Sulfuric Acid → HCID 89141974, compound

HRID 2202342Notes

Reaction equation

HRID 2202342 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][C:11](=[O:14])[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].Br[CH2:16][C:17]([CH3:19])=[CH2:18].[Cl-].[NH4+].OS(O)(=O)=O>O.[Zn].CCCCCCC.CCOC(C)=O.C1COCC1>[OH:14][C:11]1([CH2:18][C:17]([CH3:19])=[CH2:16])[CH2:10][CH2:9][N:8]([C:6]([O:5][C:1]([CH3:4])([CH3:2])[CH3:3])=[O:7])[CH2:13][CH2:12]1

Participants

9

Reactant 4

HCID 1118Sulfuric AcidHCID 25517Ammonium ChlorideHCID 3577853-Bromo-2-methyl-1-propeneHCID 735900tert-Butyl 4-oxopiperidine-1-carboxylate

Product 1

HCID 89141974HCID 89141974, compoundYield 96.2%

Reagents, catalysts & solvents 4

HCID 23994ZincCatalystHCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 21899848Ethylacetate heptaneSolvent

Conditions

Temperature
10 °C

Procedure

t-butyl-4-oxopiperidine-1-carboxylate (10 g, 0.05 mol) was dissolved in 3-bromo-2-methylprop-1-ene (16.9 g, 0.126 mol), THF (100 mL) and saturated ammonium chloride solution (500 mL). The reaction was cooled to 10° C. and zinc dust (6.6 g, 0.01 mol) was added portionwise. After addition, the reaction mixture was stirred overnight, when TLC (heptane/EtOAc 7:1) indicated that the reaction was complete. The reaction mixture was then diluted with water and acidified with 10% H2SO4 to pH 6. The reaction mixture was extracted with ethyl acetate (3×50 mL). The organic layers were combined and washed with saturated solution of NaHCO3, brine and evaporated to give tert-butyl 4-hydroxy-4-(2-methylallyl)piperidine-1-carboxylate (12.28 g). 1H NMR (CHLOROFORM-d) δ: 4.94-5.04 (m, 1H), 4.80 (s, 1H), 3.85 (dt, J=13.0, 3.4 Hz, 2H), 3.08-3.26 (m, 2H), 2.21 (s, 2H), 1.86 (s, 3H), 1.52-1.60 (m, 4H), 1.43-1.50 (m, 9H).

Workup

  1. additionAfter addition
  2. extractionThe reaction mixture was extracted with ethyl acetate (3×50 mL)
  3. washwashed with saturated solution of NaHCO3, brine
  4. customevaporated

Sources & evidence

ORD record
ord-a84972e991a846599385dd15f294bd7b
Source dataset
uspto-grants-2016_06
Patent number
US09365545B2

Reaction notes

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