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Cesium carbonate → HCID 54591302、化合物

HRID 1260187
ノート
印刷プレビュー

反応式

HRID 1260187 の反応式
Br[C:2]1[CH:3]=[C:4]([CH:28]=[CH:29][CH:30]=1)[CH2:5][N:6]1[C:10]([CH3:11])=[CH:9][C:8]([C:12]2[O:16][N:15]=[C:14]([C:17]3[CH:22]=[CH:21][C:20]([O:23][C:24]([F:27])([F:26])[F:25])=[CH:19][CH:18]=3)[N:13]=2)=[N:7]1.[Si]([O:48][CH:49]1[CH2:52][NH:51][CH2:50]1)(C(C)(C)C)(C1C=CC=CC=1)C1C=CC=CC=1.C1(P(C2CCCCC2)C2C=CC=CC=2C2C(C(C)C)=CC(C(C)C)=CC=2C(C)C)CCCCC1.C(=O)([O-])[O-].[Cs+].[Cs+]>CN(C=O)C.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].O>[CH3:11][C:10]1[N:6]([CH2:5][C:4]2[CH:3]=[C:2]([N:51]3[CH2:52][CH:49]([OH:48])[CH2:50]3)[CH:30]=[CH:29][CH:28]=2)[N:7]=[C:8]([C:12]2[O:16][N:15]=[C:14]([C:17]3[CH:22]=[CH:21][C:20]([O:23][C:24]([F:27])([F:26])[F:25])=[CH:19][CH:18]=3)[N:13]=2)[CH:9]=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 111557942-Dicyclohexylphosphino-2',4',6'-triisoprophylbiphenylHCID 178425313-((Tert-butyldiphenylsilyl)oxy)azetidineHCID 58072149HCID 58072149、化合物

生成物 1

HCID 54591302HCID 54591302、化合物

試薬・触媒・溶媒 3

HCID 9811564
Bis(dibenzylideneacetone)palladium
触媒
HCID 962Water溶媒
HCID 6228Dimethylformamide溶媒

反応条件

温度
120 °C

実験手順

A mixture of 2.0 g (4.17 mmol) of the compound from Example 1A, 1.95 g (6.26 mmol) of the compound from Example 8A, 256 mg (0.280 mmol) of tris(dibenzylideneacetone)dipalladium(0), 398 mg (0.835 mmol) of 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (X-Phos) and 2.72 g (8.35 mmol) of caesium carbonate in 20 ml of anhydrous DMF was heated to 120° C. under argon in a microwave oven (Biotage Initiator, dynamic control of the incident power) for 2.5 h. After cooling to RT, 100 ml of water were added to the reaction mixture, which was extracted three times with approx. 100 ml each time of ethyl acetate. The combined organic extracts were washed successively with water and saturated sodium chloride solution, dried over anhydrous magnesium sulphate, filtered and finally freed of the solvent on a rotary evaporator. The remaining residue was dissolved in 40 ml of THF, and 6.3 ml (6.26 mmol) of a 1 M solution of tetra-n-butylammonium fluoride (TBAF) in THF were added. After this mixture had been stirred at RT for 1 h, it was subjected to aqueous workup in the same way as described above. The remaining residue was purified by suction filtration through 200 g of silica gel with 2:1 (3 liters)→1:1 (3 liters) cyclohexane/ethyl acetate as the eluent. After concentration and drying under a high vacuum, 1.56 g (79% of theory) of the title compound were obtained.

後処理

  1. temperatureAfter cooling to RT
  2. extractionwas extracted three times with approx. 100 ml each time of ethyl acetate
  3. washThe combined organic extracts were washed successively with water and saturated sodium chloride solution
  4. dry with materialdried over anhydrous magnesium sulphate
  5. filtrationfiltered
  6. customfinally freed of the solvent on a rotary evaporator
  7. dissolutionThe remaining residue was dissolved in 40 ml of THF
  8. addition6.3 ml (6.26 mmol) of a 1 M solution of tetra-n-butylammonium fluoride (TBAF) in THF were added
  9. filtrationThe remaining residue was purified by suction filtration through 200 g of silica gel with 2:1 (3 liters)→1
  10. concentrationAfter concentration
  11. dry with materialdrying under a high vacuum, 1.56 g (79% of theory) of the title compound
  12. customwere obtained

出典と根拠

ORDレコード
ord-ffdac2a497b742619e9f3bd0c3e1acfd
出典データセット
uspto-grants-2013_06
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US08470811B2

反応ノート

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このページの内容参加物反応条件実験手順後処理出典と根拠反応ノート