Supporting Information For：
Synthesis, Characterization and Antifungal Activity of Novel Benzo[4,5]imidazo[1,2-d][1,2,4]triazine Derivatives Ling-Xia Li1,2,†, Jian Jiao1,2,†, Xiao-Bin Wang1, Min Chen1,2, Xin-Can Fu1, Wei-Jie Si1,3 and Chun-Long Yang1,2,3,* College of Sciences, Nanjing Agricultural University, Nanjing 210095, China;
[email protected] (L.-X. Li);
[email protected] (J. Jiao) 2 Jiangsu Key Laboratory of Pesticide Science, Nanjing Agricultural University, Nanjing 210095, China; 3 Key Laboratory of Monitoring and Management of Crop Diseases and Pest Insects, Ministry of Agriculture, Nanjing Agricultural University, Nanjing 210095, China; * Correspondence:
[email protected] (C.-L Yang); Tel.: +86-25-8439-5207; Fax: +86-25-8439-5207. † These authors contributed equally to this paper. 1
Contents 1. 1H NMR spectra of compound 4a .................................................................................................... 4 2. 13C NMR spectra of compound 4a ................................................................................................... 4 3. EI-MS spectra of compound 4a ........................................................................................................ 5 4. FT-IR spectra of compound 4a ......................................................................................................... 5 5. 1H NMR spectra of compound 4b ................................................................................................... 6 6. 13C NMR spectra of compound 4b .................................................................................................. 6 7. EI-MS spectra of compound 4b ....................................................................................................... 7 8. FT-IR spectra of compound 4b......................................................................................................... 7 9. 1H NMR spectra of compound 4c .................................................................................................... 8 10. 13C NMR spectra of compound 4c ................................................................................................. 8 11. EI-MS spectra of compound 4c ...................................................................................................... 9 12. FT-IR spectra of compound 4c ....................................................................................................... 9 13. 1H NMR spectra of compound 4d ................................................................................................. 9 14. 13C NMR spectra of compound 4d .............................................................................................. 10 15. EI-MS spectra of compound 4d ................................................................................................... 10 16. FT-IR spectra of compound 4d ..................................................................................................... 11 17. 1H NMR spectra of compound 4e ................................................................................................ 11 18. 13C NMR spectra of compound 4e ............................................................................................... 12 19. EI-MS spectra of compound 4e .................................................................................................... 12 20. FT-IR spectra of compound 4e ..................................................................................................... 13 21. 1H NMR spectra of compound 4f ................................................................................................ 13 22. 13C NMR spectra of compound 4f ............................................................................................... 14 23. EI-MS spectra of compound 4f .................................................................................................... 14
1
24. FT-IR spectra of compound 4f...................................................................................................... 15 25. 1H NMR spectra of compound 4g ............................................................................................... 15 26. 13C NMR spectra of compound 4g ............................................................................................... 16 27. EI-MS spectra of compound 4g.................................................................................................... 16 28. FT-IR spectra of compound 4g ..................................................................................................... 17 29. 1H NMR spectra of compound 4h ............................................................................................... 17 30. 13C NMR spectra of compound 4h .............................................................................................. 18 31. EI-MS spectra of compound 4h ................................................................................................... 18 32. FT-IR spectra of compound 4h ..................................................................................................... 19 33. 1H NMR spectra of compound 4i ................................................................................................ 19 34. 13C NMR spectra of compound 4i................................................................................................ 20 35. EI-MS spectra of compound 4i .................................................................................................... 20 36. FT-IR spectra of compound 4i ...................................................................................................... 21 37. 1H NMR spectra of compound 4j ................................................................................................ 21 38. 13C NMR spectra of compound 4j................................................................................................ 21 39. EI-MS spectra of compound 4j .................................................................................................... 22 40. FT-IR spectra of compound 4j ...................................................................................................... 23 41. 1H NMR spectra of compound 4k ............................................................................................... 23 42. 13C NMR spectra of compound 4k .............................................................................................. 24 43. EI-MS spectra of compound 4k ................................................................................................... 24 44. FT-IR spectra of compound 4k ..................................................................................................... 25 45. 1H NMR spectra of compound 4l ................................................................................................ 25 46. 13C NMR spectra of compound 4l................................................................................................ 26 47. EI-MS spectra of compound 4l .................................................................................................... 