Hole Transporting Materials
1407
was filtered off, washed with methanol, cooled to ꢁ5ꢄC, and recrystallized from methanol. Yield 20 g
(59%); mp 89–90.5ꢄC; IR (KBr): ꢃꢀ¼ 3065, 3051 (CHarom), 2982, 2915, 2839, 2748 (CHaliph), 1728
1
(C¼O), 1664 (CHO) cmꢁ1; H NMR (CDCl3, 300MHz): ꢂ ¼ 9.71 (s, CHO), 7.63–7.20 (m, 7H, Ar),
6.59 (d, 1H, J ¼ 8.6 Hz, 8-H of Ht), 5.43–5.35 (m, CH), 3.89–3.71 (m, NCH2), 3.23 (dd, 1H,
JAB ¼ 16.6Hz, JAX ¼ 4.3 Hz, HA of CH2CH), 3.05 (dd, 1H, JAB ¼ 16.6Hz, JBX ¼ 4.9 Hz, HB of
CH2CH), 2.04 (s, CH3) ppm.
3-Acetyl-1-phenyl-1,2,3,4-tetrahydroquinoline-6-carbaldehyde N,N-diphenylhydrazone
(4a, C30H27N3O2)
To a solution of 5 g 3 (17 mmol) in 9 cm3 THF 6 g N,N-diphenylhydrazine hydrochloride (25 mmol)
dissolved in 33 cm3 methanol were added. The mixture was stirred at room temperature for 2 h. The
crystalline product formed during the reaction was filtered off, washed with 2-propanol, and recrys-
tallized from ethyl acetate:methanol ¼ 1:1. Yield 6 g (77%); mp 162–164.5ꢄC; IR (KBr): ꢃꢀ¼ 3032
(CHarom), 2961, 2937, 2866 (CHaliph), 1732 (C¼O) cmꢁ1; 1H NMR (CDCl3, 300 MHz): ꢂ ¼ 7.44–7.06
(m, 18H, Ar, CH¼N), 6.73 (d, 1H, J ¼ 8.6 Hz, 8-H of Ht), 5.35–5.26 (m, CH), 3.83–3.68 (m, NCH2),
3.18 (dd, 1H, JAB ¼ 16.7Hz, JAX ¼ 4.8 Hz, HA of CH2CH), 2.96 (dd, 1H, JAB ¼ 16.7Hz, JBX ¼ 5.4 Hz,
HB of CH2CH), 1.96 (s, CH3) ppm.
3-Acetyl-1-phenyl-1,2,3,4-tetrahydroquinoline-6-carbaldehyde N-phenyl-N-methylhydrazone
(4b, C25H25N3O2)
Compound 4b was prepared according to the procedure described above for 4a except that 20 g 3
(0.07 mol), 10cm3 N-phenyl-N-methylhydrazine (0.08 mol) and 100cm3 methanol instead of THF were
used. The reaction mixturewas stored over night at room temperature. Yield 24g (89%); mp 158–160ꢄC;
1H NMR (CDCl3, 300 MHz): ꢂ ¼ 7.47–6.86 (m, 13H, Ar, CH¼N), 6.78 (d, 1H, J ¼ 8.5 Hz, 8-H of Ht),
5.33–5.29 (m, CH), 3.85–3.69 (m, NCH2), 3.38 (s, NCH3), 3.22 (dd, 1H, JAB ¼ 16.4Hz, JAX ¼ 5.0 Hz,
HA of CH2CH), 3.01 (dd, 1H, JAB ¼ 16.4Hz, JBX ¼ 5.4 Hz, HB of CH2CH), 1.97 (s, CH3) ppm.
3-Hydroxy-1-phenyl-1,2,3,4-tetrahydroquinoline-6-carbaldehyde N,N-diphenylhydrazone
(5a, C28H25N3O).
To a solution of 24 g 4a (0.05 mol) in 30 cm3 dioxane 3.4 g KOH (0.05 mol) dissolved in 10cm3 H2O
were added. The mixture was refluxed for 3 h. Dioxane was removed and the residue was extracted
with ethyl acetate and washed with H2O until neutral. The organic layer was dried (MgSO4), filtered
off, and ethyl acetate was removed. The residue was purified by column chromatography (eluent:
acetone:n-hexane¼ 1:7). Yield 16 g (73%); IR (KBr): ꢃꢀ¼ 3374 (OH), 3057, 3033 (CHarom), 2920,
2850 (CHaliph), 1590, 1493 (C¼C, C–N) cmꢁ1; 1H NMR (CDCl3, 300 MHz): ꢂ ¼ 7.44–7.06 (m, 18H,
Ar, CH¼N), 6.67 (d, 1H, J ¼ 8.6 Hz, 8-H of Ht), 4.38–4.26 (m, CH), 3.77–3.52 (m, NCH2), 3.14 (dd,
1H, JAB ¼ 16.3 Hz, JAX ¼ 4.3 Hz, HA of CH2CH), 2.96 (dd, 1H, JAB ¼ 16.3Hz, JBX ¼ 5.8 Hz, HB of
CH2CH), 2.79 (d, J ¼ 5.5 Hz, OH) ppm.
3-Hydroxy-1-phenyl-1,2,3,4-tetrahydroquinoline-6-carbaldehyde N-phenyl-N-methylhydrazone
(5b, C23H23N3O)
To a solution of 24 g 4b (0.06 mol) in 100 cm3 THF 4 g KOH (0.06 mol) dissolved in 15 cm3 H2O
were added and heated to reflux. The same amount of KOH=H2O was added after 1, 4, and 8 h.
After these additions the mixture was refluxed for another 11 h. Then the reaction mixture was
diluted with ethyl acetate and crystals formed upon standing at room temperature. The crystalline
product was filtered off, washed with 2-propanol, and recrystallized from ethyl acetate. Yield 14 g
1
(65%); mp 149–151ꢄC; H NMR (CDCl3, 300 MHz): ꢂ ¼ 7.49–6.83 (m, 13H, Ar, CH¼N), 6.71
(d, 1H, J ¼ 8.8 Hz, 8-H of Ht), 4.42–4.29 (m, CH), 3.77–3.55 (m, NCH2), 3.37 (s, CH3), 3.19 (dd,
1H, JAB ¼ 16.4 Hz, JAX ¼ 4.5 Hz, HA of CH2CH), 2.93 (dd, 1H, JAB ¼ 16.4 Hz, JBX ¼ 4.9 Hz, HB of
CH2CH), 2.11 (d, J ¼ 7.0 Hz, OH) ppm.