Synthesis of novel paracyclophanes with linear P,N-containing spacers

Article abstract of DOI:10.1007/s11172-007-0284-9

Condensation of bis(hydroxymethyl)mesityl-and bis(hydroxymethyl) phenylphosphines with N,N′-disubstituted bis(4-aminophenyl)methanes and bis(4-amino-3-carboxyphenyl)methane occurred as covalent self-assembly spontaneously giving a mixture of trans-and cis-diastereomers of 1,5,19,23-tetra-R′-3,21-di-R-1,5,19,23-tetraaza-3,21-diphospha[5.1.5.1] paracyclophanes as the major products. The trans-isomer (R is mesityl; R′ is methyl) was isolated in the individual state and structurally characterized by X-ray diffraction analysis. Sulfurization of macrocyclic diphosphines (R = Ph; R′ is 3-pyridylmethyl or 4-pyridylmethyl) gave the corresponding diphosphine disulfides, the trans-stereoisomer being isolated in the individual state.

Full text of DOI:10.1007/s11172-007-0284-9

Russian Chemical Bulletin, International Edition, Vol. 56, No. 9, pp. 1828—1837, September, 2007
1828
Synthesis of novel paracyclophanes with linear P,Nꢀcontaining spacers*
a
a
a
a
S. N. Ignat´eva,a A. S. Balueva,a A. A. Karasik, D. V. Kulikov, A. V. Kozlov, Sh. K. Latypov,
ꢀ
P. Lönnecke,b E. HeyꢀHawkins,b and O. G. Sinyashina
aA. E. Arbuzov Institute of Organic and Physical Chemistry,
Kazan Research Center of the Russian Academy of Sciences,
8 ul. Akad. Arbuzova, 420088 Kazan, Russian Federation.
Fax: +7 (843 2) 73 2253. Eꢀmail: anna@iopc.knc.ru
bInstitute of Inorganic Chemistry, Leipzig University,
29 Johannisallee, Dꢀ04103 Leipzig, Germany.**
Fax: +49 (0341) 973 9319. Eꢀmail: hey@rz.uniꢀleipzig.de
Condensation of bis(hydroxymethyl)mesitylꢀ and bis(hydroxymethyl)phenylphosphines
with N,N´ꢀdisubstituted bis(4ꢀaminophenyl)methanes and bis(4ꢀaminoꢀ3ꢀcarboxyꢀ
phenyl)methane occurred as covalent selfꢀassembly spontaneously giving a mixture of
transꢀ and cisꢀdiastereomers of 1,5,19,23ꢀtetraꢀR´ꢀ3,21ꢀdiꢀRꢀ1,5,19,23ꢀtetraazaꢀ3,21ꢀ
diphospha[5.1.5.1]paracyclophanes as the major products. The transꢀisomer (R is mesityl; R´ is
methyl) was isolated in the individual state and structurally characterized by Xꢀray diffraction
analysis. Sulfurization of macrocyclic diphosphines (R = Ph; R´ is 3ꢀpyridylmethyl or 4ꢀpyriꢀ
dylmethyl) gave the corresponding diphosphine disulfides, the transꢀstereoisomer being isoꢀ
lated in the individual state.
Key words: phosphorusꢀcontaining cyclophanes, bis(hydroxymethyl)phenylphosphine,
bis(hydroxymethyl)mesitylphosphine, N,N´ꢀdisubstituted bis(4ꢀaminophenyl)methanes,
bis(4ꢀaminoꢀ3ꢀcarboxyphenyl)methane, condensation, covalent selfꢀassembly.
Macrocycles containing soft electronꢀdonating sites
scribed9—11 cyclophanes of this type are relatively few,
mostly including macrocyclic diphosphites, diphosphoꢀ
nites, and bis(phosphoramidites).11—16 Recently, we
have developed an efficient approach to the synthesis
of cageꢀtype cyclophanes containing four phosphine
sites, namely, 1,5(1,5)ꢀdi(1,5ꢀdiazaꢀ3,7ꢀdiphosphacycloꢀ
octana)ꢀ2,4,6,8(1,4)ꢀtetrabenzenacyclooctaphanes. The
approach involves condensation of bis(hydroxymethyl)orꢀ
ganylphosphines with primary diamines containing spacꢀ
ers formed by two pꢀphenylene fragments linked by variꢀ
ous monoatomic bridges.17,18 At high concentrations of
the reagents and in the absence of templates, those reacꢀ
tions mainly yielded macrocycles via covalent selfꢀasꢀ
sembly.18 The goal of the present work was to further
develop this approach and use it for the synthesis of more
flexible cyclophanes with two tricoordinate P atoms
in the macrocycle. To solve this problem, here we
studied reactions of bis(hydroxymethyl)phenylꢀ and
bis(hydroxymethyl)mesitylphosphines with a number
of secondary diamines containing di(pꢀphenylene)meꢀ
thane spacers: bis(4ꢀmethylaminophenyl)methane 1 (see
Ref. 19), bis[4ꢀ(3ꢀpyridylmethyl)aminophenyl]meꢀ
thane (2), and bis[4ꢀ(4ꢀpyridylmethyl)aminophenyl]meꢀ
thane (3). The use of functionalized diamines made it
possible to construct cyclophanes with additional periꢀ
pheral donating sites. Bis(4ꢀaminoꢀ3ꢀcarboxyphenyl)meꢀ
(in particular, tricoordinate phosphorus atoms) are of conꢀ
stant interest primarily as a basis for development of cataꢀ
lytic systems with reactive sites inside or adjacent to the
macrocyclic cavity.1,2 In such macrocycles, secondary inꢀ
teractions of the cavity with substrates and reagents beꢀ
come possible, thus making catalytic processes more effiꢀ
cient and selective. Specific catalytic properties have been
discovered with both macrocycles containing phosphine
sites at the periphery of the cavity (such as phosphinoꢀ
cyclodextrins,3,4 phosphinocalixarenes,5 and cyclophanes
with exocyclic phosphino groups (e.g., PhanePhos6) and
compounds with P atoms in the macrocycle itself.1,2 In
addition, phosphorusꢀcontaining macrocycles are of inꢀ
terest for design of supramolecular systems: receptors and
sensors with specific properties.7,8 From either point of
view, cyclophanes with tricoordinate phosphorus atoms
in the macrocycles composed of aromatic building blocks
(e.g., mꢀ and pꢀarylene fragments capable of forming deep
hydrophobic cavities) are attractive. However, despite a
great number of known Pꢀcontaining macrocycles, deꢀ
* Dedicated to Academician G. A. Abakumov on the occasion
of his 70th birthday.
** Institut für anorganische Chemie der Universität Leipzig,
29 Johannisallee, Dꢀ04103 Leipzig, Germany.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1765—1774, September, 2007.
1066ꢀ5285/07/5609ꢀ1828 © 2007 Springer Science+Business Media, Inc.

Paracyclophanes with P,Nꢀcontaining spacers
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 9, September, 2007
1829
Scheme 1
propriate diimines with NaBH4 in ethanol as described
for bis[4ꢀ(2ꢀpyridylmethyl)aminophenyl]methane22
(Scheme 1).
