An Overview of Synthesis of 5,5-Diphenyl-2,4-imidazolidinedione from Almond and Some Synthesis of 5-(alk-3-enyl)-2,4-imidazolidinediones
The synthesize of 5,5-diphenyl-2,4-imidazoli-dinedione (Phenytoin) from almond kernels as starting materials which were ground then, through steam distillation and extraction methods, almond oil and subsequently benzaldehyde were isolated and purified. Benzaldehyde react with sodium cyanide in presence of aqueous alcohol undergone a dimolecular condensation product, benzoin. Oxidation of benzoin yielded benzil. Benzil reacted with urea in basic alcoholic solution first gave benzilic acid, and then a condensation reaction with urea and after acidification of the filtrate gave phenytoin. Construction of 5-(alk-3-enyl)-hydantoins start from unsaturated carbonyl compounds, like aldehydes, ketones and ß-ketoesters, by multi component Bucherer-Bergs reaction conditions. Some of them were acetylated at N(1) position with acetanhydride. When a-allyl-ß-ketoesters were used as substrate an unexpected decarboxylation was observed. Decarboxylation was not observed only when 2-allyl-ethylacetoacetate was used for synthesis of hydantoin while in other cases fully decarboxylated products were obtained.
Browne TR. Drug therapy reviews: drug therapy of status epilepticus. Am J Hosp Pharm 1978; 35(8): 915-22.
Ashnagar A, Gharib Naseri N, Amini M. Synthesis of 5,5-Diphenyl-2,4-imidazolidinedione (Phenytoin) from Almond. International Journal of ChemTech Research 2009; 1(1): 47-52.
Baccolini G, Boga C, Delpivo C et al. Facile synthesis of hydantoins and thiohydantoins in aqueous solution. Tetrahedron Letters 2011; 521: 1713-17.
Dziedzic B, Szadowska A, Kaminska A. Synthesis and anticonvulsant activity of 3-(M-iodophenyl)-5-benzylidine derivatives of 2-thiohydantoin. Acta Pol Pharm 1978; 35(4): 429-32.
Rodgers TR, LaMontagne MP, Markovac A et al. Hydantoins as antitumor agents. J Med Chem 1977; 20(4): 591-94.
Brown ML, Brown GB, Brouillette WJ. Effects of log P and phenyl ring conformation on the binding of 5-phenylhydantoins to the voltage-dependent sodium channel. J Med Chem 1997; 40(4): 602-607.
Sanudo M, Garcia-Valverde M, Marcaccini S et al. A diastereoselective synthesis of pseudopeptidic hydantoins by an Ugi/cyclization/Ugi sequence. Tetrahedron 2012; 68(12): 2621-29.
Hroch L, Hruskova M, Schmitz J et al. 3, 5, 5-Trisubstituted Hydantoins from Activated (Benzyloxycarbonylamino) malonic Acids. Synthesis 2012; 44: 1907-14.
Spinks A, Waring WS. Progr Med Chem 1963; 3: 313.
Ojasoo T, Raynand JP. Prog Cancer Res Ther 1983; 25: 11.
Tezon JG, Vazquez MH, Blaquier JA. Androgen-controlled subcellular distribution of its receptor in the rat epididymis: 5alpha-dihydrotestosterone-induced translocation is blocked by antiandrogens. Endocrinology 1982; 111: 2039-45.
Lefebvre FA, Séguin C, Bélanger A et al. Combined long-term treatment with an LHRH agonist and a pure antiandrogen blocks androgenic influence in the rat. Prostate 1982; 3(6): 569-78.
Were E. The Chemistry of the Hydantoins. Chem Rev 1950; 46(3): 403-70.
Zhang D, Xing XC, Cuny GD. Synthesis of Hydantoins from Enantiomerically Pure α-Amino Amides without Epimerization. J Org Chem 2006; 71: 1750-53.
Volonterio A, Zanda M. Lett Org Chem 2005; 2: 44.
Montagne C, Shipman M. Modified Bucherer-Bergs Reaction for the One-Pot Synthesis of 5,5′-Disubstituted Hydantoins from Nitriles and Organometallic Reagents. Synlett 2006: 2203-206.
Montagne C, Shiers JJ, Shipman M. Rapid generation of molecular complexity using “sequenced” multi-component reactions: one-pot synthesis of 5,5′-disubstituted hydantoins from methyleneaziridines. Tetrahedron Letters 2006; 47(52): 9207-209.
Pavia DL, Lampman GM, Kriz GS. Introduction to Organic Laboratory Techniques, a Contemporary Approach. Saunders College Publishing, New York, 1982: 295, 303.
Biltz H. Ann 1909; 368: 243.
Biltz H. Ber 1908; 41: 169.
Porter CW. Molecular Rearrangements. Chemical Catalog Co. (Reinhold Publ. Corp.). New York, 1928: 96.
Hofmann K. The chemistry of Heterocycles: Imidazole and Its Derivatives. Interscience Publishers, New York, 1953; Part 1: 230.
Ashnagar A, Gharib Naseri N, Amini M. Synthesis of 5,5-Diphenyl-2,4-imidazolidinedione (Phenytoin) from Almond. Asian J Chem 2009; 21(7): 4976-80.
Weichet J, Hodrova J, Blaha L. Coll Czech Chem Commun 1966; 31: 1323.
Giroux J, Granger R, Beaulaton IS et al. Therapie 1959; 14: 42.
Smit B, Pavlovic RZ. Synthesis of novel 5-(alk-3-enyl)-hydantoins. The 16th International Electronic Conference on Synthetic Organic Chemistry, 1-30 Nov, 2012.
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