2002 60 7, 1303 1310 ACTA CHIMICA SINICA Vol. 60, 2002 No. 7, 1303 1310 2( 1 H21,2,42 212 )2 2 ( 300071) Ξ Ξ 22(1 H21,2,42 212 )222 212 (2) 1,42, 3,,. R 1, R 1 = (CH 3 ) 3 C, R 1 = Ar, Ar., 1,42,, Studies on Synthesis and Biological Activities of 2( 1 H21,2,42 Triazol212yl)2 2Arylthioethyl Substituted Phenyl Ketones CHEN, Wen2Bin ZHANG, Yao2Mou J IN, Gui2Yu Ξ ( State Key Laboratory of Elemento2Organic Chemistry, Institute of Elemento2Organic Chemistry, Nankai University, Tianjin 300071) Abstract The title compounds (3) have been prepared by 1,42nucleophilic addition of 22(1 H21,2,42triazol2 12yl ) 222propen212one with substituted thiophenol or heterocyclic compounds containing mercapto group. Structures of these compounds were characterized by elemental analysis, 1 H NMR and IR spectral data. The results of biological evaluation reveal that most of the compounds possess good fungicidal activities. The study of the relationship of structure and activity indicates that substituent R 1 has significant effect on biological activities of the compounds. Compounds 3 exhibit higher activity against Puccinia recondita in wheat when R 1 is (CH 3 ) 3 C, than when R 1 is Ar, while the substituents on group Ar have little effect on activities. Keywords triazole, 1,42nucleophilic addition, synthesis, biological activities,, 3,,, Scheme 1.., 1 [1 4 ],,, 1. 1 [5,6 1,42, ] 1 H NMR AC2P200,TMS, Ξ E2mail : wbchen @eyou. com Received December 21, 2001 ; revised March 1, 2002 ; accepted April 4, 2002. (No. 29832050).
1304 Vol. 60, 2002 Scheme 1 MgSO 4, /, 3 (R 1 = Ar), 7818 % 9515 %., 1179 g (0101 mol) 22(1H2 1, 2, 42 212 )24,42 212 232 2 (R 1 = (CH 3 ) 3 C) 01012 mol 30 ml, 30 40 2 h,, 3 [ R 1 = (CH 3 ) 3 C], 7719 % 9516 %. 1 H NMR IR, 1, 2.,CDCl 3. MT23 C/ H/ N 2. IR NICOLET 5DX. X24.. 200 300,,. 2, 1. 2 2 1. 2. 1 2 [ R 1 = (CH 3 ) 3 C] 20 g (0115 mol) 2 (1) [ R 1 = Ac 2 O, 22(1 H21,2,42 212 )24,42 (CH 3 ) 3 C],33 ml 37 %,15 ml 212 232 (2) [ R 1 = ( CH 100 ml, 4 h, 3 ) 3 C ]. 2,, 20 g (R 1 = Ar),Ogata [8 ] 2, 6717 %. (1) N, N, N, N 2 (TMDAM) 75 ml,, ( X 1 = Cl, Y = 44 % ;X 110 115 h, 1 = F, Y = 26 %). 