Molecular Tectonics. Porous Hydrogen-Bonded Networks Built from Derivatives of Pentaerythrityl Tetraphenyl Ether

Article abstract of DOI:10.1021/jo035311h

The symmetric four-armed geometry of pentaerythrityl tetraphenyl ether (5) makes it a valuable starting point for building complex molecular and supramolecular structures. In particular, it provides a core to which multiple sites of attractive intermolecular interaction can be attached, thereby creating compounds predisposed to form complex networks by association. To facilitate exploitation of the pentaerythrityl tetraphenyl ether core in such ways, we have prepared more than 20 new derivatives by efficient methods. Of special interest are compounds 3 and 4, which incorporate four diaminotriazine groups attached to the meta and para positions of the pentaerythrityl tetraphenyl ether core. Crystallization of compounds 3 and 4 from DMSO/dioxane is directed by hydrogen bonding of the diaminotriazine groups according to well-established motifs, thereby producing three-dimensional networks. In forming these networks, each molecule of compound 3 forms a total of 12 hydrogen bonds with six others, whereas each molecule of compound 4 forms a total of 16 hydrogen bonds with four others. Both networks are highly porous and define significant interconnected channels for the inclusion of guests. In crystals of compounds 3 and 4, the fraction of the volume accessible to guests is 66% and 57%, respectively. In both cases, the pentaerythrityl tetraphenyl ether cores adopt conformations that deviate substantially from tetrahedral geometry. It is noteworthy that the inherent flexibility of the core does not favor the formation of close-packed guest-free structures.

Full text of DOI:10.1021/jo035311h

Molecu la r Tecton ics. P or ou s Hyd r ogen -Bon d ed Netw or k s Bu ilt
fr om Der iva tives of P en ta er yth r ityl Tetr a p h en yl Eth er
Dominic Laliberte´,1 Thierry Maris, and J ames D. Wuest*
De´partement de Chimie, Universite´ de Montre´al, Montre´al, Que´bec H3C 3J 7, Canada
wuest@chimie.umontreal.ca
Received September 5, 2003
The symmetric four-armed geometry of pentaerythrityl tetraphenyl ether (5) makes it a valuable
starting point for building complex molecular and supramolecular structures. In particular, it
provides a core to which multiple sites of attractive intermolecular interaction can be attached,
thereby creating compounds predisposed to form complex networks by association. To facilitate
exploitation of the pentaerythrityl tetraphenyl ether core in such ways, we have prepared more
than 20 new derivatives by efficient methods. Of special interest are compounds 3 and 4, which
incorporate four diaminotriazine groups attached to the meta and para positions of the pentaeryth-
rityl tetraphenyl ether core. Crystallization of compounds 3 and 4 from DMSO/dioxane is directed
by hydrogen bonding of the diaminotriazine groups according to well-established motifs, thereby
producing three-dimensional networks. In forming these networks, each molecule of compound 3
forms a total of 12 hydrogen bonds with six others, whereas each molecule of compound 4 forms a
total of 16 hydrogen bonds with four others. Both networks are highly porous and define significant
interconnected channels for the inclusion of guests. In crystals of compounds 3 and 4, the fraction
of the volume accessible to guests is 66% and 57%, respectively. In both cases, the pentaerythrityl
tetraphenyl ether cores adopt conformations that deviate substantially from tetrahedral geometry.
It is noteworthy that the inherent flexibility of the core does not favor the formation of close-packed
guest-free structures.
In tr od u ction
Detailed structures of molecular crystals cannot yet be
predicted reliably.2 As a result, crystal engineers continue
to rely heavily on qualitative guidelines. Among the most
effective guidelines is the principle that certain sticky
sites in molecules can form attractive intermolecular
interactions according to well-established motifs, which
have been called supramolecular synthons.3 In favorable
cases, the resulting association can lead to foreseeable
three-dimensional structures. Purposefully built mol-
ecules with arrays of sticky sites have been called tectons
from the Greek word for builder,4 and the term molecular
tectonics has been used to refer to the art and science of
constructing ordered molecular materials from tectonic
subunits.5,6
Tectons can be considered to consist of multiple per-
ipheral sticky sites linked to a core that holds them in a
suitable orientation. Previous research has emphasized
sticky sites that use hydrogen bonding to direct associa-
tion, joined to rigid cores that establish a well-defined
geometry.7-13 A representative example is tecton 1,8 in
* Corresponding author.
(1) Boehringer-Ingelheim Fellow, 2001-2002.
(2) Dunitz, J . D. Chem. Commun. 2003, 545. Desiraju, G. R. Nat.
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4696.
which four sticky diaminotriazine groups are grafted to
the para positions of a nominally tetrahedral tetraphen-
ylmethyl core. Crystallization of tecton 1 is directed by
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J . Am. Chem. Soc. 2003, 125, 1002.
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10.1021/jo035311h CCC: $27.50 © 2004 American Chemical Society
Published on Web 02/14/2004
1776
J . Org. Chem. 2004, 69, 1776-1787

Molecular Tectonics
hydrogen bonding of the diaminotriazine groups to
produce an open three-dimensional network. Approxi-
mately 42% of the volume is accessible for the inclusion
of guests, which occupy prominent parallel channels that
are nearly 12 Å across in the largest dimension. As
illustrated by the behavior of compound 1, tectons cannot
usually form normal close-packed structures and simul-
taneously obey the strong directional interactions they
are designed to form with adjacent molecules;14 instead,
open networks are favored, and significant voids are filled
with guests.
Remarkably, even analogues that are more flexible are
apparently unable to find periodic three-dimensional
structures in which the dictates of close packing and
hydrogen bonding are satisfied at the same time. For ex-
ample, crystallization of tecton 2, in which four diami-
notriazine groups are attached flexibly to a core derived
from pentaerythritol, yields an interpenetrated diamon-
doid network in which 60% of the volume is accessible
to guests.9 The guests occupy parallel helical channels
with cross sections that measure approximately 11 × 12
Å2.
The unexpectedly high porosity of the network con-
structed from tecton 2 encouraged us to examine the
behavior of related tectons with even more flexible cores.
High symmetry and structural simplicity made tectons
3 and 4 particularly attractive targets. In this paper, we
show that they can be prepared conveniently from penta-
erythritol and crystallized to produce highly porous hy-
drogen-bonded networks. In addition, we report effective
syntheses of more than 20 new derivatives of pentaeryth-
rityl tetraphenyl ether (5), which promise to be useful
building blocks for the construction of molecular materi-
als.
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Resu lts a n d Discu ssion
Syn th esis of Sim p le Der iva tives of P en ta er yth -
r ityl Tetr a p h en yl Eth er . The first synthesis of pen-
taerythrityl tetraphenyl ether (5) and various substituted
derivatives was reported in 1936 by Backer and Dijken,15
who made them by heating salts of phenols with pen-
taerythrityl tetrabromide. Surprisingly, the pentaeryth-
rityl tetraphenyl ether core remained little used until
recently, when promising applications in macromolecular
chemistry,16 medicinal chemistry,17 the construction of
dendrimers,18 and other areas19,20 have been uncovered.
However, the potential of the pentaerythrityl tetraphenyl
ether core in supramolecular chemistry is still underde-
veloped, and no use of the core in crystal engineering has
(14) For an exception, see: Fournier, J .-H.; Maris, T.; Simard, M.;
Wuest, J . D. Cryst. Growth Des. 2003, 3, 535.
(15) Backer, H. J .; Dijken, G. Rec. Trav. Chim. 1936, 55, 22.
(16) For representative applications in macromolecular chemistry,
see: Oike, H.; Hamada, M.; Eguchi, S.; Danda, Y.; Tezuka, Y.
Macromolecules 2001, 34, 2776. Fukui, H.; Yoshihashi, S.; Sawamoto,
M.; Higashimura, T. Macromolecules 1996, 29, 1862. Griffin, A. C.;
Lee, C.-M.; St Pourcain, C. B. Polym. Mater. Sci. Eng. 1995, 72, 172.
Wilson, L. M. Liq. Cryst. 1995, 18, 381.
(17) For representative applications in medicinal chemistry, see:
Mischiati, C.; J eang, K.-T.; Feriotto, G.; Breda, L.; Borgatti, M.;
Bianchi, N.; Gambari, R. Antisense Nucleic Acid Drug Dev. 2001, 11,
209. Fundueanu, G.; Esposito, E.; Mihai, D.; Carpov, A.; Desbrieres,
J .; Rinaudo, M.; Nastruzzi, C. Int. J . Pharm. 1998, 170, 11. Nishimura,
Y.; Yasui, W.; Yoshida, K.; Matsuyama, T.; Dohi, K.; Tahara, E. J pn.
J . Cancer Res. 1992, 52, 723. Collins, R. F.; Davis, M.; Edge, N.; Hill,
J . Brit. J . Pharmacol. 1958, 13, 238.
(18) For use in the construction of dendrimers, see: J iang, H.; Lee,
S. J .; Lin, W. Org. Lett. 2002, 4, 2149. Cheng, L.; Cox, J . A. Chem.
Mater. 2002, 14, 6. Constable, E. C.; Housecroft, C. E.; Cattalini, M.;
Phillips, D. New J . Chem. 1998, 193. Zhang, Y.; Thompson, L. K.;
Bridson, J . N.; Bubenik, M. Inorg. Chem. 1995, 34, 5870.
J . Org. Chem, Vol. 69, No. 6, 2004 1777

