ISSN print edition: 0366-6352 ISSN electronic edition: 1336-9075 Registr. No.: MK SR 9/7 Published monthly

Synthesis of arylthio-s-triazines

J.Drábek and M. Škrobal

Forechungsinstitut fur agrochemische Technologie, Bratislava

Abstract: A series of 2-substituted 4,6-dichloro-s-triazines (Ia) was prepd. by reaction of cyanuric chloride (I) with a thiophenol, phenol, or sulfonamide in aq. Me₂CO, followed by neutralization with NaOH. This procedure proved to be superior to a direct reaction of I with a Na thiophenolate in which 2,4-disubstitution predominated. Thus, a soln. of 18.4 g. I in 25 ml. Me₂CO was added dropwise under stirring to 100 ml. H₂O at 0-5°. After 5 min., a soln. of 11 g. PhSH in 25 ml. of Me₂CO was added, stirring continued 30 min. at 0-5°, 4 g. NaOH in 25 ml. H₂O added dropwise, the reaction mixt. stirred 30 min., extd. with C₆H₆, and the ext. evapd. to give 94.2% Ia (R = PhS, R1 = Cl) (II), m. 72°. Similarly, the following Ia were prepd. (R, R1, m.p., and % yield given): 4-MeC₆H₄S, Cl (III), 111°, 98.5; 2-MeC₆H₄S, Cl (IV), -, 95.6; 4-ClC₆H₄S, Cl (V), 120°, 96; 2,5-Cl₂C₆H₃S, Cl (VI), 110°, 93.5; 2-O₂NC₆H₄S, Cl (VII), 153°, 85; C₁₂H₂₆NH, Cl (VIII) 65°; 63; C₁₈H₃₇NH, Cl (IX), 67°, 65. A soln. of 9.2 g. I in 50 ml. of Me₂CO was added dropwise to 50 ml. H₂O at ∼0°. To this suspension, a soln. of 7.25 g. 4-ClC₆H₄SH and 2 g. NaOH in 30 ml. H₂O was added dropwise at 0°, the mixt. stirred 30 min., and extd. with C₆H₆ to yield 24% 2,4-bis(4-chlorothiophenyl)-6-chloro-s-triazine (X), m. 168°. Analogously, 23% Ia (R = R1 = 2,5-Cl₂C₆H₃S) XI, m. 144°, was obtained. I (9.2 g.), 14.1 g. pentachlorothiophenol, and 2.1 g. of NaOH similarly afforded 65 Ia (R = C₆Cl₅S, R1 = Cl), XII, m. 182°, and 10% Ia (R = R1 = C₆Cl₅S) XIII. Also, 18.4 g. I, 19.7 g. 2,4,5-Cl₃C₆H₂OH, and 4.1 g. NaOH yielded 61% Ia (R = R1 = 2,4,5-Cl₃C₆H₂O) XIV, m. 187.5°, and 34% Ia (R = 2,4,5-Cl₃C₆H₂O, R1 = Cl) (XV), m. 134.5°, while 15.5 g. I, 23 g. 2,4,5-Cl₃C₆H₂SO₂NHMe, and 3.5 g. of NaOH gave 43% Ia (R = 2,4,5-Cl₃C₆H₂SO₂NMe, R1 = Cl) XVI, m. 147°. To a soln. of 17.1g. I in 150 ml. of C₆H₆, 18 g. powd. Na salt of 2-MeC₆H₄SO₂NH₂ was added, and the mixt. stirred at room temp. 20 min. and then 3 hrs. at 80° to give 62% Ia (R = 2-MeC₆H₄SO₂NH, R1 = Cl) (XVII), m. 162°. The E.D.50 (p.p.m.) of the following compds. against Sclerotinia fructicola were given: 2-(o-chloroanilino) 4,6-dichloro-s-triazine, 0.75-3.9; II, 0.20; III, 0.22; IV, 0.42; V, 0.47; VI, 1.15; VII, 0.24; XIV, 16.8; XV, 10; XVI, 52; XVII, 22; 2-(o-toluidino)-4,6-dichloro-s-triazine, 7.9. VIII, IX, X, and XI were ineffective; XII and XIII were not tested. 25 references.

Full paper in Portable Document Format: 177a482.pdf (in Slovak)

Chemical Papers 17 (7) 482–487 (1963)