nD20=1.4175 Ткип=85-860/15 мм. ПМР (CDCl3) d (м.д.): 1.25–т. (3Н; CH3, J=7.16 Гц); 4.20–с. (2Н; СH2-N); 4.24–кв. (2H; CH2, J=7.16 Гц).
Лит.: Ткип=80-820/12 мм.[16]. ПМР (CCl4) d (м.д.): 1.33–т. (3Н; CH3, J=7 Гц); 4.25–с. (2Н; СH2-N); 4.28–кв. (2H; CH2, J=7 Гц) [16]; ИК (пленка) n (см–1): 2150 (NС); 1750(C=O) [16].
2-метил-6-нитробензотиазол (47).
В колбе с дефлегматором готовят нитрующую смесь из 0,7 мл 73% HNO3 и 0,83 мл концентрированной H2SO4 к которой прикапывают 1 мл (0,008 моль) 2-метилбензотиазола (46). Реакционную массу греют при 900 в течение 5 часов и выливают на лед. Выпавший осадок отфильтровывают и промывают большим количеством воды. Перекристаллизовывают из метанола. Получают 0,22 г (20%) 2-метил-6-нитробензотиазола (47).
Rf = 0,9 (Хл:МеОН 9:1); ТПЛ = 106–1100; ПМР d (м.д.): 2.9–с. (3H; CH3); 8.03–.д. (1H; CH, J=8.96 Гц); 8.35–д.д. (1H; CH, J=2.29 Гц); 8.78–д. (1H; CH, J=2.29Гц). Масс-спектр m/z (%): 194 (94%), 164 (48%), 148 (50%), 136 (30%), 107 (35%), 69 (30%), 63(100%).
6. Выводы.
1. Проведен анализ литературы и подобраны методы получения высоко сопряженных порфиринов.
2. Предложен новый метод синтеза 2,5-диформилпиррола.
3. Разработаны методы синтеза 5 новых соединений: диэтил 2-(пиррол-2-илметилен)малоноат (59), диэтил 2‑[(5‑формилпиррол-2-ил)метилен]малоноат (60), 2,5-диметил-3-йод-4-карбоэтоксипиррол (64), 2,5-диметил-3-карбоэтокси-4-нитропиррол (65), 2,5-диметил-3,4-дийодпиррол (67).
[1] Lash T.D. and Novak B.H. New highly conjugated porphyrin chromophores: synthesis of mono- and diphenanthroporphyrins. // Tetrahedron Letters 1995 v.36 №25 p.4381-4384.
[2] Alonso C.M.A., Neves M., et al. Reaction of b-amino-meso-tetraphenylporphyrin with a,b-unsaturated carbonyl compounds: an approach to fused pyridinoporphyrins. // Tetrahedron Letters 1997 v.38 №15 p.2757-2758.
[3] Vicente M., Jaquinod L., Khoury R., Mandrona A., Smith K.M. Synthesis and chemistry of new benzoporphyrins. // Tetrahedron Letters 1999 v.40 p.8763-8766.
[4] Silva A., Faustino M., Silva T., et al. A new approach to the synthesis of mono- and bis-pyrroloporphyrins. // Abstracts of ICPP-1, Dijon, France, 2000, post 402.
[5] Lin Y. and Lash T.D. Porphyrin synthesis by the “3+1” methodology: a superior approach for the preparation of porphyrins with fused 9.10-phenanthroline subunits. // Tetrahedron Letters 1995 v.36 p.9441-9444.
[6] Novak B.H. and Lash T.D. Porphyrins with exocyclic rings. Part 11. Synthesis and characterization of phenanthroporphyrins, a new class of modified porphyrin chromophores. // J.Org.Chem. 1998 v.63 p.3998-4010.
[7] Lash T.D., Wijesinghe C., Osuma A.T., Patel J.R. Synthesis of novel porphyrin chromophores from nitroarenes: further applications of the Barton-Zard pyrrole condensation. // Tetrahedron Letters 1997 v.38 №12 p.2031-2034.
[8] Lash T.D. Porphyrins with exocyclic rings. Part 10. Synthesis of meso,b-propanoporphyrins from 4,5,6,7-tetrahydro-1H-indoles. // Tetrahedron 1998 v.54 p.359-374.