Laliberte´ et al.
TABLE 1. On e-Step Syn th eses of Tetr a su bstitu ted
P en ta er yth r ityl Tetr a p h en yl Eth er s fr om P en ta er yth r ityl
Tetr a tosyla te
TABLE 2. On e-Step Syn th eses of
Tetr a k is(3,5-d isu bstitu ted ) P en ta er yth r ityl Tetr a p h en yl
Eth er s fr om P en ta er yth r ityl Tetr a tosyla te
entry
phenol
product
yield (%)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
X ) 4-F
6
6
7
50
78
88
71
83
83
81
82
87
76
80
89
90
92
70
X ) 4-Fa
X ) 3-F
entry
phenol
product
yield (%)
1
2
3
X ) Br (23)
X ) I (24)
X ) OCH3
20
21
22
63
80
70
a
X ) 4-NO2
X ) 3-NO2
X ) 4-Cl
X ) 3-Cl
X ) 4-Br
X ) 3-Br
X ) 2-Br
X ) 4-I
825
9
1015
11
1215
13
SCHEME 1
14
15
X ) 3-I
16
X ) 4-CN
X ) 3-CN
1726
18
X ) 4-CHO
1920
a
Reaction performed in absolute ethanol at 170 °C
reported. It is noteworthy that this route provides in one
step a wide variety of four-armed cores that can be used
for further molecular construction; in contrast, similar
derivatives of tetraphenylmethane, tetraphenylsilane,
spirobifluorene,10 and other cores that have already found
wide use in chemistry typically require multistep syn-
theses.27
Most of the reactions summarized in Table 1 are
straightforward and only several require commentary.
Our preferred conditions (NaOH, DMF, reflux) failed to
provide tetrakis[(4-nitrophenoxy)methyl)]methane (8)25
in good yield, so the reaction was carried out by a less
convenient method involving the use of absolute ethanol
at 170 °C (Table 1, entry 4).25 Improved yields of tetrakis-
[(4-fluorophenoxy)methyl]methane (6) were also obtained
in this way (Table 1, entries 1 and 2). Halogenated
pentaerythrityl tetraphenyl ethers 10-16 (Table 1, en-
tries 6-12) represent valuable starting materials for
making more elaborate molecules by standard C-C or
C-heteroatom coupling reactions.
been reported. The pioneering X-ray crystallographic
studies of pentaerythrityl tetraphenyl ether (5) reported
by Beintema and co-workers in 1935,21 as well as our
recent refinement,22 are the only previous structural
analyses of compounds of this type.23
To facilitate exploitation of the pentaerythrityl tet-
raphenyl ether core in crystal engineering and other
areas of science, we created a library of selected deriva-
tives by efficient methods. Many of the compounds were
obtained as crystalline solids that needed no chromato-
graphic purification. Our syntheses used the method
originally reported by Backer and Dijken,15 except that
salts of phenols were heated not with pentaerythrityl
tetrabromide but with pentaerythrityl tetratosylate,24
which can be prepared simply and inexpensively on a
large scale. Symmetrically tetrasubstituted pentaeryth-
rityl tetraphenyl ethers 6-19 were made directly by this
route and are listed in Table 1, along with the methods
of synthesis and the yields obtained. Of these compounds,
only 8,25 10,15 12,15 17,26 and 1920 have been previously
Similar reactions provided the tetrakis(3,5-disubsti-
tuted) derivatives 20-22 shown in Table 2. In the course
of this work, we devised new syntheses of 3,5-dibro-
mophenol (23)28 and 3,5-diiodophenol (24)29 by the routes
summarized in Scheme 1. Derivatives of 4-hydroxybi-
phenyl could also be used to make pentaerythrityl
tetrakis(biphenyl) ethers 25-28 (Table 3). Unidentified
side reactions occurring in the reaction with 4-hydroxy-
4′-iodobiphenyl under our standard conditions could be
avoided by using K2CO3 in the presence of tetrabutylam-
monium bromide (Table 3, entry 2).
(19) For other applications, see: Quast, L.; Nieger, M.; Do¨tz, K. H.
Organometallics 2000, 19, 2179. Kim, J .; Leong, A. J .; Lindoy, L. F.;
Kim, J .; Nachbaur, J .; Nezhadali, A.; Rounaghi, G.; Wei, G. J . Chem.
Soc., Dalton Trans. 2000, 3453. Schulte, J . L.; Laschat, S.; Vill, V.;
Nishikawa, E.; Finkelmann, H.; Nimtz, M. Eur. J . Org. Chem. 1998,
2499. Kim, J .; Lindoy, L. F.; Matthews, O. A.; Meehan, G. V.; Nachbaur,
J .; Saini, V. Aust. J . Chem. 1995, 48, 1917. J anda, P.; Kobayashi, N.;
Auburn, P. R.; Lam, H.; Leznoff, C. C.; Lever, A. B. P. Can. J . Chem.
1989, 67, 1109. Smolin´ski, S.; Deja, I. Tetrahedron 1971, 27, 1409.
(20) Luo, F.-T.; Chen, C.-H. Heterocycles 2001, 55, 1663.
(21) Beintema, J .; Terpstra, P.; van Weerden, W. J . Recl. Trav.
Chim. 1935, 54, 627.
(22) Laliberte´, D.; Maris, T.; Wuest, J . D. Acta Crystallogr. 2003,
E59, o799.
(23) The structure of tetrakis(phenylmethoxy)methane, an isomer
of pentaerythrityl tetraphenyl ether (5), has been determined by X-ray
crystallography. Latimer, D. R.; Weil, J . A.; Quail, J . W.; Robinson,
W. T. Can. J . Chem. 1989, 67, 143.
As summarized in Table 4, pentaerythrityl tetraphenyl
ethers made directly in one step from pentaerythrityl
(27) Fournier, J .-H.; Wuest, J . D. Can. J . Chem. 2003, 81, 376.
(28) (a) Lin, C.-H.; Tour, J . J . Org. Chem. 2002, 67, 7761. (b) Ishida,
Y.; J ikei, M.; Kakimoto, M.-A. Polym. Adv. Technol. 2000, 11, 698. (c)
Kraus, R.; Spiteller, G. Org. Mass Spectrom. 1989, 24, 861.
(29) Ho¨ger, S.; Bonrad, K.; Mourran, A.; Beginn, U.; Mo¨ller, M. J .
Am. Chem. Soc. 2001, 123, 5651. Barnes, J . H.; Cookson, R. C.; Dickson,
G. T.; Elks, J .; Poole, V. D. J . Chem. Soc. 1953, 1448.
(24) Shostakovskii, M. F.; Atavin, A. S.; Mirskova, A. N. Zh. Obshch.
Khim. 1965, 35, 804.
(25) Ashley, J . N.; Collins, R. F.; Davis, M.; Sirett, N. E. J . Chem.
Soc. 1958, 3298.
(26) Ferroni, R.; Menegatti, E.; Guarneri, M.; Taddeo, U.; Bolognesi,
M.; Ascenzi, P.; Amiconi, G. Il Farmaco 1984, 39, 901.
1778 J . Org. Chem., Vol. 69, No. 6, 2004

Molecular Tectonics
TABLE 3. On e-Step Syn th eses of P en ta er yth r ityl
Tetr a k is(bip h en yl) Eth er s fr om P en ta er yth r ityl
Tetr a tosyla te
confirmed by its reaction with 4-bromobenzonitrile to give
a good yield of tetranitrile 25 (eq 1), also made by the
route shown in Table 3.
entry
phenol
product
yield (%)
1
2
3
4
X ) Br
X ) Ia
X ) CN
X ) NO2
25
26
27
28
82
82
89
93
a
Reaction performed with K2CO3 and tetrabutylammonium
bromide
Basic hydrolysis of tetrakis[(4-cyanophenoxy)methyl)]-
methane (17)26 and its 3-substituted isomer 18 provided
the corresponding tetraacids 3631 and 37 in high yields
(Table 4, entries 8 and 9). Sonogashira coupling of
tetrakis[(4-iodophenoxy)methyl)]methane (15) and its
3-substituted isomer 16 with (trimethylsilyl)acetylene
gave the expected products 38 and 39, respectively (Table
4, entries 10 and 11), which could be converted into
tetraacetylenes 40 and 41 in excellent overall yield by
treatment with tetrabutylammonium fluoride (Table 4,
entries 12 and 13).
Syn th esis of Tecton s 3 a n d 4 w ith P en ta er yth r ityl
Tetr a p h en yl Eth er Cor es. Although tectons can be
created from the pentaerythrityl tetraphenyl ether core
in many different ways, we elected to attach diamino-
triazine groups as the sticky sites for the following
reasons: (1) these groups are easily made by the reaction
of nitriles with dicyandiamide;32 (2) they self-associate
according to established motifs to form robust networks
held together by multiple hydrogen bonds;8-10 and (3) the
structures of other tectons with diaminotriazine groups
are known,8-10 including close relatives 1 and 2, and
informative comparisons can therefore be made. Tectons
3 and 4 were synthesized in 95% and 73% yields,
respectively, by the reactions of tetrakis[(4-cyanophen-
oxy)methyl)]methane (17)26 and its 3-substituted isomer
18 with dicyandiamide under standard conditions (Table
4, entries 14 and 15).32 In both cases, colorless single
crystals suitable for X-ray diffraction could be grown from
DMSO/dioxane.
TABLE 4. F u r th er Tr a n sfor m a tion s of P en ta er yth r ityl
Tetr a p h en yl Eth er s
starting
compound (X)
product
(Y)
yield
(%)
entry
conditionsa
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
8 (4-NO2)25
9 (3-NO2)
a
a
b
c
d
e
f
g
g
h
h
i
29 (4-NH2)25
30 (3-NH2)
31 (4-NCO)
32 (4-NCS)
99
99
94
80
81
81
98
97
96
92
96
95
94
95
73
29 (4-NH2)25
29 (4-NH2)25
19 (4-CHO)18
33 (4-CH2OH)
12 (4-Br)16
17 (4-CN)26
18 (3-CN)
33 (4-CH2OH)
34 (4-CH2Cl)
35 (4-B(OH)2)
36 (4-COOH)31
37 (3-COOH)
38 (4-CtCTMS)
39 (3-CtCTMS)
40 (4-CtCH)
41 (3-CtCH)
tecton 3 (4-DAT)b
tecton 4 (3-DAT)b
15 (4-I)
16 (3-I)
38 (4-CtCTMS)
39 (3-CtCTMS)
17 (4-CN)26
18 (3-CN)
i
j
j
a
(a) H2/Pd/C; (b) triphosgene, N(C2H5)3; (c) thiophosgene,
N(C2H5)3; (d) NaBH4; (e) SOCl2; (f) (1) BuLi, (2) B(O-iPr)3, (3) HCl;
(g) (1) KOH, (2) HCl; (h) HCtCSi(CH3)3, PdCl2(PPh3)2, CuI,
N(C2H5)3; (i) tetrabutylammonium fluoride; (j) dicyandiamide,
b
KOH. DAT ) (4,6-diamino-1,3,5-triazin-2-yl).
tetratosylate (Table 1) can be subjected to further reac-
tions to give an even broader range of nominally tetra-
hedral four-armed cores 29-41 for molecular construc-
tion. In particular, reduction of tetrakis[(4-nitrophen-
oxy)methyl)]methane (8)25 and its 3-substituted isomer
9 provided the corresponding tetraamines 2925 and 30
(Table 4, entries 1 and 2). The 4-substituted tetraamine
2925 was then converted into tetraisocyanate 31 and
tetraisothiocyanate 32 (Table 4, entries 3 and 4), which
are attractive monomers for the synthesis of polyureas
and polyurethanes. In addition, lithiation of tetrakis[(4-
bromophenoxy)methyl)]methane (12),15 followed by ad-
dition of B(i-PrO)3 and then HCl, gave a high yield of
tetraboronic acid 35 (Table 4, entry 7). Previous research
in molecular tectonics has established that such com-
pounds can self-associate to form open hydrogen-bonded
networks.7,30 Moreover, tetraboronic acid 35 is a valuable
intermediate for making more complex derivatives of
pentaerythrityl tetraphenyl ether by Suzuki coupling, as
P or ou s Hyd r ogen -Bon d ed Netw or k Con str u cted
fr om Tecton 3. Tecton 3 crystallized in the orthorhombic
space group P21212 as an inclusion compound of ap-
proximate composition 3‚5DMSO‚6dioxane.33 Views of
the structure are shown in Figures 1-4. Like more rigid
analogues 1 and 2, tecton 3 self-associates by hydrogen
bonding of its diaminotriazine groups to form an open
three-dimensional network with significant volume for
the inclusion of guests. Each tecton forms a total of 14
hydrogen bonds with six neighboring tectons and two
molecules of DMSO that form an integral part of the
network.
(31) Oike, H.; Imamura, H.; Imaizumi, H.; Tezuka, Y. Macromol-
ecules 1999, 32, 4819.
(32) Simons, J . K.; Saxton, M. R. Organic Syntheses; Wiley: New
York, 1963; Collect. Vol. IV, p 78.
(30) For other boronic acids derived from pentaerythrityl phenyl
ethers, see: Draffin, S. P.; Duggan, P. J .; Duggan, S. A. M. Org. Lett.
2001, 3, 917.
(33) The composition was estimated by X-ray crystallography and
by 1H NMR spectroscopy of dissolved samples. The amount of any H2O
included could not be determined accurately.
J . Org. Chem, Vol. 69, No. 6, 2004 1779

