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SYNTHESIS AND STUDY OF THE PHOTOCHROMIC BEHAVIOR OF SUBSTITUTED 6'-NITRO-1,3,3-TRIMETHYL-5-VINYLSPIRO(INDOLINO-2,2'-[2H]CHROMENES)

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Abstract

Few 5-vinyl substituted 6’-nitro-1,3,3-trimethylspiro(indolino-2,2’-[2H]chromenes) (6’-nitro-spiropyrans) were synthesized by a one-step method from 5-formyl precursor – 5-formyl-6’-nitro-1,3,3-trimethylspiro(indolino-2,2’- [2H]chromene) (1). 5-Vinyl-6’-nitro-spiropyran (2) was prepared by the Wittig olefination of 1 with an ylide, which was generated by the action of potassium tert-butylate on methyltriphenylphosphonium bromide in THF. E-6’- Nitro-5-(1’’-nitroethene-2’’-yl)-6’-nitro-spiropyran (3) was obtained by heating 1, nitromethane, ethylenediammonium diacetate at 50°С in absolute methanol and inert atmosphere. Compounds 1’’-[6’-nitro-spiropyran-5- yl]-2’’,2’’-dicyanoethylene (4) and E-1’’-[6’-nitro-spiropyran-5-yl]-2’’-cyano-2’’-methoxycarbonylethylene (5) were prepared from initial 1 by reflux in ammonium acetate / glacial acetic acid / benzene mixture with malonodinitrile or methyl 2-cyanoacetate, respectively. The procedure for synthesizing derivatives 2’’,2’’-dimethyl-5’’-(6’-nitrospiropyran-5-yl)methylidene-1’’,3’’-dioxane-4’’,6’’-dion (6) and 5’’,5’’-dimethyl-2’’-(6’-nitro-spiropyran-5-yl)- methylidenecyclohexane-1’’,3’’-dion (7) includes the interaction of Meldrum's acid or dimedone, accordingly, with 5-formyl precursor 1 by heating in ethanol in the presence of piperidine and molecular sieves (to bind the released water). The structures of the prepared compounds and their purity have been confirmed by physico-chemical analysis. A spectral kinetic study of the photochromic properties of the substituted 5-vinyl spiropyrans was carried out in toluene and ethanol solutions. The 5-vinyl-6’-nitro-spiropyran derivatives 2–7 described in this work are of interest for further synthetic transformations.

About the Authors

A. V. Laptev
M.V. Lomonosov Moscow State University of Fine Chemical Technologies, 86, Vernadskogo pr., Moscow 119571; N.M. Emanuel Institute of Biochemical Physics RAS, Moscow, 119334
Russian Federation


A. Yu. Lukin
M.V. Lomonosov Moscow State University of Fine Chemical Technologies, 86, Vernadskogo pr., Moscow 119571
Russian Federation


N. V. Belikov
M.V. Lomonosov Moscow State University of Fine Chemical Technologies, 86, Vernadskogo pr., Moscow 119571; N.M. Emanuel Institute of Biochemical Physics RAS, Moscow, 119334
Russian Federation


O. V. Demina
N.M. Emanuel Institute of Biochemical Physics RAS, Moscow, 119334
Russian Federation


S. D. Varfolomeev
N.M. Emanuel Institute of Biochemical Physics RAS, Moscow, 119334
Russian Federation


V. A. Barachevsky
Photochemistry Center RAS, Moscow, 119421
Russian Federation


A. A. Khodonov
M.V. Lomonosov Moscow State University of Fine Chemical Technologies, 86, Vernadskogo pr., Moscow 119571; N.M. Emanuel Institute of Biochemical Physics RAS, Moscow, 119334
Russian Federation


V. I. Shvets
M.V. Lomonosov Moscow State University of Fine Chemical Technologies, 86, Vernadskogo pr., Moscow 119571
Russian Federation


References

1. Photochromism: Techniques in Chemistry / Ed. G.Y. Brown. -New York: Wiley Interscience, 1971. V. III. 853 p.

2. Photochromism: Molecules and Systems / Ed. H. Durr, H. Bouas-Laurent. - Amsterdam: Elsevier, 2003. 1218 p.

3. Organic Photochromic and Thermochromic Compounds / Ed. J.C. Crano, R.J. Guglielmetti. - New York: Plenum Press, 1999. V. 1. 400 p. V. 2. 473 p.

