A synthetic strategy toward branched oligomesogenic phosphonic acids: Comparison of alternative pathways

Article abstract of DOI:10.1016/j.tetlet.2013.11.022

This work is devoted to the elaboration of a practical scheme for the synthesis of dendritic derivatives of gallic acid containing a carboxylate-ω-alkylphosphonic acid group and three terminal promesogenic substituents. Two synthetic strategies toward the

Full text of DOI:10.1016/j.tetlet.2013.11.022

Accepted Manuscript
A synthetic strategy toward branched oligomesogenic phosphonic acids: com-
parison of alternative pathways
Maksym F. Prodanov, Olga V. Vashchenko, Valerii V. Vashchenko
PII:
S0040-4039(13)01958-8
DOI:
http://dx.doi.org/10.1016/j.tetlet.2013.11.022
TETL 43817
Reference:
To appear in:
Tetrahedron Letters
Received Date:
Revised Date:
Accepted Date:
25 April 2013
16 October 2013
7 November 2013
Please cite this article as: Prodanov, M.F., Vashchenko, O.V., Vashchenko, V.V., A synthetic strategy toward
branched oligomesogenic phosphonic acids: comparison of alternative pathways, Tetrahedron Letters (2013), doi:
http://dx.doi.org/10.1016/j.tetlet.2013.11.022
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Maksym F. Prodanov, Olga V. Vashchenko, Valerii V. Vashchenko
HO
HO
HO
HO
HO
HO
O
O
O
O
5
steps
O
(CH2)11 P OEt
OEt
3
steps Br (CH2)11
(
CH2)11
O
O
O
(
CH2)11
O
O
(CH2)11
P
OH
OH
(CH2)11
O

2
Tetrahedron Letters
journal homepage: www.elsevier.com
A synthetic strategy toward branched oligomesogenic phosphonic acids: comparison
of alternative pathways
a
a
a,*
Maksym F. Prodanov , Olga V. Vashchenko , Valerii V. Vashchenko
a
State Scientific Institution "Institute for Single Crystals", NAS of Ukraine, 60 Lenin Ave., Kharkov, Ukraine, Fax: +38 057 3410273; Tel: +38 057 3410128;
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
This work is devoted to the elaboration of a practical scheme for the synthesis of dendritic
derivatives of gallic acid containing a carboxylate--alkylphosphonic acid group and three
terminal promesogenic substituents. Two synthetic strategies toward the target compounds were
examined that differ in the sequence of the introduction of the promesogenic units and -
alkylphosphonic group.
Available online
2
009 Elsevier Ltd. All rights reserved.
Keywords:
Dendritic phosphonic acids
Promesogenic substituents
Hydrolysis
Esterification
Mesophase
Developing processes to combine the unique properties of
inorganic nanoparticles (NPs) with anisotropic organic media
Promesogenic fragments
1
-13
Anchoring
group
such as liquid crystals (LCs) is currently of significant interest.
In spite of the long-term interest in such materials, highly-stable
Spacer
(
CH2)11
(CH2)11
CH )
O
O
O
7
-15
O
over time colloids have been only recently described.
Dendritic gallic acid derivatives of type 1 (1a, Figure1) were
O
1a-e
O
(CH2)11 P OH
OH
1
3-
(
2 11
shown to be efficient stabilizers (surfactants) for such colloids.
O
1
5
a
b
c
C H17O
Their structures comprise fragments typical for LC compounds
promesogenic units) and the spacer-separated phosphonic acid
8
O
O
(
F
N
function as an anchoring group. The phosphonic acid linkage
provides reliable binding for a wide variety of inorganic materials
1
6-19
=
C H17O
8
O
O
O
O
typically composing different types of NPs: glass and SiO ,
2
2
0-22
magnetic Fe O , Fe O , CoO, Co, Co(FeO ) ,
GaN, CdS, ZnS, ZnO,
semiconductors
and others.
2
3
3
4
2 2
C H
2
3-27
28,29
30-33
9
19
d
e
ferroelectric BaTiO3
N
N
C H
8
17
Figure 1. Structural formulae of efficient dendritic surfactants 1
Despite the successful application of the surfactants of type 1,
their synthesis and isolation were not considered in detail. The
closest described structural analogues of 1 either do not contain a
phosphonic acid group or even possess a free carboxylic function
3
4-46
of gallic acid.
The synthesis of a sole example of a dendritic
gallic acid derivative with a spacer-separated phosphonic acid
47
function has been described, but this compound contained
simple O-alkyl terminal substituents instead of the promesogenic
units required here. Similar dendritic phosphonic acids were also
—
——
*
Corresponding author. Tel.: +38 057 3410128; fax: +38 057 3410273;
e-mail: valeravv@isc.kharkov.com

