Ammonium Hydroxide → HCID 58495624, compound

HRID 1190955Notes

Reaction equation

HRID 1190955 reaction equation
Cl[C:2]1[CH:7]=[CH:6][C:5]([CH2:8][S:9][CH:10]2[CH2:14][CH2:13][CH2:12][CH2:11]2)=[CH:4][N:3]=1.[Cu][C:16]#[N:17].[NH4+].[OH-].CCCCCC.CCOC(C)=O>CN(C=O)C>[CH:10]1([S:9][CH2:8][C:5]2[CH:6]=[CH:7][C:2]([C:16]#[N:17])=[N:3][CH:4]=2)[CH2:14][CH2:13][CH2:12][CH2:11]1

Participants

6

Reactant 4

HCID 14923Ammonium HydroxideHCID 21226206Ethyl acetate hexaneHCID 58495683HCID 58495683, compoundHCID 178418546HCID 178418546, compound3×

Product 1

HCID 58495624HCID 58495624, compoundYield 208.2%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent3×

Procedure

Set up reaction in 3 separate flasks. To flask number 1 slurry 2-chloro-5-cyclopentylthiomethyl-pyridine (1 g, 4.4 mmol) and copper(I) cyanide (0.78 g, 8.7 mmol) in DMF (5 mL). To flask number 2 slurry 2-chloro-5-cyclopentylthiolmethyl-pyridine (1 g, 4.4 mmol) and copper(I) cyanide (0.78 g, 8.7 mmol) in DMF (5 mL). To flask number 3 slurry 2-chloro-5-cyclopentyl-thiomethyl-pyridine (2 g, 8.8 mmol) and copper(I) cyanide (1.6 g, 17.6 mmol) in DMF (10 mL). Stir each reaction in a sealed flask at 170° C. for 16 h. Follow the reactions by GC/MS. Cool all reaction flasks to room temperature. Combine the flask contents and pour into a solution of NH4OH (120 mL) and hexane/EtOAc (1:1, 100 mL). Collect the organic phase and extract the aqueous phase twice with hexane/EtOAc (1:1, 100 mL). Concentrate in vacuo the combined organic extracts. Purify by chromatography on silica gel (90 g) eluting with hexane/EtOAc (49:1 to 4:1 gradient) to obtain the desired intermediate (2 g, 40%) that contains approximately 10% starting material. Use the material in the next step without additional purification. MS (APCI+) m/z: 218 (M)+.

Workup

  1. customreaction in 3
  2. customseparate flasks
  3. customeach reaction in a sealed flask at 170° C. for 16 h
  4. customCollect the organic phase
  5. extractionextract the aqueous phase twice with hexane/EtOAc (1:1, 100 mL)
  6. concentrationConcentrate in vacuo the combined organic extracts
  7. customPurify by chromatography on silica gel (90 g)
  8. washeluting with hexane/EtOAc (49:1 to 4:1 gradient)

Sources & evidence

ORD record
ord-9eb26d16fe1440388e60cf9efee31129
Source dataset
uspto-grants-2014_03
Patent number
US08680091B2

Reaction notes

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