Imidazolium amino acids
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 6, June, 2010
1279
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the H NMR data, the product de is > 99%. Yield 1.1 g (86%),
(m, 1 H, CH2(β)); 5.51 (d, 1 H, NCH2, 2J = 15.0 Hz); 6.46
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m.p. 191—193 °C; [α]D +1888 (c 0.1, MeOH). Found (%):
(s, 1 H, CHimid); 6.66 (m, 2 H, Ar); 6.87 (s, 2 H, Ar); 7.16
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C, 59.57; H, 4.62; N, 8.15. C42H38BrN5NiO3•0.7CH2Cl3. Calꢀ
culated (%): C, 59.72; H, 4.62; N, 8.15. 1H NMR (300 MHz,
CDCl3), δ: 2.16 (m, 2 H, H(δ); Pro, H(γ), Pro); 2.42 (m, 1 H,
H(β), Pro); 2.70 (m, 1 H, H(β), Pro); 3.45 (m, 2 H, H(δ), Pro,
(m, 2 H, Ar); 7.24 (m, 1 H, Ar); 7.33 (t, 2 H, Ar, J = 8.4 Hz);
7.45 (m, 1 H, Ar); 7.53 (m, 2 H, Ar); 7.66 (m, 1 H, Ar); 7.73
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(m, 2 H, Ar); 8.02 (d, 2 H, Ar, J = 7.2 Hz); 8.22 (d, 1 H, Ar,
3J = 8.4 Hz); 10.21 (s, 1 H, NCHN). 13C NMR (125 MHz,
CDCl3), δ: 19.71; 21.06; 24.22; 30.79; 47.88; 51.35; 57.80; 63.44;
68.13; 70.37; 70.42; 120.66; 120.90; 121.30; 123.83; 124.00;
125.14; 126.63; 128.33; 128.91; 129.02; 129.33; 129.93; 130.21;
130.30; 131.51; 133.36; 133.40; 133.46; 133.72; 138.18; 139.02;
139.92; 143.33; 173.58; 176.37; 180.86.
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H(γ), Pro); 3.49 (d, 1 H, CH2Ph, J = 12.3 Hz); 3.81 (m, 1 H,
H(α), Pro); 4.30 (m, 1 H, CH(α)); 4.35 (d, 1 H, CH2Ph,
3J = 12.3 Hz); 4.51 (dd, 1 H, CH2(β), 2J = 14.1 Hz, 3J = 4.8 Hz);
5.50 (d, 1 H, NCH2, 2J = 15.3 Hz); 5.77 (dd, 1 H, NCH2,
2J = 15.3 Hz); 5.87 (d, 1 H, Ar, 2J = 8.5 Hz); 6.13 (dd, 1 H,
CH2N, 2J = 14.1 Hz, 3J = 4.8 Hz); 6.56 (d, 1 H, Ar, 3J = 6.9 Hz);
6.66 (t, 1 H, Ar, 3J = 6.9 Hz); 7.1—7.5 (m, 14 H, Ar); 7.7
[(S)ꢀ2ꢀ({2ꢀ[(2S,1RN)ꢀ1ꢀBenzylpyrrolidineꢀ2ꢀcarboxamido]ꢀ
phenyl}(phenyl)methylideneamino)ꢀ3ꢀ[3ꢀ(2,4,6ꢀtrimethylbenzꢀ
yl)benzimidazolꢀ3ꢀuimꢀ1ꢀyl]propionatoꢀN,N´,N″,O]nickel(II)
chloride (12) was prepared from complex 4 (0.63 g, 1 mmol) and
2,4,6ꢀtrimethylbenzyl chloride (0.25 g, 1.5 mmol) in MeCN
(3 mL) as described above for compound 11. According to the
1H NMR data, the product de is > 99%. Yield 0.55 g (69%), m.p.
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(m, 3 H, Ar); 8.07 (d, 2 H, Ar, J = 7.2 Hz); 8.20 (d, 1 H, Ar,
3J = 8.7 Hz); 10.94 (s, 1 H, NCHN). 13C NMR (75 MHz,
CDCl3), δ: 24.88; 31.17; 48.35; 51.88; 58.76; 63.70; 66.61; 70.79;
112.04; 114.00; 120.82; 124.07; 125.50; 126.83; 126.98; 127.74;
127.97; 128.66; 128.91; 128.95; 129.20; 129.40; 129.79; 130.16;
130.29; 130.67; 131.22; 131.55; 132.04; 133.33; 133.52; 133.55;
133.71; 143.52; 144.50; 172.84; 175.78; 180.94.
