3,5-Dibromobenzaldehyde → HCID 86592749, compound

HRID 2423554Notes

Reaction equation

HRID 2423554 reaction equation
[C:1]([C:5]1[CH:6]=[C:7]([CH:15]=[CH:16][C:17]2[CH:18]=[C:19]([C:39]#[CH:40])[CH:20]=[C:21]([CH:23]=[CH:24][C:25]3[CH:30]=[C:29]([C:31]([CH3:34])([CH3:33])[CH3:32])[CH:28]=[C:27]([C:35]([CH3:38])([CH3:37])[CH3:36])[CH:26]=3)[CH:22]=2)[CH:8]=[C:9]([C:11]([CH3:14])([CH3:13])[CH3:12])[CH:10]=1)([CH3:4])([CH3:3])[CH3:2].Br[C:42]1[CH:43]=[C:44]([CH:47]=[C:48](Br)[CH:49]=1)[CH:45]=[O:46]>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>[C:11]([C:9]1[CH:8]=[C:7]([CH:15]=[CH:16][C:17]2[CH:18]=[C:19]([C:39]#[C:40][C:42]3[CH:43]=[C:44]([CH:47]=[C:48]([C:40]#[C:39][C:19]4[CH:20]=[C:21]([CH:23]=[CH:24][C:25]5[CH:30]=[C:29]([C:31]([CH3:32])([CH3:33])[CH3:34])[CH:28]=[C:27]([C:35]([CH3:38])([CH3:36])[CH3:37])[CH:26]=5)[CH:22]=[C:17]([CH:16]=[CH:15][C:7]5[CH:6]=[C:5]([C:1]([CH3:4])([CH3:3])[CH3:2])[CH:10]=[C:9]([C:11]([CH3:14])([CH3:13])[CH3:12])[CH:8]=5)[CH:18]=4)[CH:49]=3)[CH:45]=[O:46])[CH:20]=[C:21]([CH:23]=[CH:24][C:25]3[CH:30]=[C:29]([C:31]([CH3:34])([CH3:33])[CH3:32])[CH:28]=[C:27]([C:35]([CH3:38])([CH3:37])[CH3:36])[CH:26]=3)[CH:22]=2)[CH:6]=[C:5]([C:1]([CH3:4])([CH3:3])[CH3:2])[CH:10]=1)([CH3:12])([CH3:14])[CH3:13]

Participants

7

Reactant 2

HCID 6220773,5-DibromobenzaldehydeHCID 86592750HCID 86592750, compound

Product 1

HCID 86592749HCID 86592749, compoundYield 85%

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 3,5-bis[2-(3,5-di-tert-butylphenyl)vinyl]phenyl acetylene (3) (1.00 g, 1.88 mmol) and 3,5-dibromobenzaldehyde (191 mg, 0.725 mmol) in tetrahydrofuran (10 mL) and triethylamine (15 mL) for 15 min. Tetrakis(triphenylphosphine)palladium(0) (60 mg, 52 μmol) and copper(I) iodide (18 mg, 94 μmol) were added and nitrogen bubbled through the solution for a further 15 min and the mixture then stirred at 70° C. for 17.5 h. Once cool, the solvent was removed and the residue purified by column chromatography over silica with dichloromethane-light petroleum (1:2) as eluent to give 3,5-bis({3,5-bis[2-(3,5-di-tert-butylphenyl)vinyl]phenyl}-ethynyl)benzaldehyde (4) (714 mg, 85%) as a white solid. mp>250° C. (dec.) (Found: C, 89.5; H, 8.5; C87H102O requires C, 89.8; H, 8.8%); νmax(KBr)/cm−1 2215w (C≡C), 1703 (C═O), 1595 (C═C) and 957 (C═C—H trans); λmax(CH2Cl2)/nm 318 (log(ε/dm3 mol−1cm−1) 5.12) and 330sh (4.93); δH(400 MHz, CDCl3) 1.41 (72 H, s, t-butyl), 7.15 and 7.30 (8 H, d, J 16.5, vinylic H), 7.42 (4 H, dd, J 1.5, sp H), 7.44 (8 H, d, J 1.5, sp H), 7.69 (4 H, d, J 1, bp H), 7.71 (2 H, s, bp H), 8.02 (1 H, dd, J 1.5, cp H), 8.06 (2 H, d, J 1.5, cp H) and 10.01 (1 H, s, CHO); δc(100.6 MHz, CDCl3) 31.5, 34.9, 87.1, 91.6, 121.0, 122.5, 123.1, 124.9, 125.3, 126.8, 128.3, 131.0, 132.0, 136.1, 136.7, 138.3, 139.6, 151.1 and 191.0; m/z (MALDI) 1163.1 (M+, 100%).

Workup

  1. customnitrogen bubbled through the solution for a further 15 min
  2. temperatureOnce cool
  3. customthe solvent was removed
  4. customthe residue purified by column chromatography over silica with dichloromethane-light petroleum (1:2) as eluent

Sources & evidence

ORD record
ord-35163cc039354c64bfa4fdfd120a6b15
Source dataset
uspto-grants-2011_06
Patent number
US07960557B2

Reaction notes

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