Download/Open

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(77) O (75) O O (76) O O O (73) O (74) O HO (66) (63) O HO (64) HOHO N O OH N H OH O (89) (88) N O OH N H NH2 O (87) N O O N H _O HO (86) N O OCH3 N H OH O (85) N O OCH3 N H NH2 S (84) N O OCH3 N H NH2 O (83) (82) O O N N H NH2 O (81) O NOH NOH H O O NOH (80) O O N OH (79) (78) O O O O I (71) O HO O (61) O OH HO (59) (58) O OH HO O O HO (57) O OCH3 HO (56) O O HO (55) O O O (7) (6) O O OCH3 (5) O O O (4) O O O (3) O O OH N O OCH3 N H NO2 NO2

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Espectro 1: IV do lapachol (3). (3) O OH O 1' 10 9 8 7 6 5 4 3 2 1

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Espectro 2: EM do lapachol (3). (3) O OH O 1' 10 9 8 7 6 5 4 3 2 1

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Espectro 3: RMN de 1_{H do lapachol (3).} 11 10 9 8 7 6 5 4 3 2 1 0 Chemical Shift (ppm) 3.12 2.01 1.01 1.01 0.99 1.00 3 .2 8 3 .3 0 5 .1 7 5 .1 9 5 .1 9 5 .2 1 5 .2 1 7 .6 4 7 .6 4 7 .6 5 7 .7 3 7 .7 5 8 .0 4 8 .0 4 8 .0 6 8 .0 9 8 .1 1 8.1 8.0 7.9 7.8 7.7 Chemical Shift (ppm) 1.01 0.98 1.01 1.00 7 .7 5 7 .7 5 7.7 1 7 .6 8 7 .6 7 .6 4 7 .6 4 5.20 5.15 Chemical Shift (ppm) 1.00 5 .2 1 5.2 1 5 .2 1 5 .1 8 ₅.17 5 .1 7 3.300 3.275 Chemical Shift (ppm) 2.01 3 .3 3 .2 8 (3) O OH O 1' 10 9 8 7 6 5 4 3 2 1

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Espectro 4: RMN de 13_{C do lapachol (3).} 200 180 160 140 120 100 80 60 40 20 0 Chemical Shift (ppm) Chloroform-d 1 7 .8 3 2 2 .5 4 2 5 .7 0 1 1 9 .6 0 1 2 3 .4 0 1 2 5 .9 8 1 2 6 .6 8 1 2 9 .3 5 1 3 2 .7 9 1 1 5 2 .6 6 1 8 1 .6 1 1 8 4 .5 0 135 130 125 120 Chemical Shift (ppm) 1 3 3 .7 6 1 2 9 .3 5 1 2 6 1 2 3 .4 0 1 1 9 .6 0 (3) O OH O 1' 10 9 8 7 6 5 4 3 2 1

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Espectro 5: IV da β-lapachona (4). O O O 4a 1 2 3 4 1' 2' 5 6 6a 7 8 9 10 10a 10b (4)

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Espectro 6: E.M. da β-lapachona (4). Espectro 6: EM da β-lapachona (4). O O O 4a 1 2 3 4 1' 2' 5 6 6a 7 8 9 10 10a 10b (4)

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Espectro 7: RMN de 1_{H da β-lapachona (4).} 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 Chemical Shift (ppm) 6.07 2.04 2.02 1.05 1.00 Chloroform-d 1 .8 2 1 .8 4 1 .8 5 2 .5 4 2 .5 5 2 .5 7 7 .4 9 7 .6 0 7 .6 2 7 .6 3 7 .6 4 7 .7 8 7 .8 0 8 .0 3 8 .0 3 8 .0 5 8 .0 5 8.0 7.9 7.8 7.7 7.6 7.5 Chemical Shift (ppm) 1.05 1.02 1.00 1.00 8 .0 5 8 .0 3 8 .0 3 7 .8 0 7 .8 0 7.7 8 7 .7 8 7 .6 5 7 .6 4 7 .6 3 7 .6 2 7 .6 1 7 .6 0 7 .5 1 7 .4 9 7 .4 8 7 .4 7 2.550 Chemical Shift (... 2.04 2 .5 7 2 .5 5 2 .5 4 1.850 1.825 Chemical Shif... 2.02 1 .8 5 1 .8 4 1 .8 2 O O O 4a 1 2 3 4 1' 2' 5 6 6a 7 8 9 10 10a 10b (4)

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Espectro 8: RMN de 13_{C da β-lapachona (4).} 200 180 160 140 120 100 80 60 40 20 0 Chemical Shift (ppm) Chloroform-d 1 6 .0 4 3 1 .4 6 7 9 .1 9 1 1 2 .5 8 1 2 3 .9 9 1 2 8 .4 0 1 3 0 .5 5 1 3 2 .4 9 1 3 4 .7 1 1 6 1 .9 5 1 7 8 .4 2 1 7 9 .7 4 134 132 130 128 126 124 Chemical Shift (ppm) 1 3 2 .4 9 1 2 9 .9 O O 4a 1 2 3 4 1' 2' 5 6 6a 7 8 9 10 10a 10b (4)

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Espectro 9:IV do 2-metóxi-lapachol (6). (6) 5' 4' 3' 2' 1' 11 10 9 8 7 6 5 4 3 2 1 O O OCH₃

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Espectro 10: E.M. do 2-metóxi-lapachol (6). (6) 5' 4' 3' 2' 1' 11 10 9 8 7 6 5 4 3 2 1 O O OCH3

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Espectro 11:RMN de 1_{H do 2-metóxi-lapachol (6).} 10 9 8 7 6 5 4 3 2 1 Chemical Shift (ppm) 3.06 3.02 2.05 2.02 1.03 2.02 Chloroform-d 1 .6 6 1 .7 6 3 .2 6 3 .2 9 5 .0 6 5 .0 7 5 .0 9 5 .1 0 5 .1 1 5 .1 3 5 .1 4 5 .1 5 7 .2 5 7 .6 4 7 .6 6 7 .6 6 7 .6 8 7 .6 8 7 .7 1 8 .0 0 8 .0 1 8 .0 4 8 .0 4 8 .0 6 8 .0 6 5.15 5.10 5.05 5.00 Chemical Shift (ppm) 1.03 5 .1 5 5.1 5 5 .1 4 5 .1 3 5 .1 2 5 .1 1 5.1 0 5 .1 0 5 .0 9 5 .0 8 ₅.07 5.0 7 5 .0 6 5 .0 5 8.0 7.9 7.8 7.7 7.6 Chemical Shift (ppm) 2.05 2.02 (6) 5' 4' 3' 1' 10 6 5 4 O

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Espectro 12: RMN de 13_{C do 2-metóxi-lapachol (6).} 200 180 160 140 120 100 80 60 40 20 0 Chemical Shift (ppm) Chloroform-d 1 7 .8 3 2 2 .9 6 2 5 .7 3 6 1 .1 1 1 2 0 .0 1 1 2 6 .0 0 1 2 6 .1 4 1 3 1 .9 3 1 3 3 .1 3 1 3 3 .6 8 1 3 4 .5 8 1 5 7 .3 7 1 8 1 .7 0 1 8 5 .2 6 135.0 134.5 134.0 133.5 133.0 132.5 Chemical Shift (ppm) 1 3 4 .5 8 1 3 3 .6 8 1 3 3 .6 1 1 3 3 .1 3 126.50 126.25 126.00 125.75 Chemical Shift (ppm) 1 2 6 .1 4 1 2 6 .0 0 (6) 5' 4' 3' 2' 1' 10 9 8 7 6 5 4 3 2 1 O OCH3

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Espectro 13: IV do composto 55. 17 O O HO 15 ₁₄ 13 12a 12 11 4a 1 2 3 4 1' 2' 5 6 6a 7 8 9 10 10a 10b (55) 16

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Espectro 14: E. M. do composto 55. 17 O O HO 15 14 13 12a 12 11 4a 1 2 3 4 1' 2' 5 6 6a 7 8 9 10 10a 10b (55) 16

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Espectro 15: RMN de 1_{H do composto 55.} 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 Chemical Shift (ppm) 3.07 1.99 1.99 2.22 3.02 3.00 1.93 1.25 0.95 1.03 1.03 TMS Chloroform-d 1 .6 2 1 .6 5 2 .0 9 2 .1 4 2 .1 7 2 .4 6 2 .4 9 2 .5 7 2 .6 0 3 .0 7 3 .9 8 6 .5 6 6 .5 7 6 .6 0 6 .6 1 7 .0 4 7 .0 8 7 .0 8 7 .3 2 7 .3 5 7 .3 7 7 .4 1 7 .6 2 7 .6 6 2.50 2.25 2.00 Chemical Shift (ppm) 1.03 1.03 7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 Chemical Shift (ppm) 3.07 1.93 1.04 1.25 Chloroform-d 7 .6 7 7 .6 6 7.6 2 7 .6 0 7 .5 9 7 .5 9 7 .4 8 7 .4 8 7.4 5 7 .4 4 7 .4 1 7 .4 0 7.3 7 ₇.35 7 .3 3 7 .3 2 7 .0 8 7 .0 8 7 .0 5 7 .0 4 ₁₇ O O HO 13 12a 12 11 4a 1 2 3 4 1' 2' 5 6 6a 7 8 9 10 10a 10b (55) 16

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Espectro 16: RMN de 13C do composto 55. 200 180 160 140 120 100 80 60 40 20 Chemical Shift (ppm) Chloroform-d 24.81 26.57 30.63 75.54 76.18 105.93 121.97 125.82 129.13 134.10 140.56 161.21 199.55 128 126 Chemical Shift (ppm) 129.13 128.70 127.61 126.64 126.55 126.07 125.82 124.79 17 O O HO 12a 12 11 4a 1 2 3 4 1' 2' 5 6 6a 7 8 9 10 10a 10b (55)

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Espectro 17: IV do composto 56. 5' 4' 3' 2' 1' 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 (56) HO O OCH3

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Espectro 18: E.M. do composto 56. 5' 4' 3' 2' 1' 18 17 16 15 14 13 12 ₁₁ 10 9 8 7 6 5 4 3 2 1 (56) HO O OCH3

