Cesium fluoride → Tetraethyl 5,5'-(naphthalene-2,7-diyl)diisophthalate

HRID 1484219Notes

Reaction equation

HRID 1484219 reaction equation
Br[C:2]1[CH:11]=[CH:10][C:9]2[C:4](=[CH:5][C:6](Br)=[CH:7][CH:8]=2)[CH:3]=1.CC1(C)C(C)(C)OB([C:21]2[CH:22]=[C:23]([C:32]([O:34][CH2:35][CH3:36])=[O:33])[CH:24]=[C:25]([CH:31]=2)[C:26]([O:28][CH2:29][CH3:30])=[O:27])O1.[F-].[Cs+]>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>[CH:3]1[C:4]2[C:9](=[CH:8][CH:7]=[C:6]([C:21]3[CH:31]=[C:25]([C:26]([O:28][CH2:29][CH3:30])=[O:27])[CH:24]=[C:23]([CH:22]=3)[C:32]([O:34][CH2:35][CH3:36])=[O:33])[CH:5]=2)[CH:10]=[CH:11][C:2]=1[C:21]1[CH:31]=[C:25]([C:26]([O:28][CH2:29][CH3:30])=[O:27])[CH:24]=[C:23]([CH:22]=1)[C:32]([O:34][CH2:35][CH3:36])=[O:33]

Participants

5

Reactant 3

HCID 25953Cesium fluorideHCID 6253552,7-DibromonaphthaleneHCID 71285691Diethyl 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)isophthalate

Product 1

HCID 71283170Tetraethyl 5,5'-(naphthalene-2,7-diyl)diisophthalateYield 76%

Reagents, catalysts & solvents 1

HCID 178418397HCID 178418397, compoundCatalyst

Procedure

To a 250 mL Schlenk flask, 2,7-dibromonaphthalene (2.00 g, 6.99 mmol), diethyl 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)isophthalate (6.09 g, 17.48 mmol), CsF (4.00 g) and Pd(PPh3)4 (200 mg) were added. The flask was connected to a Schlenk line and evacuated of air then refilled with nitrogen. 160 mL of 1,2-dimethoxyethane (DME) was degassed (two hours) and added to the flask through a canula. The flask was equipped with a water condenser and refluxed under nitrogen for 2 days. The solvent was removed on a rotary evaporator. 120 mL of H2O was added and then extracted with CHCl3. The organic phase was dried with MgSO4. After removal of the CHCl3 solvent, the crude product was washed with acetone and then hexane (3×20 mL for each) to give a pure product with a yield of 76% (3.02 g) based on 2,7-dibromonaphthalene. 1H NMR (300 MHz, DMSO-d6): δ 1.39 (t, 12H), 4.42 (q, 8H), 7.90 (d, 2H), 8.11 (d, 2H), 8.45 (s, 4H), 8.52 (s, 4H).

Workup

  1. customThe flask was connected to a Schlenk
  2. customline and evacuated of air
  3. additionthen refilled with nitrogen
  4. custom160 mL of 1,2-dimethoxyethane (DME) was degassed (two hours)
  5. additionadded to the flask through a canula
  6. customThe flask was equipped with a water condenser
  7. temperaturerefluxed under nitrogen for 2 days
  8. customThe solvent was removed on a rotary evaporator
  9. addition120 mL of H2O was added
  10. extractionextracted with CHCl3
  11. dry with materialThe organic phase was dried with MgSO4
  12. customAfter removal of the CHCl3 solvent
  13. washthe crude product was washed with acetone
  14. customhexane (3×20 mL for each) to give a pure product with a yield of 76% (3.02 g)

Sources & evidence

ORD record
ord-1cd3afbe9fc74de1a5f0228dd2bef60e
Source dataset
uspto-grants-2016_08
Patent number
US09421514B2

Reaction notes

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