Abstract
Electron impact (70 eV) and chemical ionization (methane as reactant gas) mass spectra of 1-alkyl- and 1-[2-(vinyloxy)ethyl]-5-(prop-2-yn-1-ylsulfanyl)-1H-pyrrol-2-amines have been studied for the first time. The title compounds under electron impact form stable molecular ions which decompose mainly along pathways typical of the molecular ions derived from the corresponding intramolecular cyclization products, 7-alkyl- and 7-[2-(vinyloxy)ethyl]-2,7-dihydrothiopyrano[2,3-b]pyrrol-6-amines. In addition, fragment ions that could be formed only via decomposition of unrearranged molecular ion were detected. The main fragmentation pathway of their molecular ions involves cleavage of the N1-CAlk bond with the formation of stable [M − R3]+ ions (Irel 85–100%) {except for N,N-diethyl- and N,N-dipropyl-1-[2-(vinyloxy)emyl]-5-(prop-2-yn-1-ylsulfanyl)-1H-pyrrol-2-amines}. The results of quantum chemical calculations at the B3LYP/6-311+G(d,p) level of theory are consistent with the experimental data. In the chemical ionization mass spectra of 5-(prop-2-yn-1-ylsulfanyl)-1H-pyrrol-2-amines, the major peaks were those corresponding to M+· (Irel 65–100%) and [M + H]+ (Irel 75–100%). The title compounds have been found to undergo partial (5–10%) thermally induced isomerization to 5-(prop-1-yn-1-ylsulfanyl)-1H-pyrrol-2-amines under the chemical ionization conditions.
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Klyba, L.V., Nedolya, N.A., Sanzheeva, E.R., and Tarasova, O.A., Russ. J. Org. Chem., 2019, vol. 55, p. 824. https://doi.org/10.1134/S1070428019060125
Sundberg, R.J., Comprehensive Heterocyclic Chemistry, Katritzky, A.R. and Rees, C.W., Eds., Oxford: Pergamon, 1984. vol. 4, p. 313.
Gribble, G.W., Comprehensive Heterocyclic Chemistry II, Katritzky, A.R., Rees, C.W., and Scriven, E.F.V., Eds., Oxford: Pergamon, 1996. vol. 2, p. 207.
d’Ischia, M., Napolitano, A., and Pezzella, A., Comprehensive Heterocyclic Chemistry III, Katritzky, A.R., Ramsden, C.A., Scriven, E.F.V., and Taylor, R.J.K., Eds., Amsterdam: Elsevier, 2008. vol. 3, p. 353.
Joshi, S.D., More, U.A., Kulkarni, V.H., and Aminabhav, T.M., Curr. Org. Chem., 2013, vol. 17, p. 2279. https://doi.org/10.2174/13852728113179990040
Baumann, M., Baxendale, I.R., Ley, S.V., and Nikbin, N., Beilstein J. Org. Chem., 2011, vol. 7, p. 442. https://doi.org/10.3762/bjoc7.57
Domingo, V.M., Brillas, E., Torrelles, X., Rius, J., and Julia, L., J. Org. Chem., 2001, vol. 66, p. 8236. https://doi.org/10.1021/jo010514w
Rosa, A., Ricciardi, G., Baerends, E.J., Zimin, M., Rodgers, M.A.J., Matsumoto, S., and Ono, N., Inorg. Chem., 2005, vol. 44, p. 6609. https://doi.org/10.1021/ic050838t
Cirrincione, G., Almerico, A.M., Aiello, E., and Dattolo, G., The Chemistry of Heterocyclic Compounds, Taylor, E.C., Ed., New York: Wiley, 1992. vol. 48, part 2, p. 299. https://doi.org/10.1002/9780470187340.ch3
Marcotte, F.-A. and Lubell, W.D., Org. Lett., 2002, vol. 4, p. 2601. https://doi.org/10.1021/ol0262690
Unverferth, K., Engel, J., Höfgen, N., Rostock, A., Günther, R., Lankau, H.-J., Menzer, M., Rolfs, A., Liebscher, J., Müller, B., and Hofmann, H., J. Med. Chem., 1998, vol. 41, p. 63. https://doi.org/10.1021/jm970327j
Iaroshenko, V.O., Wang, Y., Sevenard, D.N., and Volochnyuk, D.M., Synthesis, 2009, p. 1851. https://doi.org/10.1055/s-0029-1216640
Ong, C.W., Yang, Y.-T., Liu, M.-C., Fox, K.R., Liu, P.H., and Tung, H.-W., Org. Biomol. Chem., 2012, vol. 10, p. 1040. https://doi.org/10.1039/C1OB06803B
Pućkowska, A., Midura-Nowaczek, K., and Bruzgo, I., Acta Pol. Pharm., 2008, vol. 65, p. 213.
