Hydrochloric Acid → HCID 70345157, compound

HRID 1738909Notes

Reaction equation

HRID 1738909 reaction equation
C[Al](C)C.[Cl-].[NH4+:6].[Cl:7][C:8]1[CH:9]=[CH:10][C:11]2[N:17]([CH2:18][CH2:19][CH2:20][CH2:21][I:22])[C:16](=[O:23])[C@@H:15]([CH2:24][C:25](OCC)=O)[O:14][C@H:13]([C:30]3[C:39]4[C:34](=[CH:35][CH:36]=[CH:37][CH:38]=4)[CH:33]=[CH:32][CH:31]=3)[C:12]=2[CH:40]=1.Cl>C1(C)C=CC=CC=1.C(OCC)(=O)C>[Cl:7][C:8]1[CH:9]=[CH:10][C:11]2[N:17]([CH2:18][CH2:19][CH2:20][CH2:21][I:22])[C:16](=[O:23])[C@@H:15]([CH2:24][C:25]#[N:6])[O:14][C@H:13]([C:30]3[C:39]4[C:34](=[CH:35][CH:36]=[CH:37][CH:38]=4)[CH:33]=[CH:32][CH:31]=3)[C:12]=2[CH:40]=1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 25517Ammonium ChlorideHCID 16682925TrimethylaluminumHCID 70346379HCID 70346379, compound

Product 1

HCID 70345157HCID 70345157, compoundYield 34%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
85 °C

Procedure

Trimethylaluminium (2M in toluene, 15.0 ml, 30.1 mmol) was added dropwise to a suspension of ammonium chloride (1.6 g, 30.1 mmol) in toluene (25 ml) at ice bath temperature under a nitrogen atmosphere. The resulting solution was stirred for 1 hour. Ethyl trans-7-chloro-5-(1-naphthyl)-1-(4-iodobutyl)-2-oxo-1,2,3,5-tetrahydro-4,1-benzoxazepine-3-acetate (5.1 g, 8.6 mmol) was added as a solid and the solution heated at 85° C. for 18 hours. The solution was cooled and acidified with 2 N hydrochloric acid cautiously. Ethyl acetate (100 ml) was added and the layers were separated. The organic layer was washed with 2 N hydrochloric acid. The combined acidic layers were re-extracted once with ethyl acetate. The combined organic layers were washed with 1N sodium hydroxide solution (2×), dried (MgSO4), concentrated under reduced pressure. The residue was purified by flash column chromatography (ethyl acetate/hexane 1:4→2:3) to give a solid which was recrystallized from ethyl acetate/hexane to afford the title compound (1.58 g, 34%) as a pink solid.

Workup

  1. temperatureThe solution was cooled
  2. customthe layers were separated
  3. washThe organic layer was washed with 2 N hydrochloric acid
  4. extractionThe combined acidic layers were re-extracted once with ethyl acetate
  5. washThe combined organic layers were washed with 1N sodium hydroxide solution (2×)
  6. dry with materialdried (MgSO4)
  7. concentrationconcentrated under reduced pressure
  8. customThe residue was purified by flash column chromatography (ethyl acetate/hexane 1:4→2:3)
  9. customto give a solid which
  10. customwas recrystallized from ethyl acetate/hexane

Sources & evidence

ORD record
ord-080d709357984506aa61d124c834d025
Source dataset
uspto-grants-1999_10
Patent number
US05965553

Reaction notes

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