Laliberte´ et al.
F IGUR E 2. (a) Partial view of the structure of crystals of
tecton 3 grown from DMSO/dioxane, showing how two of the
diaminotriazine groups of each tecton (the group not engaged
in hydrogen bonding according to the motif shown in Figure
1a, as well as one other group) each form two additional
hydrogen bonds with a neighboring tecton and a molecule of
DMSO. Hydrogen bonds appear as broken lines. For clarity,
molecules not forming an integral part of the network are
omitted, and only one of the four arms of each tecton is shown.
(b) Representation of the three-dimensional 6-connected net-
work that results when the corrugated 4-connected sheets
defined in Figure 1a (dark gray) are joined by the additional
interactions shown in Figure 2a (light gray).
F IGUR E 1. (a) Partial view of the structure of crystals of
tecton 3 grown from DMSO/dioxane, showing a central tecton
(light gray) surrounded by four hydrogen-bonded neighbors
(dark gray). Hydrogen bonds appear as broken lines, and all
guests are omitted for clarity. As shown in this view, three of
the four diaminotriazine groups of the central tecton form a
total of 10 hydrogen bonds according to standard motifs 42
and 43. The fourth diaminotriazine and one of the other three
form a total of four additional hydrogen bonds according to
the motif shown in Figure 2a. (b) Representation of the
corrugated 4-connected network defined by joining the central
carbon atom of each tecton with the centers of the set of four
neighbors shown in Figure 1a.
As shown in Figure 1a, three diaminotriazine groups
of each tecton interact with five diaminotriazine groups
provided by four neighboring tectons according to the
normal motifs 42 and 43.8-10 A third alternative, motif
44, is not observed, possibly because it would place both
cores of adjacent tectons in close proximity to substitu-
ents on the triazine rings. Lines joining the central
carbon atom of each tecton with the centers of the set of
neighbors shown in Figure 1a define a corrugated 4-con-
nected network that lies perpendicular to the c axis
(Figure 1b).
Each tecton forms four more hydrogen bonds with two
neighboring tectons and two molecules of DMSO accord-
ing to the novel motif shown in Figure 2a. These
additional interactions cause the corrugated 4-connected
sheets to become stacked along c to form a three-
dimensional 6-connected network (Figure 2b). The ulti-
mate structure of tecton 3 can be considered to result
from 2-fold interpenetration of this network along c, with
the corrugated sheets of one network interleaved between
those of the other.34,35
(34) For discussions of interpenetration in networks, see: Batten,
S. R. CrystEngComm 2001, 18, 1. Batten, S. R.; Robson, R. Angew.
Chem., Int. Ed. 1998, 37, 1460.
(35) An updated list of examples of interpenetration is available on
the web site of Dr. Stuart R. Batten at Monash University (www.chem-
.monash.edu.au).
In forming this structure, the four sticky arms of tecton
3 extend in directions that define a highly distorted
1780 J . Org. Chem., Vol. 69, No. 6, 2004

Molecular Tectonics
C-C-C angles formed by connecting the central carbon
atom with the para positions of pairs of phenyl groups.
In the structure of tecton 3, these C-C-C angles range
from 91.3° to 121.9°. Values similarly far from the
tetrahedral ideal have also been observed in the crystal
structure of pentaerythrityl tetraphenyl ether (5).22
Despite the complex connectivity, interpenetration, and
structural deformation observed in crystals of tecton 3,
66% of the volume remains accessible to guests.36-38 It
is noteworthy that a tecton with such a high degree of
flexibility appears unable to crystallize as a guest-free
structure that is both close-packed and fully hydrogen-
bonded. Molecules of DMSO and dioxane that do not form
an integral part of the network itself occupy intercon-
nected channels. The most significant channels are
aligned with the c axis and have cross sections measuring
approximately 9 × 5 Å2 at the narrowest points (Figure
3).39 The connectivity of the channels is complex, as
represented by the surface shown in Figure 4.40
In this structure, some of the molecules of DMSO and
all of the molecules of dioxane are disordered, potentially
mobile, and located in interconnected channels that in
principle provide redundant paths of escape from the
crystals. Moreover, the crystals are held together by
robust networks of hydrogen bonds. As a result, guests
can be exchanged in single crystals without loss of
crystallinity. For example, single crystals of estimated
composition 3‚5DMSO‚6dioxane33 and approximate di-
mensions 0.5 mm × 0.5 mm × 0.5 mm were suspended
in tetrahydrofuran (THF) at 25 °C for 24 h. The recovered
solid remained transparent and morphologically un-
changed and continued to diffract and to exhibit uniform
extinction between crossed polarizers. Single-crystal X-
ray diffraction established that the space group remained
unchanged, although the unit cell parameters varied in
a modest but significant way; in particular, V decreased
by 13% from 9660(2) Å3 to 8435(45) Å3. Analysis of the
product by 1H NMR spectroscopy in solution established
that included dioxane had been replaced by THF but that
only part of the included DMSO had been exchanged.
These results suggest that exchange involves disordered
molecules of DMSO and dioxane included as guests in
crystals of tecton 3; in contrast, there is little or no
F IGUR E 3. (a) View along the c axis of the network
constructed from tecton 3 showing a 3 × 2 × 4 array of unit
cells. Guests are omitted, and atoms are shown as spheres of
van der Waals radii to reveal the cross sections of the channels.
Atoms of hydrogen appear in light gray, atoms of carbon in
dark gray, and atoms of nitrogen in black. (b) Enlarged view
of the cross section of the larger channels along c.
(36) The percentage of volume accessible to guests was estimated
by the PLATON program.37 PLATON calculates the accessible volume
by allowing a spherical probe of variable radius to roll over the internal
van der Waals surface of the crystal structure. PLATON uses a default
value of 1.20 Å for the radius of the probe, which is an appropriate
model for small guests such as water. The van der Waals radii used to
define surfaces for these calculations are as follows: C: 1.70 Å, H:
1.20 Å, N: 1.55 Å, O: 1.52 Å, and S: 1.80 Å. If V is the volume of the
unit cell and Vg is the guest-accessible volume as calculated by
PLATON, then the porosity P in % is given by 100Vg/V.
(37) Spek, A. L. PLATON, A Multipurpose Crystallographic Tool;
Utrecht University: Utrecht, The Netherlands, 2001. van der Sluis,
P.; Spek, A. L. Acta Crystallogr. 1990, A46, 194.
(38) In our calculations of accessible volume, we have not included
space occupied by those molecules of DMSO that form an integral part
of the hydrogen-bonded network.
(39) The dimensions of a channel in a particular direction correspond
to the cross section of an imaginary cylinder that could be passed
through the hypothetical open network in the given direction in contact
with the van der Waals surface. Such values are inherently conserva-
tive because they (1) measure the cross section at the most narrow
constriction and (2) systematically underestimate the sizes of channels
that are not uniform and linear.
F IGURE 4. Stereoscopic representation of interconnected
channels within the network constructed from tecton 3. The
image shows a 2 × 2 × 4 array of unit cells viewed along the
c axis. The outsides of the channels appear in light gray, and
dark gray is used to show where the channels are cut by the
boundaries of the array. The surface of the channels is defined
by the possible loci of the center of a sphere of diameter 4 Å
as it rolls over the surface of the ordered network.40
(40) Representations of channels were generated by the Cavities
option in the program ATOMS (ATOMS, Version 5.1; Shape Soft-
ware: 521 Hidden Valley Road, Kingsport, TN 37663; www.shape-
software.com).
tetrahedron. A measure of the distortion of the pen-
taerythrityl tetraphenyl ether core is provided by the six
J . Org. Chem, Vol. 69, No. 6, 2004 1781

Laliberte´ et al.
F IGURE 6. View along the c axis of the network constructed
from tecton 4 showing a 2 × 2 × 2 array of unit cells. Guests
are omitted, and atoms are shown as spheres of van der Waals
radii to reveal the cross sections of the channels. Atoms of
hydrogen appear in light gray, atoms of carbon in dark gray,
and atoms of nitrogen in black.
F IGURE 5. View of the structure of crystals of tecton 4 grown
from DMSO/dioxane, showing a central tecton (light gray)
surrounded by four hydrogen-bonded neighbors (dark gray).
Hydrogen bonds appear as broken lines, and all guests are
omitted for clarity.
exchange of molecules of DMSO that are ordered because
they are an integral part of the hydrogen-bonded network
or because they form extraneous hydrogen bonds with
the network. The observed contraction of the unit cell is
presumably a consequence of replacing a larger guest
(dioxane) by a smaller guest (THF), and it allows the
inner surface of the network to optimize its interactions
with the new guest.
F IGURE 7. Stereoscopic representation of interconnected
channels within the network constructed from tecton 4. The
image shows a 1 × 1 × 2 array of unit cells viewed along the
c axis. The outsides of the channels appear in light gray, and
dark gray is used to show where the channels are cut by the
boundaries of the array. The surface of the channels is defined
by the possible loci of the center of a sphere of diameter 4 Å
as it rolls over the surface of the ordered tectonic network.40
P or ou s Hyd r ogen -Bon d ed Netw or k Con str u cted
fr om Isom er ic Tecton 4. Tecton 4 crystallized from
DMSO/dioxane in the tetragonal space group I1/a as an
inclusion compound of well-defined composition 4‚8diox-
ane,41 and its structure is shown in Figures 5-7. As
expected, tecton 4 behaves like analogues 1-3 and self-
associates by hydrogen bonding of its diaminotriazine
groups to form an open three-dimensional network with
significant volume for the inclusion of guests. In this case,
each tecton forms a total of 16 hydrogen bonds with four
neighboring tectons to create the simple and symmetric
pattern shown in Figure 5, and a noninterpenetrated
diamondoid network is formed.42 The diaminotriazine
groups of each tecton interact according to the normal
motif 43.8-10 Like tecton 3 and pentaerythrityl tetraphe-
nyl ether (5), tecton 4 has a conformation that deviates
significantly from tetrahedral geometry, and the C-C-C
angles defined by the central carbon atom and the para
phenyl carbon atoms of the core have the values 74.6°
and 129.2°.
measure approximately 4 × 2 Å2 (Figure 6),39 and the
connectivity of the channels is represented by the surface
shown in Figure 7.40 The included molecules of dioxane
are all well-ordered, and both atoms of oxygen simulta-
neously accept hydrogen bonds from NH groups of
diaminotriazines that are exposed on the walls of the
channels. This arrangement makes the network and its
guest highly complementary and explains two unusual
observations:
(1) No DMSO is included in crystals of tecton 4 grown
from DMSO/dioxane, whereas large amounts of DMSO
are included in crystals of isomer 3 grown under similar
conditions.
Approximately 57% of the volume of crystals of tecton
4 remains available for including guests in interconnected
channels.36,37 Cross sections of channels along the c axis
(2) Replacement of dioxane by THF or other polar
solvents in single crystals of tecton 4 fails to give
crystalline products.
(41) The composition was determined by X-ray crystallography and
confirmed by 1H NMR spectroscopy of dissolved samples.
(42) For a review of diamondoid hydrogen-bonded networks, see:
Zaworotko, M. J . Chem. Soc. Rev. 1994, 23, 283.
Con clu sion s
Substituted derivatives of pentaerythrityl tetraphenyl
ether (5) are easy to make and are promising four-armed
1782 J . Org. Chem., Vol. 69, No. 6, 2004

