Studies on 3-Oxoalkanenitriles: Novel Rearrangement Reactions Observed in Studies of the Chemistry of 3-Heteroaroyl-3-Oxoalkanenitriles as Novel Routes to 2-Dialkylaminopyridines

被引:10
作者
Al-Matar, Hamad M. [1 ]
Khalil, Khaled D. [1 ,2 ]
Al-Kanderi, Mona F. [1 ]
Elnagdi, Mohamed H. [1 ]
机构
[1] Kuwait Univ, Fac Sci, Dept Chem, Safat 13060, Kuwait
[2] Cairo Univ, Fac Sci, Dept Chem, Giza 12613, Egypt
来源
MOLECULES | 2012年 / 17卷 / 01期
关键词
cyanoacetylation; dialkylaminopyridine; NOE experiments; 3-Oxoalkanenitrile; X-ray; zeolite;
D O I
10.3390/molecules17010897
中图分类号
Q5 [生物化学]; Q7 [分子生物学];
学科分类号
071010 ; 081704 ;
摘要
3-Aroyl and 3-heteroaroyl substituted 3-oxoalkanenitriles were synthesized by the reactions of activated aromatic and hetero-aromatic substances with cyanoacetic acid in the presence of acetic anhydride. As part of studies focusing on the preparation of cyanoacetyl-1-N-methylbenzimidazole, we observed that reaction of N-methyl-benzimidazole with the cyanoanhydride formed by condensation of cyanoacetic acid with acetic anhydride, leads to the formation of 2-(1,3-diacetyl-2,3-dihydro-1H-benzo[d]-imidazol-2-yl) acetonitrile (5), whose structure was confirmed by X-ray crystallographic analysis. 3-Oxoalkanenitriles 3a,b were observed to undergo condensation reactions with dimethylformamide dimethyl acetal (DMFDMA) to afford the corresponding enamino-nitriles, which react with malononitrile to give 2-dialkylaminopyridines through a pathway involving a new, unexpected rearrangement process. Reactions of 3-oxoalkanenitriles with ethyl acetoacetate were found to afford 2-oxopyran-3-carbonitriles, also occurring via this unexpected rearrangement process. Mechanisms to account for both rearrangement reactions are suggested. In addition, reactions of 3-oxoalkanenitriles with acetylacetone in acetic acid in the presence of ammonium acetate result in the formation of pyridine-3-carbonitriles. Finally, upon heating in the presence of zeolite 3-oxoalkanenitriles 3b,c self-trimerized to produce the corresponding aniline derivatives 23b,c.
引用
收藏
页码:897 / 909
页数:13
相关论文
共 17 条
[11]  
ELNAGDI MH, 1984, SYNTHESIS-STUTTGART, P1
[12]  
Ibrahim HM, 2007, HETEROCYCLES, V71, P1951
[13]  
Khalil K., 2010, Eur. J. Chem, V1, P252, DOI [10.5155/eurjchem.1.4.252-258.211, DOI 10.5155/EURJCHEM.1.4.252-258.211]
[14]   Studies with enaminones and enaminonitriles: synthesis of 3-aroyl and 3-heteroaroyl-pyrazolo-[1,5-a]pyrimidines [J].
Khalil, Khaled D. ;
Al-Matar, Hamad M. ;
Al-Dorri, Doa'a M. ;
Elnagdi, Mohamed H. .
TETRAHEDRON, 2009, 65 (45) :9421-9427
[15]  
OKAMOTO Y, 1990, J CHEM RES-S, P136
[16]   A NOVEL PHOTOADDITION OF 6-CYANOURACILS TO ALKENES AND ALKYNES INVOLVING MIGRATION OF A CYANO GROUP [J].
SAITO, I ;
SHIMOZONO, K ;
MATSUURA, T .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1980, 102 (11) :3948-3950
[17]   Cyanoacetylation of indoles, pyrroles and aromatic amines with the combination cyanoacetic acid and acetic anhydride [J].
Slätt, J ;
Romero, I ;
Bergman, J .
SYNTHESIS-STUTTGART, 2004, (16) :2760-2765