2,., 1,, 108 112 / 133 Pa, 1210 g,, 6710 %. 1. 2. 2 2 (R 1 = Ar) 50 ml 2(1 H21,2,42 212 ) (1) ( R 1 = Ar) 0101 mol,30 ml, 0145 g (01015 mol), HCl,, 2 h,,,, 6214 % 6911 %. 1. 3 3 50 ml 12 222(1 H21,2,42 212 )222 212 (2) (R 1 = Ar) 110 mmol, 10 ml,, 112 mmol, 1 2 h, 20 ml 5 % NaOH,, 10 ml 3, 2. 1 2. 1. 1 2, R 1 = (CH 3 ) 3 C, [7 ], 21 H21,2,42 212 )23,32 222 (1),
No. 7 : 2(1 H21,2,42 212 )2 2 1305 HCl,pH,.,, 1 115, 2 3 h,. 2 1 H NMR. 2. 1. 2 3, 2, 1,42,,. R 1 ( t2bu Ar), R 1 = (CH 3 ) 3 C, 2 R 1 = Ar,,, (30 40 ), R 1 = Ar,,, [9 ],, R 1, R 2., HCl. 3 1 H ph 3 4,pH, NMR IR, 1, 2. 1 3 Table 1 The data of compounds 3 m. p. / Yield/ R 1 R 2 % 3a 42ClC 6 H 4 42ClC 6 H 4 94 5 92. 6 3b 42ClC 6 H 4 42FC 6 H 4 85 6 94. 1 3c 42ClC 6 H 4 42CH 3 C 6 H 4 122 3 93. 8 3d 42ClC 6 H 4 C 6 H 5 116 7 95. 5 3e C 6 H 5 42ClC 6 H 4 140 2 85. 4 3f C 6 H 5 42CH 3 C 6 H 4 146 8 91. 8 3g C 6 H 5 42FC 6 H 4 102 3 87. 7 3h C 6 H 5 C 6 H 5 144 5 90. 6 3i 42FC 6 H 4 C 6 H 5 79 80 78. 9 3j 42FC 6 H 4 42CH 3 C 6 H 4 92 4 82. 9 3k 42FC 6 H 4 42ClC 6 H 4 90 1 81. 6 3l 42FC 6 H 4 42FC 6 H 4 80 2 79. 7 3m 42BrC 6 H 4 42ClC 6 H 4 130 1 78. 8 Elemental analyses ( %, Calcd. ) C H N 53. 97 3. 56 11. 03 (53. 97) (3. 44) (11. 11) 56. 33 3. 48 11. 62 (56. 43) (3. 59) (11. 62) 60. 33 4. 25 11. 81 (60. 42) (4. 48) (11. 75) 59. 12 4. 17 12. 32 (59. 39) (4. 08) (12. 23) 58. 57 3. 98 12. 22 (59. 39) (4. 08) (12. 23) 66. 59 4. 95 13. 09 (66. 87) (5. 26) (13. 00) 62. 15 4. 06 12. 84 (62. 39) (4. 28) (12. 84) 65. 98 4. 61 13. 65 (66. 02) (4. 85) (13. 59) 62. 20 4. 30 12. 81 (62. 39) (4. 28) (12. 85) 63. 15 4. 62 12. 20 (63. 34) (4. 69) (12. 32) 56. 20 3. 57 11. 61 (56. 43) (3. 60) (11. 62) 58. 87 3. 85 12. 25 (59. 13) (3. 77) (12. 17) 48. 15 3. 20 9. 72 (48. 28) (3. 08) (9. 94)