Molecular Tectonics
crystallized twice from DMSO to afford pure tetrakis[(4-
nitrophenoxy)methyl]methane (8; 28.3 g, 45.6 mmol, 71%) as
small light-brown crystals: mp 274-275 °C (lit.25 mp 274 °C);
IR (KBr) 3108, 3080, 2959, 1608, 1592, 1514, 1497, 1461, 1343,
1251, 1174, 1111, 1050, 1032, 852, 755, 690, 657 cm-1; 1H NMR
cores for building complex molecular and supramolecular
structures. Diaminotriazine groups can be attached to
produce tectons 3 and 4, which crystallize to form
networks held together by multiple hydrogen bonds. In
these structures, the inherent flexibility of the pen-
taerythrityl tetraphenyl ether core allows tectons 3 and
4 to adopt conformations that deviate substantially from
tetrahedral geometry. Surprisingly, this flexibility does
not favor the formation of close-packed guest-free struc-
tures. Instead, the crystals include large amounts of
guests, which occupy interconnected channels. These
observations suggest that further exploration of the use
of pentaerythrityl tetraphenyl ether (5) and related cores
in crystal engineering will be highly productive.
3
(400 MHz, DMSO-d6, 373 K) δ 8.18 (d, J ) 9.2 Hz, 8H), 7.21
(d, 3J ) 9.2 Hz, 8H), 4.52 (s, 8H); 13C NMR (100 MHz, DMSO-
d6, 373 K) δ 162.9, 141.2, 124.8, 114.8, 67.1, 44.4; MS (FAB,
3-nitrobenzyl alcohol) m/e 621 (M + 1). Anal. Calcd for
C
29H24N4O12: C, 56.13; H, 3.90; N, 9.03. Found: C, 55.98; H,
3.81; N, 8.98.
Gen er a l P r oced u r e for Syn th esizin g Su bstitu ted P en -
ta er yth r ityl Tetr a p h en yl Eth er s 9-22. A stirred mixture
of pentaerythrityl tetratosylate (4.00 g, 5.31 mmol),24 a sub-
stituted phenol (26.6 mmol), and NaOH (1.06 g, 26.5 mmol)
in DMF (20 mL) was heated at reflux for 16 h. DMF was then
removed by distillation under reduced pressure, and a 3:1
mixture of water/methanol (100 mL) was added to the residue.
The resulting solid was separated by filtration, washed with
water and methanol, dried under vacuum, and then crystal-
lized to afford the desired substituted pentaerythrityl tet-
raphenyl ether.
Exp er im en ta l Section
Tetr a k is[(4-flu or op h en oxy)m eth yl]m eth a n e (6). Syn -
th esis 1. A stirred mixture of pentaerythrityl tetratosylate
(4.00 g, 5.31 mmol),24 4-fluorophenol (2.98 g, 26.6 mmol), and
NaOH (1.06 g, 26.5 mmol) in DMF (20 mL) was heated at
reflux for 24 h. The solution was then cooled, water (100 mL)
was added, and the mixture was extracted twice with diethyl
ether. The organic layers were combined, washed with water
and brine, and dried over Na2SO4. Removal of volatiles under
reduced pressure left a residue that was purified by flash
chromatography (silica, CH2Cl2 (30%)/hexane (70%), Rf 0.53)
to give tetrakis[(4-fluorophenoxy)methyl]methane (6; 1.36 g,
2.65 mmol, 50%) as a colorless solid: mp 114-115 °C; IR (KBr)
3078, 2948, 2885, 1600, 1505, 1467, 1296, 1244, 1212, 1095,
Tetr akis[(3-n itr oph en oxy)m eth yl]m eth an e (9). The prod-
uct was synthesized from 3-nitrophenol by the general proce-
dure summarized above and crystallized from DMSO to give
tetrakis[(3-nitrophenoxy)methyl]methane (9; 2.75 g, 4.43 mmol,
83%) as beige crystals: mp 192 °C; IR (KBr) 3098, 2937, 1616,
1582, 1521, 1460, 1351, 1246, 1026, 1013, 819, 736, 668 cm-1
;
1H NMR (400 MHz, DMSO-d6) δ 7.78 (s, 4H), 7.77 (d, 3J ) 8.3
3
3
3
Hz, 4H), 7.53 (dd, J ) 8.5 Hz, J ) 8.3 Hz, 4H), 7.46 (d, J )
8.5 Hz, 4H), 4.49 (s, 8H); 13C NMR (75 MHz, DMSO-d6) δ 158.9,
148.6, 130.7, 122.0, 115.9, 109.2, 66.6, 44.8; MS (FAB, 3-ni-
trobenzyl alcohol) m/e 621 (M + 1). Anal. Calcd for C29H24N4O12:
C, 56.13; H, 3.90; N, 9.03. Found: C, 55.95; H, 3.86; N, 9.04.
1060, 1037, 825, 789, 761, 514 cm-1
;
1H NMR (400 MHz,
3
3
3
CDCl3) δ 7.11 (dd, J ) 9.1 Hz, J F ) 8.2 Hz, 8H), 6.92 (dd, J
) 9.1 Hz, 4J F ) 4.3 Hz, 8H), 4.36 (s, 8H); 19F NMR (376.5 MHz,
Tetr a k is[(4-ch lor oph en oxy)m eth yl]m eth a n e (10).15 The
product was synthesized from 4-chlorophenol by the general
procedure summarized above and crystallized from benzene/
methanol to provide tetrakis[(4-chlorophenoxy)methyl]methane
(10; 2.54 g, 4.39 mmol, 83%) as colorless crystals: mp 141-
142 °C (lit.15 mp 141-142 °C); IR (KBr) 3071, 2938, 2888, 1595,
1580, 1491, 1467, 1288, 1240, 1167, 1090, 1055, 1037, 824, 712,
CDCl3) δ -126.1; 13C NMR (100 MHz, CDCl3) δ 157.6 (d, J F
1
4
2
) 238.7 Hz), 155.1 (d, J F ) 1.4 Hz), 116.0 (d, J F ) 23.0 Hz),
115.9 (d, 3J F ) 7.1 Hz), 67.4, 45.1; HRMS (FAB, 3-nitrobenzyl
alcohol) calcd for C29H24O4F4 m/e 512.161073, found 512.162644.
Anal. Calcd for C29H24F4O4: C, 67.96; H, 4.72. Found: C, 67.63;
H, 4.66.
Tetr a k is[(4-flu or op h en oxy)m eth yl]m eth a n e (6). Syn -
th esis 2. A mixture of pentaerythrityl tetratosylate (2.00 g,
2.66 mmol),24 4-fluorophenol (1.49 g, 13.3 mmol), and NaOH
(0.503 g, 12.6 mmol) in anhydrous ethanol (20 mL) was heated
in a sealed tube at 170 °C for 24 h. A workup identical to the
one described above in Synthesis 1 afforded tetrakis[(4-
fluorophenoxy)methyl]methane (6; 1.06 g, 2.07 mmol, 78%).
3
672, 505 cm-1; 1H NMR (300 MHz, CDCl3) δ 7.23 (d, J ) 9.1
3
Hz, 8H), 6.84 (d, J ) 9.1 Hz, 8H), 4.29 (s, 8H); 13C NMR (75
MHz, CDCl3) δ 157.4, 129.6, 126.3, 116.1, 67.0, 45.0; MS (FAB,
3-nitrobenzyl alcohol) m/e 576. Anal. Calcd for C29H24Cl4O4:
C, 60.22; H, 4.18. Found: C, 60.07; H, 4.19.
Tetr a k is[(3-ch lor op h en oxy)m eth yl]m eth a n e (11). The
product was synthesized from 3-chlorophenol by the general
procedure summarized above and crystallized from benzene/
methanol to produce tetrakis[(3-chlorophenoxy)methyl]methane
(7; 2.50 g, 4.32 mmol, 81%) as colorless crystals: mp 83 °C;
IR (KBr) 3064, 2940, 2887, 1595, 1577, 1484, 1463, 1428, 1308,
1243, 1152, 1096, 1052, 1038, 888, 841, 773, 667 cm-1; 1H NMR
(400 MHz, CDCl3) δ 7.20 (t, 3J ) 8.3 Hz, 4H), 6.95 (d, 3J ) 8.3
Tetr a k is[(3-flu or op h en oxy)m eth yl]m eth a n e (7). By the
method of Synthesis 1, pentaerythrityl tetratosylate (4.00 g,
5.31 mmol)24 and 3-fluorophenol (2.98 g, 26.6 mmol) were
converted into crude tetrakis[(3-fluorophenoxy)methyl]methane
(3), which was purified as described in Synthesis 1 (Rf 0.56)
to give the product as a colorless solid (2.40 g, 4.68 mmol,
88%): mp 68 °C; IR (KBr) 3068, 2939, 2889, 1618, 1592, 1491,
1466, 1277, 1266, 1161, 1134, 1045, 1036, 961, 843, 778, 756,
680, 516 cm-1; 1H NMR (400 MHz, CDCl3) δ 7.22 (dt, 3J ) 8.2
Hz, 4J F ) 6.9 Hz, 4H), 6.73-6.63 (m, 12H), 4.32 (s, 8H); 19F
NMR (282.4 MHz, CDCl3) δ -111.8; 13C NMR (75 MHz, CDCl3)
3
Hz, 4H), 6.94 (s, 4H), 6.81 (d, J ) 8.3 Hz, 4H), 4.31 (s, 8H);
13C NMR (100 MHz, CDCl3) δ 159.4, 135.1, 130.5, 121.6, 115.2,
113.3, 66.6, 44.8; MS (FAB, 3-nitrobenzyl alcohol) m/e 576.
Anal. Calcd for C29H24Cl4O4: C, 60.22; H, 4.18. Found: C,
59.89; H, 4.20.
1
3
δ 163.8 (d, J F ) 245.6 Hz), 160.1 (d, J F ) 10.9 Hz), 130.5 (d,
3J F ) 10.0 Hz), 110.5 (d, 4J F ) 2.9 Hz), 108.3 (d, 2J F ) 21.3
Hz), 102.6 (d, 2J ) 24.9 Hz), 66.7, 44.8; HRMS (FAB, 3-ni-
trobenzyl alcohol) calcd for C29H24O4F4 m/e 512.161073, found
512.161401. Anal. Calcd for C29H24F4O4: C, 67.96; H, 4.72.
Found: C, 67.53; H, 4.88.
Tetr akis[(4-br om oph en oxy)m eth yl]m eth an e (12).15 The
product was synthesized from 4-bromophenol by the general
procedure summarized above and crystallized from benzene/
hexane to afford tetrakis[(4-bromophenoxy)methyl]methane
(12; 3.28 g, 4.34 mmol, 82%) as colorless crystals: mp 153-
154 °C (lit.15 mp 153-157 °C); IR (KBr) 3095, 2927, 2880, 1591,
1579, 1486, 1463, 1452, 1286, 1233, 1172, 1071, 1026, 1001,
826, 810, 677, 505 cm-1; 1H NMR (400 MHz, CDCl3) δ 7.37 (d,
Tetr a kis[(4-n itr oph en oxy)m eth yl]m eth a n e (8).25 A mix-
ture of pentaerythrityl tetratosylate (48.1 g, 63.9 mmol)24 and
sodium 4-nitrophenolate (51.4 g, 319 mmol) in anhydrous
ethanol (500 mL) was heated in a sealed tube at 170 °C for 20
h. The mixture was cooled and filtered to separate a solid,
which was washed first with water until the washings were
no longer yellow and then with methanol. The solid was
3
3J ) 8.9 Hz, 8H), 6.81 (d, J ) 8.9 Hz, 8H), 4.31 (s, 8H); 13C
NMR (75 MHz, CDCl3) δ 157.9, 132.5, 116.6, 113.7, 66.8, 44.9;
MS (FAB, 3-nitrobenzyl alcohol) m/e 752. Anal. Calcd for
C
29H24Br4O4: C, 46.07; H, 3.20. Found: C, 46.16; H, 3.20.
J . Org. Chem, Vol. 69, No. 6, 2004 1783

