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Trifluoroacetic acid → 5,6-Dihydrophenanthridine

HRID 2181825
Notes
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Reaction equation

HRID 2181825 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[CH:5][C:6]2[C:15]([CH:16]=1)=[C:14]1[C:9]([CH:10]=[CH:11][CH:12]=[CH:13]1)=[N:8][C:7]=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][CH:51]=1>O1CCCC1.ClCCl>[CH:4]1[CH:3]=[CH:16][C:15]2[C:14]3[CH:13]=[CH:12][CH:11]=[CH:10][C:9]=3[NH:8][CH2:7][C:6]=2[CH:5]=1.[CH3:1][O:2][C:3]1[CH:16]=[C:15]2[C:6]([CH:7]([CH3:17])[N:8]([S:56]([C:53]3[CH:52]=[CH:51][C:50]([O:49][CH3:48])=[CH:55][CH:54]=3)(=[O:58])=[O:57])[C:9]3[CH:10]=[CH:11][CH:12]=[CH:13][C:14]=32)=[CH:5][CH:4]=1
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

10

Reactant 6

HCID 6422Trifluoroacetic acidHCID 74014-Methoxybenzenesulfonyl chlorideHCID 8471TriethylamineHCID 2199665,6-DihydrophenanthridineHCID 4311764Sodium borohydrideHCID 224823459-Methoxy-6-methylphenanthridine

Product 2

HCID 219966
5,6-Dihydrophenanthridine
HCID 224823209-Methoxy-5-[(4-methoxyphenyl)sulfonyl]-6-methyl-5,6-dihydrophenanthridine

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Procedure

The intermediate dihydrophenanthridine was prepared from 9-methoxy-6-methylphenanthridine (0.7 g, 3.1 mmol) by treatment with sodium borohydride (0.48 g, 12.6 mmol) and trifluoroacetic acid (0.5 mL, 6.3 mmol) in tetrahydrofuran (35 mL). In a separate, second step, the dihydrophenanthridine was treated with triethylamine (1.0 mL, 7.5 mmol) and 4-methoxybenzenesulfonyl chloride (0.77 g, 3.7 mmol, 2 equivalents) in dichloromethane (10 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 9-methoxy-5-[(4-methoxyphenyl)sulfonyl]-6-methyl-5,6-dihydrophenanthridine as a homogeneous, white solid (0.45 g, 61% from the dihydrophenanthridine), m.p. 129-130° 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-9b4d2e4d86154742b7ae7f9b4ba3686e
Source dataset
uspto-grants-2005_05
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US06894061B2

Reaction notes

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On this pageParticipantsProcedureWorkupSources & evidenceReaction notes