First International Electronic Conference on Synthetic Organic Chemistry (ECSOC-1), www.mdpi.org/ecsoc/, September 1-30, 1997
[A0028]

Regioselectivity of Arylation of 2,3'-Biquinolyl Dianion

A.V. Aksenov,*a I.V. Aksenova,a I.V. Borodaev,a and Yu. I. Smushkevichb

a Stavropol State University, Chair of Organic Chemistry, Stavropol 355009, Russia

b Russian Mendeleev University of Chemical Technology, Chair of Organic Chemistry,
9 Miusskaya sq., 125047 Moscow, Russia. E-mail: sirovsk@cacr.ioc.ac.ru

Received: 30 July 1997 / Uploaded: 30 July 1997

Abstract: Dianion of 2,3'-biquinolyl with aryl- and hetaryl halides forms product of arylation to 4'-position, which on treatment with alkyl halides or water yield 1'-alkyl-1',4'dihydro-2,3'-biquinolyls or 4'-aryl-1',4'-dihydro-2,3'-biquinolyls respectively. The oxydation of the latter leads to 4'-aryl-2,3'-biquinolyls. The cation dependence of the arylation is shown.

Keywords: Regioselectivity, arylation, 2,3'-biquinolyl dianion.

Recently we have developed the procedure for the generation of 2,3'-biquinolyl dianion (I) that allows to study its properties. The present work is devoted to its arylation and heteroarylation.

The studied reactions of such species with aryl halides include, as a rule, the transfer of electrones from the dianione (anione-radical) to halogenated derivative 2-4. Thus the dianione of diphenyl reacts with halobenzenes yielding benzoic acid after the treatment of the reaction mixture with carbon dioxide 2. We have supposed that the dianione I would also behave as an electron donor respective to aryl halides. However, we have supposed that due to bigger affinity of I to electrones comparing with that of diphenyl there can be one-electron transfer leading to the anion-radical (II). According to quantum chemical calculations the maximum spin density in II is at the 4'-position (see fig 1.).

Figure 1. The distribution of the spin density in anion-radical II (MNDO calculations).

In this case, the aryl radycal formed after the elimination of the halide ion would react with the anion radical (II) yielding the anion (III) (see Scheme 1).

Scheme 1. III a: Ar= Ph; b Ar= 1-C10H7; c Ar= 2-C5H4N; d Ar= 1-methyl-2-benzimidazolyl; e Ar= 1-isopropyl-2- benzimidazolyl; ArX= PhBr, 1-bromonaphthalene, 2-fluoropyridine, 1-methyl-2-chlorobenzimidazole, 1-iso-propyl-2-chlorobenzimidazole.

Indeed, the continuous addition of aryl or hetaryl halides to dianione I obtained in the reaction of 2,3'-biquinolyl with metallic lithium in THF1 with the subsequent treatrment of the resulting mixture with water yielded 4'-aryl(hetaryl)-1',4'-dihydro-2,3'-biquinolyls (IV a-e) with yields ranging from 64 to 78%. The treatment of the reaction mixture with alkyl halides instead of water results in formation of N-alkylation products, i.e. 1'-alkyl-4'aryl(hetaryl)-1',4'-dihydro-2,3'-biquinolyls (IV f-h) with yields being in the range 72-75% (Scheme 2).

The same results were obtained when dianion I was generated using metallic potassium or potassium naphthalide, although their use is less convenient than that of lithium. Our investigzations showed that the metal cation plays an important role in the electron transfer. Thus, 2,3'-biquinolyl does not react with potassium naphthalide in absolute THF in the presence of 1.2 molar excess of 18-crown-6 (on potassium) even during long stirring. The reaction begins on addition of dry potassium iodide.

Scheme 2: IV a Ar = Ph, R =H; b = Ar=1-C10H7, R=H; c Ar= 2-C5H4N, R=H; d Ar = 1-methyl-2-benzimidazolyl, R=H; e Ar = 1-isopropyl-2-benzimidazolyl, R = H; f Ar= Ph, R= Me; g Ar=1-C10H7, R=Me; h Ar=1-C10H7, R=CH2Ph; RX= MeI, PhCH2Cl.