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Espectro 19: RMN de 1_{H do composto 56.} 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 Chemical Shift (ppm) 3.11 3.11 3.05 2.08 2.07 1.15 1.06 1.07 1.00 Chloroform-d 1 .6 6 1 .7 1 2 .8 9 3 .0 4 3 .0 8 3 .1 6 3 .2 2 3 .3 4 3 .4 0 4 .8 8 4 .8 9 4 .9 1 4 .9 1 4 .9 2 4 .9 4 4 .9 5 6 .4 8 6 .4 9 6 .5 2 6 .9 2 6 .9 3 6 .9 6 7 .0 0 7 .0 2 7 .0 5 7 .0 9 7 .3 8 7 .5 6 7 .6 0 7 .7 3 7 .8 5 7 .8 8 7.75 7.50 7.25 7.00 Chemical Shift (ppm) 3.05 1.15 1.15 1.11 1.00 7 .8 9 7 .8 8 7 .8 5 7 .8 5 7 .7 7 ₇.73 ₇.73 7 .6 4 7 .6 4 7 .6 0 7 .6 0 7 .5 7 7 .5 6 7 .4 2 7 .4 1 7 .3 8 7 .3 8 7 .3 4 7 .0 5 7 .0 3 7.0 2 7 .0 1 7 .0 6 .9 3 6 .9 2 3.4 3.3 3.2 3.1 3.0 2.9 Chemical Shift (ppm) 2.07 1.14 1.07 0.95 3 .1 3 ₂.8 1.70 1.65 Chemical Shift (pp... 3.11 3.01 1 .7 1 1 .6 6 1 .6 6 5' 4' 3' 2' 1' 18 17 16 15 14 13 12 ₁₁ 10 9 8 7 6 5 4 3 2 1 (56) HO O OCH3

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Espectro 20: RMN de 13_{C do composto 56.} 200 180 160 140 120 100 80 60 40 20 0 Chemical Shift (ppm) Chloroform-d ₁7.9 0 6 1 .9 9 7 5 .4 5 1 3 4 .3 8 1 4 2 .7 1 1 6 9 .2 5 1 8 5 .0 2 132 130 128 126 124 122 Chemical Shift (ppm) 1 3 2 .2 8 1 3 1 .7 1 1 3 0 .4 3 1 2 9 .8 9 1 2 7 .9 8 1 2 7 .4 6 1 2 6 .7 9 1 2 5 .7 6 1 2 5 .4 6 1 2 3 .5 8 1 2 1 .9 4 5' 4' 3' 2' 1' 18 17 16 15 14 13 12 ₁₁ 10 9 8 7 6 5 4 3 2 1 (56) HO O OCH3

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Espectro 21: IV do composto 57. 17 16 15 14 13 12a 12 11 1 2 3 4 4a 1' 2' 5 5a 6 7 8 9 9a 10a 10 (57) O O HO

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Espectro 22: E.M. do composto 57. 17 16 15 14 13 12a 12 11 1 2 3 4 4a 1' 2' 5 5a 6 7 8 9 9a 10a 10 (57) O O HO

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Espectro 23: RMN de 1_{H do composto 57.} 9 8 7 6 5 4 3 2 1 0 Chemical Shift (ppm) 3.05 3.00 2.02 2.13 2.11 1.09 1.07 1.02 0.99 Chloroform-d 1 .5 6 1 .7 2 1 .7 3 1 .7 5 1 .7 9 2 .0 7 2 .1 5 2 .1 8 2 .3 6 2 .3 7 2 .3 8 2 .4 0 2 .4 9 3 .1 9 3 .2 5 3 .2 9 3 .3 5 6 .5 6 6 .5 9 6 .9 5 6 .9 6 6 .9 9 7 .0 3 7 .0 4 7 .0 7 7 .1 0 7 .3 8 7 .4 2 7 .5 6 7 .5 7 7 .7 2 7 .7 5 7 .9 0 7 .9 1 7 .9 4 7 .9 5 7.75 7.50 7.25 7.00 Chemical Shift (ppm) 3.00 1.09 1.04 1.02 1.01 7 7 7.6 7 7 ₇.5 7 .3 7 .3 7 .1 0 7 .0 9 7.0 7 .0 7 6 .9 8 ₆.9 6 .9 2.50 2.45 2.40 2.35 Chemical Shift (ppm) 1.05 2 .4 9 2 .4 7 2 .4 6 2 .4 4 2 .4 0 2 .3 8 2 .3 7 2 .3 6 2.20 2.10 Chemical Shif... 1.07 2 .2 2 2 .1 2 2 .1 0 2 .0 7 1.8 1.7 1.6 1.5 Chemical Shift (ppm) 2.11 1 .8 2 1 .8 0 1 .7 9 1 .7 7 1 .7 5 1 .7 3 1 .7 2 1 .7 0 1 .6 8 1 .6 5 1 .6 3 1 .6 0 1 .5 8 1 .5 6 1 .5 3 1 .5 1 17 16 15 14 13 12a 12 11 1 2 3 4 4a 1' 2' 5 5a 6 7 8 9 9a 10a 10 (57) O O HO

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Espectro 24: RMN de 13C do composto 57. 200 180 160 140 120 100 80 60 40 20 0 Chemical Shift (ppm) Chloroform-d 1 5 .5 6 2 4 .7 8 2 8 .5 1 3 1 .7 8 5 0 .9 8 7 2 .8 5 7 8 .2 4 1 0 9 .9 3 1 2 5 .5 2 1 2 5 .6 4 1 3 1 .8 9 1 3 4 .8 0 1 4 2 .3 2 1 6 6 .1 0 1 8 3 .3 8 132 131 130 129 128 127 126 Chemical Shift (ppm) 1 3 1 .8 9 1 3 0 .3 4 1 2 9 .6 1 2 7 .9 2 12 7 .5 1 2 6 .9 2 1 2 5 .6 4 1 2 5 .5 2 17 16 15 14 13 12a 12 11 1 2 3 4 4a 1' 2' 5 5a 6 7 8 9 9a 10a 10 (57) O O HO

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Espectro 25: IV do composto 58. 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400 Wavenumber (cm-1) 20 40 60 80 100 % T ra n smi tt a n ce 5 7 2 .7 6 6 3 6 .4 7 0 1 .9 7 7 5 2 .1 1 8 4 4 .6 8 9 4 4 .9 6 1 0 0 6 .6 8 1 1 8 2 .1 7 1 1 9 3 .7 4 1 2 3 4 .2 4 1 3 0 1 .7 4 1 3 4 0 .3 1 1 3 7 5 .0 2 1 4 5 7 .9 4 1 4 9 4 .5 9 1 5 7 3 .6 5 1 5 9 6 .8 1 6 1 8 .0 1 1 6 4 6 .9 4 2 9 1 5 .8 9 2 9 6 4 .1 3 0 3 1 .6 3 2 4 9 .5 2 19 18 1' O OH HO 3' 4' 5' 10 9 8 7 6 5 4 3 2 1 2' 11 (58) 12 13 14 15 16 17

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Espectro 26: E.M. do composto 58. 19 18 1' O OH HO 3' 4' 5' 10 9 8 7 6 5 ₄ 3 2 1 2' 11 (58) 12 13 14 15 16 17

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Espectro 27: RMN de 1_{H do composto 58.} 11 10 9 8 7 6 5 4 3 2 1 0 Chemical Shift (ppm) 6.06 3.05 2.00 2.09 1.15 1.01 3 .0 7 3 .1 7 5 .1 2 5 .1 6 5 .2 0 6 .6 4 6 .6 4 6 .6 7 7 .0 8 7 .1 1 7 .1 2 7 .3 2 7 .3 4 7 .3 5 7 .3 9 7 .5 2 7 .5 3 7 .7 0 7 .7 3 7 .7 4 7.8 7.7 7.6 7.5 7.4 7.3 Chemical Shift (ppm) 1.90 1.15 1.11 1.12 Chloroform-d 7 .7 4 7 .7 3 7 .7 0 7 .6 9 7 .5 7 7 .5 6 7.5 3 7 .5 2 7 .4 9 7 .4 8 ₇.45 7 .4 4 7 .4 1 7 .3 9 7 .3 5 7 .3 4 7 .3 2 7 .3 1 3.15 3.10 3.05 Chemical Shif... 2.09 2.07 3 .1 7 3 .1 3 3 .0 7 19 18 1' O OH HO 3' 4' 5' 10 9 8 7 6 5 ₄ 3 2 1 2' 11 (58) 12 13 16 17

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Espectro 28: RMN de 13C do composto 58. 200 180 160 140 120 100 80 60 40 20 0 Chemical Shift (ppm) 1 7 .9 6 2 2 .2 0 2 5 .8 4 5 3 .7 5 7 8 .4 8 1 0 9 .6 0 1 2 0 .6 6 1 2 3 .2 8 1 2 5 .7 5 1 2 6 .8 1 1 3 0 .2 8 1 3 4 .7 6 1 3 8 .3 1 1 4 1 .7 5 1 6 3 .9 1 2 0 1 .1 5 130 129 128 127 126 Chemical Shift (ppm) 1 3 0 .2 8 1 3 1 2 9 .9 1 1 2 8 .3 0 1 2 1 2 6 .8 1 1 2 5 .7 5 19 18 1' O OH HO 3' 4' 5' 10 9 8 7 6 5 ₄ 3 2 1 2' 11 (58) 12 13 16 17

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Espectro 29: IV do composto 59. 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 Wavenumber (cm-1) 16 24 32 40 48 56 64 72 A rb it ra ry 7 1 1 .6 2 7 7 1 .4 9 2 5 .6 8 9 8 5 .4 6 1 0 2 7 .8 9 1 2 4 1 .9 5 1 3 7 6 .9 5 1 4 5 7 .9 4 1 5 7 3 .6 5 1 5 9 8 .7 2 1 6 3 9 .2 2 2 9 5 8 .3 2 2 9 7 3 .7 4 3 2 5 7 .2 3 (59) 11 12 13 2' 1 2 3 4 5 6 7 8 9 10 5' 4' 3' O OH HO 1' 14 15

