Hockey stick-shaped LC compounds 3874.3. Synthesis4.3.1. 2-Decyloxy-6-ethynylnaphthalene, 14. (a)Alkylation of 6-bromo-2-naphthol. A mixture of 6-bromo-2-naphthol (2.5 g, 11.2 mmol), K 2 CO 3 (6.2 g,44.8 mmol), bromodecane (2.72 g, 12.3 mmol) andbutanone (60 ml) was stirred under reflux for 20 h.After cooling, the reaction mixture was filtered off andwashed with diethyl ether; the filtrate was concentratedand the residue recrystallized from a methanol/ethanol1/1 mixture; yield 3.7 g (91%), m.p. 57.0–58.5uC. 1 HNMR (CDCl 3 ) d: 7.89 (s, 1H), 7.65–7.45 (m, 3H), 7.18–7.08 (m, 2H), 4.04 (t, 2H), 1.84 (m, 2H), 1.28 (m, 14H),0.88 (t, 3H). (b) Coupling with 2-methyl-3-butyn-2-ol. Amixture of 2-bromo-6-decyloxy-naphthalene (2.0 g,5.5 mmol), PdCl 2 (PPh 3 ) 2 (38.5 mg, 0.055 mmol), CuI(5.2 mg, 0.027 mmol), triphenylphosphine (14.40 mg,0.055 mmol) and TEA (40 ml) was heated under refluxfor 40 min. Pure 2-methyl-3-butyn-2-ol (0.91 ml,8.25 mmol) was added and the reflux continued for afurther 1.5 h. After cooling, the reaction mixture wasfiltered through a celite pad, washing with 150 ml ofTHF. The filtrate was evaporated and the residuerecrystallized from acetonitrile to give a grey solid; yield1.87 g (93%), m.p. 72.3–75.0uC. IR (KBr) n max /cm 21 :3350, 2914, 2850, 1599, 1251, 1171, 857. (c) Protectivegroup elimination as acetone. In a 100 ml roundbottomedflask equipped with distillation apparatus,the intermediate 4-(6-decyloxy-naphthalen-2-yl)-2-methyl-but-3-yn-2-ol (1.35 g, 3.68 mmol) was dissolvedin toluene (40 ml); NaOH (0.50 g) was then added andthe mixture slowly heated, the acetone being distilled offover 7 h. The cooling reaction solution was filteredthrough a celite pad, washing with toluene; toluenewas removed under reduced pressure. Columnchromatography of the crude product (eluant hexane)afforded a light yellow solid; yield 0.665 g (59%), m.p.42.4–46.7uC. IR (KBr) n max /cm 21 : 3298, 2955, 2919,2850, 1626, 1597, 1469, 1387, 1229, 1021, 860. 1 H NMR(CDCl 3 ) d: 7.94 (s, 1H), 7.66 (t, J58.2 Hz, 2H), 7.47 (d,J58.4 Hz, 1H), 7.17–7.08 (m, 2H), 4.06 (t, 2H), 3.09 (s,1H), 1.82 (m, 2H), 1.28 (m, 14 H), 0.8 (m, 3H).Elemental analysis for C 22 H 28 O: calcd C 85.66, H 9.15;found C 85.78, H 9.13%.4.3.2. 1-Decyl-4-(4-ethynylphenyl)piperazine, 15. (a)Amine protection. To a 500 ml three-necked roundbottomedflask N-phenylpiperazine (14.5 ml,94.9 mmol), K 2 CO 3 (78.8 g, 519.4 mmol) and butanone(250 ml) were added and the mixture stirred at 0uC.Ethyl chloroformate (37 ml, 379.6 mmol) was addeddropwise over 1 h. After addition, the reaction mixturewas heated under reflux for a further 1 h, cooled to 0uCand then a 4% methanol solution of NaOH wascautiously added. The suspension was stirred at roomtemperature overnight and then filtered. The filtrate wasconcentrated and distilled under vacuum to give 15.44 g(69%) of colourless oil, b.p. 145–150uC (0.2 mm Hg). IR(KBr) n max /cm 21 :2981, 2921, 1700, 1598, 1434, 1230,761. 