Condensation of bis(hydroxymethyl)phenylꢀ and
bis(hydroxymethyl)mesitylphosphines with secondary diꢀ
amines 1—3 was carried out in DMF at 100—110 °C
(for 1) or room temperature (2, 3); the concentrations of
the starting reagents were 0.1—0.3 mol L–1. The roomꢀ
temperature conditions were found to be optimum for
diamines 2 and 3, though the reaction time in the case
of compound 2 was substantially longer (22 days). The
long reaction time allowed monitoring of its course
by 31P NMR spectroscopy. At early reaction steps (after
1—2 days), the 31P NMR spectra of the reaction mixture
contained, along with a signal at δ –19.70 for the starting
bis(hydroxymethyl)phenylphosphine, a signal at δ –28.50,
probably due to the corresponding (aminomethyl)(hydrꢀ
oxymethyl)phenylphosphine (A).18 Later, the spectra
showed a signal at δ –33.50 for the corresponding
bis(aminomethyl)phenylphosphine (B)18 and a signal at
δ –38.25 that became dominant at the final reaction step
and related to the target macrocyclic aminomethylꢀ
phosphine (Scheme 2).
R =
(2),
(3)
thane 4 (see Ref. 20) was also employed as a starting
reagent since structurally similar anthranilic acid reacts
with hydroxymethylphosphines as a secondary amine beꢀ
cause of strong intramolecular hydrogen bonding between
the carboxy and amino groups.21
The starting diamines 1 and 4 were prepared by acidꢀ
promoted reactions of formaldehyde with Nꢀmethylaniline
and anthranilic acid, respectively (see Refs 19, 20).
Earlier unknown bis[4ꢀ(3ꢀpyridylmethyl)aminopheꢀ
nyl]methane (2) and bis[4ꢀ(4ꢀpyridylmethyl)aminopheꢀ
nyl]methane (3) were synthesized by reduction of apꢀ
It should be noted that the reaction steps were poorly
distinguishable. In the spectra of the final reaction mixꢀ
tures, one or two closely spaced signals at δ –37 to –42
were vastly dominant. The relative contents of the correꢀ
sponding reaction products were 70—85%; in addition,
the spectra contained lowꢀintensity signals in the same
range and, in the case of bis(hydroxymethyl)mesitylꢀ
phosphine, signals at δ –95 to –105 due to unidentified
secondary phosphines resulting from successive dissociaꢀ
tion and amination of the starting Pꢀcontaining diol. The
contents of these byꢀproducts were 20—30% and we had
Scheme 2
R =
, R´ = Me (5); R =
, R´ =
(6); R =
, R´ =
(7)

1830
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 9, September, 2007
Ignat´eva et al.
much difficulty in removing them. As the result, only
macrocyclic products 5 and 6 were isolated in the indiꢀ
vidual state. Their yields were 21 and 67%, respectively.
Compound 7 was obtained as a very viscous oil containꢀ
ing the target product (~85%) and unidentified oligoꢀ
meric aminomethylphosphines.
The positiveꢀion MALDI TOF mass spectrum of comꢀ
pound 5 showed a molecular ion peak with m/z 804
corresponding to the condensation product 3,21ꢀdiꢀ
mesitylꢀ1,5,19,23ꢀtetramethylꢀ1,5,19,23ꢀtetraazaꢀ3,21ꢀ
diphospha[5.1.5.1]paracyclophane and peaks with m/z 827
and 843 due to the ions [M + Na]+ and [M + K]+ respecꢀ
tively; no peaks with higher m/z values were detected.
Like the spectrum of the reaction mixture, the 31P NMR
spectrum of compound 5 contained two closely spaced
signals at δ —41.25 and –41.30. They suggest that cycloꢀ
phane 5 is a mixture of the cisꢀ and transꢀstereoisomers.
The 1H NMR spectrum of compound 5 exhibited a double
set of signals almost for all types of protons; the ratio of
the major and minor isomers was 1.3 : 1.
The major transꢀstereoisomer of the macrocyclic
diphosphine 5 was isolated in the individual state by second
fractional recrystallization of a mixture of its isomers
from DMF. The structure of compound 5 was deterꢀ
mined by 1D and 2D NMR correlation experiments
1
1
(1H—1H COSY, H—13C HSQC, and H—13C/1H—15N
HMBC).23
First, the protons of separate spin systems were distinꢀ
guished from 2D COSY data. Then, the carbon atoms
attached to these protons were located from the 2D HSQC
1
1
spectrum. Finally, the H—13C and H—15N 2D HMBC
data (Fig. 1) were used to integrate the fragments. Thus,
C(8)Me
H(1A),
H(3)
H(4)
C(10)Me
H(1B)
H(9)
H(6A)
H(6B)
δ
C(10)Me
C(8)Me
H(9)/C(10)Me
20
H(9)/C(8)Me
H(6)/NMe
NMe
40
H(3)/C(1)
C(1)
60
80
100
120
140
160
H(3)/C(4)
C(4)
C(3)
H(1)/C(3)
H(1)/C(2)
C(8)Me/C(7)
C(10)Me/C(10)
H(6)/C(7)
H(4)/C(2)
C(2)
C(7)
H(9)/C(7)
C(10)
C(8)
C(5)
C(8)Me/C(8)
H(6)/C(5)
H(3)/C(5)
8
7
6
5
4
3
δ
Fig. 1. 1H —13C 2D HMBC NMR spectrum and a scheme of key correlations for the transꢀisomer of compound 5; 1H→13C and
1H→15N crossꢀcorrelations are indicated with solid and dashed arrows, respectively.

Paracyclophanes with P,Nꢀcontaining spacers
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 9, September, 2007
1831
C(22)
C(18)
C(23)
C(17)
P(1)
C(15)
C(19)
C(20)
C(11)
C(10)
C(26)
C(12)
C(16)
N(2)
C(13)
C(14)
C(21)
C(24)
C(25) C(3)
C(2)
C(4)
C(5)
C(9)
C(1)
N(1)
C(7)
C(6)
C(8)
Fig. 2. Molecular geometry of the transꢀisomer of cyclophane 5 in the crystal. The hydrogen atoms are omitted for clarity. The thermal
displacement ellipsoids are shown at 50% probability.
