Carbon tetrabromide → HCID 21349905, compound

HRID 2186751Notes

Reaction equation

HRID 2186751 reaction equation
O[CH2:2][CH2:3][N:4]1[C:10]2[CH:11]=[CH:12][CH:13]=[C:14]([O:15][CH2:16][C:17]([O:19][CH3:20])=[O:18])[C:9]=2[CH2:8][CH2:7][CH2:6][CH2:5]1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(Br)(Br)(Br)Br.C(=O)(O)[O-].[Na+].[C:50]1([C:56]([C:59]2[CH:64]=[CH:63][CH:62]=[CH:61][CH:60]=2)([SH:58])[CH3:57])[CH:55]=[CH:54][CH:53]=[CH:52][CH:51]=1.[H-].[Na+].[Cl-].[NH4+]>C(Cl)Cl.CN(C=O)C>[C:59]1([C:56]([C:50]2[CH:51]=[CH:52][CH:53]=[CH:54][CH:55]=2)([S:58][CH2:2][CH2:3][N:4]2[C:10]3[CH:11]=[CH:12][CH:13]=[C:14]([O:15][CH2:16][C:17]([O:19][CH3:20])=[O:18])[C:9]=3[CH2:8][CH2:7][CH2:6][CH2:5]2)[CH3:57])[CH:60]=[CH:61][CH:62]=[CH:63][CH:64]=1

Participants

10

Reactant 7

HCID 11205Carbon tetrabromideHCID 11776TriphenylphosphineHCID 24758Sodium hydrideHCID 25517Ammonium ChlorideHCID 516892Sodium BicarbonateHCID 597528HCID 597528, compoundHCID 21349894HCID 21349894, compound

Product 1

HCID 21349905HCID 21349905, compoundYield 84.4%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolvent2×HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

Methyl (1-(2-hydroxyethyl)-2,3,4,5-tetrahydro-1H-1-benzazepin-6-yloxy)acetate (370 mg) was dissolved in methylene chloride (15 ml), and the resultant solution was stirred at 0° C. Triphenylphosphine (1085 mg) and carbon tetrabromide (922 mg) were added to the solution, and the mixture was stirred at 0° C. After disappearance of the raw materials was confirmed, a saturated sodium bicarbonate aqueous solution (15 ml) was added to the reaction solution, and the mixture was then extracted with ethyl acetate. The resultant organic layer was washed with saturated brine, dried over anhydrous sodium sulfate and concentrated. The resultant residue was purified by column chromatography (silica gel:hexane/ethyl acetate=1/1) to obtain a crude product. 1,1-diphenylethanethiol (428 mg) was dissolved in DMF (10 ml) under an argon atmosphere, and the resultant solution was stirred at 0° C. Sodium hydride (65 mg) was added to the solution, and the mixture was stirred at 0° C. for 5 minutes. A solution of the crude product in DMF (3 ml) was added to the mixture at 0° C. After disappearance of the raw materials was confirmed, the reaction solution was added to a saturated ammonium chloride aqueous solution (30 ml), and then extracted with ethyl acetate. The resultant organic layer was washed with saturated brine, dried over anhydrous sodium sulfate and concentrated. The resultant residue was purified by column chromatography (silica gel:hexane/ethyl acetate=8/1) to obtain the object compound (532 mg, yield 84%).

Workup

  1. extractionthe mixture was then extracted with ethyl acetate
  2. washThe resultant organic layer was washed with saturated brine
  3. dry with materialdried over anhydrous sodium sulfate
  4. concentrationconcentrated
  5. customThe resultant residue was purified by column chromatography (silica gel:hexane/ethyl acetate=1/1)
  6. customto obtain a crude product
  7. stirringthe mixture was stirred at 0° C. for 5 minutes
  8. extractionextracted with ethyl acetate
  9. washThe resultant organic layer was washed with saturated brine
  10. dry with materialdried over anhydrous sodium sulfate
  11. concentrationconcentrated
  12. customThe resultant residue was purified by column chromatography (silica gel:hexane/ethyl acetate=8/1)

Sources & evidence

ORD record
ord-3e4e419d5a4c4aa3b900fdf25079ac5e
Source dataset
uspto-grants-2002_06
Patent number
US06407096B1

Reaction notes

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