Methanol → 4-Hexadecylamino-2-formylthiophene

HRID 850960Notes

Reaction equation

HRID 850960 reaction equation
[H-].C([Al+]CC(C)C)C(C)C.[CH2:11]([NH:27][C:28]1[CH:29]=[C:30]([C:33]#N)[S:31][CH:32]=1)[CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH3:26].C[OH:36].ClCCl.CCCCCC>C1(C)C=CC=CC=1>[CH2:11]([NH:27][C:28]1[CH:29]=[C:30]([CH:33]=[O:36])[S:31][CH:32]=1)[CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH3:26]

Participants

6

Reactant 4

HCID 887MethanolHCID 131349914-Hexadecylamino-2-cyanothiopheneHCID 21225700DiisobutylaluminumhydrideHCID 21226440Methylenechloride Hexane

Product 1

HCID 131349924-Hexadecylamino-2-formylthiophene

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent2×

Procedure

Di-isobutylaluminum hydride (14 ml., 25% solution in toluene) is added with stirring to a solution of 2.9 g. of 4-hexadecylamino-2-cyanothiophene in toluene under a nitrogen atmosphere. The temperature rises during the addition and the reaction is then stirred for 1 hour. A solution of methanol in toluene (14 ml., 1:1) is added over 30 minutes and the mixture is poured into vigorously stirred ice-cold aqueous sulfuric acid (125 ml., 5%). After 10 minutes diatomaceous earth (7.5 g.) is added, the mixture filtered and the organic layer separated. The aqueous solution is extracted twice with toluene (25 ml.) and the combined organic layers are washed with aqueous sodium bicarbonate, dried over magnesium sulfate, decolorized with charcoal, filtered and evaporated in vacuo to give crude product. The product is obtained by recrystallization from dichloromethane-hexane.

Workup

  1. additionThe temperature rises during the addition
  2. stirringthe reaction is then stirred for 1 hour
  3. additionAfter 10 minutes diatomaceous earth (7.5 g.) is added
  4. filtrationthe mixture filtered
  5. customthe organic layer separated
  6. extractionThe aqueous solution is extracted twice with toluene (25 ml.)
  7. washthe combined organic layers are washed with aqueous sodium bicarbonate
  8. dry with materialdried over magnesium sulfate
  9. filtrationfiltered
  10. customevaporated in vacuo
  11. customto give crude product

Sources & evidence

ORD record
ord-b43857b864a644fa9285a34a9ebf5612
Source dataset
uspto-grants-1983_05
Patent number
US04382143

Reaction notes

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