Propyl mercaptan → HCID 59516113, compound

HRID 1799409Notes

Reaction equation

[C:1]([O:5][C:6]([C:8]1[CH:9]=[N:10][N:11]([CH2:14][C:15]2[CH:20]=[CH:19][C:18]([C:21]([O:23][CH3:24])=[O:22])=[CH:17][CH:16]=2)[C:12]=1Cl)=[O:7])([CH3:4])([CH3:3])[CH3:2].C(=O)([O-])[O-].[K+].[K+].[CH2:31]([SH:34])[CH2:32][CH3:33].CCOC(C)=O>C(#N)CCC>[C:1]([O:5][C:6]([C:8]1[CH:9]=[N:10][N:11]([CH2:14][C:15]2[CH:20]=[CH:19][C:18]([C:21]([O:23][CH3:24])=[O:22])=[CH:17][CH:16]=2)[C:12]=1[S:34][CH2:31][CH2:32][CH3:33])=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

Conditions

Temperature: 180 °C

Procedure

5-Chloro-1-(4-methoxycarbonyl-benzyl)-1H-pyrazole-4-carboxylic acid tert-butyl ester (Intermediate #48) (397 mg, 1.13 mmol) was dissolved in butyronitrile (8 mL), potassium carbonate (470 mg, 3.40 mmol) and propanethiol (128 μl, 1.41 mmol) were added and the mixture heated to reflux and stirred at this temperature over night. The reaction mixture was transferred to a microwave vial (using ˜5 ml extra Butyronitrile to ensure complete transfer), a further 3 eq of propane thiol was added and the reaction was heated at 180° C. for 4 hours. EtOAc (˜50 mL) was added and the mixture washed with water (3×˜20 mL) and brine (˜20 ml) then dried (MgSO4), filtered and evaporated to give a yellow oil. Oil purified by column chromatography (12 g Si, eluting with 10 to 50% EtOAc in 1H) to yield the title compound as a yellow oil (274 mg, 62%).

Workup

temperaturethe mixture heated
temperatureto reflux
washthe mixture washed with water (3×˜20 mL) and brine (˜20 ml)
dry with materialthen dried (MgSO4)
filtrationfiltered
customevaporated
customto give a yellow oil
customOil purified by column chromatography (12 g Si, eluting with 10 to 50% EtOAc in 1H)

Sources & evidence

ORD record: ord-87053ed7fb3044069862089c92072d17
Source dataset: uspto-grants-2013_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08344016B2

Reaction notes

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