recently obtained starting from 5-(azidomethyl)-1,2,3-
tris(dodecyloxy)benzene using the copper (I)-catalyzed Huisgen
The majority of the steps in strategy B are not described in the
literature, even for the synthesis of remote analogues of
compounds 1. Nevertheless, Path B seems to have some
advantages over A. In particular, the introduction of the
expensive promesogenic fragments occurs at a later stage, after
the hydrolysis step. Therefore these fragments can include
sensitive to hydrolysis substituents. Additionally, the path B
allows wider variation of the promesogenic fragment structure.
4
8
―click‖ cycloaddition.
In all cases, these analogues were synthesized using an
approach where O-alkylation of gallic acid was performed in the
3
4-37
earlier steps whereas the carboxylic group was left free
functionalized in the later stages.
or
3
8-45,47
Herein we describe a practical approach for the synthesis of
dendritic derivatives 1a-e, and compare alternative approaches
Synthesis
(
Path A and Path B, Scheme 1).
The required promesogenic alkylating substrates (2a-e) were
obtained by a multi-step synthesis that is described in detail in
the Supplementary Material.
Planning of the synthesis
In general, two synthetic strategies toward target compounds 1
can be proposed (Scheme 1). Path A is based on methods
described in the literature. An advantage of this pathway is that
most of the steps are well-documented for structural analogues of
Initially, the more documented Path A (Scheme 1) was
examined. The alkylation of methyl gallate was not complete
under typical reaction conditions (K CO , prolonged reflux in
2
3
MEK). Instead, a complex mixture of presumably mono-, di- and
tri-alkylated products was formed. It was found, that in order to
complete the reaction, freshly calcinated zeolites were required to
remove water traces (for details of the procedure see the
Supplementary Material). As a result, products 3b and 3c were
obtained in 92% and 73% yields. The next step, the liberation of
the carboxylic function of alkylated methyl gallates 3 proceeded
smoothly only for cyano-derivative 3b, following a previously
1
.
Path A
Path B
HO
HO
O
2
b,2c
OMe
HO
(CH2)11 Br
i
v, vi
Bn O
Bn O
Bn O
(
CH2)11
O
34
O
O
described procedure giving acid 4b in 65% isolated yield.
4f
O
(
CH2)11
O
OH
However, in the case of alkoxy-analogue 3c, under the same
conditions only the starting ester was recovered. The ester 3c was
also found to have unanticipated high resistance toward base-
promoted hydrolysis under other conditions (Table 1).
OMe
b,3c
(
CH2)11
iii, iv
3
Bn O
Bn O
ii
O
5
O
Table 1. Hydrolysis of compounds 3b and 3c under different
basic conditions
O
(CH2)11 P OEt
OEt
Bn O
(
CH2)11
O
vii
O
Entry Starting Base
material
Conditions
Result
(
CH2)
O
11
HO
OH
O
b
6
O
O
1
2
3
4
5
6
7
8
9
1
3b
3c
3c
3c
3c
3c
3c
3c
3c
3b
KOH
KOH
KOH
LiOH
KOH
THF / EtOH/ H O, reflux
65%
HO
HO
2
(
CH2)11
(CH2) P OEt
11
a
O
EtOH/H O, reflux
n/r
n/r
n/r
n/r
2
4
b,4c
OEt
a
iii, iv
i-PrOH/ H O, reflux
2
a
THF/ H O, reflux
2
i
a
(
CH2)
11
Br
THF / EtOH/ H O, reflux
2
a
2a-e
Bu NOH PhH/ H O, reflux
n/r
4
2
a
(CH2)11
KOH
KOH
CsOH
CsOH
Bu
4
NOH /i-PrOH/H O,reflux n/r
2
O
a
O
O
Bu NOH/PhH/H O, reflux
n/r
4
2
O
(
CH2)11
O
b
DMSO/ H O, 80 C
52%
P
OEt 7a-e
OEt
2
(CH2)11
O
0
DMSO/ H O, r.t.
complex
mixture
(CH2)11
2
viii, ix
a-e
a
No reaction according to TLC and HPLC.
Isolated yield.
b
1
Scheme 1. Generalized approaches for the synthesis of
Assuming that the low reactivity of 3c was caused by its
dendritic phosphonic acids of type 1. The promesogenic unit
assignment is the same as given in Figure 1. Reagents and
conditions: (i) K CO , KI, zeolites CaA, MEK, reflux; (ii) 3b:
limited solubility in alcoholic or water-alcoholic media (Table 1,
entries 2 and 3), we tried to homogenize the reaction mixture by
adding THF as a co-solvent. But even under prolonged refluxing
the ester 3c remained unchanged (Table 1, entries 4 and 5). Two-
phase media were also inefficient (entries 6 and 8). Finally, we
succeeded in obtaining acid 4c using CsOH in DMSO/water as
the solvent (entry 9, Table 1). It is worth noting, that even in such
strong basic medium full conversion of the starting ester could
only be achieved by heating at 80 C for 4 hours; at 70 C the
reaction rate drops significantly, and below 60 C it almost stops
completely. However, these vigorous conditions are not generally
applicable. In particular, in the case of compound 3b, the cyano
groups underwent substantial hydrolysis resulting in the
formation of mono- and di-carbamoyl byproducts (see the
Supplementary Material).
2
3
KOH, THF/EtOH, reflux; 3c: CsOH, DMSO, 80 C; (iii) 11-
bromo-1-undecanol, DCC, DMAP, THF, r.t.; (iv) P(OEt)3,
1
30 °С; (v) benzyl chloride, K CO , KI, MEK, reflux; (vi)
2 3
NaOH, EtOH, reflux; (vii) H , 10% Pd/C, EtOAc, r.t.; (viii)
2
TMSBr, CH Cl , 0 °С, r.t.; (ix) H O/THF, r.t.
2
2
2
However, the latter steps including introduction of the
phosphoryl group is not described for compounds containing
terminal promesogenic substituents. It is worth also noting, that
several groups (ester, cyano, etc.), which are often included in the
promesogenic fragment, can be unstable under the hydrolysis
conditions (e.g., transformation of 3 into 4, Scheme 1).
Further progress along Path A proved to be even more

