Dichloromethane → HCID 68427637, compound

HRID 1716801Notes

Reaction equation

HRID 1716801 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([CH2:9][CH2:10][N:11]2[CH:15]([C:16]3[CH:21]=[CH:20][C:19]([CH3:22])=[C:18]([CH3:23])[CH:17]=3)[CH2:14][NH:13][C:12]2=[O:24])=[CH:5][CH:4]=1.[N:25]([O-])=O.[Na+].[Cl:29]CCl.[OH-].[NH4+]>C(O)(=O)C.O.[Zn]>[ClH:29].[NH2:25][N:13]1[CH2:14][CH:15]([C:16]2[CH:21]=[CH:20][C:19]([CH3:22])=[C:18]([CH3:23])[CH:17]=2)[N:11]([CH2:10][CH2:9][C:6]2[CH:5]=[CH:4][C:3]([O:2][CH3:1])=[CH:8][CH:7]=2)[C:12]1=[O:24]

Participants

8

Reactant 4

HCID 6344DichloromethaneHCID 14923Ammonium HydroxideHCID 23668193Sodium NitriteHCID 44542182HCID 44542182, compound

Product 1

HCID 68427637HCID 68427637, compoundYield 81%

Reagents, catalysts & solvents 3

HCID 23994ZincCatalystHCID 176Acetic AcidSolventHCID 962WaterSolvent2×

Conditions

Temperature
8 °C

Procedure

To a solution of 1-[2-(4-methoxyphenyl)ethyl]-5-(3,4-dimethylphenyl)-2-imidazolidinone (2.0 g, 0.0062 mol) in glacial acetic acid (21 mL) is added a solution of sodium nitrite (0.58 g, 0.0084 mol) in H2O (2.8 mL) at room temperature over 2 minutes. The solution is stirred for 30 minutes and then cooled to 8° C. Zinc dust (0.84 g, 0.013 mol) is added at 8° C. to 18° C. in portions and the mixture is stirred two hours at 12° C. to 18° C. The reaction is cooled in an ice bath and dichloromethane (20 mL) and H2O (20 mL) are added. Then concentrated ammonium hydroxide (34 mL) is added slowly, maintaining the temperature below 25° C. The organic layer is separated, washed with brine, dried (Na2SO4), treated with 2 M HCl/ether (3.3 mL) and concentrated. The residue is heated in ethyl acetate (8 mL) and diluted slowly with hexanes (30 mL). The resulting solid is collected and triturated with 20% ether/hexanes (50 mL). The solid is collected and re-crystallized from ethyl acetate (8 mL) to afford 1.88 g (81% yield) of the desired compound. 1H NMR (CDCl3) δ 7.06 (m, 3H), 6.95 (d, J=8.1 Hz, 2H), 6.74 (d, J=8.1 Hz, 2H), 4.42 (m, 1H), 4.25 (m, 1H), 3.90 (m, 1H), 3.75 (s, 3H), 3.60 (m, 1H), 2.89 (m, 1H), 2.71 (m, 1H), 2.58 (m, 1H), 2.21 (s, 3H), 2.20 (s, 3H). MS 340 (MH+). Anal. calcd. for C20H25N3O2HCl: C, 63.91; H, 6.97; N, 11.18. Found: C, 63.71; H, 6.67; N, 11.18.

Workup

  1. stirringthe mixture is stirred two hours at 12° C. to 18° C
  2. temperatureThe reaction is cooled in an ice bath
  3. temperaturemaintaining the temperature below 25° C
  4. customThe organic layer is separated
  5. washwashed with brine
  6. dry with materialdried (Na2SO4)
  7. additiontreated with 2 M HCl/ether (3.3 mL)
  8. concentrationconcentrated
  9. temperatureThe residue is heated in ethyl acetate (8 mL)
  10. additiondiluted slowly with hexanes (30 mL)
  11. customThe resulting solid is collected
  12. customtriturated with 20% ether/hexanes (50 mL)
  13. customThe solid is collected
  14. customre-crystallized from ethyl acetate (8 mL)

Sources & evidence

ORD record
ord-9620ff6b604a4ee1a40ff46ac9445178
Source dataset
uspto-grants-2010_09
Patent number
US07803827B2

Reaction notes

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