Thio-and selenocyanation reactions of quinone iminesderivatives of pyrido[1,2-a[benzimidazole

Article abstract of DOI:10.1080/00397911.2011.560743

The thio-and selenocyanation of quinone monoimines of pyrido[1,2-a] benzimidazole series with the participation of dithiocyanogen and triselenodicyanide in mild reaction conditions results in formation of 9-or 6-thiocyano-and 9-selenocyano-derivatives in good yields.

Full text of DOI:10.1080/00397911.2011.560743

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Thio- and Selenocyanation Reactions
of Quinone Imines—Derivatives of
Pyrido[1,2-a]benzimidazole
Oleg Y. Slabko a , Andrey V. Kachanov a & Vladimir A. Kaminskii a
a Department of Chemistry , Far Eastern Federal University ,
Vladivostok , Russia
Accepted author version posted online: 27 Dec 2011.Published
online: 14 May 2012.
To cite this article: Oleg Y. Slabko , Andrey V. Kachanov & Vladimir A. Kaminskii (2012) Thio- and
Selenocyanation Reactions of Quinone Imines—Derivatives of Pyrido[1,2-a]benzimidazole, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry,
42:16, 2464-2470, DOI: 10.1080/00397911.2011.560743
To link to this article: http://dx.doi.org/10.1080/00397911.2011.560743
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Synthetic Communications1, 42: 2464–2470, 2012
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397911.2011.560743
THIO- AND SELENOCYANATION REACTIONS
OF QUINONE IMINES—DERIVATIVES OF
PYRIDO[1,2-a]BENZIMIDAZOLE
Oleg Y. Slabko, Andrey V. Kachanov, and
Vladimir A. Kaminskii
Department of Chemistry, Far Eastern Federal University, Vladivostok,
Russia
GRAPHICAL ABSTRACT
Abstract The thio- and selenocyanation of quinone monoimines of pyrido[1,2-a]benzimida-
zole series with the participation of dithiocyanogen and triselenodicyanide in mild reaction
conditions results in formation of 9- or 6-thiocyano- and 9-selenocyano- derivatives in good
yields.
Keywords Quinone imine; selenocyanate; thiocyanate; triselenodicyanide
INTRODUCTION
Organic thiocyanates are used as intermediate products in the synthesis of dyes,
antiseptic agents, and bactericidal remedies, as insecticides and fungicides, and as
stabilizers of chlorinated hydrocarbons, lubricants, and emulsifying agents. Organic
selenocyanates play an important part as valuable reagents and intermediate pro-
ducts for synthesis of other selenorganic compounds; many of them are of great
significance as anti-inflammatory and antineoplastic drugs because of their capa-
bility to inhibit the activity of protein kinase C for development of cancer.[1]
Thiocyanation and selenocyanation of quinoid compounds by hydrogen elec-
trophilic substitution in a quinoid kernel have not been described yet. There are
some examples of obtaining thiocyano-(benzo)naphthoquinones[2] and also quinone
Received November 18, 2010.
Address correspondence to Oleg Slabko, Department of Chemistry, Far Eastern Federal
University, Vladivostok, Russia. E-mail: slabko@chem.dvgu.ru
2464

THIO- AND SELENOCYANATION OF QUINONE IMINES
2465
monoimines[3] for nucleophilic substitution of atoms of chlorine in a quinoid kernel
at interaction with potassium and ammonium thiocyanates. Analogous reaction with
N-arylsulfonyl(aroyl)-1,4-benzoquinone imines[4] and N,N0-bis(methylsulfonyl)-1,4-
benzoquinone diimine[5] leads to nucleophilic addition of the thiocyanate ion with
intramolecular cyclization. Dithiocyanogen is a well-known agent for thiocyanation
used in reactions of electrophilic attachment with alkenes and dienes[6] and in reac-
tions of electrophilic substitution with arenes, amines, and thiols.[7] There are no
examples of interaction of quinones with dithiocyanogen. Selenocyanoquinones have
not been studied. The only example is 2-selenocyanoquinone, received by oxidation
of 2,5-dimethyloxi-selenocyanobenzene with the help of cerium ammonium nitrate
applied on silica gel.[8] Recently, we developed a new, simple, and convenient method
of one pot selenocyanation of aromatic amines, indoles, and methyleneactive
compounds with the help of triselenodicyanide, obtained by oxidative coupling of
malononitrile and SeO2.[9] Earlier, triselenodicyanide was used as a selenocyanation
reagent (in reaction with aniline and N,N-dimethylaniline[10] and also polystyrene[11]
and cyanation reagent (in synthesis of cyano N-heterocycles[12]).