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155 °C; [α]D –1628 (c 0.05, MeOH). Found (%): C, 62.01;
H, 5.15; N, 7.49. C45H44ClN5NiO3•3/4CHCl3. Calculated (%):
C, 61.98; H, 5.09; N, 7.61. 1H NMR (300 MHz, CDCl3), δ: 2.14
(m, 2 H, H(δ), Pro, H(γ), Pro); 2.27 (s, 3 H, CH3); 2.29 (s, 6 H,
CH3); 2.42 (m, 1 H, H(β), Pro); 2.74 (m, 1 H, H(β), Pro); 3.44
(m, 2 H, H(α), Pro, H(γ), Pro); 3.46 (d, 1 H, CH2Ph, 2J = 12.6 Hz);
3.98 (m, 1 H, CH(α)); 4.26 and 4.42 (both AB part of ABX
[(S)ꢀ2ꢀ({2ꢀ[(2S,1RN)ꢀ1ꢀBenzylpyrrolidineꢀ2ꢀcarboxamido]ꢀ
phenyl}(phenyl)methylideneamino)ꢀ3ꢀ(3ꢀbenzhydrylbenzimidazolꢀ
3ꢀiumꢀ1ꢀyl)propionatoꢀN,N´,N″,O]nickel(II) bromide (10). To
a solution of complex 4 (0.63 g, 1 mmol) in MeCN (3 mL),
benzhydryl bromide (0.3 g, 1.2 mmol) was added and the reacꢀ
tion mixture was refluxed for 4 h under argon. The reaction
mixture was cooled to room temperature and the precipitate that
formed was filtered off, washed with diethyl ether, and dried
on the filter. According to the 1H NMR data, the product de
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system, 1 H, CH2(β), J = 4.5 Hz, J = 10.8 Hz); 4.35 (d, 1 H,
CH2Ph, 3J = 12.6 Hz); 5.68 (AB system, 2 H, NCH2, 2J = 14.7 Hz);
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5.80 (d, 1 H, NCH2, J = 8.1 Hz); 6.25 (m, 1 H, CH(α)); 6.55
(d, 1 H, Ar, 3J = 6.9 Hz); 6.63 (t, 1 H, Ar, 2J = 6.9 Hz); 6.90
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is > 99%. Yield 0.6 g (69%), m.p. 205—208 °C; [α]D +2156
(s, 2 H, Ar); 6.95 (d, 1 H, Ar, J = 11.4 Hz); 7.18 (m, 3 H, Ar);
(c 0.05, MeOH—CHCl3 (1 : 1)). Found (%): C, 65.69; H, 4.77;
7.39 (m, 5 H, Ar); 7.69 (m, 3 H, Ar); 8.06 (d, 2 H, Ar, 3J = 7.5 Hz);
8.20 (d, 1 H, Ar, 3J = 11.7 Hz), 10.79 (s, 1 H, NCHN). 13C NMR
(125 MHz, CDCl3), δ: 20.25; 21.17; 24.65; 31.19; 47.84; 48.40;
58.70; 63.59; 66.67; 70.70; 112.02; 113.89; 120.78; 124.10;
124.56; 125.48; 126.52; 126.87; 126.91; 127.73; 128.80; 128.91;
128.95; 129.71; 130.08; 130.21; 130.23; 131.09; 131.38; 131.59;
133.26; 133.49; 133.54; 133.78; 137.89; 138.46; 139.82; 143.47;
172.72; 175.83; 180.97.
N, 8.17. C48H42BrN5NiO3. Calculated (%): C, 65.85; H, 4.84;
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N, 8.00. H NMR (300 MHz, CDCl3—CD3OD (1 : 1)), δ: 1.91
(m, 1 H, H(δ), Pro); 2.00 (m, 1 H, H(γ), Pro); 2.09 (m, 1 H,
H(γ), Pro); 2.46 (m, 2 H, H(β), Pro); 2.98 (m, 1 H, H(δ),
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Pro); 3.43 (d, 1 H, CH2Ph, J = 12.3 Hz); 3.45 (m, 1 H, H(α),
Pro); 4.20 (d, 1 H, CH2Ph, 3J = 12.3 Hz); 4.57 (dd, 1 H,
CH2(β), 2J = 15.2 Hz, 3J = 4.8 Hz); 5.29 (m, 1 H, CH(α)); 6.07
(m, 1 H, CH2N); 6.56 (m, 1 H, Ar); 6.71 (t, 1 H, Ar, 3J =
= 7.2 Hz); 7.1—7.5 (m, 20 H, Ar); 7.7 (m, 3 H, Ar); 8.01
[(S)ꢀ2ꢀ({2ꢀ[(2S,1RN)ꢀ1ꢀBenzylpyrrolidineꢀ2ꢀcarboxamido]ꢀ
phenyl}(phenyl)methylideneamino)ꢀ3ꢀ(3ꢀbenzylꢀ4,5ꢀdiphenylimidꢀ
azolꢀ3ꢀuimꢀ1ꢀyl)propionatoꢀN,N´,N″,O]nickel(II) bromide (13).
