Diethyl (cyanomethyl)phosphonate → HCID 10357038, compound

HRID 2378176Notes

Reaction equation

HRID 2378176 reaction equation
[O:1]1[C:5]2[CH:6]=[CH:7][C:8]([C:10]([C:12]3[CH:20]=[CH:19][C:15]4[O:16][CH2:17][O:18][C:14]=4[CH:13]=3)=O)=[CH:9][C:4]=2[O:3][CH2:2]1.C(OP([CH2:29][C:30]#[N:31])(=O)OCC)C.C[Si]([N-][Si](C)(C)C)(C)C.[Li+].O1C2C=CC(C(C3C=C(OC)C=C(OC)C=3)=CC#N)=CC=2OCC1>C1COCC1>[O:1]1[C:5]2[CH:6]=[CH:7][C:8]([C:10]([C:12]3[CH:20]=[CH:19][C:15]4[O:16][CH2:17][O:18][C:14]=4[CH:13]=3)=[CH:29][C:30]#[N:31])=[CH:9][C:4]=2[O:3][CH2:2]1

Participants

6

Reactant 4

HCID 75676Diethyl (cyanomethyl)phosphonateHCID 2733832Lithium HexamethyldisilazideHCID 13702117HCID 13702117, compoundHCID 692032153-(2,3-Dihydrobenzo[1,4]dioxin-6-yl)-3-(3,5-dimethoxyphenyl)acrylonitrile

Product 1

HCID 10357038HCID 10357038, compoundYield 81%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Bis-benzo[1,3]dioxol-5-yl-methanone (2.41 g, 8.92 mmol), cyanomethylphosphonic acid diethyl ester (2.81 ml, 17.84 mmol) in anhydrous THF (10 ml), and lithium bis(trimethylsilyl)amide (1.0 M solution in THF, 17.84 ml, 17.84 mmol) were treated in the same manner as described above for the synthesis of 3-(2,3-dihydrobenzo[1,4]dioxin-6-yl)-3-(3,5-dimethoxyphenyl)acrylonitrile. The crude material was purified via flash column chromatography (10% EtOAc in hexane gradient to 50% EtOAc in hexane in about 40 min.) to give 3,3-bis-benzo[1,3]dioxol-5-yl-acrylonitrile as an off-white solid (2.11 g, 81%): mp, 126-128° C.; 1HNMR (DMSO-d6) δ 7.07-7.03 (2 ds, J=1.84 and J=8 Hz, 2H, Ar), 6.94 (d, J=8 Hz, 1H, Ar), 6.90 (d, J=1 Hz, 1H, Ar), 6.86 (dd, J=1.76 and J =7 Hz, 1H, Ar), 6.74 (dd, J=1.82 and J=8 Hz, 1H, Ar), 6.13 (s, 1H, double bond proton), 6.12 (s, 2H, CH2), 6.10 (s, 2H, CH2); 13C NMR (DMSO-d6) δ 160.8, 149.4, 148.4, 147.8, 147.3, 132.2, 130.9, 123.8, 123.6, 118.5, 109.4, 108.4, 108.2, 107.7, 101.8, 101.6, 93.8. Anal. Calcd. For C17H11NO4: C, 69.62; H, 3.78; N, 4.78. Found: C, 68.43; H, 3.97; N, 4.37.

Workup

  1. customThe crude material was purified via flash column chromatography (10% EtOAc in hexane gradient to 50% EtOAc in hexane in about 40 min.)

Sources & evidence

ORD record
ord-f08fb6365af04f05a9868d77ce1faaf1
Source dataset
uspto-grants-2008_12
Patent number
US07470723B2

Reaction notes

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