Gamma-Butyrolactone → HCID 13193886, compound

HRID 1649261Notes

Reaction equation

HRID 1649261 reaction equation
C(N)C=C.[CH3:5][O:6][C:7]1[C:12]([O:13][CH3:14])=[CH:11][CH:10]=[CH:9][C:8]=1[C:15]1[CH2:16][CH2:17][N:18]([CH3:21])[CH2:19][CH:20]=1.C([Li])CCC.[C:27]1(=[O:32])[O:31][CH2:30][CH2:29][CH2:28]1>O1CCCC1>[CH3:5][O:6][C:7]1[C:12]([O:13][CH3:14])=[CH:11][CH:10]=[CH:9][C:8]=1[C:15]1([C:30](=[O:31])[CH2:29][CH2:28][CH2:27][OH:32])[CH:16]=[CH:17][N:18]([CH3:21])[CH2:19][CH2:20]1

Participants

6

Reactant 4

HCID 7302Gamma-ButyrolactoneHCID 7853AllylamineHCID 11195657Pyridine, 4-(2,3-dimethoxyphenyl)-1,2,3,6-tetrahydro-1-methyl-HCID 178418339Butyllithium

Product 1

HCID 13193886HCID 13193886, compoundYield 98.8%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of 9.32 g (0.04 mol) of the allylamine, Compound IV, in 75 mL of dry tetrahydrofuran was cooled to -10° and treated with 40 mL of 1.65 M solution (0.066 mol) of n-butyl lithium. The resulting red solution was stirred at -10° for 15 min and transferred under nitrogen to a solution of 18.4 g (0.21 mol) of γ-butyrolactone in 40 mL of dry tetrahydrofuran at -76° over a period of 5 min. After the addition was complete the reaction mixture was stirred at -70° for 15 min and then quenched with 100 mL of 20% sodium hydroxide solution and stirred at room temperature for 1 hour. At the end of this period the reaction mixture was diluted with 200 mL of dichloromethane and the organic layer was separated. The aqueous layer was extracted with an additional 200 mL portion of dichloromethane. The organic layers were washed with brine, dried (K2CO3) and concentrated under reduced pressure to afford 12.6 g of product (98.8% yield) which contained Compound V and was used for the next step without further purification. A sample prepared in another experiment was purified by HPLC to afford a pure sample of Compound V; NMR (90 MHz, CDCl3): 2.63 (s, 3), 3.45 (br., 3), 3.73 (s, 3), 3.88 (s, 3), 4.3 (d, j=8 Hz, 1), 6.15 (d, J=8 Hz, 1), 6.7-7.2 (br., 3); IR (film): 3440, 2940, 1700, 1630 cm-1.

Workup

  1. additionAfter the addition
  2. stirringwas stirred at -70° for 15 min
  3. customquenched with 100 mL of 20% sodium hydroxide solution
  4. stirringstirred at room temperature for 1 hour
  5. additionAt the end of this period the reaction mixture was diluted with 200 mL of dichloromethane
  6. customthe organic layer was separated
  7. extractionThe aqueous layer was extracted with an additional 200 mL portion of dichloromethane
  8. washThe organic layers were washed with brine
  9. dry with materialdried (K2CO3)
  10. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-884cbf0223d64edc90decad588959f03
Source dataset
uspto-grants-1983_11
Patent number
US04415736

Reaction notes

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