α′-hydroxy-α,β-unsaturated Tosylhydrazones: Preparation And Use As Intermediates For Carbonyl And Enone Transpositions

Regiospecifically generated α,β-unsaturated tosylhydrazones dianions are treated with molecular oxygen, yielding α′-hydroxy-α,β-unsaturated tosylhydrazones, versatile intermediates for organic synthesis. They proved to be useful for 1,2-carbonyl and 1,2-enone transpositions, and also permitted the preparation of α′-hydroxy enones in very high yields.321929372950Morris, D.G., Carbonyl group transpositions (1982) Chem. Soc. Rev., 11, p. 397Kane, V.V., Singh, V., Martin, A., Doyle, D.L., The chemistry of 1, 2-carbonyl transposition (1983) Tetrahedron, 39, p. 345Mimura, T., Nakai, T.A., New approach to regiocontrolled enone transpositions based on the facile conversion of α, β-enone tosylhydrazones to the transposed allylic sulfides (1981) Chem. Lett., 1579Moëns, L., Baizer, M.M., Little, R.D., A stereoselective electroreductive cyclization pathway to the isolactarane-type sesquiterpene 1-sterpurene (1986) J. Org. Chem., 51, p. 4497Liotta, D., Brown, D., Hoekstra, W., Monahan R. III, Pyridinium dichromate-induced 1, 3-oxidative rearrangements of enynols (1987) Tetrahedron Lett, 28, p. 1069Fehr, C., Guntern, O., Efficient synthesis of enantiomerically pure α-ionone from (R)-and (S) -α-Damascone (1992) Helv. Chim. Acta, 75, p. 1023Buckholder, T.P., Fuchs, P.L., Total synthesis of the cephalotaxus alkaloids Dl-cephalotaxine and dl-11-Hydroxycephalotaxine and dl-Drupacine (1990) J. Am. Chem. Soc., 112, p. 9601Paquette, L.A., Wang, T.Z., Yo, N.Y., Access to naturally occuring cyclooctanoids by two-carbon intercalation. Total synthesis of (+)-ceroplastol I (1993) J. Am. Chem. Soc., 115, p. 1676Majgier-Baranowska, H., Templeton, J.F., Synthesis of steroids 5-α-and 5-β-4-ketones from the 4-en-3-one: 1,2-Carbonyl transposition (1999) Tetrahedron, 55, p. 3717Mimura, T., Nakai, T., A facile method for regioselective 1, 2-carbonyl transposition of δ2-cyclohexenone systems leading to the positionally isomeric δ2-cyclohexenones (1980) Chem. Lett., 1099Barillier, D., Levillain, J., Vazeux, M., Halides-based electrophiles mediated epoxide ring-opening reactions of α, β-epoxysulfoxides in C6-series: Deoxygenation versus dehydration and an overall 1, 2-keto transposition (1994) Tetrahedron, 50, p. 5413Bunnell, C.A., Fuchs, P.L., Rapid and unequivocal determination of syn-anti stereochemistry for toluenesulfonylhydrazone and other imine derivatives via carbon-13NMR spectroscopy. A synthetic adjunct (1977) J. Org. Chem., 42, p. 2614Dauben, W.G., Rivers, G.T., Zimmerman, W.T., The role of tosylhydrazone stereochemistry upon the regiospecificity of olefin formation (1977) J. Am. Chem. Soc., 99, p. 3414Caille, J.C., Farnier, M., Guilard, R., Substitution régiosélective d'arènesulfonylhydrazones α, β-unsaturées via la réaction de shapiro (1986) Can. J. Chem., 64, p. 824noteStemke, J.E., Bond, F.T., Efficient synthesis of deuterated olefins from arenesulfonylhydrazones (1975) Tetrahedron Lett, 1815Chamberlin, A.R., Bond, F.T., Regiochemical control in alkenyllithium generated from arenesulfonylhydrazones (1979) Synthesis, 44Chamberlin, A.R., Sheppeck J.E. II, p-Toluenesulfonylhydrazide (1995) Encyclopedia of Reagents for Organic Synthesis, 7, pp. 4953-4958. , Paquette, L.A., Ed.John Wiley & Sons: ChichesterCaglioti, L., The reduction of tosylhydrazones and of acyl tosylhydrazides (1966) Tetrahedron, 22, p. 487Elphimoff-Felkin, I., Verrier, M., Sur la formation d'intermediaires vinyliques au cours de la reduction, selon Wolff-Kishner ou Caglioti, De Quelques cetones α., β-ethyleniques cyclaniques (1968) Tetrahedron Lett., 1515Hutchins, R.O., Kacher, M., Rua, L., The synthetic utility and mechanism of the reductive deoxygenation of α., β- unsaturated p-tosylhydrazones with sodium cyanoborohydride (1975) J. Org. Chem., 40, p. 923Taylor, E.J., Djerassi, C., Mechanism of the sodium cyanoborohydride reduction of α, β-unsaturated tosylhydrazones (1976) J. Am. Chem. Soc., 98, p. 2275Han, O., Shih, Y., Liu, L., Liu, H., On the mechanism of sodium cyanoborohydride reduction of tosylhydrazones (1988) J. Org. Chem., 53, p. 2105Mancuso, A.J., Huang, S.L., Swern, D., Oxidation of long-chain and related alcohols to carbonyls by dimethyl sulfoxide "activated" by oxalyl chloride (1978) J. Org. Chem., 