Table 1. Selected geometrical parameters in structure 5
Bond
d/Å
Bond angle
ω/deg
Torsion angle
τ/deg
P(1)—C(16)
P(1)—C(1)
1.849(4)
1.868(4)
1.871(4)
1.410(5)
1.456(6)
1.458(5)
1.394(5)
1.440(5)
1.451(5)
1.382(6)
1.401(6)
1.374(6)
1.512(6)
1.505(6)
1.388(6)
1.381(6)
1.395(6)
1.410(6)
1.384(6)
1.365(6)
1.508(6)
1.507(6)
C(16)—P(1)—C(1)
C(16)—P(1)—C(15´)
C(1)—P(1)—C(15´)
C(2)—N(1)—C(25)
C(2)—N(1)—C(1)
C(25)—N(1)—C(1)
C(12)—N(2)—C(15)
C(12)—N(2)—C(26)
C(15)—N(2)—C(26)
N(1)—C(1)—P(1)
103.7(2)
104.5(2)
101.4(2)
117.0(4)
116.9(3)
112.3(4)
119.8(4)
118.8(4)
115.4(4)
112.7(3)
123.0(4)
123.9(4)
118.8(4)
121.6(4)
113.5(3)
126.2(3)
115.6(3)
122.3(4)
118.4(4)
120.8(5)
121.7(5)
117.0(4)
123.8(4)
C(15´)—P(1)—C(1)—N(1)
P(1)—C(1)—N(1)—C(25)
P(1)—C(1)—N(1)—C(2)
C(1)—N(1)—C(2)—C(7)
N(1)—C(2)—C(7)—C(6)
C(7)—C(6)—C(5)—C(8)
C(6)—C(5)—C(8)—C(9)
C(5)—C(8)—C(9)—C(10)
C(8)—C(9)—C(10)—C(11)
C(10)—C(11)—C(12)—N(2)
C(11)—C(12)—N(2)—C(15)
C(12)—N(2)—C(15)—P(1´)
C(26)—N(2)—C(15)—P(1´)
N(2)—C(15)—P(1´)—C(1´)
C(1)—P(1)—C(16)—C(17)
P(1)—C(16)—C(17)—C(22)
C(15´)—P(1)—C(16)—C(17)
P(1)—C(16)—C(21)—C(24)
111.4(4)
68.9(4)
P(1)—C(15´)
N(1)—C(2)
N(1)—C(25)
N(1)—C(1)
N(2)—C(12)
N(2)—C(15)
N(2)—C(26)
C(2)—C(3)
C(3)—C(4)
C(4)—C(5)
C(5)—C(8)
C(8)—C(9)
C(9)—C(10)
C(10)—C(11)
C(11)—C(12)
C(16)—C(17)
C(17)—C(18)
C(18)—C(19)
C(17)—C(22)
C(19)—C(23)
–70.5(4)
–50.5(4)
–175.0(4)
174.3(4)
166.4(4)
–60.4(3)
–174.6(3)
–177.7(3)
–25.2(4)
–66.3(4)
86.3(43)
172.6(4)
133.5(5)
–3.5(5)
C(3)—C(2)—N(1)
C(4)—C(5)—C(8)
C(9)—C(8)—C(5)
N(2)—C(12)—C(11)
N(2)—C(15)—P(1´)
C(21)—C(16)—P(1)
C(17)—C(16)—P(1)
C(16)—C(17)—C(22)
C(18)—C(17)—C(22)
C(20)—C(19)—C(23)
C(18)—C(19)—C(23)
C(20)—C(21)—C(24)
C(16)—C(21)—C(24)
–120.6(5)
–1.3(4)
we determined the structure of the key fragment of the
macrocycle.
dence for its centrosymmetric structure of the transꢀisoꢀ
mer. The transꢀ5 (Fig. 2; Table 1) contrasts with earlier
reported cageꢀtype cyclophanes in molecular strucꢀ
ture.17,18 1,5(1,5)ꢀDi(1,5ꢀdiazaꢀ3,7ꢀdiphosphacycloꢀ
octana)ꢀ2,4,6,8(1,4)ꢀtetrabenzenacyclooctaphanes posꢀ
sess a cavity like a truncated prism; the phenylene rings
forming its lateral walls are nearly perpendicular to the
basal plane of the macrocycle defined by the N atoms;
i.e., the diphenylenemethane fragments are in the "open
book" conformation.17,18 Structure 5 is centrosymmetric;
all the N atoms are also coplanar, while the P atoms with
the attached mesityl substituents lie on each side of the
plane. In the spacer N—C—P—C—N, one methyl group
has a pseudoaxial orientation, while the other has a
pseudoequatorial one.
To confirm our assignments of the signals for the
atoms of the macrocycle, we additionally carried out
ab initio calculations of the 13C chemical shifts
(GIAO RB3LYP/6ꢀ31G(d)//RHF/6ꢀ31G24)*. The calꢀ
culated data were in full agreement with the experiment
(R2 = 0.9986, RMS = 5.9, MAD = 5.2, a = 0.934), which
verified the conclusions about the chemical structure.
Singleꢀcrystal Xꢀray diffraction analysis of the indiꢀ
vidual stereoisomer of compound 5 provided cogent eviꢀ
* The chemical shifts were calculated for the key fragment of the
molecule with additional terminal substituents modeling the subꢀ
stituents in the macrocycle.

1832
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 9, September, 2007
Ignat´eva et al.
1
In contrast to the aforementioned cageꢀtype cycloꢀ
phanes, in which the N atoms are strongly conjugated
with the π systems of the phenylene rings,17,18 the conꢀ
figuration of two N atoms bearing the pseudoaxial subꢀ
stituents in structure 5 is intermediate between planar and
tetrahedral (the sum of the bond angles at these atoms
is 346.2°). This suggests a lower degree of conjugation.
The torsion angle between the planes of the adjacent pheꢀ
nylene rings is 69.7°. One pair of the opposite phenylene
fragments makes an angle of 73.1° with the planes of the
four N atoms, while the analogous angle for the other pair
is 138.6°. This conformation of the macrocycle is typical
of [n.1.n.1]paracyclophanes;25—27 e.g., a close structure
with nearly perpendicular adjacent aromatic rings and a
virtually collapsed cavity of the macrocycle has been found
for 2,18ꢀbis(diethylamino)ꢀ10,10,26,26ꢀtetramethylꢀ
1,3,17,19ꢀtetraoxaꢀ2,18ꢀdiphospha[3.1.3.1]paracycloꢀ
phane, in which similar diphenylenemethane fragꢀ
ments are linked by O—P—O spacers.16 Structure 5 is
elongated: the distance between the P atoms is 11.80 Å,
while the distance between the planes of the opposite
aromatic rings C(2)—C(3)—C(4)—C(5)—C(6)—C(7) and
C(2´)—C(3´)—C(4´)—C(5´)—C(6´)—C(7´), which give
the cavity walls, is only 5.85 Å. (For the aforementioned
macrocyclic bis(phosphoramidite)16 and the cageꢀtype
1,5(1,5)ꢀdi(1,5ꢀdiazaꢀ3,7ꢀdiphosphacyclooctana)ꢀ
2,4,6,8(1,4)ꢀtetrabenzenacyclooctaphanes,18 the latter
distance is 7.7 and 8.7 Å, respectively.) It should be noted
that the equivalence of all the phenylene rings and the
tively. Their H NMR spectra contain a double set of
signals almost for all proton types and, consequently, part
of the signals are complex multiplets. The integral intenꢀ
1
sity ratio of different groups of the H NMR signals sugꢀ
gests that compounds 6 and 7 are mixtures of the transꢀ and
cisꢀstereoisomers 3,21ꢀdiphenylꢀ1,5,19,23ꢀtetrakis(3ꢀ
pyridylmethyl)ꢀ and ꢀ1,5,19,23ꢀtetrakis(4ꢀpyridylmethyl)ꢀ
1,5,19,23ꢀtetraazaꢀ3,21ꢀdiphospha[5.1.5.1]paracycloꢀ
phanes, respectively. The ratio of the major and minor
stereoisomers was estimated from the intensities of the
best resolved doublets for the protons of the phenylene
groups that are ortho to the N atoms. This ratio was 3 : 1
for compound 6 and 1.5 : 1 for compound 7. Analogous
cis—trans stereoisomerism has been found in macrocyclic
diphosphites obtained from various bisphenols.16 Howꢀ
ever, compounds 6 and 7 were unstable for mass spectroꢀ
metric analysis.