26 48. FT-IR spectra of compound 4l ...................................................................................................... 27 49. 1H NMR spectra of compound 4m .............................................................................................. 27 50. 13C NMR spectra of compound 4m ............................................................................................. 28 51. EI-MS spectra of compound 4m .................................................................................................. 28 52. FT-IR spectra of compound 4m.................................................................................................... 29 53. 1H NMR spectra of compound 4n ............................................................................................... 29 54. 13C NMR spectra of compound 4n .............................................................................................. 30 55. EI-MS spectra of compound 4n ................................................................................................... 30 56. FT-IR spectra of compound 4n ..................................................................................................... 31 57. 1H NMR spectra of compound 4o ............................................................................................... 31 58. 13C NMR spectra of compound 4o ............................................................................................... 32 59. EI-MS spectra of compound 4o.................................................................................................... 32 60. FT-IR spectra of compound 4o ..................................................................................................... 33 61. 1H NMR spectra of compound 4p ............................................................................................... 33 62. 13C NMR spectra of compound 4p .............................................................................................. 34 63. EI-MS spectra of compound 4p ................................................................................................... 34 64. FT-IR spectra of compound 4p ..................................................................................................... 35 65. 1H NMR spectra of compound 4q ............................................................................................... 35 66. 13C NMR spectra of compound 4q .............................................................................................. 36 67. EI-MS spectra of compound 4q ................................................................................................... 36
2
68. FT-IR spectra of compound 4q ..................................................................................................... 37 69. 1H NMR spectra of compound 4r ................................................................................................ 37 70. 13C NMR spectra of compound 4r ............................................................................................... 38 71. EI-MS spectra of compound 4r .................................................................................................... 38 72. FT-IR spectra of compound 4r...................................................................................................... 38 73. 1H NMR spectra of compound 4s ................................................................................................ 39 74. 13C NMR spectra of compound 4s ............................................................................................... 39 75. EI-MS spectra of compound 4s .................................................................................................... 40 76. FT-IR spectra of compound 4s ..................................................................................................... 41 77. 1H NMR spectra of compound 4t ................................................................................................ 41 78. 13C NMR spectra of compound 4t................................................................................................ 42 79. EI-MS spectra of compound 4t .................................................................................................... 42 80. FT-IR spectra of compound 4t ...................................................................................................... 43 81. 1H NMR spectra of compound 4u ............................................................................................... 43 82. 13C NMR spectra of compound 4u .............................................................................................. 44 83. EI-MS spectra of compound 4u ................................................................................................... 44 84. FT-IR spectra of compound 4u ..................................................................................................... 45 85. 1H NMR spectra of compound 4v ............................................................................................... 45 86. 13C NMR spectra of compound 4v ............................................................................................... 45 87. EI-MS spectra of compound 4v.................................................................................................... 46 88. FT-IR spectra of compound 4v ..................................................................................................... 47 89. 1H NMR spectra of compound 4w .............................................................................................. 47 90. 13C NMR spectra of compound 4w.............................................................................................. 48 91. EI-MS spectra of compound 4w .................................................................................................. 48 92. FT-IR spectra of compound 4w .................................................................................................... 49 93. Selected geometric parameters of compound 4n. ..................................................................... 49 94. Hydrogen bonding data for compound 4n (Å, °). .................................................................... 50 95. Selected distances between hydrogen and carbon atoms for compound 4n (Å). ................. 50
3
1
H NMR spectra of compound 4a
1.
C NMR spectra of compound 4a
13
4
2.
EI-MS spectra of compound 4a
3.
FT-IR spectra of compound 4a
5
4.
1
H NMR spectra of compound 4b
5.
13
C NMR spectra of compound 4b
6
6.
EI-MS spectra of compound 4b %
77
100.0
264
75.0
131 105
50.0
25.0
0.0
7.
120
45 50.0
75.0
336
220
90
51
100.0
125.0
158 166 150.0
193 192
175.0
200.0
FT-IR spectra of compound 4b
7
292 234
225.0
248 250.0
337
277 275.0
300.0
325.0
350.0
8.
1
H NMR spectra of compound 4c
9.
13
C NMR spectra of compound 4c
8
10. EI-MS spectra of compound 4c % 100.0
264
75.0
50.0
131
77
25.0
220
105 0.0
90
51 45 50.0
75.0
145 100.0
125.0
158
150.0
173 175.0
193
350 207
200.0
11. FT-IR spectra of compound 4c
12. 1H NMR spectra of compound 4d
9
248 225.0
250.0
277 291 275.0
306
300.0
325.0
350.0
13.