43, p. 2480Chamberlin, A.R., Sall, D.J., Reduction of ketones to alkenes (1991) Comprehensive Organic Synthesis, 8, pp. 923-953. , Trost, B.M., Ed.Pergamon PressChandrasekhar, S., Mohapatra, S., Takhi, M., Practical and convenient reduction of sugar hydrazones to allyl alcohols (1996) Synlett, 759Mitra, R.B., Reddy, G.B., Selective cleavage of dimethylhydrazones to the carbonyl compounds using silica gel and its application in the synthesis of -9-tetradecenyl acetate (1989) Synthesis, 694Caglioti, L., Magi, M., The reaction of tosylhydrazones with lithium aluminum hydrade (1963) Tetrahedron, 19, p. 1127Blilkina, T.G., Shushunov, V.A., (1969) Reactions of Organometallic Compounds with Oxygen and Peroxides, , CRC Press, ClevelandPorter, N.A., Alkyl hydroperoxides (1992) Organic Peroxides, pp. 101-156. , Ando W., Ed.John Wiley & Sons, ChichesterCapp, C.W., Hawkins, E.G.E., Reactions of organic peroxides. 6. Reactions with amines (1953) J. Chem. Soc., p. 4106Buchi, G., Kulsa, P., Ogasawara, K., Rosati, R.L., Synthesis of velbanamine and catharanthine (1970) J. Am. Chem. Soc., 92, p. 99

Nitration Of Phenol, A Method On Semi-micro Scale For A 4 Hours Laboratory [nitração Do Fenol, Um Método Em Escala Semi-micro Para Disciplina Prática De 4 Horas]

A procedure for the nitration of phenol in a semi-micro scale, followed by separation of the formed orto- and para-nitrophenol isomers by column chromatography, is described. All the experiment, including determination of the melting point of the isolated products, require a period of 4 hours, and it is suitable for organic chemistry laboratory undergraduate courses.232270272Vogel, A.I., (1978) Textbook of Practical Organic Chemistry4th Ed., pp. 745-746. , Longman, LondonPavia, D.L., Lampman, G.M., Kriz Jr., G.S., (1982) Introduction to Organic Laboratory Techniques, a Contemporary Approach2nd Ed., pp. 231-239. , Saunders College Publ., PhiladelphiaFessenden, R.J., Fessenden, J.S., (1983) Techniques and Experiments for Organic Chemistry, , Willard Grant Press, BostonZeegers, P.J., (1993) J.Chem. Educ., 70, p. 1036Morrison, R.T., Boyd, R.N., (1992) Organic Chemistry6thed., p. 520. , Prentice Hall, Inc., New JerseyStreitwieser, A., Heathcock, C.H., Kosower, E.M., (1992) Introduction to Organic Chemistry4th Ed., pp. 1024-1032. , MacMillan Publ. Company, New YorkCarey, F.A., (1992) Organic Chemistry2nd Ed., pp. 452-498. , McGraw-Hill, Inc., New York(1996) The Merck Index, 12th Ed., , Merck & Co., Inc., New Jersey;Ouertani, M., Girard, P., Kagan, H.B., (1982) Tetrahedron Lett., 23, p. 4315. , e referências citadasMcCullough, T., Kubena, K., (1990) J.Chem. Educ., 67, p. 801Feigenbaum, A., (1986) J. Chem. Educ., 63, p. 815Ross, D.S., Hum, G.P., Blucher, W.G., (1980) J. Chem. Soc. Chem. Commun., p. 532Olah, G.A., Malhotra, R., Narang, S.C., (1989) Nitration: Methods and Mechanisms, , VCH Publ., Inc., New YorkCrouch, R.D., Nelson, T.D., Kinter, C.M., (1993) J. Chem. Educ., 70, pp. A203Flash, P., Phiri, S., Mukherjee, G., (1994) J. Chem. Educ., 71, pp. A5Mayo, D.W., Pike, R.M., Butcher, S.S., (1986) Microscale Organic Laboratory, , John Wiley & Sons, New York;Pavia, D.L., Lampman, G.M., Kriz, G.S., Engel, R.G., (1990) Introduction to Organic Laboratory Techniques, a Microscale Approach, , Saunders College Publ., WashingtonBell Jr., C.E., Clark, A.K., Taber, D.F., Rodig, O.R., (1997) Organic Chemistry Laboratory, Standard and Microscale Experiments2nd Ed., , Saunders College Publ., OrlandoQuando em concentrações adequadas, as manchas referentes aos produtos orto- e para-nitro-fenol podem ser visualizadas a olho nu, sem necessidade de reveladores especiaisAs frações contendo misturas de orto- e para-nitro-fenol não foram considerada

Efficient Access To Novel Furanofurone Compounds From Quinic Acid: Studies Of Inter-and Intramolecular Wittig Reactions On Lactones

