4,5ꢀDihydroxyimidazolidinꢀ2ꢀones (ꢀthiones)
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 1, January, 2012
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diately formed from the filtrate, which was filtered off. The filꢀ
trate was concentrated to dryness, the precipitate was washed
with water and dried. The ratio of diastereomers 2´d and 2d was
determined as 1 : 4. Together with the filtered precipitate of 2d,
the overall ratio of diastereomers 2´d and 2d was 1 : 99.
Compound 2´d. 1H NMR, : 1.05 (t, 6 H, Me, J = 7.2 Hz);
3.30—3.41 (m, 4 H, CH2); 7.20—7.29 (m, 4 H, Ph); 7.30—7.40
(m, 6 H, Ph).
Compound 2d. The yield was 37%, m.p. 162—164 C.5
Found (%): C, 66.72; H, 6.45; N, 8.22; S, 9.33. C19H22N2O2S.
Calculated (%): C, 66.64; H, 6.48; N, 8.18; S, 9.36.
2. A. N. Kravchenko, G. K. Kadorkina, A. S. Sigachev, E. Yu.
Maksareva, K. A. Lyssenko, P. A. Belyakov, O. V. Lebedev,
O. N. Kharybin, N. N. Makhova, R. G. Kostyanovsky, Menꢀ
deleev Commun., 2003, 114.
3. A. S. Sigachev, A. N. Kravchenko, G. A. Gazieva, P. A.
Belyakov, N. G. Kolotyirkina, O. V. Lebedev, N. N. Maꢀ
khova, J. Heterocycl. Chem., 2006, 1295.
4. Yu. V. Nelyubina, G. A. Gazieva, V. V. Baranov, P. A. Belyaꢀ
kov, A. O. Chizhov, K. A. Lyssenko, A. N. Kravchenko, Izv.
Akad. Nauk, Ser. Khim., 2009, 1315 [Russ. Chem. Bull., Int.
Ed., 2009, 58, 1353].
Synthesis of (4R*,5R*)ꢀ4,5ꢀdihydroxyꢀ1,3ꢀdimethylꢀ4,5ꢀ
diphenylimidazolidineꢀ2ꢀthione (2´f) and (4R*,5S*)ꢀ4,5ꢀdihydrꢀ
oxyꢀ1,3ꢀdimethylꢀ4,5ꢀdiphenylimidazolidineꢀ2ꢀthione (2f). A soꢀ
lution of KOH (0.03 mol) in water (5 mL) was added to a solution
of benzil (0.05 mol) and 1,3ꢀdimethylthiourea 5b (0.05 mol) in
methanol (50 mL). The reaction mixture was refluxed with stirꢀ
ring for 2 h, then concentrated to dryness. A precipitate of 2´f
and 2f was washed with water on the filter and dried. The ratio
of diastereomers 2´f and 2f was determined as 2 : 3.
5. V. V. Baranov, Yu. V. Nelyubina, K. A. Lyssenko, A. N.
Kravchenko, Mendeleev Commun., 2009, 19, 211.
6. E. Grillon, R. Gallo, M. Pierrot, J. Boileau, E. Wimmer,
Tetrahedron Lett., 1988, 29, 1015.
7. I. Ya. Slonim, B. M. Arshava, V. N. Keynikov, in Sovremenꢀ
nye aspekty YaMR spektroskopii polimerov [Modern Aspects of
NMR Spectroscopy of Polymers], S. V. Lebedev Research Inꢀ
stitute of Synthetic Rubber, StꢀPetersburg—Nizhnekamsk,
1994, 53 (in Russian).
Diastereoselective synthesis of (4R*,5S*)ꢀ4,5ꢀdihydroxyꢀ1,3ꢀ
dimethylꢀ4,5ꢀdiphenylimidazolidineꢀ2ꢀthione (2f). A solution of
KOH (0.03 mol) in water (5 mL) was added to a solution of
benzil (0.05 mol) and 1,3ꢀdimethylthiourea 5b (0.06 mol) in
methanol (50 mL). The reaction mixture was refluxed with stirꢀ
ring for 2 h, then cooled to ~20 C. Two days after, a precipitate
of 2f was filtered off. The filtrate was concentrated to dryness,
a precipitate of 2´f and 2f was washed with water on the filter
and dried. The ratio of diastereomers 2´f and 2f was determined
as 1 : 8. Together with the filtered precipitate of 2f, the overall
ratio of diastereomers 2´f and 2f was 1 : 11.
8. G. A. Gazieva, A. N. Kravchenko, O. V. Lebedev, Yu. A.
Strelenko, K. Yu. Chegaev, Izv. Akad. Nauk, Ser. Khim.,
1998, 1604 [Russ. Chem. Bull. (Engl. Transl.), 1998, 47, 1561].
9. A. Woerner, W. Rümens, Deutsches Pat. 962795, 1957;
Chem. Abstr., 1959, 53, 6092d.
10. M. T. Beachem, Pat. USA 3260565, 1966; Chem. Abstr.,
1967, 65, 12341.