To a solution of complex 5 (1.2 g, 1.6 mmol) in CH2Cl2 (2 mL),
benzyl bromide (0.51 g, 0.35 mL, 3 mmol) was added and the
reaction mixture was stirred for 5 days at room temperature. The
solvent was removed in vacuo, the product was purified by colꢀ
umn chromatography (HWꢀ55 resin, elution with CHCl3—aceꢀ
tone (3 : 2)). According to the 1H NMR data, the product de
3
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(d, 1 H, Ar, J = 8.7 Hz); 8.13 (d, 2 H, Ar, J = 7.2 Hz); 8.93
(s, 1 H, NCHN).
[(S)ꢀ2ꢀ({2ꢀ[(2S,1RN)ꢀ1ꢀBenzylpyrrolidineꢀ2ꢀcarboxamido]ꢀ
phenyl}(phenyl)methylideneamino)ꢀ3ꢀ[3ꢀ(2,4,6ꢀtrimethylbenzꢀ
yl)imidazolꢀ3ꢀiumꢀ1ꢀyl]propionatoꢀN,N´,N″,O]nickel(II) chloride
(11). To a solution of complex 3 (0.95 g, 1.64 mmol) in MeCN
(5 mL), 2,4,6ꢀtrimethylbenzyl chloride (0.415 g, 2.46 mmol)
was added. The reaction mixture was stirred at 40—50 °C for
24 h. The solvent was removed in vacuo, the product was puriꢀ
fied by column chromatography (HWꢀ55 resin, elution with
CDCl3—acetone (3 : 2)). According to the 1H NMR data, the
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is > 99%. Yield 0.9 g (62%), m.p. 191—193 °C; [α]D +1988
(c 0.1, MeOH). Found (%): C, 63.57; H, 4.62; N, 7.15.
C50H44BrN5NiO3•0.7CH2Cl2. Calculated (%): C, 63.37; H,
4.76; N, 7.29. 1H NMR (300 MHz, CDCl3), δ: 1.79 (m, 1 H,
H(δ), Pro); 2.01 (m, 1 H, H(γ), Pro); 2.40 (m, 1 H, H(β), Pro);
2.63 (m, 2 H, H(δ), Pro, H(γ), Pro); 3.05 (m, 1 H, H(β), Pro);
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product de is > 99%. Yield 1.05 g (86%), m.p. 145 °C; [α]D
+2056 (c 0.05, MeOH). Found (%): C, 61.37; H, 5.31; N, 8.34.
C41H42ClN5NiO3•0.6CHCl3. Calculated (%): C, 61.04; H, 5.25;
N, 8.56. 1H NMR (600 MHz, CDCl3), δ: 2.08 (m, 2 H, H(δ),
Pro, H(γ), Pro); 2.18 (s, 6 H, CH3); 2,21(s, 3 H, CH3); 2.40
(m, 1 H, H(β), Pro); 2.62 (m, 1 H, H(β), Pro); 3.41 (dd, 1 H,
H(α), Pro, 3J1 = 6.0 Hz, 3J2 = 10.5 Hz); 3.48 (m, 1 H, H(γ),
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3.33 (m, 1 H, H(α), Pro); 3.42 (d, 1 H, CH2Ph, J = 12.6 Hz);
3.91 (m, 1 H, CH(α)); 4.25 (d, 1 H, CH2Ph, 2J = 12.6 Hz); 4.43
(dd, 1 H, CH2(β), 2J = 14.4 Hz, 3J = 6.0 Hz); 4.94 (dd, 1 H,
CH2(β), 2J = 14.4 Hz, 3J = 6.0 Hz); 5.17 (d, 1 H, CH2Ph,
2J = 14.7 Hz); 5.35 (d, 1 H, CH2Ph, 2J = 14.7 Hz); 6.42 (d, 1 H,
Ar, 3J = 8.1 Hz); 6.56 (t, 1 H, Ar, 3J = 7.5 Hz); 7.0—7.5 (m,
24 H, Ar); 8.02 (d, 2 H, Ar, 3J = 7.5 Hz); 8.18 (d, 1 H, Ar,
3J = 8.7 Hz); 8.95 (s, 1 H, NCHN).
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Pro); 3.50 (d, 1 H, CH2Ph, J = 12.6 Hz); 3.60 (m, 1 H, H(δ),
Pro); 3.98 (m, 1 H, CH(α)); 4.17 (m, 1 H, CH2(β)); 4.32 (d, 1 H,
CH2Ph, 3J = 12.6 Hz); 5.40 (d, 1 H, NCH2, 2J = 15.0 Hz); 5.50