Hydrochloric Acid → HCID 178472337, compound

HRID 452533Notes

Reaction equation

HRID 452533 reaction equation
[CH2:1]([O:3][C:4]([C@H:6]1[CH2:11][CH2:10][C@H:9]([C:12]2[CH:17]=[C:16](N)[CH:15]=[CH:14][N:13]=2)[CH2:8][CH2:7]1)=[O:5])[CH3:2].[ClH:19].N([O-])=O.[Na+].[OH-].[Na+]>[Cu]Cl>[CH2:1]([O:3][C:4]([C@H:6]1[CH2:11][CH2:10][C@H:9]([C:12]2[CH:17]=[C:16]([Cl:19])[CH:15]=[CH:14][N:13]=2)[CH2:8][CH2:7]1)=[O:5])[CH3:2]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 14798Sodium HydroxideHCID 23668193Sodium NitriteHCID 178472349HCID 178472349, compound

Product 1

HCID 178472337HCID 178472337, compoundYield 27%

Reagents, catalysts & solvents 1

HCID 62652Cuprous chlorideCatalyst

Procedure

To a solution of cis/trans-4-(4-amino-pyridin-2-yl)-cyclohexanecarboxylic acid ethyl ester (1:9) (0.638 g, 2.57 mmol) in concentrated hydrochloric acid (11.0 ml, 128 mmol) was added in small portions sodium nitrite (4.43 g, 64.2 mmol) at 0-5° C. The reaction mixture was allowed to warm to room temperature. Copper (I) chloride (10.7 g, 108 mmol) was added in one portion. Stirring for 2 h was followed by quenching with 32% sodium hydroxide solution (9.52 ml, 103 mmol) at 0-5° C. The reaction mixture was partitioned between dichloromethane (50 ml) and water (20 ml). The layers were separated. The aqueous layer was extracted with two 100 ml-portions of dichloromethane. The combined organic layers were washed with one 25 ml-portion of water, dried over anhydrous sodium sulfate and concentrated in vacuo. Flash-chromatography with n-heptane/ethyl acetate as eluent gave the title compound (0.186 g, 27%) as colorless oil.

Workup

  1. customThe reaction mixture was partitioned between dichloromethane (50 ml) and water (20 ml)
  2. customThe layers were separated
  3. extractionThe aqueous layer was extracted with two 100 ml-portions of dichloromethane
  4. washThe combined organic layers were washed with one 25 ml-portion of water
  5. dry with materialdried over anhydrous sodium sulfate
  6. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-e0ae256f993e45c3b06e3bc18cd8c545
Source dataset
uspto-grants-2013_07
Patent number
US08492376B2

Reaction notes

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