A Procedure for Synthesis of 3-Halomethyl-4-oxothiazolidine-2-thiones

A Procedure for Synthesis of 3-Halomethyl-4-oxothiazolidine-2-thiones Russian Journal of Applied Chemistry, Vol. 75, No. 3, 2002, p. 513. Translated from Zhurnal Prikladnoi Khimii, Vol. 75, No. 3, 2002, p. 524. Original Russian Text Copyright C 2002 by Ginak, Aronova. BRIEF ˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝ ˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝ COMMUNICATIONS A Procedure for Synthesis of 3-Halomethyl-4-oxothiazolidine-2-thiones A. I. Ginak and E. B. Aronova St. Petersburg State Technological Institute, St. Petersburg, Russia Received October 23, 2001 Abstract-Solid-phase synthesis of 3-halomethyl-4-oxothiazolidine-2-thiones was perforomed. Halomethyl-4-oxothiazolidine-2-thiones, which are Elemental compositions and melting points of IIa3IIf ˜˜˜˜˜´˜˜˜˜˜˜˜´˜˜˜˜˜˜˜˜˜˜˜˜˜´˜˜˜˜˜˜˜˜˜˜˜˜ starting compounds for preparing biologically active ‡ ‡ Found, % ‡ substances [1], vulcanizing agents [2], and plant ‡ ‡ ˜˜˜˜˜˜˜˜˜˜ ‡ ‡‡ Calculated, % ‡ Com- growth stimulants [3], are synthesized by a multistage mp, oC Formula ‡ ˆ˜˜˜˜˜˜´˜˜˜˜˜˜· pound procedure via intermediate hydroxymethyl-4-oxothi- ‡‡ N ‡ S ‡ azolidine-2-thiones, with subsequent replacement of ˜˜˜˜˜¯˜˜˜˜˜˜˜¯˜˜˜˜˜˜¯˜˜˜˜˜˜¯˜˜˜˜˜˜˜˜˜˜˜˜ the hydroxy group in the methyl substituent under the ‡‡ 4.95 ‡ 23.60 ‡ action of SOCl , PBr , or HBr [4]. The procedure IIa ‡ 1923193 ‡ ˜˜˜˜ ‡ ˜˜˜˜ ‡C H ClNOS 2 3 11 8 2 ‡‡ 5.19 ‡ 23.77 ‡ involves the use of corrosive media and expensive ‡‡ 4.35 ‡ 20.23 ‡ IIb ‡ 1943195 ‡ ˜˜˜˜ ‡ ˜˜˜˜ ‡C H BrNOS chemicals; the loss in each stage reaches 25%. 11 8 2 ‡‡ 4.46 ‡ 20.41 ‡ ‡‡ 3.65 ‡ 17.20 ‡ We have developed a single-stage solid-phase pro- IIc ‡ 1873188 ‡ ˜˜˜˜ ‡ ˜˜˜˜ ‡C H INOS 11 8 2 ‡‡ 3.88 ‡ 17.75 ‡ cedure for preparing 3-halomethyl-4-oxothiazolidine- ‡‡ 4.62 ‡ 22.15 ‡ 2-thiones IIa3IIf by reaction of the vapors of the IId ‡ 1873188 ‡ ˜˜˜˜ ‡ ˜˜˜˜ ‡C H ClNOS 12 10 2 ‡‡ 4.91 ‡ 22.59 ‡ corresponding methylene dihalides with crystalline ‡‡ 3.94 ‡ 4.21 ‡ alkali metal salts of 4-oxothiazolidine-2-thiones I.It is IIe ‡ 1893190 ‡ ˜˜˜˜ ‡ ˜˜˜˜ ‡C H BrNOS 12 10 2 ‡‡ 4.21 ‡ 19.59 ‡ known [5] that crystals of ambifunctional compounds ‡‡ 9.34 ‡ 8.97 ‡ IIf ‡ 1513152 ‡ ˜˜˜˜ ‡ ˜˜˜˜ ‡C H ClN O S exhibit anisotropic reactivity on various crystal faces. 11 7 2 3 2 ‡‡ 8.97 ‡ 20.37 ‡ This property was used to develop a synthetic process. ˜˜˜˜˜`˜˜˜˜˜˜˜`˜˜˜˜˜˜`˜˜˜˜˜˜`˜˜˜˜˜˜˜˜˜˜˜˜ Lithium, sodium, potassium, and cesium salts of 4-oxothiazolidine-2-thiones were crystallized from The reaction was performed in an electrically heated temperature-controlled (70 3250oC) tubular organic solvents (methanol, acetone, acetonitrile, di- reactor (1 cm in diameter, 10 cm high). Alkylating methylformamide), and the crystals that exhibited the agent vapor was passed through a bed of the substrate. strongest anisotropy in alkylation were selected. The reaction progress was monitored by TLC. We found that the most anisotropic were the lithium salts of REFERENCES 4-oxothiazolidine-2-thiones crystallized from meth- 1. Brown, F.C., Chem. Rev., 1961, vol. 61, no. 5, pp. 4633 anol: the yield of the target products (see table) ex- ceeded 95%. 2. Sheshina, G.M., Ratnikova, T.V., and Ginak, A.I., c c c c c c c c c c c c MN MN XC XCH H N N C C O O C C O O Kauch. Rezina, 1978, no. 5, pp. 16 318. CH CH X X 2 2 2 2 2 2 g g g g g g g g 77 776 6 c cc c c c c c c cc c c c c c 3. Mel’nikov, N.N., Volkov, A.I., and Korotkova, O.A., S S C C C C 3 3 S S C C C C CH CHC C H H R R , , CH CHC C H H R R MX MX 4 4 64 64 6 6 e e i i e e i i S S S S Pestitsidy i okruzhayushchaya sreda (Pesticides and Environment), Leningrad: Khimiya, 1977. IIa IIa3 3IIf IIf I I 4. Borisova, M.A., Ginak, A.I., and Sochilin, E.G., Zh. where M = Li, Na, R, Cs; X = Cl, R = H (IIa); X = Org. Khim., 1972, vol. 8, no. 7, pp. 1536 31538. Br, R = H (IIb); X= I, R = H(IIc); X = Cl, R = 5. Dymshits, V.A., Khimiya organicheskikh kristallov p-CH (IId); X = Br, R = p-CH (IIe); X = Cl, R = (Chemistry of Organic Crystals), St. Petersburg: Khi- 3 3 m-NO (IIf). miya, 1994. 1070-4272/02/7503-0513$27.00 C 2002 MAIK [Nauka/Interperiodica] http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Russian Journal of Applied Chemistry Springer Journals

