Диссертация (1150167), страница 17
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A., 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 N. J., Klene M., Knox J. E., Cross J. B., Bakken V., AdamoC., 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.,111Daniels A. D., Farkas O., Foresman J. B., Ortiz J. V., Cioslowski J., Fox D. J.Gaussian 09, Revision C.01 // Gaussian: Wallingford, CT. – 2010.112БЛАГОДАРНОСТИАвтор выражает благодарности к.х.н. Музалевскому В.М.
и д.х.н., проф.Ненайденко В.Г. (химический факультет МГУ) за помощь в синтезеисходных соединений, Иванову А.Ю. (РЦ СПбГУ) за исследование ЯМРкатионов в суперкислотах, Осетровой Л.В. (ФГУП НИИСК) за регистрациюспектров ЯМР, к.х.н., доц. Боярской И.А. (институт химии СПбГУ) запомощь в проведении квантово-химических расчетов. Работа выполнена сиспользованием оборудования ресурсных центров СПбГУ «Магнитнорезонансные методы исследования» и «Рентгенодифракционные методыисследования».113ПриложениеСпектры ЯМР 1H, 13C, 19F соединений114210200190129.0(ppm)180170160150128.0(ppm)140130120126124(ppm)1101004.0С2С1F31229080706053.08665.0(ppm)59.338860.059759.820659.577959.338853.08665.04.9(ppm)59.57796.01.00001.00069.42570.45961.00001.0006Integral0.45969.4257Ha59.820660.05977.0120.64438.0122.8747127.4212127.3819139.8400139.4582128.7737128.6702128.5667127.8780127.4212127.3819125.1051122.8747120.64439.0127.8780128.7737128.6702128.566710.0125.1051139.4582139.8400Integral(ppm)H4.99094.97804.96494.96134.94844.93564.53544.51807.26007.35347.34157.32587.3134Ha3.050CF3HbCl2a4.5(ppm)2.01.0H60.0(ppm)40300.0Рис.
8. Спектр ЯМР 1H (500 MГц, CDCl3)соединения 2aPhC1F3C3C2Ph20H2aClС3(ppm)(ppm)100Рис. 9. Спектр ЯМР 13C (125 MГц, CDCl3) соединения 2a1154.99094.97804.96494.96134.94844.93564.53544.51807.35347.34157.32587.31347.26009.59.08.58.07.57.06.5(ppm)6.05.54.50(ppm)5.0(ppm)4.54.03.53.0-71.2CF3HbClД22.52.01.52.3109-71.02.3318-70.81.00001.6782Ha-70.62.33182.31094.97324.96044.94744.94404.93064.91784.50354.49964.48624.4823-70.44.50354.49964.48624.48234.96044.94744.94404.93064.91787.34527.33997.33337.31927.30677.26007.25097.23477.22067.20427.16217.14647.12847.1125-70.23.08977.20(ppm)-70.01.00001.04607.16217.14647.12847.11257.26007.25097.23477.22067.2042-69.81.00007.302.32733.01594.10877.34527.33997.33337.31927.3067-69.61.04604.10873.01592.3273IntegralCF3Cl2a(ppm)-71.4Рис.10. Спектр ЯМР 19F (470 MГц, CDCl3) соединения 2a2bД17.10(ppm)1.00.5Рис.
11. Спектр ЯМР 1H (500 MГц, CDCl3)соединения 2b116-70.4716-70.4857190-70.00180136.4962136.8602129.0170-70.10160150-70.20140130-70.301201101.0000140137.1207137.0779139.7222140.0862126124(ppm)-70.4012252.761952.686910090(ppm)80Cl70-70.5060-70.605059.699359.645759.460259.403160.181060.120459.938459.8848120.6658122.8961H60.0(ppm)40-70.70Д230C3Д2Д1Д253.0(ppm)2021.011820.9689125.1230127.1071127.3284127.2820127.8173127.7209128.7451128.5845128.5382128.5167129.4517129.2804С1F3-70.4687-70.4822-70.4120-70.4255(ppm)0.6294IntegralPhC1F3C2ClH2bД1(ppm)128.021.0(ppm)137.0(ppm)100Рис. 12.
