Диссертация (1150306), страница 15
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B!R (^'T#),: 3'*.*K*.4:&$#,*) = 8:1, 2/0.25 4') Rf = 0.46. AOG 1H(Me2SO-56, f): 8.72 (5, 2H, o-CH), 8.28 (+, :S%., 1H, NH), 7.73 (5, 2H, o-CH), 7.60–7.47 (4, 6H, 3-,#-CH), 7.26 (+, :S%., 2H, NH2).!7A;9R DEPQH9D8< 55. G&+,F*. 9#)I&4%5*1+%4& 6 (200 414*'() F 4#,&)*'# (0.5 4')5*9&F'2'% 1 .&+,F*.: 1*4"'#1+& 37 (100 414*'() F 4#,&)*'# (2 4'). X*4*/#))HJ .&+,F*.*+,&F'2'% )& 48 0 ".% 1*4)&,)*J ,#4"#.&,:.#. 8*':0#))H# 1.%+,&''H *,K%'(,.*FHF&'%,".*4HF&'% O#?- (0.5 4'), Et2O (1 4') % +:S%'% F ,#0#)%# 12 0 ".% 1*4)&,)*J ,#4"#.&,:.# )&F*I5:3#.EtHHNPhClONNH55.
;H3*5 33%. B.&I' 144 °C. ;H0%+'#)* 5'2PhPtHNClEtC20H26N6Cl2O2Pt•H2O: C, 36.04; H, 4.23; N, 12.61.NONHH-&J5#)*: C, 35.88; H, 4.18; N, 12.57%. Z!>-O!+FH+*1*/* .&I.#S#)%2 (MeOH:Me2SO = 10:1, m/z):671.111 ([M + Na]+, FH0%+'#)* 671.098), 691.166([M – Cl + Me2SO]+, FH0%+'#)* 691.154), 1261.254 ([2M – Cl]+, FH0%+'#)* 1261.249), 1319.213([2M + Na]+, FH0%+'#)* 1319.208), 1339.267 ([2M – Cl + Me2SO]+, FH0%+'#)* 1339.263).
>C (KBr,*,5#'()H# "*'*+H, +4d1): 3470(+.), 3418(+.), 3340(+%'), 3286(+.-+%') b(NdH); 3059(+'-c.),2978(+'-c.), 2939(+'-c.), 2880(+'), 2831(+') b(CdH); 1660("'), 1626(*0 +%') b(C=N); 781(+.),694(+.) f(CdH). B!R (^'T#),: 3'*.*K*.4:&$#,*) = 6:1, 3/0.5 4') Rf = 0.57. AOG 1H (Me2SO-56,f): 7.92 (+, :S%., 1H, NH), 7.81 (5, 2H, o-CH), 7.57–7.45 (4, 3H, 3-, #-CH), 7.25 (+, :S%., 2H,NH2), 3.02 (1, 2H, CH2), 1.42 (,, 3H, CH3). C.%+,&''H, ".%/*5)H# 5'2 G!7, 9H'% FH.&M#)H %I.#&1$%*))*J +4#+% F 4#,&)*'# ".% 1*4)&,)*J ,#4"#.&,:.#.!!81!L9H<;7:EF<A79 .-7P7AE<=7H<P7GED87PEF R< 8@^; Q:7A?G7;9HIAEC G9DEE:G7A<=77OHE:7G-<A7EA<. !4#+( 1*4"'#1+& (55–61) (50 414*'() % AgNO3 (17 4/, 100 414*'()+:+"#)I%.*F&'% F 4#,&)*'# (2 4'). >),#)+%F)* "#.#4#S%F:T +:+"#)I%T *+,&F'2'% )&30 4%) 9#I 5*+,:"& +F#,&, "*+'# 0#/* (".% "*':0#)%% 47) 1 .#&1$%*))*J +4#+% 5*9&F'2'%,U"'HJ (55 ºC) 4#,&)*' (10 4') F $#'23 .&+,F*.#)%2 *9.&I*F&FS#/*+2 *+&51& 47.
?+&5*1 AgCl*,K%'(,.*FHF&'%. 8*':0#))HJ /*4*/#))HJ .&+,F*. :"&.%F&'% ".% "*)%Y#))*4 5&F'#)%% (10–150 49&.) % "*':0#))H# 9#+$F#,)H# "*.*S1% ".*4HF&'% CH2Cl2 (1 4'), Et2O (1 4') % +:S%'% F,#0#)%# 12 0 ".% 1*4)&,)*J ,#4"#.&,:.# )& F*I5:3#.[46](NO3)2. ;H3*5 *1*'* 100%.