[9] Byun Y.-S. And Lightner D.A. Synthesis and properties of a bilirubin analog with propionic acid groups replaced by carboxyl. //J.Heterocycl. Chem. 1991 v.28 № 7 p.1683-1692.
[10] Cho D.H., Lee J.H., Kim B.H. An improved synthesis of 1,4-bis(3,4-dimethyl-5-formyl-2-pyrryl)butadiyne and 1,2-bis(3,4-dimethyl-5-formyl-2-pyrryl)ethyne. // J.Org.Chem. 1999 v.64 p.8048-8050.
[11] Piloty O., Hirsch P. Pyrrolsynthesen aus Aminoketonen mit ketonen und ketonsaureestern. //J.Liebigs Ann.Chem. 1913 B.395 s.63-74.
[13] Johnson A.W., Price R. 2,3,4,5-Tetramethylpyrrole. //Org. Synthesis 1962 v.42 p.90‑92.
[14] Treibs A., Schmidt R. Syntheische Arbeiten auf dem chlorophyllgebiet synthese des 2‑Desathylphylloporphyrins. //J.Liebigs Ann.Chem. 1952 B.577 s.105-115.
[15] All G.H., Knowles W.S. The mechanism of the N,N-dichloroalkylamine rearrangement. //J.Org.Chem. 1960 v.25 p.2047-2048.
[16] Титце Л., Айхер Т. //Препаративная органическая химия. Пер. с нем. под ред. Алексеева Ю.Е. М.:Мир, 1999. 704 с.
[17] Миронов А.Ф., Апаркон Х.Х., Евстигнеева Р.П. О лабильности b‑ диэтиламиноэтильной группы в условиях образования пиррольного цикла по Кнорру. //ХГС 1973 №12 стр.1643-1645.
[18] Nagafuji P. and Cushman M. A general synthesis of pyrroles and fused pyrrole systems from ketones and amino acids. //J.Org.Chem. 1996 v.61 №15 p.4999-5003.
[19] Barret A.G.M., Graboski G.G. Conjugated nitroalkenes: versatile intermediates in organic synthesis. //Chem.Rev. 1986 v.86 №5 p.751-762.
[20] Chandrasekar P. and Lash T.D. Versatile “3+1” syntheses of acenaphthoporphyrins, a new family of highly conjugated tetrapyrroles. // Tetrahedron Letters 1996 v.37 №28 p.4873‑4876.
[21] Murashima T., Tamai R., Fujita K., Uno H. and Ono N. Ambident reactivity of nitro heteroaromatic anions. // Tetrahedron Letters 1996 v.37 №46 p.8391-8394.
[22] Fumoto Y., Uno H., Ono N., et al. Preparation of 5-unsubstituted 4-formylpyrrole-2-carboxylates and conversion to cycloalkano-oligopyrroles. // J.Chem.Soc.PerkinTrans.1. 2000 p.2977-2981.
[23] Gilchrist T.L. Synthesis of aromatic heterocycles. //J.Chem.Soc.PerkinTrans.1. 1998 №3 p.615-628.
[24] Chiu P. -K., Lui K. -H., Maini P.N. Sammes M.P. Novel synthesis of 3H-pyrroles, and novel intermediates in the Paal-Knorr 1H-pyrrole synthesis: 2‑hydroxy‑3,4‑dihydro‑2H‑pyrroles from 1,4-diketones and liquid ammonia. //J.Chem.Soc.,Chem.Commun. 1987 p.109-110.
[25] Niziurski-Mann R.E. and Cava M.P. Synthesis of mixed thiophene-pyrrole heterocycles. //J.Heterocycles 1992 v.34 №10 p.2000-2021.
[26] Benary E. Synthese von pyrrol- und furan-derivaten aus dichlor-ather, acetessigester und ammoniak. //Chem.Ber. 1911 B.44 s. 493-496.
[27] Khotinsky E. Darstellung des pyrrols. //Chem.Ber. 1909 B.9 s.2506-2507.
