Phenylbutazone → 1,2-Diphenyl-4-butyl-4-pivalyloxymethyl-3,5-pyrazolidinedione

HRID 1076800

反応式

HRID 1076800 の反応式
C(=O)([O-])[O-].[K+].[K+].[CH3:7][CH2:8][CH2:9][CH2:10][CH:11]1[C:16](=[O:17])[N:15]([C:18]2[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=2)[N:14]([C:24]2[CH:25]=[CH:26][CH:27]=[CH:28][CH:29]=2)[C:12]1=[O:13].[C:30]([O:36][CH2:37]Cl)(=[O:35])[C:31]([CH3:34])([CH3:33])[CH3:32]>CC(C)=O>[C:24]1([N:14]2[C:12](=[O:13])[C:11]([CH2:10][CH2:9][CH2:8][CH3:7])([CH2:37][O:36][C:30](=[O:35])[C:31]([CH3:34])([CH3:33])[CH3:32])[C:16](=[O:17])[N:15]2[C:18]2[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=2)[CH:25]=[CH:26][CH:27]=[CH:28][CH:29]=1

参加物

5

反応物 3

HCID 4781PhenylbutazoneHCID 11430Potassium CarbonateHCID 87885Chloromethyl pivalate

生成物 1

HCID 203916791,2-Diphenyl-4-butyl-4-pivalyloxymethyl-3,5-pyrazolidinedione収率 5%

試薬・触媒・溶媒 1

HCID 180Acetone溶媒

実験手順

Potassium carbonate (2.26 g, 0.016 mole) was suspended in an acetone (125 ml) solution of phenylbutazone and the suspension was refluxed overnight. The next day pivalyloxymethyl chloride (4.99 g, 0.033 mole) was added to the resulting solution and the solution was refluxed overnight. The suspension was cooled and filtered; the residue (2.00 g, 83%) was potassium chloride. The filtrate was concentrated in vacuo and the residue was suspended in ether, then filtered. The residue was washed with ether until the washings did not contain any product by TLC. The residue from the ether suspension was the potassium salt of phenylbutazone (2.25 g, 20%). The ether was then concentrated in vacuo and the residue was absorbed on silica gel and chromatographed on neutral silica gel (CC-7, Mallinckrodt) using petroleum ether bp 30°-60° C -- ether (1:1) as the eluent to give two fractions. The first fraction (Rf 0.46, silica gel, heptane-ether, 1:1) was crystallized from heptane-petroleum ether bp 30°-60° C, 1:1 to give 0.63 g (mp 116°-117° C, 5% yield) of 1,2-diphenyl-4-butyl-4-pivalyloxymethyl-3,5-pyrazolidinedione. nmr (CDCl3) δ 4.40 ##EQU4##

後処理

  1. temperaturethe suspension was refluxed overnight
  2. temperaturethe solution was refluxed overnight
  3. temperatureThe suspension was cooled
  4. filtrationfiltered
  5. concentrationThe filtrate was concentrated in vacuo
  6. filtrationfiltered
  7. washThe residue was washed with ether until the washings
  8. concentrationThe ether was then concentrated in vacuo
  9. customthe residue was absorbed on silica gel
  10. customchromatographed on neutral silica gel (CC-7, Mallinckrodt)
  11. customether (1:1) as the eluent to give two fractions
  12. customThe first fraction (Rf 0.46, silica gel, heptane-ether, 1:1) was crystallized from heptane-petroleum ether bp 30°-60° C, 1:1

出典と根拠

ORDレコード
ord-c762fe7431954be1b7a2d1a0f3696c9c
出典データセット
uspto-grants-1976_05
特許番号
US03957803

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