1-Decyne → 3-Decanyl-6-dec-1-ynyldithieno[3,2-b:2',3'-d]thiophene

HRID 83968

Reaction equation

HRID 83968 reaction equation
Br[C:2]1[S:12][C:5]2[C:6]3[S:11][CH:10]=[CH:9][C:7]=3[S:8][C:4]=2[C:3]=1[CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH3:22].[CH:23]#[C:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH3:32]>C(N(CC)CC)C.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Cu]I>[CH2:13]([C:3]1[C:4]2[S:8][C:7]3[CH:9]=[C:10]([C:23]#[C:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH3:32])[S:11][C:6]=3[C:5]=2[S:12][CH:2]=1)[CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH3:22]

Participants

6

Reactant 2

HCID 129971-DecyneHCID 161034752-Bromo-3-decanyldithieno[3,2-b:2',3'-d]thiophene

Product 1

HCID 669250153-Decanyl-6-dec-1-ynyldithieno[3,2-b:2',3'-d]thiopheneYield 93%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 8471TriethylamineSolvent

Conditions

Temperature
130 °C

Procedure

2-bromo-3-decanyldithieno[3,2-b:2′,3′-d]thiophene (92) (4.16 g, 0.01 mol) is mixed with 1-decyne (3.6 g, 0.026 mol), tetrakis(triphenylphosphine)palladium (0.58 g, 0.5 mmol) and copper(I) iodide (0.19 g, 1.0 mmol) in triethylamine (80 mL). This mixture is bubbled with nitrogen for 5 minutes and then heated to 130° C. under argon for 16 hours. Triethylamine is evaporated and hexane (150 mL) is added. The mixture is filtered to remove solid salts and the organic layer is washed with 1M hydrochloric acid (50 mL) and brine (50 mL), then dried over MgSO4. The solvent is removed in vacuo, and the residue is purified by chromatography on silica gel eluting with hexane to yield the target compound (3.87 g, 93.0% yield). 1HNMR (CD2Cl2): δ 7.36 (d, 1H), 7.30 (d, 1H), 2.82 (t, 2H), 2.49 (t, 2H), 1.63-1.27 (m, 28H), 0.88 (m, 6H).

Workup

  1. customThis mixture is bubbled with nitrogen for 5 minutes
  2. customTriethylamine is evaporated
  3. additionhexane (150 mL) is added
  4. filtrationThe mixture is filtered
  5. customto remove solid salts
  6. washthe organic layer is washed with 1M hydrochloric acid (50 mL) and brine (50 mL)
  7. dry with materialdried over MgSO4
  8. customThe solvent is removed in vacuo
  9. customthe residue is purified by chromatography on silica gel eluting with hexane

Sources & evidence

ORD record
ord-9d2b35e796fd49cd9260fe781ff6458e
Source dataset
uspto-grants-2014_09
Patent number
US08846855B2

Linked notes

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