Lithium Hydroxide → HCID 59511126, compound

HRID 1774257Notes

Reaction equation

HRID 1774257 reaction equation
C[O:2][C:3](=[O:20])[C:4]1[CH:9]=[CH:8][C:7]([CH2:10][C:11]2([F:19])[CH2:18][CH2:17][CH2:16][CH2:15][CH2:14][C:13]#[C:12]2)=[CH:6][CH:5]=1.[Li+].[OH-]>O1CCOCC1.O>[F:19][C:11]1([CH2:10][C:7]2[CH:6]=[CH:5][C:4]([C:3]([OH:20])=[O:2])=[CH:9][CH:8]=2)[CH2:18][CH2:17][CH2:16][CH2:15][CH2:14][C:13]#[C:12]1

Participants

5

Reactant 2

HCID 3939Lithium HydroxideHCID 59511129HCID 59511129, compound

Product 1

HCID 59511126HCID 59511126, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
50 °C

Procedure

To a solution of cyclooctyne 8b (1.8 g, 6.6 mmol) in dioxane (30 mL) and H2O (7.5 mL) was added finely crushed LiOH (3.1 g, 130 mmol). The suspension was heated to 50° C. and stirred for 3 h. The dioxane was removed on a rotary evaporator and the reaction mixture was diluted with CH2Cl2 (100 mL). The organic layer was washed with 1 N HCl (2×100 mL), H2O (3×100 mL), and brine (1×25 mL), and dried over MgSO4, yielding a white solid (1.7 g, 98%, Rf=0.30 in 27:3:1 hexane/EtOAc/AcOH), mp 132.0-132.5° C. (dec). IR: 3442, 2926, 2851, 2674, 2557, 2224, 1686, 1611 cm−1. 1H NMR (DMSO-d6, 400 MHz): δ 1.39 (app quintet, 1H, J=7.6 Hz), 1.64 (m, 2H), 1.76 (m, 2H), 2.10 (m, 5H), 3.07 (s, 1H), 3.11 (d, 1H, J=8.0 Hz), 7.38 (d, 2H, J=8.0 Hz), 7.87 (d, 2H, J=8.4 Hz), 12.9 (br s, 1H). 13C NMR (DMSO-d6, 100 MHz): δ 19.8, 25.7, 29.0, 33.7, 43.7 (d, J=25.0 Hz), 47.6 (d, J=25.0 Hz), 90.7 (d, J=32.0 Hz), 95.4 (d, J=173.0 Hz), 104.5 (d, J=10.0 Hz), 129.0, 129.2, 130.4, 141.2, 167.2. 19F NMR (CD3CN, 376 MHz): δ −139.4 (m). FAB-HRMS: Calcd. for C16H18O2F+ [M+H]+: 261.1291. found: 261.1291. Anal. calcd. for C16H17O2F: C, 79.31; H, 7.49. Found: C, 79.07; H, 7.26.

Workup

  1. customThe dioxane was removed on a rotary evaporator
  2. additionthe reaction mixture was diluted with CH2Cl2 (100 mL)
  3. washThe organic layer was washed with 1 N HCl (2×100 mL), H2O (3×100 mL), and brine (1×25 mL)
  4. dry with materialdried over MgSO4
  5. customyielding a white solid (1.7 g, 98%, Rf=0.30 in 27:3:1 hexane/EtOAc/AcOH), mp 132.0-132.5° C. (dec)

Sources & evidence

ORD record
ord-30aea5534569473e91f657f5601f2cab
Source dataset
uspto-grants-2016_02
Patent number
US09260371B2

Reaction notes

Loading…