3,5-Dibromobenzaldehyde → HCID 17981373, compound

HRID 2423557Notes

Reaction equation

HRID 2423557 reaction equation
[CH2:1]([CH:3]([CH2:14][CH2:15][CH2:16][CH3:17])[CH2:4][O:5][C:6]1[CH:11]=[CH:10][C:9]([C:12]#[CH:13])=[CH:8][CH:7]=1)[CH3:2].Br[C:19]1[CH:20]=[C:21]([CH:24]=[C:25](Br)[CH:26]=1)[CH:22]=[O:23]>O1CCCC1.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>[CH2:1]([CH:3]([CH2:14][CH2:15][CH2:16][CH3:17])[CH2:4][O:5][C:6]1[CH:7]=[CH:8][C:9]([C:12]#[C:13][C:19]2[CH:20]=[C:21]([CH:24]=[C:25]([C:13]#[C:12][C:9]3[CH:10]=[CH:11][C:6]([O:5][CH2:4][CH:3]([CH2:1][CH3:2])[CH2:14][CH2:15][CH2:16][CH3:17])=[CH:7][CH:8]=3)[CH:26]=2)[CH:22]=[O:23])=[CH:10][CH:11]=1)[CH3:2]

Participants

7

Reactant 2

HCID 6220773,5-DibromobenzaldehydeHCID 17981372HCID 17981372, compound

Product 1

HCID 17981373HCID 17981373, compoundYield 79.3%

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 8028TetrahydrofuranSolventHCID 8471TriethylamineSolvent

Conditions

Temperature
70 °C

Procedure

Nitrogen was bubbled through a solution of 1-(2-Ethylhexyloxy)-4-ethynylbenzene (4) (1.69 g, 7.34 mmol) and 3,5-dibromobenzaldehyde (5) (692 mg, 2.62 mmol) in tetrahydrofuran (33 mL) and triethylamine (50 mL) for 5 min. Tetrakis(triphenylphosphine)palladium(0) (218 mg, 0.189 mmol) and copper(I) iodide (65 mg, 0.34 mmol) were added and nitrogen bubbled through the solution for a further 5 min, before stirring at 70° C. for 23 h. Once cool, the solvent was removed and the residue purified by column chromatography over silica with dichloromethane-light petroleum (1:2 to 1:1) as eluent to leave 3,5-bis[4-(2-ethylhexyloxy)phenylethynyl]benzaldehyde (6) (1.17 g, 79%) as a pale brown oil. (Found: C, 83.3; H, 8.2; C39H46O3 requires C, 83.2; H, 8.2%); νmax(film)/cm−1 2211 (C≡C) and 1704 (C═O); δH(400 MHz, CDCl3) 0.93-0.99 (12 H, m, CH3), 1.28-1.56 (16 H, m, CHCH2CH2CH2CH3 and CHCH2CH3), 1.75 (2 H, m, OCH2CH), 3.87 (4 H, d, J 6, OCH2CH), 6.90 (4 H, AA′BB′), 7.48 (4 H, AA′BB′), 7.87 (1 H, dd, J 1.5, 4-H), 7.92 (2 H, d, J 1.5, 2, 6-H) and 10.00 (1 H, s, CHO); δc(100.6 MHz, CDCl3) 11.1, 14.1, 23.1, 23.8, 29.0, 30.4, 39.3, 70.6, 86.0, 91.7, 114.1, 114.6, 125.2, 131.3, 133.5, 136.6, 139.1, 159.9 and 191.0.

Workup

  1. customnitrogen bubbled through the solution for a further 5 min
  2. temperatureOnce cool
  3. customthe solvent was removed
  4. customthe residue purified by column chromatography over silica with dichloromethane-light petroleum (1:2 to 1:1) as eluent

Sources & evidence

ORD record
ord-af49c126347b42c68a290aa996e2b37c
Source dataset
uspto-grants-2011_06
Patent number
US07960557B2

Reaction notes

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