Synthesis of Novel Bis-enaminones by KHSO4-assisted Facile Michael Addition-elimination Reaction of 3-(dimethylamino)-1-phenylprop-2-en-1-ones with Diamines in Water
Asem Satyapati Devi, Philippe Helissey, Jai Narain Vishwakarma
DOI: 10.4236/gsc.2011.12006   PDF    HTML     6,199 Downloads   14,204 Views   Citations


3-(Dimethylamino)-1-phenylprop-2-en-1-ones (formylated acetophenones) 1 reacted with aliphatic diamines in water assisted by KHSO4 to give bis-enaminones 2a-h in good yields. Compound 1 also reacted with o-phenylenediamine under similar conditions to produce bis-enaminones 3 instead of benzodiazepines 4 in excellent yields.

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A. Devi, P. Helissey and J. Vishwakarma, "Synthesis of Novel Bis-enaminones by KHSO4-assisted Facile Michael Addition-elimination Reaction of 3-(dimethylamino)-1-phenylprop-2-en-1-ones with Diamines in Water," Green and Sustainable Chemistry, Vol. 1 No. 2, 2011, pp. 31-34. doi: 10.4236/gsc.2011.12006.

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The authors declare no conflicts of interest.


[1] A.-Shanab, A. Fathi, M. Sherif, Mousa and S. A. Sayed, “Dimethylformamide Dimethyl acetal as a Building Block in Heterocyclic Synthesis,” Journal of Heterocyclic Chemistry, Vol. 46, No. 5, 2009, pp. 801-827. doi:10.1002/jhet.69
[2] M. Bulusu, P. Ettmayer, K. Weigand and M. Woi- setschlaeger, Novartis-Pharma “Phenylpyrimidineamines and Amides as Ige Inhibitors and Their Pharmaceutical Compositions and Therapeutic Uses,” PCT Int. Appl. WO 03 63,871, Chemical Abstracts, Vol. 139, 2003, p. 164802c.
[3] A. M. S. Silva, L. M. P. M. Almeida and J. A. S. Cavaleiro, “Synthesis and Molecular Structure of New O/N/O Lgands:Bis-Phenol-Pyridine and Bis-Phenol-Pyra- Zole,” Tetrahedron, Vol. 53, No. 34, 1997, pp. 11645-11658. doi:10.1016/S0040-4020(97)00733-3
[4] J. Witherington, V. Bordas, A. Gaiba, N. S. Garton, A. Naylor, A. D. Rawlings, B. P. Slingsby, D. G. Smith, A. K. Takle and R. W. Ward, ,“6-Aryl-pyrazolo[3,4-b]py- ridines: Potent Inhibitors of Glycogen Synthase Kinase- 3(GSK-3),” Bioorganic & Medicinal Chemistry Letters, Vol. 13, No. 18, 2003, pp. 3055-3057. doi:10.1016/S0960-894X(03)00645-0
[5] J. W. Baum, J. T. Bamberg and J. A. Grina, Sandoz Ltd, PCT Int Appl WO 95 19,358, 20 Jul. 1995, “Preparation of Herbicidal Aryl and (Hetero) Arylpyrimidines,” Chemical Abstracts, Vol. 123, 1995, p. 340179k.
[6] A. Kumar, D. W. Boykin, W. D. Wilson, S. K. Jones, B. K. Bender, C. C. Dykstra, J. E. Hall and R. R. Tidwell, “Anti-Pneumocystis Carinii Pneumonia Activity of Dica- Tionic 2,4-Diarylpyrimidines,” European Journal of Medicinal Chemistry, Vol. 31, No. 10, 1996, pp. 767-773. doi:10.1016/0223-5234(96)83970-5
[7] E. Bejan, H. Ait-Haddou, J. Daran and G. G. A. Balavoine, “Enaminones in the Synthesis of New Polyaza heterocycles,” European Journal of Medicinal Chemistry, Vol. 12, 1998, pp. 2907-2912.