C NMR spectra of compound 4d
13
14. EI-MS spectra of compound 4d % 100.0
264
75.0
50.0
131 77
25.0
220
105 0.0
90
51 45 50.0
75.0
145 100.0
125.0
158
150.0
173 175.0
193 200.0
10
219 225.0
291
248 250.0
275.0
306
300.0
350 325.0
350.0
15. FT-IR spectra of compound 4d
16. 1H NMR spectra of compound 4e
11
17.
C NMR spectra of compound 4e
13
18. EI-MS spectra of compound 4e % 100.0
264
75.0
220 50.0
77
131
57
25.0
193 91
45
105
158
207
0.0 50.0
75.0
100.0
125.0
150.0
175.0
200.0
12
364
234 225.0
291 250.0
275.0
300.0
325.0
350.0
375.0
19. FT-IR spectra of compound 4e
20. 1H NMR spectra of compound 4f
13
21.
C NMR spectra of compound 4f
13
22. EI-MS spectra of compound 4f %
77
100.0
75.0
384 105 220
50.0
70 264
25.0
51
118 131
163 169
0.0 50.0
75.0
100.0
125.0
150.0
175.0
339
193 291
236 251 200.0
225.0
14
250.0
275.0
300.0
325.0
350.0
375.0
23. FT-IR spectra of compound 4f
24. 1H NMR spectra of compound 4g
15
25.
C NMR spectra of compound 4g
13
26. EI-MS spectra of compound 4g %
111
100.0
356
75.0
311 139
50.0
25.0
59 0.0
75
130
90
45 50.0
254
158 172
75.0
100.0
125.0
150.0
175.0
220
189
253 200.0
16
225.0
250.0
283 275.0
297 300.0
324 325.0
355 350.0
27. FT-IR spectra of compound 4g
28. 1H NMR spectra of compound 4h
17
29.
C NMR spectra of compound 4h
13
30. EI-MS spectra of compound 4h % 100.0
298
131 111
75.0
50.0
25.0
75 45
141
63
159 192 204
0.0 50.0
75.0
370
254
90
100.0
125.0
150.0
175.0
200.0
18
326
227 233 225.0
250.0
275.0
300.0
325.0
350.0
375.0
31. FT-IR spectra of compound 4h
32. 1H NMR spectra of compound 4i
19
33.
C NMR spectra of compound 4i
13
34. EI-MS spectra of compound 4i % 100.0
298
131
75.0
50.0
111
300
25.0
75 0.0
90
158 168
51 50.0
75.0
100.0
125.0
150.0
175.0
192
220
200.0
225.0
20
384
254 263 250.0
325 340 275.0
300.0
325.0
350.0
375.0
400.0
35. FT-IR spectra of compound 4i
36. 1H NMR spectra of compound 4j
37.
C NMR spectra of compound 4j
13
21
38. EI-MS spectra of compound 4j % 100.0
298
75.0
131
50.0
300
111 25.0
75 0.0
90
158 168
51 50.0
75.0
100.0
125.0
150.0
175.0
220
188 200.0
225.0
22
254 263 250.0
325 340 275.0
300.0
325.0
350.0
384 375.0
39. FT-IR spectra of compound 4j
40. 1H NMR spectra of compound 4k
23
41.
C NMR spectra of compound 4k
13
42. EI-MS spectra of compound 4k % 100.0
298
75.0
131 50.0
57 111 25.0
254 139
90 0.0
51 50.0
75.0
100.0
125.0
158
150.0
193 175.0
200.0
398
227 234 225.0
24
325 250.0
275.0
300.0
325.0
350.0
375.0
400.0
43. FT-IR spectra of compound 4k
44. 1H NMR spectra of compound 4l
25
45.
C NMR spectra of compound 4l
13
46. EI-MS spectra of compound 4l % 100.0
70
111
254
418
75.0
139 77
50.0
227
163
298 373
25.0
220
131
51
193 50.0
75.0
100.0
125.0
150.0
175.0
200.0
325
283
0.0 225.0
26
250.0
275.0
300.0
325.0
350.0
375.0
400.0
425.0
47. FT-IR spectra of compound 4l
48. 1H NMR spectra of compound 4m
27
49.