4
Tetrahedron
unsuccessful. Thus, all our attempts to involve acids 4b or 4c in
the esterification with 11-bromo-1-undecanol using DCC/DMAP
equiv) can be recovered in high purities. The de-O-alkylation of
phosphonates 7a-e occured smoothly and furnished the desired
phosphonic acids 1 in good yields (Table 2).
4
9
(Steglich-Hassner protocol ) failed. At ambient temperature the
reactions did not occur (see the Supplementary Material, Table
SM-1), presumably due to the very low solubility of the
corresponding acids. Compound 4b also did not react at elevated
temperatures, while in the case of 4c, the formation of only N-
cyclohexyl gallic acid amide was detected. Varying the reaction
conditions (solvent, temperature, reagents ratio) resulted in either
recovery of the starting materials or formation of by-products
The phase behaviour of the dendritic phosphonic acids 1a-e
was studied using differential scanning calorimetry (DSC) and
polarized optical microscopy (POM), see Table 3 and the
Supplementary Material.
Table 3. Phase types (according to POM) and their transition
temperatures (according to DSC in the cooling mode) for new
oligomesogenic phosphonic acids 1
(
Table SM-1, Supplementary Material). Similar reaction patterns
50-54
have been reported previously:
when the DCC-acid adduct
Phase transitions temperatures and enthalpy, C (J/g)
reacts too slowly with an alcohol, the rearrangement of the
corresponding O-acyl-ureas into N-isomers occurs followed by
transformation into the undesired N-cyclohexylamide by-
products. Our attempts to carry out trans-esterification of 3b and
Iso
 79.3
7.3)
 101.3
5.8)
N
–
Smectic phases
Cr or Glass
1
1
a
 68.0

