Heterocycles in organic materials chemistry. Synthesis of di-, tri-, and tetraimide polycarboxylic acids for use in organic network assembly

Article abstract of DOI:10.3987/com-01-9242

Seven linear divalent monomers, three bent divalent amide-containing monomers, 11 bent divalent ester-containing monomers, one planar trivalent monomer, and two tetrahedral tetravalent monomers were prepared by imide-forming condensation of the appropriat

Full text of DOI:10.3987/com-01-9242

HETEROCYCLES, Vol. 55, No. 8, pp. 1527 - 1554, Received, 8th May, 2001
HETEROCYCLES
CHEMISTRY.
IN
ORGANIC
MATERIALS
SYNTHESIS OF DI-, TRI-, AND
TETRAIMIDE POLYCARBOXYLIC ACIDS FOR USE IN
ORGANIC NETWORK ASSEMBLY
Ken S. Feldman,* Yanze Liu, Joe C. Saunders, Katherine M.
Masters, and Robert F. Campbell
Department of Chemistry, The Pennsylvania State University,
University Park, Pennsylvania16802 USA
e-mail: ksf@chem.psu.edu
Abstract - Seven linear divalent monomers, three bent divalent
amide-containing monomers, 11 bent divalent ester-containing
monomers, one planar trivalent monomer, and two tetrahedral
tetravalent monomers were prepared by imide-forming
condensation of the appropriate polyamine hub with a specially
designed anhydride connector unit.
polycarboxylic acid monomers were
These polyvalent
subjected to
crystallization/photochemical crosslinking studies in an attempt
to prepare periodic, covalent organic solids. Difficulties in
achieving suitable crystals have so far frustrated efforts to reach
this goal.
The multi-dimensional polymerization of polyvalent monomers to furnish periodic, covalently linked
solids remains an enduring challenge in materials chemistry. Problems with orienting monomer units to
facilitate bond formation between divergent functionality, and the difficulty of bringing reactive ends
together in increasingly constrained lattices as polymerization proceeds, among other factors, have
conspired to thwart direct attempts at polyvalent monomer polymerization.1 An alternative indirect
strategy for accomplishing this goal has been under development in our laboratory.2 This strategy relies
on a two-stage sequence featuring initial monomer pre-organization into a periodic lattice, and subsequent
in situ covalent connection of now proximate functionality on the monomer units.3 The key connector
unit was chosen to provide organizational elements compatible with the bond-forming chemistry, and to
present these elements in a disposition that minimizes molecular motion, and therefore lattice distortion,
upon covalent union. The generic hub-spoke-connector architecture (1) (Scheme 1) was designed to meet

these criteria, where the crucial naphthalene-based connector unit bears nearly parallel carboxylic acid
and cinnamic acid moieties extending from the peri positions. Hydrogen bond-mediated dimerization of
the acidic termini of two connectors would then position the two alkenes for photochemical crosslinking,
1→2→3. This two-step procedure would thus enable monomer pre-organization through reversible and
self-correcting H-bond directed crystallization, and then replace the labile H-bond linkage with
approximately coincident, robust covalent C-C bonds in the second step. Previous reports from our
laboratory have documented the feasibility of this procedure in a simple model system (4), and have
described the synthesis of the key coupling connector, anhydride (5).2 This account details the synthesis
of families of linear divalent, bent divalent, planar trivalent, and tetrahedral tetravalent monomer units
based on the hub-spoke-connector motif (1).
In addition, the results of preliminary
crystallization/photochemical crosslinking studies with these polyacid species are disclosed.
Scheme 1
sp
o
ke
e
k
o
sp
hub
O
O
N
O
O
N
O
CO2 H
O
N
O
O
H
H
O
crystallize
O O
hv
O
H
CO2H
4
H
O O
3
O O
O
O
O
O
O
H
H
O O
H
O
H
O
1
2
H
O O
CO2CH2CH2TMS
O O
H
n = 0 ~2
O
N
O
O
N
O
5
CO2CH2CH2TMS
RESULTS AND DISCUSSION
Polyimide Polyacid Synthesis. The imidation chemistry of anhydride (5) utilized in the synthesis of the
polyfunctional monomers was developed earlier in our laboratory.4 Simple condensation of the
appropriate di-, tri-, or tetraamine core with 5 in THF or a high-boiling aromatic solvent at reflux sufficed