4. Барачевский В.А., Лашков Г.И., Чехомский В.А. Фотохромизм и его применение. - М.: Химия, 1977. 280 c.

5. Захс Э.Р., Мартынова В.П., Эфрос Л.С. Синтез и свойства спиропиранов, способных к обратимо-му раскрытию пиранового кольца // Химия гетероцикл. соедин. 1979. № 2. С. 435-459.

6. Zhou J., Li Y., Tang Y., Zhao F., Song X., Li E. Detailed investigation on a negative photochromic spiropyran // J. Photoch. Photobiol. A: Chemistry. 1995. V. 90. P. 117-123.

7. Willner I., Willner B. Biomaterials integrated with electronic elements: On route to bioelectronics // Trends in Biotechnology. 2001. V. 19. P. 222-230.

8. Willner I., Willner B. Photoswitchable biomaterials as grounds for optobioelectronic devices // Bio-electrochem. Bioenerg. 1997. V. 42. P. 43-57.

9. Bahr J.L., Kodis G, Garza L., Lin S., Moore A.L., Moore T.A., Gust D. Photoswitched singlet energy transfer in a porphyrin-spiropyran dyad // J. Am. Chem. Soc. 2001. V. 123. P. 7124-7133.

10. Grofcsika A., Baranyai P., Bitter I., Grun A., Koszegi E., Kubinyi M., Pal K., Vidoczy T. Photo-chromism of a spiropyran derivative of 1,3-calix[4]crown-5 // J. Mol. Structure. 2002. V. 614. P. 69-73.

11. Zhu L., Zhu M.-Q., Hurst J.K., Li A.D.Q. Light-controlled molecular switches modulate nanocrystal fluorescence // J. Am. Chem. Soc. 2005. V. 127. P. 8968-8970.

12. Choi H., Ku B.-S., Keum S.-R., Kang S.O., Ko J. Selective photoswitching of a dyad with diarylethene and spiropyran units // Tetrahedron. 2005. V. 61. P. 3719-3723.

13. Cho M.J., Kim G.W., Jun W.G., Lee S.K., Jin J.-I., Choi D.H. Multifunctional photochromic spiropyran dendrimers and their relaxation behaviors of photochromism // Thin Solid Films. 2006. V. 500. P. 52-60.

14. Hori T., Tagaya H., Nagaoka T., Kadokawa J., Chiba K. Photochromism of sulfonated spiropyran in a silica matrix // Appl. Surface Sci. 1997. V. 121-122. P. 530-533.

15. Khodonov A.A., Demina O.V., Lukin A.Yu., Laptev A.V., Shvets V.I., Gromov S.P., Vedernikov A.I., Strokach Yu.P., Venidiktova O.V., Valova T.M., Alfimov M.V., Barachevsky V.A. Photochromic and cation-binding properties of new crowned spiropyrans // Mol. Cryst. Liq. Cryst. 2005. V. 431. P. 215-222.

16. Laptev A.V., Lukin A.Yu., Belikov N.E., Fomin M.A., Zvezdin K.V., Demina O.V., Barachevsky V.A., Varfolomeev S.D., Shvets V.I., Khodonov A.A. Polyenic spirobenzopyrans: Synthesis and study of photochromic properties // J. Photochem. Photobiol. A: Chemistry. 2011. V. 222. № 1. P. 16-24.

17. Laptev A.V., Lukin A.Yu., Belikov N.E., Zemtsov R.V., Barachevsky V.A., Demina O.V., Varfolomeev S.D., Shvets V.I., Khodonov A.A. Synthesis and study of the photochromic behavior of 3-[6'-nitro-1,3,3-trimethylspiro(indolino-2,2'-[2H]-chromen-5-yl)]propenoic acid and its ethyl ester // High Energy Chemistry. 2010. V. 44. P. 211-215.

18. Лаптев А.В., Лукин А.Ю., Беликов Н.Е., Фомин М.А., Демина О.В., Швец В.И., Ходонов А.А. Фотохромные производные 5’-винил-6-нитроспиробензопирана и способ их получения : пат. 2458927 Рос. Федерация. - Заявка № 2011113411/04 от 07.04.2011; опубл. 20.08.2012; Бюл. № 23.

