Hydantoin Derivatives And Applied Research

Hydantoin is one of five-membered heterocyclic ring compounds and its derivatives are used widely in the fields of medicine, pesticide, printing, resin and organic synthesis . The synthesis and application of some of hydantoin derivatives were studied in this paper. 1. Synthesis of hydantoin derivatives (I )Synthesis of 5,5-dialkyl hydantoin: 5,5-dimethylhydantoin, cyclohexanespiro- hydantoin,5-methyl-5-(6?methoxy??naphthyl)hydantoin,5-methyl-5-(5?bromo-6?methoxy- 2?naphthyl)hydantoin were directly synthesized with actone, cyclohexanone, 6-methoxy -2-acetylnaphthalene or 5-bromo-6-methoxy-2-acetylnaphthalene as substrate and sodium cyanide and ammonium carbonate as reagents in water or aqueous alcohol. The synthetic conditions of cyclohexanespirohydantoin were optimized through orthogonal experiments and effects of temperature , time, material ratio, volume of solvent,different solvent on the reaction were studied. This method of synthesis of hydantoins is simple, easy and with cheap materials and good yields. 5,5-Dimethylhydantoin,cyclohexanespirohydantoin,5-methyl-5- (6?methoxy-2?naphthyl)hydantoin were synthesized with the yields of 71 .3%, 87%, 86% and 84.2% respectively. (2) Synthesis of 5-aryl hydantoin: 5-(4?hydroxyphenyl)hydantoin, 5-(2拁4?dihydoxyphenyl)hydantoin, 5-(3?methyl-4-hydroxyphenyl)hydantoin and 5-(5?bromo- 6?hydroxy-2?naphthyl)hydantoin were synthesized using phenol, 3-benzenediol, o-cresol, or l-bromo-2-naphthol as substrate, allantoin as reagent, water or acetic acid as solvent and hydrochloride acid as catalyst,in one-step. The synthetic conditions of 5-(4?hydoxyphenyl)hydantoin were optimized through orthogonal experiments and the effects of temperature, time, material ratio, solvent and concentration of catalyst on reaction were studied. This method of synthesis of hydantoin is clean, easy and with simple final treatment. 5^{4拁Hydroxyphenyl}hydantoin,5^{2?4拁dihydroxyPheflyl}hYdantOin, 5-(3?methyl-4?hydroxy- phenyl)hydantoin and 5-(5?bromo-6?hydroxy-2?naphthyl)hydafltOifl were synthesized with the yields of 64.6%, 63.5%, 52.5%,81.8% and 52.3% respectively. Furthermore, I ,3-dihydroxymethyl-5,5-dirnethylhydantOifl, I ,3-dichloride-5,5-dimethyl- hydantoin(DCDM H), and I ,3-dibrorno-5,5-dimethylhydantoin(DBDM H) were synthesized by 5,5-methylhydantoin with the yields of 97%, 96.6% and 85% respectively. 2. Application of hydantoin derivatives. (I) Synthesis of am i no acid: 5.(4?hydroxyphenyl)hydantoin cyclohexanexanespiro- hydantoin, 5-methyl-5-(6?methoxy-2?naphthyl)hydantoin and 5-methyl-5-(5?bromo-6? methoxy-2?naphthyl)hydantoin were hydroxyzed in the presence of NaOH or Ba(OH)2 to synthesize 2-amino-2-(4?hydroxyphenyl)acetic acid, I -aminocyclohexane formic acid,2-amino-2-(6?niethoxy-2?naphthyl)propionic acid with the yields of 91.6%, 85.2%, 82% and 80.2% respectively; and the effects of concentration of alkli, reaction temperature, substrates, and different alkli on reaction were studied. (2)Halogenation on aromatic nucleus: the halogenating laws of I,3-dihalo-5,5-dirnethylhydantoin on aromatic nucleus were studied using l,3-dihalo-5,5-dimethylhydantoin as halogenat- ing agents and alkyl chloride, methanol or acetone as solvent. The discussion was focused on the halogenation of I ,3-dihalo-5,Sdimethylhydantoin with 2-methoxynaphthalene, and6-methoxy-2-acylnaphtha- lene in acetone and in the presence of hydr...