Hydrochloric Acid → ethyl (2E)-2-[[4-[(5-methylsulfonyl-2-pyridinyl)oxy]-2-(oxan-4-yloxy)phenyl]hydrazinylidene]propanoate

HRID 1042108

반응식

HRID 1042108 반응식
[CH3:1][S:2]([C:5]1[CH:6]=[CH:7][C:8]([O:11][C:12]2[CH:18]=[CH:17][C:15]([NH2:16])=[C:14]([O:19][CH:20]3[CH2:25][CH2:24][O:23][CH2:22][CH2:21]3)[CH:13]=2)=[N:9][CH:10]=1)(=[O:4])=[O:3].Cl.[N:27]([O-])=O.[Na+].[CH3:31][CH:32](C(=O)C)[C:33]([O:35][CH2:36][CH3:37])=[O:34].[OH-].[K+]>O.CCCCCC.C(OCC)(=O)C.C(O)C.C(#N)C>[CH3:1][S:2]([C:5]1[CH:6]=[CH:7][C:8]([O:11][C:12]2[CH:18]=[CH:17][C:15]([NH:16]/[N:27]=[C:32](\[CH3:31])/[C:33]([O:35][CH2:36][CH3:37])=[O:34])=[C:14]([O:19][CH:20]3[CH2:25][CH2:24][O:23][CH2:22][CH2:21]3)[CH:13]=2)=[N:9][CH:10]=1)(=[O:3])=[O:4]

참가 물질

11

반응물 5

HCID 313Hydrochloric Acid2회HCID 701Ethyl 2-methylacetoacetateHCID 14797Potassium HydroxideHCID 23668193Sodium NitriteHCID 667259784-{[5-(Methylsulfonyl)pyridin-2-yl]oxy}-2-(tetrahydro-2H-pyran-4-yloxy)aniline

생성물 1

HCID 87126424ethyl (2E)-2-[[4-[(5-methylsulfonyl-2-pyridinyl)oxy]-2-(oxan-4-yloxy)phenyl]hydrazinylidene]propanoate수율 77%

시약·촉매·용매 5

HCID 702Ethanol용매2회HCID 962Water용매2회HCID 6342Acetonitrile용매HCID 8058Hexane용매HCID 8857Ethyl Acetate용매

실험 절차

4-{[5-(Methylsulfonyl)pyridin-2-yl]oxy}-2-(tetrahydro-2H-pyran-4-yloxy)aniline (25.7 g) was suspended in a mixed solvent of acetonitrile (50 mL)-ethanol (100 mL), and concentrated hydrochloric acid (21 mL) was added at 10° C. To a mixture was added dropwise sodium nitrite (5.8 g) dissolved in water (15 mL) at −5° C., and the mixture was stirred at −10° C. to −5° C. for 1 hr. The mixture was added to a mixture of ethyl 2-methyl-3-oxobutanoate (11.2 mL), potassium hydroxide (85%, 8.6 g), water (70 mL), and ethanol (100 mL) at −40 to −30° C. and the mixture was stirred at −28° C. for 30 min. To the reaction solution was added 1M hydrochloric acid (110 mL), and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over magnesium sulfate, filtered and concentrated under reduced pressure. The obtained crude product was subjected to silica gel column chromatography (ethyl acetate:hexane=30:70 to 100:0, volume ratio) to give the title compound (25.8 g, yield 77%) as a yellow amorphous solid.

후처리

  1. additionwas added at 10° C
  2. stirringthe mixture was stirred at −28° C. for 30 min
  3. extractionthe mixture was extracted with ethyl acetate
  4. washThe organic layer was washed with saturated brine
  5. dry with materialdried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. customThe obtained crude product

출처 및 근거

ORD 기록
ord-5f5d79a34cf740438b7d5267cece2c80
출처 데이터셋
uspto-grants-2013_10
특허 번호
US08557805B2

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