)
RESULTS AND DISCUSSION
In the present work, we have investigated the behavior of the quinone mono-
imines of pyrido[1,2-a]benzimidazole series in the reactions with dithyocyanogen and
triselenodicyanide.
Quinone imines 1a–c easily interact with dithyocyanogen solution, yielding
the 9-thiocyano-substituted products 2a–c. In the case of quinone imine 1d, the 6-
thiocyano-substituted product 2d was received unexpectedly.
The thiocyanation direction in position 6 in the case of a quinone imine 1d is
assumed to be caused by insufficient nucleophilic properties of position 9 in quinoid
system, due to the least degree of a coplanarity vinylamine fragment to a quinoid
kernel in comparison with quinone imines 1a–c (because of the least rigidity of struc-
ture) and, hence, due to the least degree of charge transfer from atom N10 to atom of
oxygen of quinoid carbonyl; this dependence was shown earlier.[13]
Similarly, quinone imines 1a–e react with triselenodicyanide at ambient
temperature in one pot selenocyanation reaction in a quinoid kernel.[9] Reaction is
accompanied by selective formation of 9-selenocyanoquinone imines 3a–e of the
specified series. The reaction is supposed to have an electrophilic character because
the selenocyanation of arylamines is accelerated by the electron-donating sub-
stituents. There is electron-donating powerful substituent in the ortho-position to
the atom C9 of the quinoid kernel of pyridobenzimidazole system.
The infrared (IR) spectra of the obtained thiocyanates 2a–d and selenocyanates
3a–e contain rather low-level absorption bands of vibrations of SCN (2150–
2169 cmꢀ1) and SeCN (2150–2156 cmꢀ1) groups and absorption bands of vibrations
of bands in the enaminoquinoid system. A relative displacement toward the big
wave numbers of a strip of SCN (14–17 cmꢀ1) group in the spectrum of compound
2d to the spectra of compounds 2a–c may be explained by the absence of a donor
influence of vinylamine fragment on the thiocyanate group in position 6 of the
quinoid system. In electronic spectra, there is a gypsochromic strip displacement
in the visible part of a spectrum of thiocyanates 2a–c (23–35 nm) and selenocyanates

2466
O. Y. SLABKO, A. V. KANCHANOV, AND V. A. KAMINSKII
Scheme 1. Synthesis of thio- and selenocyanates of quinone imines. R1, R2 ¼ R4, R5 ¼ (CH2)4,
R3 ¼ R6 ¼ R7 ¼ H (a); R1, R2 ¼ (CH2)4, R3 ¼ Ph, R4, R5 ¼ 1,2-(3,4-dihydronaphtho), R6 ¼ R7 ¼ H (b);
R1, R2 ¼ (CH2) 4, R3 ¼ R5 ¼ Ph, R4 ¼ R6 ¼ R7 ¼ H (c); R1 ¼ R3 ¼ R5 ¼ Ph, R2 ¼ R4 ¼ R6 ¼ R7 ¼ H (d);
R1, R2 ¼ (CH2) 4, R3 ¼ Ph, R4, R5 ¼ 1,2-(3,4-dihydronaphtho), R6, R7 ¼ benzo (e).