B.&I' 175 °C. ;H0%+'#)* 5'2(NO3)2HPhONPtNN(MeOH, m/z): 288.578 ([M d 2NO3]2+, FH0%+'#)* 288.585),O304.591 [Md 2NO3 d H + MeOH]2+, FH0%+'#)* 304.598), 576.152NHHC20H26N8O8Pt•aH2O: C, 33.81; H, 3.83; N, 15.77. -&J5#)*: C,33.70; H, 3.44; N, 15.63%. Z!>-O!+ FH+*1*/* .&I.#S#)%2HHNEtNEt([M d 2NO3 d H]+, FH0%+'#)* 576.163), 608.178 ([Md 2NO3 d H+ MeOH]+, 608.189). >C (KBr, *,5#'()H# "*'*+H, +4d1):PhH3432(+%'), 3427(+%'), 3367(+%') b(NdH); 3055(+.), 2927(+'),2853(+') b(CdH); 1669(+.), 1636(+%') b(C=N); 1384(+%') b(NdO); 780(+'), 728(+'), 706(+') f(CdH).AOG 1H (Me2SO-56, f): 9.23 (+, :S%., 1H, NH2), 9.21 (+, :S%., 1H, NH2), 7.84 (5, 2H, o-CH), 7.78(,, 1H, #-CH), 7.68 (,, 2H, 3-CH), 6.51 (+, :S%., 1H, NH), 2.46 (1, 2H, CH2), 0.84 (,, 3H, CH3).C.%+,&''H, ".%/*5)H# 5'2 G!7, 9H'% FH.&M#)H ".% 4#5'#))*4 :"&.%F&)%% .&+,F*.&1*4"'#1+& F +4#+% ^,&)*'-)%,.*4#,&) (1:1 "* *9_#4:) )& F*I5:3# ".% 1*4)&,)*J ,#4"#.&,:.#.(NO3)2HMeOHNNPtNC18H22N8O8Pt: C, 32.10; H, 3.29; N, 16.64.
-&J5#)*: C, 32.23; H,NHHNPhNH[47](NO3)2. ;H3*5 *1*'* 100%. B.&I' 173 °C. ;H0%+'#)* 5'2O3.39; N, 16.52%. Z!>-O!+ FH+*1*/* .&I.#S#)%2 (MeOH, m/z):274.574PhMeH([M d 2NO3]2+,FH0%+'#)*274.570),548.134([M d 2NO3 d H]+, FH0%+'#)* 548.132). >C (KBr, *,5#'()H#"*'*+H, +4d1): 3385(+.), 3342(+.), 3313(+.), 3171(+.-+%')b(NdH);2947(+')b(CdH);1668(+.),1632(+%')b(C=N),1384(*0 +%') b(NdO); 777(+'-c.), 689(+.) f(CdH). AOG 1H (Me2SO-56, f): 10.73 (+, :S%., 1H, NH),8.95 (+, :S%., 1H, NH2), 8.71 (+, :S%., 1H, NH2), 8.20 (5, 2H, o-CH), 7.83 (4, 1H, #-CH), 7.66 (,,2H, 3-CH), 1.24 (+, 3H, CH3).!!82!(NO3)2HPhONPtN41.51; H, 3.41; N, 13.82%. Z!>-O!+ FH+*1*/* .&I.#S#)%2O(MeOH, m/z): 336.587 ([M d 2NO3]2+, FH0%+'#)* 336.585),NHHNC28H26N8O8Pt•aH2O: C, 41.69; H, 3.37; N, 13.89.
-&J5#)*: C,NHHNPh[48](NO3)2. ;H3*5 *1*'* 100%. B.&I' 177 °C. ;H0%+'#)* 5'2672.167 ([M d 2NO3 d H]+, FH0%+'#)* 672.163). >C (KBr,Ph*,5#'()H# "*'*+H, +4d1): 3421(+.-+%'), 3366(+%'), 3186(+.-+%')Phb(NdH);H3053(+'),2960(+'),2925(+'),2854(+')b(CdH);1622(*0 +%') b(C=N); 1384(+%') b(NdO); 787(+.), 692(+.) f(CdH). AOG 1H (Me2SO-56, f): 9.37 (+,:S%., 1H, NH2), 9.35 (+, :S%., 1H, NH2), 7.99–7.97 (5 + +, :S%., 3H, o-CH + NH), 7.86–7.77 (4,2H, 2#-CH), 7.72 (,, 2H, 3-CH), 7.63–7.58 (4, 4H, o-, 3-CH).HNHONNPt[51](NO3)2.
