Ethyl Acetate → HCID 69055071, compound

HRID 2103094Notes

Reaction equation

HRID 2103094 reaction equation
[N:1]([CH2:4][CH2:5][N:6]1[C:15]2[C:10](=[CH:11][C:12]([O:18][CH3:19])=[C:13]([CH3:17])[C:14]=2[CH3:16])[CH2:9][C:8]2([CH2:22][CH2:21][CH2:20]2)[CH2:7]1)=[N+]=[N-].C(OC(=O)C)C>CO.[Pd]>[CH3:19][O:18][C:12]1[CH:11]=[C:10]2[C:15](=[C:14]([CH3:16])[C:13]=1[CH3:17])[N:6]([CH2:5][CH2:4][NH2:1])[CH2:7][C:8]1([CH2:20][CH2:21][CH2:22]1)[CH2:9]2

Participants

5

Reactant 2

HCID 8857Ethyl AcetateHCID 86605502HCID 86605502, compound

Product 1

HCID 69055071HCID 69055071, compoundYield 89.5%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 887MethanolSolvent

Procedure

A solution of 6′-methoxy-7′,8′-dimethyl-2′,4′-dihydro-1′H-spiro[cyclobutane-1,3′-quinoline] (1.12 g), 1,2-dibromoethane (2 mL) and Cs2CO3 (3.16 9) in DMF (7 mL) was heated in a bath of 110° C. for 6 hours. The mixture was cooled, water was added, and extracted with dichloromethane. The organic phase was then washed with brine, dried and evaporated. The residue was passed through a column (Hexane/EtOAc, 10:0.6) to give 1′-(2-bromoethyl)-6′-methoxy-7′,8′-dimethyl-2′,4′-dihydro-1′H-spiro[cyclobutane-1,3′-quinoline] which was then added NaN3 (1.1 g) and dissolved in dichloromethane (7 mL). After heating the solution in a bath of 90° C. for 1 hour, the mixture was cooled, mixed with water and extracted with dichloromethane. The organic phase was washed with brine, dried and evaporated. The residue was passed through a column (Hexane/EtOAc, 10:0.5-10:0.6) to give 1′-(2-azidoethyl)-6′-methoxy-7′,8′-dimethyl-2′,4′-dihydro-1′H-spiro[cyclobutane-1,3′-quinoline] (340 mg) as an oil. 1′-(2-azidoethyl)-6′-methoxy-7′,8′-dimethyl-2′,4′-dihydro-1′H-spiro[cyclobutane-1,3′-quinoline] (340 mg) was dissolved in methanol (7 mL) and ethylacetate to which 50 mg Pd/C (10%) was added. The flask was then flushed evacuated and flushed with hydrogen. Under a balloon of hydrogen for 1 hour, the mixture was filtered and evaporated to give 2-(6′-methoxy-7′,8′-dimethyl-2′,4′-dihydro-1′H-spiro[cyclobutane-1,3′-quinoline]-1′-yl)ethanamine (278 mg) as an oil. 1H-NMR (300 MHz, C2D6O) δ=6.414 (s, 1H); 3.77 (s, 3H); 3.52 (s, 2H); 3.16-2.92 (m, 4H); 2.81 (s, 2H); 2.18 (s, 3H); 2.12 (s, 3H); 2.03-1.86 (m, 4H); 1.84-1.64 (m, 2H) ppm.

Workup

  1. customThe flask was then flushed
  2. customevacuated
  3. customflushed with hydrogen
  4. filtrationthe mixture was filtered
  5. customevaporated

Sources & evidence

ORD record
ord-2e75921d84894f94b748ae851619a1dd
Source dataset
uspto-grants-2009_08
Patent number
US07576094B2

Reaction notes

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