tert-Butoxy bis(dimethylamino)methane → (E)-Methyl 2-(2-(dimethylamino)vinyl)-4-nitrobenzoate

HRID 708796Notes

Reaction equation

HRID 708796 reaction equation
[CH3:1][C:2]1[CH:11]=[C:10]([N+:12]([O-:14])=[O:13])[CH:9]=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].C(O[CH:20](N(C)C)[N:21]([CH3:23])[CH3:22])(C)(C)C>CN(C=O)C>[CH3:20][N:21]([CH3:23])/[CH:22]=[CH:1]/[C:2]1[CH:11]=[C:10]([N+:12]([O-:14])=[O:13])[CH:9]=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5]

Participants

4

Reactant 2

HCID 79885tert-Butoxy bis(dimethylamino)methaneHCID 15088700Methyl 2-methyl-4-nitrobenzoate

Product 1

HCID 87664981(E)-Methyl 2-(2-(dimethylamino)vinyl)-4-nitrobenzoateYield 70.1%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
143 °C

Procedure

To Intermediate 3A (11.35 g, 58.2 mmol) in DMF (15 ml) was added 1-tert-butoxy-N,N,N′,N′-tetramethylmethanediamine (39.6 ml, 192 mmol). The mixture was heated at 143° C. for 3.0 h. DMF was removed by vacuum distillation at 70° C. to leave a semi solid. The semi-solid was triturated with EtOAc/hexanes (1:4) and stored at 4° C. overnight. The precipitate was collected by filtration to give Intermediate 3B (10.2 g, 40.8 mmol, 70.1% yield) as a dark solid. 1H NMR (400 MHz, chloroform-d) δ ppm 8.21 (d, J=2.20 Hz, 1H) 7.87 (d, J=8.79 Hz, 1H) 7.66 (dd, J=8.79, 2.20 Hz, 1H) 7.02 (d, J=13.19 Hz, 1H) 6.12 (d, J=13.74 Hz, 1H) 3.91 (s, 3H) 2.94 (s, 6H).

Workup

  1. customDMF was removed by vacuum distillation at 70° C.
  2. customto leave a semi solid
  3. customThe semi-solid was triturated with EtOAc/hexanes (1:4)
  4. filtrationThe precipitate was collected by filtration

Sources & evidence

ORD record
ord-52010278bebe4ffe8319b105d4343d06
Source dataset
uspto-grants-2015_11
Patent number
US09174974B2

Reaction notes

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