;H3*5 *1*'* 100%. Z'#4#),)HJ &)&'%I )# 9H'FH"*')#) F +%': 5*+,&,*0)* 9H+,.*/* .&I'*Y#)%2 1*4"'#1+&.NNHEt(NO3)2HMe MeHZ!>-O!+OFH+*1*/*.&I.#S#)%2(MeOH,m/z):226.567([M d 2NO3]2+, FH0%+'#)* 226.572), 452.129 ([M d 2NO3 d H]+,NHFH0%+'#)* 452.137). >C (KBr, *,5#'()H# "*'*+H, +4d1):Et3434(+.-+%'), 3337(+.), 3170(+.) b(NdH); 2985(+'), 2920(+'), 2853(+') b(CdH); 1638(*0 +%'),1592(+.) b(C=N); 1384(*0 +%') b(NdO); 793(+'), 666(+') f(CdH). AOG 1H (Me2SO-56, f): 10.48 (+,:S%., 1H, NH), 8.88 (+, :S%., 1H, NH2), 8.65 (+, :S%., 1H, NH2), 2.81 (1, 2H, CH2), 2.24 (+, 3H,CH3), 1.23 (,, 3H, CH3).HNHONNPt[52](NO3)2. ;H3*5 *1*'* 100%.
Z'#4#),)HJ &)&'%I )# 9H'FH"*')#) F +%': 5*+,&,*0)* 9H+,.*/* .&I'*Y#)%2 1*4"'#1+&.NNHEt(NO3)2HPh PhHZ!>-O!+OFH+*1*/*.&I.#S#)%2(MeOH,m/z):288.578([M d 2NO3]2+, FH0%+'#)* 288.585), 576.151 ([M d 2NO3 d H]+,NHFH0%+'#)* 576.163). >C (KBr, *,5#'()H# "*'*+H, +4d1):Et3433(+.-+%'), 3329(+.), 3159(+.) b(NdH); 3059(+'-c.), 2990(+'), 2946(+'), b(CdH); 1653(+%'),1630(*0 +%') b(C=N); 1384(*0 +%') b(NdO); 774(+.), 698 (+.) f(CdH).
AOG 1H (Me2SO-56, f):10.50 (+, :S%., 1H, NH), 8.45 (+, :S%., 1H, NH2), 8.43 (+, :S%., 1H, NH2), 7.67 (5, 2H, o-CH),7.58–7.47 (4, 3H, 3- % #-CH), 2.84 (1, 2H, CH2), 1.29 (,, 3H, CH3).HNHOPh(NO3)2HMe MeC18H22N8O8Pt•2H2O: C, 34.38; H, 4.85; N, 14.58. -&J5#)*: C,NNNPtNHNH[53](NO3)2. ;H3*5 *1*'* 100%. B.&I' 139 °C. ;H0%+'#)* 5'2HO34.37; H, 4.95; N, 14.50%. Z!>-O!+ FH+*1*/* .&I.#S#)%2(MeOH, m/z): 274.569 ([M d 2NO3]2+, FH0%+'#)* 274.570),Ph548.142 ([M d 2NO3 d H]+, FH0%+'#)* 548.132). >C (KBr,*,5#'()H# "*'*+H, +4d1): 3443(+.-+%'), 3328(+.-+%'), 3149(+.) b(NdH); 2922(+'), 2849(+')b(CdH); 1654(+.), 1623(+%') b(C=N); 1384(*0 +%') b(NdO); 780(+'-c.), 687(+.) f(CdH). AOG 1H!83!!(Me2SO-56, f): 11.05 (+, :S%., 1H, NH), 9.04 (+, :S%., 1H, NH2), 8.72 (+, :S%., 1H, NH2), 8.22 (5,2H, o-CH), 7.86 (,, 1H, #-CH), 7.70 (,, 2H, 3-CH), 2.37 (+, 3H, CH3).HNHOPh(NO3)2HPh PhC28H26N8O8Pt•3!H2O: C, 39.28; H, 3.83; N, 13.09.
