2-Methyl-3-butyn-2-ol → HCID 14717583, compound

HRID 704365Notes

Reaction equation

HRID 704365 reaction equation
Br[C:2]1[C:7]([F:8])=[C:6]([F:9])[C:5]([C:10]2[C:15]([F:16])=[C:14]([F:17])[C:13](Br)=[C:12]([F:19])[C:11]=2[F:20])=[C:4]([F:21])[C:3]=1[F:22].[CH3:23][C:24]([OH:28])([C:26]#[CH:27])[CH3:25]>C(NC(C)C)(C)C.C([O-])(=O)C.[Cu+]>[OH:28][C:24]([CH3:25])([CH3:23])[C:26]#[C:27][C:2]1[C:7]([F:8])=[C:6]([F:9])[C:5]([C:10]2[C:15]([F:16])=[C:14]([F:17])[C:13]([C:27]#[C:26][C:24]([CH3:25])([OH:28])[CH3:23])=[C:12]([F:19])[C:11]=2[F:20])=[C:4]([F:21])[C:3]=1[F:22]

Participants

5

Reactant 2

HCID 82582-Methyl-3-butyn-2-olHCID 826004,4'-Dibromo-2,2',3,3',5,5',6,6'-octafluorobiphenyl

Product 1

HCID 14717583HCID 14717583, compound

Reagents, catalysts & solvents 2

HCID 69023Cuprous acetateCatalystHCID 7912DiisopropylamineSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of 4,4'-dibromooctafluorobiphenyl (10 g, 21.9 mmol) in degassed diisopropylamine (350 mL) was added dichlorobis(triphenylphosphine) palladium (770 mg, 1.05 mmol, 5 mol %) and copper (1) acetate (219 mg, 1.05 mmol, 5 mol %). The solution was cooled to 0° C. and to this solution was added 2-methyl 3 butyn 2-ol (2.2 equivalents, 4.0 g, 4.7 mL). The solution was allowed to warm to room temperature and was subsequently heated at 50° C. for 12 hours. The solution was cooled and filtered to remove the pecipitate of diisopropylammonium bromide. The solvent was removed at reduced pressure and the residue was chromatographed on a column of silica gel (200 g) packed with ethel acetate. An oily yellow solid was removed from the column. The addition of a couple of drops of methanol caused the oil to solidify. The resulting solid was recrystallized from a mixture of ethyl acetate/hexane (1:2) to yield 4,4'-bis(3 hydroxy-3-methyl 1-butynyl)-octafluorobiphenyl as white crytals. The yield was 8.6 (92 %), mp 119°-121° C. IR (KBr) 3400, 2960, 1475, 1365, 1210, 1170, 990, 962 cm-1. 1H NMR (80 MHz, CDCl3) δ2.7 (s, 2H), 1.53 (s, 12H); Mass Spectrum (El)(rel. intensity 462 (3.7), 447 (44.0), 432 (1.5); Anal. Calcd for C22H14F8O2 : C, 57.14; H, 3.03. Found: C,60.60; H, 4.78

Workup

  1. temperatureto warm to room temperature
  2. temperaturewas subsequently heated at 50° C. for 12 hours
  3. temperatureThe solution was cooled
  4. filtrationfiltered
  5. customto remove the pecipitate of diisopropylammonium bromide
  6. customThe solvent was removed at reduced pressure
  7. customthe residue was chromatographed on a column of silica gel (200 g)
  8. customAn oily yellow solid was removed from the column
  9. additionThe addition of a couple of drops of methanol
  10. customThe resulting solid was recrystallized from a mixture of ethyl acetate/hexane (1:2)

Sources & evidence

ORD record
ord-8cdc695479b34c6b8b821b13920b5622
Source dataset
uspto-grants-1991_01
Patent number
US04987209

Reaction notes

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