1 H NMR (CDCl 3 ) d: 7.25 (t, 2H), 6.87 (t, 3H), 4.16(q, J57.1 Hz, 2H), 3.60 (t, J55.2 Hz, 4H), 3.09 (t,J55.2 Hz, 4H), 1.28 (t, J57.1 Hz, 3H). (b) Iodination.N-protected piperazine (10.0 g, 42.6 mmol) andNaHCO 3 (5.38 g, 64 mmol) in CH 2 Cl 2 (160 ml) andwater (120 ml) were stirred at 5uC. Iodine (10.2 g,40.2 mmol) was added over 2 h. The mixture wasstirred for a further 2 h at room temperature andsodium thiosulphate added to eliminate excess iodine.The organic phase was concentrated and the residuerecrystallized from n-hexane; yield 8.28 g (54%) ofcolourless crystals, m.p. 77.3–77.6uC.1 H NMR(CDCl 3 ) d: 7.53 (d, J58.7 Hz, 2H), 6.69 (d, J58.7 Hz,2H), 4.16 (q, J57.1 Hz, 2H), 3.62 (t, J55.2 Hz, 4H),3.11 (t, J55.2 Hz, 4H), 1.28 (t, J57.1 Hz, 3H). (c) Aminedeprotection. A mixture of 4-(4-iodophenyl)piperazine-1-carboxylic acid ethyl ester (8.0 g, 22.2 mmol), KOH(32.4 g, 577.0 mmol) and hydrazine monohydrate(5.4 ml, 111.1 mmol) in ethylene glycol was heatedunder reflux for 2 h. After cooling, the reactionmixture was poured into water (250 ml) and extractedwith diethyl ether (56100 ml). The organic solution wasdried over NaSO 4 , evaporated and recrystallized fromhexane to give 3.92 g (61%) of a white solid, m.p. 131–133uC. 1 H NMR (CDCl 3 ) d: 7.51 (d, J58.8 Hz, 2H),6.65 (d, J58.8 Hz, 2H), 3.03 (m, 8 H). (d) Aminealkylation. A mixture of 1-(4-iodophenyl)piperazine(3.87 g, 13.44 mmol), K 2 CO 3 (3.71 g, 26.88 mmol), 1-bromodecane (3.07 ml, 14.78 mmol) in butanone (80 ml)was heated under reflux for 45 h. The cooling mixturewas filtered off and the filtrate concentrated to give asolid that was purified by recrystallization from ethanol;yield 4.24 g (73%), m.p. 88.6–89.0uC. 1 H NMR (CDCl 3 )d: 7.50 (d, J58.7 Hz, 2H), 6.68 (d, J58.7 Hz, 2H), 3.18(t, 4 H), 2.59 (t, 4H), 2.38 (t, 2H), 1.51 (m, 2H), 1,27(broad, 14 H), 0.86 (t, 3H). (e) Coupling with 2-methyl-3-butyn-2-ol. A mixture of 1-decyl-4-(4-iodophenyl)piperazine (2.1 g, 4.9 mmol), PdCl 2 (PPh 3 ) 2 (36.3 mg,0.05 mmol), CuI (9.5 mg, 0.05 mmol) in THF (8 ml)and TEA (20 ml) was degassed by rapid bubbling of dryargon through it for 20 min. Pure 2-methyl-3-butyn-2-ol(0.8 ml, 7.35 mmol) was added and the mixture stirred atroom temperature for 24 h. Another portion of thecatalyst was added and the reaction stirred for a further1 h. The mixture was filtered through a celite pad,washing with THF (250 ml), and the solvents wereevaporated. The residue was recrystallized from heptaneto give 1.72 g (91%) of white crystals, m.p.