Laliberte´ et al.
Tetr a k is[(3-br om op h en oxy)m eth yl]m eth a n e (13). The
product was synthesized from 3-bromophenol by the general
procedure summarized above and crystallized from benzene/
hexane to give tetrakis[(3-bromophenoxy)methyl]methane (9;
3.50 g, 4.63 mmol, 87%) as colorless crystals: mp 120-121
°C; IR (KBr) 3059, 2938, 2885, 1594, 1573, 1479, 1462, 1424,
1306, 1239, 1154, 1036, 866, 842, 774, 677 cm-1; 1H NMR (400
7.29 (d, 3J ) 7.8 Hz, 4H), 7.19 (s, 4H), 7.17 (d, 3J ) 8.1 Hz,
8H), 4.38 (s, 8H); 13C NMR (100 MHz, CDCl3) δ 158.5, 130.7,
125.5, 120.0, 118.5, 117.7, 113.6, 66.5, 44.9; MS (FAB, 3-ni-
trobenzyl alcohol) m/e 541 (M + 1). Anal. Calcd for C33H24N4O4:
C, 73.32; H, 4.48; N, 10.36. Found: C, 73.01; H, 4.42, N, 10.35.
Tetr akis[(4-for m ylph en oxy)m eth yl]m eth an e (19).20 The
product was synthesized from 4-hydroxybenzaldehyde under
an inert atmosphere of N2 by the general procedure sum-
marized above and crystallized from benzene/hexane to afford
tetrakis[(4-formylphenoxy)methyl]methane (19; 2.06 g, 3.73
mmol, 70%) as colorless crystals: mp 178-179 °C (lit.20 mp
179-180 °C; IR (KBr) 3067, 2943, 2827, 2804, 2727, 1689,
1600, 1577, 1508, 1316, 1245, 1214, 1159, 1054, 1036, 870, 834,
683, 618 cm-1; 1H NMR (400 MHz, CDCl3) δ 9.87 (s, 4H), 7.82
3
MHz, CDCl3) δ 7.16-7.09 (m, 12H), 6.86 (d, J ) 8.0 Hz, 4H),
4.30 (s, 8H); 13C NMR (100 MHz, CDCl3) δ 159.4, 130.8, 124.6,
123.1, 118.1, 113.8, 66.6, 44.9; MS (FAB, 3-nitrobenzyl alcohol)
m/e 752. Anal. Calcd for C29H24Br4O4: C, 46.07; H, 3.20.
Found: C, 45.88; H, 3.10.
Tetr a k is[(2-br om op h en oxy)m eth yl]m eth a n e (14). The
product was synthesized from 2-bromophenol by the general
procedure summarized above and crystallized from benzene/
hexane to provide tetrakis[(2-bromophenoxy)methyl]methane
(14; 3.03 g, 4.01 mmol, 76%) as colorless crystals: mp 119 °C;
IR (KBr) 3063, 2941, 2883, 1585, 1572, 1482, 1463, 1441, 1278,
(d, 3J ) 8.7 Hz, 8H), 7.06 (d, 3J ) 8.7 Hz, 8H), 4.50 (s, 8H); 13
C
NMR (75 MHz, CDCl3) δ 191.1, 163.3, 132.0, 130.5, 114.6, 66.7,
44.8; MS (FAB, 3-nitrobenzyl alcohol) 553 (M + 1); HRMS
(FAB, 3-nitrobenzyl alcohol) calcd for C33H29O8 m/e 553.18622,
found 553.18736 (M + 1). Anal. Calcd for C33H28O8: C, 71.73;
H, 5.11. Found: C, 71.35; H, 5.07.
1
1245, 1054, 1030, 747, 665 cm-1; H NMR (400 MHz, CDCl3)
3
4
3
δ 7.51 (dd, J ) 7.9 Hz, J ) 1.5 Hz, 4H), 7.28 (ddd, J ) 8.3,
3J ) 7.6 Hz, J ) 1.5 Hz, 4H), 7.03 (dd, J ) 8.3 Hz, J ) 1.3
Hz, 4H), 6.85 (ddd, 3J ) 7.9, 3J ) 7.6 Hz, 4J ) 1.3 Hz, 4H),
4.62 (s, 8H); 13C NMR (75 MHz, CDCl3) δ 155.0, 133.3, 128.8,
122.4, 113.6, 112.5, 67.6, 46.1; MS (FAB, 3-nitrobenzyl alcohol)
m/e 752. Anal. Calcd for C29H24Br4O4: C, 46.07; H, 3.20.
Found: C, 46.49; H, 3.20.
4
3
4
3,5-Dibr om op h en ol (23).28 A solution of 1,3,5-tribromoben-
zene (20.0 g, 63.5 mmol) in diethyl ether (300 mL) was stirred
at -78 °C under N2 and treated dropwise with butyllithium
(25.4 mL, 2.50 M in hexane, 63.5 mmol). The resulting mixture
was kept at -78 °C for 45 min, and then B(OCH3)3 (10.7 mL,
95.5 mmol) was added dropwise. The mixture was stirred at
-78 °C for 20 min, and then the temperature was allowed to
rise to 25 °C. After addition of aqueous HCl (1 N, 50 mL), the
organic phase was separated, and volatiles were removed by
evaporation under reduced pressure. The solid residue was
dissolved in aqueous NaOH (1 N, 250 mL), the resulting
solution was stirred and treated dropwise at 0 °C with aqueous
H2O2 (50 mL, 30% w/w), and stirring was continued until no
more gas was evolved (3 h). The mixture was then filtered,
and the pH was reduced to 2 by addition of aqueous HCl (6
N). The acidified mixture was extracted twice with CH2Cl2,
and the organic layers were combined and dried over Na2SO4.
Removal of volatiles by evaporation under reduced pressure
left a residue of 3,5-dibromophenol (23; 12.2 g, 48.4 mmol, 76%)
as an off-white solid: mp 79 °C (lit.28b mp 80 °C; lit.28c mp 76-
79 °C); IR (KBr) 3200 (b), 3063, 2941, 2884, 1585, 1573, 1481,
Tet r a k is[(4-iod op h en oxy)m et h yl]m et h a n e (15). The
product was synthesized from 4-iodophenol by the general
procedure summarized above and crystallized from benzene/
methanol to produce tetrakis[(4-iodophenoxy)methyl]methane
(15; 4.03 g, 4.27 mmol, 80%) as colorless crystals: mp 163 °C;
IR (KBr) 3063, 2936, 2884, 1584, 1484, 1465, 1282, 1238, 1173,
1049, 1001, 811, 683, 633, 504 cm-1
;
1H NMR (400 MHz,
3
3
CDCl3) δ 7.54 (d, J ) 8.6 Hz, 8H), 6.68 (d, J ) 8.6 Hz, 8H),
4.26 (s, 8H); 13C NMR (100 MHz, CDCl3) δ 158.7, 138.5, 117.2,
83.6, 66.7, 44.9; MS (FAB, 3-nitrobenzyl alcohol) m/e 944. Anal.
Calcd for C29H24I4O4: C, 36.89; H, 2.56. Found: C, 36.52; H,
2.43.
Tet r a k is[(3-iod op h en oxy)m et h yl]m et h a n e (16). The
product was synthesized from 3-iodophenol by the general
procedure summarized above and crystallized from benzene/
methanol to afford tetrakis[(3-iodophenoxy)methyl]methane
(16; 4.47 g, 4.73 mmol, 89%) as colorless crystals: mp 134-
135 °C; IR (KBr) 3078, 3051, 2933, 2882, 1587, 1567, 1476,
1460, 1417, 1303, 1236, 1157, 1033, 989, 854, 843, 774, 677
1462, 1441, 1279, 1244, 1053, 1029, 841, 747, 666 cm-1 1H
;
NMR (400 MHz, CDCl3) δ 7.25 (t, 4J ) 1.6 Hz, 1H), 6.96 (d, 4J
) 1.6 Hz, 2H), 5.36 (s, 1H); 13C NMR (100 MHz, CDCl3) δ
157.0, 126.8, 123.3, 118.1; MS (MAB) calcd for C6H4Br2O m/e
249.86334, found 249.86337. Anal. Calcd for C6H4Br2O: C,
28.61; H, 1.60. Found: C, 28.64; H, 1.44.
1
cm-1; H NMR (400 MHz, CDCl3) δ 7.31-7.28 (m, 8H), 7.00
3
3
3
4
(dd, J ) 8.1, J ) 7.9 Hz, 4H), 6.88 (dd, J ) 8.1 Hz, J ) 1.8
Hz, 4H), 4.27 (s, 8H); 13C NMR (100 MHz, CDCl3) δ 159.2,
131.0, 130.6, 124.0, 114.4, 94.6, 66.5, 44.9; MS (FAB, 3-ni-
trobenzyl alcohol) m/e 944. Anal. Calcd for C29H24I4O4: C,
36.89; H, 2.56. Found: C, 37.03; H, 2.44.
3,5-Diiod op h en ol (24).29 A sample of 1,3,5-triiodobenzene
(3.00 g, 6.58 mmol) was subjected to the same procedure used
to synthesize 3,5-dibromophenol (23). Crystallization of the
crude product from CHCl3 provided 3,5-diiodophenol (24; 1.57
g, 4.54 mmol, 69%) as colorless crystals: mp 103-104 °C (lit.29
mp 102-104 °C); IR (KBr) 3200 (b), 3070, 1576, 1558, 1410,
Tetr a k is[(4-cya n op h en oxy)m eth yl]m eth a n e (17).26 The
product was synthesized from 4-cyanophenol by the general
procedure summarized above and crystallized from 2-meth-
oxyethanol to afford tetrakis[(4-cyanophenoxy)methyl]methane
(17; 2.58 g, 4.77 mmol, 90%) as colorless crystals: mp 217-
218 °C (lit.26 mp 222-224 °C); IR (KBr) 3100, 3071, 2944, 2895,
2229, 1603, 1574, 1509, 1469, 1308, 1250, 1172, 1113, 1046,
1
1212, 874, 841, 712, 665 cm-1; H NMR (400 MHz, CDCl3) δ
7.64 (s, 1H), 7.19 (s, 2H), 4.75(s, 1H); 13C NMR (100 MHz,
CDCl3) δ 156.4, 138.1, 124.5, 94.8; MS (FAB, 3-nitrobenzyl
alcohol) m/e 346. Anal. Calcd for C6H4I2O: C, 20.83; H, 1.17.
Found: C, 20.90; H, 1.04.
3
1026, 839, 549 cm-1; 1H NMR (300 MHz, CDCl3) δ 7.59 (d, J
Tetr a k is[(3,5-d ibr om op h en oxy)m eth yl]m eth a n e (20).
The product was synthesized from pentaerythrityl tetratosyl-
ate (2.00 g, 2.66 mmol),24 3,5-dibromophenol (23; 3.35 g, 13.3
mmol), and NaOH (0.531 g, 13.3 mmol) by the general
procedure summarized above. The crude product was crystal-
lized from benzene/hexane to give tetrakis[(3,5-dibromophe-
noxy)methyl]methane (20; 1.80 g, 1.68 mmol, 63%) as colorless
crystals: mp 196 °C; IR (KBr) 3086, 2936, 2886, 1583, 1561,
) 8.7 Hz, 8H), 6.99 (d, 3J ) 8.7 Hz, 8H), 4.41 (s, 8H); 13C NMR
(75 MHz, CDCl3) δ 161.5, 134.3, 119.0, 115.4, 105.3, 66.5, 44.7;
MS (FAB, 3-nitrobenzyl alcohol) m/e 541 (M + 1). Anal. Calcd
for C33H24N4O4: C, 73.32; H, 4.48; N, 10.36. Found: C, 73.05;
H, 4.57, N, 10.32.
Tetr a k is[(3-cya n op h en oxy)m eth yl]m eth a n e (18). The
product was synthesized from 3-cyanophenol by the general
procedure summarized above and crystallized from benzene/
hexane to give tetrakis[(3-cyanophenoxy)methyl]methane (18;
2.64 g, 4.88 mmol, 92%) as colorless crystals: mp 151-152
°C; IR (KBr) 3075, 3034, 2948, 2231, 1598, 1491, 1464, 1430,
1330, 1289, 1259, 1165, 1026, 939, 849, 787, 688 cm-1; 1H NMR
1435, 1418, 1251, 1228, 1053, 1038, 895, 828, 745, 662 cm-1
;
1H NMR (400 MHz, CDCl3) δ 7.29 (t, 4J ) 1.3 Hz, 4H), 7.02 (d,
4J ) 1.3 Hz, 8H), 4.24 (s, 8H); 13C NMR (100 MHz, CDCl3) δ
159.5, 127.6, 123.5, 117.2, 66.5, 45.0; MS (FAB, 3-nitrobenzyl
alcohol) m/e 1072. Anal. Calcd for C29H20Br8O4: C, 32.50; H,
1.88. Found: C, 32.69; H, 1.79.
3
3
(300 MHz, CDCl3) δ 7.40 (dd, J ) 8.1 Hz, J ) 7.8 Hz, 4H),
1784 J . Org. Chem., Vol. 69, No. 6, 2004

