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Hydrochloric Acid → 2-(2,6-Dichloro-3-methoxycarbonyl benzoyl) acetoacetic tert-butyl ester

HRID 617438
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HRID 617438 반응식
CC[O-].CC[O-].[Mg+2].[C:8]([O:12][C:13](=[O:18])[CH2:14][C:15]([CH3:17])=[O:16])([CH3:11])([CH3:10])[CH3:9].[Cl:19][C:20]1[C:28]([C:29]([O:31][CH3:32])=[O:30])=[CH:27][CH:26]=[C:25]([Cl:33])[C:21]=1[C:22](Cl)=[O:23].Cl>C1(C)C=CC=CC=1>[C:8]([O:12][C:13](=[O:18])[CH:14]([C:22](=[O:23])[C:21]1[C:25]([Cl:33])=[CH:26][CH:27]=[C:28]([C:29]([O:31][CH3:32])=[O:30])[C:20]=1[Cl:19])[C:15]([CH3:17])=[O:16])([CH3:11])([CH3:9])[CH3:10]
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참가 물질

6

반응물 4

HCID 313Hydrochloric AcidHCID 15538Tert-butyl acetoacetateHCID 164963Magnesium ethanolateHCID 18517406Methyl 3-chlorocarbonyl-2,4-dichlorobenzoate

생성물 1

HCID 539166082-(2,6-Dichloro-3-methoxycarbonyl benzoyl) acetoacetic tert-butyl ester수율 50%

시약·촉매·용매 1

HCID 1140
Toluene
용매

실험 절차

A suspension of 1.65 g of magnesium ethylate in 30 ml of toluene was kept at 60-70° C. and 2.28 g of acetoacetic tert-butyl ester was added dropwise thereto. After the dropwise addition was completed, the resultant mixture was refluxed for two hours. Then, the reaction solution was cooled to room temperature and 3.85 g of 2,6-dichloro-3-methoxycarbonyl benzoic acid chloride was added dropwise thereto. The reaction mixture was stirred at room temperature for two hours and at 50-100° C. for three hours, then cooled to room temperature, treated with dilute hydrochloric acid, and extracted from ethyl acetate. Then, the organic layer was alkali extracted from an aqueous 5% sodium carbonate solution. The water layer was mixed with chloroform, educed with dilute hydrochloric acid, and extracted again. The organic layer was washed with saturated saline solution and dried over magnesium sulfate. The solution was distilled under a reduced pressure to expel the solvent and obtain 2.80 g of 2-(2,6-dichloro-3-methoxycarbonyl benzoyl) acetoacetic tert-butyl ester. A solution of this ester in 45 ml of toluene and 0.2 g of p-toluene sulfonic acid hydrate added thereto were refluxed together for six hours. The reaction solution was cooled, mixed with 200 ml of ethyl acetate, washed twice with 200 ml of water, further washed with saturated saline solution, and dried over magnesium sulfate. The solution was distilled under a reduced pressure to expel the solvent and obtain 2.10 g of 2,6-dichloro-3-methoxycarbonyl benzoyl acetone. nD22 1.5759.

후처리

  1. customwas kept at 60-70° C.
  2. additionAfter the dropwise addition
  3. temperaturecooled to room temperature
  4. extractionextracted from ethyl acetate
  5. extractionThen, the organic layer was alkali extracted from an aqueous 5% sodium carbonate solution
  6. additionThe water layer was mixed with chloroform
  7. extractionextracted again
  8. washThe organic layer was washed with saturated saline solution
  9. dry with materialdried over magnesium sulfate
  10. distillationThe solution was distilled under a reduced pressure

출처 및 근거

ORD 기록
ord-3be424ee68d544e1b2cc5e4abddf27b3
출처 데이터셋
uspto-grants-1999_09
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US05948917

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