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2-Methyl-3-butyn-2-ol → 4-[[4-(3-Hydroxy-3-methyl-1-butyn-1-yl)phenyl](3,3,5,5-tetramethylcyclohexylidene)methyl]phenol

HRID 1716151
Notes
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Reaction equation

HRID 1716151 reaction equation
[CH:1]12[C:9](=[C:10]([C:26]3[CH:31]=[CH:30][C:29]([OH:32])=[CH:28][CH:27]=3)[C:11]3[CH:16]=CC(/C=C/C(OC(C)(C)C)=O)=C[CH:12]=3)[CH:5]([CH2:6][CH2:7][CH2:8]1)CCC2.C(N(CC)[CH:37]([CH3:39])[CH3:38])(C)C.[CH3:42][C:43]([OH:47])([C:45]#[CH:46])[CH3:44].[NH4+].[Cl-]>CN(C=O)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I.O>[OH:47][C:43]([CH3:44])([CH3:42])[C:45]#[C:46][C:7]1[CH:6]=[CH:5][C:9]([C:10](=[C:11]2[CH2:12][C:9]([CH3:10])([CH3:1])[CH2:5][C:37]([CH3:38])([CH3:39])[CH2:16]2)[C:26]2[CH:27]=[CH:28][C:29]([OH:32])=[CH:30][CH:31]=2)=[CH:1][CH:8]=1
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

9

Reactant 4

HCID 82582-Methyl-3-butyn-2-olHCID 25517Ammonium ChlorideHCID 81531DiisopropylethylamineHCID 689795521,1-Dimethylethyl (2E)-3-{4-[bicyclo[3.3.1]non-9-ylidene(4-hydroxyphenyl)methyl]phenyl}-2-propenoate

Product 1

HCID 114069924-[[4-(3-Hydroxy-3-methyl-1-butyn-1-yl)phenyl](3,3,5,5-tetramethylcyclohexylidene)methyl]phenol
Yield 133.1%

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

To a degassed solution of 4-[(4-Iodophenyl)(3,3,5,5-tetramethylcyclohexylidene)methyl]phenol (44) (0.25 g, 0.56 mmol) in DMF (5 mL) were added Pd(PPh3)2Cl2 (40 mg, 0.06 mmol), CuI (11 mg, 0.06 mmol), N,N-diisopropylethylamine (0.45 mL, 2.52 mmol) and 2-methyl-3-butyn-2-ol (0.11 mL, 1.12 mmol). The reaction mixture was stirred at room temperature overnight, poured into saturated aqueous NH4Cl (15 mL) and water (5 mL), extracted with ethyl acetate (2×50 mL). The combined organic phase was washed with water, brine, dried over Na2SO4, filtered, and the filtrate was concentrated to give the crude product as brown oil. The crude product was purified by chromatography on a silica gel column eluted with a gradient from hexanes to 30% EtOAc in hexanes to give a light brown solid. The solid was triturated with hot hexanes containing 1% MeOH and 5% EtOAc in hexanes to afford 150 mg (67%) of the title compound (241) as off-white solid. mp 186-187° C. 1H NMR (400 MHz, DMSO-d6): δ 0.85 (s, 6H), 0.87 (s, 6H), 1.23 (s, 2H), 1.42 (s, 6H), 1.84 (s, 2H), 1.90 (s, 2H), 5.41 (s, 1H), 6.65 (d, J=8.4 Hz, 2H), 6.91 (d, J=8.3 Hz, 2H), 7.08 (d, J=8.1 Hz, 2H), 7.27 (d, J=8.0 Hz, 2H), 9.29 (s, 1H). LCMS (ESI): m/z 401 (M−H)−.

Workup

  1. extractionextracted with ethyl acetate (2×50 mL)
  2. washThe combined organic phase was washed with water, brine
  3. dry with materialdried over Na2SO4
  4. filtrationfiltered
  5. concentrationthe filtrate was concentrated
  6. customto give the crude product as brown oil
  7. customThe crude product was purified by chromatography on a silica gel column
  8. washeluted with a gradient from hexanes to 30% EtOAc in hexanes
  9. customto give a light brown solid
  10. customThe solid was triturated with hot hexanes containing 1% MeOH and 5% EtOAc in hexanes

Sources & evidence

ORD record
ord-5879f3104a814740beed89201488882a
Source dataset
uspto-grants-2010_09
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US07799828B2

Reaction notes

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