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Isobutyric Acid → Ethyl 2-(4-isopropoxy-3-nitrophenyl)-4-methyl-5-thiazolecarboxylate

HRID 1051293
ノート
印刷プレビュー

反応式

HRID 1051293 の反応式
C(=O)([O-])O.[K+].Br[C:7]1[CH:12]=[CH:11][C:10]([O:13][CH:14]([CH3:16])[CH3:15])=[C:9]([N+:17]([O-:19])=[O:18])[CH:8]=1.[CH3:20][C:21]1[N:22]=[CH:23][S:24][C:25]=1[C:26]([O:28][CH2:29][CH3:30])=[O:27].C(O)(=O)C(C)C.C(P(C(C)(C)C)C1CCCCC1)(C)(C)C>C1(C)C=CC=CC=1.Cl[Pd]Cl.[Cu](Br)Br>[CH3:20][C:21]1[N:22]=[C:23]([C:7]2[CH:12]=[CH:11][C:10]([O:13][CH:14]([CH3:16])[CH3:15])=[C:9]([N+:17]([O-:19])=[O:18])[CH:8]=2)[S:24][C:25]=1[C:26]([O:28][CH2:29][CH3:30])=[O:27]
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

9

反応物 5

HCID 6590Isobutyric AcidHCID 2986105-Thiazolecarboxylic acid, 4-methyl-, ethyl esterHCID 516893Potassium BicarbonateHCID 4643321Di-tert-butylcyclohexylphosphineHCID 222832414-Bromo-1-isopropoxy-2-nitrobenzene

生成物 1

HCID 19965110Ethyl 2-(4-isopropoxy-3-nitrophenyl)-4-methyl-5-thiazolecarboxylate
収率 66.1%

試薬・触媒・溶媒 3

HCID 24290Palladium Chloride触媒HCID 24611Copper bromide (CuBr2)触媒HCID 1140Toluene溶媒

反応条件

温度
120 °C

実験手順

A reaction mixture solution prepared by suspending 2.18 g of 4-bromo-2-nitrophenol and 2.07 g of potassium carbonate in 40 mL of dimethylformamide and adding 2.04 g of isopropyl iodide was heated under stirring at 110° C. for 14 hours under a nitrogen atmosphere. After the addition of water to the reaction mixture solution, extraction was performed using ethyl acetate. The organic layer was washed with saline, followed by drying and concentrating under reduced pressure. The resulting crude product was separated and purified by silica gel column chromatography to obtain 2.08 g of 4-bromo-2-nitro-1-(propan-2-yloxy)benzene. (2) A suspension was prepared by adding 1.05 g of potassium hydrogen carbonate, 22 mg of palladium chloride (II) and 102 mg of a copper bromide (I) dimethylsulfide complex to 2.08 g of 4-bromo-2-nitro-1-(propan-2-yloxy)benzene obtained above, followed by suspending the mixture in 15 mL of toluene. Subsequently, a reaction mixture solution prepared by adding 1.02 g of ethyl 4-methyl-1,3-thiazole-5-carboxylate, 46.2 μL of isobutyric acid and 114 mg of di-t-butylcyclohexylphosphine to the suspension was heated at 120° C. for 14 hours under a nitrogen atmosphere. The reaction mixture solution was celite-filtered to remove insoluble matter, water was added to the filtrate, extraction was performed using ethyl acetate. The organic layer was washed with saline and then dried and concentrated under reduced pressure, followed by purifying by a conventional method to obtain 1.38 g of ethyl 4-methyl-2-[3-nitro-4-(propan-2-yloxy)phenyl]-1,3-thiazole-5-carboxylate.

後処理

  1. customobtained above,
  2. customSubsequently, a reaction mixture solution prepared
  3. filtrationThe reaction mixture solution was celite-filtered
  4. customto remove insoluble matter, water
  5. additionwas added to the filtrate, extraction
  6. washThe organic layer was washed with saline
  7. customdried
  8. concentrationconcentrated under reduced pressure
  9. customby purifying by a conventional method

出典と根拠

ORDレコード
ord-df55b1ac56d747c6ae1a557af93beb26
出典データセット
uspto-grants-2016_07
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US09388174B2

反応ノート

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