Tetrahydrofuran → 3,6-Didodecylthieno[3,2-b]thiophene

HRID 2236054Notes

Reaction equation

HRID 2236054 reaction equation
Br[C:2]1[C:3]2[S:9][CH:8]=[C:7](Br)[C:4]=2[S:5][CH:6]=1.[Br-].[CH2:12]([Zn+])[CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH3:23].[CH2:25]1[CH2:29]O[CH2:27][CH2:26]1>C(OCC)C.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH2:12]([C:2]1[C:3]2[S:9][CH:8]=[C:7]([CH2:27][CH2:26][CH2:25][CH2:29][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH3:19])[C:4]=2[S:5][CH:6]=1)[CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH3:23]

Participants

6

Reactant 3

HCID 8028TetrahydrofuranHCID 106139793,6-Dibromothieno(3,2-b)thiopheneHCID 178443218HCID 178443218, compound

Product 1

HCID 598441203,6-Didodecylthieno[3,2-b]thiophene

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 3283Diethyl EtherSolvent

Conditions

Temperature
150 °C

Procedure

A 20 mL glass vial is charged with 3,6-dibromothieno[3,2-b]thiophene (1.00 g, 3.36 mmol) and Pd(dppf)Cl2 (0.14 g, 0.17 mmol, 5 mol %), and purged with nitrogen for 10 minutes. A 0.5M solution of dodecylzinc bromide in anhydrous THF (15 mL, 7.5 mmol) is added. The glass vial is placed into a microwave reactor (Emrys Creator, Personal Chemistry Ltd) and heated at 150° C. for 10 minutes with stirring. After cooling to RT, the reaction mixture is diluted with diethyl ether (100 mL) and quenched with 5% hydrochloric acid (50 mL). The organic layer is separated and the aqueous layer is re-extracted with diethyl ether (100 mL). The combined extracts are washed with water (2×50 mL), dried over sodium sulphate, and concentrated in vacuo. The crude product is filtered through a short plug of silica, eluting with petroleum ether 40-60. Recrystallisation from 2-butanone yielded the product as a pale yellow solid. 1H NMR (300 MHz, CDCl3) δ 6.95 (s, 2H), 2.70 (t, 4H), 1.74 (m, 4H), 1.22-1.42 (br, 36H), 0.88 (t, 6H). 13C NMR (75 MHz, CDCl3) δ 139.3, 135.5, 120.8, 31.9, 29.8, 29.69, 29.67, 29.6, 29.42, 29.37, 28.7, 22.7, 14.2.

Workup

  1. custompurged with nitrogen for 10 minutes
  2. customThe glass vial is placed into a microwave reactor
  3. temperatureAfter cooling to RT
  4. customquenched with 5% hydrochloric acid (50 mL)
  5. customThe organic layer is separated
  6. extractionthe aqueous layer is re-extracted with diethyl ether (100 mL)
  7. washThe combined extracts are washed with water (2×50 mL)
  8. dry with materialdried over sodium sulphate
  9. concentrationconcentrated in vacuo
  10. filtrationThe crude product is filtered through a short plug of silica
  11. washeluting with petroleum ether 40-60
  12. customRecrystallisation from 2-butanone

Sources & evidence

ORD record
ord-8aa041f6b5cd4d0ebd4af34329227740
Source dataset
uspto-grants-2010_05
Patent number
US07714098B2

Reaction notes

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