Спектр ЯМР 13С (CDCl3,125 MГц) соединения 2bCF32bД2Д1(ppm)-70.80Рис. 13. Спектр ЯМР 19F (470 MГц, CDCl3) соединения 2b11721.011820.968960.181060.120459.938459.884859.699359.645759.460259.403152.761952.6869140.0862139.7222137.1207137.0779136.8602136.4962129.4517129.2804128.7451128.5845128.5382127.8173127.7209127.3284127.2820127.1071125.1230122.8961120.66588.5-70.108.07.52c-70.207.06.5CF3-70.306.05.51.0000Ph5.0(ppm)-70.402.22(ppm)(ppm)4.5Cl4.0-70.503.53.0-70.602.52.0-70.701.51.72164.47254.45524.43747.11457.10407.07637.35067.33747.32767.32427.30837.29267.27577.26007.24847.2343CF3HbCl3.10621.35171.00004.96544.95154.93764.9247H1.35173.10621.72161.00007.101.03453.11560.45634.51932c-70.4606-70.47419.01.03454.51930.45633.1156Integral7.20(ppm)-70.3769-70.39049.50.8682Integral7.30HaД2Д1HaД2Д1Д2(ppm)1.00.5Рис.
14. Спектр ЯМР 1H (500 MГц, CDCl3) соединения 2cД1Д2(ppm)-70.80Рис. 15. Спектр ЯМР 19F (470 MГц, CDCl3) соединения 2c1182.22122.23942.26152.26152.23942.22124.98024.96754.96544.95154.93764.92474.47254.45524.43747.36547.35067.33747.32767.32427.30837.29267.27577.26007.24847.23437.11457.10407.0763(ppm)190180170(ppm)160130150140(ppm)128130120126110С1F3124(ppm)100(ppm)4.0C2Д190803.0Cl2С60.0(ppm)7060504021.329421.218719.398719.35591.92371.19123.15482.34202.3170Д12.3995Д21.19123.15484.69894.6774Ha1.92374.80(ppm)2.0С3Д248(ppm)302019.398719.3559Ph0.6421CH321.329421.2187C34.78834.77187.05147.03627.00356.98836.97596.96067.32247.31367.29987.27957.24337.23027.21692e47.68735.0(ppm)49.0077H60.405960.266760.166860.031259.927759.792159.556549.007747.68736.00.34564.96924.96044.94824.9358Hb60.405960.266760.166860.031259.927759.792159.685059.55657.01.00001.04361.07421.06930.94775.4129Integral5.00120.80148.01.04365.41290.94771.06931.07427.0123.03539.0125.2657139.0906138.5517138.3055137.9272135.6861135.5862133.2880132.4101130.9363130.8542129.0770128.3597127.9529127.8458127.4926127.3605127.2499127.1785126.7182125.2657123.0353120.801410.0129.0770128.6238128.3597127.9529127.8458127.4926127.3605127.2499127.1785126.7182130.9363130.85427.27.1(ppm)127.1785126.7182133.2880132.4101Integral7.3137.9272138.5517138.3055139.0906135.6861135.5862PhHaCF3HbCl2.40(ppm)1.00.0Рис.
16. Спектр ЯМР 1H (500 MГц, CDCl3)соединения 2eC1F3HСH3 СH3(ppm)(ppm)122(ppm)138.0100Рис. 17. Спектр ЯМР 13C (125 MГц, CDCl3) соединения 2e1192.39952.34202.31704.99544.98214.96924.96044.94824.93584.78834.77184.69894.67747.33067.32247.31367.29987.27957.24337.23027.21697.05147.03627.00356.98836.97596.960610.09.08.07.0Cl5.06.04.94.50374.48754.46894.45151.00001.8594Integral-69.9094-69.9202-70.9389-70.9524CF3-70.64.85.0(ppm)-70.8H4.74.6(ppm)-71.04.54.03.0-71.22.01.2581-70.41.5491-70.21.00004.91424.90144.88854.87444.86074.50374.48754.46894.4515-70.01.0000Cl2h4.91424.90144.88854.87444.8607PhHa-69.81.0308Integral7.41607.39667.36937.33477.32017.30627.28167.26007.19567.17897.16517.1482-69.61.03087.09601.2792Integral-69.4PhД1Cl2eД2(ppm)-71.4-71.6Рис. 18. Спектр ЯМР 19F (470 MГц, CDCl3) соединения 2eCF3HbClHД1Д24.41.00.0Рис.
19. Спектр ЯМР 1H (500 MГц, CDCl3) соединения 2h1204.06090.9041Integral10.07.27.0(ppm)6.89.08.07.06.0Д24.9(ppm)5.0(ppm)3.13342.9793H6.00731.00003.85953.8392-70.501.00004.93534.93004.91904.91284.90664.90024.48724.47754.47084.46043.85953.8392-70.404.48724.47754.47084.4604-70.301.00074.91904.91284.90664.9002-70.201.00077.34407.33567.31927.31117.26006.92376.92026.90366.88706.88356.84416.83406.82966.80796.79136.78296.77941.00000.3073Integral-70.6579-70.6714-70.3985-70.4120CF31.04192.22556.92376.92026.90366.88706.88356.84416.83406.82966.80796.79136.78296.77947.33567.31927.31117.2600Cl2.22551.04190.90414.0609PhClCl2hД1Д2(ppm)-70.60-70.70(ppm)4.0-70.80Ha3.0-70.90Рис.