For more reliable determination of the structure and
the ring size, diphosphines 6 and 7 were converted into
the corresponding diphosphine disulfides 8 and 9 via treatꢀ
ment with elemental sulfur in DMF (Scheme 3).
The MALDI TOF mass spectra of compounds 8
and 9 contain peaks with m/z 1093 corresponding to the
[M + H]+ ions of the [2+2] adducts 3,21ꢀdiphenylꢀ
1,5,19,23ꢀtetrakis(3ꢀpyridylmethyl)ꢀ and ꢀ1,5,19,23ꢀtetꢀ
rakis(4ꢀpyridylmethyl)ꢀ3,21ꢀdithioꢀ1,5,19,23ꢀtetraazaꢀ
3,21ꢀdiphospha[5.1.5.1]paracyclophanes.
No peaks with higher m/z values were observed. The
31P NMR spectra of compounds 8 and 9 show a narrow
signal at δ 40.76 and 40.10, respectively. However,
a double set of signals in the 1H NMR spectrum of disulꢀ
fide 9 suggests the presence of the transꢀ and cisꢀdiastereoꢀ
mers in the ratio 2.6 : 1; some signals for the minor isomer
are noticeably broadened. In contrast, disulfide 8 was
1
methyl groups at the N atoms in the H NMR spectra of
cyclophane 5 suggests possible rapid dynamic equilibrium
between its conformers in solutions.
The 31P NMR spectra of compounds 6 and 7 show a
signal at δ –40.31 (CDCl3) and –37.66 (DMF), respecꢀ
Scheme 3
R =
, R´ =
(6, 8);
(7, 9)

Paracyclophanes with P,Nꢀcontaining spacers
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 9, September, 2007
1833
Table 2. Bond lengths in the transꢀisomer of compound 5
Scheme 4
Bond
d/Å
Bond
d/Å
P(1)—C(16)
P(1)—C(1)
P(1)—C(15´)
N(1)—C(2)
N(1)—C(25)
N(1)—C(1)
N(2)—C(12)
N(2)—C(15)
N(2)—C(26)
C(2)—C(3)
C(2)—C(7)
C(3)—C(4)
C(4)—C(5)
C(5)—C(6)
C(5)—C(8)
C(6)—C(7)
C(8)—C(9)
1.849(4)
1.868(4)
1.871(4)
1.410(5)
1.456(6)
1.458(5)
1.394(5)
1.440(5)
1.451(5)
1.382(6)
1.396(6)
1.401(6)
1.374(6)
1.380(6)
1.512(6)
1.373(6)
1.505(6)
C(9)—C(14)
C(9)—C(10)
C(10)—C(11)
C(11)—C(12)
C(12)—C(13)
C(13)—C(14)
C(15)—P(1´)
C(16)—C(21)
C(16)—C(17)
C(17)—C(18)
C(17)—C(22)
C(18)—C(19)
C(19)—C(20)
C(19)—C(23)
C(20)—C(21)
C(21)—C(24)
1.370(6)
1.388(6)
1.381(6)
1.395(6)
1.396(6)
1.386(6)
1.871(4)
1.408(6)
1.410(6)
1.384(6)
1.508(6)
1.365(6)
1.373(6)
1.507(6)
1.389(6)
1.510(6)
isolated as one stereoisomer (1H NMR data). The correꢀ
sponding protons of the phenylene, methylene, and
pyridyl fragments are equivalent and their signals are not
broadened, which suggests a symmetrical transꢀstructure of
this isomer. Most likely, the stereoisomers of diphosphines
6 and 7 we isolated are also transꢀdiastereomers. Apparꢀ
ently, the predominant formation of [2+2] adducts is due
to spatial complementarity of their constituent di(pꢀpheꢀ
nylene)methane spacers and bis(aminomethyl)phosphine
fragments. It should be noted that reactions of bisphenols
containing analogous spacers with various bifunctional
phosphorusꢀcontaining reagents also occurs mainly as
[2+2] macrocyclization, although under high or pseudoꢀ
high dilution.12,13,15,16
As expected, the major product of condensation of
bis(hydroxymethyl)mesitylphosphine with bis(4ꢀaminoꢀ
3ꢀcarboxyphenyl)methane was also the corresponding
1,5,19,23ꢀtetraazaꢀ3,21ꢀdiphospha[5.1.5.1]paracycloꢀ
phane 10 (Scheme 4). The yield of compound 10 was 72%;
it is resistant to oxidation in the solid state and in soluꢀ
Table 3. Bond angles in the transꢀisomer of compound 5
Angle
ω/deg
Angle
ω/deg
Angle
ω/deg
C(16)—P(1)—C(1)
C(16)—P(1)—C(15´)#
С(1)—Р(1)—С(15´)#
C(2)—N(1)—C(25)
C(2)—N(1)—C(1)
C(25)—N(1)—C(1)
C(12)—N(2)—C(15)
C(12)—N(2)—C(26)
C(15)—N(2)—C(26)
N(1)—C(1)—P(1)
C(3)—C(2)—C(7)
C(3)—C(2)—N(1)
C(7)—C(2)—N(1)
C(2)—C(3)—C(4)
C(5)—C(4)—C(3)
C(4)—C(5)—C(6)
103.7(2)
104.5(2)
101.4(2)
117.0(4)
116.9(3)
112.3(4)
119.8(4)
118.8(4)
115.4(4)
112.7(3)
117.2(4)
123.0(4)
119.6(4)
120.7(4)
121.7(4)
117.0(4)
C(4)—C(5)—C(8)
C(6)—C(5)—C(8)
C(7)—C(6)—C(5)
C(6)—C(7)—C(2)
C(9)—C(8)—C(5)
C(14)—C(9)—C(10)
C(14)—C(9)—C(8)
C(10)—C(9)—C(8)
C(11)—C(10)—C(9)
C(10)—C(11)—C(12)
N(2)—C(12)—C(11)
N(2)—C(12)—C(13)
C(11)—C(12)—C(13)
C(14)—C(13)—C(12)
C(9)—C(14)—C(13)
123.9(4)
119.0(4)
122.3(4)
121.0(4)
118.8(4)
117.2(4)
121.5(4)
121.1(4)
121.5(4)
121.4(4)
121.6(4)
121.4(4)
117.0(4)
120.6(4)
122.4(5)
N(2)—C(15)—P(1´)#
C(21)—C(16)—C(17)
C(21)—C(16)—P(1)
C(17)—C(16)—P(1)
C(18)—C(17)—C(16)
C(18)—C(17)—C(22)
C(16)—C(17)—C(22)
C(19)—C(18)—C(17)
C(18)—C(19)—C(20)
C(18)—C(19)—C(23)
C(20)—C(19)—C(23)
C(19)—C(20)—C(21)
C(20)—C(21)—C(16)
C(20)—C(21)—C(24)
C(16)—C(21)—C(24)
113.5(3)
118.2(4)
126.2(3)
115.6(3)
119.3(4)
118.4(4)
122.3(4)
123.0(4)
117.5(4)
121.7(5)
120.8(5)
122.7(4)
119.2(4)
117.0(4)
123.8(4)
# The symmetry operation code used to generate the equivalent atoms is –x + 1, –y, –z + 1.

1834
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 9, September, 2007
Ignat´eva et al.
