1-Bromo-3-chloropropane → HCID 23318827, compound

HRID 1048733Notes

Reaction equation

HRID 1048733 reaction equation
Br[CH2:2][CH2:3][CH2:4][Cl:5].[OH:6][C:7]1[CH:8]=[CH:9][C:10]([N+:15]([O-:17])=[O:16])=[C:11]([CH:14]=1)[CH:12]=[O:13].C(=O)([O-])[O-].[K+].[K+]>CN(C=O)C.C(OCC)(=O)C>[Cl:5][CH2:4][CH2:3][CH2:2][O:6][C:7]1[CH:8]=[CH:9][C:10]([N+:15]([O-:17])=[O:16])=[C:11]([CH:14]=1)[CH:12]=[O:13]

Participants

6

Reactant 3

HCID 80061-Bromo-3-chloropropaneHCID 11430Potassium CarbonateHCID 392115-Hydroxy-2-nitrobenzaldehyde

Product 1

HCID 23318827HCID 23318827, compoundYield 87%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
40 °C

Procedure

Compound b2 may be prepared according to reported methods (see, e.g., Gumbley, P.; Koylu, D.; Thomas, S. W. Macromolecules 2011, 44, 7956). 1-Bromo-3-chloropropane (0.650 mL, 0.00658 moles) was added to a solution of 5-hydroxy-2-nitrobenzaldehyde (1.0 g, 0.00598 moles), and potassium carbonate (1.66 g, 0.0120 moles) in anhydrous DMF (6 mL). The solution was stirred at 40° C. for 24 hours. The reaction was diluted with ethyl acetate (75 mL) and washed with saturated sodium bicarbonate solution (75 mL), water (75 mL), and brine (75 mL). The organic layer was dried with anhydrous magnesium sulfate, which was removed by filtration. The filtrate was concentrated, and the resulting residue was subject to silica gel chromatography using a gradient of 100% hexanes to 50% ethyl acetate in hexanes. The fractions containing the product were collected, and volatiles were removed by rotary evaporation. The resulting residue was dried overnight to yield 5-(3-chloropropoxy)-2-nitrobenzaldehyde as a bright-green yellow solid (yield 87%*). 1H NMR (400 MHz, CD2Cl2) δ 10.42 (s, 1H), 8.15 (d, J=9.1 Hz, 1H), 7.32 (d, J=2.9 Hz, 1H), 7.18 (dd, J=9.0, 2.9 Hz, 1H), 4.27 (t, J=5.9 Hz, 2H), 3.76 (t, J=6.3 Hz, 2H), 2.35-2.24 (m, 2H). 13C-NMR (100 MHz, CD2Cl2) δ 189.05, 163.84, 135.04, 127.84, 119.16, 114.57, 66.28, 41.74, 32.35 HRMS m/z: calculated for C10H10ClNO4 [M+H]+, 244.0371. found, 244.0366.

Workup

  1. washwashed with saturated sodium bicarbonate solution (75 mL), water (75 mL), and brine (75 mL)
  2. dry with materialThe organic layer was dried with anhydrous magnesium sulfate, which
  3. customwas removed by filtration
  4. concentrationThe filtrate was concentrated
  5. additionThe fractions containing the product
  6. customwere collected
  7. customvolatiles were removed by rotary evaporation
  8. customThe resulting residue was dried overnight

Sources & evidence

ORD record
ord-0cbc9c23da664dc0a45018a3224a00fa
Source dataset
uspto-grants-2016_07
Patent number
US09381253B2

Reaction notes

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