[8] S. Hernandez, R. SanMartin, I. Tellitu and E. Dominguez, “Toward Safer Methodologies for the Synthesis of Polyheterocyclic Systems:Intramolecular Arylation of Arenes under Mizoroki-Heck Reaction Conditions,” Organic Letters, Vol. 5, No. 7, 2003, pp. 1095-1098. doi:10.1021/ol034148+
[9] G. A. Reynolds, J. A. Van Allan and A. K. Seidel, “Synthesis of Chromones,” Journal of Heterocyclic Chemistry, Vol. 16, No. 2, 1979, pp. 369-370. doi:10.1002/jhet.5570160234
[10] A. Pleier, H. Glas, M. Grosche, P. Sirsch and W. R. Thiel, “Microwave Assisted Synthesis of 1-Aryl-3-dimethy- laminoprop-2-enones: A Simple and Rapid Access to 3(5)-Arylpyrazoles,” Synthesis, 2001, pp. 55-62. doi:10.1055/s-2001-9761
[11] A. Z. A. Hassanien, S. A. S. Ghozlan and M. H. Elnagdi, “Enaminones as Building Blocks in Organic Synthesis: A Novel Route to Polyfunctionally Substituted Benzoni- triles, Pyridines, Eneylbenzotriazoles and Diazepines,” Journal of Heterocyclic Chemistry, Vol. 40, No. 2, 2003, pp. 225-228. doi:10.1002/jhet.5570400205
[12] P. Molina and P. M. Fresneda, “New Synthesis of Pyra- zole and Isoxazole Derivatives,” Journal of Heterocyclic Chemistry, Vol. 21, No. 2, 1984, pp. 461-464. doi:10.1002/jhet.5570210239
[13] K. Chanda, M. C. Dutta, E. Karim and J. N. Vishwa- karma, “An Efficient Microwave Assisted Solvent-Free Synthesis of Polarized Enamines,” Journal of the Indian Chemical Society, Vol. 81, No. 9, 2004, pp. 791-793.
[14] M. C. Dutta, K. Chanda, E. Karim and J. N. Vishwa- karma, “A Facile Route to Enaminones: Synthesis of 3-Alkyl/aralkyl/arylamino-1-arylprop-2-en-1-ones,”In-dian Journal of Chemistry, Vol. 36, No. 11, 2004, pp. 2471-2472.
[15] K. Chanda, M. C. Dutta, E. Karim and J. N. Vishwa- karma, “A Facile One-Pot Synthesis of Novel Substituted 1,2,3,4-Tetrahydropyrimidine, Part 2: Synthesis of 1-(Aralkyl/aryl)-3-(alkyl/aralkyl/aryl)-5-aroyl-1,2,3,4-tetrahydropyrimidines,” Journal of Heterocyclic Chemistry, Vol. 41, No. 4, 2004, pp. 627-631. doi:10.1002/jhet.5570410425
[16] M. C. Dutta, K. Chanda and J. N. Vishwakarma, “A Facile One-Pot Synthesis of Tetrahydropyrimidines. Part 3. Synthesis of [Alkanediylbis(3-alkyl/aralkyl/ aryl-3,6-dihydropyrimidine-1,5(2H)-diyl)bis(arylmethanones) and [1,4-phenylenebis(3-phenyl-3,6-dihydro- pyrimidine-1,5(2H)-diyl)]bis(phenylmethanone),” Jour- nal of Heterocyclic Chemistry, Vol. 42, No. 1, 2005, pp. 121-123. doi:10.1002/jhet.5570420118
[17] K. Surendra, N. S. Krishnaveni, V. Pavan Kumar, R. Sridhar and K. R. Rao, “Selective and Efficient Oxida- tion of Sulfides to Sulfoxides with N-Bromo- succicinimide in the Presence of Β-Cyclodextrin in Water,” Tetrahedron Letters, Vol. 46, 2005, pp. 4581-4583. doi:10.1016/j.tetlet.2005.05.011
[18] K.-H. Tong, K.-Y. Wong and T. H. Chan, “A Chemoen- zymic Approach to the Epoxidation of Alkenes in Aqueous Media,” Tetrahedron, Vol. 61, 2005, pp. 6009-6014. doi:10.1016/j.tet.2005.04.055
[19] R. Liu, C. Dong, X. Liang, X. Wang and X. Hu, “Highly Efficient Catalytic Aerobic Oxidations of Benzylic Alcohols in Water,” Journal of Organic Chemistry, Vol. 70, No. 2, 2005, pp. 729-731. doi:10.1021/jo048369k