(Nujol) in the 400—4000 cm–1 range. MALDI TOF mass specꢀ
tra were recorded on a MALDI TOFꢀDYNAMO spectrometer
with the tetrahydroxyanthracene (THA) matrix. The starting
phenylꢀ29 and mesitylphosphines30 were prepared according to
known procedures. All manipulations with phosphines were carꢀ
ried out in an inert atmosphere. Dimethylformamide was dried
and twice distilled in vacuo over P2O5; other solvents were puriꢀ
fied in common ways.
tions. This diphosphine was oxidized only under the conꢀ
ditions of the MALDI TOF experiment; the mass specꢀ
trum contains two peaks with m/z 1057 and 1073 due to
the ions [M + O + 3 K]+ and [M + 2 O + 3 K]+; no peaks
with higher m/z values were observed. Like macrocyclic
compounds 5—7, cyclophane 10 was isolated as a mixture
of the cisꢀ and transꢀdiastereomers, which is evident from
1
a double set of signals in its H NMR spectrum. Part of
Xꢀray diffraction data for compound 5. Single crystals of comꢀ
pound 5 were obtained by crystallization from DMF. Crystals
are monoclinic, C52H62N4P2, M = 805.00. At 210(2) K, a =
19.047(8) Å, b = 10.336(5) Å, c = 11.533(5) Å, α = 90°,
the signals appear as superimposed singlets or complex
multiplets resulting from stereoisomerism; the ratio of the
major (trans) and minor (cis) stereoisomers was 1.4 : 1.
The 31P NMR spectrum of compound 10 exhibits a sigꢀ
nal at δ –29.00. Its IR spectrum shows a wide band
(νmax = 3360 cm–1) due to the amino group and wide
bands due to the carboxy group (νmax = 1660 (C=O) and
3100 cm–1 (OH)). The band character and positions sugꢀ
gest that the amino and carboxy groups are linked by
strong hydrogen bonds. The presence of four carboxy
groups makes compound 10 soluble in aqueous NaOH.
The formation of macrocyclic structure 10 rather than a
cageꢀtype cyclophane, as in the condensation of other
primary diamines with bis(hydroxymethyl)organylphosꢀ
phines,17,18 can be explained by deactivation of the amino
groups with strong hydrogen bonds.
Spontaneous closure of macrocycles from four buildꢀ
ing blocks at relatively high concentrations of the starting
reagents and in the absence of templates allows these
reactions to be considered covalent selfꢀassembly proꢀ
cesses leading to selective formation of the thermoꢀ
dynamically most stable reaction products.28 This was
additionally confirmed by the fact that macrocyclization
proceeds through a great number of coexisting intermediꢀ
ates that gradually transform themselves into the most
stable dimeric macrocycle. According to the data obꢀ
tained, the formation of 1,5,19,23ꢀtetraazaꢀ3,21ꢀdiꢀ
phospha[5.1.5.1]paracyclophanes as major products
in reactions of bis(hydroxymethyl)organylphosphines
with secondary diamines containing di(pꢀphenylene)meꢀ
thane spacers is of general character and can be conꢀ
sidered a route to this novel class of macrocyclic comꢀ
pounds.
β = 99.861(8)°, γ = 90°, V = 2236.9 Å3, dcalc = 1.195 g cm–1
,
Z = 2, space group P2(1)/c (special position of the molecule in
the center of symmetry). The unit cell parameters and the inꢀ
tensities of 7946 reflections (2535 reflections with I > 2σ)
were measured on a Siemens CCD SMART diffractometer
(λMoꢀKα radiation (λ = 0.71073 Å), graphite monochromator,
ω scan mode, 2.25 < θ < 23.15°). The data obtained were proꢀ
cessed with the SAINT program.31 Absorption correction was
empirically applied with the SADABS program32 (µMo =
1.37 cm–1). The structure was solved by the direct method and
refined in the anisotropic approximation with the SHELXꢀ97
programs.33 Hydrogen atoms were located in the calculated posiꢀ
tions. The image of molecular structure 5 was depicted with the
ORTEP program.34 Final residuals were R1(I > 2σ(I )) = 0.0877
and wR2(I > 2σ(I )) = 0.1442 for 2535 independent reflections
with I 2 > 2σ and R1 = 0.1214 and wR2 = 0.1540 for all reflecꢀ
tions. Atomic coordinates, bond lengths and angles, and therꢀ
mal parameters have been deposited with the Cambridge Crysꢀ
tallographic Data Center (CCDC).
Bis[4ꢀ(3ꢀpyridylmethyl)aminophenyl]methane (2). A solution
of pyridineꢀ3ꢀcarbaldehyde (2.16 g, 20.18 mmol) in anhydrous
ethanol (10 mL) was added to a solution of bis(4ꢀaminoꢀ
phenyl)methane (2 g, 10.1 mmol) in anhydrous ethanol (20 mL).
The reaction mixture was stirred at room temperature for 20 h.
The precipitate that formed was filtered off, washed with ethaꢀ
nol, and dried in vacuo. The yield of bis[4ꢀ(3ꢀpyridylmethylꢀ
idene)aminophenyl]methane was 3.37 g (81%), m.p. 120 °C.
IR, ν/cm–1: 1628 (C=N). 1H NMR (acetoneꢀd6), δ: 4.09 (s,
3
2 H, H(1)); 7.26 (d, 4 H, H(3), JH(4),H(3) = 8.7 Hz); 7.33
3
(d, 4 H, H(4), JH(3),H(4) = 8.7 Hz); 7.50 (dd, 2 H, H(9),
3
3JH(10).H(9) = 8.0 Hz, JH(8),H(9) = 4.6 Hz); 8.35 (ddd, 2 H,
4
H(10), 3JH(9),H(10) = 8.0 Hz, 4JH(8),H(10) ≈ JH(11),H(10) ≈ 2.0 Hz);
8.66—8.71 (m, 4 H, H(6) + H(8)); 9.08 (d, 2 H, H(11),
4JH(10),H(11) = 2.0 Hz).
A
solution of bis[4ꢀ(3ꢀpyridylmethylidene)aminopheꢀ
Experimental
nyl]methane (2.73 g, 7.28 mmol) in anhydrous ethanol (50 mL)
was added to a suspension of NaBH4 (0.41 g, 10.78 mmol) in
anhydrous ethanol (20 mL). The reaction mixture was stirred at
60 °C for 5 h and left for 16 h. The solvent was removed in vacuo
and the solid residue was washed with diethyl ether and recrysꢀ
tallized from acetonitrile. The yield of compound 2 was 1.85 g
(67%), m.p. 116 °C. Found (%): C, 78.47; H, 6.54; N, 14.28.