to provide a moderate yield of polyimide in most instances. However, the incorporation of stoichiometric
amounts of the mild Lewis acid Zn(OAc)2 in the reaction mixture often led to increased yields. The
diamine-derived hubs (7a-7g) constituted the initial attempts at constructing linear divalent monomers.
These species were conveniently prepared by addition of two equivalents of anhydride (5) to the
appropriate commercially available diamine (6a-6g) under the influence of Zn(OAc)2, eq. (1) and Table 1.
The yields of diimide product (7) were variable. The simple aryl- and alkylamine precursors (6a-6c, 6f-
6g) performing acceptably, whereas the perfluoro species (6d) and the cyclohexyl-derived diamine (6e)
gave disappointingly low yields. Electronic effects in the former case and steric effects in the latter
example may have contributed to the relatively poor reactivity of these diamines, even at higher
temperatures (mesitylene vs. toluene at reflux). Deprotection of the tetraesters (7a-7g) with Bu4NF
proceeded smoothly with most substrates to yield the desired tetraacids in pure form following
precipitation from the reaction medium upon aqueous H3PO4 addition. As with the imidation reaction, the
octafluoro- and cyclohexyl-based substrates (7d) and (7e), respectively, afforded the tetraacid products in
much diminished yields. It is unclear that the now remote steric and electronic factors cited above should
influence these desilylation transformations.
2 - 2.4 equiv.
+
H2N
NH2
5
Zn(OAc)2
(1)
toluene
reflux
6a-g
RO2C
O
N
O
O
N
O
CO2R
see Table 1
for yields and
structures
RO2C
CO2R
7a-g R = CH2CH2TMS
8a-g R = H
n-Bu4NF
Table 1. Yields of tetraesters (7) and tetraacids (8) from diamines (6a-6g) (cf. Eq. (1)).
entry
7
%
8
%
entry
7
%
39a 34
8
%
6
6
F
F
F
F
F
F
F
F
a
68 98
d
b
c
38 98
59 95
e
f
38a 45
69 90
MeO
OMe
-(CH2)8-
O
g
81 85
O
a refluxing mesitylene solvent.