(-)-Quinic acid has been converted into derivatives of a furo[3,2-b]furan-2-one system using Wittig olefination reactions of lactones. Studies for this transformation included the use of microwave-assisted reactions. © Georg Thieme Verlag Stuttgart.1930453049Barco, A., Benetti, S., De Risi, C., Marchetti, P., Pollini, G.P., Zanirato, V., (1997) Tetrahedron: Asymmetry, 8, p. 3515Garg, N.K., Caspi, D.D., Stoltz, B.M., (2005) J. Am. Chem. Soc, 127, p. 5970Hanessian, S., Wang, J., Montgomery, D., Stoll, V., Stewart, K.D., Kati, W., Maring, C., Laver, W.G., (2002) Bioorg. Med. Chem. Lett, 12, p. 3425Matsuo, K., Matsumoto, T., Nishiwaki, K., (1998) Heterocycles, 48, p. 1213Matsuo, K., Sugimura, W., Shimizu, Y., Nishiwaki, K., Kuwajima, H., (2000) Heterocycles, 53, p. 1505Baptistella, L.H.B., Cerchiaro, G., (2004) Carbohydr. Res, 339, p. 665Barnwell, M.G., Hungerford, N.L., Jolliffe, K.A., (2004) Org. Lett, 6, p. 2737Cytotoxic compounds isolated from plants of Goniothalamus species. See: (a) Ruiz, P.Murga, J.Carda, M.Marco, J. A. J. Org. Chem. 2005, 70, 713Lopez-Lazaro, M., Martin-Cordero, C., Bermejo, A., Cortés, D., Ayuso, M.J., (2001) Anticancer Res, 21, p. 3493Li, R.-T., Li, S.-H., Zhao, Q.-S., Lin, Z.-W., Sun, H.-D., Lu, Y., Wang, C., Zheng, Q.-T., (2003) Tetrahedron Lett, 44, p. 3531. , Found in plants of Schisandraceae family, used in Chinese traditional medicine. SeeIsolated from plants of Scrophularia species and used in Asian herbal medicine. See: Han, J. S.Lowary, T. L. J. Org. Chem. 2003, 68, 4116Isolated from Stemona species, which present insecticidal activities. See: Kaltenegger, E.Brem, B.Mereiter, K.Kalchhauser, H.Kählig, H.Hofer, O.Vajrodaya, S.Greger, H. Phytochemistry 2003, 63, 803A potent enzyme activator used for cardiac irregularities, isolated from Caribbean sponges of the genus Plakortis. See: Hayes, P. Y.Kitching, W. J. Am. Chem. Soc. 2002, 124, 9718Mereyala, H.B., Gadikota, R.R., (2000) Tetrahedron: Asymmetry, 11, p. 743. , Compounds found in braconid wasps. SeeMurphy, P.J., Brennan, J., (1988) Chem. Soc. Rev, 17, p. 1. , and references cited thereinLakhrissi, M., Chapleur, Y., (1996) Angew. Chem., Int. Ed. Engl, 35, p. 750Lakhrissi, Y., Taillefumier, C., Lakhrissi, M., Chapleur, Y., (2000) Tetrahedron: Asymmetry, 11, p. 417Sabitha, G., Reddy, M.M., Srinivas, D., Yadov, J.S., (1999) Tetrahedron Lett, 40, p. 165Microwave labstation MicroSYNTH (Millestone) operating at 2.45 GHz, dual magnetron system with delivered microwave power of 1000 W (pulsed irradiation), equipped with a thermocouple temperature control system. All experiments were conduced in sealed vessels (20 mL - the of the reactions were no more than 10% of this) with magnetic stirringThe lactone 3 was recovered intact when treated, with or without the assistance of microwaves, with diethylphosphonoacetate and bases (Horner-Wadsworth-Emmons olefinations)Batches of several reaction mixtures were combined for chromatographic purificationReaction of Lactone 3 with Ph3PCHCOOEt under Microwave Irradiation A 20 mL microwave vessel (for reactions up to 4 bar) containing a mixture of 3 (200 mg, 0.93 mmol, freshly distilled chlorobenzene (2 mL, and ethoxycarbonyl-methylene(triphenyl) phosphorane (5, 500 mg, 1.43 mmol) was connected to a temperature sensor, and the apparatus was irradiated for 1 h in a microwave equipment programmed for temperature control: 15 min to reach 180°C and then 1 h at this temperature. After cooling, the mixture was evaporated. The residue was purified by silica gel column chromatography (hexane-EtOAc 15, to give 6 (39, and 8 (46, besides unchanged lactone 3 (10, When batches of several reaction mixtures were combined for chromatographic purification, compounds 7 (7, 9 (1, and 10 (4, were also isolated. Compound 6: [α]D 20 47.6 (c 0.58, CHCl3, IR film, νDesmaële, D., (1996) Tetrahedron Lett, 37, p. 1233Bittner, C., Burgo, A., Murphy, P.J., Sung, C.H., Thornhill, A.J., (1999) Tetrahedron Lett, 40, p. 3455Preparation of 8 via the Bromoacetyl Derivative 12 1) A solution of 3 (200 mg, 0.93 mmol) in anhyd Et2O (15 mL, under argon atmosphere, was stirred at 0°C, and anhyd pyridine (100 μL, 1.2 mmol) was added, followed by bromoacetyl bromide (100 μL, 1.15 mmol, The solution was slowly warmed to r.t, in the absence of light, and the stirring was maintained for 2 h. Then, H2O (15 mL) was added and the aqueous layer was separated and extracted two more times with Et2O (15 mL, The combined organic layers were washed sequentially with H2O (25 mL, sat. CuSO4 solution (25 mL, H2O (25 mL) and brine (25 mL, separated, and dried (MgSO4, After filtration, the solvent was concentrated to give crude 12 in 89% yield (278 mg, used without purification in the next step. For characterization, a small sample was purified by flash chromatography hexane-EtOAc 20, to give 12 as white crSmall signals, always presented on the spectral data of crude 19, were attributed to the C7-epimer of 19 (less than 8% yield). This compound probably arises from a minor C7-epimer of the dialdehyde 18. A seven-membered lactone, possible by intramolecular transesterification reaction of 19, was not observed.Data for Compound 21, 4S,5 S,7S)-7-(2-Phenylethyl)-5-(3-phenylpropyl) tetrahydrofuro|3,2-b]furan-2 (3H)-one, α]D20 -14.5 (c 0.27, CHCl3, IR (film, νmax, 1779 cm-1. 