Molecular Tectonics
Tetr akis[(3,5-diiodoph en oxy)m eth yl]m eth an e (21). The
product was synthesized from pentaerythrityl tetratosylate
(392 mg, 0.521 mmol),24 3,5-diiodophenol (24; 900 mg, 2.60
mmol), and NaOH (104 mg, 2.60 mmol) by the general
procedure summarized above. The crude product was crystal-
lized from benzene/methanol to provide tetrakis[(3,5-diiodophen-
oxy)methyl]methane (21; 601 mg, 0.415 mmol, 80%) as beige
crystals of a 2:1 solvate with benzene: mp 226 °C; IR (KBr)
3066, 2938, 2881, 1570, 1546, 1427, 1411, 1254, 1224, 1035,
2225, 1603, 1494, 1462, 1241, 1179, 1032, 1001, 820, 531 cm-1
;
3
1H NMR (400 MHz, CDCl3) δ 7.70 (d, J ) 8.3 Hz, 8H), 7.63
3
3
3
(d, J ) 8.3 Hz, 8H), 7.54 (d, J ) 8.7 Hz, 8H), 7.08 (d, J )
8.7 Hz, 8H), 4.49 (s, 8H); 13C NMR (100 MHz, CDCl3) δ 159.4,
145.2, 132.8, 132.4, 128.6, 127.3, 119.2, 115.5, 110.5, 66.7, 45.1;
MS (FAB, 3-nitrobenzyl alcohol) m/e 845 (M + 1). Anal. Calcd
for C57H40N4O4: C, 81.02; H, 4.77; N, 6.63. Found: C, 81.02;
H, 4.97; N, 6.27.
Tetr a k is[[(4′-n itr o-1,1′-biph en yl-4-yl)oxy]m eth yl]m eth -
a n e (28). The crude product was prepared from pentaeryth-
rityl tetratosylate (1.40 g, 1.86 mmol),24 4-hydroxy-4′-nitrobi-
phenyl (2.00 g, 9.29 mmol), and NaOH (0.372 g, 9.30 mmol)
by the method described above for compound 25. Crystalliza-
tion from DMF afforded tetrakis[[(4′-nitro-1,1′-biphenyl-4-yl)-
oxy]methyl]methane (28; 1.60 g, 1.73 mmol, 93%) as orange
crystals: mp 233 °C; IR (KBr) 3072, 2940, 2885, 1595, 1518,
876, 827, 708, 679, 666 cm-1
;
1H NMR (400 MHz, CDCl3) δ
4
4
7.67 (t, J ) 1.3 Hz, 4H), 7.37 (s, Ph-H), 7.22 (d, J ) 1.3 Hz,
8H), 4.18 (s, 8H); 13C NMR (100 MHz, CDCl3) δ 159.1, 138.7,
128.6 (Ph-H), 123.7, 94.9, 66.4, 45.1; MS (FAB, 3-nitrobenzyl
alcohol) m/e 1448. Anal. Calcd for C29H20I8O4‚0.5 C6H6: C,
25.85; H, 1.56. Found: C, 25.93; H, 1.47.
Tetr akis[(3,5-dim eth oxyph en oxy)m eth yl]m eth an e (22).
The product was synthesized from 3,5-dimethoxyphenol (4.10
g, 26.6 mmol) by the general procedure summarized above.
The crude product was crystallized from benzene/methanol to
afford tetrakis[(3,5-dimethoxyphenoxy)methyl]methane (22;
2.53 g, 3.72 mmol, 70%) as colorless crystals: mp 107 °C; IR
(KBr) 3005, 2951, 2841, 1621, 1593, 1476, 1426, 1194, 1147,
1340, 1243, 1176, 1109, 1041, 856, 825, 756 cm-1 1H NMR
;
(400 MHz, DMSO-d6) δ 8.23 (d, 3J ) 9.0 Hz, 8H), 7.86 (d, 3J )
9.0 Hz, 8H), 7.72 (d, 3J ) 8.9 Hz, 8H), 7.16 (d, 3J ) 8.9 Hz,
8H), 4.44 (s, 8H); 13C NMR (100 MHz, DMSO-d6) δ 159.4,
146.1, 146.0, 130.3, 128.6, 127.0, 124.0, 115.5, 66.1, 44.7. Anal.
Calcd for C53H40N4O12: C, 68.83; H, 4.36; N, 6.06. Found: C,
68.74; H, 4.31; N, 6.13.
3
1064, 818, 681 cm-1; 1H NMR (400 MHz, CDCl3) δ 6.14 (d, J
3
Tetr a k is[(4-a m in op h en oxy)m eth yl]m eth a n e (29).25
A
) 1.3 Hz, 8H), 6.11 (t, J ) 1.3 Hz, 4H), 4.31 (s, 8H), 3.78 (s,
24H); 13C NMR (100 MHz, CDCl3) δ 161.6, 160.9, 93.7, 93.6,
66.7, 55.5, 44.7; MS (FAB, 3-nitrobenzyl alcohol) m/e 681 (M
+ 1). Anal. Calcd for C37H44O12: C, 65.28; H, 6.52. Found: C,
65.19; H, 6.55.
suspension of tetrakis[(4-nitrophenoxy)methyl]methane (8;
15.4 g, 24.8 mmol) and 10% Pd/C (1.58 g) in THF (400 mL)
was stirred for 70 h at 25 °C under an atmosphere of H2 (180
psi) in a Parr reactor. The resulting mixture was filtered
through Celite, and volatiles were removed from the filtrate
by evaporation under reduced pressure. This yielded a residue
of tetrakis[(4-aminophenoxy)methyl]methane (29; 12.3 g, 24.6
mmol, 99%) as a colorless solid, which was used without any
further purification. Small beige crystals of analytical purity
could be grown by slow evaporation of solutions in THF: mp
210-211 °C (lit.25 mp 205-207 °C); IR (KBr) 3434, 3351, 3050,
Tet r a k is[[(4′-b r om o-1,1′-b ip h en yl-4-yl)oxy]m et h yl]-
m eth a n e (25). A mixture of pentaerythrityl tetratosylate (2.00
g, 2.66 mmol),24 4′-bromo-4-hydroxybiphenyl (3.31 g, 13.3
mmol), and NaOH (0.532 g, 13.3 mmol) in DMF (20 mL) was
heated at reflux for 36 h. The mixture was allowed to cool,
water (200 mL) was added, and the resulting precipitate was
separated by filtration and washed with water and methanol.
The crude solid was crystallized from benzene to give tetrakis-
[[(4′-bromo-1,1′-biphenyl-4-yl)oxy]methyl]methane (25; 2.32 g,
2.19 mmol, 82%) as colorless crystals: mp 190-191 °C; IR
(KBr) 3035, 2949, 1605, 1516, 1481, 1466, 1238, 1174, 1038,
999, 811, 736, 504 cm-1; 1H NMR (400 MHz, CDCl3) δ 7.53 (d,
2932, 2881, 1625, 1511, 1468, 1232, 1060, 1041, 832, 523 cm-1
;
1H NMR (400 MHz, DMSO-d6) δ 6.66 (d, 3J ) 8.4 Hz, 8H),
3
6.47 (d, J ) 8.4 Hz, 8H), 4.62 (s, 8H), 4.03 (s, 8H); 13C NMR
(100 MHz, DMSO-d6) δ 150.1, 142.7, 115.8, 114.9, 67.1, 44.6;
MS (FAB, 3-nitrobenzyl alcohol) m/e 500; HRMS (FAB, 3-ni-
trobenzyl alcohol) calcd for C29H32O4N4 m/e 500.24237, found
500.24150. Anal. Calcd for C29H32N4O4: C, 69.58; H, 6.44; N,
11.19. Found: C, 69.33; H, 6.78; N, 10.91.
3
3
3J ) 8.5 Hz, 8H), 7.47 (d, J ) 8.8 Hz, 8H), 7.39 (d, J ) 8.5
Hz, 8H), 7.02 (d, J ) 8.8 Hz, 8H), 4.45 (s, 8H); 13C NMR (100
3
MHz, CDCl3) δ 158.8, 139.8, 133.2, 132.0, 128.5, 128.2, 121.1,
115.3, 66.8, 45.1; MS (FAB, 3-nitrobenzyl alcohol) m/e 1056.
Anal. Calcd for C53H40Br4O4: C, 60.03; H, 3.80. Found: C,
60.22; H, 3.71.
Tet r a k is[(3-a m in op h en oxy)m et h yl]m et h a n e (30). A
similar procedure converted tetrakis[(3-nitrophenoxy)methyl]-
methane (9; 2.40 g; 3.87 mmol) into tetrakis[(3-aminophenoxy)-
methyl]methane (30; 1.91 g, 3.82 mmol, 99%). Orange crystals
of analytical purity were obtained by crystallization from
toluene: mp 112 °C; IR (KBr) 3429, 3338, 3211, 3041, 2935,
2885, 1625, 1601, 1494, 1459, 1334, 1289, 1189, 1159, 1041,
Tetr a k is[[(4′-iod o-1,1′-bip h en yl-4-yl)oxy]m eth yl]m eth -
a n e (26). A mixture of pentaerythrityl tetratosylate (0.578 g,
0.768 mmol),24 4-hydroxy-4′-iodobiphenyl (1.00 g, 3.38 mmol),
K2CO3 (0.467 g, 3.38 mmol), and tetrabutylammonium bromide
(0.272 g, 0.841 mmol) in DMF (12 mL) was heated at reflux
for 36 h. The mixture was allowed to cool, water (200 mL) was
added, and the resulting precipitate was separated by filtration
and washed with water and methanol. The crude solid was
crystallized from benzene to produce tetrakis[[(4′-iodo-1,1′-
biphenyl-4-yl)oxy]methyl]methane (26; 0.789 g, 0.632 mmol,
82%) as colorless crystals: mp 221 °C; IR (KBr) 3034, 2933,
1
835, 763, 686 cm-1; H NMR (400 MHz, DMSO-d6) δ 6.87 (t,
3J ) 8.0 Hz, 4H), 6.20-6.08 (m, 12H), 5.04 (s, 8H), 4.10 (s,
8H); 13C NMR (100 MHz, DMSO-d6) δ 159.6, 150.0, 129.6,
107.1, 102.1, 99.9, 65.7, 43.9; MS (FAB, thioglycerol) m/e 501
(M + 1); HRMS (FAB, thioglycerol) calcd for C29H33O4N4 m/e
501.25018, found 501.24900 (M + 1). Anal. Calcd for C29H32
-
N4O4: C, 69.58; H, 6.44; N, 11.19. Found: C, 69.77; H, 6.65;
N, 11.13.
1
2879, 1605, 1515, 1479, 1466, 1239, 1174, 997, 807 cm-1; H
3
NMR (300 MHz, CDCl3) δ 7.73 (d, J ) 8.5 Hz, 8H), 7.47 (d,
Tetr a k is[(4-isocya n a top h en oxy)m eth yl]m eth a n e (31).
A solution of triphosgene (1.82 g, 6.13 mmol) in dry THF (10
mL) was added dropwise under N2 to a stirred solution of
tetrakis[(4-aminophenoxy)methyl]methane (29; 2.05 g, 4.10
mmol) and triethylamine (4.57 mL, 32.8 mmol) in dry THF
(70 mL) at -78 °C. The temperature of the resulting mixture
was allowed to rise to 0 °C over 2 h, and solids were removed
by filtration through Celite. Volatiles were removed from the
filtrate by evaporation under reduced pressure to give tetrakis-
[(4-isocyanatophenoxy)methyl]methane (31; 2.34 g, 3.87 mmol,
94%) as a colorless solid, which was not subjected to further
purification: mp 45 °C (softening); IR (KBr) 2945, 2887, 2279,
3
3
3J ) 8.8 Hz, 8H), 7.26 (d, J ) 8.5 Hz, 8H), 7.02 (d, J ) 8.8
Hz, 8H), 4.44 (s, 8H); 13C NMR (100 MHz, CDCl3) δ 158.8,
140.4, 138.0, 133.2, 128.8, 128.2, 115.3, 92.5, 66.8, 45.1; MS
(FAB, 3-nitrobenzyl alcohol) m/e 1248. Anal. Calcd for
C
53H40I4O4: C, 50.99; H, 3.23. Found: C, 51.23; H, 3.16.
Tetr akis[[(4′-cyan o-1,1′-biph en yl-4-yl)oxy]m eth yl]m eth -
a n e (27). The crude product was prepared from pentaeryth-
rityl tetratosylate (1.54 g, 2.05 mmol),24 4-cyano-4′-hydroxy-
biphenyl (2.00 g, 10.2 mmol), and NaOH (0.410 g, 10.2 mmol)
by the method described above for compound 25. Crystalliza-
tion from 2-methoxyethanol gave tetrakis[[(4′-cyano-1,1′-bi-
phenyl-4-yl)oxy]methyl]methane (27; 1.54 g, 1.82 mmol, 89%)
as colorless crystals: mp 167-168 °C; IR (KBr) 3040, 2940,
1
1524, 1457, 1240, 1172, 1054, 1034, 827, 558 cm-1; H NMR
(400 MHz, CDCl3) δ 7.00 (d, 3J ) 8.8 Hz, 8H), 6.85 (d, 3J ) 8.8
J . Org. Chem, Vol. 69, No. 6, 2004 1785

