Hydrochloric Acid → HCID 11439769, compound

HRID 1791025Notes

Reaction equation

HRID 1791025 reaction equation
C[Si]([N-][Si](C)(C)C)(C)C.[Li+].Cl[CH2:12][C:13](=[CH2:36])[CH2:14][O:15][C:16]1[CH:25]=[CH:24][C:19]([C:20]([O:22][CH3:23])=[O:21])=[CH:18][C:17]=1[CH2:26][S:27]([C:30]1[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1)(=[O:29])=[O:28].O.Cl>O1CCCC1.ClCCl>[CH2:12]=[C:13]1[CH2:36][CH:26]([S:27]([C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)(=[O:29])=[O:28])[C:17]2[CH:18]=[C:19]([C:20]([O:22][CH3:23])=[O:21])[CH:24]=[CH:25][C:16]=2[O:15][CH2:14]1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 962WaterHCID 2733832Lithium HexamethyldisilazideHCID 11474906HCID 11474906, compound

Product 1

HCID 11439769HCID 11439769, compoundYield 60%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

1.33 ml of 1.06M lithium bis(trimethylsilyl)amide in tetrahydrofuran are added to 478 mg (1.21 mmol) of methyl 4-{[2-(chloromethyl)-2-propenyl]oxy}-3-[(phenylsulfonyl)methyl]benzoate dissolved in 39 ml of tetrahydrofuran. The solution is stirred for 5 minutes and then water, 1N hydrochloric acid and dichloromethane are added to the reaction medium. After separating, the aqueous phase is extracted three times with dichloromethane. The combined organic phases are washed with brine, dried and then concentrated under vacuum. The crude reaction product is purified by chromatography on silica gel (ethyl acetate/heptane 40/60) to provide 259 mg (60%) of methyl 3-methylene-5-(phenylsulfonyl)-2,3,4,5-tetrahydro-1-benzoxepin-7-carboxylate in the form of a white solid; 1H NMR (300 MHz, CDCl3): 2.98 (dd, J=13.9 and 7.1 Hz, 1H), 3.21 (dd, J=13.9 and 7.1 Hz, 1H), 3.86 (s, 3H), 4.20 (d, J=13.4 Hz, 1H), 4.45 (t, J=7.35 Hz, 1H), 4.73 (d, J=13.4 Hz, 1H), 4.99 (s, 1H), 5.09 (s, 1H), 6.98 (d, J=8.28 Hz, 1H), 7.43 (m, 2H), 7.62 (m, 3H), 7.76 (d, J=2.07 Hz, 1H), 7.94 (dd, J=8.46 and 2 Hz, 1H).

Workup

  1. customAfter separating
  2. extractionthe aqueous phase is extracted three times with dichloromethane
  3. washThe combined organic phases are washed with brine
  4. customdried
  5. concentrationconcentrated under vacuum
  6. customThe crude reaction product
  7. customis purified by chromatography on silica gel (ethyl acetate/heptane 40/60)

Sources & evidence

ORD record
ord-d1d71153d7a647bc86d1440342c2fac6
Source dataset
uspto-grants-2006_07
Patent number
US07071340B2

Reaction notes

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