The same results were obtained in the arylation reaction. Thus, dianion I obtained from 1.25 mmol 2,3'-biquinolyl and 2.7 mmol potassium does not react with bromobenzene in the presence of 3 mmol 18-crown-6 even after two hours reflux. On addition of 1.5 mmol KI the reaction proceeds in a usual way and results in formation of IVa.

Compounds IV a-e are readily oxidised by iodine in pyridine to 4'-aryl-2,3'-biquinolyls (V a-e) with nearly quantitative yield (Scheme 3).

Scheme 3: V a Ar= Ph; b Ar=1-C10H7; c Ar= 2-C5H4N; d Ar = 1-methyl-2-benzimidazolyl; e Ar = 1-iso-propyl-2-benzimidazolyl.

The structure of these compounds was confirmed by 1H NMR spectra. The characteristic feature of V a-e spectra is the movement of 3-H signal to the strong field region: Va 6.97 ppm, Vb 6.83, Vc 7.08, Vd 7.32, Ve 7.43 compared with 8.04 in case of 2,3'-biquinolyl. In our opinion it is explained by the perpendicular position of the aryl substituent shielding the proton in the 3 position.

It is worth noting that protons of two methyl groups in IVe and Ve are not equivalent (IVe 1.73 (1H, d.), 1.85 (1H, d.); Ve 0.75 (1H, d.), 1.24 (1H d.) as these groups are diastereotopic. However if IVe posess an asymmetric carbon atom in the 4' position, there is no such atom in Ve. Nevertheless, Ve also has an asymmetric cener due to the inhibited rotation about C4-C2 bond of the imidazolic ring owing to the presence of bulky substituents in both quinolyl and benzimidazole fragments.

The direction of arylation was confirmed by experiments with 4'-D-2,3'biquinolyl. In the 1H NMR spectra of IV a-e we have observed the lowering of 4-H signal intensity corresponding to deuterium content in starting biquinolyl. There is no "label" in V a-e.

Experimental section

Mass-spectra were registered on Varian MAT 331a mass-spectrometer, NMR spectra at Bruker WP-200 NMR spectrometer. The reactions were monitored by TLC on Silufol UV-254 plates, eluent ethyl acetate - hexane 2:1. THF was purified by distillation over LiAlH4 and ketine radical, and 2,3'-biquinolyl was recrystallised from benzene and sublimed.

4'-phenyl-1',4'-dihydro-2,3'-biquinolyl (IVa, C24H18N2): The solution of 0.64 g (2.5 mmol) of 2,3'-biquinolyl and 0.05 g (7 mmol) of powdered lithium in 10 mL of THF is stirred for 3 h at ambient temperature under Ar blanket. After that the solution of 0.71 g (4.5 mmol) bromobenzene in 4 mL THFis added dropwise. The reaction mixture is stirred for 1 hour at ambient temperature and refluxed for 1 h. After that 40 mL of water is added and reaction mixture is extracted with benzene (3 [lozenge] 30 mL). The organic solution is evaporated and resulting yellow oil is crystallized on benzene addition. Yield 0.65 g (78%), m.p. 212-213 deg.C (bnz.). 1H NMR spectrum (CDCl3): 5.73 (1H, s, 4'-H); 6.36 (1H, d, JNH-2'H= 5.5 Hz, NH); 6.70 (1H, d, J7'8' = 8.10 Hz, 8'-H); 6.88 (1H, d. d, J5'6' =7.64, J6'7'= 7.82 Hz, 6'-H); 7.04 (1H, d. d, J6'7' = 7.82, J7'8' =8.12 Hz, 7'-H); 7.2 (3H, m, 3''-H, 4''-H, 5''-H); 7.23 (1H, d, J5'6' =7.64 Hz, 5'-H); 7.34 (1H, d. d, J56 = 8.02, J67 = 7.51 Hz, 6-H); 7.38 (1H, d, J34 = 8.91 Hz, 3-H); 7.46 (2H, d, J= 7,1 Hz, 2''-H, 6''-H); 7.61 (1H, d. d, J67=7.51, J78 =8.61 Hz, 7-H); 7.62 (1H, d, J56 = 8.02 Hz, 5-H); 7.77 (1H, d, JNH-2'H=5.5 Hz, 2'-H); 7.86 (1H, d, J34 = 8.91 Hz, 4-H); 7.98 (1H, d, J78 =8.61 Hz, 8-H); determined, % C 86.28; H 5.29; N 8.43. C24H18N2, calculated, % C 86.19; H 5.43; N 8.38.

