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Dimethylformamide → Isopropyl 5-[acetyl-(3,5-bistrifluoromethylbenzyl)amino]-8-cyano-2,3,4,5-tetrahydrobenzo[b]azepine-1-carboxylate

HRID 2353876
ノート
印刷プレビュー

反応式

HRID 2353876 の反応式
[CH:1]([O:4][C:5]([N:7]1[CH2:13][CH2:12][CH2:11][CH:10]([N:14]([C:30](=[O:32])[CH3:31])[CH2:15][C:16]2[CH:21]=[C:20]([C:22]([F:25])([F:24])[F:23])[CH:19]=[C:18]([C:26]([F:29])([F:28])[F:27])[CH:17]=2)[C:9]2[CH:33]=[CH:34][C:35](Br)=[CH:36][C:8]1=2)=[O:6])([CH3:3])[CH3:2].[CH3:38][N:39](C)C=O>C(OCC)(=O)C.[Zn].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].[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[C:30]([N:14]([CH2:15][C:16]1[CH:21]=[C:20]([C:22]([F:25])([F:24])[F:23])[CH:19]=[C:18]([C:26]([F:29])([F:28])[F:27])[CH:17]=1)[CH:10]1[CH2:11][CH2:12][CH2:13][N:7]([C:5]([O:4][CH:1]([CH3:3])[CH3:2])=[O:6])[C:8]2[CH:36]=[C:35]([C:38]#[N:39])[CH:34]=[CH:33][C:9]1=2)(=[O:32])[CH3:31]
参加物実験手順後処理出典と根拠反応ノート

参加物

7

反応物 2

HCID 6228DimethylformamideHCID 59003154Isopropyl 5-[acetyl-(3,5-bistrifluoromethylbenzyl)amino]-8-bromo-2,3,4,5-tetrahydrobenzo[b]azepine-1-carboxylate

生成物 1

HCID 86616065Isopropyl 5-[acetyl-(3,5-bistrifluoromethylbenzyl)amino]-8-cyano-2,3,4,5-tetrahydrobenzo[b]azepine-1-carboxylate収率 51%

試薬・触媒・溶媒 4

HCID 23994Zinc触媒2 回
HCID 9811564
Bis(dibenzylideneacetone)palladium
触媒
HCID 11979704Tetrakis(triphenylphosphine)palladium触媒
HCID 8857Ethyl Acetate溶媒

実験手順

Purge with nitrogen, a solution of isopropyl-5-[acetyl-(3,5-bistrifluoromethylbenzyl)amino]-8-bromo-2,3,4,5-tetrahydrobenzo[b]azepine-1-carboxylate (0.074 g, 0.124 mmol) and zinc cyamide (0.014 g, 0.124 mmol) in N,N-dimethylformamide (2 mL) in a 10 mL microwave vial. Add tetrakis(triphenylphosphine)palladium (0) (0.0043 g, 0.0037 mmol) and irradiate the mixture at 175° C. for 0.5 h (60-80 Watts). Add a second portion of zinc cyamide (0.014 g, 0.124 mmol) and tetrakis(triphenylphosphine) palladium (0) (0.0043 g, 0.0037 mmol) and continue irradiating for 8 min. Cool the mixture to room temperature and dilute with ethyl acetate (35 mL) and wash with water (3×25 mL) and brine (25 mL each), then dry the organic layer over sodium sulfate, filter and remove the solvent under reduced pressure. Purify the residue using chromatography on silica gel, eluting with hexanes/ethyl acetate (60:40), to provide the title compound as a crushable white foam (0.034 g, 51%): ESI MS 542 (M+H).

後処理

  1. customPurge with nitrogen
  2. customcontinue irradiating for 8 min
  3. washwash with water (3×25 mL) and brine (25 mL each)
  4. dry with materialdry the organic layer over sodium sulfate
  5. filtrationfilter
  6. customremove the solvent under reduced pressure
  7. customPurify the residue
  8. washeluting with hexanes/ethyl acetate (60:40)

出典と根拠

ORDレコード
ord-464f9ca239094c4d95223b791f0c87fe
出典データセット
uspto-grants-2010_07
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US07749992B2

反応ノート

読み込み中…

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