A. Uslu et al. / Inorganica Chimica Acta 405 (2013) 140–146
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X
X
X
X
X
X
P
N
P
N
P
N
N
N
CH3
CH3
H3C
H3C
N
N
N
N
CH3
CH3
CH3
CH3
H
N
H
N
H
N
Cl
Cl
Cl
Cl
Cl
Cl
H2N
+
+
P
P
P
P
P
NH
P
NH
NH
X = Cl, Ph, SPh, NHPh
CH3
CH3
H3C
CH3
CH3
CH3
(1a-4a)
(1b-4b)
X = Cl
Ph
(1a)
(2a)
(3a)
(4a)
Cl
(1b)
(2b)
(3b)
(4b)
Ph
SPh
NHPh
SPh
NHPh
Scheme 1. The synthesis scheme of compounds (1a–4a, 1b–4b).
in APEX2 [22]. Structures were determined using the direct meth-
ods procedure in SHELXS-97 [23] and refined by full-matrix least
squares on F2 using SHELXL-97 [23]. All non-hydrogen atoms were
refined with anisotropic displacement parameters and C–H hydro-
gen atoms were placed in calculated positions and allowed to ride
on the parent atoms. The final geometrical calculations and the
molecular drawings were carried out with PLATON [24], and MERCURY
[25] programs. Structure determinations have been deposited with
the Cambridge Crystallographic Data Centre with references CCDC-
886526 for structure 2a and CCDC-886527 for structure 3b.
isolated by column chromatography using hexane:ethylacetate
(8:1) to give compounds 2a (0.23 g, 31.6%, mp. 155.0 °C) and 2b
(0.46 g, 48.1%, mp. 212.3 °C). Compound 2a was crystallized from
hexane-dichloromethane (1:4).
2.3.3. Reaction of N3P3Cl4(SPh)2 with 4-isopropylaniline to give
compounds 3a and 3b
Triethylamine (0.70 mL, 5.05 mmol) and 4-isopropylaniline
(0.68 mL, 5.05 mmol) in 10 mL dry THF were added to a stirred
solution of N3P3Cl4(SPh)2 (0.5 g, 1.01 mmol) dissolved in 10 mL
dry THF at room temperature under an argon atmosphere. The
reaction mixture was refluxed for 10 days and was followed by
TLC, which indicated product and no starting material remaining.
Triethylamine hydrochloride was then removed by filtration, and
the solvent removed under reduced pressure. The products were
isolated by column chromatography using hexane:THF (8:1) to
give compounds 3a (0.25 g, 35.8%, oily) and 3b (0.07 g, 7.8%, mp.
206.5 °C). Compound 3b was crystallized from hexane–dichloro-
methane (1:2).
2.3. Syntheses
The cyclotriphosphazene derivatives N3P3Cl4X2, (X = Ph, SPh,
NHPh), which we used as starting compounds were prepared as gi-
ven in the literature [26–28]. The reactions of cyclotriphosphazene
and gem-disubstituted derivatives of cyclotriphosphazene with 4-
isopropylaniline were done and compounds (1a–4a, 1b–4b)
(Scheme 1) were obtained.
2.3.4. Reaction of N3P3Cl4(NHPh)2 with 4-isopropylaniline to give
compounds 4a and 4b
2.3.1. Reaction of N3P3Cl6 with 4-isopropylaniline to give compounds
1a and 1b
Triethylamine (0.76 mL, 5.43 mmol) and 4-isopropylaniline
(0.74 mL, 5.43 mmol) in 10 mL dry toluene were added to a stirred
solution of N3P3Cl4(NHPh)2 (0.5 g, 1.09 mmol) dissolved in 10 mL
dry toluene at room temperature under an argon atmosphere.
The reaction mixture was refluxed for 5 days and was followed
by TLC, which indicated product and no starting material remain-
ing. Triethylamine hydrochloride was then removed by filtration,
and the solvent removed under reduced pressure. The products
were isolated by column chromatography using hexane:ethylace-
tate (3:1) to give compounds 4a (0.24 g, 15.3%, mp. 209.3 °C) and
4b (0.36 g, 16.8%, mp. 129 °C).
Triethylamine (1.60 mL,11.52 mmol) and 4-isopropylaniline
(1.58 mL, 11.52 mmol) in 20 mL dry THF were added to a stirred
solution of N3P3Cl6 (1 g, 2.88 mmol) dissolved in 20 mL dry THF
at room temperature under an argon atmosphere. The reaction
mixture was refluxed for 8 days and was followed by TLC, which
indicated product and no starting material remaining. Triethyl-
amine hydrochloride was then removed by filtration, and the sol-
vent removed under reduced pressure. The products were
isolated by column chromatography using hexane:ethylacetate
(3:1) to give compounds 1a (0.86 g, 54.9%, mp. 161.3 °C) and 1b
(0.08 g, 3.7%, mp. 212.3 °C).
2.3.2. Reaction of N3P3Cl4Ph2 with 4-isopropylaniline to give
compounds 2a and 2b
3. Results and discussion
Triethylamine (0.81 mL, 5.80 mmol) and 4-isopropylaniline
(0.79 mL, 5.80 mmol) in 10 mL dry toluene were added to a stirred
solution of N3P3Cl4(Ph)2 (0.5 g, 1.16 mmol) dissolved in 10 mL dry
toluene at room temperature under an argon atmosphere. The
reaction mixture was refluxed for 5 days and was followed by
TLC, which indicated product and no starting material remaining.
Triethylamine hydrochloride was then removed by filtration, and
the solvent removed under reduced pressure. The products were
3.1. Syntheses and characterizations of compounds 1a–4a, 1b–4b
Compounds 1a–4a and 1b–4b were obtained from the reactions
of hexachlorocyclotriphosphazene, N3P3Cl6 and gem-disubstituted
cyclotriphosphazene derivatives, N3P3Cl4X2 (X = Ph, PhS, PhNH)
with 4-isopropylaniline (Scheme 1). In present work, compounds
were prepared to cover the normal ranges of Cl-, C-, S- and N-sub-
stituents in di- or tetra- substituted 4-isopropylanilino derivatives