Diisopropylethylamine → 4-(2-Cyanoethylamino)-3-nitro-benzoic acid methyl ester

HRID 555282Notes

Reaction equation

HRID 555282 reaction equation
[CH3:1][O:2][C:3](=[O:14])[C:4]1[CH:9]=[CH:8][C:7](F)=[C:6]([N+:11]([O-:13])=[O:12])[CH:5]=1.C(O)(=O)/C=C/C(O)=O.[NH2:23][CH2:24][CH2:25][C:26]#[N:27].CCN(C(C)C)C(C)C>CN(C=O)C>[CH3:1][O:2][C:3](=[O:14])[C:4]1[CH:9]=[CH:8][C:7]([NH:27][CH2:26][CH2:25][C:24]#[N:23])=[C:6]([N+:11]([O-:13])=[O:12])[CH:5]=1

Participants

5

Reactant 3

HCID 81531DiisopropylethylamineHCID 5219721Methyl 4-fluoro-3-nitrobenzoateHCID 6433176Propanenitrile, 3-amino-, (2E)-2-butenedioate (1:1)

Product 1

HCID 669876614-(2-Cyanoethylamino)-3-nitro-benzoic acid methyl esterYield 200.3%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a solution of 4-fluoro-3-nitro-benzoic acid methyl ester (4.95 g, 24.8 mmol) in DMF (25 ml) was added 3-aminopropionitrile fumarate (3.18 g, 12.4 mmol) and DIPEA (15 ml, 84.3 mmol). The mixture was stirred at room temperature for 2 h. The solvent was evaporated under vacuum and the residue diluted with water (50 mL). It was extracted with EtOAc (3×100 mL) and the organic phase washed with brine solution and dried (Na2SO4). Removal of solvent gave 4-(2-cyanoethylamino)-3-nitro-benzoic acid methyl ester (6.19 g, 98.5%). MS-ESI m/z 250 (M+1); 1H NMR (300 MHz, CDCl3) δ 2.8 (t, 2H), 3.8 (m, 2H), 6.9 (d, 1H), 8.2 (m, 1H), 8.5 (t, 1H), 8.9 (s, 1H)

Workup

  1. customThe solvent was evaporated under vacuum
  2. additionthe residue diluted with water (50 mL)
  3. extractionIt was extracted with EtOAc (3×100 mL)
  4. washthe organic phase washed with brine solution
  5. dry with materialdried (Na2SO4)
  6. customRemoval of solvent

Sources & evidence

ORD record
ord-cf18bfcbc5ae4fe1a34a22bdeeadfeaf
Source dataset
uspto-grants-2011_11
Patent number
US08053431B2

Reaction notes

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