The synthesis of the bent, divalent monomer family commenced with the diamine amide species (12a-
12c), Scheme 2. Variation in the amide's alkyl substituent "R" was introduced in an effort to increase the
prospects for obtaining suitably crystalline material. These hubs were readily prepared from the dinitro
precursor (9) and the appropriate acyl chlorides (10a-10c). The derived diimides (13a-13c) then were
available by application of the standard Zn(OAc)2-mediated coupling procedure used successfully with
the linear divalent monomers (7a-7g). Ester deprotection within these diimides with n-Bu4NF furnished
the pure tetra acids (14a-14c) as yellow powders in excellent yield following aqueous H3PO4 workup and
extraction into EtOAc.
R
Scheme 2
R
O
NH
NH2
O
NH
H2, 10% Pd-C
87%
5
+
RCOCl
Zn(OAc)2
O2N
NO2
O2N
NO2
toluene
reflux
H2N
NH2
9
10a R = Me
10b R = n-heptyl 77% 11b R = n-heptyl
10c R = t-Bu
92% 11a R = Me
12a R = Me
12b R = n-heptyl
12c R = t-Bu
100%
83%
94%
78%
72%
97%
R
11c R = t-Bu
O
N
R1 = CH2CH2TMS
NH
13a R = Me
13b R = n-heptyl
13c R = t-Bu
O
O
N
n-Bu4NF
O
O
CO2R1
R1 = H
14a R = Me
R1O2C
100%
14b R = n-heptyl 100%
R1O2C
100%
14c R = t-Bu
CO2R1
Concerns with complications that might arise during crystallization of 14a-14c as a consequence of the
secondary amide functionality prompted synthesis of analogous ester-substituted bent divalent monomers
(20a-20h), Scheme 3 and Table 2. Acylation of 3,5-dinitrobenzoyl chloride (15) with a variety of
alcohols (16a-16h), followed by nitro-to-amine reduction, provided the diamine hubs (18a-18h) ready for
imidation. Unlike the prior series, the benzoyl esters (19a-19h) did not respond favorably to Zn(OAc)2
catalysis of the condensation with 5. Low and variable yields resulted with this Lewis acid in refluxing
aromatic solvents, and many uncharacterized byproducts accompanied these trials. However, omission of
the Lewis acid promoter and inclusion of excess Et3N furnished the desired diimides (19a-19h) when the
diamines (18a-18h) were combined with two equivalents of the anhydride (5) in the solvent indicated
(reflux). The yields of diimide were modest in all cases, but further optimization studies were deferred
pending the results of the crystallization/photocrosslinking experiments.
Deprotection of the

trimethylsilylethyl ester moieties in 19a-19h proceeded uneventfully to furnish the desired tetra acids
(20a-20h) as yellow powders.
Scheme 3
COCl
CO2R
CO2R
5
H2 , 10% Pd-C
+
ROH
16
Et3N
O2N
NO2
O2N
NO2
H2N
NH2
15
17
18
RO2C
O
O
19 R1 = CH2CH2TMS
20 R1 = H
N
N
n-Bu4NF
O
O
CO2R1
see Table 2 for
yields of 17-20
with various
R groups
R1O2C
R1O2C
CO2R1
Table 2. Yields of species en route to the bent divalent ester-containing diimides (20) (cf. Scheme 3).
entry
R
17 18 19 20 entry
R
17 18 19
20
%
57
%
%
%
%
%
%
%
a
100 94 44a 88
e
HO(CH2)6-
50 80 25b
Me
Me
HO
b
c
91 70 24b 52
87 95 34b 100
f
39 88 30b 100
HO
g
100 86 51a
98 90 37b
61
90
Me
d
87 80 48a 97
h
MeO
a THF solvent. b xylene solvent.
A single trivalent hub (24) was prepared from the sensitive triamine (22)5 and three equivalents of
anhydride (5) under Zn(OAc)2 mediation, Scheme 4. Desilylethylation of the six esters within 23
afforded the trimesic acid homologue (24) as a yellow solid. As before, even this hexaacid could be
isolated in pure form after simple acidification of the crude reaction mixture and extraction into EtOAc.
The preparation of tetrahedral tetravalent analogues of these polyimide constructs required a tetrahedrally
divergent tetraamine core. Candidate alkyl- and arylamines include the known species (25-2)6 and the
ethyl and propyl chain higher homologues of 27, 28a and 28b, respectively, which were synthesized in-

