Cesium carbonate → 3-[(1-Methyl-4-piperidinyl)sulfanyl]aniline

HRID 1822016Notes

Reaction equation

[NH2:1][C:2]1[CH:3]=[C:4]([SH:8])[CH:5]=[CH:6][CH:7]=1.Cl.Cl[CH:11]1[CH2:16][CH2:15][N:14]([CH3:17])[CH2:13][CH2:12]1.C(=O)([O-])[O-].[Cs+].[Cs+]>CN(C)C=O>[CH3:17][N:14]1[CH2:15][CH2:16][CH:11]([S:8][C:4]2[CH:3]=[C:2]([NH2:1])[CH:7]=[CH:6][CH:5]=2)[CH2:12][CH2:13]1

Participants

Conditions

Temperature: 80 °C

Procedure

Combine 3-amino-benzenethiol (1.87 mL, 17.83 mmol), 4-chloro-1-methyl-piperidine hydrochloride (2.0 g, 11.76 mmol), cesium carbonate (8.42 g, 25.87 mmol), and dimethylformamide (60 mL), stir and heat at 80° C. After 18 hr., cool to ambient temperature and filter. Wash the filtrate with water (3×20 mL) and extract with diethyl ether (2×30 mL). Combine the organic layers, dry over magnesium sulfate, filter and concentrate. Purify through a plug of silica gel using dichloromethane/2.0 M ammonia in methanol (20:1 mixture ratio) to give the title compound as a pale orange oil (1.52 g, 58%): Mass spectrum (ion spray): m/z=223.1 (M+1), 1H NMR (free base, CDCl3): 7.10 (t, J=7.8 Hz, 1H), 6.84-6.80 (m, 1H), 6.77 (t, J=2.0 Hz, 1H), 6.58 (ddd, J=0.8, 2.2, 8.0 Hz, 1H), 3.69 (bs, 2H), 3.09 (bs, 1H), 2.85 (m, 2H), 2.31 (s, 3H), 2.16-1.99 (m, 4H), 1.79-1.64 (m, 2H). 13C NMR (free base, CDCl3): 146.7, 135.2, 129.4, 122.0, 118.4, 113.7, 55.1, 46.1, 43.6, 32.5.

Workup

temperature, cool to ambient temperature
filtrationfilter
washWash the filtrate with water (3×20 mL)
extractionextract with diethyl ether (2×30 mL)
dry with materialCombine the organic layers, dry over magnesium sulfate
filtrationfilter
concentrationconcentrate
customPurify through a plug of silica gel

Sources & evidence

ORD record: ord-45e9d72a864f41a1b7ba316b29e6f2ed
Source dataset: uspto-grants-2009_10
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07608629B2

Reaction notes

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