Triethylamine → ((4-(Hexyloxy)phenyl)ethynyl)trimethylsilane

HRID 634528Notes

Reaction equation

HRID 634528 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([O:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH3:14])=[CH:4][CH:3]=1.C(N(CC)CC)C.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[C:41]([Si:43]([CH3:46])([CH3:45])[CH3:44])#[CH:42]>[Cu]I.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.CN(C=O)C>[CH2:9]([O:8][C:5]1[CH:6]=[CH:7][C:2]([C:42]#[C:41][Si:43]([CH3:46])([CH3:45])[CH3:44])=[CH:3][CH:4]=1)[CH2:10][CH2:11][CH2:12][CH2:13][CH3:14]

Participants

8

Reactant 4

HCID 8471TriethylamineHCID 11776TriphenylphosphineHCID 66111TrimethylsilylacetyleneHCID 520492Benzene, 1-bromo-4-(hexyloxy)-

Product 1

HCID 85701272((4-(Hexyloxy)phenyl)ethynyl)trimethylsilane

Reagents, catalysts & solvents 3

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

Conditions

Temperature
90 °C

Procedure

To a 500 mL N2 filled round bottom flask was added 1-bromo-4-(hexyloxy)benzene (20.5 g, 80.0 mmol, 1 equiv.) and DMF (160 mL, 0.5 M). The mixture was then sparged with bubbling N2. To this mixture was added N2-sparged triethylamine (39.0 mL, 280 mmol, 3.5 equiv.) via syringe. Finally, copper (I) iodide (254.0 mg, 1.33 mmol, 1.7%), triphenylphosphine (603.0 mg, 2.67 mmol, 3.3%) and PdCl2(PPh3)2 (933.0 mg, 1.33 mmol, 1.7%) were added as a single portion and the head space was flushed with N2. Ethynyltrimethylsilane (16.9 mL, 120.0 mmol, 1.5 equiv.) was added via syringe to the mixture. The flask was sealed with a ground glass stopper, Teflon tape, and then electrical tape and heated to 90° C. for 48 hours. After 48 hours the mixture was diluted with hexanes and extracted with 10% H3PO4 then 5% K2CO3. The organic layer was then dried with MgSO4 and filtered through a plug of SiO2 with 100% hexanes. Upon evaporation, ((4-(hexyloxy)phenyl)ethynyl)trimethylsilane was isolated as a clear oil (16.45 g, 60.2 mmol, 75%). 1H NMR (400 MHz, CDCl3) δ7.42 (d, J=9.2 Hz, 2H), 6.83 (d, J=8.8 Hz, 2H), 3.98 (t, J=6.4 Hz, 2H), 1.85-1.73 (m, 2H), 1.52-1.42 (m, 2H), 1.41-1.26 (m, 4H), 0.94 (t, J=7.6 Hz, 3H), 0.27 (s, 9H).

Workup

  1. customThe mixture was then sparged with bubbling N2
  2. additionTo this mixture was added N2-
  3. customthe head space was flushed with N2
  4. extractionextracted with 10% H3PO4
  5. dry with materialThe organic layer was then dried with MgSO4
  6. filtrationfiltered through a plug of SiO2 with 100% hexanes
  7. customUpon evaporation

Sources & evidence

ORD record
ord-d8a32145a48e447591b9a54c40c495b5
Source dataset
uspto-grants-2016_04
Patent number
US09324505B2

Reaction notes

Loading…