1H NMR (500 MHz, CDCl3, δ, 1.59 (dd, 1 H, J, 10.3, 13.4 Hz, 1.70-1.97 (m, 6 H, 2.37 (dd, 1 H, J, 4.6, 13.4 Hz, 2.61-2.79 (m, 4 H, 2.65 (d, 1 H, J, 18.8 Hz, 2.79 (dd, 1 H, J, 6.2, 18.8 Hz, 4.46 (d, 1 H, J, 6.2 Hz, 4.73 (m, 1 H, 7.16-7.34 (m, 10 H, 13C NMR (125 MHz, CDCl3, δ, 26.0, 32.2, 35.6, 36.2, 36.3, 37.0, 42.8, 77.7, 80.7, 96.5, 125.9, 126.0, 128.2, 128.3, 128.4, 141.2, 141.3, 175.5. HRMS EI, m/z calcd for C23H26O3: 350.45094found: 350.4518

Synthesis Of Analgesics Paracetamol And Phenacetin And The Sweetener Dulcin: A Project For Undergraduate Organic Chemistry Laboratory [síntese Dos Analgésicos Paracetamol E Fenacetina E Do Adoçante Dulcina: Um Projeto Para Química Orgânica Experimental]

A synthesis of artificial sweetener dulcin starting from nitrobenzene was elaborated for undergraduate organic laboratory course. Paracetamol and phenacetin, both physiologically active analgesic compounds, were also prepared as intermediates. Besides a large scope of discussion subjects related with organic synthesis, interesting lectures about analgesics and sweeteners may also be performed in this project. The advantage of this project is the adaptability according to the conditions offered by the course, i.e., convenience and/or availability of time and reagents.262284286Imamura, P.M., Baptistella, L.H.B., (2000) Quim. Nova, 23, p. 270Ferreira, V.F., Silva, F.C., Perrone, C.C., (2001) Quim. Nova, 24, p. 905Williams, B.D., Williams, B., Rodino, L., (2000) J. Chem. Educ., 77, p. 357Goldsmith, R.H., (1987) J. Chem. Educ., 64, p. 954Ellis, J.W., (1995) J. Chem. Educ., 72, p. 671Kinghorn, A.D., Kennelly, E.J., (1995) J. Chem. Educ., 72, p. 676Walters, D.E., (1995) J. Chem. Educ., 72, p. 680Furniss, B.S., Hannaford, A.J., Smith, P.W.G., Tatchell, A.R., (1989) Vogel's' Textbook of Practical Organic Chemistry, 5th. Ed., p. 854. , Longman Scientific, Technical: New YorkStrazzolini, P., Giumanini, A.G., Runcio, A., (2001) Tetrahedron Lett., 42, p. 1387Ref. 4, p. 955. A N-fenil-hidroxilamina (2) foi preparada em 1/5 da escala indicadaO éter etílico, além de ser um solvente controlado pela polícia federal, mais caro que o acetato de etilaRef. 4, p. 985Kurzer, F., (1963) Org. Synth. Coll., 4, p. 52Ref. 4, p. 966Pavia, D.L., Lampman, G.M., Kriz, G.S., (1982) Organic Laboratory Techniques. A Contemporary Approach, 2nd Ed., p. 321. , Saunders College Publishing: PhiladelphiaAger, D.J., Pantaleone, D.P., Henderson, S.A., Katritzky, A.R., Prakash, I., Walters, D.E., (1998) Angew. Chem. Int. Ed., 37, p. 1803Korolkovas, A., Burckhalter, J.H., (1988) Química Farmacêutica, , Ed. Guanabara Koogan S. A.: Rio de Janeir

An Improved Synthesis Of 2,3- And 3,4-unsaturated Pyranosides: The Use Of Microwave Energy

Tipson-Cohen reactions of sugar derivatives containing contiguous sulfonyloxy groups have been studied in a microwave oven. Considerable rate increases and high yields of the unsaturated products have been observed. © 1993.345284078410Umezawa, Okazaki, Tsuchiya, Studies on Aminosugars. XXXI. Synthesis of 3,4-Dideoxy-3-enosides and the Corresponding 3,4-Dideoxysugars (1972) Bulletin of the Chemical Society of Japan, 45, pp. 3619-3624Ireland, Norbeck, Mandel, Mandel, (1985) J. Amer. Chem. Soc., 107, pp. 3285-3294Greespoon, Keinan, Selective deoxygenation of unsaturated carbohydrates with Pd(0)/Ph2SiH2/ZnCl2. Total synthesis of (+)-(S,S)-(6-methyltetrahydropyran-2-yl)acetic acid (1988) The Journal of Organic Chemistry, 53, pp. 3723-3731Fürstner, Weidmann, Synthesis of all 2,3,4-trimethoxy-5-hexenal (5,6-dideoxy-2,3,4-tri-O-methylaldohex-5-enose) isomers (1990) The Journal of Organic Chemistry, 55, pp. 1363-1366Román, Serrano, Cuéllar, Marfil, Galbis, Synthesis of Acyclic Unsaturated Sugar Derivatives (1992) Journal of Carbohydrate Chemistry, 11, pp. 1-19Fraser-Reid, (1985) Acc. Chem. Res., 18, pp. 