N-methyl-2-pyrrolidone → 4-(Heptyloxy)benzonitrile

HRID 716380Notes

Reaction equation

HRID 716380 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([O:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH3:15])=[CH:4][CH:3]=1.[CH3:16][N:17]1C(=O)CCC1>[C-]#N.[Zn+2].[C-]#N.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH2:9]([O:8][C:5]1[CH:6]=[CH:7][C:2]([C:16]#[N:17])=[CH:3][CH:4]=1)[CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH3:15]

Participants

5

Reactant 2

HCID 13387N-methyl-2-pyrrolidoneHCID 5991021-(4-Bromophenoxy)heptane

Product 1

HCID 52310344-(Heptyloxy)benzonitrileYield 73%

Reagents, catalysts & solvents 2

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 11979704Tetrakis(triphenylphosphine)palladiumCatalyst

Conditions

Temperature
100 °C

Procedure

Prepared using General Procedure 1: A stirred a solution of 1-bromo-4-(heptyloxy)benzene (2.0 g, 7.37 mmol), zinc cyanide (1.73 g, 14.74 mmol) and tetrakis (triphenylphosphine) palladium (76.12 mg, 0.07 mol) in dry NMP (20 mL) was degassed with N2. The reaction was heated to 100° C. for 18 h while stirring under nitrogen. The reaction mixture was cooled and poured into water (100 mL) and DCM (20 mL). The solid material was removed by filtration and the filtrate was extracted with water (3×20 mL). The organic layer was dried over MgSO4 and concentrated. The crude product was purified by chromatography (EA/hexanes) to afford 1.15 g (73%) of 4-(heptyloxy)benzonitrile as a light yellow solid. LCMS-ESI (m/z) calculated for C14H19NO: 217.1. found 218.1 [M+H]+, tR=11.14 min (Method 2). 1H NMR (400 MHz, CDCl3) δ 7.64-7.50 (m, 2H), 7.05-6.83 (m, 2H), 3.99 (t, J=6.5 Hz, 2H), 1.89-1.69 (m, 2H), 1.58-1.12 (m, 8H), 0.90 (dd, J=9.1, 4.5 Hz, 3H). 13C NMR (101 MHz CDCl3) δ 162.47, 133.91, 132.78, 132.12, 129.13, 119.31, 115.18, 103.58, 68.41, 31.73, 28.98, 25.89, 22.58, 14.07.

Workup

  1. customPrepared
  2. customwas degassed with N2
  3. temperatureThe reaction mixture was cooled
  4. additionpoured into water (100 mL) and DCM (20 mL)
  5. customThe solid material was removed by filtration
  6. extractionthe filtrate was extracted with water (3×20 mL)
  7. dry with materialThe organic layer was dried over MgSO4
  8. concentrationconcentrated
  9. customThe crude product was purified by chromatography (EA/hexanes)

Sources & evidence

ORD record
ord-5c7799d35fb24845aab981089910cf83
Source dataset
uspto-grants-2015_11
Patent number
US09187522B2

Reaction notes

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