Scalable Synthesis of Tetrapodal Octaamine

Article abstract of DOI:10.1002/ejoc.201801410

An effective and high-yielding synthesis of an air stable tetrapodal octaamine, a rigid shape-persistent molecule with four ortho-phenylenediamine moieties is reported. It can be potentially transformed into a wide range of benzimidazole, benzotriazole, and pyrazine derivatives for practical applications.

Full text of DOI:10.1002/ejoc.201801410

A Journal of
Accepted Article
Title: Scalable Synthesis of Tetrapodal Octaamine
Authors: Ishfaq Ahmad, Javeed Mahmood, and Jong-Beom Baek
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10.1002/ejoc.201801410
European Journal of Organic Chemistry
COMMUNICATION
Scalable Synthesis of Tetrapodal Octaamine
Ishfaq Ahmad, Javeed Mahmood,* Jong-Beom Baek*
Abstract: An effective and high-yield synthesis of an air stable
tetrapodal octaamine, a rigid shape-persistent molecule with four
ortho-phenylenediamine moieties, is reported. It can be potentially
transformed into a wide range of benzimidazole, benzotriazole, and
pyrazine derivatives for practical applications.
designed tetrapodal octaamine has to be treated in inert
atmosphere (air free) and then needs to be used right after
reduction of the nitro precursor (no storage is possible). Although
tetrakis-phenylnediamine functionalized tetraphenylmethane
(4,4',4'',4'''-methanetetrayltetrakis(benzene-1,2-diamine))
can
potentially be formulated into a wide range of interesting materials,
including 3D porous organic polymers,[13b,13c,15b,17] metal organic
frameworks,[10b,18] and 3D cage like metal complexes,[14a] to date
its large-scale synthesis and purification has been extremely
limited.
Introduction
Rigid tetrapodal molecules, containing four identical rigid groups
protruding from a common center toward each corner of a
tetrahedron, have appealed to researchers as versatile building
blocks for the synthesis of giant three-dimensional (3D) molecules.
The formation of such bulky molecules are generally investigated
in both materials and supramolecular chemistry studies.[1]
Tetraphenylmethane[2] and its derivatives[3] are a class of shape
persistent organic units containing four rigid aromatic rings
projecting from a central carbon in a tetrahedral structure.[3-4] To
construct shape persistent structures,[5] including dendrimers and
porous polymers,[6] cage molecules,[7] interlocked structures[8] and
organic frameworks,[5,9] as well as coordination polymers[4,10] and
metal organic frameworks (MOF),[11] the tetraphenylmethane
moiety primarily provides the rigidity at a molecular structure
level.[3-4,12]
Results and Discussion
In order to efficiently synthesize tetrakis-phenylnediamine
functionalized tetraphenylmethane, a versatile and high yield
synthesis route is necessary. Here, we report a facile route for the
synthesis
of
soluble
and
air
stable
4,4',4'',4'''-
any
methanetetrayltetrakis(benzene-1,2-diamine)
purification using column chromatography.
without
Tetrakis(4-aminophenyl)methane (3) was synthesized from
tetraphenylmethane according to literature reports (SI).[19]
Tetrakis(4-nitrophenyl)methane (2) was obtained after nitration
with fuming nitric acid at −10 °C, and then the resulting product
(Figure S1 and S2) was subsequently reduced in the presence
of palladium on activated carbon (Pd/C, Caution: Pd/C can self-
The ortho (o)-phenylenediamine group is an important chemical
unit, which can be powerfully transformed into a variety of other
aromatic rings, such as quinoxalines,[13] metal salphens,[14]
benzimidazoles,[15] and etc.
.
ignite when dry) and hydrazine hydrate (N2H4 H2O) to give
compound (3) in high yield (Figure S3 and S4). The synthesis of
octaamine (6) starts with the protection of the amino groups of the
tetrakis(4-aminophenyl) methane with acetic anhydride.