Laliberte´ et al.
3
Hz, 8H), 4.29 (s, 8H); 13C NMR (100 MHz, CDCl3) δ 156.8,
126.9, 126.1, 124.6, 116.0, 67.2, 44.9; MS (FAB, 3-nitrobenzyl
alcohol) m/e 604.
MHz, DMSO-d6) δ 7.79 (s, 8H), 7.70 (d, J ) 8.3 Hz, 8H), 6.93
(d, 3J ) 8.3 Hz, 8H), 4.30 (s, 8H); 13C NMR (100 MHz, DMSO-
d6) δ 160.4, 136.0, 126.1, 113.8, 65.8, 44.4; MS (FAB, 3-ni-
trobenzyl alcohol/ethylene glycol) m/e 720. Anal. Calcd for
Tetr a k is[(4-isoth iocya n a top h en oxy)m eth yl]m eth a n e
(32). Thiophosgene (0.237 mL, 3.11 mmol) was added dropwise
at -10 °C under N2 to a stirred solution of tetrakis[(4-
aminophenoxy)methyl]methane (29; 353 mg, 0.705 mmol) and
triethylamine (0.79 mL, 5.7 mmol) in dry THF (12 mL). The
temperature of the mixture was allowed to rise to 25 °C during
1 h, water was added, and the resulting solid was separated
by filtration and washed with cold methanol. The crude
product was crystallized from CHCl3/hexane to provide tet-
rakis(4-isothiocyanatophenyl)methane (32; 379 mg, 0.567
mmol, 80%) as a colorless solid: mp 149-150 °C; IR (KBr)
3065, 2943, 2883, 2045(bs), 1602, 1580, 1503, 1465, 1301, 1244,
1167, 1055, 1036, 927, 831, 757, 637, 515 cm-1; 1H NMR (400
C
29H32B4O12‚5 H2O: C, 49.35; H, 6.00. Found: C, 48.94; H,
5.98.
Su zu k i Cou p lin g of Tetr a bor on ic Acid 35 w ith 4-Br o-
m oben zon itr ile. Under N2, deoxygenated water (15 mL) and
acetonitrile (35 mL) were added to a deoxygenated mixture of
tetraboronic acid 35 (1.34 g, 2.18 mmol), 4-bromobenzonitrile
(1.98 g, 10.9 mmol), Pd(PPh3)4 (0.500 g, 0.433 mmol), and Na2-
CO3 (2.31 g, 21.8 mmol). The mixture was stirred at 80 °C for
72 h, water (200 mL) was added, and the resulting precipitate
was separated by filtration. The crude solid was purified by
flash chromatography (silica, CH3COOC2H5 (35%)/hexane
(65%), Rf 0.29) to give tetrakis[[(4′-cyano-1,1′-biphenyl-4-yl)-
oxy]methyl]methane (27; 1.36 g, 1.61 mmol, 74%) as a colorless
solid.
3
3
MHz, CDCl3) δ 7.15 (d, J ) 7.9 Hz, 8H), 6.86 (d, J ) 7.9 Hz,
8H), 4.31 (s, 8H); 13C NMR (100 MHz, CDCl3) δ 157.5, 134.5,
127.2, 124.6, 115.7, 66.8, 44.9; MS (FAB, 3-nitrobenzyl alcohol)
m/e 668. Anal. Calcd for C33H24N4O4S4‚H2O: C, 57.71; H, 3.82;
N, 8.16; S, 18.67. Found: C, 57.74; H, 3.49; N. 8.22; S.18.57.
Tetr a k is[(4-ca r boxyp h en oxy)m eth yl]m eth a n e (36).31
A
mixture of tetrakis[(4-cyanophenoxy)methyl]methane (17; 2.00
g, 3.70 mmol) and KOH (3.00 g, 53.5 mmol) in ethylene glycol
(30 mL) was heated at reflux for 16 h. The solution was then
cooled and acidified to pH 1 by the addition of aqueous HCl (1
N). The resulting precipitate was separated by filtration,
washed with water, and dried under vacuum to provide
tetrakis[(4-carboxyphenoxy)methyl]methane (36; 2.22 g, 3.60
mmol, 97%) as a colorless solid: mp >330 °C (lit.31 mp >300
°C); IR (KBr) 3300-2500 (bs), 1683, 1604, 1428, 1302, 1245,
Te t r a k is[[4-h yd r oxym e t h yl)p h e n oxy]m e t h yl]m e t h -
a n e (33). A solution of tetrakis[(4-formylphenoxy)methyl]-
methane (19; 3.11 g, 5.63 mmol) in methanol (100 mL) was
stirred at -10 °C and treated with NaBH4 (2.55 g, 67.4 mmol),
added in small portions. The resulting mixture was stirred at
0 °C for 30 min and then at 25 °C for 7 h. The mixture was
poured into cold water (600 mL), and the resulting precipitate
was filtered, washed with water, and dried under vacuum.
Crystallization from ethanol gave tetrakis[[(4-hydroxymethyl)-
phenoxy]methyl]methane (33; 2.57 g, 4.58 mmol, 81%) as a
colorless solid: mp 136 °C; IR (KBr) 3260 (b), 2927, 2869, 1611,
1173, 1043, 846, 769 cm-1; H NMR (400 MHz, DMSO-d6) δ
1
3
3
12.62 (s, 4H), 7.86 (d, J ) 8.6 Hz, 8H), 7.07 (d, J ) 8.6 Hz,
8H), 4.40 (s, 8H); 13C NMR (100 MHz, DMSO-d6) δ 166.9,
161.9, 131.3, 123.4, 114.4, 66.3, 44.2; MS (FAB, 3-nitrobenzyl
alcohol) m/e 613. Anal. Calcd for C33H28O12‚H2O: C, 62.46; H,
4.77. Found: C, 62.03; H, 4.61.
1
1587, 1511, 1469, 1236, 1172, 1053, 1007, 825, 615 cm-1; H
3
NMR (400 MHz, DMSO-d6) δ 7.19 (d, J ) 8.5 Hz, 8H), 6.92
(d, 3J ) 8.5 Hz, 8H), 5.04 (t, 3J ) 5.5 Hz, 4H), 4.38 (d, 3J ) 5.5
Hz, 8H), 4.25 (s, 8H); 13C NMR (100 MHz, DMSO-d6) δ 157.6,
135.0, 127.9, 114.3, 66.1, 62.5, 44.5; MS (FAB, 3-nitrobenzyl
alcohol) m/e 560. Anal. Calcd for C33H36O8: C, 70.70; H, 6.47.
Found: C, 70.73; H, 6.64.
Tetr a k is[(3-ca r boxyp h en oxy)m eth yl]m eth a n e (37). A
similar procedure converted tetrakis[(3-cyanophenoxy)methyl]-
methane (18; 493 mg, 0.912 mmol) into tetrakis[(3-carboxy-
phenoxy)methyl]methane (37; 538 mg, 0.873 mmol, 96%),
which was obtained as a colorless solid: mp 302-303 °C; IR
(KBr) 3300-2500 (bs), 1688, 1592, 1453, 1289, 1243, 1041, 756,
676 cm-1; 1H NMR (300 MHz, DMSO-d6) δ 12.99 (s, 4H), 7.54-
7.47 (m, 8H), 7.37 (dd, J ) 8.0 Hz, J ) 7.9 Hz, 4H), 7.24 (d,
3J ) 7.9 Hz, 4H), 4.38 (s, 8H); 13C NMR (100 MHz, DMSO-d6)
δ 167.1, 158.5, 132.2, 129.8, 122.0, 119.5, 114.9, 66.0, 44.4; MS
(FAB, 3-nitrobenzyl alcohol) m/e 613. Anal. Calcd for C33H28O12‚
1.5 H2O: C, 61.59; H, 4.86. Found: C, 61.76; H, 4.48.
Tetr a k is[[4-[(tr im eth ylsilyl)eth yn yl]p h en oxy]m eth yl]-
m eth a n e (38). (Trimethylsilyl)acetylene (3.20 mL, 22.6 mmol)
was added dropwise at 25 °C to a stirred mixture of tetrakis-
[(4-iodophenoxy)methyl]methane (15; 4.70 g, 4.98 mmol), CuI
(0.0500 g, 0.263 mmol), and PdCl2(PPh3)2 (0.340 g, 0.484 mmol)
in deoxygenated triethylamine (60 mL). The black mixture was
kept at 25 °C for 14 h, and volatiles were then removed by
evaporation under reduced pressure. The solid residue was
purified by flash chromatography (silica, CH2Cl2 (25%)/hexane
(75%), Rf 0.24) to give tetrakis[[4-[(trimethylsilyl)ethynyl]-
phenoxy]methyl]methane (38; 3.77 g, 4.57 mmol, 92%) as a
colorless solid: mp 143 °C; IR (KBr) 2956, 2149, 1603, 1506,
1247, 1232, 1030, 863, 843, 759, 542 cm-1; 1H NMR (400 MHz,
CDCl3) δ 7.38 (d, J ) 8.8 Hz, 8H), 6.82 (d, J ) 8.8 Hz, 8H),
4.32 (s, 8H), 0.24 (s, 36H); 13C NMR (100 MHz, CDCl3) δ 159.0,
133.7, 116.1, 114.7, 105.2, 92.9. 66.8, 44.9, 0.3; MS (FAB,
3-nitrobenzyl alcohol) m/e 825; HRMS (FAB, 3-nitrobenzyl
alcohol) calcd for C49H61O4Si4 m/e 825.36469, found 825.36470
(M + 1). Anal. Calcd for C49H60O4Si4: C, 71.31; H, 7.33.
Found: C, 71.07; H, 7.71.
Te t r a k is[[(4-ch lor om e t h yl)p h e n oxy]m e t h yl]m e t h -
a n e (34). A stirred solution of tetrakis[[(4-hydroxymethyl)-
phenoxy]methyl]methane (33; 2.31 g, 4.12 mmol) in dioxane
(60 mL) was treated dropwise with SOCl2 (2.4 mL, 33 mmol)
under N2, and the mixture was then heated at reflux for 16 h.
Volatiles were removed by evaporation under reduced pres-
sure, and the residue was crystallized twice from benzene/
hexane to give tetrakis[[(4-chloromethyl)phenoxy]methyl]-
methane (34; 2.11 g, 3.33 mmol, 81%) as off-white crystals:
mp 170 °C; IR (KBr) 3044, 2935, 2882, 1610, 1512, 1472, 1305,
1239, 1172, 1063, 1046, 867, 834, 728, 656, 585 cm-1; 1H NMR
(400 MHz, CDCl3) δ 7.32 (d, 3J ) 8.5 Hz, 8H), 6.93 (d, 3J ) 8.5
Hz, 8H), 4.58 (s. 8H), 4.38 (s, 8H); 13C NMR (100 MHz, CDCl3)
δ 159.0, 130.4, 130.3, 115.0, 66.7, 46.4, 44.9; MS (FAB,
3-nitrobenzyl alcohol) m/e 632. Anal. Calcd for C33H32Cl4O4:
C, 62.48; H, 5.08. Found: C, 62.88; H, 5.08.
Tetr abor on ic Acid 35. A solution of tetrakis[(4-bromophen-
oxy)methyl]methane (12; 10.0 g, 13.2 mmol) in THF (300 mL)
was stirred vigorously with a mechanical stirrer at -78 °C
under dry N2 and treated dropwise with a solution of butyl-
lithium (26.5 mL, 2.50 M in hexane, 66.3 mmol). The resulting
mixture was kept at -78 °C for 45 min, and then B(O-iPr)3
(15.3 mL, 66.3 mmol) was added dropwise. The mixture was
stirred at -78 °C for 20 min and warmed to 25 °C during 2 h.
After addition of water (20 mL), the mixture was concentrated
by partial evaporation of volatiles under reduced pressure. The
concentrate was dissolved in aqueous NaOH (1 N, 200 mL),
and the solution was washed with dichloromethane. Aqueous
HCl (1 N) was then added until the pH was reduced to 2. The
resulting precipitate was separated by filtration and dried to
afford tetraboronic acid 35 (7.94 g, 12.9 mmol, 98%) as a
colorless solid: mp >300 °C; IR (KBr) 3400-2800, 1602, 1409,
1351, 1235, 1183, 1015, 820, 648, 624, 526 cm-1; 1H NMR (400
3
3
3
3
Tetr a k is[[3-[(tr im eth ylsilyl)eth yn yl]p h en oxy]m eth yl]-
m eth a n e (39). A similar procedure transformed tetrakis[(3-
iodophenoxy)methyl]methane (16; 1.75 g, 1.85 mmol), CuI
(0.0176 g, 0.0924 mmol), PdCl2(PPh3)2 (0.130 g, 0.185 mmol),
and (trimethylsilyl)acetylene (1.18 mL, 8.35 mmol) into tet-
rakis[[3-[(trimethylsilyl)ethynyl]phenoxy]methyl]methane (39;
1786 J . Org. Chem., Vol. 69, No. 6, 2004

