Thionyl Chloride → (7-Bromo-3-nitroquinolin-4-yl)-(4-chlorobutyl)amine

HRID 9416Notes

Reaction equation

HRID 9416 reaction equation
[Br:1][C:2]1[CH:11]=[C:10]2[C:5]([C:6]([NH:15][CH2:16][CH2:17][CH2:18][CH2:19]O)=[C:7]([N+:12]([O-:14])=[O:13])[CH:8]=[N:9]2)=[CH:4][CH:3]=1.S(Cl)([Cl:23])=O.C(=O)(O)[O-].[Na+]>ClCCl>[Br:1][C:2]1[CH:11]=[C:10]2[C:5]([C:6]([NH:15][CH2:16][CH2:17][CH2:18][CH2:19][Cl:23])=[C:7]([N+:12]([O-:14])=[O:13])[CH:8]=[N:9]2)=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 24386Thionyl Chloride2×HCID 516892Sodium BicarbonateHCID 219843704-(7-Bromo-3-nitroquinolin-4-ylamino)butan-1-ol

Product 1

HCID 21984395(7-Bromo-3-nitroquinolin-4-yl)-(4-chlorobutyl)amineYield 37.9%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

A suspension of 4-(7-bromo-3-nitroquinolin-4-ylamino)butan-1-ol (20.75 g, 61.0 mmol) in dichloromethane (220 mL) was cooled to 0° C.; thionyl chloride (4.90 mL, 67.1 mmol) was added dropwise over a period of ten minutes. The reaction was stirred at 0° C. for five minutes, allowed to warm to ambient temperature, and stirred overnight. Aqueous sodium bicarbonate (500 mL of 50%) was slowly added. The aqueous layer was separated and extracted with dichloromethane (3×100 mL). The combined organic fractions were dried over magnesium sulfate, filtered, and concentrated under reduced pressure to yield an orange semi-solid. An analysis by LCMS indicated the presence of starting material, and the semi-solid was dissolved in dichloromethane (150 mL) and treated with thionyl chloride (3.0 mL) as described above. Following the work-up procedure, the crude product was purified by column chromatography on silica gel (eluting with dichloromethane:methanol in a gradient from 100:0 to 95:5) to provide 8.3 g of (7-bromo-3-nitroquinolin-4-yl)-(4-chlorobutyl)amine as a yellow solid.

Workup

  1. temperatureto warm to ambient temperature
  2. stirringstirred overnight
  3. customThe aqueous layer was separated
  4. extractionextracted with dichloromethane (3×100 mL)
  5. dry with materialThe combined organic fractions were dried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. customto yield an orange semi-solid
  9. customthe crude product was purified by column chromatography on silica gel (
  10. washeluting with dichloromethane

Sources & evidence

ORD record
ord-b222e38a54a5496bb7a0423bbddccd3a
Source dataset
uspto-grants-2006_08
Patent number
US07091214B2

Reaction notes

Loading…