Diethyl Ether → HCID 57931195, compound

HRID 551147Notes

Reaction equation

HRID 551147 reaction equation
[CH2:1]([S:4]([N:7]1[CH2:12][CH2:11][C:10](=O)[CH2:9][CH2:8]1)(=[O:6])=[O:5])[CH2:2][CH3:3].C[Si]([C:18]#[N:19])(C)C.C(OCC)C.[N:25]1([C:31]([O:33][C:34]([CH3:37])([CH3:36])[CH3:35])=[O:32])[CH2:30][CH2:29][NH:28][CH2:27][CH2:26]1>CO.[I-].[Zn+2].[I-]>[C:18]([C:10]1([N:28]2[CH2:29][CH2:30][N:25]([C:31]([O:33][C:34]([CH3:37])([CH3:36])[CH3:35])=[O:32])[CH2:26][CH2:27]2)[CH2:11][CH2:12][N:7]([S:4]([CH2:1][CH2:2][CH3:3])(=[O:6])=[O:5])[CH2:8][CH2:9]1)#[N:19]

Participants

7

Reactant 4

HCID 3283Diethyl EtherHCID 82115Trimethylsilyl cyanide2×HCID 143452tert-Butyl piperazine-1-carboxylateHCID 208851121-(Propane-1-sulfonyl)piperidin-4-one

Product 1

HCID 57931195HCID 57931195, compound

Reagents, catalysts & solvents 2

HCID 9883512zinc(II)iodideCatalyst2×HCID 887MethanolSolvent

Procedure

To a flask in an ice-bath was added 1-(propylsulfonyl)piperidin-4-one (5.0 g, 24.4 mmol), trimethylsilylcyanide (3.25 mL, 24.2 mmol) and diethyl ether (3 mL) followed by addition of zinc iodide (0.005 g). This gave a yellow suspension which turned to an orange solution after 20 min stirring at room temperature. To the solution was added a solution of tert-butyl piperazine-1-carboxylate (4.54 g, 24.4 mmol) in methanol (35 mL). The solution was then refluxed overnight. The reaction was cooled and more trimethylsilylcyanide (0.5 eq) and zinc iodide (0.005 g) were added. The reaction was heated at reflux overnight and no starting material remained by TLC. The reaction mixture was evaporated to dryness and the product crystallised from ethyl acetate/iso-hexane to give tert-butyl 4-[4-cyano-1-(propylsulfonyl)piperidin-4-yl]piperazine-1-carboxylate as an off-white crystalline solid. 1H NMR (360 MHz, CDCl3): δ 3.80 (d, J=13.5 Hz, 2 H); 3.48 (t, J=4.9 Hz, 4 H); 3.15-3.09 (m, 2 H); 2.93-2.89 (m, 2 H); 2.60 (t, J=4.9 Hz, 4 H); 2.22 (d, J=13.4 Hz, 2 H); 1.91-1.81 (m, 4 H); 1.47 (s, 9 H); 1.07 (t, J=7.4 Hz, 3 H).

Workup

  1. customThis gave a yellow suspension which
  2. temperatureThe solution was then refluxed overnight
  3. temperatureThe reaction was cooled
  4. temperatureThe reaction was heated
  5. temperatureat reflux overnight
  6. customThe reaction mixture was evaporated to dryness
  7. customthe product crystallised from ethyl acetate/iso-hexane

Sources & evidence

ORD record
ord-5d485eedaf6b4c699661540c674c78c4
Source dataset
uspto-grants-2011_05
Patent number
US07947714B2

Reaction notes

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