3a–e (15–30 nm) with simultaneous decreasing of a molar extinction in comparison
with spectra of the initial quinone imines 1a–e. This is likely to be explained by low-
ering the degree of intramolecular transfer from donor–vinylamine fragment to a
carbonyl group of the quinoid kernel caused by the inductive electron-accepting
influence of the thiocyanate and selenocyanate groups. In an electronic spectrum
of thiocyanate 2d, there is bathochromic displacement of a strip in a visible part
of a spectrum (28 nm) toward the strip in the spectrum of initial compound 1d. Poss-
ibly this is an effect of increasing planarization of the conjugated enaminoquinoid
system in the case of 6-substitution.
Data of 1H NMR spectra of compounds 2a–c and 3a–e unequivocally testify to
substitution in position 9 because the signal of proton H9 disappears, and a signal of
proton H7 becomes a doublet and undergoes a small shift (0.2–0.3 ppm), whereas in
the spectra of initial quinoneimines 1a–e the signal of proton H7 is doublet-doublet.
It may be interpreted as electron-accepting influence of SCN and SeCN groups.
In contrast, there is disappearance of a signal of proton H6, with preservation of
4
doublet signals of protons H7 and H9 with J (1.5 Hz) in the thiocyanate 2d spec-
trum. Multiplicity and position of signals of other protons of pyridobenzimidazole
system are similar to the spectral data of initial quinone imines 1a–e. Values of
pseudomolecular ions in mass spectra of compounds 2a–d and 3a–e correspond to
the calculated ones.
CONCLUSION
In summary, we offer a new, simple, and efficient method for the synthesis of
thio- and selenocyanates of heterocyclic quinone imines using dithiocyanogen and
triselenodicyanide, respectively, by means of general electrophilic substitution of
hydrogen in quinoid structure. The mild reaction conditions, simple procedure,
and good yields are the main advantages of this method, which make it a valid
contribution to the existing methodologies.

THIO- AND SELENOCYANATION OF QUINONE IMINES
2467
EXPERIMENTAL
IR spectra and electronic absorption spectra were recorded on a Fourier trans-
form (FT)–IR spectrophotometer Spectrum BX-II in KBr and Ultraviolet–Visible
1
spectrophotometer Cintra-5 in ethanol (visible region), respectively. NMR H spec-
tra were received on a Bruker AC-250 spectrometer (250 MHz) with tetramethylsi-
lane (TMS) as the internal standard and CDCl3 as solvent. Elemental analysis was
obtained on a Flash EA 1112 CHN=MAS200 elemental analyzer. High-performance
liquid chromatography (HPLC) analysis carried out on a HP 1100 LC=MSD instru-
ment with column Hypersil ODS (4 ꢁ 125 mm), a mobile phase 2-propanole=water
(60:40), rate of flow of 0.3 mL=min, temperature 55 ꢂC, and diode matrix. Conditions
of shooting of the mass spectrum were API-ES source and positive polarity. Melting
points were obtained on a Buchi B-540 and Boe¨tius instruments and are uncorrected.
¨
Reactions and purity of products were monitored by thin-layer chromatography
(TLC) using Silufol UV-254 and Sorbfil plates. Preparative chromatography was
performed using silica gel (60-120 mesh) as sorbent.
All received compounds were synthesized by typical experimental procedures,
but isolation and purification methods were different. Compounds 1a–e, dithiocya-
nogen and triselenodicyanide, were prepared by reported procedures.[14,15,9]
Thiocyanates 2a–d: Typical Experimental Procedure
Freshly made solution of dithiocyanogene in dry CH2Cl2 was added to a stirred
solution of compounds 1a–d (0.5 mmol) in dry CH2Cl2 (8 mL) by drops over a period
of 1 h under ice-cold=NaCl conditions until the spot of starting compound 1 on TLC
had disappeared. After completion of the reaction, the mixture was evaporated up to
5 mL of volume and was purified by preparative TLC in petroleum ether=EtOAc 1:1
(2a) and 2:1 (2b–d) as eluent.