347-354Dauben, Kowalczyk, Lichtenthaler, (1990) J. Org. Chem., 55, pp. 2391-2398Carbohydr. Chem., pp. 1-26. , For a review of these methods see Unsaturated DerivativesTipson, Cohen, (1965) Carbohydr. Res., 1, pp. 338-340Albano, Horton, Tsuchiya, (1966) Carbohydr. Res., 2, pp. 349-362Defaye, (1968) Bull. Soc. Chim. France, pp. 2099-2102Fraser-Reid, Boctor, Some aspects of the formation of hex-2-enopyranosides from methyl 2,3-di-O-methanesulfonyl-α-D-glucopyranosides (1969) Canadian Journal of Chemistry, 47, pp. 393-401Yamazaki, Matsuda, Sugiyama, Seto, Yamaoka, Steric and electrostatic effects on the elimination of 2- and 3-sulphonyloxy-groups from methyl 4,6-O?benzylidenehexopyranosides (1977) Journal of the Chemical Society, Perkin Transactions 1, pp. 1981-1984Hesek, Wilson, (1974) Anal. Chem., 46, p. 1160Abu-Samra, Morris, Koirtyohann, (1975) Anal. Chem., 47, pp. 1475-1477Fischer, (1986) Anal. Chem., 58, pp. 261-263Mukai, Tanaka, Ikeda, (1976) C. A., 85, p. 35167s. , Japan Kokai JP 51037890 (1976)Giguere, Bray, Duncan, Majetich, (1986) Tetrahedron Lett., 27, pp. 4945-4948Gedye, Smith, Westaway, Ali, Baldisera, Laberge, Roussell, (1986) Tetrahedron Lett., 27, pp. 279-282Abramovitch, APPLICATIONS OF MICROWAVE ENERGY IN ORGANIC CHEMISTRY. A REVIEW (1991) Organic Preparations and Procedures International, 23, pp. 683-711Mingos, Baghurst, (1991) Chem. Soc. Rev., 20, pp. 1-47Bram, Loupy, Majdoub, Gutierrez, Ruiz-Hitzky, (1990) Tetrahedron, 46, pp. 5167-5176Richardson, (1969) Carbohydr. Res., 10, pp. 395-402Radatus, Clarke, An Improved Synthesis of Methyl 4,6-O-Benzylidene-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside (1980) Synthesis, pp. 47-48For example, the reaction with 1 using the substrate: sodium iodide: zinc-copper couple in molar proportions 1:5:5 took 15 min, furnishing 3 in 42% yiel

Preparation Of (+)-α-terpineol From (+)-limonene: Monoterpenes With Pleasant Odor In A Project For Undergraduate Organic Chemistry Laboratory [preparação Do (+)-α-terpineol A Partir Do (+)-limoneno: Monoterpenos De Odor Agradável Em Um Projeto Para Química Orgânica Experimental]

A synthesis of (+)-α-terpineol from (+)-limonene was proposed as a project for undergraduate organic laboratory course. Terpineol is a useful flavor and fragrance compound, and several aspects of this preparation are suited for experimental organic classes, including basic techniques for extraction and analyses of essential oils, different reaction types and the possibility of a high degree of student interest.32410691071Baptistella, L.H.B., Giacomini, R.A., Imamura, P.M., (2003) Quim. Nova, 26, p. 284Imamura, P.M., Baptistella, L.H.B., (2000) Quim Nova, 23, p. 270Singh, K.L., Tandon, S., Kahol, A.P., Aggarwal, K.K., Kumar, S., (1998) J. Med. Arom. Plant Sci., 20, p. 779Lawrence, B.M., Allures bussiness media: carol stream (1976) Em Progress in Essential Oils em Perfumer & Flavorist, , Gleason-Allured, J., edVerghese, J., (1970) Flavour Ind., 1, p. 545Bauer, K., Garbe, D., Surburg, H., (1990) Common Fragrance and Flavor Materials: Preparation, Properties and Uses, 2nd Ed., , VCH Verlagsgesellschft mbH: WeinheimMullen, P.A., (2005) U.S. Pat. Appl. Publ. US 2005002980 A1 20050106, 142, p. 70307. , CARice, P.J., Coats, J.R., (1994) ACS Symposium Series, 557, p. 92Beldock, D.T., Beldock, J.A., (1991) PCT Int. Appl. WO 9115118 A1 19911017, 116, p. 53708. , CAYoung-Cheol, Y., Han-Young, C., Won-Sil, C., Clark, J.M., Young-Joon, A., (2004) J. Agric. Food Chem., 52, p. 2507Singer, B.C., Destaillats, H., Hodgson, A.T., Nazaroff, W.W., (2006) Indoor Air, 16, p. 179Knoeppel, H., Schauenburg, H., (1989) Environ. Int., 15, p. 413Pitarokili, D., Couladis, M., Panayotarou, N.P., Tzakou, O., (2002) J. Agric. Food Chem., 50, p. 6688Kobayashi, A., Okamoto, H., Okada, F., (2004) PCT Int. Appl. WO 2004028519 A1 20040408, 140, p. 292244. , CABasařová, P., Bartovská, L., Kořínek, K., Horna, D., (2005) J. Colloid Interface Sci., 286, p. 333Sarika, Y., Srivastava, A.K., (2007) J. Appl. Polym. Sci., 103, p. 476Roman-Aguirre, M., De La Torre-Saenz, L., Flores, W.A., Robausanchez, A., Elguezabal, A.A., (2005) Catal. Today, 310, pp. 107-108. , e referências citadas;Sethi, V.K., Andotra, S.S., Thappa, R.K., Dhar, K.L., Indian Patent in 195195 A1 20050128 2005, 146, p. 359001. , CAPakdel, H., Sarron, S., Roy, C., (2001) J. Agric. Food