4'-(1-naphthyl)-1',4'-dihydro-2,3'-biquinolyl (IVb C28H20N2): Obtained just as above out of 0.64 g (2.5 mmol) 2,3'-biquinolyl, 0.05 g (7 mmol) Li and 0.72 g (3.5 mmol) 1-bromonaphthalene. Yield 0.7 g (73%), m.p. 196-197 deg.C (bnz). 1H NMR spectrum (CDCl3): 6.38 (1H, d, JNH-2'H= 5.7 Hz, NH); 6.64 (1H, s, 4'-H); 6.72 (1H, d. d, J5'6' =7.72, J6'7'= 7.92 Hz, 6'-H); 6.74 (1H, d, J7'8' = 8.06 Hz, 8'-H); 7.01 (1H, d. d, J6'7' = 7.92, J7'8' =8.06 Hz, 7'-H); 7.23 (1H, d, J5'6' =7.72 Hz, 5'-H); 7.27-7.33 (3H, m, 6'-H, 3''-H, 6''-H); 7.49 (1H, d, J34 = 8.83 Hz, 3-H); 7.51-7.8 (7H, m, arom.); 7.81 (1H, d, J34 = 8.83 Hz, 4-H); 7.86 (1H, d, JNH-2'H=5.7 Hz, 2'-H); 9.01 (1H, d, J = 8.54, 8''-H or 8-H); determined, % C 87.71; H 5.12; N 7.17. C28H20N2. Calculated, % C 87.46; H 5.25; N 7.29.

4'-(2-pyridyl)-1',4'-dihydro-2,3'-biquinolyl (IVc, C23H17N3): Just as IVa out of 0.64 g (2.5 mmol) 2,3'-biquinolyl, 0.05 g (7 mmol) Li and 0.34 g (3.5 mmol) 2-fluoropyridine. Yield 0.56 g (67%), m.p. 219-220deg. C (bnz). 1H NMR spectrum (CDCl3): 5.88 (1H, s, 4'-H); 6.60 (1H, d, JNH-2'H= 5.3 Hz, NH); 6.72 (1H, d, J7'8' = 7.94 Hz, 8'-H); 6.88 (1H, d. d, J5'6' =7.68, J6'7'= 7.79 Hz, 6'-H); 6.98 (1H, m, 5''-H); 7.07 (1H, d. d, J6'7' = 7.79, J7'8' =7.94 Hz, 7'-H); 7.34 (1H, d, J5'6' =7.68 1.63 Hz, 5'-H); 7.38 (1H, d. d., J56 = 7.98, J67 = 7.62 Hz, 6-H); 7.46 (1H, d, J34 = 8.96 Hz, 3-H); 7.5 (2H, m, 3''-H, 4''-H); 7.57 (1H, d. d., J67=7.62, J78 =8.46 Hz, 7-H); 7.62 (1H, d, J56 = 7.98 Hz, 5-H); 7.88 (1H, d, J34 = 8.96 Hz, 4-H); 7.90 (1H, d, J78 =8.46, J68 = 1.1 Hz, 8-H); 7.92 (1H, d, JNH-2'H=5.3 Hz, 2'-H); 8.51 (1H, d. d., J5''6'' = 4.7, J4''6'' = 1.7 Hz, 6''-H); determined, % C 82.64; H 4.98; N 12.38. C23H17N3. Calculated, % C 82.36; H 5.11; N 12.53.