Selenocyanates 3a–e: Typical Experimental Procedure
SeO2 (2.0 mmol) was added to a solution of propanedinitrile (1.0 mmol) in
DMSO (1 mL); the mixture was exposed for 10–15 min to the beginning of exothermic
reaction, cooled, and filtered. The solution received triselenodicyanide and added to a
solution of compounds 1a–e (0.5 mmol) in DMSO (3 mL). A reaction mixture was stir-
red at an ambient temperature for 20ꢀ30 h (controlled by TLC), and diluted with 3
volumes of water. Saturated solution NaCl (3 mL) was added; the dropped precipitate
was filtered off, washed with water (3 ꢁ 3 mL), and dried. In the case of compounds 3c
and d, a precipitate represented practically chromatographically pure products
(recrystallized from hexane=acetone mixture); in other cases, a precipitates was puri-
fied by preparative TLC in petroleum ether=EtOAc 1:1 (3a) and 2:1 (3b, e) as eluent.
Data
1,2;4,4a-Di
(tetramethylene)-8-oxo-3,4,4a,8-tetrahydropyrido[1,2-a]
benzimidazole-9-yl thiocyanate (2a). Red powder, 69% yield, mp 158–160 ꢂC.
1H NMR (250 MHz, CDCl3), d, ppm: 1.25–2.45 (m, 17H), 2.93 (m, 2H, CH2),

2468
O. Y. SLABKO, A. V. KANCHANOV, AND V. A. KAMINSKII
3
3
6.82 (d, 1H, H7, J ¼ 9.8 Hz), 7.20 (d, 1H, H6, J ¼ 9.8 Hz). IR (KBr) n, cmꢀ1: 2150
(SCN), 1678 (C1¼C2), 1624, 1607 (C¼O, C¼N), 1588, 1564 (C¼Cquin.). UV (EtOH)
k
max, nm: 455. C20H21N3OS (351.47): calcd. C, 68.18; H, 5.86; N, 12.07. Found: C,
68.35; H, 6.02; N, 11.96. MS (ESI): 352 (M þ Hþ).
1,2-(3,4-Dihydronaphtho)-4,4a-tetramethylene-8-oxo-3,4,4a,8-tetrahy-
dropyrido[1,2-a]benzimidazole-9-yl thiocyanate (2b). Brown powder, 78%
1
yield, mp 234–236 ꢂC. H NMR (250 MHz, CDCl3), d, ppm: 1.25–2.45 (m, 11H),
3
3
2.75 (m, 2H, CH2), 3.50 (d, 1H, H3, J ¼ 9.0 Hz), 6.72 (d, 1H, ArH, J ¼ 7.0 Hz),
6.91 (d, 1H, H7, J ¼ 10.0 Hz), 7.10–7.40 (m, 9H, H6, ArH). IR (KBr) n, cmꢀ1
:
3
2154 (SCN), 1625 (C1¼C2), 1619, 1606 (C¼O, C¼N), 1579, 1558 (C¼Cquin.). UV
(EtOH) kmax, nm: 460. C30H25N3OS (475.61): calcd. C, 75.69; H, 5.23; N, 8.97.
Found: C, 75.76; H, 5.30; N, 8.84. MS (ESI): 476 (M þ Hþ).
4,4a-Tetramethylene-8-oxo-1,3-diphenyl-3,4,4a,8-tetrahydropyrido[1,2-a]
benzimidazole-9-yl thiocyanate (2c). Orange powder, 72% yield, mp 218–220 ꢂC.
3
1H NMR (250 MHz, CDCl3), d, ppm: 1.20–2.20 (m, 9H), 3.83 (dd, 1H, H3, J ¼
3
3
3
9.0 Hz, J ¼ 4.5 Hz), 6.15 (d, 1H, H2, J ¼ 4.5 Hz), 6.88 (d, 1H, H7, J ¼ 9.8 Hz),
7.20–7.40 (m, 11H, H6, ArH). IR (KBr) n, cmꢀ1: 2155 (SCN), 1642 (C1¼C2),
1626, 1605 (C¼O, C¼N), 1581, 1557 (C¼Cquin.). UV (EtOH) kmax, nm: 440.
C28H23N3OS. (449.57): calcd. C, 74.60; H, 5.02; N, 9.43. Found: C, 74.81; H,
5.16; N, 9.35. MS (ESI): 450 (M þ Hþ).
