Dimethylformamide → (+)-4,5-dihydro-1-[[ethoxy(4-phenylbutyl)phosphinyl]acetyl]-3-phenyl-1H-pyrazole-5-carboxylic acid, 1-(2,2-dimethyl-1-oxopropoxy)-2-ethoxy-2-oxoethyl ester

HRID 1757936Notes

Reaction equation

HRID 1757936 reaction equation
[CH2:1]([O:3][P:4]([CH2:16][C:17]([N:19]1[CH:23]([C:24]([OH:26])=[O:25])[CH2:22][C:21]([C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)=[N:20]1)=[O:18])([CH2:6][CH2:7][CH2:8][CH2:9][C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)=[O:5])[CH3:2].CN(C)C=O.Cl[CH:39]([O:45][C:46](=[O:51])[C:47]([CH3:50])([CH3:49])[CH3:48])[C:40]([O:42][CH2:43][CH3:44])=[O:41].[F-].[K+]>C(OCC)(=O)C>[CH2:1]([O:3][P:4]([CH2:16][C:17]([N:19]1[CH:23]([C:24]([O:26][CH:39]([O:45][C:46](=[O:51])[C:47]([CH3:50])([CH3:49])[CH3:48])[C:40]([O:42][CH2:43][CH3:44])=[O:41])=[O:25])[CH2:22][C:21]([C:27]2[CH:28]=[CH:29][CH:30]=[CH:31][CH:32]=2)=[N:20]1)=[O:18])([CH2:6][CH2:7][CH2:8][CH2:9][C:10]1[CH:11]=[CH:12][CH:13]=[CH:14][CH:15]=1)=[O:5])[CH3:2]

Participants

6

Reactant 4

HCID 6228DimethylformamideHCID 522689Potassium FluorideHCID 13102397(+)-4,5-dihydro-1-[[ethoxy(4-phenylbutyl)phosphinyl]acetyl]-3-phenyl-1H-pyrazole-5-carboxylic acidHCID 13102402Ethyl 2-chloro-2-pivaloyloxyacetate2×

Product 1

HCID 57251309(+)-4,5-dihydro-1-[[ethoxy(4-phenylbutyl)phosphinyl]acetyl]-3-phenyl-1H-pyrazole-5-carboxylic acid, 1-(2,2-dimethyl-1-oxopropoxy)-2-ethoxy-2-oxoethyl ester

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

A solution of 2.0 g. of (+)-4,5-dihydro-1-[[ethoxy(4-phenylbutyl)phosphinyl]acetyl]-3-phenyl-1H-pyrazole-5-carboxylic acid, from Example 1(c), in 30 ml. of dry dimethylformamide under argon at room temperature is treated with 1.2 g. of ethyl 2-chloro-2-pivaloyloxyacetate, from part (a), and 0.58 g. of anhydrous potassium fluoride. After stirring for 48 hours the mixture is diluted with ethyl acetate and washed with water (3×). The organic fraction is dried (MgSO4) and concentrated in vacuo to give crude product. Flash chromatography on silica gel and elution with acetone/hexane (2:1) gives homogeneous (+)-4,5-dihydro-1-[[ethoxy(4-phenylbutyl)phosphinyl]acetyl]-3-phenyl-1H-pyrazole-5-carboxylic acid, 1-(2,2-dimethyl-1-oxopropoxy)-2-ethoxy-2-oxoethyl ester as an oil.

Workup

  1. washwashed with water (3×)
  2. dry with materialThe organic fraction is dried (MgSO4)
  3. concentrationconcentrated in vacuo
  4. customto give crude product
  5. washFlash chromatography on silica gel and elution with acetone/hexane (2:1)

Sources & evidence

ORD record
ord-085d73ef94f840608201750572a4ffdc
Source dataset
uspto-grants-1983_02
Patent number
US04371526

Reaction notes

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