Hydrochloric Acid → HCID 131725739, compound

HRID 1824630Notes

Reaction equation

HRID 1824630 reaction equation
[CH3:1][Si:2]([CH3:13])([CH3:12])[C:3]#[C:4][C:5]1[CH:11]=[CH:10][C:8](N)=[CH:7][CH:6]=1.Cl.N([O-])=O.[Na+].[CH-:19]1[CH:23]=[CH:22][CH:21]=[CH:20]1.[CH-:24]1[CH:28]=[CH:27][CH:26]=[CH:25]1.[Fe+2:29]>O.C1(C)C=CC=CC=1>[CH3:1][Si:2]([CH3:13])([CH3:12])[C:3]#[C:4][C:5]1[CH:11]=[CH:10][C:8]([C-:19]2[CH:23]=[CH:22][CH:21]=[CH:20]2)=[CH:7][CH:6]=1.[CH-:24]1[CH:28]=[CH:27][CH:26]=[CH:25]1.[Fe+2:29]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 7611Bis(eta-cyclopentadienyl) ironHCID 110524294-[(Trimethylsilyl)ethynyl]anilineHCID 23668193Sodium Nitrite

Product 1

HCID 131725739HCID 131725739, compoundYield 44%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 1140TolueneSolvent

Conditions

Temperature
0 °C

Procedure

4-[2-(Trimethylsilyl)ethynyl]aniline (Takahashi et al. (1980) Synthesis, 8: 627–630) (1.0 g, 5.3 mmol) was suspended in a mixture of conc. HCl (2.4 mL) and H2O (10 mL) and cooled to 0° C. under stirring. A solution of NaNO2 (0.40 g, 5.8 nmol) in H2O (2 mL) was added while the temperature was carefully maintained between 0–5° C. After the addition was complete, the mixture was stirred for 30 min at 0° C. The resulting diazonium salt solution was then added slowly to a solution of ferrocene (0.49 g, 2.7 mmol) in toluene (100 mL) at 0° C., resulting in gas evolution. After the addition was complete, the mixture was stirred for 1 h at 0° C., warmed to rt and stirring was continued for an additional 16 h. The layers were separated and the aqueous layer was extracted with toluene (3×50 mL). The combined organic layers were washed with satd aq NaHCO3 (3×50 mL), brine (3×50 mL), dried (MgSO4) and filtered. The solvent was removed under reduced pressure and the resulting residue was purified by column chromatography (silica, CH2Cl2/hexanes, 1:1) to remove unreacted ferrocene. Elution with CH2Cl2 afforded 0.42 g (44%) of compound 3. 1H NMR δ 0.27 (s, 9H), 4.02 (s, 5H), 4.35 (A2B2, J=1.5 Hz, 2H), 4.65 (A2B2, J=1.5 Hz, 2H), 7.40 (s, 4H); 13C NMR δ 0.04, 66.5, 69.3, 69.7, 84.1, 94.0, 105.5, 120.2, 125.6, 132.0, 140.1; FAB-MS obsd 358.0851, calcd exact mass 358.0840 (C21H22FeSi).

Workup

  1. temperaturewas carefully maintained between 0–5° C
  2. additionAfter the addition
  3. stirringthe mixture was stirred for 30 min at 0° C
  4. customresulting in gas evolution
  5. additionAfter the addition
  6. stirringthe mixture was stirred for 1 h at 0° C.
  7. temperaturewarmed to rt
  8. stirringstirring
  9. customThe layers were separated
  10. extractionthe aqueous layer was extracted with toluene (3×50 mL)
  11. washThe combined organic layers were washed with satd aq NaHCO3 (3×50 mL), brine (3×50 mL)
  12. dry with materialdried (MgSO4)
  13. filtrationfiltered
  14. customThe solvent was removed under reduced pressure
  15. customthe resulting residue was purified by column chromatography (silica, CH2Cl2/hexanes, 1:1)
  16. customto remove unreacted ferrocene
  17. washElution with CH2Cl2

Sources & evidence

ORD record
ord-a025d3fdf90041d1a64aa6754b6749e6
Source dataset
uspto-grants-2006_05
Patent number
US07042755B1

Reaction notes

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