[28] Chiu P. -K. and Sammes M.P. The synthesis and chemistry of azolenines. Part 18. Preparation of 3-etoxycarbonyl‑3H‑pyrroles via the Paal‑Knorr reaction, and sigmatropic rearrangements involving competitive ester migrations to C‑2, C‑4 and N. //Tetrahedron 1990 v.46 №10 p.3439-3456.
[29] Rigo B., Valligny D., Taisne S., Couturier D. Disilylated compounds as precursors of heterocycles. //J.Synth.Commun. 1988 v.18 p.170-171.
[30] Hendrickson J.B., Ress R.W., Templeton J.F. General heterocycle synthesis. Use of acetyl‑enedicarboxylic esters. //J.Am.Chem.Soc. 1964 v.86 p.107-111.
[31] Grob C.A., Schacl H.P. Eine nene pyrroling- synthese II. Teil untersuchungen inder pyrrolreihe. //Helv.Chim.Acta 1955 v.38 p.1121-1127.
[32] Spence J.D. and Lash T.D. Porphyrins with exocyclic rings. Part 14. Synthesis of tetraacenaphthoporphyrins, a new family of highly conjugated porphyrins with record‑breaking long‑ wavelengh electronic absorptions. //J.Org.Chem. 2000 v.65 p.1530-1539.
[33] Bastian J.A. and Lash T.D. Porphyrins with exocyclic rings. Part 12. Synthesis of meso, b‑butano- and meso, b‑pentanoporphyrins from cycloalka[b]pyrrole. //Tetrahedron 1998 v.54 p.6299-6310.
[34] Gotthardt H., Huisgen R. And Bayer H.O. 1.3-Dipolar cycloaddition reactions. L III. The question of the 1.3-dipolar nature of 2-oxazolin-5-ones. //J.Am.Chem.Soc. 1970 v.92 p.4340‑4343.
[35] Arcadi A. and Rossi E. Synthesis of functionalised furans and pyrroles through annulation reactions of 4-pentynones. //Tetrahedron 1998 v.54 p.15253-15272.
[36] Sessler J.L., Davis J.M., Lynch V. Synthesis and characterization of a stable smaragdyrin isomer. //J.Org.Chem. 1998 v.63 p.7062-7065.
[37] Alberola A., Ortega A.G., et.al. Versatility of Weinreb amides in the Knorr pyrrole synthesis. //Tetrahedron 1999 v.55 p.6555-6566.
[38] Hombrecher H.K., Horter G. Synthesis of pyrroles via ethyl N- (3‑oxo‑1‑alkenyl) glycinates. //Synthesis 1990 p.389-391.
[39] Ferraz H.M.C., Oliveira E.O., et.al. A new and efficient approach to cyclic b‑enamino esters and b‑enamino ketones by iodine- promoted cyclization. //J.Org.Chem. 1995 v.60 p.7357-7359.
[40] Ferraz H.M.C., Pereira F.L.C., et.al. Synthesis of N‑substituted pyrrole and tetrahydroindole derivatives from alkenyl b‑dicarbonyl compounds. //Tetrahedron 1999 v.55 p.10915‑10924.
[41] Рындина С.А., Кадушкин А.В., Соловьева Н.П., Граник В.Г. Циклизация Торпа‑ Циглера в синтезе 3‑ амино‑ 4‑ цианопиррола. //ХГС 2000 т.26 с.1643-1655.
[42] Chen N., Lu Y., Gadamasetti K., et.al. A short, facile synthesis of 5-substituted 3‑amino‑1H‑pyrrole‑2‑carboxylates. //J.Org.Chem. 2000 v.65 p.2603-2605.
[43] Порфирины: структура, свойства, синтез. // Под ред. Ениколопяна Н.С. М.: Наука, 1985. 333с.
[44] Rose E., Soleihavoup M., et al. Bis-faced aminoporphyrin templates for the synthesis of chiral catalysts and hemeprotein analogues. // J.Org.Chem. 1998 v.63 №6 p.2042-2044.
[45] Ono N., Muratani E., et al. Synthesis of 2,7,12,17‑tetraaryl-3,8,13,18-tetranitroporphyrins; electronic effects on aggregations of porphyrins. // J.Chem.Soc., Perkin Trans.1 1998 №22 p.3819-3824.