house (Scheme 5).7 Attempted tetraimidation of the three tetraamines (25, 26, and 27) with excess
anhydride (5) under a variety of experimental conditions led, at best, to only partially imidated products.
The rigid tetraamines (25) and (26) were too insoluble in any of the solvents examined to enter into a
productive imidation process at all. The more soluble pentaerythitol derivative (27) proceeded as far as a
diimide product (15%) upon reaction with excess 5 in refluxing mesitylene. Resubmission of this
partially imidated product to more anhydride did not afford further imide formation. Apparently,
unfavorable steric constraints hinder attachment of the third or fourth anhydride unit to the now densely
packed core. The tetraamines (28a) and (28b) were designed to alleviate this steric crowding problem.
Application of the Zn(OAc)2-mediated condensation conditions to these tetraamines and excess 5 did
indeed afford modest yields of the desired tetraimide products (29a) and (29b). Deprotection of these
octaesters with Bu4NF and extraction of the crude, acidified reaction mixture with EtOAc did not in these
cases provide the octaacid products sufficiently pure for the subsequent crystallization studies. Pure
yellow, powdery octaacids (30a) and (30b) could be obtained by dissolution of the impure materials in
aqueous base, removal of impurities with an EtOAc wash, reacidification and extraction into EtOAc/THF.
Scheme 4
imide
N
NH2
O
O
5
N
N
Zn(OAc)2
R
R
toluene
reflux
O
O
CO2R
21 R = NO2
22 R = NH2
H2/Pd/C
64%
RO2C
RO2C
23 R1 = CH 2CH2TMS
24 R1 = H 93%
CO2R
n-Bu4NF
Crystallization/Photochemistry Studies. The attempts at growing suitable crystals from the MeCN,
THF, DME, dioxane, CH2Cl2, EtOAc, toluene, benzene, hexane, heptane, and octane) in various
combinations within the context of several different crystallization techniques (slow evaporation, slow
cooling, vapor diffusion, liquid diffusion). The results were quite variable and no trends emerged. The
model system diacid (4) furnished high quality 1 mm x 3 mm rods upon vapor diffusion of heptane into a
DME solution containing a trace of MeOH at 4 oC.2b The tetra-, hexa- and octaacids described herein had,
in general, only limited solubility in ethereal (or less polar) solvents, which rendered many crystallization
attempts problematical. Eventually, through extensive trial-and-error, crystals of variable sizes/qualities
were deposited from several substrates as indicated in Table 3. One of these crystalline solids proved
suitable for X-Ray crystallographic analysis, the needles deposited from tetraacid (8f) (Figure 1).

Unfortunately, the disruptive role of DMSO on the intended carboxylic acid H-bond dimerization scheme
is evident. The alkene moieties are held far from the critical bonding distance (< 4.2 Å),8 and not
surprisingly, irradiation of a solid crystalline sample of 8f did not lead to any observed chemistry.
Furthermore, in no instance did irradiation of any of the crystalline samples listed in Table 3 furnish any
new compounds or any evidence of photooligomerization.
NH2
Scheme 5
NH2
H2N
H2N
H2N
NH2
NH2
H2N
NH2
CO2R
27
H2N
NH2
25
26
CO2R
H2N
imide
N
O
N
n
H2N
H2N
NH2
5, Zn(OAc)2
n
n
n
n
n
O
mesitylene
reflux
O
n
N
NH2
n
N
28a n = 1
28b n = 2
34%
27%
O
imide
CO2R
n-Bu4NF
R = CH2CH2TMS
R = H
29a n = 1
29b n = 2
30a n = 1
30b n = 2
80%
80%
CO2R
Table 3. Crystals obtained from the polyacid polyimides described herein.
entry poly- recrystalization
crystal
entry poly- recrystalization
crystal
acid
8f
solvent; technique
DMSO, EtOH;
liquid diffusion
description
needles
acid solvent; technique description
a
b
e
f
20d
20h
THF, DME;
needles
plates
slow evaporation
THF, DMSO;
slow evaporation
14c
DME,
MeOH, irregular
clusters
heptane;
liquid diffusion
c
20a
20b
THF/i-PrOH, heptane; needles
vapor diffusion
g
30a
DME;
slow cooling
needles
d
THF, H2O;
needles
slow evaporation