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Espectro 30: E.M. do composto 59. (59) 11 12 13 2' 1 2 3 4 5 6 7 8 9 10 5' 4' 3' O OH HO 1' 14 15

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Espectro 31: RMN de 1_{H do composto 59.} (59) 11 12 13 2' 1 2 3 4 5 6 7 8 9 10 5' 4' 3' O OH HO 1' 14 15

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Espectro 32: RMN de 13C do composto 59. (59) 11 12 13 2' 1 2 3 4 5 6 7 8 9 10 5' 4' 3' O OH HO 1' 14 15

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Espectro 33: RMN de H x H COSY do composto 59. (59) 11 12 13 2' 1 2 3 4 5 6 7 8 9 10 5' 4' 3' O OH HO 1' 14 15

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Espectro 34: RMN de HET-COSY (J2_{e J}3_{) do composto 59.} (59) 11 12 13 2' 1 2 3 4 5 6 7 8 9 10 5' 4' 3' O OH HO 1' 14 15

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Espectro 35: IV do composto 61. 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 Wavenumber (cm-1) 60 65 70 75 80 % T ra n smi tt a n ce 6 6 1 .4 7 7 6 9 .4 7 8 6 2 .0 4 1 0 6 8 .3 9 1 1 3 3 .9 6 1 2 5 3 .5 2 1 3 6 7 .3 1 1 4 5 4 .0 9 1 6 1 4 .1 5 1 7 2 7 .9 3 2 9 3 1 .3 2 2 9 7 1 .8 2 3 4 3 6 .5 8 (61) 12 8 O O HO 11 2' 1 2 3 4 5 6 7 9 10 9a 3a 5a 9b 1'

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Espectro 36: E.M. do composto 61. (61) 12 8 O O HO 11 2' 1 2 3 4 5 6 7 9 10 9a 3a 5a 9b 1'

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Espectro 37: RMN de 1_{H do composto 61.} (61) 12 8 O O HO 11 2' 1 2 3 4 5 6 7 9 10 9a 3a 5a 9b 1'

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Espectro 38: RMN de 13C do composto 61. (61) 12 8 O O HO 11 2' 1 2 3 4 5 6 7 9 10 9a 3a 5a 9b 1'

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Espectro 39: IV do composto 63. 11 109 8 7 6 5 4 3 2 1 O HO (63) 12 13 14 15 16 17 4000 3500 3000 2500 2000 1500 1000 500 Wavenumber (cm-1) 10 20 30 40 50 60 70 80 90 100 % T ra n smi tt a n ce 5 5 1 .5 5 6 1 9 .0 5 6 3 4 .4 8 7 0 3 .9 7 4 2 .4 7 7 6 7 .5 4 9 1 7 .9 6 9 7 1 .9 6 1 0 0 4 .7 5 1 0 4 7 .1 7 1 1 0 1 .1 7 1 1 3 5 .8 9 1 1 5 3 .2 4 1 1 9 1 .8 1 1 2 3 4 .2 4 1 2 9 0 .1 6 1 3 7 5 .0 2 1 4 4 8 .3 1 6 3 9 .2 2 2 8 4 8 .3 9 2 9 1 5 .8 9 2 9 7 7 .6 3 0 2 1 .9 6 3 0 7 2 .1 3 4 4 2 .3 7

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Espectro 40: E.M. do composto 63. 11 109 8 7 6 5 4 3 2 1 O HO (63) 12 13 14 15 16 17

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Espectro 41: RMN 1H do composto 63. 11 109 8 7 6 5 4 3 2 1 O HO (63) 12 13 14 15 16 17 12 11 10 9 8 7 6 5 4 3 2 1 0 Chemical Shift (ppm) 6.05 3.15 1.03 2.09 1.03 2.09 Chloroform-d 2 .2 1 2 .2 5 2 .2 8 2 .3 2 2 .3 3 2 .3 7 2 .4 0 2 .4 4 4 .6 5 4 .7 2 4 .7 3 4 .8 4 4 .9 0 5 .3 6 5 .4 0 5 .4 5 5 .4 8 5 .5 3 5 .5 7 7 .2 0 7 .2 4 7 .2 8 7 .4 8 7 .5 5 7 .7 5 7 .7 5 7 .7 6 7 .7 8 7.8 7.7 7.6 7.5 7.4 Chemical Shift (ppm) 6.05 7 .7 8 7 .7 6 7 .7 5 7 .7 5 7 .7 3 7 .7 2 7 .6 9 7 .6 6 7 .6 5 7 .6 0 7 .5 87 .5 6 7 .5 5 7 .5 2 7 .5 2 7 .4 8 7 .4 8 7.3 7.2 Chemical Shift (ppm) 3.15 Chloroform-d 7 .2 8 7.2 4 7 .2 2 7.2 0 5.5 5.4 Chemical Shift (ppm) 1.03 5 .5 7 5 .5 3 5 .5 0 5 .4 8 5 .4 5 5 .4 4 5 .4 0 5 .3 6 5.0 4.9 4.8 4.7 4.6 Chemical Shift (ppm) 2.09 4 .9 0 4 .8 9 4 .8 4 4 .8 4 4 .7 3 4 .7 2 4 .6 5 2.5 2.4 2.3 2.2 Chemical Shift (ppm) 2.09 2 .4 4 2 .4 0 2 .3 7 2 .3 3 2 .3 2 2 .2 8 2 .2 5 2 .2 1

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Espectro 42: RMN 13C do composto 63. 11 109 7 6 5 4 3 2 1 (63) 12 13 14 15 16 17 200 180 160 140 120 100 80 60 40 20 0 Chemical Shift (ppm) Chloroform-d 4 8 .9 1 7 9 .5 3 1 1 9 .5 0 1 2 3 .1 5 1 2 3 .9 9 1 2 6 .0 6 1 2 8 .1 2 1 2 8 .3 7 1 2 9 .1 3 1 3 1 .3 2 1 3 5 .0 1 1 3 7 .4 2 1 4 0 .0 8 2 0 2 .9 0 131 130 129 128 127 126 125 124 123 122 121 120 119 Chemical Shift (ppm) 1 3 1 .3 2 ₁29 .1 3 1 2 8 .9 3 1 2 8 .4 1 ₁28 .3 7 1 2 8 .1 2 1 2 7 .2 0 1 2 6 .0 6 1 2 3 .9 9 1 2 3 .1 5 1 1 9 .5 0 129.00 128.50 Chemical Shift (ppm) 1 2 9 .1 3 1 2 8 .9 3 1 2 8 .4 1 ₁28 .3 7

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Espectro 43: IV do composto 64. 4000 3500 3000 2500 2000 1500 1000 500 Wavenumber (cm-1) 20 40 60 80 100 % T ra n smi tt a n ce 6 1 9 .0 5 6 3 2 .5 5 6 9 6 .1 9 7 4 0 .5 4 8 9 0 .9 7 9 1 0 .2 5 9 4 6 .8 9 9 6 2 .3 2 9 8 9 .3 2 1 0 0 6 .6 8 1 0 5 2 .9 6 1 0 9 5 .3 9 1 1 3 3 .9 6 1 2 5 3 .5 2 1 2 9 2 .0 9 1 3 2 6 .8 1 1 4 0 5 .8 7 1 4 4 8 .3 1 4 7 9 .1 6 1 6 3 9 .2 2 1 6 7 7 .7 9 2 8 4 8 .3 9 2 9 1 5 .8 9 2 9 7 5 .6 7 3 0 1 8 .1 3 0 6 6 .3 1 3 4 1 7 .3 20 19 18 17 1615 14 13 12 11 (64) 10 9 8 7 6 5 4 3 2 1 HOHO

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Espectro 44: E.M. do composto 64. 20 19 18 17 16 15 14 13 12 11 (64) 10 9 8 7 6 5 4 3 2 1 HOHO

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Espectro 45: RMN 1_{H do composto 64.} 20 19 18 17 1615 14 13 12 11 (64) 10 9 8 7 6 5 4 3 2 1 HOHO 10 9 8 7 6 5 4 3 2 1 0 Chemical Shift (ppm) 4.00 4.00 2.16 2.14 2.09 2.00 Chloroform-d 2 .2 0 2 .2 3 2 .2 7 2 .3 0 2 .5 5 2 .6 0 2 .6 2 2 .6 7 4 .9 2 5 .0 1 5 .0 6 5 .4 5 5 .5 0 5 .5 3 5 .5 4 5 .5 8 5 .5 9 5 .6 2 5 .6 3 7 .3 0 7 .3 1 7 .3 3 7 .3 5 7 .3 6 7 .4 7 7 .5 0 7 .6 8 7 .7 2 7.80 7.75 7.70 7.65 Chemical Shift (ppm) 2.09 7 .7 2 7 .7 1 7 .6 9 ₇.69 7.6 8 7.5 7.4 7.3 Chemical Shift (ppm) 4.00 2.04 Chloroform-d 7 .5 1 7 .5 0 7.4 8 7 .4 7 7 .4 0 ₇.39 7 .3 6 7.3 5 7.3 3 7 .3 1 7 .3 0 5.6 5.5 5.4 Chemical Shift (ppm) 2.00 5 .6 2 5 .6 1 5.5 9 5.5 8 5 .5 5 5.5 4 5 .5 3 5 .5 0 5 .5 0 5.1 5.0 4.9 Chemical... 4.00 5 .0 6 5 .0 1 4 .9 2 2.7 2.6 Chemical S... 2.16 2 .6 7 2 .6 2 2.6 0 2 .5 5 2.25 2.00 1.75 Chemical Shift (ppm) 2.14 2.11 2 .3 0 ₂.30 2 .2 8 2 .2 7 2 .2 3 2 .2 0

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Espectro 46: RMN 13_{C do composto 64.} 19 18 17 1615 14 13 12 11 (64) 10 9 8 7 6 5 4 3 2 1 HOHO 180 160 140 120 100 80 60 40 20 0 Chemical Shift (ppm) Chloroform-d 3 9 .9 2 7 8 .0 4 1 1 9 .2 3 1 2 3 .6 5 1 2 5 .3 5 1 2 7 .7 3 1 3 1 .9 4 1 3 3 .8 3 1 3 9 .6 3 128.0 127.5 Chemical Shift (ppm) 1 2 7 .7 3 1 2 7 .6 7

