530
GEIES et al.
18.90; S 8.52. C20H15N5OS. Anal. calcd., %: C 64.33; added and the mixture was refluxed for 1 h. The solid
H 4.05; N 18.75; S 8.59. IR
cm–1): 1690 (C=O). product was filtered off washed several times with ethꢀ
1H NMR (CDCl3): 2.23 (3 H, s,CH3), 2.42 (3 H, s, anol and air dried.
CH3), 6.15 (1 H, s, H pyrazole), 6.44–6.46 (2 H, t, 2.4,
2 CHpyrrolyl), 7.15–7.16 (2 H, t, 2, 2 CHpyrrolyl), 7.47–
7.50 (2 H, m, Ar–H), 8.39–8.43 (2 H, m, Ar–H).
( ,
ν
J
Compound (Xa) was separated from ethanol as yelꢀ
low crystals, mp 184–185 , yield 52%. Found, %: C
65.24; H 4.02; N 18.02; S 8.43. C21H15N5OS. Anal.
calcd., %: C 65.44; H 3.92; N 18.17; S 8.32. IR
cm–1): 1660 (C=O); 1600 (C=N). 1H NMR (CDCl3):
.46–6.48 (2 H, t, 2, 2 CHpyrrolyl), 7.12–7.14 (2 H, t,
A, 2 CHpyrrolyl), 7.43–7.61 (4 H, m, Ar–H), 8.15–
J
°
C
N1ꢀ[Phenyl]ꢀN2ꢀ[3ꢀpyrrolylthieno[2,3ꢀ
b
]quinoxaꢀ
( ,
ν
linꢀ2ꢀylcarbonyl]thiosemicarbazide (VII) A mixture of
.
6
J
J
the carbohydrazide (III) (5 mmol) and phenyl isothioꢀ
cyanate (0.005 mol) in absolute ethanol (30 mL) was
heated on a water bath for 30 min, the solid product
separated from the hot mixture was filtered off and
recrystallized from ethanol into white crystals of comꢀ
2
8.37 (7 H, m, Ar–H and 2 NH).
Compound (Xb) was separated from ethanol as yelꢀ
low crystals, mp 166–168
63.48; H 4.42; N 16.65; S 7.66. C21H15N5OS. Anal.
calcd., %: C 63.60; H 4.12; N 16.86; S 7.72. IR
cm–1):
1660 (C=O), 1600 (C=N). 1H NMR (CDCl3): 6.46–
6.48 (2 H, t, 2, 2 CHpyrrolyl), 7.12–7.14 (2 H, t, 2.4,
°C, yield 54%. Found, %: C
pound (VII), mp 150–152
59.22; H 3.80; N 18.62; S, 14.62. C22H16N6OS2. Anal.
calcd., %: C 59.44; H 3.63; N 18.90; S 14.43. IR
cm–1): 3300, 3400 (NH), 1670 (C=O), 1230 (C=S).
1H NMR (CDCl3): 6.4–6.42 (2 H, t,
2.4,
2 CHpyrrolyl), 7.14–7.15 (2 H, t, 2, 2 CHpyrrolyl), 7.36–
°C, yield 77%. Found, %: C
( ,
ν
( ,
ν
J
J
J
2 CHpyrrolyl), 7.43–7.61 (4 H, m, Ar–H), 8.15–8.37 (7
H, m, Ar–H and 2 NH).
J
7.48 (5 H, m, Ar–H), 8.07, 8.22 (2 H, 2s, 2 NH),
8.33–8.41 (4 H, m, Ar–H), 9.2 (1 H, s, NH).
Pyrrolo[1",2":1',6']pyrazino[2',3':4,5]thieno[2,3ꢀ
]quinoxalinꢀ]2]ꢀ(1H)ꢀone (XI). A sample of comꢀ
b
3ꢀPyrrolylꢀ2ꢀ(4ꢀphenyl[1,2,4]triazolꢀ3ꢀylꢀ2(1H
thione)thieno[2,3ꢀ ]quinoxaline (VIII). A mixture of
)
pound (IX) (1 g) in dry xylene (20 mL) was refluxed for
2 h till effervescence due to nitrogen gas evolution was
ceased and a solid was separated. The solid product
was filtered off and recrystallized from dioxane into
pale yellow crystals of compound (XI), mp 313–
b
thiosemicarbazide derivative (VII) (0.005 mol) and
alcoholic potassium hydroxide (50 mL, 10%) was
refluxed for 3 h, the solvent was reduced to one half
under reduced pressure, then cooled. Acidification
with dilute hydrochloric acid gave orange precipitate
which was washed with water and air dried. Recrystalꢀ
lisation from dioxan afford orange crystals of comꢀ
314
19.54; S 11.03. C15H8N4OS. Anal. calcd., %: C 61.63; H
2.76; N 19.17; S 10.97. IR
cm–1): 3300 (NH), 1670
(C=O); 1610 (C=N). H NMR (DMSOꢀ 6): 6.58–
6.6 (2 H, t, 2.4, 2 CHpyrrolyl), 7.19–7.21 (2 H, t, 2.6,
°C, yield 58%. Found, %: C 61.81; H 2.63; N
( ,
ν
1
d
pound (VIII), mp 150–152
C 62.05; H 3.28; N 19.84; S 14.93. C22H14N6S2. Anal.
