Pyridine → 3-Chloro-4-acetotoluidide

HRID 47844

반응식

HRID 47844 반응식
C(O[C:5](=[O:7])[CH3:6])(=O)C.[Cl:8][C:9]1[CH:10]=[C:11]([CH:13]=[CH:14][C:15]=1[CH3:16])[NH2:12].N1C=CC=CC=1>C(OCC)(=O)C>[C:5]([NH:12][C:11]1[CH:13]=[CH:14][C:15]([CH3:16])=[C:9]([Cl:8])[CH:10]=1)(=[O:7])[CH3:6]

참가 물질

5

반응물 3

HCID 1049PyridineHCID 72553-Chloro-4-methylanilineHCID 7918Acetic Anhydride

생성물 1

HCID 235373-Chloro-4-acetotoluidide수율 65.3%

시약·촉매·용매 1

HCID 8857Ethyl Acetate용매

실험 절차

Acetic anhydride (78 ml, 0.825 mol) was added in portions (using a dropping funnel) during a 45 min period to a stirred, cooled in an ice-bath solution of 3-chloro-4-methylaniline (106.2 g, 0.75 mol) in ethyl acetate (550 ml, dried over MgSO4 prior to use) and anhydrous pyridine (66.6 ml, 0.825 mol) under argon. During the reaction the temperature of the reaction mixture varied between 10-20° C. Stirring was continued for 20 min; then the ice-water bath was removed and the reaction mixture was stirred for 18 h at room temperature. The solvents were removed in vacuo and the light brown solid residue was triturated with ether (350 ml) and left to stand in a fridge overnight. The solid was collected by filtration, washed with cold ether (100 ml) and hexanes (100 mL), dried over P2O5 to afford a white solid (90 g). The filtrate was concentrated in vacuo, triturated with ether to afford an additional 28.1 g of the product. Total yield 118.1 g (86%); mp 105-106° C.; 1H-NMR (CDCl3) 2.17, 2.32 (2×s, 6H, 4-CH3, CH3CO), 7.14 (d, J=8.22 Hz, 1H, 6-H), 7.25 (2×dd, J=1.9, 6.5 Hz, 1H, 5-H), 7.58 (d, J=1.8 Hz, 1H, 3-H); MS (FAB, m/z) 184, 186 [(M+H)+ 100%, 30% respectively; Cl isotopic pattern].

후처리

  1. dry with materialdried over MgSO4
  2. customDuring the reaction the temperature of the reaction mixture
  3. customvaried between 10-20° C
  4. customthen the ice-water bath was removed
  5. stirringthe reaction mixture was stirred for 18 h at room temperature
  6. customThe solvents were removed in vacuo
  7. customthe light brown solid residue was triturated with ether (350 ml)
  8. waitleft
  9. waitto stand in a fridge overnight
  10. filtrationThe solid was collected by filtration
  11. washwashed with cold ether (100 ml) and hexanes (100 mL)
  12. dry with materialdried over P2O5

출처 및 근거

ORD 기록
ord-8780bd74c9c743828e0e3212785354d9
출처 데이터셋
uspto-grants-2004_03
특허 번호
US06699861B1

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