8-Oxo-1,3,4a-triphenyl-3,4,4a,8-tetrahydropyrido[1,2-a]benzimidazole-
1
6-yl thiocyanate (2d). Dark red powder, 84% yield, mp 237–239 ꢂC. H NMR
3
2
(250 MHz, CDCl3), d, ppm: 1.70 (dd, 1H, H4ax., J ¼ 12.5 Hz, J ¼ ꢀ11.5 Hz), 3.30
(dd, 1H, H4eq., 3J ¼ 8.3 Hz, 2J ¼ 11.5 Hz), 3.45 (kd, 1H, H3, 3J ¼ 12.5 Hz, 3J ¼ 8.3 Hz,
3J ¼ 2.5 Hz), 4.86 (d, 1H, H9, 4J ¼ 1.5 Hz), 5.64 (d, 1H, H2, 3J ¼ 2.5 Hz), 6.92 (d, 1H,
4
H7, J ¼ 1.5 Hz), 7.20-7.70 (m, 15H, ArH). IR (KBr) n, cmꢀ1: 2169 (SCN), 1644
(C1¼C2), 1605 (C¼O, C¼N), 1589, 1563 (C¼Cquin.). UV (EtOH) kmax, nm: 485.
C30H21N3OS. (471.57): calcd. C, 76.35; H, 4.29; N, 9.08. Found: C, 76.41; H,
4.49; N, 8.91. MS (ESI): 472 (M þ Hþ).
1,2;4,4a-Di(tetramethylene)-8-oxo-3,4,4a,8-tetrahydropyrido[1,2-a]ben-
zimidazole-9-yl selenocyanate (3a). Dark red powder, 66% yield, mp
1
146–148 ꢂC. H NMR (250 MHz, CDCl3), d, ppm: 1.25–2.45 (m, 17H), 2.95 (m,
3
3
2H, CH2), 6.86 (d, 1H, H7, J ¼ 9.8 Hz), 7.22 (d, 1H, H6, J ¼ 9.8 Hz). IR (KBr, n,
cmꢀ1): 2153 (SeCN), 1672 (C1¼C2), 1618, 1602 (C¼O, C¼N), 1582, 1555 (C¼Cquin.).
UV (visible region, EtOH, kmax, nm): 460. C20H21N3OSe (398.36): calcd. C, 60.06; H,
5.22; N, 10.87. Found: C, 60.30; H, 5.31; N, 10.55. MS (ESI): 400 (M þ Hþ).
1,2-(3,4-Dihydronaphtho)-4,4a-tetramethylene-8-oxo-3,4,4a,8-tetrahy-
dropyrido[1,2-a] benzimidazole-9-yl selenocyanate (3b). Red powder, 80%
1
yield, mp 220–222 ꢂC. H NMR (250 MHz, CDCl3), d, ppm: 1.25–2.20 (m, 11H),
3
3
2.75 (m, 2H, CH2), 3.50 (d, 1H, H3, J ¼ 11.0 Hz), 6.66 (d, 1H, ArH, J ¼ 8.5 Hz),
6.93 (d, 1H, H7, J ¼ 10.0 Hz), 7.10–7.40 (m, 9H, H6, ArH). IR (KBr) n, cmꢀ1
:
3
2154 (SeCN), 1648 (C1¼C2), 1621, 1607 (C¼O, C¼N), 1578, 1562 (C ¼ Cquin). UV
(EtOH) kmax, nm: 461. C30H25N3OSe (522.50): calcd. C, 68.53; H, 4.65; N, 8.16.
Found: C, 68.96; H, 4.82; N, 8.04. MS (ESI): 524 (M þ Hþ).