4'-(1-methyl-2-benzimidazolyl)-1',4'-dihydro-2,3'-biquinolyl (IVd, C26H20N4):Just as IVa out of 0.64 g (2.5 mmol) 2,3'biquinolyl, 0.05 g (7 mmol) Li and 0.58 g (3.5 mmol) 1-methyl-2-chlorobenzimidazole. Yield 0.66 g (68%), m.p. 266-267 deg.C (bnz). 1H NMR spectrum (CDCl3): 4.44 (3H, s, Me); 6.36 (1H, s, 4'-H); 6.70 (1H, d, J7'8' = 8.05 Hz, 8'-H); 6.81 (1H, d. d., J5'6' =7.68, J6'7' = 7.34 Hz, 6'-H); 6.92 (1H, d. d., J6'7' = 7.34, J7'8' =8.05, 7'-H); 7.09 (1H, d, J5'6' =7.68 Hz, 5'-H); 7.13 (1H, d. t., J4''5'' = 8.55, J5''6'' = 7.38, J5''7'' = 1.63 Hz, 5''-H); 7.21 (1H, d. t., J5''6'' = 7.38, J6''7'' = 7.67, J4''6'' = 2.35 Hz, 6''-H); 7.29 (1H, d. d., J56 = 8.04, J67 = 7.31 Hz, 6-H); 7.38 (1H, d. d., J6''7'' =7.67, J5''7'' = 1.63 Hz, 7''-H); 7.41 (1H, d, JNH-2'H=5.49 Hz, 2'-H); 7.43 (1H, d, J34 = 9.14 Hz, 3-H); 7.53 (1H, d. d., J67=7.31, J78 =8.04 Hz, 7-H); 7.59 (1H, d. d., J4''5'' =8.55, J4''6'' = 2.35 Hz, 4''-H); 7.6 (1H, d., J56 = 8.04 Hz, 5-H); 7.78 (1H, d, J78 =8.04 Hz, 8-H); 7.80 (1H, d, J34 = 9.14 Hz, 4-H); 10.39 (1H, d, JNH-2'H= 5.49 Hz, NH); determined, % C 80.63, H 5.11, N 14.26, C26H20N4. Calculated C 80.39, H 5.19, N 14.42.

4'-(1-iso-propyl-2-benzimidazolyl)-1',4'-dihydro-2,3'-biquinolyl (IVe, C28H24N4): Just as IVa out of 0.64 g (2.5 mmol) 2,3'biquinolyl, 0.05 g (7 mmol) Li and 0.68 g (3.5 mmol) 1-iso-propyl-2-chlorobenzimidazol. Yield 0.67 g (64 %), m.p. 206-208deg. C (bnz). ). 1H NMR spectrum (CDCl3): 1.73 (3H, d., J= 6.95, Me); 1.85 (3H, d, J= 6.95, Me); 5.86 (1H, m, CH); 6.58 (1H, s, 4'-H); 6.81 (1H, d, J7'8' = 7.98, Hz, 8'-H); 6.85 (1H, d. d., J5'6' =7.58, J6'7' = 7.42 Hz, 6'-H); 7.0 (1H, d. d., J6'7' = 7.42, J7'8' =7.98 Hz, 7'-H); 7.1 (2H, m, 5''-H, 6''H); 7.2 (1H, d, J5'6' = 7.58 Hz, 5'-H); 7.30 (1H, d. d., J56 = 8.08, J67 = 7.41 Hz, 6-H); 7.48 (1H, d, J34 = 9.05 Hz, 3-H); 7.5 (1H, d, JNH-2'H=5.49 Hz, 2'-H); 7.54-7.61 (4H, m, 5-H, 7-H, 4''-H, 7''-H); 7.79 (1H, d, J34 = 9.05 Hz, 4-H); 7.88 (1H, d, J78 =8.34 Hz, 8-H); 10.33 (1H, d, JNH-2'H= 5.49 Hz, NH); determined, % C 80.95; H 5.68; N 13.37. C28H24N4. Calculated, % C 80.74; H 5.81; N 13.45.

