Potassium Cyanide → tert-butyl 1-(2-(7-cyano-2-oxoquinolin-1(2H)-yl)ethyl)piperidin-4-ylcarbamate

HRID 255171ノート

反応式

HRID 255171 の反応式
Br[C:2]1[CH:11]=[C:10]2[C:5]([CH:6]=[CH:7][C:8](=[O:28])[N:9]2[CH2:12][CH2:13][N:14]2[CH2:19][CH2:18][CH:17]([NH:20][C:21](=[O:27])[O:22][C:23]([CH3:26])([CH3:25])[CH3:24])[CH2:16][CH2:15]2)=[CH:4][CH:3]=1.[C-:29]#[N:30].[K+].C1(P(C2C=CC=CC=2)C2C3OC4C(=CC=CC=4P(C4C=CC=CC=4)C4C=CC=CC=4)C(C)(C)C=3C=CC=2)C=CC=CC=1>C(#N)C.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[C:29]([C:2]1[CH:11]=[C:10]2[C:5]([CH:6]=[CH:7][C:8](=[O:28])[N:9]2[CH2:12][CH2:13][N:14]2[CH2:19][CH2:18][CH:17]([NH:20][C:21](=[O:27])[O:22][C:23]([CH3:25])([CH3:26])[CH3:24])[CH2:16][CH2:15]2)=[CH:4][CH:3]=1)#[N:30]

参加物

6

反応物 3

HCID 9032Potassium CyanideHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 60200428tert-butyl {1-[2-(7-bromo-2-oxoquinolin-1(2H)-yl)ethyl]piperidin-4-yl}carbamate2 回

生成物 1

HCID 60200429tert-butyl 1-(2-(7-cyano-2-oxoquinolin-1(2H)-yl)ethyl)piperidin-4-ylcarbamate

試薬・触媒・溶媒 2

HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 6342Acetonitrile溶媒

実験手順

A mixture of tert-butyl {1-[2-(7-bromo-2-oxoquinolin-1(2H)-yl)ethyl]piperidin-4-yl}carbamate (Intermediate 16) (9.85 g, 21.9 mmol) and potassium cyanide (2.14 g, 32.8 mmol) in dry acetonitrile (60 mL) was degassed and flushed with nitrogen three times. Tributyltinchloride (0.059 mmol, 1.13 mL of a 51.6 mM solution in heptane) was added, followed by 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (63 mg, 0.11 mmol) and tris(dibenzylideneacetone)dipalladium (0) (100 mg, 0.11 mmol) and it was degassed and flushed with nitrogen like above. The mixture was stirred for 30 minutes at room temperature and then degassed and flushed with nitrogen again. It was heated at 85° C. for 20 hours. The solvent was removed under reduced pressure and the residue taken up in dichloromethane (500 mL) and washed with water (200 mL). The aqueous phase was back-extracted once with dichloromethane (200 mL) and combined organic phases were dried over sodium sulfate. Solvent was removed under reduced pressure and the residue was crystallized from acetonitrile (60 mL) to give the product as a colorless solid, 6.57 g (76%), mp 202° C.

後処理

  1. customwas degassed
  2. customflushed with nitrogen three times
  3. additionTributyltinchloride (0.059 mmol, 1.13 mL of a 51.6 mM solution in heptane) was added
  4. customwas degassed
  5. customflushed with nitrogen like above
  6. customdegassed
  7. customflushed with nitrogen again
  8. temperatureIt was heated at 85° C. for 20 hours
  9. customThe solvent was removed under reduced pressure
  10. washwashed with water (200 mL)
  11. extractionThe aqueous phase was back-extracted once with dichloromethane (200 mL)
  12. dry with materialwere dried over sodium sulfate
  13. customSolvent was removed under reduced pressure
  14. customthe residue was crystallized from acetonitrile (60 mL)

出典と根拠

ORDレコード
ord-dc07fae6b576432bb4f0c66337946e6d
出典データセット
uspto-grants-2011_01
特許番号
US07875715B2

反応ノート

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