25H24N4. Calculated (%): C, 78.95; H, 6.31; N, 14.74. IR,
ν/cm–1: 3264 (N—H). 1H NMR (CD3CN), δ: 3.64 (s, 2 H,
H(1)); 4.29 (br.s, 2 H, H(6)A); 4.31 (br.s, 2 H, H(6)B); 4.83
(br.s, 2 H, NH); 6.53 (d, 4 H, H(4), JH(3),H(4) = 8.3 Hz);
All NMR experiments were carried out at 303 K. 31P NMR
spectra were recorded on Bruker MSL 400 (161.98 MHz) and
CXPꢀ100 spectrometers (36.47 MHz). 1H NMR spectra were
recorded on Bruker AVANCE 600 (600.13 MHz, wideꢀline
5ꢀmm probe) and Bruker MSL 400 spectrometers (400.13 MHz).
13C and 15N NMR spectra were recorded on a Bruker
AVANCE 600 spectrometer (150.90 (13C) and 60.81 MHz
C
(
15N)). Chemical shifts are given on the δ scale with reference to
SiMe4 (δ 0.0 (1H) and 0.0 (13C)), CH3CN (δ 239.5 (15N)), and
H3PO4 (δ 0.0 (31P)). The 2D HMBC experiment was optimized
for the coupling constants JH,C = 9.0 Hz and JH,N = 8.0 Hz.
IR spectra were recorded on a Bruker Vectorꢀ22 spectrometer
3
3
6.92 (d, 4 H, H(3), JH(4),H(3) = 8.3 Hz); 7.27 (dd, 2 H,
H(9), JH(8),H(9) = 7.3 Hz, JH(10),H(9) = 4.7 Hz); 7.69 (br.d,
2 H, H(8), JH(9),H(8) = 7.3 Hz); 8.43 (dd, 4 H, H(10),
3
3
3

Paracyclophanes with P,Nꢀcontaining spacers
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 9, September, 2007
1835
4
3JH(9),H(10) = 4.7 Hz, JH(11),H(10) = 1.3 Hz); 8.56 (d, 2 H,
The mixture of stereoisomers 5 (0.08 g) was recrystallized
from DMF under slow cooling. The precipitate was filtered off,
washed with ethanol, and dried in vacuo (0.1 Torr) for 4 h. The
yield of transꢀ5 was 0.02 g, m.p. 167—170 °C. 1H NMR
(DMFꢀd7), δ: 2.29 (s, 6 H, C(10)—CH3); 2.33 (s, 12 H,
C(8)—CH3); 2.90 (s, 12 H, N—CH3); 3.57 (d, 2 H, H(1)A,
4
H(11), JH(10),H(11) = 1.3 Hz).
Bis[4ꢀ(4ꢀpyridylmethylidene)aminophenyl]methane was obꢀ
tained as described above from bis(4ꢀaminophenyl)methane (5 g,
25.2 mmol) and pyridineꢀ4ꢀcarbaldehyde (5.4 g, 50.5 mmol).
The yield was 8.2 g (86%), m.p. 133 °C. IR, ν/cm–1: 1629
1
2
(C=N). H NMR (acetoneꢀd6), δ: 4.05 (s, 2 H, H(1)); 7.29 (d,
2JH,H = 14.1 Hz); 3.62 (d, 2 H, H(1)B, JH,H = 14.1 Hz); 4.11
4 H, H(3), 3JH(4),H(3) = 8.2 Hz); 7.34 (d, 4 H, H(4), 3JH(3),H(4)
=
(dd, 4 H, H(6)A, JH,H = 15.0 Hz, JH,P = 1.5 Hz); 4.37 (dd,
2
2
3
2
2
8.2 Hz); 7.83 (d, 4 H, H(8), JH(9),H(8) = 5.8 Hz); 8.65 (s, 2 H,
H(6)); 8.73 (d, 4 H, H(9), JH(8),H(9) = 5.8 Hz).
4 H, H(6)B, JH,H = 15.0 Hz, JH,P = 2.2 Hz); 6.40 (d, 8 H,
3
3
3
H(4), JH(3),H(4) = 8.7 Hz); 6.94 (d, 8 H, H(3), JH(4),H(3) =
8.7 Hz); 6.96 (s, 4 H, H(9)). 13C{1H} NMR (DMFꢀd7), δ: 20.93
(s, C(10)—CH3); 23.53 (d, C(8)—CH3, 3JC,P = 16.3 Hz); 39.90
Bis[4ꢀ(4ꢀpyridylmethyl)aminophenyl]methane (3) was
obtained analogously from NaBH4 (0.61 g, 16.05 mmol)
and bis[4ꢀ(4ꢀpyridylmethylidene)aminophenyl]methane (4 g,
10.63 mmol). The reaction time was 10 h. The yield of comꢀ
pound 3 recrystallized from acetone was 3.6 g (89%), m.p. 63 °C.
Found (%): C, 78.55; H, 6.61; N, 14.32. C25H24N4. Calcuꢀ
lated (%): C, 78.95; H, 6.31; N, 14.74. IR, ν/cm–1: 3285
(N—Hbound); 3415 (N—Hfree). 1H NMR (CDCl3), δ: 3.73 (s,
2 H, H(1)); 4.23 (br.s, 2 H, NH); 4.29—4.33 (m, 4 H, H(6));
1
(s, N—CH3); 40.68 (s, C(1)); 55.11 (d, C(6), JC,P = 18.3 Hz);
113.91 (s, C(4)); 129.36 (s, C(3)); 130.09 (s, C(9)); 131.02
1
(s, C(2)); 132.50 (d, C(7), JC,P = 25.9 Hz); 139.68 (s, C(10));
2
144.85 (d, C(8), JC,P
= 13.7 Hz); 147.50 (s, C(5)).
31P{1H} NMR (DMFꢀd7), δ: –41.25. 15N NMR (DMFꢀd7),
δ: 49.00.
3,21ꢀDiphenylꢀ1,5,19,23ꢀtetra(3ꢀpyridylmethyl)ꢀ1,5,19,23ꢀ
tetraazaꢀ3,21ꢀdiphospha[5.1.5.1]paracyclophane (6). A mixture
of phenylphosphine (0.8 g, 7.27 mmol) and paraformaldehyde
(0.43 g, 14.33 mmol) was stirred at 90—100 °C to homogenizaꢀ
tion, cooled, and dissolved in dry degassed DMF (5 mL). Then a
solution of diamine 2 (2.74 g, 7.21 mmol) in DMF (22 mL) was
added. The reaction mixture was stirred at room temperature for
22 days. Volatile components were removed in vacuo and the
residue was stirred with diethyl ether. The resulting powdery
precipitate was filtered off, washed with ether, and dried in vacuo
(0.1 Torr) for 4 h. The yield of compound 6 as a 3 : 1 mixture
of the transꢀ and cisꢀstereoisomers was 2.5 g (67%), m.p.
117—120 °C. Found (%): C, 76.74; H, 6.31; N, 10.61; P, 5.91.
3
6.47 (d, 4 H, H(4), JH(3),H(4) = 8.2 Hz); 6.95 (d, 4 H, H(3),
3JH(4),H(3) = 8.2 Hz); 7.26 (d, 4 H, H(8), JH(9),H(8) = 5.5 Hz);
8.51 (d, 4 H, H(9), JH(8),H(9) = 5.5 Hz).
