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Tributylphosphine → 4-(4-Chlorophenyl)-3-(3-cyanophenyl)-2-butanol

HRID 2354500
ノート
印刷プレビュー

反応式

HRID 2354500 の反応式
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8][CH:9]([C:13]2[CH:18]=[CH:17][CH:16]=[C:15](Br)[CH:14]=2)[CH:10]([OH:12])[CH3:11])=[CH:4][CH:3]=1.C(P(CCCC)CCCC)CCC.[CH3:33][N:34](C)C=O.O>[C-]#N.[Zn+2].[C-]#N.C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2].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]>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8][CH:9]([C:13]2[CH:18]=[CH:17][CH:16]=[C:15]([C:33]#[N:34])[CH:14]=2)[CH:10]([OH:12])[CH3:11])=[CH:4][CH:3]=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

7

反応物 3

HCID 13831TributylphosphineHCID 21962138N,N-Dimethylformamide--water (1/1)HCID 574387144-(4-Chlorophenyl)-3-(3-bromophenyl)-2-butanol

生成物 1

HCID 115293394-(4-Chlorophenyl)-3-(3-cyanophenyl)-2-butanol

試薬・触媒・溶媒 3

HCID 11186Zinc cyanide (Zn(CN)2)触媒
HCID 635956
Ferrocene-1,1'-bis-(diphenylphosphine)
触媒
HCID 9811564Bis(dibenzylideneacetone)palladium触媒

反応条件

温度
115 °C

実験手順

To a solution of 4-(4-chlorophenyl)-3-(3-bromophenyl)-2-butanol (1.5 kg, 4.6 mol) in dimethylformamide/water (volume ratio 99:1, 15 L total) was added zinc cyanide (0.39 kg, 3.3 mol), 1,1′-bis(diphenylphosphino)ferrocene (115 g, 0.21 mol) and tris(dibenzylideneacetone)dipalladium (76 g, 0.08 mol). The reaction mixture was stirred and degassed at room temperature for 1 h, and heated at 115° C. for 6 h before cooling to room temperature. Tributylphosphine (46 mL, 0.17 mol) was then added. After stirring for 1 h, the reaction was quenched with aqueous ammonia (1.56 L). After stirring for 1 h, the mixture was filtered through solka floc, and the cake was washed with isopropyl acetate. The filtrate was washed with water (5 L), and the aqueous layer was extracted with isopropyl acetate (4 L). The organic layers were combined, washed with water (10 L×2) and concentrated to give the title compound, which was used for the ensuing reaction after azeotroping with toluene.

後処理

  1. customdegassed at room temperature for 1 h
  2. temperaturebefore cooling to room temperature
  3. stirringAfter stirring for 1 h
  4. customthe reaction was quenched with aqueous ammonia (1.56 L)
  5. stirringAfter stirring for 1 h
  6. filtrationthe mixture was filtered through solka floc
  7. washthe cake was washed with isopropyl acetate
  8. washThe filtrate was washed with water (5 L)
  9. extractionthe aqueous layer was extracted with isopropyl acetate (4 L)
  10. washwashed with water (10 L×2)
  11. concentrationconcentrated

出典と根拠

ORDレコード
ord-e70693eb204d462a94aa2a37fe51724e
出典データセット
uspto-grants-2010_07
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US07754188B2

反応ノート

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