1306 Vol. 60, 2002 m. p. / Yield/ R 1 R 2 % 3n (CH 3 ) 3 C C 6 H 5 49 50 93. 6 3o (CH 3 ) 3 C 42ClC 6 H 4 64 5 90. 1 3p (CH 3 ) 3 C 42CH 3 C 6 H 4 52 3 79. 2 3q (CH 3 ) 3 C CH 2 C 6 H 5 72 4 95. 6 Thick 3r (CH 3 ) 3 C R 3 liquid 91. 5 3s (CH 3 ) 3 C R 4 118 9 91. 0 3t (CH 3 ) 3 C R 5 126 7 97. 6 3u (CH 3 ) 3 C R 6 128 9 81. 0 Thick 3v (CH 3 ) 3 C R 7 liquid 83. 4 3w (CH 3 ) 3 C R 8 52 4 77. 9 3x (CH 3 ) 3 C R 9 119 21P 78. 0 Elemental analyses ( %, Calcd. ) C H N 62. 05 6. 54 14. 79 (62. 25) (6. 62) (14. 52) 55. 60 5. 65 12. 88 (55. 63) (5. 60) (12. 98) 63. 09 7. 00 13. 70 (63. 33) (6. 98) (13. 85) 63. 56 7. 02 13. 95 (63. 33) (6. 98) (13. 85) 66. 74 8. 16 11. 56 (66. 85) (8. 08) (11. 69) 56. 10 6. 94 21. 79 (56. 40) (6. 63) (21. 92) 57. 46 6. 78 20. 95 (57. 63) (6. 95) (21. 00) 58. 44 6. 20 22. 45 (58. 36) (5. 99) (22. 68) 57. 26 6. 14 21. 15 (57. 00) (6. 00) (21. 00) 59. 20 6. 51 21. 49 (59. 35) (6. 29) (21. 86) 55. 54 5. 13 15. 99 (55. 47) (5. 24) (16. 17) 2 3 IR 1 H NMR Table 2 IR and 1 H NMR data of compounds 3 IR ( / cm - 1, KBr) C O C N (Tr) C H (Tr) 1 H NMR (CDCl 3 / TMS), J H2H (Hz) 3a 1684 1502, 1475 3089 3b 1681 1501, 1432 3086 3168 (d, J = 7105, 2H, CH 2 S), 6124 (t, 1H, CH), 6198 7. 14 (m, 4H, C 6 H 4 ), 7148 7. 64 (m, 4H, C 6 H 4 ), 8113 (s, 1H, TrH), 9161 (s, 1H, TrH) 3152 3. 66 (m, 2H, CH 2 S), 5. 98 6. 14 (m, 1H, CH), 6. 96 7. 06 (m, 4H, C 6 H 4 ), 7148 7. 60 (m, 4H, C 6 H 4 ), 7198 (s, 1H, TrH), 8183 (s, 1H, TrH)
No. 7 : 2(1 H21,2,42 212 )2 2 1307 IR ( / cm - 1, KBr) C O C N (Tr) C H (Tr) 1 H NMR (CDCl 3 / TMS), J H2H (Hz) 3c 1684 1501, 1418 3087 3d 1683 1502, 1423 3085 3e 1684 1503, 1426 3085 3f 1683 1501, 1445 3084 3g 1687 1504, 1445 3081 3h 1687 1501, 1478 3081 3i 1684 1502, 1426 3085 3j 1683 1501, 1432 3087 3k 1678 1501, 1473 3086 3l 1679 1501, 1464 3087 3m 1683 1501, 1476 3083 3n 1713 1502, 1478 3120 2134 (s, 3H, CH 3 ), 3159 (dq, 2H, CH 2 S), 6106 (q, 1H, CH), 7119 7125 (m, 4H, C 6 H 4 ), 7147 7156 (m, 4H, C 6 H 4 ), 8103 (s, 1H, TrH), 8199 (s, 1H, TrH) 3163 (dq, 2H, CH 2 S), 6101 (q, 1H, CH), 7130 (s, 5H, C 6 H 5 ), 7142 7156 (m, 4H, C 6 H 4 ), 7192 (s, 1H, TrH), 8152 (s, 1H, TrH) 3161 ( dq, 2H, CH 2 S), 6105 ( q, 1H, CH), 7132 7146 (m, 4H, C 6 H 4 ), 7153 7190 (m, 5H, C 6 H 5 ), 7192 ( s, 1H, TrH), 8152 (s, 1H, TrH) 2133 (s, 3H, CH 3 ), 3159 (dq, 2H, CH 2 S), 6108 (q, 1H, CH), 7112 7124 (m, 4H, C 6 H 4 ), 7138 7174 (m, 5H, C 6 H 5 ), 