Hydrochloric Acid → HCID 131725738, compound

HRID 1824629Notes

Reaction equation

HRID 1824629 reaction equation
[I:1][C:2]1[CH:8]=[CH:7][C:5](N)=[CH:4][CH:3]=1.Cl.N([O-])=O.[Na+].[CH-:14]1[CH:18]=[CH:17][CH:16]=[CH:15]1.[CH-:19]1[CH:23]=[CH:22][CH:21]=[CH:20]1.[Fe+2:24]>O.C1(C)C=CC=CC=1>[I:1][C:2]1[CH:8]=[CH:7][C:5]([C-:14]2[CH:18]=[CH:17][CH:16]=[CH:15]2)=[CH:4][CH:3]=1.[CH-:19]1[CH:23]=[CH:22][CH:21]=[CH:20]1.[Fe+2:24]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 7611Bis(eta-cyclopentadienyl) ironHCID 108934-IodoanilineHCID 23668193Sodium Nitrite

Product 1

HCID 131725738HCID 131725738, compoundYield 55%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 1140TolueneSolvent

Conditions

Temperature
0 °C

Procedure

4-Iodoaniline (8.8 g, 40 mmol) was suspended in a mixture of conc. HCl (20 mL) and H2O (50 mL) and cooled to 0° C. A solution of NaNO2 (3.3 g, 48 mmol) in H2O (10 mL) was added dropwise with stirring while the temperature was carefully maintained at 0–5° C. After the addition was completed, the mixture was stirred for 30 min at 0° C. The resulting diazonium salt solution was then added slowly to a solution of ferrocene (3.7 g, 20 mmol) in toluene (100 mL) at 0° C. An instantaneous evolution of gas was observed. After complete addition, the reaction mixture was stirred at 0° C. for 1 h. Then the mixture was warmed to rt and stirring was continued for 16 h. The layers were separated and the aqueous layer was extracted with toluene (3×100 mL). The combined organic layers were washed with satd aq NaHCO3 (3×100 mL), brine (3×100 mL), dried (MgSO4) and filtered. The solvent was removed under reduced pressure and the resulting residue was purified by column chromatography (silica, petroleum ether/diethyl ether, 10:2) to afford 4.2 g (55%) of an orange solid: mp 119–121° C.; 1H NMR δ 4.02 (s, 5H), 4.33 (t, J=1.5 Hz, 2H), 4.61 (t, J=1.5 Hz, 2H), 7.20,7.58 (AA′BB′, J=7.8 Hz, 4H); 13C NMR δ 66.4, 69.2, 69.7, 84.1, 90.5, 127.9, 137.3, 139.2; FAB-MS obsd 387.9420 calcd exact mass 387.9411 (C16H13FeI).

Workup

  1. temperaturewas carefully maintained at 0–5° C
  2. additionAfter the addition
  3. stirringthe mixture was stirred for 30 min at 0° C
  4. additionAfter complete addition
  5. stirringthe reaction mixture was stirred at 0° C. for 1 h
  6. temperatureThen the mixture was warmed to rt
  7. stirringstirring
  8. customThe layers were separated
  9. extractionthe aqueous layer was extracted with toluene (3×100 mL)
  10. washThe combined organic layers were washed with satd aq NaHCO3 (3×100 mL), brine (3×100 mL)
  11. dry with materialdried (MgSO4)
  12. filtrationfiltered
  13. customThe solvent was removed under reduced pressure
  14. customthe resulting residue was purified by column chromatography (silica, petroleum ether/diethyl ether, 10:2)

Sources & evidence

ORD record
ord-92fca8414beb4b11a74bb3376a1c627a
Source dataset
uspto-grants-2006_05
Patent number
US07042755B1

Reaction notes

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