DIOGO MONTES VIDAL IDENTIFICAÃÃO E SÃNTESE DOS ...

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xxii ABSTRACT Chapter I: The Poplar crop has gaining attention in the southern region of Brazil, principally to supply the match industry and manufacturing matchsticks boxes. The poplar moth Condylorrhiza vestigialis, is considered the major pest of this culture. The defoliation caused by this Lepidoptera occurs on the higher phase of plant grown, affecting seriously the production. The natural pheromone was extracted from female pheromonal glands by the use of solvent extraction, between the 7 th and 10 th hours of scotophase. Y-olfactometer bioassays showed great attractiveness of males to extracts with notable behavioral changing with exposure to natural compounds. The electroantennographic activity of these compounds in male antennae was tested in GC- EAD assays, and it was observed the presence of six possible pheromonal components. The chemical structure of the compounds was studied by analyzing their chromatographic profiles, mass (GC-MS) and infrared spectra (GC- FTIR), as well as by analysis of microderivatizations products with 4-methyl-1,2,4- triazolina-3 ,5-dione (MTAD), with DMDS and isomerization of double bonds employing thiophenol. The spectroscopic and chromatographic information obtained indicated that the compounds refer to aldehydes belonging to the type I Lepidoptera pheromonal class and their structures were identified as: E-hexadec-12-enal (1), (11E,14Z)-hexadeca-11 ,14-dienal (2), Z-hexadec-14-enal (3), (10Z,12E)-hexadeca-10,12-dienal (4), (10E, 12Z)-hexadeca-10,12-dienal (5) and (10E,12E)-hexadeca-10,12-dienal (6). The chemical structure of the compound 2 has to be confirmed by its respective synthesis which is underway. Chapter II: Brazil is one of the major soybean producers in the world. In the piercing-sucking complex that occurs in soybean crops, Edessa meditabunda is considered a secondary pest. The behavioral responses of males and females to aeration extracts from conspecifics suggested the presence of a male sex pheromone. GC analyses of aeration extracts released by males and females revealed the presence of two male-specific compounds in a ratio of 92:8. GC-EAD assays indicated that the major component is bioactive in females, supporting the bioassay data. Analysis of the mass and infrared spectra of the male specific compounds suggested that they were both methyl branched long chain methyl esters. The structure of these methyl esters were proposed based on the mass spectra (EI) of the respective hydrocarbons obtained from microderivatizations, as
xxiii being methyl 4,8,12-trimethylpentadecanoate (major) and methyl 4,8,12- trimethyltetradecanoate (minor). A synthetic route based on a sequence of Grignard reactions, starting from ciclopropyl methyl ketone was developed to obtain the synthetic standards after 11 steps. The synthetic standards co-eluted with the natural pheromone on three different GC stationary phases. Y-olfactometer assays employing the synthetic standards were strongly attractive to females, either for the major compound as for the mixture with the minor on the same proportion found in natural extracts.
Page 1 and 2: DIOGO MONTES VIDAL IDENTIFICAÇÃO
Page 3 and 4: Dedico Ao Lito e à Lita por todo o
Page 5 and 6: iii À minha família que tanto amo
Page 7 and 8: v 3.2.4 Determinação dos Índices
Page 9 and 10: vii 3.2.5 Síntese de 1-bromo-4,8-d
Page 11 and 12: ix ESPECTRO DE RMN DE 1H DO COMPOST
Page 13 and 14: xi ESPECTRO DE RMN DE 1 H DO COMPOS
Page 15 and 16: xiii Esquema 27: Microderivatizaç
Page 17 and 18: xv Figura 23: Espectro de massas re
Page 19 and 20: xvii ÍNDICE DE TABELAS Tabela 1: A
Page 21 and 22: xix APRESENTAÇÃO A presente disse
Page 23: xxi microderivatizações, como sen
Page 27 and 28: 2 1 - INTRODUÇÃO 1.1- Ecologia qu
Page 29 and 30: 4 1.2 Condylorrhiza vestigialis (Le
Page 31 and 32: 6 2 - OBJETIVOS 2.1 - Objetivo Gera
Page 33 and 34: Figura 4: Sequência de métodos ex
Page 35 and 36: 10 3.1.2 Extração de glândulas f
Page 37 and 38: 12 3.2.2 Cromatografia gasosa acopl
Page 39 and 40: 14 [24, 29] 3.3.4 Metiolação de l
Page 41 and 42: 16 [21, 32] 3.5.3 Síntese de 2-(4-
Page 43 and 44: 18 13 C RMN (50 MHz, CDCl 3 ) : 14,
Page 45 and 46: 20 3.5.9 Síntese de 2-(dodec-11-in
Page 47 and 48: 22 Figura 8: Detecção simultânea
Page 49 and 50: 700 895 944 975 24 0,3 1411 1470 17
Page 51 and 52: 26 O N O N N O N O R 1 N N R 2 R 3
Page 53 and 54: 28 O H O (E,Z) H O Bombykal (E,Z) P
Page 55 and 56: 30 espectroscópicas mencionadas an