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Espectro 47: IV do composto 66. 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400 Wavenumber (cm-1) 48 56 64 72 80 88 96 % T ra n smi tt a n ce 4 8 5 .9 8 6 3 8 .3 3 6 6 9 .1 9 6 7 8 .8 3 7 0 0 .0 4 7 5 5 .9 7 8 2 3 .4 7 9 3 5 .3 2 9 9 5 .1 1 0 2 5 .9 6 1 0 4 9 .1 1 1 3 3 .9 6 1 1 8 0 .2 4 1 2 2 0 .7 4 1 2 4 5 .8 1 1 3 5 9 .5 9 1 3 8 0 .8 1 4 3 8 .6 6 1 4 4 6 .3 7 1 4 9 0 .7 3 1 5 7 5 .5 8 1 5 9 4 .8 7 1 6 7 2 .0 1 1 8 7 6 .4 3 1 9 5 9 .3 5 2 9 2 1 .6 7 2 9 5 2 .5 3 2 9 8 1 .4 6 3 0 0 6 .5 3 3 0 2 1 .9 6 3 0 5 8 .6 3 0 7 2 .1 3 4 6 1 .6 5 17 16 15 ₁₄ 13 12 (66) 11 10 9 8 7 6 5 4 3 2 1 O OH

(51)

Espectro 48: E.M. do composto 66. 17 16 15 ₁₄ 13 12 (66) 11 10 9 8 7 6 5 4 3 2 1 O OH

(52)

Espectro 49: RMN 1_{H do composto 66.} 17 13 12 (66) 11 10 9 8 7 6 ₂ 1 O 11 10 9 8 7 6 5 4 3 2 1 0 Chemical Shift (ppm) 3.23 1.00 1.00 1.00 1.00 Chloroform-d 2 .9 4 2 .9 4 2 .9 6 2 .9 8 2 .9 9 3 .1 0 3 .1 2 3 .1 4 3 .1 6 4 .1 9 4 .9 9 4 .9 9 5 .0 3 5 .1 2 5 .6 8 5 .6 9 5 .7 2 5 .7 4 5 .7 6 5 .7 8 7 .2 6 7 .2 8 7 .3 8 7 .4 9 7 .5 0 7 .7 1 7 .7 2 7 .7 3 3.1 3.0 2.9 Chemical Shift (ppm) 1.00 1.00 3 .1 6 3 .1 4 3 .1 2 3 .1 0 3 .1 0 3 .0 0 2 .9 9 2 .9 8 2 .9 7 2 .9 6 2 .9 4 2 .9 4 5.125 5.100 Chemical Shift (... 1.00 5 .1 3 5 .1 2 5 .1 2 5 .1 0 5 .1 0 5 .1 0 5.025 4.975 Chemical Shift (ppm) 1.00 5 .0 4 5 .0 3 5 .0 3 5 .0 3 5 .0 0 4 .9 9 4 .9 9 4 .9 8 5.75 5.70 Chemical Shift (ppm) 1.00 5 .7 8 5 .7 6 5 .7 6 5 .7 4 5 .7 2 5 .7 1 5.6 9 5 .6 8 7.750 7.700 Chemical Shift (ppm) 2.00 7 .7 4 7.7 3 7 .7 2 7 .7 2 7 .7 1 7.5 7.4 7.3 Chemical Shift (ppm) 3.23 3.00 2.03 Chloroform-d 7 .5 1 7 .5 0 7 .4 9 7 .4 8 7 .4 5 7.4 5 7 .4 3 7 .4 1 7.4 0 7 .3 8 7 .3 8 7 .3 6 7 .3 3 7 .3 2 7 .3 0 ₇.28 7 .2 6

(53)

Espectro 50: RMN 13_{C do composto 66.} 17 16 15 ₁₄ 13 12 (66) 11 10 9 8 7 6 5 4 3 2 1 O OH 200 180 160 140 120 100 80 60 40 20 0 Chemical Shift (ppm) Chloroform-d 4 3 .8 7 8 1 .3 2 1 2 0 .2 8 1 2 5 .5 3 1 2 8 .0 3 1 3 0 .0 8 1 3 2 .2 1 1 3 2 .7 0 1 3 4 .4 2 1 4 1 .6 6 2 0 0 .7 2 132.50 132.25 Chemical Shift (ppm) 1 3 2 .7 0 1 3 2 .2 1 130.0 129.5 129.0 128.5 128.0 Chemical Shift (ppm) 1 3 0 .0 8 1 2 8 .8 1 1 2 8 .0 3 1 2 7 .9 7

(54)

Espectro 51: E.M do composto 68. 14 13 12 11 10b 10a 10 9 8 7 6a 6 5 4a 4 3 2' 1' 2 1O O OH (68)

(55)

Espectro 52: RMN de 1_{H do composto 68.} 14 13 12 11 10b 10a 10 9 8 7 6a 6 5 4a 4 3 2' 1' 2 1O O OH (68) 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 Chemical Shift (ppm) 6.04 2.18 2.08 2.08 1.05 1.05 1.00 0.78 Chloroform-d 1 .1 7 1 .5 0 1 .7 6 1 .7 7 1 .8 0 1 .8 3 2 .3 0 2 .3 3 2 .3 5 2 .4 7 2 .5 1 2 .5 7 2 .6 6 2 .6 9 3 .9 3 4 .7 9 4 .8 1 4 .8 8 4 .8 9 4 .9 7 4 .9 8 5 .3 8 5 .4 2 5 .4 7 5 .5 0 5 .5 6 5 .5 9 7 .3 2 7 .3 2 7 .3 5 7 .3 6 7 .4 2 7 .4 3 7 .4 6 7 .6 0 7 .6 1 7 .7 4 7 .7 4 7 .7 8 7.80 7.75 Chemical Shift... 1.05 7.65 7.60 Chemical Shif... 1.04 7 7.450 7.425 7.400 Chemical Shift (ppm) 1.05 7 .4 7 7 .4 6 7 .4 3 7 .4 2 7 .3 9 7 .3 8 7.350 7.325 7.300 Chemical Shift (ppm) 1.00 7 .2 7 .2 8 2.50 2.25 Chemical Shift (ppm) 1.61 0.89 0.79 2 .6 9 2 .6 6 2 .6 3 ₂.60 2.5 4 2 .3 8 2 .3 5 2 .3 3 2 .3 0 2 .2 5 2 .2 2 1.9 1.8 1.7 Chemical Shift (ppm) 1.69 1 .8 7 1 .8 3 1 .7 6 1 .7 3

(56)

O O₍₅₎ 1 2 1' 2' 3 4 4a 5 5a 6 7 8 9 1010a 9a

(57)

Espectro 54: RMN de 13_{C do composto 5.} O O O (5) 1 2 1' 2' 3 4 4a 5 5a 6 7 8 9 1010a 9a

(58)

Espectro 55: IV do composto 71. O O I (71) 1 2 3 4 5 1' 2' 4a 6 6a 7 8 9 10 11 ₁₂ 13 14 10a _10b 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400 Wavenumber (cm-1) 10 15 20 25 30 35 40 45 50 A rb it ra ry 4 4 3 .5 5 5 7 4 .6 9 6 1 1 .3 3 6 7 6 .9 7 7 1 .4 8 3 6 .9 7 8 9 2 .8 9 9 1 9 .8 9 9 7 1 .9 6 1 0 0 2 .8 2 1 0 8 5 .7 4 1 1 7 8 .3 1 1 2 4 5 .8 1 1 3 2 6 .8 1 1 3 4 4 .1 6 1 3 6 5 .3 8 1 3 9 2 .3 8 1 4 5 0 .2 3 1 4 6 9 .5 2 1 5 1 5 .8 1 5 7 7 .5 1 1 5 9 6 .8 1 6 4 5 .0 1 1 7 1 8 .2 9 1 8 1 0 .8 6 1 8 3 2 .0 7 1 9 0 5 .3 6 1 9 2 6 .5 7 1 9 5 1 .6 4 2 8 4 0 .6 8 2 9 1 0 .1 2 9 2 3 .6 2 9 4 2 .8 9 2 9 7 3 .7 4 3 0 6 2 .4 5

(59)

Espectro 56: E.M do composto 71. O O I (71) 1 2 3 4 5 1' 2' 4a 6 6a 7 8 9 10 11 ₁₂ 13 14 10a _10b

(60)

Espectro 57: RMN de 1_{H do composto 71.} O O I (71) 1 2 3 4 5 1' 2' 4a 6 6a 7 8 9 10 11 ₁₂ 13 14 10a _10b

(61)

Espectro 58: RMN de 13_{C do composto 71.} O O I (71) 1 2 3 4 5 1' 2' 4a 6 6a 7 8 9 10 11 ₁₂ 13 14 10a _10b

(62)

Espectro 59: RMN de H x H COSY do composto 71. O O I (71) 1 2 3 4 5 1' 2' 4a 6 6a 7 8 9 10 11 ₁₂ 13 14 10a _10b

(63)

Espectro 60: RMN HET-COSY (J1_{) do composto 71.} O O I (71) 1 2 3 4 5 1' 2' 4a 6 6a 7 8 9 10 11 ₁₂ 13 14 10a _10b

(64)

Espectro 61: RMN HET-COSY (J2 e J3) do composto 71. O O I (71) 1 2 3 4 5 1' 2' 4a 6 6a 7 8 9 10 11 ₁₂ 13 14 10a _10b

(65)

Espectro 62: IV do composto 73. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 O (73) 4000 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400 Wavenumber (cm-1) 10 20 30 40 50 60 70 80 90 100 % T ra n smi tt a n ce 5 3 9 .9 8 7 3 0 .9 7 5 0 .1 9 9 9 1 .2 5 1 0 1 6 .3 2 1 1 0 5 .0 3 1 1 3 2 .0 3 1 1 7 8 .3 1 1 2 3 6 .1 7 1 2 8 4 .3 8 1 4 0 7 .8 1 4 5 0 .2 3 1 5 9 8 .7 2 1 6 8 3 .5 8 2 8 8 8 .8 9 2 9 2 9 .3 9 3 0 6 4 .3 8

