Sodium hydride → HCID 24857760, compound

HRID 556154Notes

Reaction equation

CCOP(OCC)([CH2:6][C:7]#[N:8])=O.[H-].[Na+].[Cl:14][C:15]1[CH:16]=[C:17]([CH:22]2[C:31]3[C:26](=[CH:27][CH:28]=[CH:29][CH:30]=3)[CH2:25][C:24](=O)[CH2:23]2)[CH:18]=[CH:19][C:20]=1[Cl:21]>C1COCC1>[Cl:14][C:15]1[CH:16]=[C:17]([CH:22]2[C:31]3[C:26](=[CH:27][CH:28]=[CH:29][CH:30]=3)[CH:25]=[C:24]([CH2:6][C:7]#[N:8])[CH2:23]2)[CH:18]=[CH:19][C:20]=1[Cl:21]

Participants

Conditions

Temperature: 0 °C

Procedure

To a stirred solution of diethyl cyanomethyl phosphonate EtO2POCH2CN (0.324 mL, 2 eq) in THF (2 mL) was added sodium hydride (60 mg, 60% in oil) in portions. After 30 minutes, 4-(3,4-dichlorophenyl)-3,4-dihydronaphthalen-2(1H)-one (beta-tetralone) (291 mg, 1 mmol) was added as a solution in THF (3 mL). After the mixture was stirred for two hours at 0° C., the reaction was quenched with ammonium chloride solution, extracted with MTBE, dried over sodium sulfate and evaporated. The residue was separated on silica to give the unsaturated nitrile (0.24 g, 77%) as a pale-green oil. GC-MS Rt=14.59 min, m/z=313 (M+). 1H NMR (CDCl3, δ): 7.37 (d, J=8.3 Hz, 1H), 7.3 (m, 2H), 7.2 (m, 2H), 7.00 (dd, J=2.1, 8.3 Hz, 1H), 6.84 (d, J=7.4 Hz, 1H), 6.64 (bs, 1H), 4.17 (t, J=8.1 Hz, 1H), 3.21 (bs, 2H), 2.69 (dd, J=6.9, 17.3 Hz, 1H), 2.52 (dd, J=8.4, 17.2 Hz, 1H). 13C NMR (CDCl3, δ, mult): 143.9(0), 135.2(0), 132.9(0), 132.5(0), 130.7(1), 130.5(1), 130.0(1), 128.2(1), 127.7(1), 127.5(1), 126.8(1), 126.4(1), 116.5(0), 43.1(1), 35.1(2), 25.1(2).

Workup

customthe reaction was quenched with ammonium chloride solution
extractionextracted with MTBE
dry with materialdried over sodium sulfate
customevaporated
customThe residue was separated on silica

Sources & evidence

ORD record: ord-11895913da7745f282095849f2cc400a
Source dataset: uspto-grants-2011_11
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08053603B2

Reaction notes

Loading…