BIPHILIC PROPERTIES
1471
(no. 14), a 8.7930(7), b 9.2612(7), c 21.1879(17) Å,
α 79.412(4), β 85.798(5), γ 68.942(4)º, V 1582.7(2) Å3,
Z 2, dcalc 1.305 g cm–3 , μ 0.255 mm–1, F(000) 652. The
structure was solved by the direct method and refined
by the least-squares method in full-matrix anisotropic
approximation using SHELXS97 and SHELXL97
programs [8, 9]. For the refinement were used
4909 reflexes with I > 2σ(I), (430 of refined param-
eters, 11.4 reflexes per a parameter, weight scheme w =
1/[σ2(Fo2) + (0.046Р)2 + 0.4482Р], where Р = (Fo2 +
2Fc2)/3 is applied, the ratio of maximal (average) shift
to error in the final cycle is 0.009 (0.003). Corrections
for extinction were introduced with SADABS program
residue was added 5 ml of ethanol, the precipitate was
filtered off and used further without purification.
2-(4,5-Ditosyl-1,3-thiazol-2-yl)-3-phenyl(p-fluoro-
phenyl)acrylonitrils (IVa, IVb). To 0.7 mmol of
compound IIa was added 7 mmol of an appropriate
aldehyde. The mixture was heated for 10 h at 140ºС,
cooled to 20ºС, 5 ml of ethanol was added, the
precipitate was filtered off and purified by
crystallization from ethanol.
2-[5-Arylsulfonyl-4-(p-methoxyphenylоxy)-1,3-
thiazol-2-yl]triphenylphosphoranylideneacetonitriles
(Va, Vb). To a solution of 0.7 mmol of compound IIa,
IIb in 5 ml of THF was added 0.7 mmol of sodium p-
methoxyphenoxide, the mixture was left for 24 h at
20ºС, the solvent was removed in a vacuum, 5 ml of
ethanol was added, the precipitate was filtered off and
purified by crystallization from ethanol.
(the minimal/maximal correction ratio Тmin/Tmax
=
0.607). The carbon atoms С29–С35 of tosyl group as
well as the respective hydrogen atoms are disordered
over two positions A and C with occupancies 53 and
47%, respectively. All hydrogen atoms were located
geometrically. Final divergence factors are: R1(F2) =
0.094, RW(F2) = 0.123, GOF = 1.034 over all reflexes
and R1(F) = 0.051 RW(F2) = 0.106, GOF = 1.034 over
the reflexes with I > 2σ(I). Residual electron density
from differential Fourier synthesis after the final
refinement cycle is 0.32 and –0.34 е Å–3.
2-[5-Arylsulfonyl-4-(phenylthio)-1,3-thiazol-2-yl]-
triphenylphosphoranylilideneacetonitriles (VIa, VIb).
To a solution of 0.7 mmol of compound IIa, IIb in
5 ml of THF was added 0.7 mmol of sodium thio-
phenoxide, the mixture was left for 24 h at 20ºС, the
solvent was removed in a vacuum, 5 ml of ethanol was
added, the precipitate was filtered off and purified by
crystallization from ethanol.
Elemental analyses and constants of newly syn-
thesized compounds are listed in Table 1, their spectral
data are collected in Table 2.
2-[4-Piperidino (morpholino, benzylamino)-5-
tosyl-1,3-thiazol-2-yl]triphenylphosphoranylidene-
acetonitriles (VIIa–VIIc). A mixture of 0.7 mmol of
compound IIa and 7 mmol of an appropriate nitrogen
base was heated for 10 h at 120ºС, cooled to 20ºС,
5 ml of ethanol was added, precipitate was filtered off
and purified by crystallization from ethanol.
2,4,5-Tritosyl-1,3-thiazole (Ia) is synthesized in
accordance with [1].
4-Tosyl-2-phenylsulfonyl-5-p-chlorophenylsulfo-
nyl-1,3-thiazol (Ib) is prepared by known procedure
[2].
2-[(4,5-Ditosyl)-1,3-thiazol-2-yl]triphenylphosphor-
anylideneacetonitrile (IIa) and 2-[(4-tosyl-5-p-
chlorophenylsulfonyl)-1,3-thiazol-2-yl]triphenylphos-
phoranylilideneacetonitrile (IIb). To a solution of
0.5 mmol of compound Ia or Ib in 10 ml of THF was
added 1 mmol of triphenylphosphoranylideneaceto-
nitrile and 1 mmol of triethylamine. The mixture was
heated for 10 h at 60ºС, the solvent was removed in a
vacuum and to the residue was added 5 ml of ethanol,
the precipitate was filtered off and compound IIa was
purified by recrystallization from a mixture of ethanol
and acetonitrile (10:1), compound IIb, from acetonitrile.
3-(4,5-Ditosyl-1,3-thiazol-2-yl)-2H-chromen-2-one
(VIIIa). To a solution of 0.7 mmol of compound III in
10 ml of ethanol was added 0.8 mmol of salycilic
aldehyde and 1 drop of piperidine. The mixture was
heated to 40ºС for 1 h and left at 20ºС for 24 h, the
solvent was removed in a vacuum, 10 ml of sodium
carbonate and then 2 ml of concn. hydrochloric acid
was added, and the mixture was refluxed for 1 h. The
precipitate formed was filtered off and purified by
crystallization from a mixture of ethanol and DMF
(10:1).
2-(2,4-Ditosyl-1,3-thiazol-2-yl)acetonitrile (III).
To a suspension of 0.7 mmol of compound IIa in 6 ml
of acetic acid was added 0.14 mmol of phosphorus
oxychloride. The mixture was heated at 100ºС for
15 min, the solvent was removed in a vacuum, to the
7-Hydroxy-3-(4,5-ditosyl-1,3-thiazol-2-yl)-2H-
chrоmеn-2-one (VIIIb). To a solution of 0.7 mmol of
compound III in 10 ml of ethanol was added 0.8 mmol
of 2,4-dihydroxybenzaldehyde and 1 drop of piperi-
dine. The mixture was heated to 40ºС for 1 h and left
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 7 2009