(3-Bromopropyl)benzene → HCID 59557776, compound

HRID 2403771Notes

Reaction equation

HRID 2403771 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]([Cl:11])=[C:6]([CH:10]=1)[C:7]([OH:9])=O.C(Cl)(=O)C(Cl)=O.[Al+3].[Cl-].[Cl-].[Cl-].[Br:22][CH2:23][CH2:24][CH2:25][C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1>C(Cl)Cl.CN(C=O)C>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([Cl:11])=[C:6]([C:7]([C:29]2[CH:30]=[CH:31][C:26]([CH2:25][CH2:24][CH2:23][Br:22])=[CH:27][CH:28]=2)=[O:9])[CH:10]=1

Participants

7

Reactant 4

HCID 12503(3-Bromopropyl)benzeneHCID 331275-Bromo-2-chlorobenzoic acidHCID 65578Oxalyl chlorideHCID 6451240Aluminum(III) Chloride

Product 1

HCID 59557776HCID 59557776, compound

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolvent2×

Procedure

To a stirred suspension of 5-bromo-2-chlorobenzoic acid (2.31 g, 9.80 mmol) and oxalyl chloride (1.41 g, 11.11 mmol) in CH2Cl2 (30 mL) was added 0.05 mL of DMF. Once the vigorous evolution of gas ceased, the reaction was stirred overnight and then the volatiles were removed under reduced pressure. The resulting crude 5-bromo-2-chlorobenzoyl chloride was dissolved in dichloromethane (30 mL), and the solution was cooled to 0˜5° C. Then AlCl3 (1.31 g, 9.8 mmol) was added in portions, the mixture was stirred for 30 min, and (3-bromopropyl)benzene (1.50 g, 6.53 mmol) in dichloromethane (4 mL) was added. The reaction solution was warmed to room temperature and stirred for 4 h. The reaction was quenched by pouring into ice water. The suspension was diluted with water and extracted 3× with CH2Cl2. The combined organic extracts were washed 2× with 1N HCl, 1× with water, 2× with 1M NaOH, and 2× with brine, and then dried over Na2SO4. After removal of the volatiles, the crude product was purified by column chromatography (eluent EA:PE=1:20) to obtain intermediate DD (2.4 g) as a light yellow oil. 1H-NMR (CDCl3, 400 MHz): δ 7.68˜7.66 (d, 2H), 7.50˜7.47 (dd, 1H), 7.42 (d, 1H), 7.28˜7.19 (m, 3H), 3.33 (t, J=6.8 Hz, 2H), 2.80 (t, J=7.6 Hz, 2H), 2.17˜2.10 (m, 2H).

Workup

  1. customthe volatiles were removed under reduced pressure
  2. dissolutionThe resulting crude 5-bromo-2-chlorobenzoyl chloride was dissolved in dichloromethane (30 mL)
  3. temperaturethe solution was cooled to 0˜5° C
  4. stirringthe mixture was stirred for 30 min
  5. stirringstirred for 4 h
  6. customThe reaction was quenched
  7. additionby pouring into ice water
  8. additionThe suspension was diluted with water
  9. extractionextracted 3× with CH2Cl2
  10. washThe combined organic extracts were washed 2× with 1N HCl, 1× with water, 2× with 1M NaOH, and 2× with brine
  11. dry with materialdried over Na2SO4
  12. customAfter removal of the volatiles
  13. customthe crude product was purified by column chromatography (eluent EA:PE=1:20)
  14. customto obtain intermediate DD (2.4 g) as a light yellow oil

Sources & evidence

ORD record
ord-9393511fe6fa4b4faf544626913ce55f
Source dataset
uspto-grants-2014_08
Patent number
US08802637B2

Reaction notes

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