Chem., 49, p. 4337Yuasa, Y., Yuasa, Y., (2006) Org. Process Res. Dev., 10, p. 1231De Matos, M., Coelho, R.B., Sanseverino, A.M., (2004) Synth. Commun., 34, p. 541Ubillus, F., De Pastor Abram, A., (2001) Bol. Soc. Quim. Peru, 67, p. 11Nomura, M., Tada, T., Inoue, T., Fujihara, Y., (1993) Chem. Express, 8, p. 689Roberts, R.M.G., (1976) J. Chem. Soc., Perkin Trans., 2, p. 1374Linares-Palomino, P.J., Salido, S., Altarejos, J., Nogueras, M., Sánchez, A., (2006) J. Chem. Educ., 83, p. 1052Matsubara, Y., Hiraga, Y., Kuwata, M., (1975) Jpn Kokai Tokkyo Koho 50131946Application JP 74-39117 (19740405), 84, p. 150791. , CAGreenberg, F.H., (1968) J. Chem. Educ., 45, p. 537Mackenzie, C.A., (1971) Experimental Organic Chemistry, 4th Ed., p. 303. , Prentice-Hall, Inc.: New JerseyRothenberger, O.S., Krasnoff, S.B., Rollins, R.B., (1980) J. Chem. Educ., 57, p. 741Pavia, D.L., Lampman, G.M., Kriz, G.S., Engel, R.G., (2002) Microscale and Macroscale Techniques in the Organic Laboratory, 277, p. 333. , Harcourt Coll. Publis.: OrlandoConstantino, M.G., Da Silva, G.V.J., Donate, P.M., (2003) Fundamentos de Química Experimental, , EDUSP: SPPavia, D.L., Lampman, G.M., Kriz, G.S., (1996) Introduction to Spectroscopy, , Saunders Coll. Publis.: Orlandohttp://www.abecittus.com.br/subproautos-br.html, Vide, por exemplo, http:// www.cosmeticosbr.com.br/conteudohttp://aliceweb.aesenvolvimento.gov. br, acessadas em Janeiro 2009Da Silva-Santos, A., Antunes, A., D'Avila, L., Bizzo, H., Souza-Santos, L., (2005) Perfumer & Flavorist, 30, p. 50Craveiro, A.A., Queiroz, D.C., (1993) Quim Nova, 16, p. 224Várias empresas nacionais vendem o (+)-limoneno (por exemplo, Dierberger, Cittosuco, Cutrale). Em nosso Instituto, a maior parte do limoneno utilizado nos foi gentilmente cedido pela empresa Cittosuco, de Limeira, por intermédio do Prof. Dr. L. E. S. BarataApesar de não ser possível a visualização nítida do limoneno em CCD, o tricloroacetato 2 é facilmente visível tanto por revelação com vapor de iodo quanto por borrifamento com solução de anisaldeido/HOAc (vide Parte Experimental) seguida por aquecimento da placaUma análise do material bruto por espectroscopia no IV permite a caracterização do éster. Tentativas de purificaç ão por coluna filtrante de sílica, para análises adicionais, ou mesmo conservação em geladeira para utilização posterior já foram efemadas, e nem sempre levaram a resultados satisfatórios. Nesses casos, o rendimento de 2 pode ser sensivelmente diminuído por decomposiçãoNormalmente, uma única amostra, mais pura, é empregada para os espectros de RMN 1H e RMN 13C. O mesmo pode ser feito para a medida de rotação ópticaAmoore, J.E., (1963) Nature, 198, p. 211Ohloff, G., (1986) Experientia, 42, p. 271Kraft, P., Bajgrowicz, J.A., Denis, C., Fráter, G., (2000) Angew. Chem., Int. Ed., 39, p. 2980Zarzo, M., (2007) Biol. Rev., 82, p. 455(1989) Vogel's Textbook of Practical Organic Chemistry, 5th Ed., p. 172. , Pearson Ed.: Harlow, Variantes dessa montagem, mosttadas em vários livros de química orgânica experimental, também são perfeitamente adequadasCRC Handbook of Terpenoids, Monoterpenoids, p. 193. , Como cerca de 98% do óleo da casca da laranja é constituído por limoneno (por CG), é perfeitamente possível comparar os dados obtidos àqueles descritos na literatura para o (+)-limoneno. Vide, por exemplo(1982), Dev, S. ed.CRC Press, Inc.: Boca RatonThe Sadtler Spectral Handbook, , http://www.knowitall.com/academic/welcome.aspReactivos de Coloración Para Cromatografia em Capa Fina y en Papel, 60, p. 27. , Solução de pulverização: misturar 0,5 mL de anisaldeído a 50 mL de ácido acético glacial e adicionar 1 mL de ácido sulfúrico concentrado. Tratamento: após pulverização, aquecer a placa cromatográfica a 100-105 °C até a intensidade máxima de coloração das manchas E Merck, n°Uma alternativa a essa evaporação do solvente à secura é uma extração da mistura reacional com hexano ou heptano. Nesse caso, a mistura reacional é transferida para um funil de separação e extraída com o solvente orgânico (3×10 mL), as fases orgânicas reunidas são lavadas com água (2×10 mL), secas sobre sulfato de sódio anidro, filtradas e o solvente é evaporado sob pressão reduzida. O resíduo está pronto a ser purificado por cromatografia em colunaSe a purificação do terpineol não for realizada no mesmo dia, e este foi normalmente o caso, ele deve ser guardado em geladeiraJin, Y., (2006) Chem. Commun., pp. P290