388 R. Cristiano et al.117.0–125.4uC. IR (KBr) n max /cm 21 :3160, 2918, 2849,2819, 2778, 2222, 1606, 1514, 1465, 1286, 1245, 1171,824. 1 H NMR (CDCl 3 ) d: 7.24 (d, J58.0 Hz, 2H), 6.76(d, J58.0 Hz, 2H), 3.24 (m, 4 H), 2.59 (m, 4H), 2.37(m, 2H), 1.59 (broad, 8H), 1.26 (broad, 14 H), 0.88 (t,3H). (f) Protective group elimination as acetone.The intermediate 4-[4-(4-decylpiperazin-1-yl)phenyl]-2-methyl-3-butyn-2-ol (1.71 g, 4.44 mmol) was dissolvedin toluene (50 ml). NaOH (0.5 g) was added and themixture slowly heated and acetone distilled off over 6 h.Toluene was removed under reduced pressure and theresidue recrystallized from acetonitrile to give 1.16 g(80%) of a light yellow crystal, m.p. 69.9uC. IR (KBr)n max /cm 21 :3311, 2929, 2848, 2774, 2096, 1605, 1510,1247, 1157, 1138, 820. 1 H NMR (CDCl 3 ) d: 7.37 (d,J58.7 Hz, 2H), 6.82 (d, J58.7 Hz, 2H), 3.25 (m, 4 H),2.97 (s, 1H), 2.59 (m, 4H), 1.59 (broad, 8H), 2.38 (m,2H), 1.51 (m, 2H), 1.27 (m, 14H), 0.88 (t, 3H).Elemental analysis for C 22 H 34 N 2 : calcd C 80.93, H10.50, N 8.58; found C 80.98, H 10.47, N 8.33%.4.3.3. 2-(4-Decyloxyphenyl)-5-[4-(4-heptyloxyphenylethynyl)phenyl]-1,3,4-oxadiazole,1. A mixture of 0.5 g(1.09 mmol)of2-(4-bromophenyl)-5-(4-decyloxyphenyl)-1,3,4-oxadiazole (9), PdCl 2 (PPh 3 ) 2 (70 mg, 0.1 mmol),CuI (9.5 mg, 0.05 mmol) and triphenylphosphine(26.2 mg, 0.1 mmol) in TEA (25 ml) was stirred underreflux for 45 min. 1-Heptyloxy-4-ethynylbenzene (10)(0.235 g, 1.09 mmol) dissolved in 5 ml of TEA was thenadded dropwise. The reaction mixture was heated underreflux for a further 2.5 h, cooled at room temperatureand filtered, washing with THF (80 ml). The solventswere evaporated and the crude product wasrecrystallized from ethanol to give the product(0.348 g, 54 %). IR (KBr) n max /cm 21 : 2921, 2849, 2211,1603, 1511, 1497, 1468, 1247, 839, 830.1 H NMR(CDCl 3 ) d: 8.07 (t, 4H, J57.3 Hz), 7.63 (d, 2H,J58.0 Hz), 7.47 (d, 2H, J58.3 Hz), 7.01 (d, 2H,J58.3 Hz), 6.88 (d, 2H, J58.1 Hz), 4.0 (m, 4H), 1.78(m, 4H), 1.27 (broad, 22H), 0.89 (t, 6H). 13 CNMR(CDCl 3 ) d: 164.62, 163.67, 161.98, 159.57, 133.16,131.87, 128.64, 126.96, 126.59, 122.95, 115.96, 114.93,114.56, 114.42, 92.57, 87.37, 68.24, 68.06, 31.86, 31.73,29.52, 29.31, 29.11, 25.95, 22.63, 22.58, 14.07. Elementalanalysis for C 39 H 48 N 2 O 3 : calcd C 79.02, H 8.16, N 4.73;found C 79.13, H 8.14, N 4.64%.4.3.4. 2-(4-Decyloxyphenyl)-5-[4-(4-decyloxyphenylethynyl)phenyl]-1,3,4-oxadiazole,2. This compound wassynthesized as described for compound 1, using 1-decyloxy-4-ethynylbenzene (11); yield 49%. IR (KBr)n max /cm 21 : 2920, 2848, 2209, 1606, 1503, 1464, 1247,836. 1 H NMR (CDCl 3 ) d: 8.08 (d, 2H, J58.2 Hz), 8.05(d, 2H, J58.6 Hz), 7.63 (d, 2H, J58.3 Hz), 7.47 (d, 2H,J58.6 Hz), 7.01 (d, 2H, J58.7 Hz), 6.87 (d, 2H,J58.7 Hz), 4.0 (m, 4H), 1.78 (m, 4H), 1.27 (broad,28H), 0.88 (t, 6H). 