(
(30.1)
b
–
 46.7
(0.9)
 29.7

3
c with 11-bromo-1-undecanol under acid catalysis also failed
(
(8.7)
and led to complex reaction mixtures. The reactions of the
corresponding acid chlorides also did not result in formation of
the desired compounds.
a)
1
1
c
d
 230.5
 101.8
–
–
 199.0
 67.0
(19.1)


(
6.6)
 87.2
0.5)
1
e
 84.0  72.0
(2.3) (3.2)
 56.0

The failure in the synthesis of the target compounds 1
following Path A prompted us to change the strategy. The
alternative synthetic approach depicted in Scheme 1 (Path B)
employs a key intermediate 6 that can be converted into the
desired surfactants of type 1 in two simple steps: alkylation of the
phenolic hydroxy groups of the gallic acid fragment with
promesogenic intermediates 2a-e followed by mild de-O-
(
(36.7)
a)
measured using POM in the heating mode, the melting is
accompanied with decomposition
All of the synthesized dendritic phosphonic acids show
sequences of phase transitions which are reproducible over
several cycles ―heat-cool‖ except high-melting compound 1c,
which starts to decompose above its melting point. Using the
POM and DSC data, it is difficult to determine definitely the
mesophase types since very fine and untypical textures were
observed (see the Supplementary Material). The assignment is
also hampered by the nature of the studied compounds which are
surfactants thereby providing vertical alignment even on glass
substrates treated with polyvinyl alcohol. Taking into account the
high viscosities of the birefringent melt and rather high iso-
mesophase enthalpy values, the appearance of smectic type
phase(s) can be assumed for almost all compounds (see Table 3).
For compound 1e the highest-temperature phase in the
mesophase sequence can be assigned to the nematic (N) due to
both relatively low viscosity and enthalpy values (0.5 J/g). More
definite assignment requires further investigation and will be
described elsewhere.
5
5
alkylation of 7a-e with TMSBr.
The key compound 6 was obtained in five steps (see Scheme
1
). Alkylation of methyl gallate with benzyl chloride followed by
5
6
hydrolysis resulted in the formation of acid 4f in high yield.
Esterification of 4f with 11-bromo-1-undecanol using the
4
9
Steglich-Hassner procedure, and subsequent treatment with
5
7
triethyl phosphite, furnished smoothly diethylphosphonate 5.
Catalytic debenzylation of 5 over Pd/C resulted in the formation
of key compound 6 in an overall yield of 54% based on methyl
gallate.
The alkylation procedure (6  7a-e, Scheme 1) is similar to
that described above for compound 3 (Path A, Scheme 1) and the
full conversion of tri-hydroxy phosphonate
corresponding product 7 also required the application of zeolites
see Table 2).
6 into the
(
In conclusion, we have proposed a convenient and practical
route for the synthesis of novel dendritic derivatives of gallic acid
containing carboxylate--alkylphosphonic acid groups as focal
point and three terminal promesogenic substituents. The route is
tolerant to hydrolysis-sensitive groups such as cyano and ester
functions. The advantages of the proposed synthetic strategy
(Path B) are revealed when the synthesis of a large range of
dendritic phosphonic acids is required due to the fewer synthetic
steps in comparison with Path A.
Table 2. Synthesis of target compounds 1 and 7 according to
Path B
Promesogenic alkylators
Yield (%)
 7 7  1
6
6
4
69
2
a
7
6
0
2
90
78
2
b
Acknowledgments
2
c
Financial support from the National Academy of Science of
Ukraine (projects # 0110U003977, # 0112U004502 and research
fellowship #288-12.10.2011). We also thank to Dr. N. Gorobets
for the valued and fruitful discussions.
6
8
5
6
74
91
2
d
2
e
Supplementary Material
It should be noted that purification of phosphonates 7a-e can
be easily achieved by flash chromatography instead of repeated
crystallizations, as was required for purification of esters 3.
Moreover, the excess of the expensive alkylators 2a-e (up to 0.5
Supplementary data associated with this article can be found,
in the online version, at http://dx.doi.org/...

