In situ ATR-FTIR Combined with SIMPLISMA Algorithm to Investigate the Synthesis Mechanism of 4-Amino-3, 5-dimethyl Pyrazole

doi:10.1007/s40242-016-6189-0

Abstract

Abstract:

In situ attenuated total refletion-Fourier transform infrared spectroscopy(ATR-FTIR) was used to monitor and acquire spectral information on the synthesis of 4-amino-3,5-dimethyl pyrazole. Principal component analysis(PCA) was used to determine the number of principle components(PCs). The score vectors of the PCs were analysed using the simple-to-use interactive self-modelling mixture analysis(SIMPLISMA) algorithm to obtain spectral and concentration profiles for the reactants, intermediates and product. The vibrational frequencies of the interme-diates were calculated via density functional theory(DFT) at the level of the B3LYP/6-311++G(d,p) basis set, and the geometrical configurations of the intermediates were simultaneously optimized. Finally, a reasonable synthesis mechanism for 4-amino-3,5-dimethyl pyrazole was determined based on the changes observed in the feature peaks. The results from the SIMPLISMA algorithm correlated well with the quantum chemistry calculations. This proved that the SIMPLISMA algorithm combined with ATR-FTIR can be used to determine the synthesis mechanism for 4-amino-3,5-dimethyl pyrazole and can even provide a new, useful method to explore dynamic synthesis reaction mechanisms.

Key words: 4-Amino-3,5-dimethyl pyrazole, Synthesis mechanism, In situ attenuated total refletion-Fourier transform infrared spectroscopy(ATR-FTIR), Simple-to-use interactive self-modelling mixture analysis(SIMPLISMA) algorithm, Density functional theory

GAO Xinyu, MA Junxiu, RUAN Fangqi, ZHANG Tianlong, LI Hua. In situ ATR-FTIR Combined with SIMPLISMA Algorithm to Investigate the Synthesis Mechanism of 4-Amino-3, 5-dimethyl Pyrazole[J]. Chemical Research in Chinese Universities, 2016, 32(6): 985-991.