Organic constituents with the tetraphenylmethane unit are of
great interest due to their unique structure.[5] When each phenyl
ring of the tetraphenylmethane is functionalized, its predefined
geometry and rigidity allow the formation of diamond-like 3D
network polymers.[5] Tetraphenylmethane decorated with an o-
diamine group at each phenyl ring can be a crucial unit for diverse
modifications. For example, the o-phenylenediamine constituents
promptly condense with diketone containing molecules to provide
diverse heterocyclic functionalities and organic frameworks.[13,17]
However, one major drawback associated with molecules
containing the o-phenylenediamine moiety is their oxidative
instability. Rapid oxidation occurs after reduction of the
corresponding aromatic nitro precursor.[16] Consequently, the
[*]
I. Ahmad, Prof. J. Mahmood, Prof. Jong-Beom Baek Corresponding
Author(s)
School of Energy and Chemical Engineering/Centre for Dimension
Controllable Organic Frameworks
Ulsan National Institute of Science and Technology (UNIST)
Ulsan 44919 South Korea
E-mail: jabbeak@unist.ac.kr , javeed@unist.ac.kr
Homepage: http://jbbaek.unist.ac.kr
Scheme 1. Our New Three Step Synthesis of Air Stable Tetrapodal
Octaamine 8HCl (6)
Supporting information and ORCID(s) from the author(s) for this
article are available on the www under https
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10.1002/ejoc.201801410
European Journal of Organic Chemistry
COMMUNICATION
Subsequent in-situ nitration to the ortho position of para-
aminophenyl (p-aminophenyl) with potassium nitrate (KNO3) in
the presence of para-toluene sulfonic acid (p-TSA) at room
temperature results in the high yield of 4 (Scheme 1).[20] The ortho
nitro derivative (4) was recrystallized from dimethylformamide
(DMF) and a small amount of water to give a light-yellow powder
(Figure S5 and S6). The purified 4 was refluxed in aqueous
ethanol in the presence of sodium hydroxide (NaOH) to remove
used in gas storage, opto-electronics, asymmetric catalysis,[1d]
and beyond.
As a proof of concept, the compound 6 was treated with benzil
׳
and 4,4 -dimethoxybenzil to give compounds 7 and 8 in ethyl
glycol/ethanol in the presence of potassium acetate (Scheme 2).
The compounds 7 and 8 were isolated in ~60% yield after column
chromatography and were characterized by NMR, HR-MS and EA
(Figure S11-S14). The synthesis of
benzimidazole derivatives of the
compound 6 were also carried out. To
prepare benzimidazole derivatives
compound 6 was treated with 4-
methoxybenzoic
nitrobenzoic
acid
acid
and
obtain
10 in
4-
to
compounds
9
and
polyphosphoric acid (PPA) at
145 °C.[15c] The resultant products
were characterized by Direct Insertion
Probe MS (DIP-MS). Due to poor
solubility further purification and
characterization was not possible.
These quinoxaline and benzimidazole
Scheme 2. Synthesis of quinoxaline derivatives (7, 8) of tetrapodal octamine
derivatives illustrate that
a broad
range of materials can be designed
and synthesized using this new tetrapodal octamine building
block.
the acetyl protecting groups. The product, 4,4',4'',4'''-
methanetetrayltetrakis(2-nitroaniline) (5), was precipitated in
water after evaporation of the ethanol. The resulting yellowish
solid was collected by filtration and washed with water, which was
technically pure enough to proceed without further purification
(Figure S7 and S8).
Finally, the ortho nitro derivative (5)
was reduced to tetrapodal octaamine
octahydrochloride in ethanol in the
presence of tin(II) chloride dihydrate
(SnCl2·2H2O)
and
concentrated
hydrochloric acid (37% HCl). The
product (6) was recrystallized while
cooling to room temperature. The
crystals were collected by filtration and
washed with concentrated HCl (3×8
mL). The precipitate was also washed
with ethyl acetate to remove unbound
HCl from the material. After drying, the
crystals were dissolved again in warm
Scheme 3. Synthesis of benzimidazole derivative (9, 10) of tetrapodal octamine.
water and recrystallized by adding concentrated HCl. Creamy
white powdery crystals formed were collected and dried (Figure
S9 and S10). The crystals were stable in a sealed vial on the
bench top for at least six months.
