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Diethyl Oxalate → 1,4-Dihydro-1-phenyl-7-tosylamino-indeno[1,2-c]pyrazole-3-carboxylic acid, ethyl ester

HRID 21549
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HRID 21549 반응식
[S:1]([NH:11][C:12]1[CH:20]=[C:19]2[C:15]([CH2:16][CH2:17][C:18]2=O)=[CH:14][CH:13]=1)([C:4]1[CH:10]=[CH:9][C:7]([CH3:8])=[CH:6][CH:5]=1)(=[O:3])=[O:2].[C:22]([O:29][CH2:30][CH3:31])(=[O:28])[C:23](OCC)=O.[O-]CC.[Na+].[C:36]1([NH:42][NH2:43])[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=1>C(O)C.C(O)(=O)C>[C:36]1([N:42]2[C:18]3[C:19]4[C:15]([CH2:16][C:17]=3[C:23]([C:22]([O:29][CH2:30][CH3:31])=[O:28])=[N:43]2)=[CH:14][CH:13]=[C:12]([NH:11][S:1]([C:4]2[CH:10]=[CH:9][C:7]([CH3:8])=[CH:6][CH:5]=2)(=[O:3])=[O:2])[CH:20]=4)[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=1
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참가 물질

7

반응물 4

HCID 7268Diethyl OxalateHCID 7516PhenylhydrazineHCID 2723922Sodium ethoxideHCID 199326296-Tosylamino-indan-1-one

생성물 1

HCID 1317190211,4-Dihydro-1-phenyl-7-tosylamino-indeno[1,2-c]pyrazole-3-carboxylic acid, ethyl ester

시약·촉매·용매 2

HCID 176Acetic Acid
용매
HCID 702Ethanol용매

실험 절차

6-Tosylamino-indan-1-one, m.p. 202°-204° C., (4.2 g) is reacted with diethyl oxalate (20.5 g) in anhydrous ethanol (125 ml) containing sodium ethoxide (3.75 g) under stirring in inert atmosphere at room temperature for 2 hours. The reaction mixture is diluted with ice water and extracted with hexane. The aqueous phase is acidified to pH 3 with N HCl and extracted with ethyl acetate. The organic solution is washed with water until neutral and then is evaporated to dryness in vacuo to give crude 2-ethoxalyl-6-tosylamino-indan-1-one, which is reacted with phenylhydrazine (1.65 g) in acetic acid (60 ml) at 60° C. for 2 hours. The reaction mixture is diluted with ice water and the precipitate is filtered, washed with water, dissolved in CHCl3 and evaporated to dryness in vacuo. Purification over a SiO2 column using hexane/ethyl acetate 7/3 as eluent yields pure 1,4-dihydro-1-phenyl-7-tosylamino -indeno[1,2-c]pyrazole-3-carboxylic acid, ethyl ester (3.3 g), which is reacted with acetonitrile (12 ml) in anhydrous dioxane (50 ml) in the presence of 50% sodium hydride (1.1 g) under stirring at 60° C. for 4 hours. After cooling the reaction mixture is diluted with ice water and acidified to pH 4 with citric acid. The precipitate is extracted with ethyl acetate, washed with 5% NaHCO 3 aqueous solution and then with water. By concentration to a small volume in vacuo the product crystallizes. The precipitate is filtered and washed with ethyl acetate to yield pure 3-(1,4-dihydro-1-phenyl-7-tosylamino-indeno [1,2-c]pyrazol-3-yl)-3-oxo-propanenitrile (2.1 g), which is reacted with phenyl isocyanate (0.55 g) in dimethylformamide (15 ml) in the presence of triethylamine (0.65 ml) at room temperature for 30 minutes. The reaction mixture is diluted with ice water and acidified to pH 2 with 2N HCl.

후처리

  1. extractionextracted with hexane
  2. extractionextracted with ethyl acetate
  3. washThe organic solution is washed with water until neutral and
  4. customthen is evaporated to dryness in vacuo
  5. customto give crude 2-ethoxalyl-6-tosylamino-indan-1-one, which
  6. filtrationthe precipitate is filtered
  7. washwashed with water
  8. dissolutiondissolved in CHCl3
  9. customevaporated to dryness in vacuo
  10. customPurification over a SiO2 column

출처 및 근거

ORD 기록
ord-34394f7dffde4ba7a50a9c9ecdaa7e6c
출처 데이터셋
uspto-grants-1995_06
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US05424308

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