1,2-Dichloroethane → HCID 18545693, compound

HRID 1267504Notes

Reaction equation

HRID 1267504 reaction equation
[CH2:1]([N:3]([CH2:27][CH3:28])[C:4](=[O:26])[C:5]1[CH:10]=[CH:9][C:8]([C:11](=[C:18]2[CH2:24][CH:23]3[NH:25][CH:20]([CH2:21][CH2:22]3)[CH2:19]2)[C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)=[CH:7][CH:6]=1)[CH3:2].[CH:29](=O)[CH2:30][CH3:31].CC(O)=O.[BH-](OC(C)=O)(OC(C)=O)OC(C)=O.[Na+].[OH-].[Na+].[Cl:53]CCCl>C(Cl)Cl.CCOCC>[ClH:53].[CH2:27]([N:3]([CH2:1][CH3:2])[C:4](=[O:26])[C:5]1[CH:6]=[CH:7][C:8]([C:11](=[C:18]2[CH2:24][CH:23]3[N:25]([CH2:29][CH2:30][CH3:31])[CH:20]([CH2:21][CH2:22]3)[CH2:19]2)[C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)=[CH:9][CH:10]=1)[CH3:28]

Participants

9

Reactant 6

HCID 111,2-DichloroethaneHCID 176Acetic AcidHCID 527PropanalHCID 14798Sodium HydroxideHCID 5049666Sodium triacetoxyborohydrideHCID 10270786HCID 10270786, compound

Product 1

HCID 18545693HCID 18545693, compound

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 6344DichloromethaneSolvent

Procedure

A slurry of 0.4 g (1.0 mmol) N,N-diethyl-4-[(8-azabicyclo[3.2.1]oct-3-ylidene)phenylmethyl]benzamide, 0.11 mL (1.5 mmol) propionaldehyde, 0.1 mL (1.7 mmol) HOAc, and 0.5 g (2.3 mmol) NaBH(OAc)3 in 20 mL DCE was allowed to stir for 16 h. The reaction was made strongly basic with 3N NaOH and diluted with CH2Cl2. The organic layer was separated, washed with brine, dried over K2CO3, filtered, and concentrated. The remaining oil was absorbed onto silica gel and purified by flash chromatography eluted with 5% 0.5 M NH3 in MeOH 95% CH2Cl2. The pure product (0.25 g, 0.6 mmol) was taken up in Et2O, filtered, and precipitated after the addition of ethereal HCl; mp 184-184° C. MS m/z (MH+) 417. 1H NMR 300 MHz (CD3OD) δ 7.2-7.45 (m, 9H), 3.95-4.05 (m, 2H), 3.45-3.6 (m, 2H), 3.2-3.3 (m, 2H), 2.95-3.05 (m, 2H), 2.55-2.7 (m, 4H), 2.2-2.3 (m, 2H), 1.95-2.05 (m, 2H), 1.7-1.85 (m, 2H), 1.0-1.35 (br m, 9H). Anal calc C28H36N2O HCl.0.5H2O: C, 72.78; H, 8.29; N, 6.06. Found: C, 73.01; H, 7.94; N, 5.85.

Workup

  1. customThe organic layer was separated
  2. washwashed with brine
  3. dry with materialdried over K2CO3
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customThe remaining oil was absorbed onto silica gel
  7. custompurified by flash chromatography
  8. washeluted with 5% 0.5 M NH3 in MeOH 95% CH2Cl2
  9. filtrationfiltered
  10. customprecipitated
  11. additionafter the addition of ethereal HCl

Sources & evidence

ORD record
ord-447fff5222174152b2ab5cbe610c1929
Source dataset
uspto-grants-2003_04
Patent number
US06552036B2

Reaction notes

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