11. R. Neville, J. Org. Chem., 1958, 23, 1588.
12. C. J. Broan, A. R. Butler, D. Reed, I. H. Sadler, J. Chem.
Soc., Perkin Trans. 2, 1989, 731.
13. A. R. Butler, E. Leitch, J. Chem. Soc., Perkin Trans. 2,
1977, 1972.
When 0.07 mol of 1,3ꢀdimethylthiourea 5b was used in a similar
experiment, the ratio of diastereomers 2´f and 2f changed to 1 : 13.
14. A. R. Butler, E. Leitch, J. Chem. Soc., Perkin Trans. 2,
1980, 103.
1
Compound 2´f. H NMR, : 2.94 (s, 6 H, Me); 7.14—7.19
(m, 4 H, Ph); 7.32—7.36 (m, 6 H, Ph).
15. H. Petersen, Textilveredlung, 1968, 3, 51.
Compound 2f. M.p. 170—172 C. 1H NMR, : 2.91 (s, 6 H,
Me); 6.80—6.93 (m, 4 H, Ph); 6.98—7.08 (m, 6 H, Ph).
13C NMR, : 30.16 (Me); 95.07 (s, Ph); 126.76, 127.30, 127.48
(CH, Ph); 137.71 (s, Ph); 183.63 (CS). Found (%): C, 64.97;
H, 5.75; N, 8.92; S, 10.26. C17H18N2O2S. Calculated (%):
C, 64.94; H, 5.77; N, 8.91; S, 10.20.
1,3ꢀDimethylꢀ5,5ꢀdiphenylꢀ2ꢀthioxoimidazolidinꢀ2ꢀone (10a).
A solution of KOH (0.03 mol) in water (5 mL) was added to
a solution of diastereomers 2´f—2f (2 : 3) (0.05 mol) and 1,3ꢀdiꢀ
methylthiourea 5b (0.01 mol) in methanol (50 mL). The reacꢀ
tion mixture was refluxed for 2 h and concentrated to dryness.
A precipitate of 10a was recrystallized from Et2O. The yield was
95%. M.p. 142—143 C.12 1H NMR, : 2.84 (s, 6 H, 2 Me);
6.78—7.09 (m, 10 H, 5 Ph). Found (%): C, 68.82; H, 5.41;
N, 9.46; S, 10.86. C17H16N2OS. Calculated (%): C, 68.89;
H, 5.44; N, 9.45; S, 10.82.
16. A. N. Kravchenko, K. A. Lyssenko, I. E. Chikunov, P. A.
Belyakov, M. M. Il´in, V. V. Baranov, Yu. V. Nelyubina,
V. A. Davankov, T. S. Pivina, N. N. Makhova, M. Yu. Anꢀ
tipin, Izv. Akad. Nauk, Ser. Khim., 2009, 390 [Russ. Chem.
Bull., Int. Ed., 2009, 58, 395].
17. A. N. Kravchenko, A. S. Sigachev, E. Yu. Maksareva, G. A.
Gazieva, N. S. Trunova, B. V. Lozhkin, T. S. Pivina, M. M.
Il´in, Yu. V. Nelyubina, V. A. Davankov, O. V. Lebedev,
N. N. Makhova, V. A. Tartakovsky, Izv. Akad. Nauk, Ser.
Khim., 2005, 680 [Russ. Chem. Bull., Int. Ed., 2005, 54, 691].
18. C. Song, Zh. Longjie, Zh. Chuanmeng, T. Xiuhong, S. Huaꢀ
jun, F. Xin, Q. Xuhong, Monatsh. Chem., 2008, 139, 923.
19. H. C. Carrington, W. S. Waring, J. Chem. Soc., 1950, 354.
20. V. V. Baranov, G. A. Gazieva, Yu. V. Nelyubina, A. N.
Kravchenko, N. N. Makhova, Zh. Org. Khim., 2011, 47, 1564
[Russ. J. Org. Chem. (Engl. Transl.), 2011, 47].
21. G. A. Gazieva, Yu. V. Nelyubina, A. N. Kravchenko, A. S.
Sigachev, I. V. Glukhov, M. I. Struchkova, K. A. Lyssenko,
N. N. Makhova, Izv. Akad. Nauk, Ser. Khim., 2009, 1884
[Russ. Chem. Bull., Int. Ed., 2009, 58, 1945].
22. G. M. Sheldrick, SHELXTL v. 5.10, Structure Determination
Software Suit, Bruker AXS, Madison, Wisconsin, USA, 1998.
This work was financially supported by the Division of
Chemistry and Materials Science of the Russian Academy
of Sciences (Program for Basic Research "Biomolecular
and Medical Chemistry" (OKhꢀ9)) and State Contract
No. 02.740.11.0258.
References
1. S. L. Vail, R. H. Barker, P. G. Mennitt, J. Org. Chem., 1965,
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Received September 6, 2011;
in revised form October 19, 2011