Molbank 2006, M480

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Synthesis of 5,5-diphenyl-3-(methylthiomethyl)hydantoin and 5,5-diphenyl-3-(methysulfonylomethyl)hydantoin

 

Maria Grzegożek* , Krystyna Nowak, Barbara Szpakiewicz

 

Institute of Organic Chemistry and Technology, Cracow University of Technology, ul. Warszawska 24, PL-31155 Kraków, Poland,

Tel/Fax (048-12) 628-20-37

e-mail: [email protected]

*Author to whom correspondence should be addressed

 

Received: 9 October 2005 / Accepted: 18 October 2005 / Published: 31 March 2006

 

Keywords: hydantoin derivatives, DMSO, oxidation

 

In view of potential biological activity of 5,5-diphenylhydantoin  derivatives (psychotropic  agents)[1-3] we obtained 5,5-diphenyl-3-(methylthiomethyl)hydantoin (2) in reaction of  5,5-diphenylhydantoin (1) with DMSO and subsequently undergo its oxidation reaction to 5,5-diphenyl-3-(methysulfonylomethyl)hydantoin (3) [4].

 

 

 

 

 

 

 

 

 

 

5,5-diphenyl-3-(methylthiomethyl)hydantoin (2)

A solution of  5,5-diphenylhydantoin (1) (commercial product) (17.5 g, 0.069 mol) in dimethylsulfoxide (DMSO, 350ml) was refluxed for 16 hrs, then cooled and poured into water (350 ml). The precipitated solid was filtered off, washed with water and dried. After two recrystalizations from methanol 5,5-diphenyl-3-methylthiomethylhydantoin (2, 20.5 g, 94.6%) was obtained as colorless needles.

 

Melting point: 124-131oC.

 

1H NMR (DMSO-d6, 80 MHz): δ= 9.80 (s, 1H, NH), 7.40 (s,10H, Ph), 4.56 (s, 2H, CH2), 2.15 (s, 3H, CH3).

 

IR (KBr, cm-1): 3270 (NH), 1780 (C=O).

 

MS (70eV) m/z (%): 312 (100), 297 (17.9), 265 (42.0), 251(67.9), 237 (100).

 

Elemental Analysis: Calculated for C17H16N2O2S (312.39): C 65.40, H 5.10, N 9.00; found C 65.20, H 5.10, N 8.80.

 

5,5-diphenyl-3-(methysulfonylomethyl)hydantoin (3)

A solution of 5,5-diphenyl-3-(methylthiomethyl)hydantoin (2) (5.0 g, 0.016mol), glacial acetic acid (100 ml) and 30% H2O2 (100 ml) was allowed to stand at room temperature for 20 hrs. Then the solution was neutralized with 50% NaOH to pH 7. The precipitated solid was filtered off, washed several times with water and dried. 5,5-Diphenyl-3-(methylsulfonyl-methyl)hydantoin (3, 5.1 g, 95.3%). After recrystallization from water-methanol (7:3) mixture, compound 3 as colorless needles (4.35 g, 81.3%) was obtained.

 

Melting point: 196-197oC

 

1H NMR (DMSO-d6, 80 MHz): δ= 9.98 (s, 1H, NH), 7.39 (s, 10H, Ph), 4.97 (s, 2H, CH2), 3.15 (s, 3H, CH3).

 

IR (KBr, cm-1): 3365 (NH), 1785 and 1734 (C=O), 1140 (SO2).

 

Elemental Analysis: Calculated for C17H16N2O4S (344.39): C 59.30, H 4.60, N 8.10; found C 59.10, H 4.60, N 8.00.

 

References:

1. W.O.Foye, Principles of Medicinal Chemistry, Lea & Febiger, Philadelphia, 1989.

2. C.Avendano-Lopez, G.Gonzalez-Trigo, Advances in Heterocyclic Chemistry (ed.:A.R.Katrizky), Academic Press, Inc., Orlando, 1985, 38, chapter 4.

3. R.L.Hudkins, D.L.DeHaven-Hudkind, Bioorg.Med.Chem.Lett. 1994, 4, 2185.

4. W.Czuba, M.Grzegożek, A.Kaniewska, K.Nowak, H.Poradowska, D.Sędzik-Hibner, B.Szpakiewicz, and C.Walkowicz, Pol.J.Chem., 60, 459 (1986).

 

Sample Availability: Available from MDPI.

 

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