Dimethylamine → 1-(4-Benzyloxyphenyl)-1-(dimethylamino)-2-(4-methoxyphenyl)ethylene

HRID 1379688Notes

Reaction equation

HRID 1379688 reaction equation
[CH3:1][NH:2][CH3:3].[CH2:4]([O:11][C:12]1[CH:17]=[CH:16][C:15]([C:18](=O)[CH2:19][C:20]2[CH:25]=[CH:24][C:23]([O:26][CH3:27])=[CH:22][CH:21]=2)=[CH:14][CH:13]=1)[C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1.CCOCC>C1(C)C=CC=CC=1.Cl[Ti](Cl)(Cl)Cl>[CH2:4]([O:11][C:12]1[CH:17]=[CH:16][C:15]([C:18]([N:2]([CH3:3])[CH3:1])=[CH:19][C:20]2[CH:25]=[CH:24][C:23]([O:26][CH3:27])=[CH:22][CH:21]=2)=[CH:14][CH:13]=1)[C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1

Participants

6

Reactant 3

HCID 674DimethylamineHCID 3283Diethyl EtherHCID 189237831-(4-(Benzyloxy)phenyl)-2-(4-methoxyphenyl)ethanone

Product 1

HCID 539811911-(4-Benzyloxyphenyl)-1-(dimethylamino)-2-(4-methoxyphenyl)ethyleneYield 77%

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 1140TolueneSolvent3×

Conditions

Temperature
0 °C

Procedure

Dimethylamine (55 mL, 0.15 mol) in 100 mL of toluene was added over ten min at 0°-5° C. to a 600 mL toluene suspension of 1-(4-benzyloxyphenyl)-2-(4-methoxyphenyl)ethan-l-one (50 g, 0.15 mol), then stirred 15 min at 0° C. A 50 mL toluene solution of TiCl4 (9.8 mL, 0.09 mol) was added dropwise over 1 h to the reaction mixture, keeping the temperature below 5° C. The brown suspension was stirred 16 h at rt then filtered through Hyflo Super Cel to give a yellow filtrate. Two Et2O washes of the filter bed were combined with the filtrate and the solution was concentrated to a thick amber oil. The oil was triturated with Et2O/ pet. ether and filtered to give 41 g (77%) of yellow solid: mp 60° C.; 1H NMR (CDCl3) d 2.64 (s, 6H, NMe2), 3.71 (s, 3H, OCH3), 5.07 (s, 2H, OCH2), 5.42 (s, 1H, =CH), 6.57-6.60 (d, 2H, J=9 Hz, ArH), 6.67-6.70 (d, 2H, J=9 Hz, ArH), 6.86-6.89 (d, 2H, J=9 Hz, ArH), 6.90-6.93 (d, 2H, J=9 Hz, ArH), 7.18-7.21 (d, 2H, J=9 Hz, ArH), 7.40-7.45 (m, 5H, ArH); MS(FD) 360[M+1]+Anal. Calcd for C24H25NO2 : C, 80.19; H, 7.01; N, 3.90. Found: C, 80.41; H, 7.12; N, 4.09.

Workup

  1. customthe temperature below 5° C
  2. stirringThe brown suspension was stirred 16 h at rt
  3. filtrationthen filtered through Hyflo Super Cel
  4. customto give a yellow filtrate
  5. concentrationthe solution was concentrated to a thick amber oil
  6. customThe oil was triturated with Et2O/ pet. ether
  7. filtrationfiltered

Sources & evidence

ORD record
ord-300902156f70407987e52ba1c15a6490
Source dataset
uspto-grants-1997_09
Patent number
US05672609

Reaction notes

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