3
3
3
3
3
4
5. Mocanu, A. S.; Amela-Cortes, M.; Molard, Y.; Cîrcu, V.; Cordier,
S. Chem. Commun. 2011, 47, 2056.
6. Molard, Y.; Dorson, F.; Circu, V.; Roisnel, T.; Artzner, F.;
Cordier, S. Angew. Chem. Int. Ed. 2010, 49, 3351.
7. Terazzi, E.; Rogez, G.; Gallani, J.-L.; Donnio, B. J. Am. Chem.
Soc. 2013, 135, 2708.
8. Percec, V.; Schlueter, D.; Ungar, G.; Cheng, S. Z. D.; Zhang, A.
Macromolecules 1998, 31, 1745.
9. Kouwer, P. H. J.; Mehl, G. H. J. Am. Chem. Soc. 2003, 125,
References and notes
1
.
Hegmann, T.; Qi, H.; Marx, V. M. J. Inorg. Organomet. Polym.
007, 17, 483.
2
2
3
.
.
Bisoyi, H. K.; Kumar, K. Chem. Soc. Rev. 2011, 40, 306.
Stamatoiu, O.; Mirzaei, J.; Fend, X.; Hegmann, T. Top. Curr.
Chem. 2012, 318, 331.
4
5
6
7
.
.
.
.
Nealon, G.L.; Greget, R.; Dominguez, C.; Nagy, Z.T.; Guillon, D.;
Gallani, J.-L.; Donnio, B. Beilstein. J. Org. Chem. 2012, 8, 349.
Gardner, D. F.; Evans, J. S; Smalyukh, I. I. Mol. Cryst. Liq. Cryst.
1
1172.
0. Kouwer, P. H. J.; Pourzand, J.; Mehl, G. H. Chem. Commun.
004, 66.
2
011, 545, 1227.
2
Cordoyiannis, G.; Kurihara, L. K.; Martinez-Miranda, L. J.;
Glorieux, Ch.; Thoen, J. Phys. Rev. E, 2009, 79, 011702.
Prodanov, M. F.; Kolosov, M. A.; Krivoshey, A. I.; Fedoryako, A.
P.; Yarmolenko, S.N.; Semynozhenko, V. P.; Goodby, J. W.;
Vashchenko, V. V. Liq. Cryst. 2012, 39, 1512.
4
4
1. Donnio, B.; Binnemans, K. Chem. Mater. 2005, 17, 6589.
2. Aprahamian, I.; Yasuda, T.; Ikeda, T.; Saha, S.; Dichtel, W.R.;
Isoda, K;. Kato, T.; Fraser Stoddart, J. Angew. Chem. Int. Ed.
2
007, 46, 4675.
4
3. Baranoff, E. D.; Voignier, J.; Yasuda, T.; Heitz, V.; Sauvage, J.-
P.; Kato, T. Angew. Chem. Int. Ed. 2007, 46, 4680.
4. Kouwer, P. H. J.; Mehl, G. H. J. Mater. Chem. 2009, 19,1564.
5. Mocanu, A. S.; Amela-Cortes, M.; Molard, Y.; Cîrcu, V.; Cordier,
S. Chem. Commun. 2009, 47, 3597.
6. Rosen, B. M.; Wilson, C. J.; Wilson, D. A.; Peterca, M.; Imam, M.
R.; Percec, V. Chem. Rev. 2009, 109, 6275.
7. Pittelkow, M.; Nielsen, C. B.; Broeren, M. A. C.; van Dongen, J.
L. J.; van Genderen, M. H. P.; Meijer, E. W.; Christensen, J. B.
Chem.-Eur. J. 2005, 11, 5126.
8. Fleutot, S.; Nealon, G. L.; Pauly, M.; Pichon, B. P.; Leuvrey, C.;
Drillon, M.; Gallani, J.-L.; Guillon, D.; Donnio, B.; Begin-Colin,
S. Nanoscale 2013, 5, 1507.
