Toluene → (1,1'-Biphenyl)-2-carbonitrile

HRID 2253548Notes

Reaction equation

HRID 2253548 reaction equation
[C-]#N.[Na+].C1(C)C=CC=CC=1.C[NH:12][CH2:13][CH2:14]NC.Br[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=1[C:24]1C=[CH:28][CH:27]=[CH:26][CH:25]=1>N.[Cu]I>[C:24]1([C:19]2[CH:20]=[CH:21][CH:22]=[CH:23][CH:18]=2)[C:14]([C:13]#[N:12])=[CH:28][CH:27]=[CH:26][CH:25]=1

Participants

7

Reactant 4

HCID 1140TolueneHCID 8070N,N'-DimethylethylenediamineHCID 8929Sodium CyanideHCID 163292-Bromobiphenyl

Product 1

HCID 141162(1,1'-Biphenyl)-2-carbonitrileYield 98%

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 (98 mg, 2.0 mmol), CuI (31 mg, 0.16 mmol, 10 mol %), and KI (55 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 2-bromobiphenyl (285 μL, 1.65 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% aq 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 light yellow oil which crystallized upon storing in a refrigerator (289 mg, 98% yield). Mp 34-37° C. (lit., 35-37° C. See Sain, B.; Sandhu, J. S. J. Org. Chem. 1990, 55, 2545). 1H NMR (400 MHz, CDCl3, J values are reported in Hz, lit. See Hassan, J.; Hathroubi, C.; Gozzi, C.; Lemaire, M. Tetrahedron 2001, 57, 7845): δ 7.80 (ddd, J=7.8, J=1.5, J=0.5, 1H), 7.68 (td, J=7.8, J=1.3, 1H), 7.61-7.44 (m, 7H); 13C NMR (100 MHz, CDCl3): 145.9, 138.6, 138.5, 134.2, 133.3, 130.5, 129.2, 129.1, 128.0, 119.2, 111.7; IR (neat, cm−1): 2224, 1597, 1500, 1477, 1451, 1433, 759, 735, 700. Anal. Calcd. for C13H9N: C, 87.12; H, 5.06; N, 7.82. Found: C 86.84; H 5.22; N 7.94.

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-a8135901d2a04cd79bb6ccb448e3bf78
Source dataset
uspto-grants-2008_01
Patent number
US07323608B2

Reaction notes

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