A. N. Kostyuk et al. / Tetrahedron Letters 43 (2002) 5423–5425
5425
toluene was added. After 5 h, triethylamine hydrochlo-
ride was removed by filtration and the toluene was evap-
orated in vacuo. The residue was triturated with
petroleum and crystallized from 2-propyl alcohol to give
11. Kostyuk, A. N.; Lysenko, N. V.; Marchenko, A. P.;
Koidan, G. N.; Pinchuk, A. N.; Tolmachev, A. A. Phos-
phorus Sulfur Silicon Relat. Elem. 1998, 139, 209–229.
12. To a stirred solution of 2.5 mmol of 1 and 30 mmol of
triethylamine in 20 ml of dry benzene, a solution of 2.5
mmol of phosphorus tribromide in 5 ml of dry benzene
was added. A solution of 10 mmol of morpholine in 5 ml
of dry benzene was then added. After 2 h, 2.5 mmol of
finely ground elemental sulfur was added. After the sulfur
had dissolved, the precipitated solid was filtered and
benzene was evaporated in vacuo. The residue was tritu-
rated with octane and crystallized from ethanol to give 8.
1H NMR (300 MHz, CDCl3): 3.07 (8H, t, 3J=4.5 Hz,
-N(CH2-CH2)2O), 3.17 (2H, d, 3JPH=3.5 Hz, -CH2-),
3.65 (8H, t, 3J=4.5 Hz, -N(CH2-CH2)2O), 4.39 (2H, s,
1
3
2. H NMR (300 MHz, CDCl3): 1.34 (3H, t, J=7.1 Hz,
-CH3), 3.25 (2H, s, -CH2-), 4.29 (2H, q, 3J=7.1 Hz,
4
-O-CH2-), 4.48 (2H, s, N-CH2-), 6.51 (1H, d, J=1.5 Hz,
3
4
N-C6Hꢀ), 7.23 (2H, dd, J=7.8 Hz, J=2.1 Hz, CHo-Ph),
7.38–7.47 (3H, m, CHm,p-Ph), 7.63 (1H, d, 4J=1.5 Hz,
N-C2Hꢀ).
7. To a stirred solution of 10 mmol of 1 in 15 ml of dry
benzene a solution of 10 mmol of tosyl isocyanate in 15
ml of dry benzene was added. The precipitated solid was
crystallized from acetonitrile to give 3. 1H NMR (300
MHz, DMSO-d6): 2.39 (3H, s, -CH3), 2.97 (2H, s, -CH2-),
4.49 (2H, s, N-CH2-), 7.14 (1H, s, N-C6Hꢀ), 7.28–7.48
3
N-CH2-), 6.55 (1H, s, N-C2Hꢀ), 6.85 (1H, d, JPH=15.6
Hz, N-C6Hꢀ), 7.22 (2H, dd, 3J=7.8 Hz, 4J=2.1 Hz,
CHo-Ph), 7.35–7.45 (3H, m, CHm,p-Ph).
3
(8H, m, CH), 7.79 (2H, d, J=7.9 Hz, C2%H), 11.55 (1H,
s, -NH-).
13. The product was prepared according to the procedure
applied to the substance 8,12 but instead of sulfur, 0.35 ml
50% H2O2 was added. The precipitated solid was filtered
and the benzene was evaporated in vacuo. The residue
was crystallized from ethanol to give 9. Compound 9:
8. To a stirred solution of 10 mmol of 1 in 15 ml of dry
benzene a solution of 10 mmol of 2-nitrophenylsulphenyl
chloride in 15 ml of dry benzene was added. After 24 h,
triethylamine hydrochloride was removed by filtration
and the toluene was evaporated in vacuo to give 4. The
residue was crystallized from a mixture of methanol–ace-
1
yield 12%; mp 228–229°C; H NMR (300 MHz, CDCl3):
3
1
3.00–3.12 (8H, m, -N(CH2-CH2)2O), 3.64 (8H, t, J=4.2
tonitrile (1:1). H NMR (300 MHz, CDCl3): 3.14 (2H, s,
-CH2-), 4.40 (2H, s, N-CH2-), 6.48 (1H, s, N-C6Hꢀ), 6.62
(1H, s N-C2Hꢀ), 7.23–7.49 (7H, m, CH), 7.60 (1H, t,
Hz, -N(CH2-CH2)2O), 5.19 (2H, s, N-CH2-), 7.37–7.42
(5H, m, CHPh), 7.81 (1H, dd, 3JPH=8.7 Hz, 4JHH=1.8
Hz, C4H), 8.18 (1H, dd, 3JPH=9.3 Hz, 4JHH=1.8 Hz,
C6H).
