Ethanethiol → 2,8-Dihydroxy-5-[4-[2-(1-piperidinyl)ethoxy]phenyl]-6H-benzo[c]phenanthridine

HRID 612740

Reaction equation

HRID 612740 reaction equation
C[O:2][C:3]1[CH:4]=[CH:5][C:6]2[C:19]3[N:18]([C:20]4[CH:25]=[CH:24][C:23]([O:26][CH2:27][CH2:28][N:29]5[CH2:34][CH2:33][CH2:32][CH2:31][CH2:30]5)=[CH:22][CH:21]=4)[CH2:17][C:16]4[C:11](=[CH:12][CH:13]=[C:14]([O:35]C)[CH:15]=4)[C:10]=3[CH:9]=[CH:8][C:7]=2[CH:37]=1.C(S)C.[Cl-].[Al+3].[Cl-].[Cl-]>C(Cl)Cl>[OH:2][C:3]1[CH:4]=[CH:5][C:6]2[C:19]3[N:18]([C:20]4[CH:21]=[CH:22][C:23]([O:26][CH2:27][CH2:28][N:29]5[CH2:30][CH2:31][CH2:32][CH2:33][CH2:34]5)=[CH:24][CH:25]=4)[CH2:17][C:16]4[C:11](=[CH:12][CH:13]=[C:14]([OH:35])[CH:15]=4)[C:10]=3[CH:9]=[CH:8][C:7]=2[CH:37]=1

Participants

5

Reactant 3

HCID 6343EthanethiolHCID 6451240Aluminum(III) ChlorideHCID 109180382,8-Dimethoxy-5-[4-[2-(1-piperidinyl)ethoxy]phenyl]-6H-benzo[c]phenanthridine

Product 1

HCID 104122492,8-Dihydroxy-5-[4-[2-(1-piperidinyl)ethoxy]phenyl]-6H-benzo[c]phenanthridineYield 60.5%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A solution of the product of Example 13 (195 mg, 0.39 mmol) in methylene chloride (25 mL) was treated with ethanethiol (200 mg, 220 mL, 3.2 mmol) and aluminum chloride (320 mg, 2.4 mmol). After stirring for 4 h at ambient temperature, the mixture was quenched carefully with THF (25 mL) and saturated sodium bicarbonate (25 mL). The layers were separated, the aqueous layer was extracted with THF (25 mL), and the combined organic layers were dried (sodium sulfate) and concentrated. The residue was purified by radial chromatography (silica gel, 1:1 hexane:ethyl acetate, 10-20% methanol, under an ammonia atmosphere) to provide 110 mg (60%) of the title compound as a tan foam. An analytical sample was crystallized from methanol as a light red solid: 1H NMR (300 MHz, dimethylformamide-d7) d 9.92 (br s, 1H), 9.74 (br s, 1H), 7.99 (d, J=8.8 Hz, 1H), 7.78 (d, J=8.5 Hz, 1H), 7.69 (d, J=9.0 Hz, 1H), 7.63 (d, J=8.7 Hz, 1H), 7.23 (d, J=2.0 Hz, 1H), 6.98 (dd, J=9.0, 2.1 Hz, 1H), 6.84 (dd, J=8.4, 2.1 Hz, 1H), 6.73 (m, 5H), 3.92 (t, J=5.9 Hz, 2H), 2.57 (t, J=5.9 Hz, 2H), 2.38 (m, 4H), 1.4-1.5 (m, 4H), 1.3-1.4 (m, 2H); IR (KBr) 3560, 3490 cm-1 ; MS (FD+) m/e 466 (M+); Anal. calc'd. for C30H30N2O3.0.5H2O: C, 75.75; H, 6.58; N, 5.89. Found: C, 75.32; H, 6.76; N, 5.95.

Workup

  1. customthe mixture was quenched carefully with THF (25 mL) and saturated sodium bicarbonate (25 mL)
  2. customThe layers were separated
  3. extractionthe aqueous layer was extracted with THF (25 mL)
  4. dry with materialthe combined organic layers were dried (sodium sulfate)
  5. concentrationconcentrated
  6. customThe residue was purified by radial chromatography (silica gel, 1:1 hexane

Sources & evidence

ORD record
ord-d527b213816441fda207c5d19c1ba30c
Source dataset
uspto-grants-1999_12
Patent number
US06004971

Linked notes

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