7199 (s, 1H, TrH), 8176 (s, 1H, TrH) 3165 ( d, J = 6184, 2H, CH 2 S), 6124 ( t, 1H, CH), 7135 7176 (m, 9H, C 6 H 5, C 6 H 4 ), 8113 ( s, 1H, TrH), 9151 (s, 1H, TrH) 3164 (dq, 2H, CH 2 S), 6111 (q, 1H, CH), 7127 7142, 7154 7162, 7171 7175 (m, 10H, 2 C 6 H 5 ), 7197 ( s, 1H, TrH), 8174 (s, 1H, TrH) 3167 ( d, 2H, J = 7108, CH 2 S), 6118 ( t, 1H, CH), 7102 7112, 7129 7135, 7174 7184 ( m, 9H, C 6 H 4, C 6 H 5 ), 8106 (s, 1H, TrH), 9126 (s, 1H, TrH) 2133 (s, 3H, CH 3 ), 3161 (dq, 2H, CH 2 S), 6104 (q, 1H, CH), 7105 7127, 7173 7182 (m, 8H, 2 C 6 H 4 ), 7199 (s, 1H, TrH), 8163 (s, 1H, TrH) 3164 (dq, 2H, CH 2 S), 6114 (q, 1H, CH), 7105 7113, 7122 7133, 7178 7185 (m, 8H, 2 C 6 H 4 ), 8102 ( s, 1H, TrH), 9102 (s, 1H, TrH) 3163 ( d, 2H, J = 5165, CH 2 S), 6117 ( t, 1H, CH), 6199 7114, 7132 7143, 7176 7184 (m, 8H, 2 C 6 H 4 ), 8104 (s, 1H, TrH), 9111 (s, 1H, TrH) 3164 ( dq, 2H, CH 2 S), 6111 ( q, 1H, CH), 7123 7129 (m, 4H, C 6 H 4 ), 7154 7164 (m, 4H, C 6 H 4 ), 8102 ( s, 1H, TrH), 9101 (s, 1H, TrH) 1105 ( s, 9H, ( CH 3 ) 3 C), 3131 3149 ( m, 2H, CH 2 ), 5148 5158 (t, 1H, CH), 7124 7134 (m, 5H, C 6 H 5 ), 7191 (s, 1H, TrH), 8125 (s, 1H, TrH)
1308 Vol. 60, 2002 Compd1 IR ( / cm - 1, KBr) C O C N (Tr) C H (Tr) 1 H NMR (CDCl 3 / TMS), J H2H (Hz) 3o 1710 1501, 1474 3090 3p 1711 1501, 1473 3105 1109 ( s, 9H, ( CH 3 ) 3 C), 3137 3152 ( m, 2H, CH 2 ), 5148 5164 (t, 1H, CH), 7124 7132 (m, 4H, C 6 H 4 ), 7188 (s, 1H, TrH), 8116 (s, 1H, TrH) 1101 (s, 9H, (CH 3 ) 3 C), 2128 ( s,3h,ch 3 ), 3120 3148 (m, 2H, CH 2 ), 5146 5152 (t, 1H, CH), 7106 7124 (m, 4H, C 6 H 4 ),7188 (s, 1H, TrH), 8116 (s, 1H, TrH) 3q 1707 1496, 1470 3098 1104 ( s, 9H, ( CH 3 ) 3 C), 2181 3117 ( m, 2H, CH 2 ), 3161, 3163 ( d, 2H, CH 2 ), 5129 5133 (t, 1H, CH), 7129 7133 (m, 5H, C 6 H 5 ),7190 (s, 1H, TrH), 8111 (s, 1H, TrH) 3r 1708 1502, 1476 3089 3s 1707 1501, 1464 3096 3t 1709 1501, 1471 3100 1103 (s, 9H, (CH 3 ) 3 C), 1130 (s, 9H, (CH 3 ) 3 C) 2182 3169 (m, 2H, CH 2 ), 3159, 3161 ( d, 2H, CH 2 ) 5123 5132 (t, 1H, CH), 7120 7138 (m, 4H, C 6 H 4 ),7189 (s, 1H, TrH), 8132 (s, 1H, TrH) 1118 (s, 9H, (CH 3 ) 3 