Baraldi, P.G., Zaid, A.N., Preti, D., Fruttarolo, F., Tabrizi, M.A., Iaconinoto, A., Pavani, M.G., Carrion, M.D., Cara, C.L.L., and Romagnoli, R., Arkivoc, 2006, part (vii), p. 20. https://doi.org/10.3998/ark.5550190.0007.704
Broyles, S.S., Kremer, M., and Knutson, B.A., J. Virol., 2004, vol. 78, p. 2137. https://doi.org/10.1128/JVI.78.4.2137-2141.2004
Chien, T.-C., Meade, E.A., Hinkley, J.M., and Townsend, L.B., Org. Lett., 2004, vol. 6, p. 2857. https://doi.org/10.1021/ol049207d
Nair, V., Vinod, A.U., and Rajesh, C.A., J. Org. Chem., 2001, vol. 66, p. 4427. https://doi.org/10.1021/jo001714v
Tarasova, O.A., Nedolya, N.A., Vvedensky, V.Yu., Brandsma, L., and Trofimov, B.A., Tetrahedron Lett., 1997, vol. 38, p. 7241. https://doi.org/10.1016/S0040-4039(97)01680-8
Nedolya, N.A., Tarasova, O.A., Albanov, A.I., and Trofimov, B.A., Synthesis, 2016, vol. 48, p. 4278. https://doi.org/10.1055/s-0035-1561492
Brandsma, L., Nedolya, N.A., Tarasova, O.A., and Trofimov, B.A., Chem. Heterocycl. Compd., 2000, vol. 36, p. 1241. https://doi.org/10.1023/A:1017582315266
Brandsma, L. and Nedolya, N.A., Synthesis, 2004, p. 735. https://doi.org/10.1055/s-2004-816005
Nedolya, N.A. and Trofimov, B.A., Chem. Heterocycl. Compd., 2013, vol. 49, p. 152. https://doi.org/10.1007/s10593-013-1236-y
Nedolya, N.A., Tarasova, O.A., Albanov, A.I., and Trofimov, B.A., J. Org. Chem., 2017, vol. 82, p. 7519. https://doi.org/10.1021/acs.joc.7b01217
Nedolya, N.A., Tarasova, O.A., Albanov, A.I., and Trofimov, B.A., Synthesis, 2018, vol. 50, p. 4313. https://doi.org/10.1055/s-0037-1609561
Nedolya, N.A., Brandsma, L., Tarasova, O.A., Verkruijsse, H.D., and Trofimov, B.A., Tetrahedron Lett., 1998, vol. 39, p. 2409. https://doi.org/10.1016/S0040-4039(98)00211-1
Brandsma, L., Nedolya, N.A., and Trofimov, B.A., Eur. J. Org. Chem., 1999, p. 2663. https://doi.org/10.1002/(SICI)1099-0690(199910)1999:10
Nedolya, N.A., Tarasova, O.A., Albanov, A.I., and Trofimov, B.A., Tetrahedron Lett., 2010, vol. 51, p. 5316. https://doi.org/10.1016/j.tetlet.2010.07.179
Nedolya, N.A., Brandsma, L., Tarasova, O.A., Albanov, A.I., and Trofimov, B.A., Russ. J. Org. Chem., 2011, vol. 47, p. 659. https://doi.org/10.1134/S1070428011050034
Tarasova, O.A., Nedolya, N.A., Albanov, A.I., and Trofimov, B.A., Eur. J. Org. Chem., 2018, p. 5961. https://doi.org/10.1002/ejoc.201800987
Klyba, L.V., Nedolya, N.A., Tarasova, O.A., and Sanzheeva, E.R., Russ. J. Org. Chem., 2013, vol. 49, p. 384. https://doi.org/10.1134/S1070428013030123