(66)

Espectro 63: E.M do composto 73. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 O (73)

(67)

Espectro 64: RMN 1H do composto 73. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 O (73) 11 10 9 8 7 6 5 4 3 2 1 0 Chemical Shift (ppm) 3.00 2.29 1.00 2.22 1.00 1 .5 6 2 .6 1 6 .8 7 6 .8 7 7 .5 8 7 .5 9 7 .6 1 7 .6 3 7 .6 3 7 .6 5 8 .0 6 8 .0 8 8 .2 8 8 .6 9 8 .7 0 8 .7 1 8.75 8.70 8.65 Chemical Shift (ppm) 2.29 8 8 ₈ ₈ 8.300 8.275 Chemical Shift (ppm) 1.00 8 ₈ 8 8 .2 8 8 8 8.09 8.07 Chemical Shift... 1.00 7.65 7.60 Chemical Shift (ppm) 2.22 2.00 7 .6 7 ₇.5 ₇.5 6.875 6.850 Chemical Shift (pp... 1.00 2.600 Chemical Shi... 3.00

(68)

Espectro 65: RMN 13_{C do composto 73.} 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 O (73) 200 180 160 140 120 100 80 60 40 20 0 Chemical Shift (ppm) Chloroform-d 1 4 .2 5 1 0 2 .4 2 1 2 0 .1 6 1 2 3 .5 4 1 2 3 .9 1 1 2 6 .9 0 1 2 8 .3 7 1 4 8 .1 5 1 5 4 .3 0 128 127 126 125 124 123 122 121 120 119 Chemical Shift (ppm) 1 2 8 .3 7 1 2 7 .9 5 1 2 7 .4 1 1 2 6 .9 0 1 2 6 .7 7 1 2 5 .2 0 1 2 4 .8 6 1 2 3 .9 1 1 2 3 .5 4 1 2 3 .4 2 1 2 2 .4 0 1 2 1 .3 9 1 2 0 .1 6

(69)

Espectro 66: IV do composto 74. (74) O 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400 Wavenumber (cm-1) -20 0 20 40 60 80 A rb it ra ry 6 1 5 .1 9 6 5 1 .8 3 7 2 5 .1 2 7 5 2 .1 1 8 2 1 .5 4 8 8 7 .1 1 9 4 3 .0 4 1 0 3 3 .6 7 1 0 8 3 .8 2 1 1 5 7 .1 1 1 8 6 .0 3 1 2 2 0 .7 4 1 2 5 7 .3 8 1 3 1 3 .3 1 1 3 6 1 .5 2 1 4 5 0 .2 3 1 5 1 0 .0 1 1 6 0 6 .4 4 1 6 3 7 .2 9 1 6 9 3 .2 2 1 7 2 2 .1 5 2 8 5 2 .2 5 2 9 2 5 .5 3 2 9 5 6 .3 9 3 0 6 6 .3 1

(70)

Espectro 67: E.M. do composto 74. (74) O 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17

(71)

Espectro 68: RMN 1H do composto 74. (74) O 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 12 11 10 9 8 7 6 5 4 3 2 1 0 Chemical Shift (ppm) 4.37 3.02 2.12 1.00 1.00 0.97 1.01 1 1 .6 3 .1 5 3 .1 7 3 .1 9 3 .2 0 3 .6 9 3 .7 1 3 .7 2 3 .7 5 5 .2 5 5 .2 7 5 .2 8 5 .3 1 5 .3 1 5 .3 2 5 .3 4 7 .2 7 7 .5 3 7 .6 0 7 .6 4 7 .6 6 8 .0 8 8 .0 9 8 .1 1 8 .6 5 8 .6 7 8 .6 9 8 .7 0 8.675 Chemical Shi... 2.12 8 .7 1 8 .7 0 8 .6 9 8 .6 9 8 .6 7 8 .6 5 8.100 8.075 Chemical Shift (p... 1.00 8 .1 1 8 .1 0 8 .0 9 8 .0 8 7.65 7.60 Chemical Shift (ppm) 4.37 7 .6 8 7 .6 8 7 .6 6 7 .6 6 7 .6 5 7 .6 4 7 .6 4 7 .6 3 7 .6 2 7 .6 1 7 .6 0 7 .5 9 7 .5 8 7.525 7.500 Chemical Shift (ppm) 0.96 7 .5 3 7 .5 3 7 .5 1 7 7 .5 1 7 .4 9 7 .4 9 5.325 5.275 Chemical Shift (ppm) 1.00 5 .3 4 5 .3 2 5 .3 2 5 .3 1 5 .3 1 5 .3 0 5 .2 9 5 .2 8 5 .2 8 5 .2 7 5 .2 7 5 .2 5 3.725 3.675 Chemical S... 0.97 3 .7 5 3 .7 2 3 .7 1 3 .6 9 3.200 3.150 Chemical Shi... 1.01 3 .2 0 3 .1 9 3 .1 7 3 .1 5 1.650 1.625 Chemical S... 3.02 1 1

(72)

Espectro 69: RMN 13C do composto 74. (74) O 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 200 180 160 140 120 100 80 60 40 20 0 Chemical Shift (ppm) 2 2 .4 0 3 6 .8 0 8 0 .2 9 1 1 3 .6 1 1 2 2 .0 7 1 2 2 .9 9 1 2 3 .0 7 1 2 3 .3 2 1 2 6 .3 8 1 2 6 .9 8 1 3 0 .3 9 1 3 1 .1 8 1 5 2 .7 5 126.50 Chemical Shift (ppm) 1 2 6 .9 1 2 6 .7 3 1 2 6 .4 1 2 6 .3 8 123.0 122.5 122.0 Chemical Shift (ppm) 1 2 3 .3 2 1 2 3 .2 4 1 2 3 .0 7 1 2 2 .9 9 1 2 2 .2 4 1 2 2 .0 7

(73)

Espectro 70: IV do composto 75. 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400 Wavenumber (cm-1) 40 48 56 64 72 80 88 96 % T ra n smi tt a n ce 4 6 0 .9 1 4 7 2 .4 8 5 4 5 .7 6 6 1 7 .1 2 7 3 6 .6 9 7 6 3 .6 9 8 4 0 .8 2 8 8 1 .3 2 9 1 4 .1 1 9 3 7 .2 5 9 6 6 .1 8 1 0 5 4 .8 9 1 0 6 6 .4 6 1 0 8 7 .6 7 1 1 0 1 .1 7 1 1 3 2 .0 3 1 2 3 0 .3 8 1 2 6 8 .9 5 1 3 0 3 .6 6 1 3 3 0 .6 6 1 3 7 8 .8 8 1 4 4 0 .5 9 1 4 8 6 .8 7 2 8 6 7 .6 8 2 9 1 2 .0 3 2 9 2 1 .6 7 2 9 6 7 .9 6 2 9 8 3 .3 9 (74) O 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17

(74)

Espectro 71: E.M. do composto 75. O O (75) 11 109 8 7 6 5 4 3 2 1 ₁₂ 13 14 15 16 17 18 19 20

(75)

Espectro 72: RMN 1H do composto 75. O O (75) 1 1 1 0 9 8 7 6 5 4 3 2 1 _{1 2} 1 3 1 4 1 5 1 6 1 7 1 8 1 9 2 0 9 8 7 6 5 4 3 2 1 Chemical Shift (ppm) 6.00 4.12 2.11 2.06 2.04 2.03 Chloroform-d 1 .5 8 1 .6 0 1 .6 1 1 .6 4 2 .4 4 2 .4 6 2 .4 8 2 .4 9 4 .4 2 4 .4 3 4 .4 5 4 .4 6 4 .4 8 4 .4 9 4 .5 0 7 .3 1 7 .3 3 7 .3 4 7 .3 5 7 .3 6 7 .3 7 7 .7 0 7 .7 2 7 .8 3 7 .8 5 7.875 7.850 7.825 7.800 Chemical Shift (ppm) 2.06 7 .8 7 7.750 7.725 7.700 7.675 Chemical Shift (ppm) 2.05 7 .7 7 .7 7.375 7.350 7.325 7.300 Chemical Shift (ppm) 4.12 7 .3 1 7 .3 3 7 .3 3 7 .3 4 7 .3 5 7 .3 6 7 .3 7 7 .3 7 4.50 4.45 4.40 Chemical Shift (ppm) 2.04 4 .4 2 4 4 4 .5 0 2.475 Chemical ... 2.03 1.150 1.125 Chemical ... 6.00 1.600 Chemical Shift ... 2.11 1 .5 1 .6

(76)

Espectro 73: RMN H x H COSY do composto 75. O O (75) 1 1 1 09 8 7 6 5 4 3 2 1 ₁₂ 1 3 1 4 1 5 1 6 1 7 1 8 1 9 20

(77)

Espectro 74: RMN 13_{C do composto 75.} O O (75) 1 1 1 09 8 7 6 5 4 3 2 1 _{1 2} 1 3 1 4 1 5 1 6 1 7 1 8 1 9 2 0 200 180 160 140 120 100 80 60 40 20 0 Chemical Shift (ppm) Chloroform-d 2 1 .5 7 4 8 .7 4 7 4 .7 5 9 0 1 2 2 .7 1 1 2 7 1 2 7 .8 3 1 2 8 .0 4 1 2 9 .0 6 1 3 8 .4 8 129.0 128.5 128.0 127.5 Chemical Shift (ppm) 1 2 9 .0 6 1 2 8 .0 4 1 2 7 .8 3 1 2 7 77 76 75 Chemical Shi... 7 4 .7

(78)

Espectro 75: IV do composto 76. (76) 20 19 18 17 16 15 14 13 12 1 2 3 4 5 6 7 8 9 10 11 O O 4000 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400 Wavenumber (cm-1) 40 48 56 64 72 80 88 96 % T ra n smi tt a n ce 5 4 3 .8 6 1 9 .0 6 5 7 .6 7 3 2 .8 7 5 9 .8 8 2 7 .3 8 7 9 .3 9 1 2 .1 9 3 5 .3 9 6 8 .1 9 9 8 .9 1 0 4 3 1 0 7 8 1 1 2 8 1 2 2 6 1 2 3 6 1 2 9 7 1 3 5 3 1 3 7 6 1 4 4 4 1 4 8 4 2 8 8 8 2 9 2 5 2 9 6 7 3 0 2 9 3 0 6 6

