Iodine → 4-(Propargyloxy)benzaldehyde

HRID 1471329Notes

Reaction equation

HRID 1471329 reaction equation
C([C:3]1[CH:10]=[CH:9][C:6]([CH:7]=[O:8])=[CH:5][CH:4]=1)#C.[O:11]=[C:12](CC)[CH2:13][C:14](OC)=O.CC1(C)CC(=O)CC(=O)C1.C([O-])(=O)C.[NH4+].II>C(O)C>[CH2:12]([O:11][C:3]1[CH:4]=[CH:5][C:6]([CH:7]=[O:8])=[CH:9][CH:10]=1)[C:13]#[CH:14]

Participants

7

Reactant 5

HCID 807IodineHCID 31358DimedoneHCID 121699Methyl 3-oxovalerateHCID 517165Ammonium AcetateHCID 27716454-Ethynylbenzaldehyde

Product 1

HCID 18975334-(Propargyloxy)benzaldehydeYield 136.2%

Reagents, catalysts & solvents 1

HCID 702EthanolCatalyst

Procedure

A mixture of 4-ethynylbenzaldehyde (1) (171 mg, 1.27 mmol), methyl 3-oxopentanoate (175 mg, 1.27 mmol), dimedone (181 mg, 1.27 mmol), ammonium acetate (101 mg, 1.27 mmol), I2 (97 mg, 0.38 mmol), and ethanol (10 drops) is stirred under argon for 5.5 h, quenched with 5% Na2S2O3 (30 mL), and extracted with ethyl acetate (50 mL and 30 mL). The extract is washed (5% Na2S2O3, H2O, and brine) and dried. After solvent removal at reduced pressure, the residue is purified on silica gel (33% to 60% ethyl acetate/hexane) to give 277 mg (60%) of 2 (BI-3029) as a cream solid, mp 234-236° C. IR 3332, 2933, 1704, 1610, 1482, 1214 cm−1; 1H NMR (CDCl3) δ 0.93 (s, 3H, CH3), 1.10 (s, 3H, CH3), 1.26 (t, J=7.2 Hz, 3H, CH2CH3), 2.07-2.42 (m, 4H, COCH2, CH2), 2.76-2.89 (m, 2H, CH2CH3), 3.02 (s, 1H, CH≡C), 3.63 (s, 3H, OCH3), 5.09 (s, 1H, CH), 5.90 (bs, 1H, NH), 7.27 (d, J=8.1 Hz, 2H, 3,5-ArH), 7.37 ppm (d, J=8.1 Hz, 2H, 2,6-ArH).

Workup

  1. customquenched with 5% Na2S2O3 (30 mL)
  2. extractionextracted with ethyl acetate (50 mL and 30 mL)
  3. washThe extract is washed (5% Na2S2O3, H2O, and brine)
  4. customdried
  5. customAfter solvent removal at reduced pressure
  6. customthe residue is purified on silica gel (33% to 60% ethyl acetate/hexane)

Sources & evidence

ORD record
ord-1d1a080d2e5a4c35b91b8c4bef97d4ab
Source dataset
uspto-grants-2015_04
Patent number
US09012217B2

Reaction notes

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