Benzene → 7-Methoxy-3,4-dihydronaphthalene-1-carbonitrile

HRID 895222Notes

Reaction equation

HRID 895222 reaction equation
[CH3:1][O:2][C:3]1[CH:12]=[C:11]2[C:6]([CH2:7][CH2:8][CH2:9][C:10]2=O)=[CH:5][CH:4]=1.C1C=CC=CC=1.C[Si]([C:24]#[N:25])(C)C.P(Cl)(Cl)(Cl)=O>[I-].[Zn+2].[I-].N1C=CC=CC=1>[CH3:1][O:2][C:3]1[CH:12]=[C:11]2[C:6]([CH2:7][CH2:8][CH:9]=[C:10]2[C:24]#[N:25])=[CH:5][CH:4]=1

Participants

7

Reactant 4

HCID 241BenzeneHCID 24813Phosphorus oxychlorideHCID 812767-Methoxy-1,2,3,4-tetrahydronaphthalen-1-oneHCID 82115Trimethylsilyl cyanide

Product 1

HCID 115212017-Methoxy-3,4-dihydronaphthalene-1-carbonitrile

Reagents, catalysts & solvents 2

HCID 9883512zinc(II)iodideCatalystHCID 1049PyridineSolvent

Procedure

To a mixture of 7-methoxy-1-tetralone (39.65 g, 0.23 mol), zinc iodide (1.73 g, 5.4 mmol), and benzene (100 mLs) was added trimethylsilylcyanide (25.0 g. 0.25 mol). The mixture was stirred overnight at room temperature. Pyridine (350 mL) was added and phosphorous oxychloride (100 mL) was then added dropwise, with a slight temperature increase. The mixture was heated to reflux and held for 6 hr. TLC showed one mid-Rf spot for the desired product. The mixture was stirred overnight at room temperature. The mixture was carefully poured onto ice/hydrochloric acid (about 1.5 liter of 10% HCl). The total volume was 2 liters. This mixture was extracted with ethyl acetate (3×500 mLs), the organics combined and washed with water (2×500 mLs) and then brine (500 mLs). The ethyl acetate was dried over magnesium sulfate and evaporated off provide a liquid which on standing solidified. This crude solid was slurried in hexane and filtered to give 31.3 g (74%) of a tan solid. Some of this material was purified by silica gel chromatography (10% ethyl acetate-hexanes) to provide a solid: mp 47-49° C.; 1H NMR (DMSO-d6): δ 2.44-2.50 (2H, m), 2.72 (2H, t, J=8.4 Hz), 6.81 (1H, d, J=2.6 Hz), 6.90 (1H, dd, J=2.9 Hz, J=8.2 Hz), 7.17-7.19 (2H, m); MS m/z 168 ([M−H]−);

Workup

  1. temperatureincrease
  2. temperatureThe mixture was heated
  3. temperatureto reflux
  4. waitheld for 6 hr

Sources & evidence

ORD record
ord-91d7929763bb43f6858aa2a9a9c6472f
Source dataset
uspto-grants-2005_07
Patent number
US06914074B2

Reaction notes

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