Toluene → 4-(3-Nitro-5-thiomorpholinopyridin-2-yl)morpholine

HRID 1431258ノート

反応式

HRID 1431258 の反応式
Cl[C:2]1[CH:3]=[C:4]([N+:14]([O-:16])=[O:15])[C:5]([N:8]2[CH2:13][CH2:12][O:11][CH2:10][CH2:9]2)=[N:6][CH:7]=1.C1(C)C=CC=CC=1.CC(C1C=C(C(C)C)C(C2C=CC=CC=2P(C2CCCCC2)C2CCCCC2)=C(C(C)C)C=1)C.CC(C)([O-])C.[K+].[NH:64]1[CH2:69][CH2:68][S:67][CH2:66][CH2:65]1>CCOC(C)=O.O.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[N+:14]([C:4]1[C:5]([N:8]2[CH2:13][CH2:12][O:11][CH2:10][CH2:9]2)=[N:6][CH:7]=[C:2]([N:64]2[CH2:69][CH2:68][S:67][CH2:66][CH2:65]2)[CH:3]=1)([O-:16])=[O:15]

参加物

9

反応物 5

HCID 1140TolueneHCID 67164ThiomorpholineHCID 111557942-Dicyclohexylphosphino-2',4',6'-triisoprophylbiphenylHCID 23665647Potassium tert-butoxideHCID 596312064-(5-Chloro-3-nitropyridin-2-yl)morpholine

生成物 1

HCID 596312804-(3-Nitro-5-thiomorpholinopyridin-2-yl)morpholine

試薬・触媒・溶媒 3

HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 962Water溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
115 °C

実験手順

A stirred solution of 4-(5-chloro-3-nitropyridin-2-yl)morpholine (400 mg, 1.64 mmol) in toluene (15.7 mL, 147.7 mmol) was treated with Pd2dba3 (75 mg, 0.082 mmol), X-Phos (78 mg, 0.16 mmol), potassium tert butoxide (368 mg, 3.28 mmol) and thiomorpholine (203 mg, 1.97 mmol). The reaction was heated at 115° C. overnight. After this time the reaction was cooled to rt and diluted with EtOAc (100 mL) and water (50 mL). The separated organic layer was washed with NaHCO3 (satd aq. solution, 40 mL), brine (40 mL) and then dried over magnesium sulfate, filtered and evaporated in vacuo. Column chromatography (hexanes:EtOAc, 1:0 to 1:2) gave 4-(3-nitro-5-thiomorpholinopyridin-2-yl)morpholine as a red oil. Mass Spectrum (ESI) m/e=311.2 (M+1).

後処理

  1. temperatureAfter this time the reaction was cooled to rt
  2. washThe separated organic layer was washed with NaHCO3 (satd aq. solution, 40 mL), brine (40 mL)
  3. dry with materialdried over magnesium sulfate
  4. filtrationfiltered
  5. customevaporated in vacuo

出典と根拠

ORDレコード
ord-83602b98774c44c5ad10d40c24bdc3f3
出典データセット
uspto-grants-2015_01
特許番号
US08940724B2

反応ノート

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