Hydrochloric Acid → HCID 11234930, compound

HRID 1791030Notes

Reaction equation

HRID 1791030 reaction equation
C[Si]([N-][Si](C)(C)C)(C)C.[Li+].[CH2:11]=[C:12]1[CH2:18][CH:17]([S:19]([C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)(=[O:21])=[O:20])[C:16]2[CH:28]=[C:29]([C:32]([O:34][CH3:35])=[O:33])[CH:30]=[CH:31][C:15]=2[O:14][CH2:13]1.[CH2:36](Br)[CH:37]=[CH2:38].Cl>O1CCCC1.ClCCl.O>[CH2:38]([C:17]1([S:19]([C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)(=[O:21])=[O:20])[C:16]2[CH:28]=[C:29]([C:32]([O:34][CH3:35])=[O:33])[CH:30]=[CH:31][C:15]=2[O:14][CH2:13][C:12](=[CH2:11])[CH2:18]1)[CH:37]=[CH2:36]

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 7841Allyl bromideHCID 2733832Lithium HexamethyldisilazideHCID 11439769HCID 11439769, compound

Product 1

HCID 11234930HCID 11234930, compoundYield 67%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

0.023 ml (1.1 equivalents) of 1,3-dimethylpropyleneurea and then 0.189 ml (1.1 equivalents) of 1.06M lithium bis(trimethylsilyl)amide in tetrahydrofuran are added at ambient temperature to 61 mg (0.17 mmol) of methyl 3-methylene-5-(phenylsulfonyl)-2,3,4,5-tetrahydro-1-benzoxepin-7-carboxylate, prepared according to example 1, in solution in 1.8 ml of tetrahydrofuran. The reaction medium then assumes a dark yellow color. After stirring for 15 minutes, 0.0165 ml (1.1 equivalents) of allyl bromide is added. After stirring for 5 minutes, water, 1N hydrochloric acid and dichloromethane are added. After separating the organic and aqueous phases, the aqueous phase is extracted three times with dichloromethane. The combined organic phases are washed with brine, are dried and are finally concentrated under vacuum. The crude reaction product is then purified by chromatography on silica gel (ethyl acetate/heptane 25/55) to give 51 mg (67%) of methyl 5-allyl-3-methylene-5-(phenylsulfonyl)-2,3,4,5-tetrahydro-1-benzoxepin-7-carboxylate in the form of an oil; 1H NMR (300 MHz, CDCl3): 3.25 (m, 4H), 3.9 (s, 3H), 4.25 (d, J=14.3 Hz, 1H), 4.6 (d, J=14.3 Hz, 1H), 4.93 (s, 1H), 5.10 (s, 1H), 5.21 (m, 2H), 5.83 (m, 1H), 6.86 (d, J=8.5 Hz, 1H), 7.4 (m, 4H), 7.57 (m, 1H), 7.95 (dd, J=8.46 and 2 Hz, 1H), 8.21 (d, J=2.07 Hz, 1H).

Workup

  1. customprepared
  2. stirringAfter stirring for 5 minutes
  3. customAfter separating the organic and aqueous phases
  4. extractionthe aqueous phase is extracted three times with dichloromethane
  5. washThe combined organic phases are washed with brine
  6. customare dried
  7. concentrationare finally concentrated under vacuum
  8. customThe crude reaction product
  9. customis then purified by chromatography on silica gel (ethyl acetate/heptane 25/55)

Sources & evidence

ORD record
ord-fc1f3eb907b64e0188308cae0d70581a
Source dataset
uspto-grants-2006_07
Patent number
US07071340B2

Reaction notes

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