Glyoxylic Acid → HCID 86737262, compound

HRID 903468Notes

Reaction equation

HRID 903468 reaction equation
BrC1C=CC(C(=O)CC)=CC=1.C(O)(=O)C=O.[OH-].[Na+].[Br:19][C:20]1[CH:33]=[CH:32][C:23]([C:24](/[C:26](/[CH3:31])=[CH:27]\[C:28]([OH:30])=O)=[O:25])=[CH:22][CH:21]=1.[NH:34]1[CH2:41][CH2:40][CH2:39][C@H:35]1[C:36]([OH:38])=[O:37].C1N=CN(C(N2C=NC=C2)=O)C=1>O1CCCC1.O.C(O)C.O>[Br:19][C:20]1[CH:21]=[CH:22][C:23]([C:24](/[C:26](/[CH3:31])=[CH:27]\[C:28]([N:34]2[CH2:41][CH2:40][CH2:39][C@H:35]2[C:36]([OH:38])=[O:37])=[O:30])=[O:25])=[CH:32][CH:33]=1

Participants

10

Reactant 6

HCID 760Glyoxylic AcidHCID 14798Sodium HydroxideHCID 66312p-BromopropiophenoneHCID 682631,1'-CarbonyldiimidazoleHCID 145742L-ProlineHCID 23337592HCID 23337592, compound

Product 1

HCID 86737262HCID 86737262, compound

Reagents, catalysts & solvents 3

HCID 962WaterSolvent2×HCID 8028TetrahydrofuranSolventHCID 19096565Water ethanolSolvent

Procedure

To a slurry of 16.0 g. of p-bromopropiophenone and 8.0 g. of glyoxylic acid in 90 ml. of water is added (with cooling) a mixture of 20 g. of 50% sodium hydroxide in 280 ml. of ethanol-water (1:1). The mixture is allowed to stand at room temperature for 20 hours and then heated to the boiling point for 30 minutes. The mixture is diluted with 800 ml. of ice and water, stirred several minutes and filtered. The filtrate is acidified with 5 N HCl and filtered to give 12.5 g. of β-(4-bromobenzoyl)crotonic acid as tan crystals, m.p. 137°-144° C. The preceding compound (5.0 g.) is coupled with L-proline with N,N-carbonyldiimidazole in tetrahydrofuran to give 1-[β-(4-bromobenzoyl)crotonyl]-L-proline. A mixture of the preceding compound with thiolacetic acid in acetonitrile gives the product of the example as a glass.

Workup

  1. temperature(with cooling)
  2. additiona mixture of 20 g
  3. temperatureheated to the boiling point for 30 minutes
  4. additionThe mixture is diluted with 800 ml
  5. filtrationfiltered
  6. filtrationfiltered
  7. customto give 12.5 g

Sources & evidence

ORD record
ord-ad690439b2b1471ba8a77044a966c25d
Source dataset
uspto-grants-1980_10
Patent number
US04226775

Reaction notes

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