(79)

Espectro 76: E.M. do composto 76. (76) 20 19 18 17 16 15 14 13 12 1 2 3 4 5 6 7 8 9 10 11 O O

(80)

Espectro 77: RMN 1H do composto 76. (76) 20 19 18 17 16 15 14 13 12 1 2 3 4 5 6 7 8 9 10 11 O O 11 10 9 8 7 6 5 4 3 2 1 0 Chemical Shift (ppm) 4.18 3.02 2.13 1.00 1.05 1.00 2.00 1.00 Chloroform-d 1 .1 3 1 .1 4 1 .3 6 1 .3 8 1 .5 6 1 .6 0 2 .1 5 2 .1 6 2 .1 8 2 .4 7 2 .4 9 2 .5 1 2 .5 2 3 .9 4 3 .9 6 3 .9 7 3 .9 9 4 .0 1 4 .5 5 4 .5 7 4 .5 8 4 .5 9 4 .6 1 4 .6 2 7 .3 2 7 .3 3 7 .3 4 7 .3 5 7 .3 8 7 .6 9 7 .7 1 7 .8 3 7 .8 5 7 .8 6 7.825 7.775 Chemical Shift (ppm) 2.12 7 .8 6 7.8 5 7 .8 5 7 .8 3 7 .8 1 7.725 7.700 7.675 Chemical Shift (ppm) 2.13 7 .7 2 7 .7 2 7.7 1 7 .7 1 7 .7 0 7 .6 9 7.375 7.350 7.325 7.300 Chemical Shift (ppm) 4.18 7 .3 8 7 .3 8 7.3 7 7 .3 6 7 .3 5 7 .3 5 7 .3 5 7 7 .3 4 7 .3 3 7 .3 3 7 .3 3 7.3 2 4.65 4.60 4.55 Chemical Shift (ppm) 1.00 4 .6 2 4 .6 1 4.5 9 4 .5 9 4 .5 8 4 .5 8 4 .5 7 4 .5 5 4 .5 4 4.05 4.00 3.95 3.90 Chemical Shift (ppm) 1.05 4 .0 2 4 .0 1 3 .9 9 3 .9 9 3.9 7 3 .9 6 3 .9 4 2.500 Chemica... 1.00 2 .5 2 2 .5 1 2 .4 9 2 .4 7 2.175 2.150 Chemical Shift... 2.00 2 .1 8 2 .1 8 2 .1 5 1.575 Chemic... 1.00 1 .6 0 1 .5 7 1 .5 6 1 .5 4 1.375 Chemic... 3.00 1.125 Chemical ... 3.02 1 .1 4 1 .1 3

(81)

Espectro 78: RMN H x H COSY do composto 76. (76) 20 19 18 17 16 15 14 13 12 1 2 3 4 5 6 7 8 9 10 11 O O

(82)

Espectro 79: RMN 13C do composto 76. (76) 20 19 18 17 16 15 14 13 12 1 2 3 4 5 6 7 8 9 10 11 O O 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 Chemical Shift (ppm) 2 1 .2 9 2 1 .6 6 4 7 .3 2 4 8 .3 8 7 3 .4 6 7 3 .9 7 9 0 .9 3 9 1 .9 0 1 2 2 .7 5 1 2 2 .9 0 1 2 6 .9 2 1 2 8 .2 0 1 3 0 .8 7 1 3 6 .6 6 1 3 9 .6 0 127.5 127.0 Chemical Shift (p... 1 2 7 .7 3 1 2 7 .5 7 1 2 6 129.0 128.5 128.0 Chemical Shift (ppm) 1 2 8 .8 8 1 1 2 8 .1 7 1 2 8 .1 127.75 127.50 Chemical Shift (... 1 2 7 .7 1 2 7

(83)

Espectro 80: IV do composto 77. 18 (77) 6 5 4 3 2 1 O 7 8 9 10 11 12 13 14 15 16 17 4000 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400 Wavenumber (cm-1) 40 48 56 64 72 80 88 96 % T ra n smi tt a n ce 4 4 5 2 6 0 6 9 7 6 8 5 9 2 9 7 1 0 1 0 1 0 1 1 1 2 1 2 1 3 1 4 1 4 1 5 1 5 1 6 2 8 2 9 3 0 3 0 3 0

(84)

Espectro 81: E.M. do composto 77. 18 (77) 6 5 4 3 2 1 O 7 8 9 10 11 12 13 14 15 16 17

(85)

Espectro 82: RMN 1H do composto 77. 18 (77) 6 5 4 3 2 1 O 7 8 9 10 11 12 13 14 15 16 17 11 10 9 8 7 6 5 4 3 2 1 0 Chemical Shift (ppm) 3.24 1.00 3.13 Chloroform-d 6 .1 5 7 .1 6 7 .1 8 7 .1 8 7 .2 0 7 .2 3 7 .2 5 7 .3 3 7 .3 8 7 .4 8 7 .5 0 7 .5 1 7.50 7.45 7.40 7.35 7.30 7.25 7.20 7.15 Chemical Shift (ppm) 3.24 2.14 2.13 2.12 0.95 Chloroform-d 7 .5 1 ₇.50 ₇.48 7 .4 0 7 .4 0 7 .3 8 7 .3 8 7 .3 5 7 .3 4 7 .3 3 7 .3 2 7 .3 1 7 .2 8 7 .2 7 7 .2 7 7 .2 6 7 .2 5 7 .2 5 7 .2 3 7 .2 2 7 .2 0 ₇.20 7 .2 0 7.1 8 7 .1 8 7 .1 7 7 .1 6 7 .1 6 6.16 6.14 Chemical Shift ... 1.00 6 .1 5 6 .1 5 2.400 2.375 2.350 Chemical Shift (ppm) 3.13

(86)

Espectro 83: RMN 13C do composto 77. (77) 6 5 4 3 2 1 O 7 8 9 10 11 12 13 14 15 16 17 200 180 160 140 120 100 80 60 40 20 0 Chemical Shift (ppm) Chloroform-d 1 3 .5 6 1 1 0 .1 0 1 2 3 .1 1 1 2 5 .8 7 1 2 8 .2 8 1 2 8 1 3 1 .4 2 1 3 4 .6 6 1 4 6 .7 2 1 5 1 .2 7 128 127 126 Chemical Shift (ppm) 1 2 8 1 2 8 .5 2 1 2 8 .2 1 2 7 .0 0 1 2 6 .9 0 1 2 5 .8 7

(87)

Espectro 84: IV do composto 78.

Espectro 85: E.M. do composto 78.

3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400 Wavenumber (cm-1) 60 65 70 75 80 85 % T ra n s m it ta n c e (78) a 4 a 6 a 10 ₁₀_b 2' 1' 13 12 11 10 9 6 8 7 5 4 3 2 1 _O O

(88)

Espectro 86: RMN de 1_{H do composto 78.} (78) a 4 a 6 a 10 ₁₀_b 2' 1' 13 12 11 10 9 6 8 7 5 4 3 2 1 _O O

(89)

Espectro 87: RMN de 13_{C do composto 78.} (78) a 4 a 6 a 10 ₁₀_b 2' 1' 13 12 11 10 9 6 8 7 5 4 3 2 1 _O O

(90)

Espectro 88: IV do composto 79. (79) 11 1'' 1' 10_b 6a 4_a 10a 10 9 8 7 6 5 4 3 2 1O O N OH 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400 Wavenumber (cm-1) 84 86 88 90 92 94 96 98 100 102 % T ra n smi tt a n ce 3 9 5 .3 4 4 1 6 .5 6 5 5 3 .4 8 7 3 2 .8 3 8 3 8 .9 8 8 3 .2 5 8 9 6 .7 5 9 4 6 .8 9 9 8 9 .3 2 1 0 2 9 .8 2 1 1 0 1 .1 7 1 1 5 1 .3 1 1 1 7 6 .3 8 1 2 3 6 .1 7 1 2 5 7 .3 8 1 3 1 3 .3 1 1 3 7 6 .9 5 1 4 0 7 .8 1 4 5 6 .0 2 1 5 2 7 .3 7 1 5 9 1 .0 1 1 6 1 4 .1 5 2 8 5 6 .1 1 2 9 2 1 .6 7 2 9 7 1 .8 2 3 4 3 0 .8

(91)

Espectro 89: E.M. do composto 79. (79) 11 1'' 1' 10b 6a 4a 10a 10 9 8 7 6 5 4 3 2 1O O N OH

(92)

Espectro 90: RMN de 1H do composto 79. (79) 11 1'' 1' 10b 6a 4a 10a 10 9 8 7 6 ₅ 4 3 2 1O O N OH 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 Chemical Shift (ppm) 6.09 2.04 2.01 0.97 0.75 Chloroform-d 1 .8 4 1 .8 7 1 .9 0 2 .5 7 2 .6 0 2 .6 3 7 .4 2 7 .4 3 7 .4 5 7 .4 6 7 .4 9 7 .5 0 7 .5 4 7 .8 9 7 .9 2 8 .2 4 8 .2 8 1 7 .9 9 2.625 2.575 Chemical Shift (... 2.01 2 .6 3 2 .5 1.875 1.825 Chemical Sh... 2.09 1 .9 1 .8 4 8.300 8.250 Chemical Shift (ppm) 0.97 8 .2 8 8 .2 7 8 .2 5 8 .2 4 8 .2 4 7.925 7.875 Chemical Shift ... 1.02 7 .9 2 7 .9 1 7 .9 1 7 .8 9 7 .8 8 7.55 7.50 7.45 7.40 Chemical Shift (ppm) 2.04 7 .5 5 7 .5 4 7 .5 2 7 .5 1 7 .5 0 7 .4 7 7 .4 6 7 .4 5 7 .4 3 7 .4 2 18.1 17.8 Chemica... 0.75 1 7 .9 9

(93)