9. Pielartzik, H.; Irmisch-Pielartzik, B.; Eicher, U. T. In Methods in
Organic Chemistry. 4th edition. Carboxylic Acids and Carboxylic
Acid Derivates; Falbe, J., Ed.; Georg Thieme Verlag: Stuttgart,
8
9
1
.
.
Mirzaei, J.; Reznikov, M.; Hegmann, T. J. Mater. Chem. 2012, 22,
2
2350.
4
4
Marx, V. M.; Girgis, H. P.; Heiney, A.; Hegmann, T. J. Mater.
Chem. 2008, 18, 2983.
0. Draper, M. I.; Saez, M. S.; Cowling, J. P.; Heinrich, G. B.;
4
4
Donnio, B.; Guillon, D.; Goodby, J. W. Adv. Funct. Mat. 2011,
2
1, 1260.
1
1
1
1. Cowling, J. S. J.; Toader, V.; Lavigne, C.; Saez, I. M.; Lennox, R.
B.; Goodby, J. W.; Reven, L. Soft Matter 2012, 8, 173.
2. Soule, E. R.; Milette, J.; Reven, L.; Rey, A. D. Soft Matter 2012,
4
4
8
, 2860.
3. Prodanov, M. F.; Pogorelova, N. V.; Kryshtal, A. P.; Klymchenko,
A. S.; Mely,Y.; Semynozhenko, V. P.; Krivoshey, A. I.; Reznikov,
Y. A.; Yarmolenko, S. N.; Goodby, J. W.; Vashchenko, V. V.
Langmuir 2013, 29, 9301.
1
1
4. Buluy, O.; Burseva, D.; Hakobyan, M. R.; Goodby, J. W.;
Kolosov, M. A.; Reznikov, Yu.; Hakobyan, R. S.; Slyusarenko,
K.; Prodanov, M. F.; Vashchenko, V. V. Mol. Cryst. Liq. Cryst.
1
985; Vol. E5, pp 674-678.
5
5
5
5
0. Nagvekar, D. S; Delaviz, Y; Prasad, A.; Merola, J. S.; Marand, H.;
Gibson, H. J. Org. Chem. 1996, 61, 1211.
1. Ionita, P.; Whitwood, A. C.; Gilbert, B. C. J. Chem. Soc., Perkin
Trans. 2, 2001, 1453.
2
012, 560, 149.
5. Vashchenko, V. V.; Prodanov, M.; Pogorelova, N.; Kurochkin, O.;
Popova, E.; Krivoshey, A.; Klymchenko, A.; Fedoryako, A.;
Yarmolenko, S.; Gamzaeva, S.; Reznikov, Y.; Goodby, J. Abstract
Book, 24th International Liquid Crystal Conference, Mainz,
Germany, Aug 19th - 24th, 2012; PIII-095.
2. Alvaro, M.; García, H.; Miranda, M. A.; Primo, J. Tetrahedron
1
992, 48, 3437.
3. Brecknell, D. J.; Carman, R. M.; Day, P. J. Aust. J. Chem., 1984,
7, 2323.
3
1
1
1
1
2
6. Neves, B. R. A.; Salmon, M. E.; Russell, P. E. Jr.; Troughton, E.
B. Langmuir 2001, 17, 8193.
7. Hanson, E. L.; Schwartz, J.; Nickel, B.; Koch, N.; Danisman, M.
F. J. Am. Chem. Soc. 2003, 125, 16074.
5
5
4. Geffken, D.; Zinner, G. Chem. Ber. 1975, 108, 3730.
5. McKenna, C. E.; Higa, M. T.; Cheung, N. H.; McKenna, M.-C.
Tetrahedron Lett. 1977, 197, 155.
6. Ren, Y.; Himmeldirk, K.; Chen, X. J. Med. Chem. 2006, 49, 2829.
7. Bhattacharya, A. K.; Thyagarajan, G. Chem. Rev. 1981, 81, 415.
