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Diethyl Ether → 2,6-Difluoro-N,N-di(propan-2-yl)benzene-1-carboximidamide

HRID 646653
ノート
印刷プレビュー

反応式

HRID 646653 の反応式
CC[Mg+].[Br-].CCOCC.[CH:10]([NH:13][CH:14]([CH3:16])[CH3:15])([CH3:12])[CH3:11].[F:17][C:18]1[CH:25]=[CH:24][CH:23]=[C:22]([F:26])[C:19]=1[C:20]#[N:21]>C1(C)C=CC=CC=1>[CH:10]([N:13]([CH:14]([CH3:16])[CH3:15])[C:20](=[NH:21])[C:19]1[C:18]([F:17])=[CH:25][CH:24]=[CH:23][C:22]=1[F:26])([CH3:12])[CH3:11]
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

6

反応物 4

HCID 3283Diethyl EtherHCID 7912DiisopropylamineHCID 746952,6-DifluorobenzonitrileHCID 178461630HCID 178461630、化合物

生成物 1

HCID 237265252,6-Difluoro-N,N-di(propan-2-yl)benzene-1-carboximidamide収率 95.9%

試薬・触媒・溶媒 1

HCID 1140Toluene溶媒

反応条件

温度
0 °C

実験手順

A solution of EtMgBr in ether (8.0 ml, 3.0 M, 23 mmol) was added to a solution of diisopropylamine (2.5 g, 23.8 mmol) in toluene (60 ml) at 50° C. The mixture was stirred for 1 h and a white precipitate formed. The mixture was cooled to 0° C. and 2,6-difluorobenzonitrile (3.33 g, 23 mmol) was added. The mixture was allowed to warm to room temperature and stirred for 16 hours subsequently. The conversion, determined by GC, appeared to be 98%. The mixture was quenched with an aqueous solution of ammonium chloride (10%, 100 ml). The organic phase was separated from the aqueous phase and the latter was extracted twice with diethylether (200 ml). The combined organic phases were dried over sodium sulphate, filtered and the solvent was removed under reduced pressure giving 5.30 g (91%) of pure product. The ligand was characterized by 1H NMR 300 MHz (CDCl3) δ (ppm): 7.2 (m, 1H), 6.8 (m. 2H), 5.5 (bs, 1H), 3.7 (bs, 1H), 1.5 (bs, 6H), 1.0 (bs 6H), by 13C NMR 75 MHz (CDCl3) δ (ppm): 158.9 dd, J=238 Hz, J=8 Hz), 155.7, 130.1, v130.0, 129.8, 112.1, 112.0, 111.9, 111.8, 52.0 (bs), 36.2 (bs), 21.3, 20.5 and by 19F NMR 282 MHz (CDCl3) δ (ppm): −113.5

後処理

  1. customa white precipitate formed
  2. temperatureto warm to room temperature
  3. stirringstirred for 16 hours subsequently
  4. customThe mixture was quenched with an aqueous solution of ammonium chloride (10%, 100 ml)
  5. customThe organic phase was separated from the aqueous phase
  6. extractionthe latter was extracted twice with diethylether (200 ml)
  7. dry with materialThe combined organic phases were dried over sodium sulphate
  8. filtrationfiltered
  9. customthe solvent was removed under reduced pressure

出典と根拠

ORDレコード
ord-7e21529159244a83a1aca719812bd350
出典データセット
uspto-grants-2010_04
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US07705172B2

反応ノート

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