Pyridine → Methyl 8-cyano-5,6-dihydro-2-naphthoate

HRID 1417904Notes

Reaction equation

HRID 1417904 reaction equation
[CH3:1][O:2][C:3]([C:5]1[CH:14]=[C:13]2[C:8]([CH2:9][CH2:10][CH2:11][C:12]2=O)=[CH:7][CH:6]=1)=[O:4].C[Si]([C:20]#[N:21])(C)C.N1C=CC=CC=1.P(Cl)(Cl)(Cl)=O>C1C=CC=CC=1.[I-].[Zn+2].[I-]>[C:20]([C:12]1[C:13]2[CH:14]=[C:5]([C:3]([O:2][CH3:1])=[O:4])[CH:6]=[CH:7][C:8]=2[CH2:9][CH2:10][CH:11]=1)#[N:21]

Participants

7

Reactant 4

HCID 1049PyridineHCID 24813Phosphorus oxychlorideHCID 82115Trimethylsilyl cyanideHCID 10987358Methyl 8-oxo-5,6,7,8-tetrahydronaphthalene-2-carboxylate

Product 1

HCID 14756558Methyl 8-cyano-5,6-dihydro-2-naphthoateYield 47.1%

Reagents, catalysts & solvents 2

HCID 9883512zinc(II)iodideCatalystHCID 241BenzeneSolvent

Procedure

A solution of 1-tetralon-7-carboxylic acid methyl ester (3.50 g, 0.017 mol), trimethylsilylcyanide (1.98 g, 0.02 mol) and zinc iodide (0.10 g) in benzene (20 mL) was stirred at ambient temperature over 15 hours. Then added, sequentially and dropwise, was pyridine (20 mL) and phosphorous oxychloride (4.0 mL, 6.55 g, 0.0425 mol). The reaction mixture was stirred at reflux over 1 hour then evaporated to dryness under reduced pressure. The residue was taken up in chloroform, backwashed with water, dried over anhydrous magnesium sulfate and evaporated to dryness under reduced pressure to give methyl 8-cyano-5,6-dihydro-2-naphthoate (1.70 g, 0.008 mol, 47%) as a yellow solid. mp=73°-75° C.; 1H NMR (CDCl3) d 8.0-7.9 (m, 1H), 7.3-7.2 (m, 1H), 6.95 (t, 1H, J=4.8 Hz), 3.95 (s, 3H), 2.9 (t, 2H, J=8.3 Hz), 2.6-2.4 (m, 3H).

Workup

  1. additionThen added
  2. temperatureat reflux over 1 hour
  3. customthen evaporated to dryness under reduced pressure
  4. dry with materialdried over anhydrous magnesium sulfate
  5. customevaporated to dryness under reduced pressure

Sources & evidence

ORD record
ord-1171d27f375644f8bd624b03188ae1e3
Source dataset
uspto-grants-1999_03
Patent number
US05879657

Reaction notes

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