THIO- AND SELENOCYANATION OF QUINONE IMINES
2469
4,4a-Tetramethylene-8-oxo-1,3-diphenyl-3,4,4a,8-tetrahydropyrido[1,2-
a] benzimidazole-9-yl selenocyanate (3c). Red powder, 87% yield, mp 242–
1
244 ꢂC. H NMR (250 MHz, CDCl3), d, ppm: 1.45–2.20 (m, 9H), 3.83 (dd, 1H, H3,
3J ¼ 9.0 Hz, 3J ¼ 4.5 Hz), 6.16 (d, 1H, H2, 3J ¼ 4.5 Hz), 6.91 (d, 1H, H7, 3J ¼ 9.8 Hz),
7.30 (d, 1H, H6, J9.8 Hz), 7.15–7.45 (m, 10H, ArH). IR (KBr) n, cmꢀ1: 2156 (SeCN),
1645 (C1¼C2), 1620, 1608 (C¼O, C¼N), 1584, 1559 (C¼Cquin.). UV (EtOH) kmax
,
nm: 448. C28H23N3OSe (496.46): calcd. C, 67.50; H, 4.32; N, 8.58. Found: C,
67.74; H, 4.67; N, 8.46. MS (ESI): 498 (M þ Hþ).
8-Oxo-1,3,4a-triphenyl-3,4,4a,8-tetrahydropyrido[1,2-a]benzimidazole-
9-yl thiocyanate (3d). Orange powde, 96% yield, mp 143–145 ꢂC (dec.)ꢀ1H NMR
3
2
(250 MHz, CDCl3), d, ppm: 1.85 (dd, 1H, H4ax., J ¼ 13.5 Hz, J ¼ ꢀ13.2 Hz), 3.55
(dd, 1H, H4
,
3J ¼ 6.6 Hz, 2J ¼ ꢀ13.2 Hz), 3.67 (kd, 1H, H3, 3J ¼ 13.5 Hz,
eq.
3J ¼ 6.6 Hz, 3J ¼ 3.4 Hz), 6.08 (d, 1H, H2, 3J ¼ 3.4 Hz), 6.88 (d, 1H, H7, 3J ¼ 10.0 Hz),
7.20–7.60 (m, 16H, H6, ArH). IR (KBr) n, cmꢀ1: 2150 (SeCN), 1642 (C1¼C2), 1624,
1604 (C¼O, C¼N), 1586, 1561 (C ¼ Cqiun.). UV (EtOH) kmax, nm: 455.
C30H21N3OSe (518.47): calcd. C, 69.41; H, 3.87; N, 8.23. Found: C, 69.50; H,
4.08; N, 8.10. MS (ESI): 520 (M þ Hþ).
6,7-Benzo-1,2-(3,4-dihydronaphtho)-4,4a-tetramethylene-8-oxo-3,4,4a,
8-tetrahydropyrido[1,2-a]benzimidazole-9-yl selenocyanate (3e). Orange
1
powder, 90% yield, mp 234–236 ꢂC. H NMR (250 MHz, CDCl3), d, ppm: 1.25–
2.40 (m, 11H), 2.75 (m, 2H, CH2), 3.51 (d, 1H, H3, 3J ¼ 9.5 Hz), 6.71 (d, 1H,
ArH, 3J ¼ 7.3 Hz), 7.10–7.40 (m, 3H, ArH), 7.68 (td, 1H, ArH, 3J ¼ 7.6 Hz,
4
3
3
4
3J ¼ 7.3 Hz, J ¼ 1.7 Hz), 7.73 (td, 1H, ArH, J ¼ 7.8 Hz, J ¼ 7.3 Hz, J ¼ 1.7 Hz),
8.34 (dd, 1H, ArH, 3J ¼ 7.6 Hz, 4J ¼ 1.7 Hz), 8.37 (dd, 1H, ArH, 3J ¼ 7.8 Hz,
4J ¼ 1.7 Hz). IR (KBr) n, cmꢀ1: 2153 (SeCN), 1654 (C1¼C2), 1624, 1605 (C¼O,
C¼N), 1581, 1562 (C¼Cquin.). UV (EtOH) kmax, nm: 440. C34H27N3OSe (572.56):
calcd. C, 71.48; H, 4.92; N, 7.28. Found: C, 71.32; H, 4.75; N, 7.34. MS (ESI):
574 (M þ Hþ).
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