Triphenylphosphine → methyl 2-(4-ethoxybenzyloxy)-6,7-dihydro-5H-benzocycloheptene-8-carboxylate

HRID 1169335Notes

Reaction equation

HRID 1169335 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH2:20]([O:22][C:23]1[CH:30]=[CH:29][C:26]([CH2:27][OH:28])=[CH:25][CH:24]=1)[CH3:21].O[C:32]1[CH:33]=[CH:34][C:35]2[CH2:41][CH2:40][CH2:39][C:38]([C:42]([O:44][CH3:45])=[O:43])=[CH:37][C:36]=2[CH:46]=1.N(C(OC(C)C)=O)=NC(OC(C)C)=O>C1COCC1>[CH2:20]([O:22][C:23]1[CH:30]=[CH:29][C:26]([CH2:27][O:28][C:32]2[CH:33]=[CH:34][C:35]3[CH2:41][CH2:40][CH2:39][C:38]([C:42]([O:44][CH3:45])=[O:43])=[CH:37][C:36]=3[CH:46]=2)=[CH:25][CH:24]=1)[CH3:21]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 803454-Ethoxybenzyl alcoholHCID 22989944methyl 2-hydroxy-6,7-dihydro-5H-benzocycloheptene-8-carboxylate

Product 1

HCID 22990168methyl 2-(4-ethoxybenzyloxy)-6,7-dihydro-5H-benzocycloheptene-8-carboxylateYield 58%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To triphenylphosphine (590 mg, 2.25 mmol), 4-ethoxybenzyl alcohol (342 mg, 2.25 mmol) and methyl 2-hydroxy-6,7-dihydro-5H-benzocycloheptene-8-carboxylate (327 mg, 1.50 mmol) dissolved in THF (6 ml) was added at 0° C. a solution of diisopropyl azodicarboxylate (0.439 ml, 2.23 mmol) in THF (2 ml), and the resulting mixture was stirred at room temperature for 6 hours. The reaction mixture was concentrated under reduced pressure and the residue was subjected to column chromatography (silica gel: 50 g, ethyl acetate/hexane=1/25→1/19). The objective fractions were concentrated under reduced pressure, diisopropyl ether was added to the residue and an insoluble material was collected by filtration. The insoluble material was washed with diisopropyl ether and was then dried under reduced pressure to obtain methyl 2-(4-ethoxybenzyloxy)-6,7-dihydro-5H-benzocycloheptene-8-carboxylate (308 mg, 0.87 mmol, 58%).

Workup

  1. concentrationThe reaction mixture was concentrated under reduced pressure
  2. concentrationThe objective fractions were concentrated under reduced pressure, diisopropyl ether
  3. additionwas added to the residue
  4. filtrationan insoluble material was collected by filtration
  5. washThe insoluble material was washed with diisopropyl ether
  6. customwas then dried under reduced pressure

Sources & evidence

ORD record
ord-46a33065fd3244839a5147be87fb6861
Source dataset
uspto-grants-2003_09
Patent number
US06627651B1

Reaction notes

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