Trifluoroacetic acid → 5,6-Dihydrophenanthridine

HRID 2181844Notes

Reaction equation

HRID 2181844 reaction equation
[Br:1][C:2]1[CH:15]=[CH:14][C:13]2[C:4](=[C:5]3[C:10](=[C:11]([CH2:16][CH3:17])[N:12]=2)[CH:9]=[C:8]([F:18])[CH:7]=[CH:6]3)[CH:3]=1.[BH4-].[Na+].FC(F)(F)C(O)=O.C1C=CC2C3C=CC=CC=3NCC=2C=1.C(N(CC)CC)C.[CH3:49][O:50][C:51]1[CH:56]=[CH:55][C:54]([S:57](Cl)(=[O:59])=[O:58])=[CH:53][CH:52]=1>O1CCCC1.ClCCl>[CH:8]1[CH:7]=[CH:6][C:5]2[C:4]3[CH:3]=[CH:2][CH:15]=[CH:14][C:13]=3[NH:12][CH2:11][C:10]=2[CH:9]=1.[Br:1][C:2]1[CH:15]=[CH:14][C:13]2[N:12]([S:57]([C:54]3[CH:53]=[CH:52][C:51]([O:50][CH3:49])=[CH:56][CH:55]=3)(=[O:59])=[O:58])[CH:11]([CH2:16][CH3:17])[C:10]3[C:5](=[CH:6][CH:7]=[C:8]([F:18])[CH:9]=3)[C:4]=2[CH:3]=1

Participants

10

Reactant 6

HCID 6422Trifluoroacetic acidHCID 74014-Methoxybenzenesulfonyl chlorideHCID 8471TriethylamineHCID 2199665,6-DihydrophenanthridineHCID 4311764Sodium borohydrideHCID 224823802-Bromo-6-ethyl-8-fluorophenanthridine

Product 2

HCID 2199665,6-DihydrophenanthridineHCID 224823412-Bromo-6-ethyl-8-fluoro-5-[(4-methoxyphenyl)sulfonyl]-5,6-dihydrophenanthridine

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Procedure

The intermediate dihydrophenanthridine was prepared from 2-bromo-6-ethyl-8-fluorophenanthridine (3.27 g, 10.8 mmol) by treatment with sodium borohydride (2.03 g, 53.8 mmol) and trifluoroacetic acid (3.31 mL, 43.0 mmol) in tetrahydrofuran (43 mL). In a separate, second step, the dihydrophenanthridine was treated with triethylamine (9.0 mL, 65 mmol) and 4-methoxybenzenesulfonyl chloride (2.44 g, 11.8 mmol) in dichloromethane (11 mL) according to the procedure and in the same manner as described in Example 32, Method A, Step d. The crude product was purified by flash column chromatography on silica gel, eluting with a mixture of ethyl acetate-hexane (1:9 to 1:4 gradient), to afford 2-bromo-6-ethyl-8-fluoro-5-[(4-methoxyphenyl)sulfonyl]-5,6-dihydrophenanthridine as a homogeneous, yellow, crystalline, solid, m.p. 133-136° C.;

Workup

  1. customThe crude product was purified by flash column chromatography on silica gel
  2. washeluting with a mixture of ethyl acetate-hexane (1:9 to 1:4 gradient)

Sources & evidence

ORD record
ord-931871b17bf045cf984988a113911d7b
Source dataset
uspto-grants-2005_05
Patent number
US06894061B2

Reaction notes

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