A Procedure for Synthesis of 3-Halomethyl-4-oxothiazolidine-2-thiones

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Kluwer Academic Publishers-Plenum Publishers
Copyright
Copyright © 2002 by MAIK “Nauka/Interperiodica”
Subject
Chemistry; Chemistry/Food Science, general
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1070-4272
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1608-3296
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10.1023/A:1016192115787
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Abstract

Russian Journal of Applied Chemistry, Vol. 75, No. 3, 2002, p. 513. Translated from Zhurnal Prikladnoi Khimii, Vol. 75, No. 3, 2002, p. 524. Original Russian Text Copyright C 2002 by Ginak, Aronova. BRIEF ˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝ ˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝˝ COMMUNICATIONS A Procedure for Synthesis of 3-Halomethyl-4-oxothiazolidine-2-thiones A. I. Ginak and E. B. Aronova St. Petersburg State Technological Institute, St. Petersburg, Russia Received October 23, 2001 Abstract-Solid-phase synthesis of 3-halomethyl-4-oxothiazolidine-2-thiones was perforomed. Halomethyl-4-oxothiazolidine-2-thiones, which are Elemental compositions and melting points of IIa3IIf ˜˜˜˜˜´˜˜˜˜˜˜˜´˜˜˜˜˜˜˜˜˜˜˜˜˜´˜˜˜˜˜˜˜˜˜˜˜˜ starting compounds for preparing biologically active ‡ ‡ Found, % ‡ substances [1], vulcanizing agents [2], and plant ‡ ‡ ˜˜˜˜˜˜˜˜˜˜ ‡ ‡‡ Calculated, % ‡ Com- growth stimulants [3], are synthesized by a multistage mp, oC Formula ‡ ˆ˜˜˜˜˜˜´˜˜˜˜˜˜· pound procedure via intermediate hydroxymethyl-4-oxothi- ‡‡ N ‡ S ‡ azolidine-2-thiones, with subsequent replacement of ˜˜˜˜˜¯˜˜˜˜˜˜˜¯˜˜˜˜˜˜¯˜˜˜˜˜˜¯˜˜˜˜˜˜˜˜˜˜˜˜ the hydroxy group in the methyl substituent under the ‡‡ 4.95 ‡ 23.60 ‡ action of SOCl , PBr , or HBr [4]. The procedure IIa ‡ 1923193 ‡ ˜˜˜˜ ‡ ˜˜˜˜ ‡C H ClNOS 2 3 11 8 2 ‡‡ 5.19 ‡ 23.77 ‡ involves the use of corrosive media and expensive ‡‡ 4.35 ‡ 20.23 ‡ IIb ‡ 1943195 ‡ ˜˜˜˜ ‡ ˜˜˜˜ ‡C H BrNOS chemicals; the loss in each stage reaches 25%. 