[46] Tse M.K., Zhou Z., et al. Regioselective bromination and subsequent suzuki cross-coupling of highly electron deficient 5,10,15,20-tetrakis(trifluoromethyl)porphyrin. // Tetrahedron 2000 v.56 p.7779-7783.
[47] Czuchajonski L., Habdas J., et al. Porphyrinyl-uridines as the first water soluble porphyrinyl-nucleosides. // Tetrahedron Letters 1991 v.32 p.7511-7514.
[48] Shin J.-Y., Minezawa N., et al. Study for expanded porphyrins producted during the condensation reaction of pentafluorobenzaldehyde and pyrrole. // Abstracts of ICPP-1, Dijon, France, 2000, post 562.
[49] Ono N. A new synthesis of highly conjugated porphyrins. // Abstracts of ICPP-1, Dijon, France, 2000, sym 147.
[50] Ono N., Hironaga H., et al. A new synthesis of pyrroles and porphyrins fused with aromatic rings. // J.Chem.Soc., Perkin Trans.1 1996 p.417-423.
[51] Nguyen L.T., Senge M.O., Smith K.M. One-pot synthesis of regiochemically pure porphyrins from two different pyrroles. // Tetrahedron Letters 1994 v.35 p.7581-7584.
[52] Nguyen L.T., Senge M.O., Smith K.M. Simple methology for syntheses of porphyrins possessing multiple peripheral substituents with an element of symmetry. // J.Org.Chem. 1996 v.61 p.998-1003.
[53] Березин Б.Д. // Координационные соединения порфиринов и фталоцианина / М.: Наука 1978 150с.
[54] Arsenault G.P., Bullock E., MacDonald S.F. Pyrromethanes and porphyrins there from. // J.Am.Chem.Soc. 1960 v.82 p.4384-4387.
[55] Clarke O.J., Boyle R.W. Selective synthesis of asymmetrically substituted 5,15‑diphenylporphyrins. // Tetrahedron Letters 1998 v.39 p.7167-7168.
[56] Lee C.-H., Li F., Iwamoto K., Lindsey J.S. Synthetic approaches to regioisomerically pure porphyrins bearing four different meso-substituents. // Tetrahedron 1995 v.51 p.11645-11654.
[57] Balasubramanian T., Lindsey J.S. synthesis of b-substituted porphyrin building blocks and conversion to diphenylethyne-linked porphyrin dimers. // Tetrahedron 1999 v.55 p.6771‑6784.
[58] Maruyama K., Nagata T., Ono N., Osuka A. A synthesis of unsymmetric porphyrin dimers // Bull.Chem. Soc.Jpn. 1989 v.62 p.3167-3170.
[59] Ema T., Kuroda Y., Ogoshi H. Selective syntheses of unsymmetrical meso-arylporphyrins. // Tetrahedron Letters 1991 v.32 p.4529-4532.
[60] Wallaca D.M., Leung S.H., Senge M.O., Smith K.M. Rational tetraarylporphyrin syntheses: tetararylporphyrins from the MacDonald route. // J.Org.Chem. 1993 v.58 p.7245-7257.
[61] Мамардашвили Н.Ж., Голубчиков О.А. Синтез порфиринов из дипирролилметанов. // Успехи химии 2000 т.69 с.342-354.
[62] Scog W.R., Yong H.N., Youngkyu D. Synthesis, structures and electrchemical characterization of ferrocene-substituted porphyrin and porphodimethene. // Inorg.Chim.Acta 2000 v.309 p.49-56.
[63] Tjahjono D.H., Akutsu T., et al. Cationic porphyrins bearing diazolium rings: synthesis and their interaction with calf thymus DNA. // Biochimica et Biophysica Acta/General Subjects 1999 v..1472 p.333-343.
[64] Smith K.M., Craig J., Medforth D.T.L. Syntheses, stability and tumorcidal activity of porphyrin dimers and trimers with ether linkages. // Tetrahedron Letters 1990 v.31 p.7265-7270.
[65] Khoury R.G., jaquinod L., Smith K.M. Metal ion-induced self assembly of open-chain tetrapyrrole derivatives: double stranded dinuclear complexes from 10-oxo-5,15-biladienes. // Tetrahedron 1998 v.54 p.2339-2346.