Sialic Acids - From The Comprehension Of Their Involvement In Biological Processes To Antiinfluenza Drug Design [Ácidos Siálicos - Da Compreensão Do Seu Envolvimento Em Processos Biológicos Ao Desenvolvimento De Fármacos Contra O Agente Etiológico Da Gripe]

Sialic acids are nine-carbon carbohydrates that occur widely in nature and occupy the terminal portions of some glycoproteins and glycolipids of cell membranes. These carbohydrates are closely involved in cell-cell interactions and in processes such as microbial infection, inflammation, etc. Studies on the participation of sialic acids in biological processes have provided comprehension about their role in the infection by the influenza virus, the causal agent of flu. In this article, we present an overview of the importance of sialic acids in the influenza virus infection and how the knowledge of their involvement in this process has allowed the development of selective and efficient drugs against the virus.282306316Nelson, D.L., Cox, M.M., (2000) Lehninger Principles of Biochemistry, 3a Ed., , Worth Publisher: New York, cap. 3Voet, D., Voet, J.G., (1995) Biochemistry, 2a Ed., , John Wiley & Sons Inc.: New York, cap. 10 e 11Berg, J.M., Tymoczko, J., Stryer, L., (2002) Biochemistry, 5a Ed., , W. H. Freeman and Campany: New York, cap.11http://superfund.pharmacy.arizona.edu/toxamb/index.html, Imagem adaptada de Peña, C. E.Carter, D. E.Ayala-Fierro, FDwek, R.A., (1996) Chem. Rev., 96, p. 683Angata, T., Varki, A., (2002) Chem. Rev., 102, p. 439Varki, A., (1991) FASEB J., 5, p. 226Maru, I., Ohta, Y., Murata, K., Tsukada, Y., (1996) J. Biol. Chem., 271, p. 16294Keppler, O.T., Horstkorte, R., Pawlita, M., Schmidt, C., Reutter, W., (2001) Glycobiology, 11, pp. 11RJacobs, C.L., Goon, S., Yarema, K.J., Hinderlich, S., Hang, H.C., Chai, D.H., Bertozzi, C.R., (2001) Biochemistry, 40, p. 12864DeNinno, M.P., (1991) Synthesis, p. 583Gottschalk, A., (1951) Nature, 167, p. 845Koeller, K.M., Wong, C.H., (2000) Chem. Rev., 100, p. 4465Wilson, J.C., Von Itzstein, M., (2003) Curr. Drugs Targets: Infect. Disord., 4, p. 389Kiefel, M.J., Von Itzstein, M., (2002) Chem. Rev., 102, p. 471Kiefel, M.J., Von Itzstein, M., (1999) Prog. Med. Chem., 36, p. 1Sears, P., Wong, C.H., (1999) Angew. Chem., Int. Ed., 38, p. 2300Mammen, M., Choi, S.K., Whitesides, G.M., (1998) Angew. Chem., Int. Ed., 37, p. 2754Slee, D.H., Romano, S.J., Yu, J., Nguyen, T.N., John, J.K., Rahya, N.K., Axe, F.U., Ripka, W.C., (2001) J. Med. Chem., 44, p. 2094Gomes, L., (2001) J. Pneumol., 27, p. 97(2000) O Caminho Do Influenza: Ameaça Antiga, p. 1581. , Revista ISTOÉReportagem de capa, JaneiroForleo-Neto, E., Halker, E., Santos, V.J., Paiva, T.M., Toniolo-Neto, J., (2003) Rev. Soc. Bras. Med. Trop., 36, p. 267Cox, N.J., Subbarao, K., (1999) Infections Disease Clinics of North America, 354, p. 1277Hayden, F.G., Belshe, R.B., Clover, R.D., Hay, A.J., Oakes, M.G., Soo, W.N., (1989) Engl. J. Med., 321, p. 1696Keyser, L.A., Karl, M., Nafziger, A.N., Bertino Jr., J.S., (2000) Arch. Intern. Med., 160, p. 1485Hay, A.J., Wolstenholme, A.J., Skehel, J.J., Smith, M.H., (1985) EMBO J., 4, p. 3021Saul, H., (1995) New Scientist, p. 26Demicheli, V., Jefferson, T., Rivetti, D., Deeks, J., (2000) Vaccine, 18, p. 957Calfee, D.P., Hayden, F.G., (1998) Drugs, 56, p. 537Laver, W.G., Bischofberger, N., Webster, R.G., (1999) Scientific American, 280, p. 78Oxford, J.S., Lambkin, R., (1998) Drugs Discovery Today, 3, p. 448(1999) Weekly Report, 48, p. 1Wilson, I.A., Skehel, J.J., Wiley, D.C., (1981) Nature, 289, p. 366Wiley, D.C., Wilson, J.C., Skehel, J.J., (1981) Nature, 289, p. 373Palese, P., Schulman, J.L., Boto, G., Meindl, P., (1974) Virology, 59, p. 490Air, G.M., Laver, W.G., (1989) Proteins: Struct. Funct. Genet., 6, p. 341Corfield, T., (1992) Glycobiology, 2, p. 509Liu, C., Eichelberger, M.C., Compans, R.W., Air, G.M., (1995) J. Virol., 69, p. 1099http://isi3.isiknowledge.com/portal.cgi, O termo pesquisado foi "sialic acid"Prichett, T.J., Brossmer, R., Rose, U., Paulson, J.C., (1987) Virology, 160, p. 502Toogood, P.L., Galliker, P.K., Glick, G.D., Knowler, J.R., (1991) J. Med. Chem., 34, p. 3140Sauter, N.K., Bednarski, M.D., Wurzburg, B.A., Hanson, J.E., Whitesides, G.M., Skehel, J.J., Wiley, D.C., (1989) Biochemistry, 