Sodium borohydride → HCID 69216910、化合物

HRID 1394285ノート

反応式

HRID 1394285 の反応式
[CH3:1][N:2]([CH3:18])[C:3]1([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[CH2:8][CH2:7][C:6](=[CH:9][C:10]#[N:11])[CH2:5][CH2:4]1.[BH4-].[Na+]>CO.O.O.O.O.O.O.[Ni](Cl)Cl>[NH2:11][CH2:10][CH2:9][CH:6]1[CH2:5][CH2:4][C:3]([N:2]([CH3:1])[CH3:18])([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[CH2:8][CH2:7]1

参加物

5

反応物 2

HCID 4311764Sodium borohydrideHCID 69216446HCID 69216446、化合物

生成物 1

HCID 69216910HCID 69216910、化合物

試薬・触媒・溶媒 2

HCID 11791229Dichloronickel;hexahydrate触媒HCID 887Methanol溶媒

実験手順

(4-Dimethylamino-4-phenylcyclohexylidene)acetonitrile (1.16 g, 4.8 mmole) was dissolved in methanol (30 ml). Nickel(II) chloride hexahydrate (2.28 g, 9.6 mmole) was added to this solution. NaBH4 (1.82 mg, 48 mmole) was then added in portions with stirring and ice water cooling. Once addition was complete, stirring was continued at RT for 1 h. The resultant black nickel boride was removed by suction filtration after addition of 2M hydrochloric acid (15 ml) and washed with 2M hydrochloric acid (3×10 ml). The hydrochloric, aqueous-methanolic solution was reduced to half its volume in order to remove the methanol. The remaining aqueous phase was extracted with ether (3×10 ml) to remove neutral substances. The aqueous phase was then alkalised by addition of conc. aqueous ammonia solution and again extracted with ether (3×20 ml). The combined extracts were washed with saturated NaCl-solution (30 ml), dried over Na2SO4 and then evaporated. The resultant crude product could be purified by column chromatography [silica gel 60 (100 g); MeOH (1000 ml)]. However, this did not result in separation of the diastereoisomers. [4-(2-Aminoethyl)-1-phenylcyclohexyl]dimethylamine was obtained as a colorless oil in a yield of 643 mg (54%).

後処理

  1. additionOnce addition
  2. stirringstirring
  3. customThe resultant black nickel boride was removed by suction filtration
  4. additionafter addition of 2M hydrochloric acid (15 ml)
  5. washwashed with 2M hydrochloric acid (3×10 ml)
  6. customto remove the methanol
  7. extractionThe remaining aqueous phase was extracted with ether (3×10 ml)
  8. customto remove neutral substances
  9. additionThe aqueous phase was then alkalised by addition of conc. aqueous ammonia solution
  10. extractionagain extracted with ether (3×20 ml)
  11. washThe combined extracts were washed with saturated NaCl-solution (30 ml)
  12. dry with materialdried over Na2SO4
  13. customevaporated
  14. customThe resultant crude product could be purified by column chromatography [silica gel 60 (100 g); MeOH (1000 ml)]
  15. customHowever, this did not result in separation of the diastereoisomers

出典と根拠

ORDレコード
ord-752d4f458fa344a4bb67502446c68084
出典データセット
uspto-grants-2008_03
特許番号
US07348354B2

反応ノート

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