Piperidine → pyrrolidinyl-N-tert-butylcarbamate

HRID 366307Notes

Reaction equation

HRID 366307 reaction equation
[C:1]([NH:5][C:6](=[O:8])[O-:7])([CH3:4])([CH3:3])[CH3:2].C[Si](C)(C)[CH:11]1[CH2:16][CH2:15][CH2:14][CH2:13][NH:12]1.C[Si](C)(C)C1CCCN1.CC1C=C(C2CCCCN2)C=CC=1.CC1C=C(C2CCCN2)C=CC=1.N1CCCCC1.N1CCCC1.[H-].[Na+].C(OC(OC(OC(C)(C)C)=O)=O)(C)(C)C.C(=O)(O)[O-].[Na+]>O1CCCC1>[N:12]1([N:5]([C:1]([CH3:4])([CH3:3])[CH3:2])[C:6](=[O:7])[O-:8])[CH2:13][CH2:14][CH2:15][CH2:16][CH2:11]1.[N:12]1([N:5]([C:1]([CH3:4])([CH3:3])[CH3:2])[C:6](=[O:7])[O-:8])[CH2:13][CH2:14][CH2:15][CH2:16]1

Participants

13

Reactant 10

HCID 8082PiperidineHCID 24758Sodium hydrideHCID 31268PyrrolidineHCID 90495Di-tert-butyl dicarbonateHCID 516892Sodium BicarbonateHCID 35440982-(3-Methylphenyl)pyrrolidineHCID 44294402-(3-Methylphenyl)piperidineHCID 177527332-TrimethylsilylpyrollidineHCID 21252905Tert-butylcarbamateHCID 232891542-Trimethylsilylpiperidine

Product 2

HCID 131722116piperidinyl-N-tert-butylcarbamateYield 89%HCID 131722117pyrrolidinyl-N-tert-butylcarbamateYield 95%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
5 °C

Procedure

It is necessary to use a protecting group to prepare certain amines. A suitable protecting group is tert-butylcarbamate ("BOC") which was used to prepare 2-trimethylsilylpiperidine, 2-trimethylsilylpyrollidine, 2-(3-methylphenyl)piperidine, and a 2-(3-methylphenyl)pyrrolidine. The BOC group was attached by generating the anion from either piperidine or pyrrolidine using sodium hydride in tetrahydrofuran. This solution was cooled to 5° C. and a slight excess of di-tert-butyldicarbonate added. After two hours, the solution was poured into saturated sodium bicarbonate and the layers separated. The organic layer was dried over magnesium sulfate and the solvent removed by rotary evaporation. Distillation at reduced pressure provided either piperidinyl-N-tert-butylcarbamate (bp 95° C., 3 mm Hg, 89% yield) or pyrrolidinyl-N-tert-butylcarbamate (bp 69° C., 1 mm Hg, 95% yield).

Workup

  1. customthe layers separated
  2. dry with materialThe organic layer was dried over magnesium sulfate
  3. customthe solvent removed by rotary evaporation
  4. distillationDistillation at reduced pressure

Sources & evidence

ORD record
ord-5c825c7c9bfe4311b39db5b57b4e7279
Source dataset
uspto-grants-2000_10
Patent number
US06130180

Reaction notes

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