Gamma-Valerolactone → HCID 86658323, compound

HRID 1890273Notes

Reaction equation

HRID 1890273 reaction equation
C[Al](C)C.[C:5](=[N:18][NH2:19])([C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1.[C:20]1(=[O:26])[O:25][CH:23]([CH3:24])[CH2:22][CH2:21]1.ClCCl.O>CCCCCCC.ClCCl>[C:6]1([C:5]([C:12]2[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=2)=[N:18][NH:19][C:20](=[O:26])[CH2:21][CH2:22][CH:23]([OH:25])[CH3:24])[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1

Participants

7

Reactant 4

HCID 7921Gamma-Valerolactone2×HCID 79304DiphenylmethylidenehydrazineHCID 16682925TrimethylaluminumHCID 21908982Water methylene chloride

Product 1

HCID 86658323HCID 86658323, compoundYield 76%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolvent2×HCID 8900HeptaneSolvent

Procedure

At room temperature, 6.0 ml (12.0 mmol) of a 2.0 M trimethylaluminium solution in heptane are added dropwise to a solution of 0.78 g (4.0 mmol) of benzophenone hydrazone in 10 ml of dichloromethane, and the mixture is stirred for 30 min. A solution of 0.40 g (4.0 mmol) of γ-valerolactone in 5 ml of dichloromethane is then added dropwise to the reaction mixture. The reaction mixture is stirred at reflux for 2 h. A further 0.12 g (1.20 mmol) of γ-valerolactone is added, and the reaction mixture is stirred at reflux for 1 h. After cooling, dichloromethane/water is added to the reaction mixture. The organic phase is separated off and the aqueous phase is extracted with dichloromethane. The combined organic phases are dried over Na2SO4 and freed from the solvent under reduced pressure. Purification by column chromatography on silica gel (cyclohexane/ethyl acetate) gives 0.9 g (76%) of the desired product; (log P(HCOOH): 2.25); 1H-NMR (ppm): δ (DMSO-d6)=1.01 (d, 1H), 1.10 (d, 2H), 1.45-1.72 (m, 2H), 2.16-2.26 (m, 1H), 2.75-2.86 (m, 1H), 3.51-3.57 (m, 0.3H), 3.65-3.71 (m, 0.7H), 4.43 (d, 0.3H), 4.52 (d, 0.7H), 7.25-7.62 (m, 10H), 8.99 (s, 1H); LC-MS: m/z=297 [M+H]+

Workup

  1. stirringThe reaction mixture is stirred
  2. temperatureat reflux for 2 h
  3. stirringthe reaction mixture is stirred
  4. temperatureat reflux for 1 h
  5. temperatureAfter cooling
  6. customThe organic phase is separated off
  7. extractionthe aqueous phase is extracted with dichloromethane
  8. dry with materialThe combined organic phases are dried over Na2SO4
  9. customPurification by column chromatography on silica gel (cyclohexane/ethyl acetate)

Sources & evidence

ORD record
ord-c26312da726d41498fd4924fd7ca7c89
Source dataset
uspto-grants-2013_08
Patent number
US08507472B2

Reaction notes

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