Triethylamine → HCID 86762463, compound

HRID 1028860Notes

Reaction equation

HRID 1028860 reaction equation
C(Cl)(=O)C(Cl)=O.[C:7]([O:14][CH3:15])(=[O:13])/[CH:8]=[CH:9]/[C:10]([O-:12])=O.[C:16]([O:24][NH:25][CH2:26][CH2:27][CH2:28][CH2:29][NH:30][C:31](=[O:37])[O:32][C:33]([CH3:36])([CH3:35])[CH3:34])(=[O:23])[C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1.C(N(CC)CC)C.[NH4+].[Cl-]>C(Cl)Cl.CN(C1C=CN=CC=1)C.CN(C=O)C>[C:16]([O:24][N:25]([CH2:26][CH2:27][CH2:28][CH2:29][NH:30][C:31]([O:32][C:33]([CH3:36])([CH3:35])[CH3:34])=[O:37])[C:10](=[O:12])/[CH:9]=[CH:8]/[C:7]([O:14][CH3:15])=[O:13])(=[O:23])[C:17]1[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=1

Participants

9

Reactant 5

HCID 8471TriethylamineHCID 25517Ammonium ChlorideHCID 65578Oxalyl chlorideHCID 21721168(E)-4-methoxy-4-oxobut-2-enoateHCID 86762462HCID 86762462, compound

Product 1

HCID 86762463HCID 86762463, compoundYield 72%

Reagents, catalysts & solvents 3

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolvent2×

Procedure

Oxalyl chloride (0.39 mL, 4.5 mmol) was added dropwise to a solution of mono-methyl fumarate (0.64 g, 4.9 mmol) in distilled CH2Cl2 (7 mL) at 0° C., then a drop of anhydrous DMF was added. The resulting mixture was stirred at this temperature for 20 minutes before it was warmed to room temperature and stirred for another 30 minutes. A solution of 3 (1.16 g, 3.75 mmol) in distilled CH2Cl2 (3 mL) was added at 0° C., followed by the addition of freshly distilled triethylamine (1.05 mL, 7.5 mmol) and DMAP (0.049 g, 0.40 mmol). The reaction was stirred at room temperature for 2 h. A saturated aqueous solution of NH4Cl was added and the aqueous layer was extracted with ethyl acetate, dried over anhydrous Na2SO4, filtered and concentrated in vacuo to give a crude oil, which was purified by column chromatography on silica gel (hexanes/ethyl acetate=10:1) to afford 4 (1.14 g, 2.7 mmol) as a colorless oil in 72% yield: IR (thin film): 3368, 2976, 1768, 1713, 1520, 1240, 1170, 1006 cm−1; 1H NMR (400 MHz, CDCl3): δ 8.15-8.03 (m, 2H), 7.68 (t, J=7.5 Hz, 1H), 7.52 (t, J=7.7 Hz, 2H), 7.13 (d, J=15.7 Hz, 1H), 6.92 (d, J=15.4 Hz, 1H), 4.65-4.56 (br, 1H), 3.89 (t, J=6.9 Hz, 2H), 3.73 (s, 3H), 3.18-3.13 (m, 2H), 1.75-1.70 (m, 2H), 1.61-1.52 (m, 2H), 1.39 (s, 9H) ppm; 13C NMR (101 MHz, CDCl3): δ 165.80, 164.62, 156.15, 135.03, 133.03, 131.28, 130.37, 129.20, 126.24, 79.31, 52.43, 52.39, 48.38, 40.20, 28.54, 27.48, 24.50 ppm. HRMS (m/z): [M+Na]+ calcd. for C21H28N2NaO7, 443.1788; found, 443.1792.

Workup

  1. stirringstirred for another 30 minutes
  2. stirringThe reaction was stirred at room temperature for 2 h
  3. extractionthe aqueous layer was extracted with ethyl acetate
  4. dry with materialdried over anhydrous Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customto give a crude oil, which
  8. customwas purified by column chromatography on silica gel (hexanes/ethyl acetate=10:1)

Sources & evidence

ORD record
ord-f781036359f54c7d88dc458a6498a30d
Source dataset
uspto-grants-2014_05
Patent number
US08735622B2

Reaction notes

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