This synthesis strategy of tetrapodal octaamine is an efficient,
facile and high-yield method with practical uses. The most
appealing feature is the formation of an air-stable hydrochloride
salt form of tetrapodal octaamine. With a convenient and high-
yield synthetic route, tetrapodal octaamine octahydrochloride (6)
is an potentially attractive building block for diverse applications,
such as supramolecular superstructures, 3D covalent organic
network structures,[5],[9d] dendritic macromolecules[6b] and
rotaxanes[21]. Specifically, 3D porous materials can be extensively
Conclusions
In summary, we report a facile and efficient route for the scalable
synthesis of othro-diamine functionalized tetraphenylmethane
(4,4',4'',4'''-methanetetrayltetrakis(benzene-1,2-diamine)), which
is air-stable and thus can be stored in a vial on the benchtop at
ambient conditions for several months without exceptional
precaution. The extra advantage associated with this synthetic
route is that it does not involve column chromatography for the
purification of all three compounds (4, 5 and 6). Air stable
tetrapodal octaamine 6 can be a useful precursor and/or a
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10.1002/ejoc.201801410
European Journal of Organic Chemistry
COMMUNICATION
mL), and dried under reduced pressure (0.05 mmHg). Then, the product
was further washed with ethyl acetate to remove unbound HCl. The
product was recrystallized from diluted HCl solution. Concentrated HCl
was added to the boiling water containing the compound 6 slowly until the
solution remains transparent. On cooling down to room temperature
creamy white powdery crystals were formed (1.87 g, 95.71 %): mp 286-
288 °C; 1H NMR (400 MHz, DMSO-d6) δ 7.15-7.13 (d, J = 8 Hz,4H), 7.06
(s, 4H), 7.01-6.99 (d, J = 8 Hz, 4H); 13C NMR (400 MHz, DMSO-d6) δ
143.93, 129.00, 127.07, 125.21, 124.58, 122.76, 62.84 Anal. Calcd for
C25H36N8Cl8: C, 41.04, H, 4.96, N, 15.30, Cl, 38.73. Found: C, 41.54, H,
4.95, N, 15.58. HRMS (EI) calcd for C25H28N8 440.2437, found 440.2448.
building block for a variety of condensation reactions for extended
tetraphenylmethane derivatives.
Experimental Section
General Methods. All the reagents and solvents were purchased from
Sigma-Aldrich unless otherwise stated. Solvents were degassed with
nitrogen purging prior to use. All the reactions were carried out under
nitrogen atmosphere using oven dried glassware. Tetraphenylmethane
was purchased from Alfa Aesar. Tetrakis(4-aminophenyl) methane was
synthesized according to a procedure described in the literature.[19] Proton
(1H) and carbon thirteen (13C) nuclear magnetic resonance (NMR) spectra
were recorded on an AVANCE III HD 400 MHz FT-NMR (Bruker)
spectrometer. Elemental analysis (EA) was performed with a Thermo
Scientific Flash 2000 Analyzer. Melting points were measured on a KSP1N
automatic melting point meter (A. Krüss Optronic GmbH, Germany). High
resolution mass spectra (HRMS) measurements were conducted using
JEOL/JMS-700 (2).
Tetrakis(2,3-diphenylquinoxalin-6-yl) methane (7).
A mixture of
ethylene glycol (10 mL) and ethanol (10 mL) was added in a three-neck
round bottom flask (100 mL) containing compound (6) (100 mg, 0.14
mmol) and benzil (143.4 mg, 0.68 mmol) under nitrogen atmosphere.
Potassium acetate (105 mg, 1.07 mmol) was also added to the reaction
mixture and heated to 110 °C for 12 h. After completion of the reaction, the
mixture was cool to room temperature and poured into ice cold water to
precipitate out the product as a light yellow solid. Then, the crude product
was purified by column chromatography on silica gel (hexane/EtOAc, 4:1)
to obtain pure product as a white powder (99 mg, 64 %). mp 275-278 °C;
1H NMR (400 MHz, CDCl3) δ 8.34 (s, 4H), 8.15-8.13 (d, J = 8 Hz, 4H),
7.80-7.78 (d, J = 8 Hz, 4H), 7.52-7.46 (dd, J = 8 Hz 16H), 7.35-7.33 (t, J =
8 Hz, 12H), 7.31-7.27 (t, J = 8 Hz, 12H); 13C NMR (400 MHz, CDCl3) δ
154.29, 154.13, 146.72, 141.28, 140.36, 139.10, 139.04, 134.19, 130.31,
129.96, 129.13, 128. 90, 128.40. 65.90; Anal. Calcd for C81H52N8: C, 85.54,
H, 4.61, N, 9.85. Found: C, 85.15, H, 5.16, N, 9.25. HRMS (ESI) m/z: [M +
Na]+ calcd for C81H52N8Na: 1159.4213, found 1159.4211.