Espectro 91: RMN de 13_{C do composto 79.} (79) 1'' 1' 10b 4a 10a 10 9 8 6 5 4 3 2 1O 200 180 160 140 120 100 80 60 40 20 0 Chemical Shift (ppm) Chloroform-d 1 5 .3 9 3 1 .3 6 7 9 .3 6 1 0 9 .8 6 1 2 2 .3 8 1 2 3 .3 8 1 2 5 .5 7 1 3 0 .0 8 1 3 0 .5 7 1 4 3 .0 6 1 6 4 .0 2 1 8 0 .8 6 130.0 127.5 125.0 122.5 Chemical Shift (ppm) 1 3 0 .0 8 1 2 8 .9 2 1 2 5 .5 7 ₁23 12

(94)

Espectro 92: IV do composto 80. 10 10a 9a 9 8 7 6 5a 5 2' 1' 4a 4 3 2 1 O NOH O (80) 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 Wavenumber (cm-1) 20 40 60 80 100 % T ra n smi tt a n ce 5 1 8 .7 7 5 6 3 .1 2 6 7 3 .0 5 6 9 8 .1 2 7 6 5 .6 1 8 1 9 .6 1 8 8 7 .1 1 9 1 7 .9 7 9 4 1 .1 1 1 0 2 7 .8 9 1 0 5 2 .9 6 1 1 1 4 .6 7 1 1 6 4 .8 1 1 1 9 7 .6 1 2 7 2 .8 1 1 3 3 8 .3 8 1 3 7 1 .1 6 1 4 0 2 .0 2 1 4 6 1 .8 1 5 6 5 .9 4 1 5 9 2 .9 4 1 6 2 1 .8 7 1 6 3 9 .2 2 2 9 3 7 .1 2 9 7 5 .6 7 3 1 6 0 .8 1

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Espectro 93: E.M do composto 80. 10 10a 9a 9 8 7 6 5a 5 2' 1' 4a 4 3 2 1 O NOH O (80)

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Espectro 94: RMN de 1_{H do composto 80.} 10 10a 9a 9 8 7 6 5a 5 2' 1' 4a 4 3 2 1 O NOH O (80)

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Espectro 95: RMN de 13_{C do composto 80.} 10 10a 9a 9 8 7 6 5a 5 2' 1' 4a 4 3 2 1 O NOH O (80)

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Espectro 96: IV do composto 81. 5' 4' 3' 2' 1' 12 11 10 9 8 7 6 5 4 3 2 1 NOH NOH H O (81) 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400 Wavenumber (cm-1) 84 86 88 90 92 94 96 98 % T ra n smi tt a n ce

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Espectro 97: E.M. do composto 81. 5' 4' 3' 2' 1' 12 11 10 9 8 7 6 5 4 3 2 1 NOH NOH H O (81)

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Espectro 98: RMN de 1_{H do composto 81.} 5' 4' 3' 2' 1' 12 11 10 9 8 7 6 5 4 3 2 1 NOH NOH H O (81)

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Espectro 99: RMN de 13C do composto 81. 5' 4' 3' 2' 1' 12 11 10 9 8 7 6 5 4 3 2 1 NOH NOH H O (81)

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Espectro 100: RMN H x H COSY do composto 81. 5' 4' 3' 2' 1' 12 11 10 9 8 7 6 5 4 3 2 1 NOH NOH H O (81)

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Espectro 101: RMN HET-COSY (J1) do composto 81. 5' 4' 3' 2' 1' 12 11 10 9 8 7 6 5 4 3 2 1 NOH NOH H O (81)

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Espectro 102: RMN HET-COSY (J2 e J3) do composto 81. 5' 4' 3' 2' 1' 12 11 10 9 8 7 6 5 4 3 2 1 NOH NOH H O (81)

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Espectro 103: IV do composto 82. 7 8 4a 12 11 10 9a 9 6 5a 5 4 2' 1' 3 2 1 (82) O O N N H NH₂ O 10a 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 Wavenumber (cm-1) 65 70 75 80 85 90 95 100 % T ra n smi tt a n ce 5 4 9 .6 2 6 0 1 .6 9 6 5 7 .6 2 6 7 3 .0 5 7 7 9 .1 1 8 7 5 .5 4 9 4 6 .8 9 1 0 1 6 .3 2 1 1 1 6 .6 1 1 5 3 .2 4 1 1 6 2 .8 8 1 1 9 5 .6 7 1 3 0 9 .4 5 1 3 4 6 .0 9 1 4 1 5 .5 2 1 4 5 2 .1 6 1 5 7 9 .4 4 1 6 2 1 .8 7 1 6 5 6 .5 8 2 9 2 1 .6 7 2 9 7 1 .8 2 3 2 0 7 .0 9 3 2 8 6 .1 6 3 4 4 6 .2 3 3 4 7 7 .0 8

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Espectro 104: E.M. do composto 82. 7 8 4a 12 11 10 9a 9 6 5a 5 4 2' 1' 3 2 1 (82) O O N N H 10a

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Espectro 105: RMN de 1H do composto 82. 7 8 4a 10 9a 9 6 5a 5 4 2' 1' 3 2 1 (82) O O 10a

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Espectro 106: RMN de 13_{C do composto 82.} 7 8 4a 12 11 10 9a 9 6 5a 5 4 2' 1' 3 2 1 (82) O O N N H NH2 O 10a

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Espectro 107 RMN HET-COSY (J2_{e J}3_{) composto 82.} 7 8 4a 12 11 10 9a 9 6 5a 5 4 2' 1' 3 2 1 (82) O O N N H NH2 O 10a

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Espectro 108: IV do composto 83. 14 (83) O OCH3 N N H C NH2 O 1 2 4 5 7 8 9 10 11 3 12 1' 2' ₃_' 4' 5' 13 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400 Wavenumber (cm-1) 70 75 80 85 90 95 100 % T ra n smi tt a n ce 4 9 5 .6 2 5 7 0 .8 4 6 5 1 .8 3 7 0 0 .0 4 7 5 7 .9 7 8 4 .9 8 5 8 .1 8 9 0 6 .3 9 9 6 0 .3 9 1 0 4 9 .1 1 0 8 3 .8 2 1 1 2 4 .3 1 1 2 2 4 .6 1 3 1 7 .1 6 1 3 5 1 .8 8 1 3 8 0 .8 1 4 4 0 .5 9 1 5 3 1 .2 3 1 6 0 0 .6 5 1 6 4 5 .0 1 1 6 8 5 .5 1 2 9 3 1 .3 2 2 9 6 7 .9 6 3 2 3 0 .2 3 3 2 8 0 .3 7 3 4 6 5 .5 1 3 5 5 6 .1 5

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Espectro 109: E.M do composto 83. 14 (83) O OCH3 N N H CNH2 O 1 2 4 5 7 8 9 10 11 3 12 1' 2' ₃_' ₄' 5' 13

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Espectro 110: RMN de 1H do composto 83. 14 (83) O OCH3 N N H C NH2 O 1 2 4 5 7 8 9 10 11 3 12 1' 2' ₃_' 4' 5' 13

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Espectro 111: RMN de 13_{C do composto 83.} 200 180 160 140 120 100 80 60 40 20 0 Chemical Shift (ppm) DMSO-d6 1 7 .8 1 2 2 .3 4 2 5 .4 4 6 1 .4 4 1 2 1 .2 4 1 2 8 .7 7 1 2 9 .2 0 1 3 0 .3 2 1 3 2 .1 3 1 3 4 .0 5 1 5 5 .1 9 1 5 7 .7 5 1 8 4 .0 8 134 132 130 128 126 124 122 Chemical Shift (ppm) 1 3 4 .0 5 1 3 2 .3 6 132 .1 3 1 3 0 .3 2 1 2 9 .2 0 1 2 8 .7 7 1 2 8 .6 3 1 2 5 .1 6 1 2 4 .3 0 1 2 1 .2 4 14 (83) O OCH3 N N H CNH2 O 1 2 4 5 7 8 9 10 11 3 12 1' 2' ₃_' 4' 5' 13

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Espectro 112: IV do composto 84. (84) O OCH3 N N H 1 2 4 5 6 7 8 9 10 11 3 1' 2' ₃_' ₄' 5' NO2 NO2 12 13 14 15 16 17 18 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 Wavenumber (cm-1) 20 30 40 50 60 70 80 90 100 % T ra n smi tt a n ce 4 5 7 7 7 7 8 9 9 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 2 2 2 3 3

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Espectro 113: E.M do composto 84. (84) O OCH3 N N H 1 2 4 5 6 7 8 9 10 11 3 1' 2' ₃_' 4' 5' NO2 NO2 12 13 14 15 16 17 18

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Espectro 114: RMN de 1_{H do composto 84.} (84) O OCH3 N N H 1 2 4 5 6 7 8 9 10 11 3 1' 2' 3' 4' 5' NO2 NO2 12 13 14 15 16 17 18 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 Chemical Shift (ppm) 4.17 2.19 3.03 2.13 3.04 1.02 0.98 0.97 Chloroform-d 3 .3 7 3 .3 9 5 .1 5 7 .5 1 7 .5 4 7 .6 6 7 .7 0 8 .1 2 8 .1 5 8 .2 6 8 .2 8 8 .3 1 8 .4 2 8 .4 7 9 .1 6 1 3 .9 7 8.5 8.0 7.5 Chemical Shift (ppm) 4.17 2.19 8 .4 7 8 .4 2 8 .3 1 8 .2 8 8 .2 6 8 .1 5 8 .1 2 7 .7 0 7 .6 6 7 .6 3 7 .5 8 ₇.54 7 .5 1 5.2 5.1 5.0 Chemical Shift (ppm) 0.97 5 .1 5 3.4 3.3 Chemical Shift (... 2.13 3 .3 9 3 .3 7

