Ethanethiol → HCID 22907022, compound

HRID 1379701Notes

Reaction equation

HRID 1379701 reaction equation
[Al+3].[Cl-].[Cl-].[Cl-].C(S)C.[N:8]1([CH2:14][CH2:15][O:16][C:17]2[CH:22]=[CH:21][C:20]([C:23]3[C:28]([C:29]4[CH:34]=[CH:33][C:32]([O:35]C)=[CH:31][CH:30]=4)=[CH:27][CH:26]=[C:25]([CH3:37])[N:24]=3)=[CH:19][CH:18]=2)[CH2:13][CH2:12][CH2:11][CH2:10][CH2:9]1.[H][H]>ClCCCl.CC(C)=O>[N:8]1([CH2:14][CH2:15][O:16][C:17]2[CH:18]=[CH:19][C:20]([C:23]3[C:28]([C:29]4[CH:30]=[CH:31][C:32]([OH:35])=[CH:33][CH:34]=4)=[CH:27][CH:26]=[C:25]([CH3:37])[N:24]=3)=[CH:21][CH:22]=2)[CH2:13][CH2:12][CH2:11][CH2:10][CH2:9]1

Participants

7

Reactant 4

HCID 6343EthanethiolHCID 6451240Aluminum(III) ChlorideHCID 18923780HCID 18923780, compoundHCID 178418361HCID 178418361, compound

Product 1

HCID 22907022HCID 22907022, compoundYield 81.5%

Reagents, catalysts & solvents 2

HCID 111,2-DichloroethaneSolvent2×HCID 180AcetoneSolvent

Procedure

The AlCl3 (1.2 g, 9 mmol) was stirred in 30 mL of DCE at 0° C., ethanethiol (1 mL, 14 mmol) was added, and the mixture stirred for 15 min. The 2-[4-[2-(1-piperidinyl)ethoxy]phenyl]-3-(4-methoxyphenyl)-6-methylpyridine (0.5 g, 1.2 mmol) in 20 mL DCE was added dropwise to the reaction mixture and stirred for 2 h as it was allowed to come to rt, then quenched with 25 mL THF at 0° C., followed by 25 mL 1N HCl and worked up. The free base gave a very clean NMR, but the elemental analysis was low for carbon and hydrogen, so it was taken up in 50 mL hot acetone, citric acid H2O (0.2 g, 0.9 mmol) was added, then heated 10 min, concentrated, triturated with Et2O, filtered, and dried in vacuo to give 0.38 g (72 % yield) of product as the citrate salt: mp 90°-100° C.; 1H NMR (CDCl3) (free base) d 1.34-1.66 (comp, 6H, piperidine), 2.42-2.65 (comp, 7H, pyr-CH3 and piperidine), 2.70-2.79 (m, 2H, CH2 N), 3.95-4.10 (m, 2H, OCH2), 6.50-6.59 (m, 4H, ArH), 6.76-6.85 (d, 2H, J=8 Hz, ArH), 6.98-7.05 (d, 1H, J=8 Hz, ArH), 7.10-7.21 (m, 2H, ArH), 7.41-7.50 (d, 1H, J=8 Hz, ArH); MS(FAB) 398 [M+i]+Anal. Calcd for C25H28N2O2 ·C6H8O7 : C, 64.13; H, 6.25; N, 4.82. Found: C, 63.99; H, 6.36; N, 4.58.

Workup

  1. stirringstirred for 2 h as it
  2. customto come to rt
  3. customquenched with 25 mL THF at 0° C.
  4. customThe free base gave a very clean NMR
  5. temperatureheated 10 min
  6. concentrationconcentrated
  7. customtriturated with Et2O
  8. filtrationfiltered
  9. customdried in vacuo

Sources & evidence

ORD record
ord-928b01732488461c8cb1046501bd7f28
Source dataset
uspto-grants-1997_09
Patent number
US05672609

Reaction notes

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