N,N',N'',N'''-(methanetetrayltetrakis(2-nitrobenzene-4,1-
diyl))tetraacetamide (4). Tetrakis(4-aminophenyl) methane (3, 2 g, 5.26
mmol) and acetic anhydride (90 mL) were charged into a three-necked
round-bottom flask (250 mL). The mixture was stirred for 30 min, and then
p-toluenesulfonic acid monohydrate (4.50 g, 23.67 mmol) was added. The
solution was cooled to 0 °C in an ice bath and KNO3 (2.23 g, 22.09 mmol)
was slowly added. The ice bath was removed, and the solution was stirred
overnight at room temperature, resulting in a cloudy pinkish orange
solution. The reaction mixture was poured into water (700 mL), giving a
yellow precipitate, which was collected by suction filtration and washed
with water. The product was recrystallized from DMF with the addition of a
small amount of water. To the boiling DMF water was slowly to avoid any
turbidity of the solution and the addition was continued until the solution
maintains transparency. The light-yellow powder was precipitated out from
the solution after cooling to room temperature (3.72 g, 97 %): mp 242-
244°C; 1H NMR (400 MHz, DMSO-d6) δ 10.35 (s, 4H), 7.72 (s, 4H), 7.65-
7.63 (d, J = 8 Hz, 4H), 7.54-7.52 (d, J = 8 Hz, 4H) δ 2.07 (s, 12H); 13C NMR
(400 MHz, DMSO) δ 169.0, 141.9, 140.8, 136.6, 130.7, 125.7, 125.5, 62.6.
Anal. Calcd for C33H28N8O12: C, 54.40, H, 3.87, N, 15.38, O, 26.35. Found:
C, 54.41 H, 3.92, N, 15.48, O, 26.38. HRMS calcd for C33H28N8O12
728.1827, found 728.1804.
Tetrakis(2,3-bis(4-methoxyphenyl)quinoxalin-6-yl)methane
(8).
Compound (6) (100 mg, 0.14 mmol) and 4,4׳-dimethoxybenzil (184.3 mg,
0.68 mmol) were charged into a three-neck round bottom flask (100 mL)
containing ethanol (10 mL) and ethylene glycol (10 mL). Then, potassium
acetate (105 mg, 1.07 mmol) was added. The reaction mixture was under
reflux for 12 h. After completion of the reaction, the mixture was allowed to
cool to room temperature and poured into ice cold water to precipitate out
the product. Then, the crude product was purified by column
chromatography on silica gel (hexane/EtOAc, 7:3) to obtain pure product
1
as a white powder (125 mg, 66 %). mp 246-248 °C; H NMR (400 MHz,
(CD3)2CO-d6) δ 8.23 (s, 4H), 7.91-7.89 (d, J = 8 Hz, 4H), 7.68-7.66 (d, J =
8 Hz, 4H), 7.44-7.41(d, J = 8 Hz, 8H), 7.38-7.36 (d, J = 8 Hz, 8H), 6.79-
6.77 (d, J = 8 Hz, 8H), 6.71-6.69 (d, J = 8 Hz, 8H), 3.70 (s, 12H) 3.64 (s,
12H); 13C NMR (400 MHz, acetone-d6) δ 161.07, 160.99, 154.00, 153.82,
147.11, 141.43, 140.44, 134.40, 132.50, 132.45, 132.13, 130.64, 129.19,
114.21, 114. 13, 66.26. 55.55; Anal. Calcd for C89H68N8O8: C, 77.60, H,
4.98, N, 8.13, O, 9.29 Found: C, 77.41 H, 4.96, N, 7.89. O, 10. 12. HRMS
(ESI) m/z: [M + Na]+ calcd for C89H68N8O8Na: 1399.5058, found 1399.5052.
