Tert-Butyl nitrite → HCID 59542569, compound

HRID 1809093Notes

Reaction equation

HRID 1809093 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][CH2:11][CH:10]([C:14]2[S:15][C:16](N)=[C:17]([C:19]([O:21]CC)=[O:20])[CH:18]=2)[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].N(OC(C)(C)C)=O.[Cl-].[NH4+]>[Cu](Cl)Cl>[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][CH2:11][CH:10]([C:14]2[S:15][CH:16]=[C:17]([C:19]([OH:21])=[O:20])[CH:18]=2)[CH2:9]1)=[O:7])([CH3:4])([CH3:2])[CH3:3]

Participants

5

Reactant 3

HCID 10906Tert-Butyl nitriteHCID 25517Ammonium ChlorideHCID 59542607HCID 59542607, compound

Product 1

HCID 59542569HCID 59542569, compoundYield 84.6%

Reagents, catalysts & solvents 1

HCID 24014Cupric ChlorideCatalyst

Procedure

3-(5-Amino-4-ethoxycarbonyl-thiophen-2-yl)-piperidine-1-carboxylic acid tert-butyl ester (1.45 g, 4.1 mmol) was added to a suspension of t-butyl nitrite (6.1 mmol) and copper (II) chloride (4.1 mmol) in IMS (100 mL). The reaction was stirred for 30 minutes. Saturated aqueous ammonium chloride (7 mL) was added and the mixture stirred overnight. The solvent was removed under vacuum and product partitioned between ethyl acetate and water. The organic layer was dried over magnesium sulphate, filtered and the solvent removed. The residue was purified by column chromatography on silica, eluting with 0%-40% ethyl acetate in cyclohexane. The fractions containing the desired product were concentrated under vacuum to give the title compound as a pale yellow oil (1.08 g). LCMS m/z 362.20 [M+Na]+ RT=4.30 min (Analytical Method 4).

Workup

  1. stirringthe mixture stirred overnight
  2. customThe solvent was removed under vacuum and product
  3. custompartitioned between ethyl acetate and water
  4. dry with materialThe organic layer was dried over magnesium sulphate
  5. filtrationfiltered
  6. customthe solvent removed
  7. customThe residue was purified by column chromatography on silica
  8. washeluting with 0%-40% ethyl acetate in cyclohexane
  9. additionThe fractions containing the desired product
  10. concentrationwere concentrated under vacuum

Sources & evidence

ORD record
ord-a2830691fc45464994635098a2b0e7bd
Source dataset
uspto-grants-2013_01
Patent number
US08362008B2

Reaction notes

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