=6.6), 0.89 (d, 3H, J=6.6).

Workup

  1. filtrationThe mixture was filtered through Celite
  2. concentrationconcentrated to an oil

Sources & evidence

ORD record
ord-69436f83fd7747a3aac97e8f5e2876f3
Source dataset
uspto-grants-2007_05
Patent number
US07214690B2

Reaction notes

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