3
3
3,21ꢀDimesitylꢀ1,5,19,23ꢀtetramethylꢀ1,5,19,23ꢀtetraꢀ
azaꢀ3,21ꢀdiphospha[5.1.5.1]paracyclophane (5). A mixture of
mesitylphosphine (1.13 g, 7.43 mm) and paraformaldehyde
(0.45 g, 15 mmol) was stirred at 100—115 °C to homogenizaꢀ
tion, cooled, and dissolved in dry degassed DMF (15 mL). Then
a solution of diamine 1 (1.68 g, 7.43 mmol) in DMF (9 mL) was
added. The reaction mixture was stirred at 110 °C for 48 h and
concentrated in vacuo to one third of its volume. Acetonitrile
(20 mL) was added. The liquid over the resulting viscous colorꢀ
less resin was decanted and volatile components were removed
in vacuo. The residue was dissolved in a minimum amount of
DMF and again reprecipitated. The resulting glassy residue was
stirred with ethanol (30 mL) at room temperature for a day. The
white powdery precipitate that formed was filtered off, washed
with ethanol, dried in vacuo (0.1 Torr) for 3 h, and recrystallized
from DMF. The resulting fine crystalline precipitate was filtered
off, washed with DMF and ethanol, and dried in vacuo (0.1 Torr)
for 4 h. The yield of compound 5 as a 1.3 : 1 mixture of the
transꢀ and cisꢀisomers was 0.63 g (21%), m.p. 165—169 °C.
Found (%): C, 77.14; H, 7.89; N, 6.65; P, 7.52. C52H62N4P2.
Calculated (%): C, 77.61; H, 7.71; N, 6.97; P, 7.71.
1H NMR (DMFꢀd7), δ: 2.28 (s, C(10)—CH3ꢀcis); 2.29
(s, C(10)—CH3ꢀtrans) (total intensity
C(8)—CH3ꢀtrans); 2.35 (s, C(8)—CH3ꢀcis) (total intensity
12 H); 2.86 (s, N—CH3ꢀcis); 2.90 (s, N—CH3ꢀtrans) (total inꢀ
tensity 12 H); 3.57 (d, H(1)Aꢀtrans, JH,H = 14.1 Hz); 3.62 (m,
H(1)Bꢀtrans + H(1)Aꢀcis); 3.68 (d, H(1)Bꢀcis, JH,H = 10.7 Hz)
(total intensity 4 H); 4.11 (dd, H(6)Aꢀtrans, JH,H = 15.0 Hz,
2JH,P = 1.5 Hz); 4.14 (br.d, H(6)Aꢀcis, JH,H = 15.4 Hz) (total
intensity 4 H); 4.35 (dd, H(6)Bꢀcis, JH,H = 15.4 Hz, JH,P
3.7 Hz); 4.37 (dd, H(6)Bꢀtrans, 2JH,H = 15.0 Hz, 2JH,P = 2.2 Hz)
C
66H62N8P2. Calculated (%): C, 77.04; H, 6.03; N, 10.90;
P, 6.03. 1H NMR (CDCl3), δ: 3.66—3.83 (m,
H,
H(6)ꢀcis + H(6)ꢀtrans)); 3.86 (br.s, 4 H, H(1)ꢀcis + H(1)ꢀtrans));
4.29—4.43 (m, H, H(11)ꢀcis H(11)ꢀtrans)); 6.54
8
8
+
3
(br.d, H(4)ꢀcis, JH(3),H(4) = 8.0 Hz); 6.62 (d, H(4)ꢀtrans,
3JH(3),H(4) = 7.6 Hz) (total intensity 8 H); 6.94 (br.s, 8 H,
H(3)ꢀcis
+ H(3)ꢀtrans); 7.06 (br.s, 4 H, H(14)ꢀcis +
+ H(14)ꢀtrans), 7.20—7.39 (m, 10 H, H(8) + H(10) + H(13)
(cis + trans)); 7.47 (br.s, 4 H, H(9)ꢀcis + H(9)ꢀtrans); 8.30 (br.s,
4 H, H(16)ꢀcis + H(16)ꢀtrans)); 8.40 (br.s, 4 H, H(15)ꢀcis +
+ H(15)ꢀtrans)). 31P{1H} NMR (CHCl3), δ: –40.31.
3,21ꢀDiphenylꢀ1,5,19,23ꢀtetra(4ꢀpyridylmethyl)ꢀ1,5,19,23ꢀ
tetraazaꢀ3,21ꢀdiphospha[5.1.5.1]paracyclophane (7). A mixture
of phenylphosphine (0.45 g, 4.09 mmol) and paraformaldehyde
(0.25 g, 8.16 mmol) was stirred at 90—100 °C to homogenizaꢀ
tion, cooled, and dissolved in dry degassed DMF (15 mL).
A solution of diamine 3 (1.55 g, 4.07 mmol) in DMF (15 mL)
was added and the reaction mixture was stirred at room temꢀ
perature for a day. Volatile components were thoroughly reꢀ
moved in vacuo. The resulting very viscous oil (2.03 g) was a
1.5 : 1 mixture of transꢀ and cisꢀ7 (85% purity). The yield of
compound 7 was 82%.
6 H); 2.33 (s,
2
2
2
2
2
2
=
3
(total intensity 4 H); 6.40 (d, H(4)ꢀtrans, JH(3)H(4) = 8.7 Hz);
6.48 (d, H(4)ꢀcis, 3JH(3),H(4) = 8.5 Hz) (total intensity 8 H); 6.94
1H NMR (DMFꢀd7), δ: 3.60 (s, H(1)ꢀcis)); 3.62 (s,
H(1)ꢀtrans)) (total intensity 4 H); 4.08—4.23 (m, 8 H,
H(6)ꢀcis + H(6)ꢀtrans); 4.35 (br.d, H(11)Aꢀcis, 2JH,H = 14.0 Hz);
3
(d, 8 H, H(3)ꢀcis + H(3)ꢀtrans, JH(4),H(3) ≈ 8.7 Hz); 6.96 (s,
4 H, H(9)ꢀcis + H(9)ꢀtrans). 31P{1H} NMR (DMFꢀd7), δ: –41.25
(transꢀ5), –41.30 (cisꢀ5). MALDI TOF MS (THA),
m/z (Irel (%)): 804 [M]+ (45), 827 [M + Na]+ (100), 843
[M + K]+ (67).
4.45 (d, H(11)Aꢀtrans, JH,H = 17.8 Hz) (total intensity 4 H);
2
4.57 (d, H(11)Bꢀtrans, 2JH,H = 17.8 Hz); 4.67 (br.d, H(11)Bꢀcis,
2JH,H = 14.0 Hz) (total intensity 4 H); 6.53 (br.d, H(4)ꢀcis,
3
3JH(3),H(4) = 8.2 Hz); 6.64 (d, H(4)ꢀtrans, JH(3),H(4) = 7.6 Hz)

1836
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 9, September, 2007
Ignat´eva et al.
