Sodium Bicarbonate → Ethyl 1-[(1,1-dimethylethoxy)carbonyl]-3,6-dihydro-4(2H)-pyridineacetate

HRID 1374141Notes

Reaction equation

HRID 1374141 reaction equation
[CH2:1]([O:3][C:4](=[O:19])[CH:5]=[C:6]1[CH2:11][CH2:10][N:9]([C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13])[CH2:8][CH2:7]1)[CH3:2].C(OC(N1CCC(=O)CC1)=O)(C)(C)C.C([N-]C(C)C)(C)C.[Li+].C(=O)([O-])O.[Na+]>O1CCCC1.C(O)(=O)C>[CH2:1]([O:3][C:4](=[O:19])[CH2:5][C:6]1[CH2:11][CH2:10][N:9]([C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13])[CH2:8][CH:7]=1)[CH3:2]

Participants

7

Reactant 4

HCID 516892Sodium BicarbonateHCID 735900tert-Butyl 4-oxopiperidine-1-carboxylateHCID 2724682Lithium diisopropylamideHCID 10333298tert-Butyl 4-(2-ethoxy-2-oxoethylidene)piperidine-1-carboxylate

Product 1

HCID 9970303Ethyl 1-[(1,1-dimethylethoxy)carbonyl]-3,6-dihydro-4(2H)-pyridineacetateYield 109.7%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of 300 mg of (1-tert-butoxycarbonylpiperidin-4-ylidene)acetic acid ethyl ester (which had been prepared by Horner-Wittig reaction of commercially available 1-tert-butoxycarbonyl-4-piperidone and triethyl phosphonoacetate by the method known per se) in 30 ml of tetrahydrofuran was cooled to −78° C., to which 1.3 ml of a tetrahydrofuran solution (1.5 M) of lithium diisopropylamide was added and stirred for 15 minutes. Thereafter 150 μl of acetic acid was added, and the system was warmed up to room temperature, over an hour. The reaction liquid, to which saturated aqueous sodium hydrogencarbonate solution was added, was extracted with chloroform. The chloroform layer was dried over sodium sulfate and the solvent was distilled off therefrom to provide 329 mg of (1-tert-butoxycarbonyl-1,2,5,6-tetrahydropyridin-4-yl)acetic acid ethyl ester. This ester was dissolved in 10 ml of tetrahydrofuran, cooled to 0° C., and to which 80 mg of lithium aluminium hydride was added. The reaction liquid was stirred for 15 minutes and to which an excessive amount of sodium sulfate decahydrate was added, followed by 2 hours' stirring at room temperature. The insoluble matter was filtered off, and the filtrate was concentrated to provide 228 mg of 2-(1-tert-butoxycarbonyl-1,2,5,6-tetrahydropyridin-4-yl)ethanol.

Workup

  1. additionwas added
  2. customThe reaction liquid
  3. extractionwas extracted with chloroform
  4. dry with materialThe chloroform layer was dried over sodium sulfate
  5. distillationthe solvent was distilled off

Sources & evidence

ORD record
ord-6d24847997434ff7b2a6c9fec2ea3863
Source dataset
uspto-grants-2007_01
Patent number
US07164024B2

Reaction notes

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