Triethylamine → 2-(4-chloro-2-nitrobenzoyl)-2-cyano-N-ethyl-N-methylacetamide

HRID 2231157Notes

Reaction equation

HRID 2231157 reaction equation
[C:1]([CH2:3][C:4]([N:6]([CH2:8][CH3:9])[CH3:7])=[O:5])#[N:2].C(N(CC)CC)C.[Cl:17][C:18]1[CH:26]=[CH:25][C:21]([C:22](Cl)=[O:23])=[C:20]([N+:27]([O-:29])=[O:28])[CH:19]=1.[OH-].[Na+]>C1COCC1.CCOCC>[Cl:17][C:18]1[CH:26]=[CH:25][C:21]([C:22]([CH:3]([C:1]#[N:2])[C:4]([N:6]([CH2:8][CH3:9])[CH3:7])=[O:5])=[O:23])=[C:20]([N+:27]([O-:29])=[O:28])[CH:19]=1

Participants

7

Reactant 4

HCID 8471TriethylamineHCID 14798Sodium HydroxideHCID 108677844-Chloro-2-nitrobenzoyl chlorideHCID 212859352-Cyano-N-ethyl-N-methyl-acetamide

Product 1

HCID 212859892-(4-chloro-2-nitrobenzoyl)-2-cyano-N-ethyl-N-methylacetamideYield 45%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

2-cyano-N-ethyl-N-methylacetamide (5.56 g; 0.044 mol) and triethylamine (13.36 g; 0.132 mol) were dissolved in dry THF (100 ml) under dry nitrogen, and 4-chloro-2-nitrobenzoyl chloride (9.68 g; 0.044 mol) in dry THF (100 ml) added dropwise over 45 min. The mixture was stirred at room temperature under dry nitrogen for 18 hours, during which time a precipitate was formed. The solution was filtered, washing the solid with THF and adding the washings to the solution, and evaporated, giving a residue which was treated with 2M sodium hydroxide solution (200 ml), and this then washed with CH2Cl2 (2×100 ml). The aqueous solution was acidified to pH 1 with concentrated hydrochloric acid, and extracted into CH2Cl2 (3×200 m). The extracts were combined, dried (Na2SO4), filtered and evaporated, giving a very viscous oil which solidified. Trituration with ether (20 ml) gave 2-(4-chloro-2-nitrobenzoyl)-2-cyano-N-ethyl-N-methylacetamide (6.10 g; 45%) as a solid, m.p. 95°-98° C., (Found, C: 49.60; H: 3.87; N: 13.25; Cl: 12.28. C13H12ClN3O4 requires C: 50.40; H: 3.88; N: 13.57; Cl: 11.47%, d (CDCl3); 60 MHz) 1.3 (3H, t, J=7, Hz), 3.2 (3H, s), 3.7 (2H, q, J=7 Hz), 7.4-7.55 (1H, d, J=8 Hz), 7.6-7.8 (1H, dd, J=8, 2 Hz), 8.1 (1H, d, J=2 Hz) and 16.4 (1H, br, s), vmax (nujol) 2200, 1590 (shoulder) and 1500.

Workup

  1. customwas formed
  2. filtrationThe solution was filtered
  3. washwashing the solid with THF
  4. additionadding the washings to the solution
  5. customevaporated
  6. customgiving a residue which
  7. washthis then washed with CH2Cl2 (2×100 ml)
  8. extractionextracted into CH2Cl2 (3×200 m)
  9. dry with materialdried (Na2SO4)
  10. filtrationfiltered
  11. customevaporated
  12. customgiving a very viscous oil which

Sources & evidence

ORD record
ord-81672b0d54494c99bcce1e8fbe813a4c
Source dataset
uspto-grants-1988_11
Patent number
US04781750

Reaction notes

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