-&J5#)*: C,NNNPtNHHONH[54](NO3)2. ;H3*5 *1*'* 100%. B.&I' 156 °C. ;H0%+'#)* 5'239.10; H, 3.54; N, 13.22%. Z!>-O!+ FH+*1*/* .&I.#S#)%2(MeOH, m/z): 336.578 ([M d 2NO3]2+, FH0%+'#)* 336.585),Ph672.158 ([M d 2NO3 d H]+, FH0%+'#)* 672.163). >C (KBr,*,5#'()H# "*'*+H, +4d1): 3429(+.-+%'), 3316(+.-+%'), 3134(+.) b(NdH); 2935(+'), 2854(+')b(CdH); 1654(+.), 1626(+%') b(C=N); 1384(*0 +%') b(NdO); 774(+'-c.), 693(+.) f(CdH). AOG 1H(Me2SO-56, f): 11.23 (+, :S%., 1H, NH), 8.64 (+, :S%., 1H, NH2), 8.62 (+, :S%., 1H, NH2), 8.26 (5,2H, o-CH), 7.87 (,, 1H, #-CH), 7.78–7.68 (4, 5H, CH), 7.57 (,, 2H, 3-CH). C.%+,&''H, ".%/*5)H#5'2 G!7, 9H'% FH.&M#)H ".% 4#5'#))*4 :"&.%F&)%% .&+,F*.& 1*4"'#1+& F +4#+% ^,&)*')%,.*4#,&) (1:1 "* *9_#4:) )& F*I5:3# ".% 1*4)&,)*J ,#4"#.&,:.#.5.4.3 $7A9;7@98D79 788H9GEF<A7> 8E@9;<A7> ED87PEF PhC(R)=NOH (R = Me, NH2) 8DEPQH9D8EP %&"'!-[PtCl2(EtCN)2] (26).C .&+,F*.: 1*4"'#1+& 26 (10.0 4/, 22.4 414*'() F 200 41' !DCl3 ".% 1*4)&,)*J,#4"#.&,:.# 5*9&F'2'% F 1&0#+,F# +,&)5&.,& )%,.*4#,&) 5 41' % I&,#4 .&+,F*.
*1+%4& (R = Me,3.2 4/, 24.0 414*'(; R = NH2 3.4 4/, 25.1 414*'() F 360 41' !DCl3. !4#+( "#.#4#S&'% % 9H+,.*"#.#)#+'% F &4":': 5'2 AOG. 74":': +.&I: Y# "#.#)#+'% F +"#1,.*4#,. AOG. B#4"#.&,:.&.#&1$%*))*J +4#+% "*55#.Y%F&'&+( .&F)*J 23.0 ºC. G&+0U, 1*)+,&), +1*.*+,#J .#&1$%%FH"*')2'% "* K*.4:'#k=ot(c oximeoc complexc oxime1ln( o)o" c complex ) c oximec complex/5#t – F.#42, ".*S#5S## "*+'# )&0&'& .#&1$%%;!+* – )&0&'()H# 1*)$#),.&$%% .#&/#),*F;+ – 1*)$#),.&$%% .#&/#),*F F 4*4#), F.#4#)% t.G&+0U, 5*F#.%,#'()H3 %),#.F&'*F ".*F*5%'% 4#,*5*4 )&%4#)(S%3 1F&5.&,*F "* 11 (R =Me) % 14 ,*01&4 (R = NH2). 8*1&I&,#'()H4% 2F'2T,+2 5&))H# "* F.#4#)% *, )&0&'& .#&1$%% 5*50%-)*J 1*)F#.+%% 1*4"'#1+&: ~4 4%) F .#&1$%% + 9#)I&4%5*1+%4*4 % ~130 4%) F .#&1$%% +&$#,*K#)*)*1+%4*4.!!84!5.5 aD8Q9:7P9A;<HIA<> @<8;I D SH<F9 45.5.1 !7A;9R O9H<;ABO PEAE-#-7P7AE<=7H<P7GED87PABO DEPQH9D8EF QH<;7AB(II) 68–74(EZV<> P9;EG7D<)8*.*S*1 &4%5*1+%4& (65–67) (100 414*'() 5*9&F'2'% 1 "#.#4#S%F*4: .&+,F*.:1*4"'#1+& 30 %'% 63 (100 414*'() F 3'*.*K*.4# (2 4').
E#.#I 10 4%) .&+,F*.%,#'( :"&.%F&'%".% "*)%Y#))*4 5&F'#)%% 5* *9_U4& 0.5 4'. ?9.&I*F&'%+( 4&+'2)%+,H# *+,&,1%, 1*,*.H# 9H'%I&1.%+,&''%I*F&)H "*5 F*I5#J+,F%#4 PD. !F#,'*-YU',H# "*.*S1% *,K%'(,.*F&'%, ".*4H'%Et2O (2 "*.$%% "* 1 4') % +:S%'% F ,#0#)%# 12 0 ".% 1*4)&,)*J ,#4"#.&,:.# )& F*I5:3#.HNClPtNMe2NNClNMe2[68](Cl). ;H3*5 89%. ;H0%+'#)* 5'2 C14H22N6OCl2Pt•2H2O:C, 28.39; H, 4.42; N, 14.19.
