Dimethylamine → (Dihydro-3,3-diphenyl-3H-furan-2-ylidene)dimethylammonium bromide

HRID 1604432Notes

Reaction equation

HRID 1604432 reaction equation
[Br:1][CH2:2][CH2:3][C:4]([C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:5](O)=[O:6].O=S(Cl)Cl.[CH3:24][NH:25][CH3:26].C([O-])([O-])=O.[Na+].[Na+].BrCCC(C1C=CC=CC=1)(C1C=CC=CC=1)C(Cl)=O>C(Cl)(Cl)Cl.O.C1(C)C=CC=CC=1>[Br-:1].[CH3:24][N+:25]([CH3:26])=[C:5]1[C:4]([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[CH2:3][CH2:2][O:6]1

Participants

9

Reactant 5

HCID 674DimethylamineHCID 10340Sodium CarbonateHCID 24386Thionyl ChlorideHCID 27569594-Bromo-2,2-diphenylbutyric acidHCID 222500664-Bromo-2,2-diphenylbutyric chloride

Product 1

HCID 2723589(Dihydro-3,3-diphenyl-3H-furan-2-ylidene)dimethylammonium bromide

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 1140TolueneSolventHCID 6212ChloroformSolvent

Procedure

To a suspension of 4-bromo-2,2-diphenylbutyric acid from Step A (227 g, 0.70 mol) in CHCl3 (1500 ml) was added dropwise SOCl2 (160 ml). This mixture was refluxed for 4 hrs and allowed to cool, and the solvent was removed in vacuo. The crude 4-bromo-2,2-diphenylbutyroyl chloride (227 g, 93%) was used without further purification. To a solution of dimethylamine (54 g, 0.12 mol) and Na2CO3 (25.4 g, 0.24 mol) in H2O (100 ml) was added dropwise a solution of 4-bromo-2,2-diphenylbutyroyl chloride (33.8 g, 0.1 mol) in toluene (100 ml), while the temperature was maintained between 0 and 5° C. The mixture was stirred for an additional 2 hrs and extracted with CHCl3. The organic layer was dried (MgSO4) and the solvent was removed in vacuo. The residue was crystallized from i-BuCOMc to give pure dimethyl-(tetrahydro-3,3-diphenyl-2-furylidene)ammonium bromide. (17.3 g, 50%): mp 181-182°: UV max (95% EtOH) 255 nm (540) and 261 (425); IR (KBr) 1675-1680 cm-1 (C=N); nmr (CDCl3) δ3.03 (s, 3), 3.50 (t, 2), 3.8 (s, 3), 4.89 (t, 2), and 7.51 ppm (s, 10).

Workup

  1. temperatureThis mixture was refluxed for 4 hrs
  2. temperatureto cool
  3. customthe solvent was removed in vacuo
  4. customThe crude 4-bromo-2,2-diphenylbutyroyl chloride (227 g, 93%) was used without further purification
  5. temperaturewhile the temperature was maintained between 0 and 5° C
  6. extractionextracted with CHCl3
  7. dry with materialThe organic layer was dried (MgSO4)
  8. customthe solvent was removed in vacuo
  9. customThe residue was crystallized from i-BuCOMc

Sources & evidence

ORD record
ord-8f61b6259b394fa88e44ce9fd5c23a1d
Source dataset
uspto-grants-1999_11
Patent number
US05994372

Reaction notes

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