1-Hexyne → HCID 13748693, compound

HRID 2350825Notes

Reaction equation

HRID 2350825 reaction equation
[CH:1]#[C:2][CH2:3][CH2:4][CH2:5][CH3:6].C([Li])CCC.[CH3:12][C:13]([CH3:25])([C:16](=[O:24])[CH:17]([N:19]1[CH:23]=[N:22][CH:21]=[N:20]1)[CH3:18])[CH2:14][F:15]>C1COCC1>[CH3:25][C:13]([CH3:12])([C:16]([CH:17]([N:19]1[CH:23]=[N:22][CH:21]=[N:20]1)[CH3:18])([OH:24])[C:1]#[C:2][CH2:3][CH2:4][CH2:5][CH3:6])[CH2:14][F:15]

Participants

5

Reactant 3

HCID 127321-HexyneHCID 127695401-Fluoro-2,2-dimethyl-4-(1H-1,2,4-triazol-1-yl)pentan-3-oneHCID 178418339Butyllithium

Product 1

HCID 13748693HCID 13748693, compoundYield 56.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a stirred solution of hex-1-yne (1.23 g, 15 mmol) in dry THF (40 ml) was added n-butyl lithium (6 ml of 2.6M, 15 mmol) at -78° C. under a nitrogen atmosphere. After 15 minutes, a solution of 2,2-dimethyl-1-fluoro-4-(1H-1,2,4-triazol-1-yl)-pentan-3-one (2.5 g, 13 mmol) in dry THF (20 ml) was added dropwise. Upon complete addition the mixture was allowed to warm to room temperature and stirred for 18 hours. The reaction mixture was then poured onto ice and extracted with ether (2×250 ml). The ethereal solution was washed with saturated brine solution then dried over anhydrous magnesium sulphate and the solvent removed. The resulting yellow oil was chromatographed (silica gel, petrol/diethyl ether elution) to give a yellow gum (2.0 g, 56.5%) which was a mixture of the RS/SR and the RR/SS forms. This gum was then purified by preparative chromatography to give the pure RS/SR form as a white solid (0.24 g, 6.8%), mp. 72°-74° C. (Found: C, 63.5; H, 9.0; N, 15.0C15H24FN3O requires C, 64.1; H, 8.5; N, 14.95%); IR 3200, 2950, 2225, 1360, 1280, 1200, 1140, 1000, 870, 680 cm-1 ; NMR (90 MHz; CDCl3) 0.8 (6H, s); 0.9 (3H, t, J 7 Hz); 1.2-1.56 (4H, m); 1.72 (3H, d, J 6.3 Hz); 2.24 (2H, m); 3.8 (1H, br); 4.36 (2H, dq, J 46.8 and 6.3 Hz), 4.8 (1H, q, J 6.3 Hz); 7.95 (1H, s); 8.24 (1H, s); m/z 282 (M+H+) 206, 185, 109, 97 (100%), 82. The RR/SS component could not be isolated in a pure state thus, a 1:1 mixture of the RS/SR and RR/SS forms was obtained as a yellow oil (0.34 g, 9.6%); NMR (90 MHz; CDCl3) 0.8 (6H, s); 0.92 (3H, t, J 7 Hz); 1.2-1.56 (4H, m); 1.66 (3H, d, J 6.3 Hz); 2.13 (2H, m); 3.8 (1H, br); 4.36 (2H, dq, J 46.8 and 6.3 Hz), 4.76 (1H, q, J 6.3 Hz); 7.93 (1H, s); 8.26 (1H, s); m/z 282 (M+H+), 206, 185, 109, 97 (100%), 82.

Workup

  1. additionUpon complete addition the mixture
  2. additionThe reaction mixture was then poured onto ice
  3. extractionextracted with ether (2×250 ml)
  4. washThe ethereal solution was washed with saturated brine solution
  5. dry with materialthen dried over anhydrous magnesium sulphate
  6. customthe solvent removed
  7. customThe resulting yellow oil was chromatographed
  8. wash(silica gel, petrol/diethyl ether elution)

Sources & evidence

ORD record
ord-d2c50b80aa7c4f839b66cabaa25cdb52
Source dataset
uspto-grants-1989_10
Patent number
US04871389

Reaction notes

Loading…