calcd., %: C 61.95; H 3.31; N 19.70; S 15.03. IR ( ,
°C, yield 51%. Found, %:
J
J
2 CHpyrrolyl), 7.83–7.86 (2 H, m, Ar–H), 8.17–8.25 (2 H,
m, Ar–H), 8.32 (1 H, s, NH).
ν
cm–1): 3320 (NH). H NMR (DMSOꢀ
(2, t, 2.4, 2CHpyrrolyl), 7.09–7.10 (2 H, t,
.41–7.47 (5 H, m, Ar–H), 8.16 (1 H, s, NH), 8.37–
8.45 (4 H, m, Ar–H).
d
6): 6.36–6.38
1
Pyrrolo[1",2":1',6')pyrazino[2',3':4,5]thieno[2,3ꢀ
]quinoxalinꢀ2ꢀ(1H)ꢀthione (XII). A mixture of comꢀ
J
J2, 2 CHpyrrolyl),
b
7
pound (XI) (5 mmol) and phosphorus pentasulfide
(5 mmol) in dry pyridine was refluxed for 54 h then
cooled. The reaction mixture was poured onto
ice/water mixture containing 20 mL acetic acid. The
solid separated was filtered off and recrystallised from
dioxane into orange crystals of compound (XII) mp
3ꢀPyrrolylthieno[2,3ꢀb]quinoxalineꢀ2ꢀcarboazide (IX).
To a cooled solution of compound (III) (5 mmol) in aceꢀ
tic acid (20 mL), sodium nitrite solution (0.01 mol in 2
mL H2O) was added dropwise with stirring. After
addition was finished, the stirring was continued for
another 1 h and the mixture was allowed to stand for
3 h. The solid product was filtered off, washed several
times with water and air dried. Compound (IX) was
subjected to the next step without further purification.
345–346
18.35; S 20.63. C15H8N4S2. Anal. calcd., %: C 58.42;
H 2.61; N 18.17; S 20.79. IR
cm–1): 3320 (NH). 1H
NMR (CF3CO2D): 6.71–6.73 (2 H, t, 2, 2 CHpyrrolyl),
.35–6.37 (2 H, t, 2.4, 2 CHpyrrolyl), 8.06–8.13 (2 H,
°C, yield 68%. Found, %: C 58.64; H 2.51; N
( ,
ν
J
7
J
mp 127
26.22; S 9.83. C15H8N6OS. Anal. calcd., %: C 55.89; H
3.13; N 26.07; S 9.95. IR
cm–1): 2130 (N3), 1670
(C=O); 1610 (C=N). H NMR (CDCl3): 6.51–6.52
(2, t, 2, 2 CHpyrrolyl), 7.15–7.17 (2 H, t, 2.4,
°C, yield 66%. Found, %: C 56.02; H 2.96; N
m, Ar–H), 8.33–8.37 (2 H, m, Ar–H).
2ꢀMethylthiopyrrolo[1",2":1',6']pyrazmo[2',3':4,5]
thieno[2,3ꢀb]quinoxaline (XIII). A mixture of pyraꢀ
zinethione derivative (XII) (2 mmol) and methyl
iodide (5 mmol) in ethanol (30 mL) in presence of
anhydrous potassium carbonate (2 g) was refluxed for
2 h, then filtered. The solid product separated from the
( ,
ν
1
J
J
2 CHpyrrolyl), 7.76–7.81 (2 H, m, Ar–H), 8.15–8.22 (2
H, m, Ar–H).
N1ꢀ[Phenyl or 4ꢀmethoxyphenyl]ꢀN2ꢀ[3ꢀpyrroꢀ cold solution was filtered off and recrystallised from
lylthieno[2,3ꢀ
b
]quinoxalinꢀ2ꢀyl] urea (Xa,b)
.
A mixꢀ ethanol into yellow crystals of compound (XIII) mp
, yield 71%. Found, %: C 59.63; H 3.22; N
ture of the azide derivative (2 mmol) and aromatic 269–270
°C
amine (2 mmol) was fused together until nitrogen gas 17.45; S 19.82. C16H10N41S2. Anal. calcd.: C 59.61; H
effervescence was ceased then ethanol 10 mL was 3.13; N 17.38; S 19.89. H NMR (DMSOꢀ
d6): 3.10
RUSSIAN JOURNAL OF BIOORGANIC CHEMISTRY Vol. 38
No. 5
2012