Water → 4-tert-Butylphenylacetylene

HRID 423439Notes

Reaction equation

HRID 423439 reaction equation
[Li+].[CH3:2]C([N-]C(C)C)C.[CH:9]1[C:14]2[C:15]3[C:28](=O)[C:20]4S[C:22]5C=CC=[CH:24][C:23]=5[C:19]=4[C:18](=O)[C:16]=3SC=2C=CC=1.O>C1COCC1>[C:23]([C:19]1[CH:18]=[CH:16][C:15]([C:14]#[CH:9])=[CH:28][CH:20]=1)([CH3:22])([CH3:24])[CH3:2]

Participants

5

Reactant 3

HCID 962WaterHCID 2724682Lithium diisopropylamideHCID 10615659HCID 10615659, compound

Product 1

HCID 27573024-tert-Butylphenylacetylene

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
24.5 °C

Procedure

In another flame dried flask, a solution of 1-tert-butyl-4-ethynyl-benzene (3.56 g, 22.5 mmol) in THF (20 ml) is prepared, and the freshly prepared LDA is added to this solution within 10 minutes. The temperature is maintained in the range between 23-26° C. by cooling, and the solution is stirred for another 10 minutes at ambient temperature. Then dibenzo[d,d′]benzo[1,2-b;4,5-b′]dithiophene-6,12-dione (educt 1) (2.40 g, 7.5 mmol) is added as a solid, and the mixture heated to 50° C. and stirred for 52 hours at this temperature. The clear red solution is poured carefully into water (100 ml), and the product extracted with chloroform (80 ml). The aqueous layer is extracted again with chloroform (80 ml), and the combined organic layers are washed with brine and dried (sodium sulphate). Removal of the solvent leaves the crude product as light brown crystals. The crystals are refluxed in methanol (50 ml) (incompletely dissolved) and the mixture allowed to crystallise over night. The solid is then filtered off and washed with methanol thrice (7 ml each time) and dried in vacuo to give the product as beige crystals. 1H-NMR (CDCl3, 300 MHz) δ 1.29 (s, 9H, C(CH3)3); 3.09 (s, 1H, OH); 7.27, 7.36 (AA′BB′, 4H, Ph H); 7.43, 7.48 (2 “tr”, 1H each), 7.89 pp (d, J=6.5 Hz, 1H), 8.54 (d, J=8.2 Hz, 1H) benzothiophene H. 13C-NMR (CDCl3, 75 MHz) δ 31.47 (C(CH3)3); 35.17 (q, C(CH3)3); 64.79 (q, COH); 87.80, 88.69 (2 q, C≡C); 118.96 (q), 123.03, 124.84, 125.13, 125.77 (benzothiophene CH); 125.46, 131.76 (Ph CH); 130.90 (q), 136.15 (q), 140.37 (q), 144.11 (q), 152.48 (q).

Workup

  1. customIn another flame dried flask
  2. temperatureby cooling
  3. temperaturethe mixture heated to 50° C.
  4. stirringstirred for 52 hours at this temperature
  5. extractionthe product extracted with chloroform (80 ml)
  6. extractionThe aqueous layer is extracted again with chloroform (80 ml)
  7. washthe combined organic layers are washed with brine
  8. dry with materialdried (sodium sulphate)
  9. customRemoval of the solvent
  10. customleaves the crude product as light brown crystals

Sources & evidence

ORD record
ord-4274c38b96484b63b712e9e9b220c862
Source dataset
uspto-grants-2012_01
Patent number
US08101776B2

Reaction notes

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