S. Pektaßs et al. / Inorganica Chimica Acta 474 (2018) 51–65
53
2.3. Syntheses
Calc. for C31H47N8O2P3 (%): C, 56.70; H, 7.21; N, 17.06. Found: C,
56.64; H, 7.16; N, 17.06. IR (KBr, cmꢀ1):
2958–2848 (CAH aliph.),
m
2.3.1. Syntheses of the compounds (1 and 2)
1589 (C@C), 1234 (asymm.), 1190 (symm.) (P@N). ESI-MS (Ir%): m/
Tyramine Schiff base {2-[(E)-2-(4-hydroxyphenylethyl)imi-
nomethyl]phenol} (1) was prepared according to a published pro-
cedure in which salicylaldehyde was reacted with tyramine in dry
MeOH [26]. The molecular structural determination of 1 has been
reported [27], and a different polymorph of 1 was studied by
experimental (MS, FT-IR, NMR and X-ray diffraction) and computa-
tional [density functional theory (DFT)] methods from the point of
the tautomerism in solution and the solid state by our research
group [28]. It was observed that the phenol-imine tautomer is pre-
dominant for tyramine Schiff base (1) in both DMSO solution and
the solid state [28]. However, in 2-hydroxy aldimine Schiff bases,
z 657 {[MH]+, 100}.
2.3.3.2.
40,40,60,60-Tetra(1-piperidinyl)-3-(4-hydroxyphenylethyl)-
3H,4H-spiro{[1,3,2-benzoxazaphosphinine]-2,20-[1,3,5,2,4,6]triazat-
riphosphinine]} (4b). Compound (4b) was prepared from Pip (1.19
g, 14.0 mmol) and 3 (0.72 g, 1.40 mmol) (24 h), column chro-
matography [silica gel (30 g), toluene/THF (8/1), Rf = 0.26], crystal-
lized from benzene/THF (2/1). Yield: 0.43 g (45%). mp: 181 °C. Anal.
Calc. for C35H55N8O2P3 (%): C, 58.98; H, 7.78; N, 15.72. Found: C,
59.02; H, 7.83; N, 15.68. IR (KBr, cmꢀ1):
m 2916–2816 (CAH aliph.),
1589 (C@C), 1261 (asymm.), 1172 (symm.) (P@N). ESI-MS (Ir%): m/
it is found as the polarity of the medium increases, the phenol-
z 713 {[MH]+, 100}.
⁄
imine [(OAH. . .N),
nm)] tautomer decreases, while keto-amine [(O. . .HAN), n ?
p
?
p
transition of the C@N group (300–340
40,40,60,60-Tetra(4-morpholinyl)-3-(4-hydroxyphenylethyl)-
⁄
p
2.3.3.3.
transition of the C@O group (>400 nm)] tautomer increases [29].
3H,4H-spiro{[1,3,2-benzoxazaphosphinine]-2,20-[1,3,5,2,4,6]triazat-
riphosphinine]} (4c). Compound (4c) was prepared from Morp
(1.26 g, 14.5 mmol) and 3 (0.75 g, 1.45 mmol) (48 h), column chro-
matography [silica gel (30 g), toluene/THF (1/1), Rf = 0.35], crystal-
lized from toluene/THF (1/1). Yield: 0.65 g (63%). mp: 170 °C. Anal.
Calc. for C31H47N8O6P3 (%): C, 51.66; H, 6.57; N, 15.55. Found: C,
Compound (2) was prepared from the reduction of 1 (8.80 g,
36.00 mmol) with borax (2.78 g, 7.20 mmol) and sodium borohy-
dride (2.76 g, 73.00 mmol) in dry MeOH (300 mL). The mixture
was heated at reflux for 4 h. MeOH was then evaporated and the
residue was extracted with chloroform (100 mL, three times).
Yield: 6.92 g (78%). mp: 99 °C. Anal. Calc. for C15H17NO2 (%): C,
74.05; H, 7.04; N, 5.76. Found; C, 74.11; H, 7.02; N, 5.69%. IR
51.64; H, 6.55; N, 15.56. IR (KBr, cmꢀ1):
m 2958–2846 (CAH aliph.),
1593 (C@C), 1215 (asymm.), 1170 (symm.) (P@N), 1130 (CAO).
(KBr, cmꢀ1):
m 2841–2800 (CAH aliph.), 1589 (C@C). ESI-MS (Ir%):
ESI-MS (Ir%): m/z 721 {[MH]+, 100}.
m/z 244 {[MH]+, 100}.
2.3.3.4.