Molecular Tectonics
1.46 g, 1.77 mmol, 96%), which was obtained after flash
chromatography (Rf 0.36) as a colorless solid: Tg (TGA) 46.2
°C; IR (KBr) 3072, 2959, 2897, 2158, 1597, 1574, 1469, 1284,
1250, 1174, 1156, 1034, 956, 842, 784, 759, 684, 645 cm-1; 1H
alcohol) m/e 877 (M + 1); HRMS (FAB, 3-nitrobenzyl alcohol)
calcd for C41H41N20O4 m/e 877.361965, found 877.362190 (M
+ 1).
Tecton 4. A similar procedure converted tetrakis[(3-cy-
anophenoxy)methyl]methane (18; 600 mg, 1.11 mmol) into
tecton 4 (710 mg, 0.810 mmol, 73%), which was obtained as a
colorless solid: mp 188-189 °C; IR (KBr) 3500-2900, 1609,
1540, 1446, 1422, 1389, 1236, 1143, 1023, 824, 795, 737, 683,
616 cm-1; 1H NMR (400 MHz, DMSO-d6) δ 7.87-7.81 (m, 8H),
3
3
NMR (400 MHz, CDCl3) δ 7.19 (dd, J ) 8.2 Hz, J ) 7.7 Hz,
3
3
4H), 7.07 (d, J ) 7.7 Hz, 4H), 7.03 (s, 4H), 6.88 (d, J ) 8.2
Hz, 4H), 4.31 (s, 8H), 0.26 (s, 36H); 13C NMR (100 MHz, CDCl3)
δ 158.4, 129.5, 125.1, 124.3, 117.5, 116.0, 105.0, 94.3, 66.4, 44.9,
0.2; HRMS (FAB, 3-nitrobenzyl alcohol) calcd for C49H60O4Si4
m/e 824.35687, found 824.35930. Anal. Calcd for C49H60O4Si4:
C, 71.31; H, 7.33. Found: C, 71.07; H, 7.84.
3
3
7.34 (t, J ) 8.1 Hz, 4H), 7.16 (d, J ) 8.1 Hz, 4H), 6.76 (bs,
16H), 4.43 (s, 8H); 13C NMR (100 MHz, DMSO-d6) δ 169.8,
167.4, 158.3, 138.7, 129.2, 120.6, 117.4, 113.2, 66.4, 44.3; MS
(FAB, 3-nitrobenzyl alcohol) m/e 877 (M + 1); HRMS (FAB,
3-nitrobenzyl alcohol) calcd for C41H41N20O4 m/e 877.361965,
found 877.361672 (M + 1).
Tetr a k is[(4-eth yn ylp h en oxy)m eth yl]m eth a n e (40). At
25 °C, tetrabutylammonium fluoride (1.0 M in THF, 20 mL,
20 mmol) was added to a stirred solution of tetrakis[[(4-
[(trimethylsilyl)ethynyl]phenoxy]methyl]methane (38; 3.30 g,
4.00 mmol) in THF (50 mL). After 3 h water was added, and
the product was extracted with CH3COOC2H5. The extracts
were dried over MgSO4 and filtered through silica gel. Volatiles
were then removed by evaporation under reduced pressure,
and the residue was crystallized from CH3COOC2H5/hexane
to provide tetrakis[(4-ethynylphenoxy)methyl]methane (40;
2.04 g, 3.80 mmol, 95%) as a colorless solid: mp 174 °C; IR
(KBr) 3296, 2942, 2893, 2109, 1602, 1506, 1471, 1290, 1244,
Cr ysta lliza tion of Tecton s 3 a n d 4. Single crystals
suitable for X-ray diffraction were obtained by allowing
dioxane to diffuse slowly into solutions of tectons 3 and 4 in
DMSO during 1 week at 25 °C. Tecton 3 crystallized as
aggregates of colorless needles, whereas tecton 4 gave colorless
blocks.
X-r a y Cr ysta llogr a p h ic Stu d ies. Data were collected
using a Bruker SMART 2000 diffractometer with Cu KR
radiation at 223 K. The structures were solved by direct
methods using SHELXS-97 and refined with SHELXL-97.43
All non-hydrogen atoms were refined anisotropically, whereas
hydrogen atoms were placed in ideal positions and refined as
riding atoms.
1169, 1050, 1029, 833, 609, 535 cm-1
;
1H NMR (400 MHz,
3
3
CDCl3) δ 7.42 (d, J ) 8.8 Hz, 8H), 6.86 (d, J ) 8.8 Hz, 8H),
4.34 (s, 8H), 3.01 (s, 4H); 13C NMR (100 MHz, CDCl3) δ 159.1,
133.8, 115.0, 114.8, 83.6, 76.3, 66.7, 44.8; MS (FAB, 3-ni-
trobenzyl alcohol) m/e 536, 537; HRMS (FAB, 3-nitrobenzyl
alcohol) calcd for C37H29O4 m/e 537.20660, found 537.20450 (M
+ 1). Anal. Calcd for C37H28O4: C, 82.81; H, 5.26. Found: C,
82.82; H, 5.44.
Str u ctu r e of Tecton 3. Crystals of compound 3 belong to
the orthorhombic space group P21212 with a ) 25.711(2) Å, b
) 37.260(3) Å, c ) 10.0841(9) Å, V ) 9660.5(15) Å3, Dcalcd
)
Tetr a k is[(3-eth yn ylp h en oxy)m eth yl]m eth a n e (41). A
similar procedure using tetrakis[[3-[(trimethylsilyl)ethynyl]-
phenoxy]methyl]methane (39; 845 mg, 1.02 mmol) and tet-
rabutylammonium fluoride (1.0 M, 5.0 mL, 5.0 mmol) provided
tetrakis[(3-ethynylphenoxy)methyl]methane (41; 515 mg, 0.960
mmol, 94%) as colorless crystals: mp 118-119 °C; IR (KBr)
3299, 3070, 2946, 2886, 2111, 1594, 1583, 1490, 1462, 1425,
1.227 g/cm3, and Z ) 4. Full-matrix least-squares refinements
on F2 led to final residuals Rf ) 0.1242, Rw ) 0.3075, and GoF
) 1.244 for 12458 reflections with I > 2σ(I).
Str u ctu r e of Tecton 4. Crystals of compound 4 belong to
the tetragonal space group I1/a with a ) b ) 27.734(1) Å, c )
10.4865(4) Å, V ) 8065.8(5) Å3, Dcalcd ) 1.303 g/cm3, and Z )
4. Full-matrix least-squares refinements on F2 led to final
residuals Rf ) 0.0447, Rw ) 0.1318, and GoF ) 1.047 for 3737
reflections with I >2σ(I).
1320, 1283, 1260, 1155, 1041, 858, 789, 686 cm-1 1H NMR
;
3
3
(400 MHz, CDCl3) δ 7.22 (dd, J ) 8.2 Hz, J ) 7.8 Hz, 4H),
7.10 (d, 3J ) 7.8 Hz, 4H), 7.07 (s, 4H), 6.92 (d, 3J ) 8.2 Hz,
4H), 4.33 (s, 8H), 3.06 (s, 4H); 13C NMR (100 MHz, CDCl3) δ
158.3, 129.5, 125.1, 123.2, 117.8, 115.9, 83.4, 76.6, 66.4, 44.7;
MS (FAB, 3-nitrobenzyl alcohol) m/e 536, 537; HRMS (FAB,
3-nitrobenzyl alcohol) calcd for C37H28O4 m/e 536.198760, found
536.197948. Anal. Calcd for C37H28O4: C, 82.81; H, 5.26.
Found: C, 82.76; H, 5.31.
Ack n ow led gm en t. We are grateful to the Natural
Sciences and Engineering Research Council of Canada,
the Ministe`re de l’EÄ ducation du Que´bec, the Canada
Foundation for Innovation, the Canada Research Chairs
Program, and Merck Frosst for financial support. In
addition, acknowledgment is made to the donors of the
Petroleum Research Fund, administered by the Ameri-
can Chemical Society, for support of this research.
Tecton 3. A mixture of tetrakis[(4-cyanophenoxy)methyl]-
methane (17; 2.58 g, 4.77 mmol), dicyandiamide (3.21 g, 38.2
mmol), and powdered KOH (1.07 g, 19.1 mmol) in 2-methoxy-
ethanol (90 mL) was heated at reflux for 16 h. The resulting
mixture was cooled to 25 °C, and water (100 mL) was added.
The resulting precipitate was separated by filtration and
washed thoroughly with hot water. The crude solid was
crystallized from DMF and triturated with CH3OH to give
tecton 3 (3.98 g, 4.54 mmol, 95%) as a colorless solid: mp 210-
212 °C; IR (KBr) 3500-2900 (bs), 1607, 1539, 1442, 1397, 1243,
Su p p or tin g In for m a tion Ava ila ble: ORTEP drawings
and tables of crystallographic data, atomic coordinates, aniso-
tropic thermal parameters, and bond lengths and angles for
1
compounds 3 and 4; H and 13C NMR spectra for compounds
3, 4, and 31. This material is available free of charge via the
Internet at http://pubs.acs.org.
J O035311H
1
1162, 1049, 815 cm-1; H NMR (300 MHz, DMSO-d6) δ 8.20
3
3
(d, J ) 8.7 Hz, 8H), 7.09 (d, J ) 8.7 Hz, 8H), 6.67 (bs, 16H),
4.43 (s, 8H); 13C NMR (100 MHz, DMSO-d6) δ 169.7, 167.4,
160.9, 129.9, 129.4, 114.1, 66.4, 44.1; MS (FAB, 3-nitrobenzyl
(43) Sheldrick, G. M. SHELXS-97, Program for the Solution of
Crystal Structures and SHELXL-97, Program for the Refinement of
Crystal Structures; Universita¨t Go¨ttingen: Germany, 1997.
J . Org. Chem, Vol. 69, No. 6, 2004 1787