4-Chlorophenyl isothiocyanate → cyclohexylmethyl N-(4-chlorophenyl)-3-(trimethylsilyl)thiopropynimidate

HRID 1918466Notes

Reaction equation

HRID 1918466 reaction equation
[C:1]([Si:3]([CH3:6])([CH3:5])[CH3:4])#[CH:2].C([Li])CCC.CCCCCC.[Cl:18][C:19]1[CH:24]=[CH:23][C:22]([N:25]=[C:26]=[S:27])=[CH:21][CH:20]=1.Br[CH2:29][CH:30]1[CH2:35][CH2:34][CH2:33][CH2:32][CH2:31]1>C1COCC1>[Cl:18][C:19]1[CH:24]=[CH:23][C:22]([N:25]=[C:26]([S:27][CH2:29][CH:30]2[CH2:35][CH2:34][CH2:33][CH2:32][CH2:31]2)[C:2]#[C:1][Si:3]([CH3:6])([CH3:5])[CH3:4])=[CH:21][CH:20]=1

Participants

6

Reactant 4

HCID 164804-Chlorophenyl isothiocyanateHCID 66111TrimethylsilylacetyleneHCID 137636Cyclohexane, (bromomethyl)-HCID 178418244HCID 178418244, compound

Product 1

HCID 58579810cyclohexylmethyl N-(4-chlorophenyl)-3-(trimethylsilyl)thiopropynimidateYield 11%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
0 °C

Procedure

Ethynyl trimethyl silane (0.89 g) was dissolved to dry THF (15 mL), n-butyl lithium/hexane solution (1.6 mol./L; 5 mL) was added thereto at −78° C., and then it was warmed to 0° C. The mixture was cooled to −78° C., THF (4 mL) solution of 4-chlorophenyl isothiocyanate (1.44 g) was added dropwise, and then the mixture was allowed to warm to 0° C. THF (5 mL) solution of bromomethylcyclohexane (1.52 g) was added thereto under ice-cooling, and then the mixture was stirred at 50° C. for 6 hours. The reaction solution was concentrated. The residue was subjected to silica gel column chromatography (hexane/ethyl acetate=20/1) to obtain cyclohexylmethyl N-(4-chlorophenyl)-3-(trimethylsilyl)thiopropynimidate (0.34 g).

Workup

  1. additionwas added
  2. temperatureThe mixture was cooled to −78° C.
  3. temperatureto warm to 0° C
  4. temperatureunder ice-cooling
  5. concentrationThe reaction solution was concentrated

Sources & evidence

ORD record
ord-b611bc1bf4b64b789d7a735962d2be4f
Source dataset
uspto-grants-2013_12
Patent number
US08618329B2

Reaction notes

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