20. Спектр ЯМР 19F (470 MГц, CDCl3)соединения 2hOCH3HaMeO2.0CF3HbClMeO2jД13.8(ppm)1.00.0Рис. 21. Спектр ЯМР 1H (500 MГц, CDCl3) соединения 2j1211902j180MeO-68.8(ppm)170160-69.2150-69.6112(ppm)149(ppm)1401302j-70.0120110100(ppm)-70.490-70.880-71.27060.0(ppm)60-71.65040-72.03052.587052.2837C255.802355.780955.934455.920159.445959.685059.635059.924159.8777H60.159660.1168Cl127.3534127.3213127.7459112.4829111.4480111.2553111.0626MeO60.3559C128.7202128.5239C1F31.1512-70.4339-70.4468-70.4890-70.50522002148.3690149.0257148.8187MeOC1.0000IntegralH3OCH3C3Д2Д159.555.8(ppm)53(ppm)C120-72.4100Рис.
22. Спектр ЯМР 13C (125 MГц, CDCl3) соединения 2jCF3ClД2MeOД1(ppm)-72.8Рис.23. Спектр ЯМР 19F (470 MГц, CDCl3) соединения 2j12260.355960.159660.116859.924159.877759.685059.635059.445955.934455.920155.802355.780952.587052.2837112.4829111.4480111.2553111.0626149.0257148.8187148.3690140.0077139.5759132.3245131.7535128.7202128.5239127.7459127.3534127.3213125.0873125.0623122.8319120.8763120.0876137.0(ppm)190180132(ppm)129.0170160150140130120(ppm)110126(ppm)124100904.0Д1803.53.0(ppm)12270602.5С1502.01.5128.0(ppm)403021.004620.96184.51.91101.14621.02471.9288(ppm)21.004620.96185.0(ppm)3.12264.9(ppm)3.00761.00001.01202l59.806359.735059.570860.445160.281060.209660.041959.970559.806359.735059.570855.174351.998251.60925.54.47254.45594.43424.89784.88984.88484.87254.8600Ha51.60922l6.01.00001.01206.960.445160.281060.209660.041959.97056.5114.1102113.87827.0Hb51.9982H2.09406.0079(ppm)55.1743Cl7.5127.6139C1F38.0128.33832.0940MeO120.6729C28.5128.8807Me158.7288137.2349136.9708136.9387136.8531132.1603131.6821129.7800129.4089129.2697128.8807128.3383127.6139127.3569125.1301122.8997120.67297.0CF3HbCl122.8997125.1301MeO7.1129.4089129.26976.0079IntegralHa113.8782C3114.1102H9.0129.78009.5131.6821Integral7.2132.1603137.2349136.9708136.9387136.85316.87166.85436.83976.82247.24327.22977.21297.19997.18377.15237.12237.10652.32482.30793.76833.7854Me2.32482.30794.92404.91104.89784.88984.88484.87254.86004.47254.45594.43423.78543.76837.24327.22977.21297.19997.18377.15237.12237.10656.87166.85436.83976.8224Д2Д1Д22.30(ppm)1.0С2(ppm)200.5Рис.
24. Спектр ЯМР 1H (500 MГц, CDCl3) соединения 2lС2Д2(ppm)60.0(ppm)CH3(ppm)21.0(ppm)10Рис. 25. Спектр ЯМР 13C (125 MГц, CDCl3) соединения 2l1238.28.07.87.67.47.27.06.86.66.46.26.0ClH5.85.6(ppm)5.45.25.04.8(ppm)4.64.4H3CO4.24.03.8-70.80(ppm)3.63.43.77723.79153.79153.77724.48804.47824.47204.4620-70.701.1906C1.8221C2-70.603.0655H1-70.504.48804.47824.47204.4620-70.401.0000-70.30Integral6.94.88394.87124.85824.84504.8318-70.204.88394.87124.85824.84504.83181.00000.4995IntegralCl1.00001.03107.17.0(ppm)6.88006.86276.85226.83497.31267.29577.27077.24027.23227.21497.1840-70.101.03107.26.88006.86276.85226.83497.31267.29577.27077.24027.23227.21497.1840-70.002.23023.98867.32.23022.5136MeO3.98862.5136IntegralMeCF3CF3Д12lД2(ppm)-70.90Рис. 26.
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