19. Лаптев А.В., Лукин А.Ю., Беликов Н.Е., Швец В.И., Демина О.В., Барачевский В.А., Ходонов А.А. 5-Формил-замещенные индолиновые спиробензопираны и способ их получения : пат. 2358977 Рос. Федерация. - Заявка № 2008112485/04 от 02.04.2008; опубл. 20.06.2009; Бюл. № 17.

20. Ono H., Osada C. Photochromic compound : pat. 3692800 USA (US). press. 19.09.1972.

21. Tomasulo M., Kaanumal S.L., Sortino S., Raymo F.M. Synthesis and properties of benzo-phenone−spiropyran and naphthalene−spiropyran conjugates // J. Org. Chem. 2007. V. 72. P. 595-605.

22. Sakata, T., Yan Y., Marriott G. Family of site-selective molecular optical switches // J. Org. Chem. 2005. V. 70. P. 2009-2013.

23. Самойлова Н.П., Гальберштам М.А. Способ получения 1,3,3-триметил-5,6’-динитроспиро(2’H-1’-бензопиран)-2,2'-индолина : А.с. СССР 455955. Заявка от 5.01.1975. Бюл. № 1.

24. Самойлова Н.П. Способ получения 5-галоидзамещенных бензопираниндолинов : А.с. СССР 469696. Заявка от 5.05.1975. Бюл. № 17.

25. Захс Э.Р., Звенигородская Л.А., Лешенюк Н.Г., Мартынова В.П. Бромирование спиропиранов и восстановление их нитропроизводных // Химия гетероцикл. соедин. 1977. № 10. С. 1320-1326.

26. Самойлова Н.П., Гальберштам М.А. О некоторых реакциях замещения в ряду фотохромных индолинспирохроменов // Химия гетероцикл. соедин. 1977. № 8. С. 1065-1068.

27. Kakurai T., Takano T. Photochromic compounds : Pat. 61076490 Japan (JP). - press. 18.04.1986.

28. Miyashita A. Spiropyran compound, optically active spiropyran compound, and use thereof : pat. 5521269 USA (US). - заявка № 335756; заявл. 14.11.1994 press. 28.05.1996.

29. Mistry B.B., Patel R.G., Patel V.S. Synthesis and characterization of photochromic homo-polymer/copolymer // J. Appl. Polymer Sci. 1997. V. 64. № 5. P. 841-848.

30. Lukyanov B.S., Metelitsa A.V., Lukyanova M.B., Mukhanov E.L., Borisenko N.I., Alekseenko Y.S., Bezugliy S.O. Photochromism of the spiropyran thin solid films // Mol. Cryst. Liq. Cryst. 2005. V. 431. P. 51-56.

31. Barachevsky V.A., Karpov P.E. Photonics of nanostructured systems based on photochromic spiro compounds // High Energy Chemistry. 2007. V. 41. P. 188-189.

32. Aggregation Processes in Solution / Ed. E. Wynne-Jones, J. Gormally. - Amsterdam: Elsever, 1983. Chap. 10-12.

33. Uznanski P. From spontaneously formed aggregates to J-aggregates of photochromic spiropyran // Synthetic Metals. 2000. V. 109. P. 281-285.

34. Levin P.P., Tatikolov A.S., Laptev A.V., Lukin A.Yu., Belikov N.E., Demina O.V., Khodonov A.A., Shvets V.I., Varfolomeev S.D. The investigation of the intermediates of spiropyran retinal analogs by laser flash photolysis techniques with different excitation wavelengths // J. Photochem. Photobiol. A: Chemistry. 2012. V. 231. P. 41-44.

35. Barachevsky V.A., Khodonov A.A., Belikov N.E., Laptev A.V., Lukin A.Yu., Demina O.V., Luyksaar S.I., Krayushkin M.M. Properties of photochromic retinals // Dyes & Pigments. 2012. V. 92. P. 831-837.


For citation:


Laptev A.V., Lukin A.Yu., Belikov N.V., Demina O.V., Varfolomeev S.D., Barachevsky V.A., Khodonov A.A., Shvets V.I. SYNTHESIS AND STUDY OF THE PHOTOCHROMIC BEHAVIOR OF SUBSTITUTED 6'-NITRO-1,3,3-TRIMETHYL-5-VINYLSPIRO(INDOLINO-2,2'-[2H]CHROMENES). Fine Chemical Technologies. 2013;8(4):18-26. (In Russ.)

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