1'-methyl-4'-phenyl-1',4'-dihydro-2,3'-biquinolyl (IVf, C25H20N2): The solution of 0.64 g (2.5 mmol) 2,3'-biquinolyl and 0.05 g (7 mmol) of powdered Li in 10 mL THF is stirred under Ar blanket at ambient temperature for 3 h, then the solution of 0.71 g (4.5 mmol) of bromobenzene in 4 mL THF is added dropwise. The reaction mixture is stirred for 1 h at room temperature, than refluxed for 1 h. The mixture is cooled to room temperature 0.71 g MeI in 2 mL THF is added and mixture is stirred for 1 h. The mixture is poured into 50 ml of water and extracted with benzene (3 [lozenge] 30 mL). The organic solution is evaporated and resulting yellow oil is crystallized on hexane addition. Yield 0.65 g (75%), m.p. 173-174 deg.C (EtOH). 1H NMR spectrum (CDCl3): 3.38 (3H, s, Me); 5.68 (1H, s, 4'-H); 6.84 (1H, d, J7'8' = 8.12 Hz, 8'-H); 6.89 (1H, d. d., J5'6' =7.61, J6'7'= 7.76 Hz, 6'-H); 7.12 (1H, d. d., J6'7' = 7.76, J7'8' =8.12 Hz, 7'-H); 7.19 (3H, m, 3''-H, 4''-H, 5''-H); 7.27 (1H, d, J5'6' =7.61 Hz, 5'-H); 7.35 (1H, d. d., J56 = 7.99, J67 = 7.56 Hz, 6-H); 7.42 (1H, d, J34 = 9.01 Hz, 3-H); 7.48 (2H, d, J= 7.13 Hz, 2''-H, 6''-H); 7.64 (1H, d. d., J67=7.56, J78 =8.53 Hz, 7-H); 7.67 (1H, d, J56 = 7.99 Hz, 5-H); 7.81 (1H, s, 2'-H); 7.91 (1H, d, J34 = 9.01 Hz, 4-H); 7.99 (1H, d, J78 =8.53 Hz, 8-H); determined, %,: C 86.44; H 5.67; N 7.89. .C25H20N2. Calculated, % C 86.18; H 5.79; N 8.03.

1'-methyl-4'-(1-naphthyl)-1',4'-dihydro-2,3'-biquinolyl (IVg, C29H22N2): Just as IVf out of 0.64 g (2.5 mmol) 2,3'biquinolyl, 0.05 g (7 mmol) Li, 0.72 g (3.5 mmol) 1-bromonaphthalene and 0.71 g (5 mmol) MeI. Yield 0.73 g (73%), m.p. 151-153 deg.C (benzene-hexane). 1H NMR spectrum (CDCl3): 3.51 (3H, s, Me); 6.59 (1H, s, 4'-H); 6.77 (1H, d. d., J5'6' =7.78, J6'7'= 7.62 Hz, 6'-H); 6.88 (1H, d, J7'8' = 8.04 Hz, 8'-H); 7.1 (1H, d. d., J6'7' = 7.62, J7'8' =8.04 Hz, 7'-H); 7.23-7.28 (4H, m, 5'-H, 6'-H, 3''-H, 6''-Í); 7.49 (1H, d, J34 = 8.79 Hz, 3-H); 7.51-7.8 (7H, m, arom.); 7.81 (1H, d, J34 = 8.88 Hz, 4-H); 7.83 (1H, s, 2'-H); 8.99 (1H, d, J = 8.54, 8''-H or 8-H); determined, %,: C 87.64; H 5.47; N 6.89. C29H22N2. Calculated, %: C 87.41; H 5.56; N 7.03.

