Hydrochloric Acid → HCID 18980008, compound

HRID 2256993Notes

Reaction equation

HRID 2256993 reaction equation
[CH3:1][O:2][C:3]1[C:9](=[O:10])[NH:8][C:7]2[CH:11]=[CH:12][CH:13]=[CH:14][C:6]=2[C:5](=[O:15])[CH:4]=1.[Cl-].[Li+].[CH:18](NC(C)C)([CH3:20])[CH3:19].C([Li])CCC.O=C1N([Li])C2C=CC=CC=2C(=O)C([Li])=C1OC.C(Br)C=C.Cl>O1CCCC1.O>[CH2:20]([C:4]1[C:5](=[O:15])[C:6]2[CH:14]=[CH:13][CH:12]=[CH:11][C:7]=2[NH:8][C:9](=[O:10])[C:3]=1[O:2][CH3:1])[CH:18]=[CH2:19]

Participants

10

Reactant 7

HCID 313Hydrochloric AcidHCID 7841Allyl bromideHCID 7912DiisopropylamineHCID 433294Lithium ChlorideHCID 107506631H-1-Benzazepine-2,5-dione, 3-methoxy-HCID 178418339ButyllithiumHCID 178506766HCID 178506766, compound

Product 1

HCID 18980008HCID 18980008, compoundYield 34%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
20 °C

Procedure

A solution of 3-methoxy-2,5-dioxo-2,5-dihydro-1H-benz[b]-azepine (10 g), lithium chloride (12.5 g) and diisopropylamine (7.5 mL) in tetrahydrofuran (200 mL) was cooled to -70° C.; and butyllithium (2.5M in hexanes, 43 mL) was added, maintaining the temperature below -60° C. The mixture was warmed to 20° C. for 1 hour, and cooled to -70° C. A portion of the resulting 2,5-dihydro-2,5-dioxo-1,4-dilithio-3-methoxy-1H-benz[b]azepine solution (0.188M in tetrahydrofuran, 26 mL) was added to a solution of allyl bromide (0.85 mL) in tetrahydrofuran (15 mL) at -70° C. The mixture was warmed to room temperature, diluted with water, acidified (2N hydrochloric acid) and extracted with ethyl acetate. The combined organic extracts were washed with brine, dried and evaporated. The solid was purified by chromatography, with ethyl acetate:toluene (1:3) as the eluent, to give the title compound (0.189 g, 34%); NMR: 5.77 (m,1); 4.99 (d,1) 4.94 (s,1) 3.29 (d,2); MS: m/z=244(M+1).

Workup

  1. temperaturemaintaining the temperature below -60° C
  2. temperaturecooled to -70° C
  3. temperatureThe mixture was warmed to room temperature
  4. extractionextracted with ethyl acetate
  5. washThe combined organic extracts were washed with brine
  6. customdried
  7. customevaporated
  8. customThe solid was purified by chromatography, with ethyl acetate:toluene (1:3) as the eluent

Sources & evidence

ORD record
ord-25480fb06b114284a172e0ea8e08184f
Source dataset
uspto-grants-1997_08
Patent number
US05656626

Reaction notes

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