4-Iodobenzaldehyde → HCID 10613729, compound

HRID 1824622Notes

Reaction equation

HRID 1824622 reaction equation
I[C:2]1[CH:9]=[CH:8][C:5]([CH:6]=[O:7])=[CH:4][CH:3]=1.[C:10]([S:13][CH2:14][C:15]1[CH:20]=[CH:19][C:18]([C:21]#[CH:22])=[CH:17][CH:16]=1)(=[O:12])[CH3:11]>[Cu]I.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[CH:6]([C:5]1[CH:8]=[CH:9][C:2]([C:22]#[C:21][C:18]2[CH:19]=[CH:20][C:15]([CH2:14][S:13][C:10](=[O:12])[CH3:11])=[CH:16][CH:17]=2)=[CH:3][CH:4]=1)=[O:7]

Participants

5

Reactant 2

HCID 966574-IodobenzaldehydeHCID 107028581-[4-(S-Acetylthiomethyl)phenyl]acetylene

Product 1

HCID 10613729HCID 10613729, compoundYield 88.3%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalyst

Procedure

Samples of 4-iodobenzaldehyde (1.18 g, 5.00 mmol), 7 (950 mg, 5.00 mmol), CuI (52 mg, 270 μmol) and Pd(PPh3)2Cl2 (23 mg, 33 μmol) were placed in a Schlenk flask. The flask was evacuated via vacuum pump for 3 min and then the flask was backflushed with argon for 3 min. The process of evacuation and flushing was repeated 3 times. At this point the argon flow rate was increased and the threaded stopcock was removed. Deareated THF (5.0 mL) and DIEA (5.0 mL) were added in succession to the flask by gastight syringe. The threaded stopcock was replaced, the argon flow rate was reduced and the flask was immersed in an oil bath thermostated at 40° C. The reaction was stopped after 40 h. The mixture was then filtered and evaporated. The resulting orange-brown solid was chromatographed (silica, CH2Cl2/hexanes, 2:3, then 1:1, then 3:2) to afford yellowish-white crystals. Recrystallization (ethyl acetate/heptane) gave 1.30 g (88.2%) of white crystals. mp 128–129° C.; 1H NMR δ 2.49 (s, 3H), 4.07 (s, 2H), 7.25, 7.43 (AA′BB′, 2×2H), 7.59, 7.79 (AA′BB′, 2×2H), 9.95 (s, 1H); 13C NMR δ 30.9, 33.9, 89.5, 93.9, 122.1, 129.8, 130.1, 130.2, 132.7, 132.7, 136.1, 139.5, 192.0, 195.4; FAB-MS obsd 294.0717, calcd exact mass 294.0715; Anal. Calcd. for C18H14O2S: C, 73.44; H, 4.79; S, 10.89; Found: C, 73.18; H, 4.82; S, 10.88.

Workup

  1. customThe flask was evacuated via vacuum pump for 3 min
  2. customThe process of evacuation and flushing
  3. temperatureAt this point the argon flow rate was increased
  4. customthe threaded stopcock was removed
  5. additionDeareated THF (5.0 mL) and DIEA (5.0 mL) were added in succession to the flask by gastight syringe
  6. customthe flask was immersed in an oil bath
  7. customat 40° C
  8. waitThe reaction was stopped after 40 h
  9. filtrationThe mixture was then filtered
  10. customevaporated
  11. customThe resulting orange-brown solid was chromatographed (silica, CH2Cl2/hexanes, 2:3
  12. custom1:1, then 3:2) to afford yellowish-white crystals
  13. customRecrystallization (ethyl acetate/heptane)

Sources & evidence

ORD record
ord-3b30a7736c04470baa96f09ee0eb46bd
Source dataset
uspto-grants-2006_05
Patent number
US07042755B1

Reaction notes

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