1'-benzyl-4'-(1'-naphthyl)-1',4'-dihydro-2,3'-biquinolyl (IVh, C35H26N2): Just as IVf out of 0.64 g (2.5 mmol) 2,3'biquinolyl, 0.05 g (7 mmol) Li, 0.72 g (3.5 mmol) 1-bromonaphthalene and 0.44 g (3.5 mmol) PhCH2Cl. Yield 0.85 g (72%), m.p. 143-144 (EtOH). 1H NMR spectrum (CDCl3): 5.1 (2H, d, J = 4.38 Hz, CH2); 6.69 (1H, s, 4'-H); 6.77 (1H, d. d., J5'6' =7.58, J6'7'= 7.36 Hz, 6'-H); 6.78 (1H, d, J7'8' = 7.82 Hz, 8'-H); 6.95 (1H, d. d., J6'7' = 7.36, J7'8' = 7.82 Hz, 7'-H); 7.04 (1H, d, J5'6' =7.58 Hz, 5'-H); 7.29-7.59 (8H, m, arom.); 7.41 (1H, d, J34 = 8.91 Hz, 3-H); 7.42-7.8 (7H, m, arom.); 7.81 (1H, d, J34 = 8.91 Hz, 4-H); 7.93 (1H, s, 2'-H); 9.03 (1H, d, J = 8.56, 8''-H or 8-H); determined, %,: C 88.75; H 5.44; N 5.81 C35H26N2. Calculated, %: C 88.58; H 5.52; N 5.90.

4'-phenyl -2,3'-biquinolyl (Va, C24H16N2): The solution of 0.42 g (1.25 mmol) 4'-phenyl-1',4'-dihydro-2,3'-biquinolyl (IVa) and 0.33 g I2 in 5 mL pyridine is refluxed for 10 min. The reaction mixture is poured into 100 mL of water containing 1 g Na2S2O3 and 0.5 g NaOH, the forming white precipitate is filtered out and washed with water (3 [lozenge] 30 mL). Yield 0.4 g (95%), m.p. 133-134 deg.C (bnz). 1H NMR spectrum (CDCl3): 6.97 (1H, d, J34 = 8.54 Hz, 3-H); 7.35 (5H, m, Ph); 7.52 (1H, d. d., J5'6' =8.11, J6'7'= 6.95 Hz, 6'-H); 7.56 (1H, d. d., J56 = 8.04, J67 = 7.01 Hz, 6-H); 7.72 (1H, d. d., J6'7' = 6.95, J7'8' =8.38 Hz, 7'-H); 7.74 (1H, d. d., J67=7.01, J78 =8.31 Hz, 7-H); 7.76 (1H, d., J56 = 8.04 Hz, 5-H); 7.79 (1H, d, J5'6' = 8.11 Hz, 5'-H); 7.84 (1H, d, J34 = 8.54 Hz, 4-H); 8.19 (1H, d, J7'8' = 8.38 Hz, 8'-H); 8.25 (1H, d, J78 =8.31 Hz, 8-H); 9.40 (1H, s, 2'-H); mass spectrum (m/z 70 eV) 332 (M+), determined, %,: C 86.92; H 4.75; N 8.33. C24H16N2. Calculated, %: C 86.71; H 4.86; N 8.43.

4'-(1-naphthyl)2,3'-biquinolyl (Vb, C28H18N2): Just as 4'-phenyl-2,3'-biquinolyl (V a), out of 0.48 g (1.25 mmol) 4'-(1-naphthyl)-1',4'-dihydro-2,3'-biquinolyl (IVb) and 0.33 g (1.3 mmol) I2. Yield 0.44 g (92%), m.p. 158-159 deg.C (benzene-hexane). 1H NMR spectrum (CDCl3): 6.83 (1H, d, J34 = 8.55 Hz, 3-H); 7.31 (3H, m, 2''-H, 3''-H, 6''-H); 7.39 (1H, d, J34 = 8.55 Hz, 4-H); 7.43-7.48 (3H, m, 7''-H, 8''-H, 6'-H); 7.63 (2H, d, J = 8.04 Hz, 4''-H, 5''-H); 7.68 (1H, d. d., J56 = 8.04, J67 = 7.03 Hz, 6-H); 7.71 (1H, d. d., J6'7' = 6.95, J7'8' =8.34 Hz, 7'-H); 7.73 (1H, d. d., J67=7.03, J78 =8.28 Hz, 7-H); 7.89 (1H, d, J56 = 8.04 Hz, 5-H); 7.92 (1H, d, J5'6' = 8.11 Hz, 5'-H); 8.10 (1H, d, J7'8' = 8.34 Hz, 8'-H); 8.28 (1H, d, J78 =8.28 Hz, 8-H); 9.55 (1H, s, 2'-H); mass spectrum (m/z 70 eV) 382 (M+), determined, %,: C 88.17; H 4.53; N 7.3. C28H18N2. Calculated, %: C 87.92; H 4.75; N 7.33.

