4-Methylmorpholine → 2-Cyanoethyl 1-isocyanatomethyl-1-Cyclohexane Acetate

HRID 584540ノート

反応式

HRID 584540 の反応式
C[N:2]1[CH2:7]COCC1.ClC(OCC)=[O:10].[C:14]([CH2:16][CH2:17][O:18][C:19]([CH2:21][C:22]1([CH2:28]C(O)=O)[CH2:27][CH2:26][CH2:25][CH2:24][CH2:23]1)=[O:20])#[N:15].[N-]=[N+]=[N-].[Na+]>C1COCC1>[N:2]([CH2:28][C:22]1([CH2:21][C:19]([O:18][CH2:17][CH2:16][C:14]#[N:15])=[O:20])[CH2:23][CH2:24][CH2:25][CH2:26][CH2:27]1)=[C:7]=[O:10]

参加物

6

反応物 4

HCID 79724-MethylmorpholineHCID 10928Ethyl chloroformateHCID 33557Sodium AzideHCID 223409601-[(2-Cyanoethoxycarbonyl)methyl]-1-Cyclohexane Acetic Acid

生成物 1

HCID 858637522-Cyanoethyl 1-isocyanatomethyl-1-Cyclohexane Acetate収率 64.1%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

反応条件

温度
-20 °C

実験手順

1.5 mL of N-methyl morpholine (13.62 mmol) and 1.3 mL of ethyl chloroformate (13.03 mmol) was added to a solution of 1-[(2-cyanoethoxycarbonyl)-methyl]-1-cyclohexane acetic acid (5) (11.84 mmol) in 30 mL of anhydrous THF at −20° C. under nitrogen atmosphere. The reaction mixture was stirred at −20° C. for 20 minutes, warmed to −5° C., an aqueous solution of NaN3 (29.61 mmol, in 3.5 mL of H2O) was added and then stirred for 30 minutes at −5° C. to −10° C. Then, THF was removed under reduced pressure and the residue was extracted with CH2Cl2 and dried over Na2SO4. After concentration in vacuo the crude product was dissolved in 20 mL of anhydrous toluene and refluxed for 20 minutes. The mixture was cooled to room temperature and toluene was removed under reduced pressure. The residue was purified on silica gel (15% ethyl acetate in hexane) to afford 1.9 g (64%) of the title compound. 1H NMR (CDCl3): δ 4.29 (2H, t, J=6.0 Hz); 3.42 (2H, s); 2.73 (2H, t, J=6.0 Hz); 2.44 (2H, s); 1.49-1.39 (10H, m).

後処理

  1. temperaturewarmed to −5° C.
  2. stirringstirred for 30 minutes at −5° C. to −10° C
  3. customThen, THF was removed under reduced pressure
  4. extractionthe residue was extracted with CH2Cl2
  5. dry with materialdried over Na2SO4
  6. concentrationAfter concentration in vacuo the crude product
  7. dissolutionwas dissolved in 20 mL of anhydrous toluene
  8. temperaturerefluxed for 20 minutes
  9. temperatureThe mixture was cooled to room temperature
  10. customtoluene was removed under reduced pressure
  11. customThe residue was purified on silica gel (15% ethyl acetate in hexane)

出典と根拠

ORDレコード
ord-6e5cd8c2e0a44e3cbcc050f7210bd435
出典データセット
uspto-grants-2005_08
特許番号
US06927036B2

反応ノート

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