13 C NMR (CDCl 3 ) d: 162.67, 160.28,133.87, 132.60, 129.33, 127.67, 127.31, 123.71, 116.72,115.27, 93.28, 88.10, 68.95, 68.77, 32.57, 30.23, 29.83,26.67, 23.35, 14.79. Elemental analysis for C 42 H 54 N 2 O 3 :calcd C 79.46, H 8.57, N 4.41; found C 79.24, H 8.36, N4.30%.4.3.5. 2-(4-Decyloxyphenyl)-5-[4-(4-dodecyloxyphenylethynyl)phenyl]-1,3,4-oxadiazole,3. This compound wassynthesized as described for compound 1, using 1-dodecyloxy-4-ethynylbenzene (12); yield 56%. IR (KBr)n max /cm 21 : 2919, 2850, 1605, 1511, 1497, 1253, 811. 1 HNMR (CDCl 3 ) d: 8.08 (m, 4H), 7.64 (d, 2H, J57.7 Hz),7.48 (d, 2H, J57.7 Hz), 7.02 (d, 2H, J58.0 Hz), 6.88 (d,2H, J58.0 Hz), 4.0 (m, 4H), 1.79 (m, 4H), 1.27 (broad,32H), 0.88 (t, 6H). 13 C NMR (CDCl 3 ) d: 164.65, 163.72,162.03, 159.60, 133.19, 131.90, 128.69, 127.00, 126.63,122.99, 116.00, 114.97, 114.59, 92.60, 87.39, 68.27,68.11, 31.88, 29.56, 29.34, 25.98, 22.67, 14.10.Elemental analysis for C 44 H 58 N 2 O 3 : calcd C 79.72, H8.82, N 4.23; found C 79.70, H 9.09, N 4.07%.4.3.6. 2-[4-(6-Decyloxy-naphthalen-2-ylethynyl)-phenyl]-5-(4-decyloxy-phenyl)-1,3,4-oxadiazole, 5. This compoundwas synthesized as described for compound 1,using 2-decyloxy-6-ethynylnaphthalene (14), with a littlemodification in the work-up. The product was insolublein TEA, so the reaction mixture was filtered and washedwith TEA (50 ml). The white solid residue was purifiedby column chromatography (silica gel, chloroform), andtwice recrystallized from ethanol affording the pureproduct; yield: 65%. IR (KBr) n max /cm 21 : 2919, 2850,1612, 1497, 1470, 1256, 842. 1 H NMR (CDCl 3 ) d: 8.07(m, 5H), 7.70 (m, 4H), 7.54 (d, 2H, J58.6 Hz), 7.19–7.00(m, 4H), 4.06 (m, 4H), 1.83 (m, 4H), 1.28 (broad, 28H),0.88 (t, 6H).13 C NMR (CDCl 3 ) d: 164.69, 163.72,162.05, 158.11, 134.45, 132.06, 131.62, 129.33, 128.72,128.35, 126.87, 126.68, 123.26, 119.86, 117.37, 116.04,115.00, 106.61, 93.07, 88.32, 68.29, 68.14, 31.86, 29.55,29.31, 29.18, 26.08, 25.99, 22.66, 14.08. Elementalanalysis for C 46 H 56 N 2 O 3 : calcd C 80.66, H 8.24, N4.09; found C 80.11, H 8.79, N 4.07%.4.3.7. 1-Decyl-4-(4-{4-[5-(4-decyloxyphenyl)-1,3,4-oxadiazol-2-yl]phenylethynyl}phenyl)piperazine,6. This compoundwas synthesized as described for compound 1,using 1-decyl-4-(4-ethynylphenyl)piperazine (15), withsimilar work-up as described for compound 5; yield 55%of a light yellow powder. IR (KBr) n max /cm 21 : 2921,2849, 2209, 1602, 1515, 1496, 1468, 1244, 840, 818. 1 H
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AUTOBIOGRAFIARodrigo Cristiano nasc
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Rodrigo CristianoMATERIAIS MOLECULA
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À minha esposa Cláudia.