4'-(2-pyridyl)-2,3'-biquinolyl (Vc, C23H15N3): Just as 4'-phenyl-2,3'-biquinolyl (V a), out of 0.42 g (1.25 mmol) 4'-(2-pyridyl)-1',4'-dihydro-2,3'-biquinolyl (IVc) and 0.33 g (1.3 mmol) I2. Yield 0.4 g (94 %), m.p. 93-94 deg.C (bnz). 1H NMR spectrum (CDCl3): 7.08 (1H, d, J34 = 8.54 Hz, 3-H); 7.18 (1H, d. d., J3''4'' = 7.69, J3''5'' = 1.28 Hz, 3''-H); 7.31 (1H, d. t., J4''5'' = 7.54, J5''6'' = 4.7, J3''5'' = 1.28 Hz, 5''-H); 7.55 (1H, d. d., J56 = 8.04, J67 = 7.01 Hz, 6-H); 7.59 (1H, d. t., J3''4'' = 7.69, J4''5'' =7.54, J4''6'' = 1.7 Hz, 4''-H); 7.71 (1H, d. d., J6'7' = 6.95, J7'8' =8.34 Hz, 7'-H); 7.73 (1H, d. d., J5'6' =8.11, J6'7'= 6.95 Hz, 6'-H); 7.74 (1H, d. d., J67=7.01, J78 =8.32 Hz, 7-H); 7.76 (1H, d, J56 = 8.04 Hz, 5-H); 7.79 (1H, d, J5'6' = 8.11 Hz, 5'-H); 7.91 (1H, d, J34 = 8.54 Hz, 4-H); 8.11 (1H, d, J7'8' = 8.34 Hz, 8'-H); 8.26 (1H, d, J78 =8.32 Hz, 8-H); 8.81 (1H, d. d., J5''6'' = 4.7, J4''6'' = 1.7 Hz, 6''-H); 9.43 (1H, s, 2'-H); mass spectrum (m/z 70 eV) 333 (M+), determined, %,: C 82.89; H 4.47; N 12.64. C23H15N3. Calculated, %: C 82.85; H 4.54; N 12.61.

4'-(1-methyl-2-benzimidazolyl)-2,3'biquinolyl (Vd, C26H18N4): Just as 4'-phenyl-2,3'-biquinolyl (Va), out of 0.48 g (1.25 mmol) 4'-(1-methyl-2-benzimidazolyl)-1',4'-dihydro-2,3'-biquinolyl (IVd), and 0.33 g (1.3 mmol) I2. Yield 0.46 g (95 %), m.p. 338-340 deg.C (EtOH). 1H NMR spectrum (CDCl3): 3.25 (1H, s, Me); 7.31 (1H, d, J5'6' = 8.1 Hz, 5'-H); 7.32 (1H, d, J34 = 8.4 Hz, 3-H); 7.38 (1H, d. t., J4''5'' = 8.52, J5''6'' = 7.41, J5''7'' = 1.61 Hz, 5''-H); 7.51 (1H, d. d., J5'6' =8.1, J6'7'= 6.94 Hz, 6'-H); 7.53 (1H, d. d., J6''7'' =7.65, J5''7'' = 1.61 Hz, 7''-H); 7.55 (1H, d. d., J56 = 8.06, J67 = 7.14 Hz, 6-H); 7.58 (1H, d. t., J5''6'' = 7.41, J6''7'' = 7.61, J4''6'' = 2.23 Hz, 6''-H); 7.68 (1H, d. d., J6'7' = 6.94, J7'8' =8.32 Hz, 7'-H); 7.73 (1H, d, J56 = 8.06 Hz, 5-H); 7.82 (1H, d. d., J67=7.14, J78 =8.21 Hz, 7-H); 7.87 (1H, d. d., J4''5'' =8.52, J4''6'' = 2.23 Hz, 4''-H); 7.93 (1H, d, J7'8' = 8.32 Hz, 8'-H); 7.94 (1H, d, J34 = 8.4 Hz, 4-H); 8.29 (1H, d, J78 =8.21 Hz, 8-H); 9.61 (1H, s, 2'-H); mass spectrum (m/z 70 eV) 386 (M+), determined, %,: C 80.94; H 4.59; N 14.47. C26H18N4. Calculated, %: C 80.81; H 4.69; N 14.5.