Klyba, L.V., Nedolya, N.A., Tarasova, O.A., and Sanzheeva, E.R., Russ. J. Org. Chem., 2014, vol. 50, p. 35. https://doi.org/10.1134/S1070428014010072
Klyba, L.V., Nedolya, N.A., Tarasova, O.A., Zhanchipova, E.R., and Volostnykh, O.G., Russ. J. Org. Chem., 2010, vol. 46, p. 1038. https://doi.org/10.1134/S1070428010070134
Klyba, L.V., Tarasova, O.A., Nedolya, N.A., and Sanzheeva, E.R., Russ. J. Org. Chem., 2016, vol. 52, p. 1587. https://doi.org/10.1134/S1070428016110063
Klyba, L.V., Tarasova, O.A., and Nedolya, N.A., Russ. J. Org. Chem., 2016, vol. 52, p. 1773. https://doi.org/10.1134/S1070428016120101
Becke, A.D., J. Chem. Phys., 1993, vol. 98, p. 5648. https://doi.org/10.1063/L464913
Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Scalmani, G., Barone, V., Mennucci, B., Petersson, G.A., Nakatsuji, H., Caricato, M., Li, X., Hratchian, H.P., Izmaylov, A.F., Bloino, J., Zheng, G., Sonnenberg, J.L., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Vreven, T., Montgomery, J.A., Jr., Peralta, J.E., Ogliaro, F., Bearpark, M., Heyd, J.J., Brothers, E., Kudin, K.N., Staroverov, V.N., Kobayashi, R., Normand, J., Raghavachari, K., Rendell, A., Burant, J.C., Iyengar, S.S., Tomasi, J., Cossi, M., Rega, N., Millam, J.M., Klene, M., Knox, J.E., Cross, J.B., Bakken, V., Adamo, C., Jaramillo, J., Gomperts, R., Stratmann, R.E., Yazyev, O., Austin, A.J., Cammi, R., Pomelli, C., Ochterski, J.W., Martin, R.L., Morokuma, K., Zakrzewski, V.G., Voth, G.A., Salvador, P., Dannenberg, J.J., Dapprich, S., Daniels, A.D., Farkas, Ö., Foresman, J.B., Ortiz, J.V., Cioslowski, J., and Fox, D.J. Gaussian 09, Revision A.01, Wallingford CT: Gaussian, 2009.
Peng, C. and Schlegel, H.B., Isr. J. Chem., 1993, vol. 33, p. 449. https://doi.org/10.1002/ijch.199300051
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This study was performed using the facilities of the Baikal Joint Analytical Center, Siberian Branch, Russian Academy of Sciences.
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The authors declare the absence of conflict of interests.
Russian Text © The Author(s), 2019, published in Zhurnal Organicheskoi Khimii, 2019, Vol. 55, No. 12, pp. 1857–1869.
For communication XIX, see [1].
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Klyba, L.V., Nedolya, N.A., Sanzheeva, E.R. et al. Mass Spectra of New Heterocycles: XX. Electron Impact and Chemical Ionization Mass Spectra of 5-(Prop-2-yn-1-ylsulfanyl)-1H-pyrrol-2-amines. Russ J Org Chem 55, 1853–1863 (2019). https://doi.org/10.1134/S1070428019120078
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DOI: https://doi.org/10.1134/S1070428019120078