1,2-Dichloroethane → HCID 118414928, compound

HRID 1054310Notes

Reaction equation

HRID 1054310 reaction equation
[Cl:1][CH2:2][CH2:3]Cl.CN(C=O)C.C(Cl)(C(Cl)=O)=O.OC1C=[C:19]([C:41]([O:43][CH2:44][CH3:45])=[O:42])[C:20]2[C:25]([CH3:26])=[N:24][N:23]([CH2:27][C:28]3[CH:33]=[CH:32][C:31]([O:34][C:35]4[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=4)=[CH:30][CH:29]=3)[C:21]=2[N:22]=1>O>[Cl:1][C:2]1[CH:3]=[C:19]([C:41]([O:43][CH2:44][CH3:45])=[O:42])[C:20]2[C:25]([CH3:26])=[N:24][N:23]([CH2:27][C:28]3[CH:29]=[CH:30][C:31]([O:34][C:35]4[CH:36]=[CH:37][CH:38]=[CH:39][CH:40]=4)=[CH:32][CH:33]=3)[C:21]=2[N:22]=1

Participants

6

Reactant 4

HCID 111,2-DichloroethaneHCID 6228DimethylformamideHCID 65578Oxalyl chlorideHCID 178469342HCID 178469342, compound

Product 1

HCID 118414928HCID 118414928, compound

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
0 °C

Procedure

(see, e.g., Sercel, A. D., et al., Synthetic Communications 2007, 37, 4199-4208). Fresh Vilsmeier's reagent was prepared as follows: to a stirring solution of 1.2 DCE (4 mL) was added DMF (0.2 mL, 2.6 mmol). The resulting solution was cooled down to 0° C. and (COCl)2 (0.22 mL, 2.6 mmol) was added dropwise. The viscous suspension was stirred at room temperature for 10 min, and then 49 (104 mg, 0.26 mmol) was added to the mixture. The suspension was heated to reflux overnight. The mixture was diluted with H2O (10 mL) and extracted with EtOAc (15 mL×2). The organic layers were washed with brine, dried (Na2SO4) and concentrated under reduced pressure to provide the title compound (120 mg, quantitative yield) as a yellow oil. Crude was used in the next reaction without further purification. 1H NMR (500 MHz, CDCl3) δ 7.56 (s, 1H), 7.31 (t, J=8.2 Hz, 4H), 7.08 (t, J=7.4 Hz, 1H), 6.97 (d, J=7.7 Hz, 2H), 6.93 (d, J=8.5 Hz, 2H), 5.59 (s, 2H), 4.48 (q, J=7.1 Hz, 2H), 2.69 (s, 3H), 1.46 (t, J=7.1 Hz, 3H). 13C NMR (125 MHz, CDCl3) δ 164.34, 157.00, 156.91, 151.20, 150.30, 141.77, 135.67, 131.25, 129.71, 129.54, 123.37, 119.00, 118.78, 117.69, 110.41, 62.31, 50.03, 16.16, 14.20.

Workup

  1. temperatureThe suspension was heated
  2. temperatureto reflux overnight
  3. extractionextracted with EtOAc (15 mL×2)
  4. washThe organic layers were washed with brine
  5. dry with materialdried (Na2SO4)
  6. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-8111f628f66a4f5fa3f7c2b9d49473a1
Source dataset
uspto-grants-2016_07
Patent number
US09394303B2

Reaction notes

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