The ortho-substituted N,N-diacetylaniline as a selective acetylating reagent

Tetrahedron Letters

Volumn 38, Issue 21, 1997, Pages 3751-3754

  Murakami, Yasuoki ^a   Kondo, Kazuhiro ^a   Miki, Kazuki ^a   Akiyama, Yoko ^a   Watanabe, Toshiko ^a   Yokoyama, Yuusaku ^a  

^a TOHO UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

AMIDE; AMINE;

ACETYLATION; ARTICLE; DRUG SYNTHESIS; IN VITRO STUDY; REACTION ANALYSIS;

EID: 0030940363     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(97)00745-4     Document Type: Article

References (33)

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27. 2, 0 °C, 2 h) gave no selectivity (8 : 9 = 1 : 1).
28. Slow acetylation (12 h) occurred with 2-methyl-N,N-diacetylaniline 2a, but gave satisfactory results (87% yield, N-acetylbenzylamine 8 : N-acetyl-N-methylbenzylamine 10 = > 15 : 1).
29. 1H NMR (400 MHz) analysis.
30. 4) (1 equiv) gave N-acetylbenzylamine 8 in lower yield (60-65%) than ours with similar selectivity.
31. The acetanilide 19 can be recovered in >95% yield and recycled by acetylation (see ref. 17). (formula presented)
32. 2O (22.5 mL, 224 mmol) at 0 °C. The reaction mixture was stirred at 100 °C for 12 h, allowed to cool, and concentrated. The residue was purified by silica gel column (20%EtOAc in benzene) to give 2c (90%, 6.60 g) as a colorless solid. This reagent 2c can be stored at rt under air for a few years without decomposition.
33. 3) to give N-acetyl-N′-propylethylenediamine (93%, 82.1 mg) as a colorless solid. *NH-type silica gel chromatorex NHDM1020® purchased from Fuji Silysia Chemical Ltd.