References

[1] Pagoria P. F., Lee G. S., Mitchell A. R., Thermochimica Acta, 2002, 384(1), 187
[2] Rollas S., Ergenç N., Oral B., Journal of Faculty Pharmacy of Is-tanbul University, 2005, 38(1), 71
[3] Mukherjee S., Gowen A., Anal. Chim. Acta, 2015, 895, 12
[4] Steinfeldt N., Bentrup U., Ja?hnisch K., Ind. Eng. Chem. Res., 2009, 49(1), 72
[5] Niu Z., Liu G., Yin H., Fuel, 2016, 172, 1
[6] Togkalidou T., Tung H. H., Sun Y., Org. Process Res. De., 2002, 6, 317
[7] Liu H., Liu P., You K., Catal. Commun., 2010, 11(10), 887
[8] Kassouf A., Ruellan A., Bouveresse D. J. R., Talanta, 2016, 147, 569
[9] Jaumot J., Gargallo R., de Juan A., Chemometr. Intell. Lab., 2005, 76(1), 101
[10] Garrido M., Rius F. X., Larrechi M. S., Anal. Bioanal. Chem., 2008, 390, 2059
[11] Workman J. Jr., Koch M., Lavine B., Anal. Chem., 2009, 81(12), 4623
[12] Wu N., Sun K. L., Liu Y., Yang X. F., Li H., Chem. Res. Chinese Universities, 2013, 29(4), 759
[13] Sui R., Rizkalla A. S., Charpentier P. A., Cryst. Growth Des., 2008, 8(8), 3024
[14] Windig W., Guilment J., Anal. Chem., 1991, 63(14), 1425
[15] Windig W., Stephenson D. A., Anal. Chem., 1992, 64(22), 2735
[16] Cao L., de Harrington P. B., Liu J., Anal. Chem., 2005, 77(8), 2575
[17] Bogomolov A, Engler M., Melichar M., J. Chemometr., 2010, 24(7), 544
[18] Windig W., Hecler C. E., Agblevor F. A., Evans R. J., Chemom. Intei. Lab. Syst., 1992, 14(1), 195
[19] Sánchez F. C., Massart D. L., Anal. Chim. Acta, 1994, 298(3), 331
[20] Vennila P., Govindaraju M., Venkatesh G., J. Mol. Struct., 2016, 1111, 151
[21] Frisch M. J., Trucks G. W., Schlegel H. B., Scuseria G. E., Robb M. A., Cheeseman J. R., Montgomery J. A. Jr., Vreven T., Kudin K. N., Burant J. C., Millam J. M., Iyengar S. S., Tomasi J., Barone V., Mennucci B., Cossi M., Scalmani G., Rega N., Petersson G. A., Nakatsuji H., Hada M., Ehara M., Toyota K., Fukuda R., Hasegawa J., Ishida M., Nakajima T., Honda Y., Kitao O., Nakai H., Klene M., Li X., Knox J. E., Hratchian H. P., Cross J. B., Adamo C., Jaramillo J., Gomperts R., Stratmann R. E., Yazyev O., Austin A. J., Cammi R., Pomelli C., Ochter-ski J. W., Ayala P. Y., Morokuma K., Voth G. A., Sal-vador P., Dannenberg J. J., Zakrzewski G., Dapprich S., Daniels A. D., Strain M. C., Farkas O., Malick D. K., Rabuck A. D., Raghavachari K., Foresman J. B., Ortiz J. V., Cui Q., Baboul A. G., Clifford S., Cioslowski J., Stefanov B. B., Liu G., Liashenko A., Piskorz P., Komaromi I., Martin R. L., Fox D. J., Keith T., Al-Laham M. A., Peng C. Y., Nanayakkara A., Challacombe M., Gill P. M. W., Johnson B., Chen W., Wong M. W., Gonzalez C., Pople J. A., Gaussian 03, Revision D.01, Gaussian Inc., Wallingford CT, 2004
[22] Luo Y. F., Ge Z. X., Wang B. Z., Zhang H. H., Liu Q., J. Energy Mater., 2007, 15(3), 205
[23] Rinnan Å., van den Berg F., Trac-Trend Anal. Chem., 2009, 28(10), 1201
[24] Lauro C. H., Brandao L. C., Baldo D., Reis R. A., Davim J. P., Measurement, 2014, 58, 73
[25] Graps A., IEEE Comp. Sc. Eng., 1995, 2(2), 50
[26] Camacho J., Picó J., Ferrer A., Anal. Chim. Acta, 2009, 642(1), 59
[27] Wold S., Esbensen K., Geladi P., Chemom. Intei. Lab. Syst., 1987, 2, 37
[28] Medeghini L., Mignardi S., De Vito C., Microchem. J., 2016, 125, 224
[29] Dewaest M., Villemejane C., Bouveresse D. J. R., Food Hydrocolloid, 2016, 58, 298
[30] Kassouf A., Ruellan A., Bouveresse D. J. R., Talanta., 2016, 147, 569
[31] Juneja A., Rana B., Agrawal R. K., Biomed. Signal. Process, 2016, 27, 122
[32] Malinowski E. R., 1988, 3(1), 49
[33] Malinowski E. R., Howery D. G., Factor Analysis Chemistry, Wein-heim-Interscience, New York, 1980
[34] Lee C., Yang W., Parr R. G., Phys. Rev. B, 1988, 37(2),785
[35] Becke A. D., J. Chem. Phys., 1993, 98(7), 5648
[36] Sri N. U., Chaitanya K., Prasad M. V. S., Veeraiah V., Spectrochim Acta A, 2012, 97, 728
[37] Barsberg S., J. Phys. Chem. B, 2010, 114(36), 11703