-&J5#)*: C, 28.43; H, 4.48; N,14.14%. Z!>-O!+ FH+*1*/* .&I.#S#)%2 (MeOH, m/z):O451.069 ([M – NCNMe2 – Cl]+, FH0%+'#)* 451.061), 521.120([M – Cl]+, FH0%+'#)* 521.114). >C (KBr, *,5#'()H#H2N"*'*+H, +4–1): 3419(+%'), 3363(+%') b(N–H); 3030(*0 +'),Me2984(*0 +'), 2952(*0 +') b(C–H); 2305 (+.) b(C!N); 1660(+.-+%'), 1620(+.-+%') b(C=N). AOG 1H (Me2SO-56, f): 8.84 (+, :S%., 1H, NH2), 8.55 (+, :S%., 1H,NH2), 7.65 (+, :S%., 1H, NH), 7.43 (5, 2H, CH), 7.30 (5, 2H, CH), 3.10 (+, 6H, N(CH3)2), 2.71 (+, 6H,N(CH3)2), 2.35 (+, 3H, CH3).HNClPtNMe2NNClNMe2[69](Cl).
;H3*5 87%. ;H0%+'#)* 5'2 C13H19N7OCl2Pt•2H2O:C, 27.87; H, 3.84; N, 16.25. -&J5#)*: C, 27.91; H, 3.83; N,16.28%. Z!>-O!+ FH+*1*/* .&I.#S#)%2 (MeOH, m/z):O462.044 ([M – NCNMe2 – Cl]+, FH0%+'#)* 462.040), 532.095H2N([M – Cl]+, FH0%+'#)* 532.093). >C (KBr, *,5#'()H#CN"*'*+H, +4–1): 3424(+%'), 3360(+%') b(N–H); 3033(*0 +'),2988(*0 +'), 2952(*0 +') b(C–H); 2305(+.) % 2247(+%') b(C!N); 1666(+.-+%'), 1624(+.-+%') b(C=N).AOG 1H (Me2SO-56, f): 8.88 (+, :S%., 1H, NH2), 8.57 (+, :S%., 1H, NH2), 7.88 (+, :S%., 1H, NH),7.82 (5, 2H, CH), 7.59 (5, 2H, CH), 3.15 (+, 6H, N(CH3)2), 2.76 (+, 6H, N(CH3)2).!!85!HNClNMe2PtNMe2NCl;H3*582%.;H0%+'#)*5'2C13H19N7O3Cl2Pt•2H2O: C, 25.05; H, 3.72; N, 17.73. -&J5#)*:C, 25.00; H, 3.76; N, 17.79%.
Z!>-O!+ FH+*1*/*ON[70](Cl)..&I.#S#)%2 (MeOH, m/z): 482.037 ([M – NCNMe2 – Cl]+,FH0%+'#)* 482.030), 552.086 ([M – Cl]+, FH0%+'#)* 552.083).H2N>C (KBr, *,5#'()H# "*'*+H, +4–1): 3421(+%'), 3360(+%')NO2b(N–H); 3030(*0 +'), 2986(*0 +'), 2952(*0 +') b(C–H); 2305(+.) b(C!N); 1666(+.-+%'), 1622(+.-+%') b(C=N); 1520(+%') b(N=O)a+; 1342(+%') b(N=O)c. AOG 1H(Me2SO-56, f): 8.90 (+, :S%., 1H, NH2), 8.59 (+, :S%., 1H, NH2), 7.93 (+, :S%., 1H, NH), 7.82 (5,2H, CH), 7.55 (5, 2H, CH), 3.15 (+, 6H, N(CH3)2), 2.77 (+, 6H, N(CH3)2).HNClPtNC5H10NNClNC5H10[71](Cl).;H3*584%.;H0%+'#)*5'2C20H30N6OCl2Pt•2H2O: C, 35.72; H, 5.10; N, 12.50.-&J5#)*: C, 35.81; H, 5.12; 12.53%. Z!>-O!+ FH+*1*/*O.&I.#S#)%2 (MeOH, m/z): 491.098 ([M – NCNC5H10 – Cl]+,FH0%+'#)*H2N491.092),601.181([M – Cl]+,FH0%+'#)*601.176).