1,4-Dichlorobenzene → HCID 18544379, compound

HRID 1268493Notes

Reaction equation

HRID 1268493 reaction equation
[Br:1][C:2]1[CH:14]=[CH:13][C:12]2[C:11]3[C:6](=[CH:7][C:8](I)=[CH:9][CH:10]=3)[C:5]([CH2:19][CH:20]=[CH2:21])([CH2:16][CH:17]=[CH2:18])[C:4]=2[CH:3]=1.IC1C=CC2C3C(=CC(I)=CC=3)C(CC=C)(CC=C)C=2C=1.[C:43]1([NH:49][C:50]2[CH:55]=[CH:54][CH:53]=[CH:52][CH:51]=2)[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=1.C(=O)([O-])[O-].[K+].[K+].C1C(Cl)=CC=C(Cl)C=1>C(Cl)Cl.[Cu].[Cu]I.C1(C)C=CC=CC=1>[Br:1][C:2]1[CH:14]=[CH:13][C:12]2[C:11]3[C:6](=[CH:7][C:8]([N:49]([C:50]4[CH:51]=[CH:52][CH:53]=[CH:54][CH:55]=4)[C:43]4[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=4)=[CH:9][CH:10]=3)[C:5]([CH2:19][CH:20]=[CH2:21])([CH2:16][CH:17]=[CH2:18])[C:4]=2[CH:3]=1

Participants

10

Reactant 5

HCID 46851,4-DichlorobenzeneHCID 11430Potassium CarbonateHCID 11487DiphenylamineHCID 18544381HCID 18544381, compoundHCID 18544384HCID 18544384, compound

Product 1

HCID 18544379HCID 18544379, compoundYield 55%

Reagents, catalysts & solvents 4

HCID 23978CopperCatalystHCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 1140TolueneSolventHCID 6344DichloromethaneSolvent

Procedure

A mixture of 2-bromo-7-iodo-9,9-diprop-2-enylfluorene (major component) and 2,7-diiodo-9,9-diprop-2-enylfluorene (45.3 g, 0.1 mol), diphenylamine (17.0 g, 0.1 mol), potassium carbonate (30.38 g, 0.22 mol), copper bronze (4.8 g, 76 mmol), copper(I) iodide (1.0 g, 5.25 mmol), dichlorobenzene (85 mL) and toluene (50 mL), was heated to reflux, and toluene and water were distilled off to get a reaction temperature of 182-183° C. After 7 hours, the reaction was cooled, diluted with 100 mL methylene chloride and filtered. The salts were washed with 3×50 mL methylene chloride. The combined filtrate was concentrated and chromatographed over a column of alumina (800 g). Elution with 10% toluen-heptane gave the product, 27.21 g, 55% yield, m.p. 141.4-143.3° C. Mass Spec: m/z 539 (M+, iodo analog), 491,493 (M+, desired bromo). Anal. Calcd. for C31H26BrN: C, 75.61%; H, 5.32%; N, 2.84%; Br, 16.23%. Found: C, 74.02%; H, 5.37%; N, 2.68%; Br, 12.42%; I, 6.19%.

Workup

  1. temperaturewas heated
  2. temperatureto reflux
  3. distillationtoluene and water were distilled off
  4. customto get a reaction temperature of 182-183° C
  5. temperaturethe reaction was cooled
  6. filtrationfiltered
  7. washThe salts were washed with 3×50 mL methylene chloride
  8. concentrationThe combined filtrate was concentrated
  9. customchromatographed over a column of alumina (800 g)
  10. washElution with 10% toluen-heptane
  11. customgave the product, 27.21 g, 55% yield, m.p. 141.4-143.3° C

Sources & evidence

ORD record
ord-bcf4bc21c8be4dc6837b7143f2bcc109
Source dataset
uspto-grants-2003_04
Patent number
US06555682B1

Reaction notes

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