Page 57 and 58: 32 A reação de metiolação tamb
Page 59 and 60: 34 Figura 21: Análises em CG-EAD o
Page 61 and 62: 2751 3014 Absorbância 1389 1412 14
Page 63 and 64: 1385 1416 967 1472 1713 38 0,04 285
Page 65 and 66: 40 HO HO HBr DHP Br Br OH OH Toluen
Page 67 and 68: 42 O espectro de RMN de 1 H (págin
Page 69 and 70: 44 aminopropil)amideto de potássio
Page 71 and 72: 84.7 80.7 79.8 68.0 46 HO (16) HO (
Page 73 and 74: 48 5 - CONSIDERAÇÕES FINAIS E PER
Page 75 and 76:
50 1- INTRODUÇÃO O Brasil é o se
Page 77 and 78:
52 ( ) 3 (3Z,6Z,9Z)-eicosa-3,6,9-tr
Page 79 and 80:
54 O Voláteis de E. heros O (2E,4Z
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56 Bioensaios em olfatômetro tipo
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58 3- METODOLOGIA 3.1 Microderivati
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60 13 C RMN (50 MHz, CDCl 3 ) : 0,1
Page 87 and 88:
62 Dados espectroscópicos 26b: 1 H
Page 89 and 90:
64 Dados espectroscópicos 28a: 1 H
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66 13 C RMN (50 MHz, CDCl 3 ) : 12,
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68 reacional foi submetido à atmos
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70 EM m/z (%): 210 (4); 182 (1); 15
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72 “não resposta” quando o ins
Page 99 and 100:
Absorbância 1439 1463 2871 1744 74
Page 101 and 102:
76 Para determinar o número e a po
Page 103 and 104:
78 4.2 Síntese do 4,8,12-trimetilp
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80 4.2.1 Preparação do 2-ciclopro
Page 107 and 108:
82 4.2.3 Preparação do 1-bromo-4,
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84 (x1,000,000) 1.5 1.0 0.5 0.0 -0.
Page 111 and 112:
86 Mecanismo Intermolecular O H O C
Page 113 and 114:
88 Figura 47: Co-injeção do éste
Page 115 and 116:
90 Figura 49: Co-injeção do éste
Page 117 and 118:
92 mistura feromonal mediando o com
Page 119 and 120:
94 REFERÊNCIAS BIBLIOGRÁFICAS: [1
Page 121 and 122:
[39] KOVATS, E., Gas-chromatographi
Page 123 and 124:
[77] ALDRICH, J. R., HOFFMANN, M. P
Page 125 and 126:
2750 3014 1391 1413 1474 1715 Absor
Page 127 and 128:
2743 3014 1472 Absorbância 2962 97
Page 129 and 130:
61.8 33.7 31.1 29.2 Br (8) 104 ESPE
Page 131 and 132:
Br (9) 1.00 2.24 4.35 2.31 8.48 106
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108 ESPECTRO DE MASSAS DO COMPOSTO
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98.8 80.6 79.9 67.1 62.3 31.4 30.8
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1.86 4.00 12.60 2.72 112 ESPECTRO D
Page 139 and 140:
2934 2955 Transmitância (%) 2855 3
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84.7 68.0 63.0 32.7 29.5 29.4 29.4
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0.98 2.38 2.44 2.10 0.96 22.00 118
Page 145 and 146:
Page 147 and 148:
129.3 126.9 58.0 12.9 HO 122 ESPECT
Page 149 and 150:
ESPECTROS SELECIONADOS PARA O CAPÍ
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71.2 45.6 25.7 21.0 17.2 14.7 0.7 0
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71.3 35.5 25.0 20.5 8.3 0.5 0.1 (24
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Page 157 and 158:
136.9 136.7 116.8 115.6 29.1 28.6 2
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Page 161 and 162:
135.600 135.446 125.179 124.433 71.
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137.4 137.2 124.2 123.0 71.2 43.3 4
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Page 167 and 168:
138.7 138.5 135.7 135.5 135.3 124.6
Page 169 and 170:
138.7 138.6 137.3 137.1 123.6 122.4
Page 171 and 172:
Page 173 and 174:
135.4 135.3 135.1 125.3 124.9 124.5
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137.1 136.9 135.4 135.3 125.3 124.5
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Page 179 and 180:
139.3 138.7 138.6 135.8 135.5 135.2
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138.7 138.6 137.1 136.8 135.4 135.2
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Page 185 and 186:
171.1 138.3 138.3 138.2 135.4 135.3
Page 187 and 188:
171.1 138.4 138.3 138.2 137.0 137.0
Page 189 and 190:
Page 191 and 192:
171.2 65.0 39.5 39.4 37.4 37.2 33.1
Page 193 and 194:
171.2 65.0 37.5 37.4 37.4 37.3 37.3
Page 195 and 196:
Page 197 and 198:
63.5 39.5 39.4 37.5 37.4 37.3 37.3
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63.5 37.5 37.4 37.4 37.3 37.3 37.3
Page 201 and 202:
Page 203 and 204:
174.6 51.4 39.5 39.4 37.4 37.4 37.0
Page 205 and 206:
174.6 51.4 37.5 37.4 37.4 37.3 37.3
Page 207:
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