4,4',4'',4'''-Methanetetrayltetrakis(2-nitroaniline) (5). In a three-necked
round-bottom flask (500 mL), compound 4 (2.24 g, 3.07 mmol) was
dispersed in ethanol (300 mL), and sodium hydroxide (0.81 g, 20.13 mmol)
in water (14 mL) was slowly added. The mixture was refluxed for 2 h with
stirring and then cooled to room temperature. The solution was
concentrated by the evaporation of ethanol on a rotary evaporator. Then
water (100 mL) was added to isolate product, which was collected on a
Buchner funnel as a yellow powder (1.70 g, 98 %): mp ˃ 350 °C; 1H NMR
(400 MHz, DMSO-d6) δ 7.71 (s, 4H), 7.59 (s, 8H, -NH2), 7.06-7.04 (d, J =
8 Hz, 4H), 7.01-6.99 (d, J = 8 Hz, 4H); 13C NMR (400 MHz, DMSO-d6) δ
145.60, 139.27, 131.87, 129.42, 125.02, 119.93, 60.34. Anal. Calcd for
C25H20N8O8: C, 53.57, H, 3.60, N, 19.99, O, 22.84. Found: C, 53.57, H,
3.58, N, 19.62, O, 22.66. HRMS (EI) calcd for C25H20N8O8 560.1404, found
560.1402.
Bis(2-(4-methoxyphenyl)-1H-benzo[d]imidazol-5-yl)bis(2-(4-methox-
yphenyl)-1H-benzo[d]imidazol-6-yl)methane (9) Compound 6 (0.20 g,
0.27 mmol), 4-methoxybenzoic acid (0.33g, 2.16 mmol) and
polyphosphoric acid (5.00 g) were taken in a three-neck round bottom flask
(100 mL). The temperature of the reaction was slowly increased to 145 °C
and continued for 40 h. After cooling down to room temperature the mixture
was poured into ice cold water and basified with sodium hydroxide to
precipitate out the product. Because of poor solubility in NMR solvents,
characterization by NMR was not possible. DIP-MS calcd for C57H44N8O4
904.3486, Found 905.2.
4,4',4'',4'''-Methanetetrayltetrakis(benzene-1,2-diamine)
(6).
A
suspension of compound 5 (1.50 g, 2.68 mmol) and tin(II) chloride
dihydrate (24 g, 105 mmol) in ethanol (150 mL) and concentrated
hydrochloric acid (90 mL) were charged into three-necked round-bottom
flask (500 mL), and refluxed for 24 h with stirring. After cooling the reaction
mixture down to room temperature, creamy white precipitates were
collected by filtration, washed with concentrated hydrochloric acid (3 × 24
Bis(2-(4-nitrophenyl)-1H-benzo[d]imidazol-5-yl)bis(2-(4-nitrophenyl)-
1H-benzo[d]imidazol-6-yl)methane (10) Compound 6 (0.20 g, 0.27
mmol), 4-nitrobenzoic acid (0.36 g, 2.16 mmol) and polyphosphoric acid
(7.00 g) were charged into a three-neck round bottom flask (100 mL). The
temperature was slowly raised to 145 °C and continued for 40 h. After
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10.1002/ejoc.201801410
European Journal of Organic Chemistry
COMMUNICATION
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This research was supported by the Creative Research Initiative
(CRI, 2014R1A3A2069102), BK21 Plus (10Z20130011057), and
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Keywords: Synthesis design • Amine • Fused-ring systems •
Tetrapodal • 3D octamine • tetraphenylmethane
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This article is protected by copyright. All rights reserved.

10.1002/ejoc.201801410
European Journal of Organic Chemistry
COMMUNICATION
Table of Contents
COMMUNICATION
A high yield synthesis of an air stable
and a rigid shape-persistent tetrapodal
octaamine, is reported. It can be
potentially transformed into a wide
Tetrapodal Octaamine
Ishfaq Ahmad, Javeed Mahmood,*
Jong-Beom Baek*
range
of
functionalities,
e.g.,
Page No. – 1-5
benzimidazole, benzotriazole, and
pyrazine, for application-oriented 3D
organic framework synthesis.
Scalable Synthesis of Tetrapodal
Octaamine
*Tetrapodal octamine, 3D organic frameworks
This article is protected by copyright. All rights reserved.