Toluene → 1-Naphthalenecarbonitrile

HRID 2253547Notes

Reaction equation

HRID 2253547 reaction equation
[C-]#N.[Na+].C1(C)C=CC=CC=1.C[NH:12][CH2:13][CH2:14]NC.Br[C:18]1[C:27]2[C:22](=[CH:23][CH:24]=[CH:25]C=2)[CH:21]=[CH:20][CH:19]=1>N.[Cu]I>[C:14]1([C:13]#[N:12])[C:27]2[C:22](=[CH:21][CH:20]=[CH:19][CH:18]=2)[CH:23]=[CH:24][CH:25]=1

Participants

7

Reactant 4

HCID 1140TolueneHCID 70011-BromonaphthaleneHCID 8070N,N'-DimethylethylenediamineHCID 8929Sodium Cyanide

Product 1

HCID 68461-NaphthalenecarbonitrileYield 94.3%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 222AmmoniaSolvent

Conditions

Temperature
130 °C

Procedure

A Schlenk tube was charged with NaCN (95 mg, 1.94 mmol), CuI (31 mg, 0.16 mmol, 10 mol %), and KI (54 mg, 0.33 mmol, 20 mol %), briefly evacuated and backfilled with argon three times. Anhydrous toluene (1.2 mL), N,N′-dimethylethylenediamine (175 μL, 1.64 mmol), and 1-bromonaphthalene (225 μL, 1.62 mmol) were added under argon. The Schlenk tube was sealed with a Teflon valve and the reaction mixture was stirred at 130° C. for 24 h. The resulting suspension was allowed to reach room temperature, diluted with 30% aqueous ammonia (2 mL) and extracted with ethyl acetate (4×2 mL). The combined organic phases were dried over MgSO4, concentrated, and the residue was purified by flash chromatography on silica gel (hexane/ethyl acetate 20:1) to provide the desired product as a pale yellow solid (234 mg, 94% yield). Mp 35-36° C. (lit. 37° C., See Blum, J.; Oppenheimer, E.; Bergmann, E. J. Am. Chem. Soc. 1967, 89,2338). 1H NMR (400 MHz, CDCl3, J values are reported in Hz, lit. See Abraham, R. J.; Reid, M. Magn. Reson. Chem. 2000, 38, 570): δ 8.27 (d, J=8.4, 1H), 8.11 (d, J=8.3, 1H), 7.96 (d, J=8.1, 1H), 7.94 (dd, J=7.2, J=1.1, 1H), 7.73 (ddd, J=8.3, J=6.9, J=1.34, 1H), 7.65 (ddd, J=8.3, J=7.1, J=1.2, 1H), 7.55 (dd, J=8.3, J=7.1, 1H); 13C NMR (100 MHz, CDCl3): 133.7, 133.2, 133.1, 132.8, 129.1, 129.0, 128.0, 125.6, 125.4, 118.3, 110.6; IR (neat, cm−1): 2222, 1604, 1513, 1376, 855, 802, 772, 684, 451. Anal. Calcd. for C11H7N: C, 86.25; H, 4.61; N, 9.14. Found: C, 86.04; H 4.61; N 9.05.

Workup

  1. custombriefly evacuated
  2. customThe Schlenk tube was sealed with a Teflon valve
  3. customto reach room temperature
  4. extractionextracted with ethyl acetate (4×2 mL)
  5. dry with materialThe combined organic phases were dried over MgSO4
  6. concentrationconcentrated
  7. customthe residue was purified by flash chromatography on silica gel (hexane/ethyl acetate 20:1)

Sources & evidence

ORD record
ord-ab0a22ac5a3d42eda1469cd48faa56f4
Source dataset
uspto-grants-2008_01
Patent number
US07323608B2

Reaction notes

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