28, p. 8388Weinhold, E.G., Knowles, J.R., (1992) J. Am. Chem. Soc., 114, p. 9270Spevak, W., Nagy, J.O., Charych, D.H., Schaefer, M.E., Gilbert, J.H., Bednarski, M.D., (1993) J. Am. Chem. Soc., 115, p. 1146Koketsu, M., Nitoda, T., Sugino, H., Juneja, L.R., Kim, M., Yamamoto, T., Abe, N., Wong, C.H., (1997) J. Med. Chem., 40, p. 3332Kamitakahara, H., Suzuki, T., Nishigori, N., Suzuki, Y., Kanie, O., Wong, C.H., (1998) Angew. Chem., Int. Ed., 37, p. 1524Varghese, J.N., Laver, W.G., Colman, P.M., (1983) Nature, 303, p. 35Colman, P.M., Varghese, J.N., Laver, W.G., (1983) Nature, 303, p. 41Chong, A.K.J., Pegg, M.S., Taylor, N.R., Von Itzstein, M., (1992) Eur. J. Biochem., 207, p. 335Griffin, J.A., Campans, R.W., (1979) J. Exp. Med., 150, p. 379Miller, C.A., Wang, P., Flashner, M., (1978) Biochem. Biophys. Res. Commun., 83, p. 1479Taylor, N.R., Von Itzstein, M., (1994) J. Med. Chem., 37, p. 616Dyason, J.C., Von Itzstein, M., (2001) Aust. J. Chem., 54, p. 663Sollis, S.L., Smith, P.W., Howes, P.D., Cherry, P.C., Bethell, R.C., (1996) Bioorg. Med. Chem. Lett., 6, p. 1805Bossart-Whitaker, P., Carson, M., Babu, Y.S., Smith, C.D., Laver, W.G., Air, G.M., (1993) J. Mol. Biol., 232, p. 1069Von Itzstein, M., Dyason, J.C., Oliver, S.W., White, H.F., Wu, W.Y., Kok, G.B., Pegg, M.S., (1996) J. Med. Chem., 39, p. 388Masuda, T., Shibuya, S., Arai, M., Yoshida, S., Tomozawa, T., Ohno, A., Yamashita, A., Honda, T., (2003) Bioorg. Med. Chem. Lett., 13, p. 669http://www.omedon.co.uk/influenza/, e referências citadasSmith, P.W., Sollis, S.L., Howes, P.D., Cherry, P.C., Bethell, R.C., (1996) Bioorg. Med. Chem. Lett., 6, p. 1805Smith, P.W., Robison, J.E., Evans, D.N., Sollis, S.L., Howes, P.D., Trivedi, N., Bethell, R.C., (1999) Bioorg. Med. Chem. Lett., 9, p. 601Smith, P.W.S.L., Howes, P.D., Trivedi, N., (2000) Bioorg. Med. Chem. Lett., 10, p. 1257Williams, M., Bischofberger, N., Swaminathan, S., Kim, C.U., (1995) Bioorg. Med. Chem. Lett., 5, p. 2251Finley, J.B., Atigadda, V.R., Duarte, F., Zhao, J.J., Brouillette, W.J., Air, G.M., Luo, M., (1999) J. Mol. Biol., 295, p. 1107Kim, C.U., Lew, W., Willians, M.A., Wu, H., Zhang, L., Chen, X., Escarpe, P.A., Stevens, R.C., (1998) J. Med. Chem., 41, p. 2451Lew, W., Chen, X., Kim, C.U., (2000) Curr. Med. Chem., 7, p. 663Lew, W., Wu, H., Chen, X., Graves, B.J., Escarpe, P.A., MacArthur, H.L., Mendel, D.B., Kim, C.U., (2000) Bioorg. Med. Chem. Lett., 10, p. 1257Karpf, M., Trussardi, R., (2001) J. Org. Chem., 66, p. 2044Hanessian, S., Wang, J., Montgomery, D., Stoll, V., Stewart, K.D., Kati, W., Maring, C., Laver, W.G., (2002) Bioorg. Med. Chem. Lett., 12, p. 3425Kim, C.U., Lew, W., Willians, M.A., Liu, H., Zhang, L., Swaminathan, S., Bischofberger, N., Stevens, R.C., (1997) J. Am. Chem. Soc., 119, p. 681Ryan, D.M., Ticehurst, J., Dempsey, M.H., Penn, C.R., (1994) Antimicrob. Agents Chemother., 38, p. 2270Li, W., Escarpe, P.A., Eisenberg, E.J., Cundy, K.C., Sweet, C., Jakeman, K.J., Merson, J., Mendel, D.B., (1998) Antimicrob. Agents Chemother., 42, p. 647Mendel, D.B., Tai, C.Y., Escarpe, P.A., Li, W., Sidwell, R.W., Huffman, J.H., Sweet, C., Kim, C.U., (1998) Antimicrob. Agents Chemother., 42, p. 640http://www.tamiflu.comYamamoto, T., Kumazawa, H., Inami, K., Teshima, T., Shiba, T., (1992) Tetrahedron Lett., 33, p. 5791Babu, Y.S., Chand, P., Bantia, S., Kotian, P., Dehghani, A., El-Kattan, Y., Lin, T.H., Montgomery, J.A., (2000) J. Med. Chem., 43, p. 3482Bantia, S., Parker, C.D., Ananth, S.L., Horn, L.L., Andries, K., Chand, P., Kotian, P.L., Babu, Y.S., (2001) Antimicrob. Agents Chemother., 45, p. 1162Wang, G.T., Chen, Y., Wang, S., Gentles, R., Sowin, T., Kati, W., Muchmore, S., Laver, W.G., (2001) J. Chem. Soc., 44, p. 1192Luo, G., Torri, A., Harte, W.E., Danetz, S., Cianci, C., Tiley, L., Day, S., Krystal, M., (1997) J. Virol., 71, p. 4062Luo, G., Colonno, R., Krystal, M., (1996) Virology, 226, p. 66Yoshimoto, J., Kakui, M., Iwasaki, H., Fujiwara, T., Sugimoto, H., Hattori, N., (1999) Arch. Virol., 144, p. 865Yoshimoto, J., Yagi, S., Ono, J., Sugita, K., Hattori, N., Fujioka, T., Fujiwara, T., Hashimoto, N., (2000) J. Pharm. Pharmacol., 52, p. 1247McKimm-Breschkin, J.L., (2000) Antiviral Res., 47, p. 1Baum, E.Z., Wagaman, P.C., Ly, L., Turchi, I., Le, J., Bucher, D., Bush, K., (2003) Antiviral Res., 59, p. 1