1-Tetradecyne → HCID 19812014, compound

HRID 373167Notes

Reaction equation

HRID 373167 reaction equation
[Li][CH2:2][CH2:3][CH2:4][CH3:5].[CH:6]#[C:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16]CCC.C1(OC#[N:28])C=CC=CC=1>CCOCC>[C:2](#[N:28])[C:3]#[C:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH3:16]

Participants

5

Reactant 3

HCID 698231-TetradecyneHCID 70740Phenyl cyanateHCID 178418339Butyllithium

Product 1

HCID 19812014HCID 19812014, compoundYield 77.9%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Conditions

Temperature
70 °C

Procedure

n-BuLi (2.2 M, 24.3 mL, 53.5 mmol) was added dropwise to a cooled (-78° C.) slurry of tetradecyne (10.3 g, 52.7 mmol) in anhydrous ether (60 mL) at a rate not allowing the temperature to rise above -40° C. The resulting slurry was stirred (5 minutes, 70° C.), then phenyl cyanate (6.9 g, 58.0 mmol) was added dropwise at a rate not allowing the temperature to rise above -60° C. The resulting slurry was stirred (45 minutes, -78° C.) then warmed (25° C.). The resulting solution was diluted with ether (140 mL), washed with 1.5 N NaOH (2×100 mL), washed with brine (1×100 mL), then dried (MgSO4), and concentrated in vacuo. The resulting oil was chromatographed on silica (pentane to 95:5 pentane:ether) to yield 9.0 g (77.8%) of 2-pentadecynenitrile as a pale yellow liquid.

Workup

  1. customto rise above -40° C
  2. customto rise above -60° C
  3. stirringThe resulting slurry was stirred (45 minutes, -78° C.)
  4. temperaturethen warmed (25° C.)
  5. washwashed with 1.5 N NaOH (2×100 mL)
  6. washwashed with brine (1×100 mL)
  7. dry with materialdried (MgSO4)
  8. concentrationconcentrated in vacuo
  9. customThe resulting oil was chromatographed on silica (pentane to 95:5 pentane:ether)

Sources & evidence

ORD record
ord-b878424b7d4244a586e862c1762eba40
Source dataset
uspto-grants-1992_11
Patent number
US05162360

Reaction notes

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