C NMR spectra of compound 4m
13
50. EI-MS spectra of compound 4m %
91
100.0
75.0
50.0
111
25.0
254 298
131 177
0.0 50
100
388
221
51 65 150
193
268
200
250
28
312 300
346 350
390 400
418 432
51. FT-IR spectra of compound 4m
52. 1H NMR spectra of compound 4n
29
53.
C NMR spectra of compound 4n
13
54. EI-MS spectra of compound 4n
%
91
100.0
75.0
336
291
50.0
119 25.0
234
65 0.0
45 50.0
103
59
130
145 172
75.0
100.0
125.0
150.0
189
175.0
207 220 200.0
30
225.0
337 248 250.0
262
277 275.0
305 300.0
325.0
350.0
55. FT-IR spectra of compound 4n
56. 1H NMR spectra of compound 4o
31
57.
C NMR spectra of compound 4o
13
58. EI-MS spectra of compound 4o %
91
100.0
75.0
278
50.0
131
234 350
25.0
45
65 70
207
103
148 159
0.0 50.0
75.0
100.0
125.0
150.0
306
180 192 175.0
200.0
32
248 225.0
250.0
263
298 275.0
300.0
325.0
350.0
59. FT-IR spectra of compound 4o
60. 1H NMR spectra of compound 4p
33
61.
C NMR spectra of compound 4p
13
62. EI-MS spectra of compound 4p % 100.0
278
75.0
91 131
50.0
234 25.0
119
70 0.0
148 159
45 50.0
364
75.0
100.0
125.0
150.0
207 220
180 175.0
200.0
34
225.0
320 250.0
275.0
300.0
325.0
350.0
375.0
63. FT-IR spectra of compound 4p
64. 1H NMR spectra of compound 4q
35
65.
C NMR spectra of compound 4q
13
66. EI-MS spectra of compound 4q % 100.0
278
75.0
91 131
50.0
234 25.0
119
70 0.0
148 159
45 50.0
364
75.0
100.0
125.0
150.0
207 220
180 175.0
200.0
36
225.0
320 250.0
275.0
300.0
325.0
350.0
375.0
67. FT-IR spectra of compound 4q
68. 1H NMR spectra of compound 4r
37
69.
C NMR spectra of compound 4r
13
70. EI-MS spectra of compound 4r % 100.0
278
75.0
50.0
131
91
234 25.0
57 119 0.0
51
77
50.0
75.0
148 100.0
125.0
150.0
378
207 180 175.0
248 200.0
71. FT-IR spectra of compound 4r
38
225.0
250.0
280 275.0
305 300.0
325.0
350.0
375.0
72. 1H NMR spectra of compound 4s
73.
C NMR spectra of compound 4s
13
39
74. EI-MS spectra of compound 4s %
91
100.0
234
75.0
398 70 119
50.0
207
278
25.0
163 145
0.0 50.0
75.0
100.0
353 220
103
51
125.0
150.0
188 175.0
305
263 200.0
225.0
40
250.0
275.0
300.0
336 325.0
350.0
375.0
400.0
75. FT-IR spectra of compound 4s
76. 1H NMR spectra of compound 4t
41
77.
C NMR spectra of compound 4t
13
78. EI-MS spectra of compound 4t %
95
100.0
282 131
75.0
50.0
238
25.0
75 45
103
138
158
63
50.0
211 225
184
0.0 75.0
100.0
125.0
150.0
354 310
175.0
200.0
42
225.0
267 250.0
275.0
356 300.0
325.0
350.0
79. FT-IR spectra of compound 4t
80. 1H NMR spectra of compound 4u
43
81.
C NMR spectra of compound 4u
13
82. EI-MS spectra of compound 4u %
131
100.0
344 75.0
155 50.0
90
183 103
25.0
416 50
70 145
0.0 50
100
150
200
372
300
220 233
200
273 250
44
373
314 300
350
400
83. FT-IR spectra of compound 4u
84. 1H NMR spectra of compound 4v
85.
C NMR spectra of compound 4v
13
45
86. EI-MS spectra of compound 4v %
111
100.0
75.0
311 356
50.0
139 25.0
59
75
90
158
45
189
159
205
0.0 50.0
75.0
100.0
125.0
150.0
358
254
175.0
200.0
46
227 233 225.0
268 250.0
275.0
297 300.0
325 325.0
350.0
87. FT-IR spectra of compound 4v
88. 1H NMR spectra of compound 4w
47
89.
