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(S)-(-)-2,2'-Bis(di-p-tolylphosphino)-1, 1'-binaphthyl → 5-nitro-3-phenylsulfanyl-1-(2-trimethylsilanylethoxymethyl)-1H-indazole

HRID 1452912
ノート
印刷プレビュー

反応式

HRID 1452912 の反応式
I[C:2]1[C:10]2[C:5](=[CH:6][CH:7]=[C:8]([N+:11]([O-:13])=[O:12])[CH:9]=2)[N:4]([CH2:14][O:15][CH2:16][CH2:17][Si:18]([CH3:21])([CH3:20])[CH3:19])[N:3]=1.[S:22]1[CH:26]=[CH:25][CH:24]=[C:23]1[C:27]([O-])=O.[Na+].[CH3:31]C1C=CC(P(C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC(C)=CC=2)C2C=CC(C)=CC=2)C2C=CC(C)=CC=2)=CC=1.CC(C)([O-])C.[Na+]>C1(C)C=CC=CC=1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O.C(OCC)(=O)C>[N+:11]([C:8]1[CH:9]=[C:10]2[C:5](=[CH:6][CH:7]=1)[N:4]([CH2:14][O:15][CH2:16][CH2:17][Si:18]([CH3:21])([CH3:20])[CH3:19])[N:3]=[C:2]2[S:27][C:23]1[CH:31]=[CH:22][CH:26]=[CH:25][CH:24]=1)([O-:13])=[O:12]
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 4

HCID 4189906(S)-(-)-2,2'-Bis(di-p-tolylphosphino)-1, 1'-binaphthylHCID 225672723-Iodo-5-nitro-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-indazoleHCID 23672340Sodium 2-thenoateHCID 23676156Sodium t-butoxide

生成物 1

HCID 225671635-nitro-3-phenylsulfanyl-1-(2-trimethylsilanylethoxymethyl)-1H-indazole収率 507.1%

試薬・触媒・溶媒

4
HCID 167845palladium(II) acetate触媒HCID 962Water溶媒HCID 1140Toluene溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
80 °C

実験手順

5-Nitro-3-phenylsulfanyl-1-(2-trimethylsilanylethoxymethyl)-1H-indazole can be obtained in the following way: 2 g of 3-iodo-5-nitro-1-(2-trimethylsilanylethoxymethyl)-1H-indazole and then 0.88 g of sodium thiophenate are added to a solution, under argon, of 0.11 g of palladium acetate, of 0.36 g of (R)-(+)-2,2′-bis(di-p-tolylphosphino)-1,1′-binaphthyl and of 0.64 g of sodium tert-butoxide in 40 ml of toluene. The reaction mixture is heated at a temperature in the region of 80° C. for 21 hours, and is then cooled to a temperature in the region of 20° C. After dilution with 100 ml of ethyl acetate and 80 ml of water and then settling out, the aqueous phase is extracted with 100 ml of ethyl acetate. The organic extracts are pooled, washed with 60 ml of a saturated aqueous sodium chloride solution, dried over magnesium sulfate, filtered and then concentrated to dryness under reduced pressure (2 kPa) at a temperature in the region of 25° C. The residue thus obtained is filtered through silica (particle size 15-35 μm), eluting with pure dichloromethane. The filtrate is concentrated to dryness under reduced pressure (2 kPa) at a temperature in the region of 20° C. The residue is purified by chromatography under argon pressure (50 kPa), on a column of 80 g of silica (particle size 40-63 μm), eluting successively with pure cyclohexane then with cyclohexane/ethyl acetate (95/5; 90/10 by volume) mixtures. The fractions containing the expected product are pooled and concentrated to dryness under reduced pressure (2 kPa) at a temperature in the region of 25° C. 1.08 g of 5-nitro-3-phenylsulfanyl-1-(2-trimethylsilanylethoxymethyl)-1H-indazole are thus obtained in the form of an orange oil (Rf=0.35, silica gel thin layer chromatography, eluent: cyclohexane/ethyl acetate (80/20 by volume)).

後処理

  1. temperatureis then cooled to a temperature in the region of 20° C
  2. extractionthe aqueous phase is extracted with 100 ml of ethyl acetate
  3. washwashed with 60 ml of a saturated aqueous sodium chloride solution
  4. dry with materialdried over magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated to dryness under reduced pressure (2 kPa) at a temperature in the region of 25° C
  7. customThe residue thus obtained
  8. filtrationis filtered through silica (particle size 15-35 μm)
  9. washeluting with pure dichloromethane
  10. concentrationThe filtrate is concentrated to dryness under reduced pressure (2 kPa) at a temperature in the region of 20° C
  11. customThe residue is purified by chromatography under argon pressure (50 kPa)
  12. washon a column of 80 g of silica (particle size 40-63 μm), eluting successively with pure cyclohexane
  13. additionThe fractions containing the expected product
  14. concentrationconcentrated to dryness under reduced pressure (2 kPa) at a temperature in the region of 25° C

出典と根拠

ORDレコード
ord-654d9313f7304ce290ce7d60d78b3c70
出典データセット
uspto-grants-2009_01
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US07473701B2

反応ノート

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