Hydrochloric Acid → HCID 10331340, compound

HRID 1646925Notes

Reaction equation

HRID 1646925 reaction equation
CC1(C)CCCC(C)(C)N1.C([Li])CCC.[Cl:16][C:17]1[CH:22]=[N:21][CH:20]=[CH:19][N:18]=1.[CH3:23][N:24]1[CH2:29][CH2:28][CH2:27][C:26](=[O:30])[CH2:25]1.Cl>C1COCC1.CCCCCC.CCOCC.C(O)C>[Cl:16][C:17]1[C:22]([C:26]2([OH:30])[CH2:27][CH2:28][CH2:29][N:24]([CH3:23])[CH2:25]2)=[N:21][CH:20]=[CH:19][N:18]=1

Participants

10

Reactant 5

HCID 313Hydrochloric AcidHCID 130352,2,6,6-TetramethylpiperidineHCID 73277ChloropyrazineHCID 796563-Piperidinone, 1-methyl-HCID 178418339Butyllithium

Product 1

HCID 10331340HCID 10331340, compoundYield 53.4%

Reagents, catalysts & solvents 4

HCID 702EthanolSolventHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent3×HCID 8058HexaneSolvent

Conditions

Temperature
-77 °C

Procedure

A solution of 7.2 ml 2,2,6,6-tetramethylpiperidine (0.034 mol) in 300 ml of dry THF was cooled to -8° C. as 25 ml of 1.6 M butyllithium (0.04 mol) in hexane was added dropwise. The reaction was stirred 20 min then cooled to -77° C. A solution of 2.9 ml of 2-chloropyrazine (0.031 mol) in 5 ml of THF was added dropwise to the reaction. After another 15 min, 3.5 g of 1-methylpiperidin-3-one (0.035 mol) in 10 ml of THF was added dropwise. After the addition, the reaction was stirred 1.5 h followed by addition of a mixture of 8 ml of concentrated HCl and 4 ml of ethanol. The cooling was removed and when the temperature had reached -15° C., 20 ml of 5 N NaOH was added. The volatile organics were evaporated and the aqueous residue was extracted 4 × with 30 ml of CH2Cl2. The extracts were washed with brine, dried and the solvent evaporated to give a brown solid that was dissolved in 300 ml of ether and filtered. The ether was evaporated and the residue recrystallized from hexane to give 3.77 g of (1), 53% yield, mp 111°-112° C. NMR ppm (CDCl3) 1.7-2.2 (5H,m), 2.4 (3H, s), 2.7 (1H, d), 2.85-3.05 (2H, m), 4.4 (1H, bs), 8.35 (1H, d), 8.5 (1H, d). Anal. C10H14ClN3O, requires C: 52.75; H: 6.20; N: 18.46%. Found C: 52.64; H: 6.21; N: 18.21%.

Workup

  1. additionwas added dropwise
  2. waitAfter another 15 min
  3. additionAfter the addition
  4. stirringthe reaction was stirred 1.5 h
  5. customThe cooling was removed
  6. customhad reached -15° C.
  7. addition20 ml of 5 N NaOH was added
  8. customThe volatile organics were evaporated
  9. extractionthe aqueous residue was extracted 4 × with 30 ml of CH2Cl2
  10. washThe extracts were washed with brine
  11. customdried
  12. customthe solvent evaporated
  13. customto give a brown solid that
  14. filtrationfiltered
  15. customThe ether was evaporated
  16. customthe residue recrystallized from hexane

Sources & evidence

ORD record
ord-b683ee1a6c85459d9625a924db28ac8b
Source dataset
uspto-grants-1993_01
Patent number
US05182283

Reaction notes

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