3
3J=7.6 Hz, C5%H), 8.21 (1H, d, J=8.1 Hz, C3%H).
9. To a solution of 6 mmol of 1 in 5 ml of dry DMF, 2 ml
of POCl3 was added at 0°C. The mixture was maintained
at 50°C for 90 min, then cooled and poured onto ice and
neutralized with a solution of NaHCO3. The precipitated
solid was crystallized from a mixture of ethanol–water
(2:1) to give 5. 1H NMR (300 MHz, DMSO-d6): 3.02
(2H, s, -CH2-), 4.59 (2H, s, N-CH2-), 7.25 (1H, s, N-
C6Hꢀ), 7.32–7.47 (6H, m, CH), 9.21 (1H, s, CHO).
2,4-Dinitrophenylhydrazone derivative: mp 210–212°C;
1H NMR (300 MHz, DMSO-d6): 3.23 (2H, s, -CH2-),
4.58 (2H, s, N-CH2-), 6.79 (1H, s, N-C6Hꢀ), 7.28 (1H, s,
N-C2Hꢀ), 7.32–7.47 (5H, m, CHPh), 7.88 (1H, d, 3J=10.2
Hz, C6%H), 8.24 (1H, s, CHꢀN), 8.29 (1H, dd, 3J=10.2
Hz, 4J=2.3 Hz, C5%H), 8.83 (1H, d, 4J=2.3 Hz, C3%H),
11.48 (1H, s, -NH-).
14. Compound 5: 13C NMR (75 MHz, DMSO-d6): 24.3 C(4),
60.3 N-CH2-, 89.6 C(3)-CN, 117.7 CN, 123.3 C(5)-CHO,
131.4 C(o-Ph), 131.9 C(p-Ph), 132.7 C(m-Ph), 140.5
C(ipso-Ph), 146.6 C(2), 152.5 C(6), 192.8 CHO. Com-
pound 8: 13C NMR (75 MHz, CDCl3): 24.2 (2JPC=8.0
Hz) C(4), 45.1 -N(CH2-CH2)2O, 57.97 N-CH2-, 66.8
(3JPC=7.2 Hz) -N(CH2-CH2)2O, 82.3 (3JPC=11.8 Hz)
C(3)-CN, 102.0 (1JPC=129.0 Hz) C(5)-P, 119.6 CN,
127.4 C(o-Ph), 128.7 C(p-Ph), 129.2 C(m-Ph), 135.3
C(ipso-Ph), 141.2 (2JPC=21.6 Hz) C(6), 142.0 C(2).
Compound 9: 13C NMR (75 MHz, CDCl3): 44.5
-N(CH2-CH2)2O, 53.8 N-CH2-, 66.9 (3JPC=3.5 Hz)
-N(CH2-CH2)2O, 106.1 (3JPC=20.3 Hz) C(3)-CN, 107.3
(1JPC=130.6 Hz) C(5)-P, 114.8 CN, 128.7 C(o-Ph), 129.1
C(p-Ph), 129.4 C(m-Ph), 134.3 C(ipso-Ph), 147.1 C(4),
149.3 (2JPC=16.4 Hz) C(6), 159.0 C(2)ꢀO.
10. Bennasar, M.-L.; Vidal, B.; Bosch, J. J. Org. Chem. 1997,
62, 3597–3609.