(total intensity 8 H); 6.86—6.95 (m, 8 H, H(3)ꢀcis + H(3)ꢀtrans);
7.08 (br.s, 6 H, H(8) + H(10) (cis + trans)); 7.37 (br.s, 8 H,
H(13)ꢀcis + H(13)ꢀtrans)); 7.73—7.83 (m, 4 H, H(9)ꢀcis +
+ H(9)ꢀtrans); 8.38 (br.s, H(14)ꢀtrans); 8.47 (br.s, H(14)ꢀcis)
(total intensity 8 H). 31P{1H} NMR (DMF), δ: –37.66.
of compound 10 as a 1.3 : 1 mixture of the transꢀ and cisꢀstereoꢀ
isomers was 0.71 g (72%), m.p. 169 °C. Found (%): C, 67.23;
H, 6.08; N, 5.87; P, 7.02. C52H54N4O8P2. Calculated (%):
C, 67.53; H, 5.84; N, 6.06; P, 6.71. IR, ν/cm–1: 1660 br (C=O),
3100 br (OH), 3360 br (N—H). 1H NMR (DMFꢀd7), δ: 2.17
(br.s, C(8)—CH3ꢀtrans); 2.21 (br.s, C(8)—CH3ꢀcis) (total inꢀ
tensity 12 H); 2.48 (br.s, 6 H, C(10)—CH3(cis + trans)); 3.69 (s,
H(1)ꢀcis); 3.71 (s, H(1)ꢀtrans) (total intensity 4 H); 3.85—4.28
(m, 8 H, H(6)ꢀcis + H(6)ꢀtrans); 6.70—6.75 (m, 8 H, H(4)ꢀcis +
+ H(4)ꢀtrans)); 6.80—6.89 (m, 8 H, H(3)ꢀcis + H(3)ꢀtrans);
7.15 (s, H(9)ꢀcis); 7.17 (s, H(9)ꢀtrans) (total intensity 4 H); 7.69
(br.s, 4 H, H(5)ꢀcis + H(5)ꢀtrans). 31P{1H} NMR (DMF),
δ: –30.51. MALDI TOF MS (THA), m/z (Irel (%)): 1057
[M + O + 3 K]+ (100), 1073 [M + 2 O + 3 K]+ (74).
3,21ꢀDiphenylꢀ1,5,19,23ꢀtetra(3ꢀpyridylmethyl)ꢀ3,21ꢀdithioꢀ
1,5,19,23ꢀtetraazaꢀ3,21ꢀdiphospha[5.1.5.1]paracyclophane (8).
Sulfur (0.022 g, 0.68 mmol) was added to a solution of diꢀ
phosphine 6 (0.3 g, 0.29 mmol) in DMF (10 mL). The reaction
mixture was heated to homogenization and kept for 16 h. The
solvent was partially removed in vacuo and the precipitate that
formed was filtered off, washed with diethyl ether, and dried
in vacuo (0.1 Torr) for 2 h. The yield of transꢀ8 was 0.12 g (40%),
m.p. 246 °C. Found (%): C, 72.09; H, 6.01; N, 9.97; P, 5.93;
S, 6.04. C66H62N8P2S2. Calculated (%): C, 72.53; H, 5.68;
N, 10.25; P, 5.67; S, 5.86. 1H NMR (CDCl3), δ: 3.76 (s, 4 H,
This work was financially supported by the Council on
Grants of the President of the Russian Federation (Proꢀ
gram for State Support of Leading Scientific Schools of
the Russian Federation, Grant NShꢀ5148.2006.3), the
Russian Foundation for Basic Research (Project Nos 06ꢀ
03ꢀ32754a and 05ꢀ03ꢀ32558a), the DFG International
Foundation (436RUS17/56/04), and the Volkswagen Inꢀ
ternational Foundation (Grant No. I/82 020).
Products were studied at the NMR Department of the
Federal Collective Spectral Analysis Center for physical
and chemical investigations of the structure, properties,
and composition of matter and materials (CKP SAC) and
the Federal CKP for physical and chemical investigations
of matter and materials (FCKP PCI) (State Contracts of
the Ministry of Education and Science of the Russian
Federation 02.451.11.7036 and 02.451.11.7019).
2
H(1)); 4.18 (d, 4 H, H(11)A, JH,H = 15.5 Hz); 4.27 (d, 4 H,
H(11)B, 2JH,H = 15.5 Hz); 4.43 (d, 4 H, H(6)A, 2JH,H = 17.0 Hz);
2
4.64 (d, 4 H, H(6)B, JH,H = 17.0 Hz); 6.65 (d, 8 H, H(4),
3
3JH(3),H(4) = 8.4 Hz); 6.92 (d, 8 H, H(3), JH(4),H(3) = 8.4 Hz);
3
3
7.09 (dd, 4 H, H(14), JH(13),H(14) = 7.8 Hz, JH(15),H(14)
=
3
4.8 Hz); 7.35 (br.d, 4 H, H(13), JH(14),H(13) = 7.8 Hz); 7.40
(ddd, 4 H, H(9), JH(8),H(9) = 8.0 Hz, JH(10),H(9) = 7.2 Hz,
4JP,H = 2.4 Hz); 7.51 (t, 2 H, H(10), 3JH(9),H(10) = 7.2 Hz); 7.79
(dd, 4 H, H(8), JP,H = 11.4 Hz, JH(9),H(8) = 8.0 Hz); 8.19 (d,
4 H, H(16), JH(15),H(16) = 1.2 Hz); 8.39 (br.d, 4 H, H(15),
3
3
3
3
4
3JH(14),H(15) = 4.8 Hz). 31P{1H} NMR (CDCl3), δ: 40.75.
MALDI TOF MS (THA), m/z (Irel (%)): 1093 [M + H]+ (100).
3,21ꢀDiphenylꢀ1,5,19,23ꢀtetra(4ꢀpyridylmethyl)ꢀ3,21ꢀdithioꢀ
1,5,19,23ꢀtetraazaꢀ3,21ꢀdiphospha[5.1.5.1]paracyclophane (9).
Sulfur (0.04 g, 1.25 mmol) was added to a solution of diphosphine
7 (0.65 g, 0.63 mmol) in DMF (10 mL). The reaction mixture
was heated to homogenization and kept for 16 h. The solvent
was removed in vacuo and the residue was stirred with diethyl
ether at room temperature. The resulting powdery precipitate
was filtered off, washed with ether, and dried in vacuo (0.1 Torr)
for 3 h. The yield of compound 9 as a 2.6 : 1 mixture of the
transꢀ and cisꢀstereoisomers was 0.45 g (65%), m.p. 122—124 °C.
Found (%): C, 72.04; H, 5.92; N, 10.31; P, 5.55; S, 6.21.
C66H62N8P2S2. Calculated (%): C, 72.53; H, 5.68; N, 10.25;
P, 5.67; S, 5.86. 1H NMR (DMFꢀd7), δ: 3.55—4.10 (m, 12 H,
H(1) + H(11) (cis + trans)); 4.60—4.92 (m, 8 H, H(6)ꢀcis +
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+ H(6)ꢀtrans); 6.52 (br.d, H(4)ꢀcis, JH(3),H(4) = 8.2 Hz); 6.69
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Received February 9, 2007;
in revised form April 6, 2007