Trifluoroacetic acid → 5,6-Dihydrophenanthridine

HRID 2181829Notes

Reaction equation

HRID 2181829 reaction equation
[CH3:1][O:2][C:3]1[C:4]2[C:13]([CH:14]=[CH:15][CH:16]=1)=[C:12]1[C:7]([CH:8]=[CH:9][CH:10]=[CH:11]1)=[N:6][C:5]=2[CH3:17].[BH4-].[Na+].FC(F)(F)C(O)=O.C1C=CC2C3C=CC=CC=3NCC=2C=1.C(N(CC)CC)C.[CH3:48][O:49][C:50]1[CH:55]=[CH:54][C:53]([S:56](Cl)(=[O:58])=[O:57])=[CH:52][C:51]=1[CH3:60]>O1CCCC1.ClCCl>[CH:16]1[CH:15]=[CH:14][C:13]2[C:12]3[CH:11]=[CH:10][CH:9]=[CH:8][C:7]=3[NH:6][CH2:5][C:4]=2[CH:3]=1.[CH3:1][O:2][C:3]1[CH:16]=[CH:15][CH:14]=[C:13]2[C:4]=1[CH:5]([CH3:17])[N:6]([S:56]([C:53]1[CH:54]=[CH:55][C:50]([O:49][CH3:48])=[C:51]([CH3:60])[CH:52]=1)(=[O:58])=[O:57])[C:7]1[CH:8]=[CH:9][CH:10]=[CH:11][C:12]=12

Participants

10

Reactant 6

HCID 6422Trifluoroacetic acidHCID 8471TriethylamineHCID 2199665,6-DihydrophenanthridineHCID 4311764Sodium borohydrideHCID 159153174-Methoxy-3-methylbenzene-1-sulfonyl chlorideHCID 224822867-Methoxy-6-methylphenanthridine

Product 2

HCID 2199665,6-DihydrophenanthridineHCID 224823047-Methoxy-5-[(4-methoxy-3-methylphenyl)sulfonyl]-6-methyl-5,6-dihydrophenanthridine

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Procedure

The intermediate dihydrophenanthridine was prepared from 7-methoxy-6-methylphenanthridine, (Example 36, Step b, 0.61 g, 2.7 mmol), by treatment with sodium borohydride (0.62 g, 16 mmol) and trifluoroacetic acid (0.84 mL, 10.8 mmol) in tetrahydrofuran (12 mL). In a separate, second step, the dihydrophenanthridine was treated with triethylamine (0.85 mL, 6.1 mmol) and 4-methoxy-3-methylbenzenesulfonyl chloride (0.67 g, 3.0 mmol, 2 equivalents) in dichloromethane (3 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 yield 7-methoxy-5-[(4-methoxy-3-methylphenyl)sulfonyl]-6-methyl-5,6-dihydrophenanthridine as a homogeneous, white solid (0.21 g, 34% from the dihydrophenanthridine);

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-3971a9a5d0d04ddbb83884dac893cbcb
Source dataset
uspto-grants-2005_05
Patent number
US06894061B2

Reaction notes

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