4'-(1-iso-propyl-2-benzimidazolyl)-2,3'-biquinolyl (Ve, C28H22N4): Just as 4'-phenyl-2,3'-biquinolyl (Va), out of 0.52 g (1.25 mmol) 4'-(1-iso-propyl-2-benzimidazolyl)-1',4'-dihydro-2,3'-biquinolyl (IVe) and 0.33 g (1.3 mmol) I2. Yield 0.47 g (91 %), m.p. 221-222 deg.C (bnz). 1H NMR spectrum (CDCl3): 0.72 (3H, d, J= 6.83, Me); 1.24 (3H, d, J= 6.83, Me); 4.16 (1H, m, CH); 7.31 (1H, d, J5'6' = 8.14 Hz, 5'-H); 7.36 (1H, d. t., J4''5'' = 8.55, J5''6'' = 7.38, J5''7'' = 1.63 Hz, 5''-H); 7.43 (1H, d, J34 = 8.78 Hz, 3-H); 7.5 (1H, d. d., J6''7'' =7.67, J5''7'' = 1.63 Hz, 7''-H); 7.52 (1H, d. d., J5'6' =8.14, J6'7'= 6.97 Hz, 6'-H); 7.55 (1H, d. d., J56 = 8.04, J67 = 7.11 Hz, 6-H); 7.59 (1H, d. t., J5''6'' = 7.38, J6''7'' = 7.67, J4''6'' = 2.25 Hz, 6''-H); 7.7 (1H, d. d., J6'7' = 6.97, J7'8' =8.31 Hz, 7'-H); 7.74 (1H, d, J56 = 8.04 Hz, 5-H); 7.81 (1H, d. d., J67=7.11, J78 =8.21 Hz, 7-H); 7.92 (1H, d. d., J4''5'' =8.55, J4''6'' = 2.25 Hz, 4''-H); 7.93 (1H, d, J34 = 8.78 Hz, 4-H); 8.06 (1H, d, J7'8' = 8.31 Hz, 8'-H); 8.28 (1H, d, J78 =8.21 Hz, 8-H); 9.57 (1H, s, 2'-H); mass spectrum (m/z 70 eV) 414 (M+), determined, %,: C 81.24; H 5.27; N 13.49. C28H22N4. Calculated, %: C 81.13; H 5.35; N 13.52.

Acknowledgement: The work was supported by Russian Foundation of Basic Research (RFBR), grant No. 96-03-32036a.

References

. Aksenov, A.V.; Aksenova, I.V.; Borovlev, I.V.; Bumber, A.A.; Pozharskii, A.F.; Smushkevich, Yu.I. Khim Geterotsikl Soed. [Heterocycl. Cpd.] 1996, p. 1391

. Eisch, J. J. J. Org. Chem., 1963, p. 707.

. Banerji, A.; Maiti, S. Tetrahedron, 1994, p. 9079.

. Holy, N. L. Chem. Rev., 1974, p. 243

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