Iodine → 6-Fluorophenanthridine

HRID 342888Notes

Reaction equation

HRID 342888 reaction equation
[CH:1]1[C:14]2[C:5](=[N:6][CH:7]=[C:8]3[C:13]=2[CH:12]=[CH:11][CH:10]=[CH:9]3)[CH:4]=[CH:3][CH:2]=1.II.[F:17]F>S(S([O-])=O)([O-])(=O)=O.[Na+].[Na+]>[F:17][C:7]1[N:6]=[C:5]2[C:14](=[C:13]3[C:8]=1[CH:9]=[CH:10][CH:11]=[CH:12]3)[CH:1]=[CH:2][CH:3]=[CH:4]2

Participants

5

Reactant 3

HCID 807IodineHCID 9189PhenanthridineHCID 24524Fluorine2×

Product 1

HCID 6409346-FluorophenanthridineYield 48%

Reagents, catalysts & solvents 1

HCID 656671Sodium PyrosulfiteSolvent

Procedure

A solution containing phenanthridine (1.0 g, 5.6 mmol) and iodine (1.4 g, 5.6 mmol) in CF2ClCFCl2 (30 ml) was placed in a fluorination apparatus fitted with a drying tube filled with soda lime. Elemental fluorine (7 mmol) as a 10% mixture in dry nitrogen was then passed through the stirred solution using narrow bore PTFE tubing at ca. 15 ml/min. After the fluorine had been added the solution was poured into 10% aqueous sodium metabisulfite solution (30 ml) and extracted with dichloromethane. The organic extracts were dried and evaporated to an orange oil (0.91 g). GC/MS analysis showed a 17% conversion of starting material. Column chromatography on silica get with dichloromethane as eluant gave 6-fluoro-phenanthridine (0.09 g, 48%); RF 0.78 (CH2Cl2); δH (400 MHz, CDCl3, Me4Si) 7.61 ppm (1H, d d d, JH1,H2 =JH2,H3 =7.8, JH2,H4 1.2, H-2), 7.69 (2H, m, H-3 and H-9), 7.88 (1H, d d d, JH7,H8 8.4, JH8,H9 7.2, JH8,H10 1.4, H-8), 7.97 (1H, d d, JH3,H4 8.0, JH2,H4 1.2, H-4), 8.21 (1H, d d, JH9,H10 8.0, JH8,H10 1.4, H-10 8.45 (1H, d d, JH1,H2 8.0, JH1,H3 0.8, H-1), 8.52 (1H, d d, JH7,H8 8.4, JH7,H9 1.2, H-7); δF (376 MHz. CDCl3, CFCl3) -68.2 ppm (s); δC (100 MHz, CDCl3, Me4Sl) 117.3 ppm (d, J 35.1,C-6a), 122.2 (d, 3J 3.8, C-7), 122.2 (s, C-1), 123.9 (d, 4J 1.9, C-10b), 124.2 (s, C-10), 126.5 (d, 6J 2.3, C-2), 127.9 (s, C-9), 128.7 (d, 4J 1.6, C-4), 129.4 (s, C-3), 132.1 (s, C-8), 136.5 (d, 3J 7.2, C-10a), 141.5 (d, 3J 17.9, C-4a), 158.1 (d, 1J 248.7, C-6); m/z (E1+) 197 (M+, 100%).

Workup

  1. customfitted with a drying tube
  2. extractionextracted with dichloromethane
  3. customThe organic extracts were dried
  4. customevaporated to an orange oil (0.91 g)
  5. customColumn chromatography on silica get with dichloromethane as eluant

Sources & evidence

ORD record
ord-87f33b0ef7844329946be5c5efc12bb5
Source dataset
uspto-grants-1999_01
Patent number
US05859255

Reaction notes

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