Dimethyl acetylenedicarboxylate → HCID 76721669, compound

HRID 1258132Notes

Reaction equation

HRID 1258132 reaction equation
[C:1]([C:7]([O:9][CH3:10])=[O:8])#[C:2][C:3]([O:5][CH3:6])=[O:4].[O:11]1[C:15]2[CH:16]=[CH:17][C:18]([CH:20]3[CH2:22][NH:21]3)=[CH:19][C:14]=2[O:13][CH2:12]1>O1CCCC1>[CH3:6][O:5][C:3](=[O:4])[C:2]([N:21]1[CH2:22][CH:20]1[C:18]1[CH:17]=[CH:16][C:15]2[O:11][CH2:12][O:13][C:14]=2[CH:19]=1)=[CH:1][C:7]([O:9][CH3:10])=[O:8]

Participants

4

Reactant 2

HCID 12980Dimethyl acetylenedicarboxylateHCID 12316717Aziridine, 2-(1,3-benzodioxol-5-yl)-

Product 1

HCID 76721669HCID 76721669, compoundYield 59.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
25 °C

Procedure

Dimethyl acetylene dicarboxylate (75 μL, 0.61 mmol, 1.0 equiv) was added via syringe to a stirred solution of aziridine 15 (100 mg, 0.61 mmol, 1.0 equiv) in tetrahydrofuran (1.0 mL) at 25° C. The resulting bright yellow solution was stirred at 25° C. for 2 d. The reaction mixture was concentrated by rotary evaporation. The residue was purified by silica gel column chromatography (1% triethylamine and 24% ethyl acetate in benzene) to afford 26 (110 mg, 57% yield, 3:1 E:Z mixture) as a yellow film. E-26: Rf=0.31 (1% triethylamine and 24% ethyl acetate in benzene); 1H NMR (500 MHz, C6D6) δ 6.64 (m, 1H, ArH), 6.52-6.54 (m, 2H, ArH), 5.30 (s, 1H, vinyl H), 5.22-5.25 (m, 2H, OCH2O), 3.52 (s, 3H, OCH3), 3.34 (s, 3H, OCH3), 2.84 (dd, 1H, J=6, 3.5 Hz, ArCHN), 1.84 (d, 1H, J=6 Hz, CH2N), 1.71 (d, 1H, J=3.5 Hz, CH2N).

Workup

  1. concentrationThe reaction mixture was concentrated by rotary evaporation
  2. customThe residue was purified by silica gel column chromatography (1% triethylamine and 24% ethyl acetate in benzene)

Sources & evidence

ORD record
ord-d624ac62c8b049afb96a65dd3dba37bc
Source dataset
uspto-grants-2013_06
Patent number
US08466142B2

Reaction notes

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