Water → HCID 69204352, compound

HRID 2378306Notes

Reaction equation

HRID 2378306 reaction equation
C(OP([CH2:9][C:10]#[N:11])(=O)OCC)C.C[Si]([N-][Si](C)(C)C)(C)C.[Li+].[O:22]1[C:26]2[CH:27]=[CH:28][C:29]([C:31]([C:33]3[CH:38]=[CH:37][CH:36]=[C:35]([O:39][CH3:40])[CH:34]=3)=O)=[CH:30][C:25]=2[O:24][CH2:23]1.O>C1COCC1>[O:22]1[C:26]2[CH:27]=[CH:28][C:29]([C:31]([C:33]3[CH:38]=[CH:37][CH:36]=[C:35]([O:39][CH3:40])[CH:34]=3)=[CH:9][C:10]#[N:11])=[CH:30][C:25]=2[O:24][CH2:23]1

Participants

6

Reactant 4

HCID 962WaterHCID 75676Diethyl (cyanomethyl)phosphonateHCID 2733832Lithium HexamethyldisilazideHCID 24820456HCID 24820456, compound

Product 1

HCID 69204352HCID 69204352, compoundYield 46%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of cyanomethylphosphonic acid diethyl ester (2.1 mL, 13.6 mmol) in anhydrous THF (15 mL) was added lithium bis(trimethylsilyl)amide (1.0 M solution in THF, 13.6 mL, 13.6 mmol) at 0° C. and stirred for 30 min at room temperature followed by addition of benzo[1,3]dioxol-5-yl-(3-methoxy-phenyl)-methanone (1.74 g crude, 6.8 mmol) in THF (15 mL) and refluxed for one hour. The reaction mixture was poured into water (50 mL), extracted with CH2Cl2 (2×50 mL). The combined organic phases were washed with brine (50 mL), dried over MgSO4, and purified via flash column chromatography (EtOAc, Hexane) to give 3-benzo[1,3]dioxol-5-yl-3-(3-methoxy-phenyl)-acrylonitrile as an oil (0.87 g, 46% yield): 1H NMR (DMSO-d6) δ 3.77 and 3.78 (2s, 3H, OCH3), 6.10 and 6.13 (2s, 2H, CH2), 6.23 and 6.27 (2s, 1H, CH), 6.69-7.46 (m, 7H, Ar); 13C NMR (DMSO-d6) δ 55.2, 55.2, 94.4, 95.6, 101.6, 101.8, 107.4, 108.2, 108.3, 109.3, 113.7, 114.6, 115.0, 118.2, 120.9, 121.2, 123.7, 123.8, 129.7, 129.8, 130.6, 131.6, 138.6, 139.6, 147.3, 147.9, 148.5, 149.4, 159.1, 159.2, 160.9, 161.1. LC/MS showed desired peak at 280 for (M+1)+1 positive ion mass.

Workup

  1. temperaturerefluxed for one hour
  2. extractionextracted with CH2Cl2 (2×50 mL)
  3. washThe combined organic phases were washed with brine (50 mL)
  4. dry with materialdried over MgSO4
  5. custompurified via flash column chromatography (EtOAc, Hexane)

Sources & evidence

ORD record
ord-53cb47bd4aee4cd9b8af8fc732b9caf3
Source dataset
uspto-grants-2008_12
Patent number
US07470723B2

Reaction notes

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