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VÍNDICEINTRODUÇÃO ..............
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VIILISTA DE FIGURASFigura 1. Proces
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IXFigura 31. Espectro de RMN de 1 H
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XIFigura 63. Espectros de (a) UV e
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XIIILISTA DE TABELASTabela 1. Os ti
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XVTGA - Análise termogravimétrica
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XVIIABSTRACTThe synthesis and chara
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Introdução 19A química orgânica
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Introdução 21fenômenos possuem t
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Introdução 23elétrico é aplicad
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Introdução 25(Figura 3). A verdad
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Introdução 27investigar a conexã
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Introdução 29com um banco de dado
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Introdução 31descrever a estrutur
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Introdução 33Nas fases esméticas
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Introdução 35OHC 6 H 13OOOC 11 H
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Introdução 37O interesse na sínt
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Introdução 39Figura 17. Represent
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Introdução 41Figura 19. Esquema d
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Introdução 43mais comum nesses ma
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Introdução 45formam estruturas su
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Introdução 47do material quando n
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Introdução 491,3,4-oxadiazolN NOO
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Introdução 51R 2 OR 1OR 2N N ONON
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Introdução 53estável através de
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RESULTADOS EDISCUSSÃO
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Resultados e Discussão 57aromátic
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Resultados e Discussão 59Esquema 3
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Resultados e Discussão 61mantendo-
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Resultados e Discussão 63(ν C≡C
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Resultados e Discussão 65funcional
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Resultados e Discussão 67ROORROOO4
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Resultados e Discussão 69Uma rota
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Resultados e Discussão 71baNNOc d
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Resultados e Discussão 73Tabela 3.
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Resultados e Discussão 75Para o co
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Resultados e Discussão 77porque o
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Resultados e Discussão 795. CLs cu
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Resultados e Discussão 81gerado a
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Resultados e Discussão 835.2. Prop
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Resultados e Discussão 85(a)Cr-CrC
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Resultados e Discussão 87(a)(b)Fig
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Resultados e Discussão 89Esses com
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Resultados e Discussão 91catalíti
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Resultados e Discussão 93a complet
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Resultados e Discussão 95A banda l
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Resultados e Discussão 97constante
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Resultados e Discussão 99A não-pl
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Resultados e Discussão 101(a)(b)T
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Resultados e Discussão 103(e)trans
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Resultados e Discussão 1056.5. Pro
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Resultados e Discussão 107composto
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Resultados e Discussão 109composto
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Resultados e Discussão 1117. Tris-
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Resultados e Discussão 113Esquema
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Resultados e Discussão 115A caract
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Resultados e Discussão 117ppm rela
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Resultados e Discussão 1197.2. Est
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Resultados e Discussão 121Figura 7
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Resultados e Discussão 123N21-N22
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Resultados e Discussão 125método
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Resultados e Discussão 127após lo
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Resultados e Discussão 129baseado
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Resultados e Discussão 131aquecime
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Resultados e Discussão 133composto
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Resultados e Discussão 1357.5. Est
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Resultados e Discussão 137estabili
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Conclusões 1398. CONCLUSÕESEm ger
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SEÇAO EXPERIMENTAL
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Seção Experimental 143respectivam
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Seção Experimental 1457,08 (m, 2H
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Seção Experimental 147K 2 CO 3 (7
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Seção Experimental 149H, -CH 2 NC
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Seção Experimental 1512918, 2851,
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- Page 237: In summary, we performed the synthe
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