Acetic Acid → HCID 10505413, compound

HRID 369513Notes

Reaction equation

HRID 369513 reaction equation
C(O)(=O)C.[CH2:5]([NH2:12])[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1.C([BH3-])#N.[Na+].[CH2:17]([O:19][C:20]1[C:21]([O:39][CH2:40][C:41]2[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=2)=[CH:22][C:23]2[CH2:24][CH2:25][C@@H:26]3[C@@H:35]([C:36]=2[CH:37]=1)[CH2:34][CH2:33][C@@:31]1([CH3:32])[C@H:27]3[CH2:28][CH2:29][C:30]1=O)[CH3:18]>ClCCCl.C(Cl)Cl.CCCCCC.C(Cl)Cl.CCCCCC>[CH2:17]([O:19][C:20]1[C:21]([O:39][CH2:40][C:41]2[CH:42]=[CH:43][CH:44]=[CH:45][CH:46]=2)=[CH:22][C:23]2[CH2:24][CH2:25][C@@H:26]3[C@@H:35]([C:36]=2[CH:37]=1)[CH2:34][CH2:33][C@@:31]1([CH3:32])[C@H:27]3[CH2:28][CH2:29][C@@H:30]1[NH:12][CH2:5][C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1)[CH3:18]

Participants

9

Reactant 4

HCID 176Acetic Acid2×HCID 7504Benzylamine2×HCID 5003444Sodium cyanoborohydride2×HCID 10787419HCID 10787419, compound

Product 1

HCID 10505413HCID 10505413, compoundYield 89%

Reagents, catalysts & solvents 4

HCID 111,2-DichloroethaneSolventHCID 6344DichloromethaneSolventHCID 8058HexaneSolventHCID 21226440Methylenechloride HexaneSolvent

Procedure

Glacial acetic acid (0.8 mL), benzylamine (1.6 mL, 15 mmol), and sodium cyanoborohydride (0.9 g, 14 mmol) were added under an argon atmosphere to a solution of 17-keto derivative (18) (2 g, 5 mmol) in anhydrous 1,2-dichloroethane (30 mL). The resulting mixture was stirred at room temperature for 72 h. Additional amounts of anhydrous benzylamine (0.4 mL), acetic acid (0.2 mL), and sodium cyanoborohydride (0.25 g) were added to the mixture, and stirring was continued for 24 h. The solvent was removed under reduced pressure, the residue was diluted with water (50 mL), and extracted with ethyl acetate (3×150 mL). The combined organic layer was washed with water (100 mL), sodium bicarbonate solution (100 mL), brine (100 mL), and dried over anhydrous sodium suleate. The organic layer on evaporation under reduced pressure gave crude product (3.1 g) which was subjected to column chromatography on silica gel using hexane, followed by hexane-CH2Cl2 (1:1), and finally CH2Cl2. Appropriate fractions were combined and evaporated under reduced pressure to give pure amine derivative (19) (2.2 G, 89%). The mp for aminederivative (19) could not be determined as it was a sticky solid which was used without any further purification: IR (KBr) 2921, 1608, 1508, 1453, 1264, 1209, 1119, 1019, 729 cm-1 ; 1H NMR (CDCl3) δ 7.52-7.25 (m, 11 H), 6.85 (s, 1 H), 6.65 (s, 1 H), 4.20 (q, J=8.5 Hz, J=8.5 Hz, 2 H), 3.80 (s, 2 H) 2.75 (m, 1 H) 2.65 (t, J=8.5 Hz, 1 H), 2.35-2.12 (m, 4 H), 2.10 (s, 2 H), 1.85 (m, 4 H), 1.75-1.52 (m, 6 H), 1.40 (t, J=8.5, 3 H), 0.78 (s, 3 H).

Workup

  1. stirringstirring
  2. waitwas continued for 24 h
  3. customThe solvent was removed under reduced pressure
  4. additionthe residue was diluted with water (50 mL)
  5. extractionextracted with ethyl acetate (3×150 mL)
  6. washThe combined organic layer was washed with water (100 mL), sodium bicarbonate solution (100 mL), brine (100 mL)
  7. dry with materialdried over anhydrous sodium suleate
  8. customThe organic layer on evaporation under reduced pressure
  9. customgave crude product (3.1 g) which
  10. customevaporated under reduced pressure

Sources & evidence

ORD record
ord-e909ecff113449ce97d7930627c3790f
Source dataset
uspto-grants-2000_10
Patent number
US06136992

Reaction notes

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