11 8 2 ‡‡ 4.46 ‡ 20.41 ‡ ‡‡ 3.65 ‡ 17.20 ‡ We have developed a single-stage solid-phase pro- IIc ‡ 1873188 ‡ ˜˜˜˜ ‡ ˜˜˜˜ ‡C H INOS 11 8 2 ‡‡ 3.88 ‡ 17.75 ‡ cedure for preparing 3-halomethyl-4-oxothiazolidine- ‡‡ 4.62 ‡ 22.15 ‡ 2-thiones IIa3IIf by reaction of the vapors of the IId ‡ 1873188 ‡ ˜˜˜˜ ‡ ˜˜˜˜ ‡C H ClNOS 12 10 2 ‡‡ 4.91 ‡ 22.59 ‡ corresponding methylene dihalides with crystalline ‡‡ 3.94 ‡ 4.21 ‡ alkali metal salts of 4-oxothiazolidine-2-thiones I.It is IIe ‡ 1893190 ‡ ˜˜˜˜ ‡ ˜˜˜˜ ‡C H BrNOS 12 10 2 ‡‡ 4.21 ‡ 19.59 ‡ known [5] that crystals of ambifunctional compounds ‡‡ 9.34 ‡ 8.97 ‡ IIf ‡ 1513152 ‡ ˜˜˜˜ ‡ ˜˜˜˜ ‡C H ClN O S exhibit anisotropic reactivity on various crystal faces. 11 7 2 3 2 ‡‡ 8.97 ‡ 20.37 ‡ This property was used to develop a synthetic process. ˜˜˜˜˜`˜˜˜˜˜˜˜`˜˜˜˜˜˜`˜˜˜˜˜˜`˜˜˜˜˜˜˜˜˜˜˜˜ Lithium, sodium, potassium, and cesium salts of 4-oxothiazolidine-2-thiones were crystallized from The reaction was performed in an electrically heated temperature-controlled (70 3250oC) tubular organic solvents (methanol, acetone, acetonitrile, di- reactor (1 cm in diameter, 10 cm high). Alkylating methylformamide), and the crystals that exhibited the agent vapor was passed through a bed of the substrate. strongest anisotropy in alkylation were selected. The reaction progress was monitored by TLC. We found that the most anisotropic were the lithium salts of REFERENCES 4-oxothiazolidine-2-thiones crystallized from meth- 1. Brown, F.C., Chem. Rev., 1961, vol. 61, no. 5, pp. 4633 anol: the yield of the target products (see table) ex- ceeded 95%. 2. Sheshina, G.M., Ratnikova, T.V., and Ginak, A.I., c c c c c c c c c c c c MN MN XC XCH H N N C C O O C C O O Kauch. Rezina, 1978, no. 5, pp. 16 318. CH CH X X 2 2 2 2 2 2 g g g g g g g g 77 776 6 c cc c c c c c c cc c c c c c 3. Mel’nikov, N.N., Volkov, A.I., and Korotkova, O.A., S S C C C C 3 3 S S C C C C CH CHC C H H R R , , CH CHC C H H R R MX MX 4 4 64 64 6 6 e e i i e e i i S S S S Pestitsidy i okruzhayushchaya sreda (Pesticides and Environment), Leningrad: Khimiya, 1977. IIa IIa3 3IIf IIf I I 4. Borisova, M.A., Ginak, A.I., and Sochilin, E.G., Zh. where M = Li, Na, R, Cs; X = Cl, R = H (IIa); X = Org. Khim., 1972, vol. 8, no. 7, pp. 1536 31538. Br, R = H (IIb); X= I, R = H(IIc); X = Cl, R = 5. Dymshits, V.A., Khimiya organicheskikh kristallov p-CH (IId); X = Br, R = p-CH (IIe); X = Cl, R = (Chemistry of Organic Crystals), St. Petersburg: Khi- 3 3 m-NO (IIf). miya, 1994. 1070-4272/02/7503-0513$27.00 C 2002 MAIK [Nauka/Interperiodica]

Journal

Russian Journal of Applied ChemistrySpringer Journals

Published: Oct 13, 2004

References

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