1,2-Dichloroethane → HCID 19611597, compound

HRID 1956690Notes

Reaction equation

HRID 1956690 reaction equation
C(O[BH-](O[C:11](=O)[CH3:12])OC(=O)C)(=O)C.[Na+].[C:15]([C:17]1[CH:30]=[CH:29][C:20]([CH2:21][N:22]2[C:26]([CH:27]=O)=[CH:25][N:24]=[CH:23]2)=[CH:19][CH:18]=1)#[N:16].CCO[C:34]([CH3:36])=O.[Cl:37][CH2:38][CH2:39]Cl>>[C:15]([C:17]1[CH:30]=[CH:29][C:20]([CH2:21][N:22]2[C:26]([CH2:27][NH:22][CH2:26][CH2:25][NH:24][C:11]3[CH:12]=[CH:36][CH:34]=[C:38]([Cl:37])[CH:39]=3)=[CH:25][N:24]=[CH:23]2)=[CH:19][CH:18]=1)#[N:16]

Participants

5

Reactant 4

HCID 111,2-DichloroethaneHCID 8857Ethyl AcetateHCID 5049666Sodium triacetoxyborohydrideHCID 106322894-[(5-Formylimidazol-1-yl)methyl]benzonitrile

Product 1

HCID 19611597HCID 19611597, compound

Conditions

Temperature
0 °C

Procedure

The amine hydrochloride from Step A (978 mg) was partitioned between dilute aqueous NaHCO3 solution and methylene chloride. The aqueous layer was washed with three portions of CH2Cl2, and the combined organics were dried (Na2SO4), filtered, and concentrated in vacuo to provide the free amine. To a solution of the amine in 11 mL of 1,2-dichloroethane at 0° C. was added 4 Å powdered molecular sieves (2 g), followed by sodium triacetoxyborohydride (3.04 g). The aldehyde from Step E of Example 1 (1.21 g) was added, and the reaction was stirred at 0° C. After 15 hours, , the reaction was poured into EtOAc, washed with sat. aq. NaHCO3, and the aqueous layer was extracted with EtOAc. The combined organics were washed with brine, dried (Na2SO4), filtered, and concentrated in vacuo. The resulting product was taken up in 60 mL of 5:1 benzene:CH2Cl2, and propylamine (10 mL) was added. The reaction was stirred for 12 hours, then concentrated in vacuo, and purified by silica gel chromatography (5% MeOH/CHCl3) to provide the titled compound (1.33 g) as a white foam.

Workup

  1. customThe amine hydrochloride from Step A (978 mg) was partitioned between dilute aqueous NaHCO3 solution and methylene chloride
  2. washThe aqueous layer was washed with three portions of CH2Cl2
  3. dry with materialthe combined organics were dried (Na2SO4)
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customto provide the free amine
  7. washwashed with sat. aq. NaHCO3
  8. extractionthe aqueous layer was extracted with EtOAc
  9. washThe combined organics were washed with brine
  10. dry with materialdried (Na2SO4)
  11. filtrationfiltered
  12. concentrationconcentrated in vacuo
  13. additionCH2Cl2, and propylamine (10 mL) was added
  14. stirringThe reaction was stirred for 12 hours
  15. concentrationconcentrated in vacuo
  16. custompurified by silica gel chromatography (5% MeOH/CHCl3)

Sources & evidence

ORD record
ord-31b6572f49914c6383732b6714027735
Source dataset
uspto-grants-1998_07
Patent number
US05780492

Reaction notes

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