Diethyl Ether → HCID 44251362, compound

HRID 1879527Notes

Reaction equation

HRID 1879527 reaction equation
[CH2:1]([Si:3]([C:8]#[CH:9])([CH2:6][CH3:7])[CH2:4][CH3:5])[CH3:2].C(O[CH2:13][CH3:14])C.[CH2:15]([Li])[CH2:16][CH2:17][CH3:18].[CH3:20][C:21]1[C:42]2[C:25](=[CH:26][C:27]3[C:28](=O)[C:29]4[C:38]([C:39](=O)[C:40]=3[CH:41]=2)=[CH:37][C:36]2[C:31](=C(C)C=CC=2C)[CH:30]=4)[C:24]([CH3:47])=[CH:23][CH:22]=1>Cl.O.O1CCCC1>[CH3:15][C:16]1[C:36]2[C:31](=[CH:30][C:29]3[C:38]([CH:37]=2)=[C:39]([C:9]#[C:8][Si:3]([CH2:6][CH3:7])([CH2:4][CH3:5])[CH2:1][CH3:2])[C:40]2[C:27](=[CH:26][C:25]4[C:42]([CH:41]=2)=[C:21]([CH3:20])[CH:22]=[CH:23][C:24]=4[CH3:47])[C:28]=3[C:2]#[C:1][Si:3]([CH2:8][CH3:9])([CH2:6][CH3:7])[CH2:4][CH3:5])[C:13]([CH3:14])=[CH:18][CH:17]=1

Participants

8

Reactant 4

HCID 3283Diethyl EtherHCID 637947(Triethylsilyl)acetyleneHCID 59330261HCID 59330261, compoundHCID 178418339Butyllithium

Product 1

HCID 44251362HCID 44251362, compoundYield 61%

Reagents, catalysts & solvents 3

HCID 313Hydrochloric AcidSolventHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

A 3-necked 500 mL RBF is charged with triethylsilylacetylene (6.1 mL, 34.11 mmol) and anhydrous diethyl ether (100 mL) under nitrogen. The solution is cooled to 0° C. and a solution of 2.5 M n-butyllithium in hexanes (12.4 mL, 31.01 mmol) is added dropwise. The reaction mixture is removed from the ice-bath and stirred for 1 h at 22° C. 1,4,8,11-Tetramethyl-6,13-pentacenequinone 8 (1.13 g, 3.10 mmol) is added and the reaction mixture is stirred at 22° C. for 2 h. Anhydrous tetrahydrofuran (100 mL) is added and the reaction mixture is stirred for a further 18 h. A saturated solution of stannous(II) chloride in 10% HCl solution (20 mL) is added and the solution is stirred under nitrogen for 30 mins. The reaction mixture is poured into water (300 mL) and extracted with dichloromethane (300 mL). The aqueous layer is re-extracted with dichloromethane (2×100 mL). The combined extracts are dried over sodium sulfate and concentrated in vacuo. The crude product is dissolved in a small volume of dichloromethane, acetone (100 mL) is added, and the mixture is stirred for 30 mins. The solid is filtered off, washed with cold acetone and methanol, and dried under vacuum to yield the product 9 as a dark blue solid (1.15 g, 61%): 1H-NMR (300 MHz, CDCl3) δ9.40 (s, 4H), 7.16 (s, 4H), 2.82 (s, 12H), 1.30 (t, 18H, 3J=8 Hz), 0.94 (q, 12H, 3J=8 Hz); 13C-NMR (75 MHz, CDCl3) δ 132.8, 132.4, 130.1, 125.9, 123.2, 118.2, 107.6, 104.1, 19.6, 8.0, 4.8.

Workup

  1. customThe reaction mixture is removed from the ice-bath
  2. stirringthe reaction mixture is stirred at 22° C. for 2 h
  3. stirringthe reaction mixture is stirred for a further 18 h
  4. stirringthe solution is stirred under nitrogen for 30 mins
  5. extractionextracted with dichloromethane (300 mL)
  6. extractionThe aqueous layer is re-extracted with dichloromethane (2×100 mL)
  7. dry with materialThe combined extracts are dried over sodium sulfate
  8. concentrationconcentrated in vacuo
  9. dissolutionThe crude product is dissolved in a small volume of dichloromethane, acetone (100 mL)
  10. additionis added
  11. stirringthe mixture is stirred for 30 mins
  12. filtrationThe solid is filtered off
  13. washwashed with cold acetone and methanol
  14. customdried under vacuum

Sources & evidence

ORD record
ord-02b198b4693c4b1b8251009bfd2f2889
Source dataset
uspto-grants-2012_11
Patent number
US08318048B2

Reaction notes

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