[20] D. Biondini, L. Brinchi, R. Germani, L. Goracci and G. Savelli, “Dehydrogenation of Amines to Nitriles in Aqueous Micelles,” European Journal of Organic Chemistry, Vol. 2005, No. 14, 2005, pp. 3060-3063. doi:10.1002/ejoc.200500047
[21] X. Wu, X. Li, F. King and J. Xiao, “Insight into and Practical Application of pH-Controlled Asymmetric Transfer Hydrogenation of Aromatic Ketones in Water,” Angewandte Chemie International Edition, Vol. 44, No. 22, 2005, pp. 3407-3411. doi:10.1002/anie.200500023
[22] R. Nakao, H. Rhee and Y. Uozumi, “Hydrogenation and Dehalogenation under Aqueous Conditions with an Am- phiphilic-Polymer-Supported Nanopalladium Catalyst,” Organic Letters, Vol. 7, 2005, pp. 163-165. doi:10.1021/ol047670k
[23] G. Stavber, M. Zupan, M. Jereb and S. Stavber, “Selective and Effective Fluorination of Organic Compounds in Water Using Selectfluor F-TEDA-BF4,” Organic Letters, Vol. 6, No. 26, 2004, pp. 4973-4976. doi:10.1021/ol047867c
[24] Z. Zha, A. Hui, Y. Zhou, Q. Miao, Z. Wang and H. Zhang, “A Recyclable Electrochemical Allylation in Water,” Organic Letters, Vol. 7, No. 10, 2005, pp. 1903- 1905. doi:10.1021/ol050483h
[25] L. Chen and C.-J. Li, “A Remarkably Efficient Coupling of Acid Chlorides with Alkynes in Water,” Organic Letters, Vol. 6, No. 18, 2004, pp. 3151-3153. doi:10.1021/ol048789w
[26] L. Botella and C. Nájera, “Mono- and β,β-Double-Heck Reactions of α,β-Unsaturated Carbonyl Compounds in Aqueous Media,” Journal of Organic Chemistry, Vol. 70, No. 11, 2005,pp. 4360- 4369. doi:10.1021/jo0502551
[27] J. Dambacher, W. Zhao, A. El-Batta, R. Anness, C. Jiang and M. Bergdahl, “Water is an Efficient Medium for Wittig Reactions Employing Stabilized Ylides and Aldehydes,” Tetrahedron Letters, Vol. 46, No. 26, 2005, pp. 4473-4477. doi:10.1016/j.tetlet.2005.04.105
[28] H. Yanai, A. Saito and T. Taguchi, “Intramolecular Diels-Alder Reaction of 1,7,9-Decatrienoates Catalyzed by Indium(III) Trifluoromethanesulfonate in Aqueous Media,” Tetrahedron, Vol. 61, No. 30, 2005, pp. 7087-7093. doi:10.1016/j.tet.2005.05.062
[29] P. Gogoi, P. Hazarika and D. Konwar, “Surfactant/ I2/Water: An Efficient System for Deprotection of Oxi- mes and Imines to Carbonyls under Neutral Conditions in Water,” Journal of Organic Chemistry, Vol. 70, No. 11, 2005, pp. 1934- 1936. doi:10.1021/jo0480287
[30] A. S. Devi, M. C. Dutta, R. L. Nongkhlaw and J. N. Vishwakarma, “KHSO4 Assisted Michael Addition- Elimi-Nation Reactions of Formylated Acetophenones in Water: A Facile General Green Route to 3-(Alkyl/aral- kyl/aryl)amino-1-arylprop-2-en-1-ones,” Journals of The Indian Chemical Society, Vol. 87, 2010, pp. 739-742.
[31] K. Bowden, E. A. Braude, E. R. H. Jones and B. C. L. Weedon, “Researches on Acetylinic Compounds. Part II. A. The Addition of Amines to Ethynyl Ketones. B. Auxochromic Properties and Conjugating Power of the Amino Group,” Journal of the Chemical Society, 1946, pp. 45-52.

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