C), 2139 (s, 6H, 2 CH 3 ), 3144 3188 (m, 2H, CH 2 ), 5194 6104 (q, 1H, CH), 6174 (s, 1H,C 4 HN 2 ), 7191 (s, 1H, TrH), 8125 (s, 1H, TrH) 1117 ( s, 9H, (CH 3 ) 3 C), 2113 ( s, 3H, CH 3 ), 2143 ( s, 6H, 2 CH 3 ), 3146 3183 (m, 2H, CH 2 ), 5194 6102 (m, 1H, CH), 7192, 8133 (ds, 2H, 2 TrH) 3u 1709 1499, 1478 3109 1121 (s, 9H, (CH 3 ) 3 C), 2103 (s, 3H, CH 3 ), 4168 4173 (m, 2H, CH 2 ), 6142 6150 (t, 1H, CH), 7124 7151 (m, 5H, C 6 H 5 ), 7190 (s, 1H, TrH), 8144 (s, 1H, TrH) 3v 1707 1503, 1488 3095 1122 ( s, 9H, (CH 3 ) 3 C), 2103 ( s, 3H, CH 3 ), 3164 ( s, 3H, OCH 3 ), 4168 4172 (d, 2H, CH 2 ), 6142 6150 (t, 1H, CH), 6196 7116 (m, 4H, C 6 ), 7194 (s, 1H, TrH), 8154 (s, 1H, TrH) 3w 1713 1522, 1475 3189 1118 (s, 9H, (CH 3 ) 3 C), 2102 (s, 3H, CH 3 ), 4152 4177 (m, 2H, CH 2 ), 5115 (s, 2H, CH 2 ), 6138 6146 (t, 1H, CH), 7115 7126 (m, 5H, C 6 H 5 ), 7179 ( s, 1H, TrH), 8136 (s, 1H, TrH) 3x 1710 1501, 1459 3093 1122 ( s, 9H, ( CH 3 ) 3 C), 3167 4131 ( m, 2H, CH 2 ), 6119 6127 (q, 1H, CH), 7132 7187 (m, 4H, C 7 H 4 NS), 7190 (s, 1H, TrH), 8144 (s, 1H, TrH)
No. 7 : 2(1 H21,2,42 212 )2 2 1309 2. 2 3 2. 3 1680 cm - 1, C H 3100 cm - 1,,, C N 1510 cm - 1, 3, 1480 cm - 1, 2 R 1 = Ar, 3f.. 80 %,, 3 (313 317),, 3b, 3k,, CH 2 A ; R 1 = t2bu, ABX AB, 3, [10 ], 90 %,, ;, 60 % 90 %. 3 5. 3 3 Table 3 The fungicidal activities against Puccinia recondita in wheat of compounds 3 (500) / % / % / % / % 3a 10 3g 20 3m 10 3s 100 3b 20 3h 40 3n 100 3t 100 3c 10 3i 20 3o 20 3u 100 3d 0 3j 10 3p 100 3v - 3e 0 3k 50 3q 0 3 w 93. 5 3f 80 3l 30 3r 80 3x 90 4 3 Table 4 The fungicidal activities of compounds 3 / % (500) (50) 3a 10 0 71. 4 92. 5 84. 2 52. 2 42. 9 3b 15 0 100 100 89. 5 78. 3P 71. 4 3c 0 0 35. 7 87. 5 84. 2 30. 4 42. 9 3d 0 0 35. 7 75. 0 68. 4 39. 1 42. 9 3k 40-100 96. 2 85. 3 62. 2 78. 6 3m 0-57. 1 95. 0 73. 7 43. 5 57. 1 5 3 Table 5 The fungicidal activities against R. Solani in rice of some compounds 3 (500) / % / % / % 3f 59. 3 3p 74. 3 3u 19. 8 3k 85. 5 3q 77. 9 3v 65. 2 3m 43. 4 3s 63. 3 3 w 69. 7 3n 89. 4 3t 66. 1 3x 62. 8
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