[66] Dolphin D.M., Johnson A.W., Long J. Porphyrinogens and porphodimethenes, intermediates in the synthesis of meso-tetraphenylporphyrins from pyrroles and benzaldehyde. // J.Heterocycl.Chem. 1970 v.7 p.275-283.
[67] Smith K.M., Minnetian O.M. Anomalous cyclization of 1,19-dimethyl-a,c-dimethyl-a,c-biladiens: direct synthesis of meso-aminoporphyrin derivatives. // Synth.Commun. 1985 v.15 p.75-80.
[68] Smith K.M., Minnetian O.M. Cyclization of 1’,8’-dimethyl-a,c-biladiene salts to give porphyrins: a study with various oxidizing agents. // J.Chem.Soc.,Perkin Trans.1 1986 p.277‑280.
[69] Boudif A., Gimenez S., Loock B., Momenteau M. vic-Diacrylic ester porphyrins as starting materials for monobenzoporphyrins and opp-dibenzoporphyrins syntheses. // Can.J.Chem. 1998 v.76 p.1215-1219.
[70] Boudif A., Momenteau M. A new convergent method for porphyrin synthesis based on a “3+1” condensation. // J.Chem.Soc.,Perkin Trans.1 1996 p.1235-1241.
[71] Kai S., Suzuki M., Masaki Y. The first synthesis of mononazaporphyrins bearing a nitrogen atom at the peripheral position. // Tetrahedron Letters 1998 v.39 p.4063-4066.
[72] Lash T.D., Chandrasekar P., et al. Porphyrins with exocyclic rings. Part 13. Synthesis and spectroscopic characterization of highly modified porphyrin chromophores with fused acenaphthylene and benzothiadiazole. // J.Org.Chem. 1998 v.63 p.8455-8469.
[73] Lash T.D., Thompson M.L., et al. Recent studies on the synthesis of porphyrins with fused aromatic rings. // Abstracts of ICPP-1, Dijon, France, 2000, post 469.
[74] Сизов А.Ю., Яновская Л.А., Домбровский В.А. Синтез эфиров 2-замещенных 4-кетопентановых кислот алкилированием СН-кислот хлорацетоном в условиях межфазного катализа. // Известия РАН 1990 №2 с.473-474.
[75] Cresp T.M., Sargent M.V. Synthesis and paratropicity of heteroatom-bridged annulenones.//J.Chem.Soc., Perkin Trans.1.1973.N.23.P.2961-2971.
[76] Muchowski J.M. and Hess P. Lithiation of the 6-dimethylamino-1-azafulvene dimer. A versatile synthesis of 5-substituted pyrrole-2-carboxaldehydes. //J.Tetrahedron Lett.1988.V.29.N26.P.777-780.
[77] Muchowski J.M. and Hess P. Lithiation of the dimer of 3-bromo-6-dimethylamino-1-azafulvene. Efficacious synthesis of 4-mono- and 4,5-disubstituted pyrrole-2-carboxaldehydes.//J.Tetrahedron Lett.1988.V.29.P. 3215-3219.
[78] Bergman J., Renstroem L., Sjoerberg B. The synthesis of pyrrole-2.5-dicarbaldehydes.// J.Tetrahedron. 1980. V.36. P.2505-2509.
[79] Muradin-Szweykowska M., Peters A.J. and Lugtenburg J. The interaction of bacterioopsin with 11,14-bridged retinals. The sinthesis of 13-demethyl-11,14-imino,13-demethyl-11,14-thio-13-demethyl-11,14-etheno-11,14-imino-retinal and their binding with bacterioopsin.//J.Tetrahedron.1984.V.101.P.5537-5540.
[80] Degani I., Fochi R. and Regondi V. The synthesis of pyrrole-2,5-dicarbaldehydes.//Synthesis.1981.N51.P.4623-4636.
[81] Cadamuro S., Degani I., Dughera S., Fochi R., Gatti A. and Piscopo L. General methods for synthesizing 2,4-diacylpyrroles and their precursors containing one or two masked acyl groups.//J. Chem. Soc. Perkin Trans.1 1993.N22.P.273-279.