C NMR spectra of compound 4w
13
90. EI-MS spectra of compound 4w %
77
100.0
146 277
75.0
50.0
336 105 25.0
92 51
0.0
118
143 204 171
45 50.0
75.0
100.0
125.0
150.0
220
337
192
175.0
200.0
48
263
234 248
225.0
250.0
291 275.0
310
300.0
325.0
350.0
91. FT-IR spectra of compound 4w
92. Selected geometric parameters of compound 4n. Bond Lengths Bond
Dist. (Å)
Bond
Dist. (Å)
O1–C9
1.202(2)
C1–C2
1.396(3)
O2–C10
1.190(2)
C1–C6
1.397(3)
O3–C10
1.327(2)
C2–C3
1.377(3)
O3–C11
1.460(3)
C3–C4
1.395(3)
N1–C1
1.410(2)
C4–C5
1.390(3)
N1–C7
1.293(2)
C5–C6
1.391(3)
N2–C6
1.406(2)
C7–C8
1.490(2)
N2–C7
1.401(2)
C12–C13
1.390(3)
N2–C9
1.402(2)
C12–C17
1.398(3)
N3–N4
1.423(2)
C13–C14
1.394(3)
N3–C8
1.471(2)
C14–C15
1.390(3)
N3–C12
1.440(2)
C15–C16
1.390(3)
N4–C9
1.408(2)
C16–C17
1.389(3)
N4–C10
1.417(2)
C15–C18
1.513(3)
Bond Angles Angle
(°)
Angle
(°)
C10–O3–C11
116.59(16)
N1–C7–N2
114.06(13)
C1–N1–C7
104.51(14)
N1–C7–C8
131.16(14)
49
C6–N2–C7
105.60(13)
N2–C7–C8
114.78(14)
C6–N2–C9
128.08(13)
N3–C8–C7
107.83(12)
C7–N2–C9
125.77(13)
O1–C9–N2
122.52(15)
N4–N3–C8
109.18(12)
O1–C9–N4
125.60(17)
N4–N3–C12
112.75(12)
N2–C9–N4
111.86(13)
C8–N3–C12
118.51(13)
O2–C10–O3
126.63(17)
N3–N4–C9
119.26(14)
O2–C10–N4
123.85(16)
N3–N4–C10
118.07(13)
O3–C10–N4
109.53(14)
C9–N4–C10
122.54(13)
N3–C12–C13
121.63(15)
N1–C1–C2
128.83(17)
N3–C12–C17
120.24(14)
N1–C1–C6
111.04(15)
C13–C12–C17
118.00(14)
C2–C1–C6
120.12(16)
C12–C13–C14
120.41(17)
C1–C2–C3
117.69(19)
C13–C14–C15
122.23(18)
C2–C3–C4
121.5(2)
C14–C15–C16
116.66(16)
C3–C4–C5
122.05(18)
C14–C15–C18
122.36(16)
C4–C5–C6
115.81(18)
C16–C15–C18
120.98(17)
N2–C6–C1
104.76(13)
C15–C16–C17
122.10(17)
N2–C6–C5
132.38(17)
C12–C17–C16
120.59(16)
C1–C6–C5
122.84(17)
93. Hydrogen bonding data for compound 4n (Å, °). D–H···A
d(D–H)
d(H···A)
d(D···A)
∠(DHA)
C8–H8B···O3a
0.9700
2.500
3.385(3)
152.00
C17–H17···N4
0.9300
2.4500
2.761(3)
100
Symmetry code for compound 4n: (a) -x,-y,-z.
94. Selected distances between hydrogen and carbon atoms for compound 4n (Å). Bond
Dist. (Å)
Bond
Dist. (Å)
H3···C12
3.4404(23)
H4···C12
3.5022(26)
H3···C13
3.8177(27)
H4···C13
3.1355(26)
H3···C14
3.8124(31)
H4···C14
3.1414(26)
H3···C15
3.4249(26)
H4···C15
3.5343(29)
H3···C16
2.9135(24)
H4···C16
3.8278(32)
50
H3···C17
2.8950(24)
H4···C17
51
3.8172(29)