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Espectro 115: RMN de 13_{C do composto 84.} (84) O OCH3 N N H 1 2 4 5 6 7 8 9 10 11 3 1' 2' ₃_' ₄' 5' NO2 NO2 12 13 14 15 16 17 18 200 180 160 140 120 100 80 60 40 20 0 Chemical Shift (ppm) Chloroform-d 1 8 .0 2 2 3 .2 1 2 5 .6 8 6 2 .1 1 1 1 6 .7 1 1 2 0 .3 7 1 2 3 .1 6 1 2 9 .6 0 1 2 9 .9 6 1 3 2 .9 0 1 3 3 .6 8 1 3 5 .5 1 1 3 9 .6 6 1 4 4 .0 5 1 5 7 .0 6 1 8 4 .5 5 134 132 130 128 126 124 122 120 Chemical Shift (ppm) 1 3 5 .5 1 1 3 3 .6 8 1 3 3 .5 2 13 2 .9 0 1 3 2 .4 8 1 3 1 .3 8 1 2 9 .9 6 1 2 9 .6 0 1 2 6 .3 7 1 2 3 .6 7 1 2 3 .1 6 12 0 .3 7

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Espectro 116: IV do composto 85. 14 (85) 13 5' 4' 3' 2' 1' 12 3 11 10 9 8 7 6 5 4 2 1 O OCH3 N N H C S NH2 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400 Wavenumber (cm-1) 56 64 72 80 88 96 % T ra n smi tt a n ce 4 2 6 .2 4 7 8 .2 7 5 2 6 .4 8 6 9 8 .1 2 7 7 7 .1 8 8 5 8 .1 8 9 1 0 .2 5 9 4 8 .8 2 9 6 4 .2 5 1 0 2 7 .8 9 1 0 5 2 .9 6 1 1 0 8 .8 9 1 2 1 6 .8 8 1 3 1 5 .2 4 1 3 4 9 .9 5 1 4 3 6 .7 3 1 4 5 0 .2 3 1 5 2 1 .5 8 1 5 9 6 .8 1 6 3 9 .2 2 1 7 0 0 .9 3 2 0 7 3 .1 4 2 8 5 2 .2 5 2 9 2 3 .6 2 9 6 4 .1 3 1 5 6 .9 5 3 2 9 9 .6 6 3 4 2 3 .0 8

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Espectro 117: E.M. do composto 85. 14 (85) 13 5' 4' 3' 2' 1' 12 3 11 10 9 8 7 6 5 4 2 1 O OCH3 N N H C S NH2

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Espectro 118: RMN de 1H do composto 85. 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 Chemical Shift (ppm) 3.07 3.01 2.28 2.03 2.00 0.88 1.12 0.70 Chloroform-d 1 .6 7 1 .7 7 3 .3 0 3 .3 3 5 .0 7 5 .0 8 5 .1 0 5 .1 0 5 .1 4 6 .9 5 7 .4 8 7 .5 2 7 .5 5 7 .5 6 7 .5 9 7 .6 2 8 .0 9 8 .1 0 8 .1 4 1 1 .7 0 8.15 8.10 8.05 8.00 Chemical Shift (ppm) 2.00 8 .1 4 8 .1 3 8 .0 8 .0 7 8 .0 7 8 .0 6 8 .0 6 7.55 7.45 Chemical Shift (ppm) 2.28 7 .6 3 7 .6 2 7.5 9 7 .5 8 7 .5 6 7 .5 5 7 .5 2 7 .5 1 7 .4 8 7 .4 7 7.00 6.90 Chemical Shift (ppm) 0.88 6 .9 5 5.20 5.15 5.10 5.05 5.00 Chemical Shift (ppm) 1.12 5 .1 4 5 .1 4 5 .1 3 5 .1 1 5 .1 0 5 .1 0 5 .0 8 5 .0 7 5 .0 6 3.35 3.25 Chemical Shift (p... 2.03 3 .3 3 .3 0 1.80 1.70 1.60 Chemical Shift (ppm) 3.07 3.04 1 .7 7 1 .6 7 1 .6 7 14 (85) 13 5' 4' 3' 2' 1' 12 3 11 10 9 8 7 6 5 4 2 1 O OCH3 N N H C S NH2

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Espectro 119: RMN de 13_{C do composto 85.} (85) ₅_' 4' 3' 2' 1' 3 11 10 7 6 5 4 2 1 O 200 180 160 140 120 100 80 60 40 20 0 Chemical Shift (ppm) Chloroform-d 1 7 .9 5 2 2 .9 4 2 5 .6 4 6 1 .7 6 1 2 0 .1 6 1 2 9 .5 8 1 3 0 .1 9 1 3 2 .4 1 1 3 3 .3 1 1 3 3 .6 3 1 5 7 .3 0 1 7 9 .5 4 1 8 4 .5 8 134 132 130 128 126 124 122 120 Chemical Shift (ppm) 1 3 3 .1 1 1 3 2 1 3 1 .5 8 1 3 0 1 2 9 1 2 6 .4 1 2 3 .1

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Espectro 120: IV do composto 86. O OCH3 N NH O OH 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 1' 2' _3' _4' 5' (86) 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 Wavenumber (cm-1) 80 85 90 95 100 % T ra n smi tt a n ce 7 6 1 .7 6 8 4 8 .5 4 1 1 1 2 .7 4 1 1 7 2 .5 3 1 2 3 2 .3 1 1 2 5 1 .5 9 1 2 6 5 .0 9 1 3 4 9 .9 5 1 3 8 4 .6 6 1 4 5 6 .0 2 1 4 8 8 .8 1 5 1 7 .7 3 1 6 0 6 .4 4 1 6 3 9 .2 2 2 9 2 9 .3 9 2 9 7 1 .8 1 3 4 3 0 .8

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Espectro 121: E.M. do composto 86. O OCH3 N NH O OH 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 1' 2' _3' _4' 5' (86)

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O OCH3 N NH O OH 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 1' 2' _3' _4' 5' (86)

(125)

O OCH3 N NH O OH 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 1' 2' _3' _4' 5' (86)

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Espectro 124: RMN HET-COSY (J1_{) do composto 86.} O OCH3 N NH O OH 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 1' 2' _3' _4' 5' (86)

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Espectro 125: RMN HET-COSY (J2 e J3) do composto 86. O OCH3 N NH O OH 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 1' 2' _3' _4' 5' (86)

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Espectro 126: IV do composto 87. 4a 18 17 16 15 14 13 12 11 10a 10 9a 9 8 7 6 5a 5 4 2' 1' 3 2 1 (87) O O N N H HO O 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400 Wavenumber (cm-1) 75 80 85 90 95 100 % T ra n smi tt a n ce 5 2 4 .5 5 5 6 8 .9 1 5 9 3 .9 8 6 2 8 .6 9 6 4 9 .9 7 0 9 .6 9 7 7 9 .1 1 8 4 6 .6 1 9 1 2 .1 8 1 0 0 0 .8 1 1 4 1 .6 1 1 6 6 .7 1 2 3 6 .1 1 2 7 8 .5 1 3 0 9 .4 1 3 4 6 .0 1 4 1 3 .5 1 5 0 8 .0 1 5 4 0 .8 1 5 7 7 .5 1 6 0 8 .3 1 6 5 4 .6 1 6 7 9 .7 2 8 5 2 .2 2 9 7 5 .6 2 9 9 4 .9 3 1 6 2 .7 3 1 9 7 .4 3 3 4 4 .0

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Espectro 127: E.M. do composto 87. 4a 18 17 16 15 14 13 12 11 10a 10 9a 9 8 7 6 5a 5 4 2' 1' 3 2 1 (87) O O N N H HO O

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Espectro 128: EM-ES íons negativos do composto 87. 4a 18 17 16 15 14 13 12 11 10a 10 9a 9 8 7 6 5a 5 4 2' 1' 3 2 1 (87) O O N N H HO O

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Espectro 129: RMN de 1_{H do composto 87.} 4a 18 17 16 15 14 13 12 11 10a 10 9a 9 8 7 6 5a 5 4 2' 1' 3 2 1 (87) O O N N H HO O

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Espectro 130: RMN de 13_{C do composto 87.} 4a 18 17 16 15 14 13 12 11 10a 10 9a 9 8 7 6 5a 5 4 2' 1' 3 2 1 (87) O O N N H HO O

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Espectro 131: RMN H x H COSY do composto 87. 4a 18 17 16 15 14 13 12 11 10a 10 9a 9 8 7 6 5a 5 4 2' 1' 3 2 1 (87) O O N N H HO O

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Espectro 132: RMN HET-COSY (J1) do composto 87. 4a 18 17 16 15 14 13 12 11 10a 10 9a 9 8 7 6 5a 5 4 2' 1' 3 2 1 (87) O O N N H HO O

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Espectro 133: RMN HET-COSY (J2_{e J}3_{) do composto 87.} 4a 18 17 16 15 14 13 12 11 10a 10 9a 9 8 7 6 5a 5 4 2' 1' 3 2 1 (87) O O N N H HO O

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Espectro 134: IV do composto 88. (88) O OH N N H NH2 O 1 2 1' 2' 3 4 5 6 7 8 9 10 3' 4' 5' 11 12 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400 Wavenumber (cm-1) 65 70 75 80 85 90 95 100 % T ra n smi tt a n ce 4 8 5 .9 8 5 4 5 .7 6 5 6 3 .1 2 6 7 1 .1 2 7 3 4 .7 6 7 7 3 .3 3 8 4 2 .7 5 9 3 5 .3 2 1 0 2 4 .0 3 1 1 4 3 .6 1 1 7 8 .3 1 1 2 5 9 .3 1 1 3 0 1 .7 4 1 3 3 4 .5 2 1 3 8 4 .6 6 1 4 3 4 .8 1 5 5 6 .3 1 5 7 5 .5 8 1 5 9 4 .8 7 1 6 8 9 .3 6 2 8 5 6 .1 1 2 9 2 1 .6 7 2 9 4 8 .6 7 3 1 2 4 .1 7 3 2 1 6 .7 3 3 2 8 6 .1 6 3 4 7 9 .0 1

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Espectro 135: E.M. do composto 81. (88) O OH N N H NH2 O 1 2 1' 2' 3 4 5 6 7 8 9 10 3' 4' 5' 11 12

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Espectro 136: EM-ES íons negativos do composto 88. (88) O OH N N H NH2 O 1 2 1' 2' 3 4 5 6 7 8 9 10 3' 4' 5' 11 12