Mendeleev
Communications
Mendeleev Commun., 2009, 19, 101–102
Synthesis and phosphorylation of
2,2',7,7'-tetra(phenylamino)-1,1'-binaphthalene
Edward E. Nifant’ev,a Vera I. Maslennikova,*a Lyudmila V. Shelenkova,a
Irina I. Levinab and Dmitrii M. Polekhina
a Department of Chemistry, Moscow State Pedagogical University, 119021 Moscow, Russian Federation.
Fax: +7 499 248 0162; e-mail: him-vim@mail.ru
b N. M. Emanuel Institute of Biochemical Physics, Russian Academy of Sciences, 119991 Moscow,
Russian Federation. Fax: +7 499 137 4101; e-mail: ibcp@sky.chph.ras.ru
DOI: 10.1016/j.mencom.2009.03.017
The reaction of 2,2',7,7'-tetrahydroxydinaphthylmethane with aniline in the presence of aniline salts involves the rupture of C–C
bonds and the elimination of a methylene bridge and is completed by the formation of 2,2',7,7'-tetra(phenylamino)-1,1'-binaph-
thalene, the phosphorylation of which with 2-chloro-1,3,2-dioxaphosphinane and dichloroisopropyl phosphite yields original
polycyclic phosphamide architectures.
Due to high complexation ability, polyaminoaromatic com-
14
pounds are perspective building blocks for the design of complex
13
supramolecular systems.1 The most easy and convenient syn-
12
11
thesis of these substances is the amination of polyhydroxy-
aromatic analogues. The direct transformation of phenols and
naphthols to corresponding amino derivatives is performed using
numerous methods differing in reagents, preferred substrates
and techniques.2–9 However, the substitution of an amino group
for hydroxyl is of practical importance only for the simplest
derivatives of naphthalene and resorcinol. The amination of
more complicated hydroxyl aromatic compounds is still not
understood.
NH2
NH NH
NH
6
7
8
5
4
HO
HO
OH
OH
9
3
10
+
1
2
NH NH
NH
1
In this work, 2,2',7,7'-tetrahydroxydinaphthylmethane 1 was
used as a substrate for amination. The point of departure in our
work was the use of a German patent of 1893,10 which indicated
the possibility of amination of tetrahydroxydinaphthylmethane
1, but the structure of tetraamination products was not established.
The method is easy for carrying out, and it does not require
expensive reagents and catalysts.
According to the patented procedure,10 a mixture of dinaph-
thylmethane 1, aniline, and aniline hydrochloride was heated
to 200 °C for 6 h. The study of the isolated products by NMR
spectroscopy† and mass spectrometry showed that the reaction
proceeded unusually, with the rupture of C–C bonds and the
elimination of a methylene bridge. A new C–C bond formed
between two α-naphthyl fragments. Finally, the reaction was
completed by the formation of 2,2',7,7'-tetra(phenylamino)-
1,1'-binaphthalene 2 (green powder, mp 132–134 °C) (Scheme 1).
Signals of aromatic protons and NH groups were detected in
the 1H NMR spectrum of binaphthalene 2, and only signals from
carbon atoms of aromatic rings were identified in its 13C NMR
spectrum. No signals of methylene bridge atoms were found in
any of these spectra.
2
3
Scheme 1
ture. The yield of tetraamine 2 was 38.4%, and that of diamine
3 was 3%.
The microwave irradiation of the reaction mixture increased
the yield of binaphthalene 2 to 51%, reduced the reaction
time to 2 h and decreased the process temperature to 145 °C.‡
However, the yield of compound 3 also increased propor-
tionally. When aniline hydrochloride was replaced by aniline
hydrophosphite, no diamine 3 was found in the reaction
mixture, but the amount of gum increased appreciably, which
decreased the yield of target compound 2 to 26%.
Since oligophosphorylated derivatives of 2 may be useful for
the design of macroheterocyclic receptor systems and ligands
for metal complex catalysts, we started investigating the phos-
phorylation of this compound. In distinction from tetrahydroxy-
dinaphthylmethane 1,11,12 tetraaminobinaphthalene 2 did not react
with phosphorous amides in the temperature range 20–100 °C.
The 31P NMR spectra of reaction mixtures remained unchanged
for a month. Therefore, trivalent phosphorus acid chlorides, which
have a higher reactivity, were used as reagents in this case.
The phosphorylation of binaphthalene 2 by 2-chloro-5,5-di-
methyl-1,3,2-dioxaphosphinane 4 was performed in acetonitrile
in the presence of triethylamine at 20–25 °C and the reagent
ratio 2:4 = 1:6 (Scheme 2).
Along with binaphthalene 2, a small amount of 2,7-bis-
(phenylamino)naphthalene 3 was present in the reaction mix-
†
1H NMR ([2H6]acetone) d: 6.89 (tt, 4H, H14, 3JHH 7.4 Hz, 4JHH 2.1 Hz),
7.09 (dd, 4H, H3,6
,
3JHH 8.9 Hz, JHH 2.1 Hz), 7.23–7.30 (m, 16H,
4
H12,13), 7.34 (d, 2H, H8, 4JHH 2.2 Hz), 7.53 (br. s, 4H, NH), 7.64 (d, 4H,
H4,5 3JHH 8.8 Hz). 13C NMR ([2H6]acetone) d: 109.80 (s, C12 or C16),
,
117.80 (s, C1 or C8), 118.49 (s, C14), 121.16 (s, C3 or C6), 125.10 (s,
C10), 129.42 (s, C4 or C5), 129.91 (s, C13 or C15), 136.97 (s, C9), 142.69 (s,
C2 or C7), 144.24 (s, C11). MS (MALDI), m/z: 618 [M+], 619 [M + H+].
‡
Reactions were performed in a Bruker MWS-3 microwave digestion
system with optical temperature control.
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