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Cesium carbonate → Methyl 3-[[5-(1,4-dioxa-8-azaspiro[4.5]decan-8-yl)-2-methyl-benzoyl]amino]-2,4-dimethyl-benzoate

HRID 1427106
ノート
印刷プレビュー

反応式

HRID 1427106 の反応式
Br[C:2]1[CH:3]=[CH:4][C:5]([CH3:23])=[C:6]([CH:22]=1)[C:7]([NH:9][C:10]1[C:11]([CH3:21])=[C:12]([CH:17]=[CH:18][C:19]=1[CH3:20])[C:13]([O:15][CH3:16])=[O:14])=[O:8].[O:24]1[C:28]2([CH2:33][CH2:32][NH:31][CH2:30][CH2:29]2)[O:27][CH2:26][CH2:25]1.C([O-])([O-])=O.[Cs+].[Cs+].C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>O1CCOCC1.O.CC([O-])=O.CC([O-])=O.[Pd+2]>[O:24]1[C:28]2([CH2:33][CH2:32][N:31]([C:2]3[CH:3]=[CH:4][C:5]([CH3:23])=[C:6]([CH:22]=3)[C:7]([NH:9][C:10]3[C:11]([CH3:21])=[C:12]([CH:17]=[CH:18][C:19]=3[CH3:20])[C:13]([O:15][CH3:16])=[O:14])=[O:8])[CH2:30][CH2:29]2)[O:27][CH2:26][CH2:25]1
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

8

反応物 4

HCID 10796Cesium carbonateHCID 674351,4-Dioxa-8-azaspiro(4.5)decaneHCID 634876Binap, (A+-)-2 回HCID 86707319Methyl 3-[(5-bromo-2-methyl-benzoyl)amino]-2,4-dimethyl-benzoate

生成物 1

HCID 86707339Methyl 3-[[5-(1,4-dioxa-8-azaspiro[4.5]decan-8-yl)-2-methyl-benzoyl]amino]-2,4-dimethyl-benzoate収率 44.62%

試薬・触媒・溶媒 3

HCID 167845palladium(II) acetate触媒2 回HCID 962Water溶媒HCID 312751,4-Dioxane溶媒

反応条件

温度
90 °C

実験手順

To a solution of methyl 3-[(5-bromo-2-methyl-benzoyl)amino]-2,4-dimethyl-benzoate (0.5 g, 1.33 mmol), 1,4-dioxa-8-azaspiro(4.5)decane (228.34 mg, 1.59 mmol) and Cs2CO3 (1.3 g, 3.99 mmol) in 1,4-dioxane (10 ml) is added Pd(OAc)2 (29.84 mg, 132.89 μmol) followed by racemic-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (82.75 mg, 132.89 μmol). The reaction mixture is purged with nitrogen for 10 minutes and then heated to 90° C. After 3 hours, very small amount of the product is formed. To the reaction mixture is added Pd(OAc)2 (29.84 mg, 132.89 μmol) followed by racemic-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (82.75 mg, 132.89 μmol) and heated to 100° C. After 12 hours, the reaction is cooled to ambient temperature and diluted with water and extracted with EtOAc. The combined organic layers are washed with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting residue is purified by flash chromatography (silica gel) using 0-100% ethyl acetate in hexane to afford the title compound as a brown solid (0.26 g, 44.62%). Mass spectrum (m/z): 439.2 (M+1).

後処理

  1. customThe reaction mixture is purged with nitrogen for 10 minutes
  2. customvery small amount of the product is formed
  3. temperatureheated to 100° C
  4. waitAfter 12 hours
  5. temperaturethe reaction is cooled to ambient temperature
  6. extractionextracted with EtOAc
  7. washThe combined organic layers are washed with brine
  8. dry with materialdried over sodium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated under reduced pressure
  11. customThe resulting residue is purified by flash chromatography (silica gel)

出典と根拠

ORDレコード
ord-f033765e1c2a40318fc405a25f3c5347
出典データセット
uspto-grants-2015_01
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US08933098B2

反応ノート

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