5
5
8. Nie, H. Y.; Walzak, M. J.; McIntyre, N. S. J. Phys. Chem. B 2006,
1
10, 21101.
9. Gouzman, I.; Dubey, M.; Carolus, M. D.; Schwartz, J.; Bernasek,
S. L. Surf. Sci. 2006, 600, 773.
0. Yee, C.; Kataby, G.; Ulman, A.; Prozorov, T.; White, H.; King,
A.; Rafailovich, M.; Sokolov, J.; Gedanken, A. Langmuir 1999,
1
5, 7111.
2
2
2
1. Sahoo, Y.; Pizem, H.; Fried, T.; Golodnitsky, D.; Burstein, L.;
Sukenik, C. N.; Markovich, G. Langmuir 2001, 17, 7907.
2. Baldi, G.; Bonacchi, D.; Franchini, C. M.; Gentili, D.; Lorenzi, G.;
Ricci, A.; Ravagli, C. Langmuir 2007, 23, 4026.
3. Simpkins, B. S.; Hong, S.; Stine, R.; Mäkinen, A. J.; Theodore, N.
D.; Mastro, M. A.; Eddy, C. R. Jr.; Pehrsson, P. E. J. Phys. D:
Appl. Phys. 2010, 43, 015303.
2
2
2
4. Green, M.; J. Mater. Chem. 2010, 20, 5797.
5. Kopping, J. T.; Patten, T. E. J. Am. Chem. Soc. 2008, 130, 5689.
6. Morris-Cohen, A. J.; Donakowski, M. D.; Knowles, K. E.; Weiss,
E. A. J. Phys. Chem. C 2010, 114, 897.
2
2
7. Perkins, C. L. J. Phys. Chem. C 2009, 113, 18276.
8. Kim, P.; Doss, N. M.; Tillotson, J. P.; Hotchkiss, P. J.; Pan, M.-J.;
Marder, S. R.; Li, J.; Calame, J. P.; Perry,; Joseph W. ACS Nano
2
009, 3, 2581.
2
9. Schulmeyer, T.; Paniagua, S. A.; Veneman, P. A.; Jones, S. C.;
Hotchkiss, P. J.; Mudalige, A.; Pemberton, J. E.; Marder, S. R.;
Armstrong, N. R. J. Mater. Chem. 2007, 17, 4563.
3
3
0. Queffélec, C.; Petit, M.; Janvier, P.; Knight, D. A.; Bujoli, B.
Chem. Rev. 2012, 112, 3777.
1. Gao, W.; Dickinson, L.; Grozinger, C.; Morin, F. G.; Reven, L.
Langmuir 1996, 12, 6429.
3
3
2. Traina, C. A. ; Schwartz, J. Langmuir 2007, 23, 9158.
3. Holland, G. P.; Sharma, R.; Agola, J. O.; Amin, S.; Solomon, V.
C.; Singh, P.; Buttry, D. A.; Yarger, J. L. Chem. Mater. 2007, 19,
2
519.
3
4. Terazzi, E. ; Bourgogne, C.; Welter, R.; Gallani, J.-L.; Guillon,
D.; Rogez, G.; Donnio, B. Angew. Chem. Int. Ed. 2008, 120, 500.

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A synthetic strategy toward branched
oligomesogenic phosphonic acids:
comparison of alternative pathways
Leave this area blank for abstract info.
Maksym F. Prodanov, Olga V. Vashchenko, Valerii V. Vashchenko
HO
HO
HO
HO
HO
HO
O
O
O
O
5
steps
O
(CH2)11 P OEt
OEt
3
steps Br (CH2)11
(
CH2)11
O
O
O
(
CH2)11
O
O
(CH2)11
P
OH
OH
(CH2)11
O