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Triethylamine → 4-Trifluoromethyl-3-methylthio-2-hydroxybenzoic acid ethyl ester

HRID 59591
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HRID 59591 반응식
[CH3:1][S:2][CH2:3][C:4](=[O:11])[CH2:5][C:6]([O:8][CH2:9][CH3:10])=[O:7].C(N(CC)CC)C.C(O[CH:22]=[CH:23][C:24](=O)[C:25]([F:28])([F:27])[F:26])C.[OH-].[Na+]>C1(C)C=CC=CC=1>[CH2:9]([O:8][C:6](=[O:7])[C:5]1[CH:22]=[CH:23][C:24]([C:25]([F:28])([F:27])[F:26])=[C:3]([S:2][CH3:1])[C:4]=1[OH:11])[CH3:10]
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참가 물질

6

반응물 4

HCID 8471TriethylamineHCID 14798Sodium HydroxideHCID 27803954-Ethoxy-1,1,1-trifluoro-3-buten-2-oneHCID 122340394-Methylsulfanyl-3-oxo-butyric acid ethyl ester

생성물 1

HCID 1184961194-Trifluoromethyl-3-methylthio-2-hydroxybenzoic acid ethyl ester

시약·촉매·용매 1

HCID 1140
Toluene
용매

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온도
0 °C

실험 절차

100 g of ethyl 4-(methylsulphanyl)-3-oxobutanoate and 27.8 g of triethylamine were initially charged in 260 ml of toluene and cooled to 0° C. under nitrogen. Then 102.8 g of 4-ethoxy-1,1,1-trifluorobut-3-en-2-one were added dropwise at 0-7° C. within 30 minutes and the mixture was stirred for a further 5 h. After 16 hours, the reaction was warmed up to 18° C. The reaction mixture was concentrated, admixed with 150 ml of acetonitrile and concentrated at 5 mbar. The crude product was admixed with 2 equivalents of 10% sodium hydroxide solution while stirring and cooling with ice-water and stirred for 1 h, and the solids were filtered off with suction, washed three times with 50 ml of 3.5% sodium hydroxide solution and dried by suction. The solids were then admixed with 150 ml of water and 150 ml of toluene, and adjusted to pH 1 with about 150 ml of 10% HCl, and further HCl was metered in with continued stirring until the pH remains below 3. Then the filtered phases were separated and the water phase was extracted once more with toluene. The combined toluene phases were dried and concentrated: Yield 122.3 g (78% of theory). 1H NMR (CDCl3, 400 MHz): δ=11.77 ppm (1H, s), 7.93 ppm (1H, d), 7.23 ppm (1H, d), 4.47 ppm (2H, q), 2.44 ppm (3H, s), 1.45 ppm (3H, t).

후처리

  1. waitAfter 16 hours
  2. temperaturethe reaction was warmed up to 18° C
  3. concentrationThe reaction mixture was concentrated
  4. concentrationconcentrated at 5 mbar
  5. stirringwhile stirring
  6. stirringstirred for 1 h
  7. filtrationthe solids were filtered off with suction
  8. washwashed three times with 50 ml of 3.5% sodium hydroxide solution
  9. customdried by suction
  10. stirringwith continued stirring until the pH
  11. customThen the filtered phases were separated
  12. extractionthe water phase was extracted once more with toluene
  13. dry with materialThe combined toluene phases were dried
  14. concentrationconcentrated

출처 및 근거

ORD 기록
ord-9eb04f0b69d341b9bd82cfb75118fe2e
출처 데이터셋
uspto-grants-2016_09
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US09440917B2

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