40,40,60,60-Tetra(1,4,7-dioxazonan-7-yl)-3,4-dihydro-3-(4-
2.3.2. Synthesis of partly substituted spiro-cyclotriphosphazene
{40,40,60,60-Tetrachloro-3-(4-hydroxyphenylethyl)-3H,4H-spiro{[1,3,2-
benzoxazaphosphinine]-2,20-[1,3,5,2,4,6]triazatriphosphinine]}} (3)
K2CO3 (7.27 g, 52.6 mmol) was added to a stirred solution of 2
(3.19 g, 13.0 mmol) in dry THF (200 mL). The mixture was heated
at reflux for 4 h and then cooled to room temperature. A solution
of N3P3Cl6 (4.56 g, 13.0 mmol) in dry THF (100 mL) and triethy-
lamine (5.30 g, 52.6 mmol) was added. The mixture was stirred
for four days at ambient temperature with argon being passed over
the reaction mixture. The precipitated triethylaminehydrochloride
and excess of K2CO3 were filtered off, and the solvent was evapo-
rated at reduced pressure. The crude product was subjected to col-
umn chromatography [silica gel 60 (230–400 mesh) (30 g) as
adsorbent and toluene/THF mixture (8/1) as the eluent, Rf = 0.46]
and crystallized from toluene/THF mixture (8/1). Yield: 4.85 g
(72%). mp: 148 °C. Anal. Calc. for C15H15Cl4N4O2P3 (%): C, 34.78;
H, 2.92; N, 10.82. Found; C, 34.83; H, 2.96; N, 10.73%. IR (KBr,
hydroxyphenylethyl)-3H,4H-spiro{[1,3,2-benzoxazaphosphinine]-
2,20-[1,3,5,2,4,6]triazatriphosphinine]} (4d). Compound (4d) was
prepared from DASD (2.15 g, 15.0 mmol) and 3 (0.78 g, 1.50 mmol)
(48 h), column chromatography [silica gel (30 g), toluene/THF
(1/1), Rf = 0.35], crystallized from toluene/THF (1/1). Yield: 0.69 g
(49%). mp: 165 °C. Anal. Calc. for C43H63N8O10P3 (%): C, 54.66; H,
6.72; N, 11.86. Found: C, 54.71; H, 6.79; N, 11.80. IR (KBr, cmꢀ1):
m
2949–2846 (CAH aliph.), 1591 (C@C), 1197 (P@N), 1145 (CAO).
ESI-MS (Ir%): m/z 945 {[MH]+, 100}.
2.3.3.5. 40,40,60,60-Tetra{1-[4-(2-aminoethyl)pyrrolidinyl]}-3,4-dihy-
dro-3-(4-hydroxyphenylethyl)-3H,4H-spiro{[1,3,2-benzoxazaphos-
phinine]-2,20-[1,3,5,2,4,6]triazatriphosphinine]}
(4e). Compound
(4e) was prepared from AEPyr (1.61 g, 14.1 mmol) and 3 (0.73 g,
1.41 mmol) (48 h), column chromatography [silica gel (30 g),
THF, Rf=0.06], obtained the oily crude product. Yield: 0.61 g
(52%). Anal. Calc. for C39H67N12O2P3 (%): C, 56.51; H, 8.15; N,
cmꢀ1):
m
2958–2926 (CAH aliph.), 1589 (C@C), 1242 (asymm.),
20.28. Found: C, 56.47; H, 8.12; N, 20.31. IR (KBr, cmꢀ1):
m 3192
1173 (symm.) (P@N), 593 (asymm.), 527 (symm.) (PACl). ESI-MS
(NAH), 2958–2873 (CAH aliph.), 1585 (C@C), 1230 (asymm.),
(fragments are based on 35Cl, Ir%): m/z 519 {[MH]+, 100}.
1192 (symm.) (P@N). ESI-MS (Ir%): m/z 829 {[MH]+, 84}.
2.3.3. Syntheses of fully substituted spiro-cyclotriphosphazenes
Fully substituted spiro-cyclotriphosphazenes (4a–g) were pre-
pared by similar methods; therefore, the experimental procedure
of the preparation was only described in detail for the first case.
2.3.3.6. 40,40,60,60-Tetra{1-[4-(2-aminoethyl)piperidinyl]}-3,4-dihydro-
3-(4-hydroxyphenylethyl)-3H,4H-spiro{[1,3,2-benzoxazaphos-
phinine]-2,20-[1,3,5,2,4,6]triazatriphosphinine]} (4f). Compound (4f)
was prepared from AEPip (1.84 g, 14.3 mmol) and 3 (0.74 g, 1.43
mmol) (48 h), column chromatography [silica gel (30 g), THF, Rf =
0.08], obtained the oily crude product. Yield: 0.67 g (53%). Anal.
Calc. for C53H75N12O2P3 (%): C, 58.35; H, 8.54; N, 18.99. Found: C,
2.3.3.1.
40,40,60,60-Tetra(2-pyrrolidinyl)-3-(4-hydroxyphenylethyl)-
3H,4H-spiro{[1,3,2-benzoxazaphosphinine]-2,20-[1,3,5,2,4,6]triazat-
riphosphinine]} (4a). A solution of Pyr (0.68 g, 9.60 mmol) in dry
THF (50 mL) was added to a stirred solution of 3 (0.50 g, 0.96
mmol) in dry THF (200 mL) at room temperature. The mixture
was stirred for 72 h at room temperature under argon and moni-
tored by TLC indicating no starting material remaining. The precip-
itated Pyr hydrochloride was filtered off, and the solvent was
evaporated. The crude product was subjected to column chro-
matography [silica gel 60 (230–400 mesh) (30 g) as adsorbent
and toluene/THF (6/1) mixture as the eluent, Rf = 0.17] and crystal-
lized from toluene/THF (6/1). Yield: 0.28 g (44%). mp: 78 °C. Anal.
58.33; H, 8.49; N, 18.99. IR (KBr, cmꢀ1):
m 3207 (NAH), 2929–
2800 (CAH aliph.), 1587 (C@C), 1174 (P@N). ESI-MS (Ir%): m/z
885 {[MH]+, 40}.
2.3.3.7. 40,40,60,60-Tetra{4-[4-(2-aminoethyl)morpholinyl]}-3,4-dihy-
dro-3-(4-hydroxyphenylethyl)-3H,4H-spiro{[1,3,2-benzoxazaphos-
phinine]-2,20-[1,3,5,2,4,6]triazatriphosphinine]}
(4g). Compound
(4g) was prepared from AEMorp (1.78 g, 1.37 mmol) and 3 (0.71
g, 1.37 mmol) (48 h), column chromatography [silica gel (30 g),
THF, Rf = 0.10], obtained the oily crude product. Yield: 0.61 g