ethyl 9',10'-difluoro-8'-nitro-7'-oxospiro[cyclobutane-1,3'(2'H)-[7H]pyrido[1,2,3-de][1,4]benzoxazine]-6'-carboxylate → Ethyl 8'-amino-9',10'-difluoro-7'-oxospiro-[cyclobutane-1,3'(2'H)-[7H]pyrido[1,2,3-de][1,4]benzoxazine]-6'-carboxylate

HRID 444764Notes

Reaction equation

HRID 444764 reaction equation
[F:1][C:2]1[C:3]([F:27])=[C:4]2[O:9][CH2:8][C:7]3([CH2:12][CH2:11][CH2:10]3)[N:6]3[CH:13]=[C:14]([C:22]([O:24][CH2:25][CH3:26])=[O:23])[C:15](=[O:21])[C:16]([C:17]=1[N+:18]([O-])=O)=[C:5]23.[H][H]>CN(C=O)C.[Pd]>[NH2:18][C:17]1[C:16]2[C:15](=[O:21])[C:14]([C:22]([O:24][CH2:25][CH3:26])=[O:23])=[CH:13][N:6]3[C:7]4([CH2:12][CH2:11][CH2:10]4)[CH2:8][O:9][C:4]([C:5]=23)=[C:3]([F:27])[C:2]=1[F:1]

Participants

5

Reactant 2

HCID 58134645ethyl 9',10'-difluoro-8'-nitro-7'-oxospiro[cyclobutane-1,3'(2'H)-[7H]pyrido[1,2,3-de][1,4]benzoxazine]-6'-carboxylateHCID 178418361HCID 178418361, compound

Product 1

HCID 58134855Ethyl 8'-amino-9',10'-difluoro-7'-oxospiro-[cyclobutane-1,3'(2'H)-[7H]pyrido[1,2,3-de][1,4]benzoxazine]-6'-carboxylateYield 88%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 6228DimethylformamideSolvent

Procedure

A solution of ethyl 9′,10′-difluoro-8′-nitro-7′-oxospiro[cyclobutane-1,3′(2′H)-[7H]pyrido[1,2,3-de][1,4]benzoxazine]-6′-carboxylate (580 mg, 1.53 mmol) in DMF (30 mL) was treated with hydrogen under atmospheric pressure over 10% Pd/C (60 mg) at 50° C. for 3 hours. The catalyst was removed by filtration with Celite and the filtrate was poured into ice-water. The resulting precipitate was stirred for 1 hour and collected by filtration, washed with water and dried to yield the title compound (468 mg, 88%) as a pale yellow solid. 1H-NMR (400 MHz, DMSO-d6) δ 1.29 (3H, t, J=7.3 Hz), 1.92-2.02 (2H, m), 2.10-2.19 (2H, m), 2.61-2.69 (2H, m), 4.23 (2H, q, J=7.3 Hz), 4.39 (2H, s), 7.38 (2H, brs), 8.65 (1H, brs). ESIMS (+): 351 [M+H]+.

Workup

  1. customThe catalyst was removed by filtration with Celite
  2. additionthe filtrate was poured into ice-water
  3. filtrationcollected by filtration
  4. washwashed with water
  5. customdried

Sources & evidence

ORD record
ord-737792b860b34115b3b166f9f34a873f
Source dataset
uspto-grants-2013_07
Patent number
US08476261B2

Reaction notes

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