Ethyl Acetate → HCID 86728137, compound

HRID 627676Notes

Reaction equation

HRID 627676 reaction equation
[CH3:1][C:2]1([CH3:38])[S:7](=[O:9])(=[O:8])[C@@H:6]2[CH2:10][CH2:11][S:12][C:13]3[CH:18]=[CH:17][C:16]([N+:19]([O-])=O)=[CH:15][C:14]=3[C@@:5]2([CH3:22])[N:4]=[C:3]1[N:23]([C:31]([O:33][C:34]([CH3:37])([CH3:36])[CH3:35])=[O:32])[C:24](=[O:30])[O:25][C:26]([CH3:29])([CH3:28])[CH3:27].CCOC(C)=O>[Pd].CO>[NH2:19][C:16]1[CH:17]=[CH:18][C:13]2[S:12][CH2:11][CH2:10][C@H:6]3[S:7](=[O:8])(=[O:9])[C:2]([CH3:38])([CH3:1])[C:3]([N:23]([C:24]([O:25][C:26]([CH3:27])([CH3:28])[CH3:29])=[O:30])[C:31](=[O:32])[O:33][C:34]([CH3:35])([CH3:36])[CH3:37])=[N:4][C@:5]3([CH3:22])[C:14]=2[CH:15]=1

Participants

5

Reactant 2

HCID 8857Ethyl AcetateHCID 86728138HCID 86728138, compound

Product 1

HCID 86728137HCID 86728137, compoundYield 89.5%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 887MethanolSolvent

Procedure

A flask was charged with tert-butyl N-[(4aR,11bR)-3,3,11b-trimethyl-10-nitro-4,4-dioxo-5,6-dihydro-4aH-[1]benzothiepino[4,5-b][1,4]thiazin-2-yl]-N-tert-butoxycarbonyl-carbamate (1.18 g, 2.071 mmol), 10 wt. % Pd/C (0.220 g, 0.207 mmol), EtOAc (4.14 ml) and MeOH (4.14 ml). The flask was purged with nitrogen, evacuated, and filled with hydrogen. The reaction was stirred at RT under hydrogen atmosphere for 16 h. The reaction was incomplete, so another 100 mg of 10 wt. % Pd/C was added, and stirring under hydrogen was continued. After 8 h, the reaction was complete. The mixture was filtered through Celite and washed with EtOAc. The filtrate was concentrated to provide tert-butyl N-[(4aR,11bR)-10-amino-3,3,11b-trimethyl-4,4-dioxo-5,6-dihydro-4aH-[1]benzothiepino[4,5-b][1,4]thiazin-2-yl]-N-tert-butoxycarbonyl-carbamate (1.00 g, 89%) as a dark foamy solid. LC/MS (ESI+) m/z=562.2 (M+Na). tert-Butyl N-[(4aS,11bR)-10-amino-3,3,11b-trimethyl-4,4-dioxo-5,6-dihydro-4aH-[1]benzothiepino[4,5-b][1,4]thiazin-2-yl]-N-tert-butoxycarbonyl-carbamate was prepared following the same hydrogenation procedure. The product was isolated as a dark foamy solid in 90% yield. LC/MS (ESI+) m/z=562.2 (M+Na).

Workup

  1. customThe flask was purged with nitrogen
  2. customevacuated
  3. additionfilled with hydrogen
  4. additionso another 100 mg of 10 wt. % Pd/C was added
  5. stirringstirring under hydrogen
  6. waitAfter 8 h
  7. filtrationThe mixture was filtered through Celite
  8. washwashed with EtOAc
  9. concentrationThe filtrate was concentrated

Sources & evidence

ORD record
ord-1f43f796680147a3869d7928c02529ac
Source dataset
uspto-grants-2016_04
Patent number
US09309263B2

Reaction notes

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