In summary, a variety of polyvalent monomers, characterized by divergent poly(carboxylic acid/cinnamic
acid)-tipped spokes extending from a central core, were synthesized by dehydrative condensation of
polyamine hubs with a key naphthalic anhydride. Crystallization/photochemical crosslinking studies with
these species were disappointing in that no evidence for covalent network formation was forthcoming.
Future studies will focus on modifications of the monomer design to facilitate crystallization from non-
participating solvents.
Figure 1. ORTEP of the crystal structure of tetraacid (8f) (crystallized from DMSO/ethanol).
ACKNOWLEDGMENT
We thank the National Science Foundation (CHE 9727305) for financial support of this work.
EXPERIMENTAL
THF and ether were purified by distillation from sodium/benzophenone under Ar immediately before use.
Moisture and oxygen sensitive reactions were carried out in flame-dried glassware under Ar. Solvents for
chromatography (Et O, EtOAc, CH Cl , hexane) were distilled from CaH prior to use. Flash column
2
2
2
2

chromatography was carried out under positive pressure using 32-63 µm silica gel and the indicated
solvents.9 Melting points are uncorrected. CIMS were obtained with isobutane as the reagent gas, and
EIMS were obtained at 50-70 eV. FAB HRMS were obtained from the mass spectrometry laboratory at
the University of Texas at Austin. Combustion analyses were performed by either Galbraith Laboratories,
Knoxville, TN or Midwest Microlab, Indianapolis, IN.
General Procedure A. The polyamine core and 1 – 1.1 equiv of anhydride (5) per –NH2 were dissolved
in the indicated solvent (~ 0.02 – 0.05 M). Zn(OAc)2•2H2O was added (~ 1 - 2 equiv per equiv of 5) and
the solution was purged with Ar and brought to reflux. After TLC indicated consumption of anhydride
(hours to days), the reaction mixture was cooled to rt and diluted with CH2Cl2. The solution was washed
with an equal volume of 1M H3PO4 and brine, dried over Na2SO4, filtered, and concentrated in vacuo.
Silica gel flash chromatography of the residue in the indicated solvent system furnished the pure
polyimide.
General Procedure B. The polyiimide poly(trimethylsilylethyl) ester was dissolved/suspended in THF (~
0.2 - 0.5 M). A solution of 1M n-Bu4NF in THF containing ~ 1.5 – 2.0 equiv F– per ester was added and
the reaction mixture was stirred at rt. When TLC analysis indicated consumption of starting material
(hours to ~ 1 day), the solution was diluted with 2 volumes of THF and added to an equal volume of 1M
H3PO4. If a precipitate was observed, simple filtration afforded the pure polyacid following washing with
water, THF, and then Et2O, and drying in vacuo. If no precipitate was observed, the mixture was
extracted with several volumes of EtOAc, and the combined organic phases were washed with brine,
dried with Na2SO4, filtered, and concentrated in vacuo to deliver pure polyacid product.
General Procedure C. A solution of 3,5-dinitrobenzoyl chloride in toluene or THF (~ 0.4 M) was added
via syringe to a stirring solution of alcohol (~ 0.3 M) and 6 equiv of pyridine in the same solvent. The
solution was brought to reflux for 20 min, cooled to rt, and poured into an equal volume of ice cold 1N
HCl. The mixture was extracted with toluene, and the combined organic phases were washed in sequence
with water, 1M potassium carbonate, and brine, and then dried over Na2SO4. The toluene solution was
concentrated in vacuo. The crude powder or oil was purified by silica gel flash column chromatography
with the indicated solvent system.
General Procedure D. A solution of the dinitro compounds (17a-h) in THF, EtOAc, or MeOH as
indicated (~ 0.05 M) was treated with ~ 190 mg of 10% Pd/C per mmol substrate. The flask was purged
with Ar, and then charged with 1 atm of H2 gas. The solution was stirred at rt with TLC monitoring.

After starting material was consumed, the mixture was purged with Ar, filtered through Celite, and
concentrated in vacuo to provide the pure diamino products (18a-h).
Diimide (7a). Following General Procedure A, 1,4-diaminobenzene and anhydride (5) were combined to
afford 7a as a tan solid following silica gel flash chromatography with 10% EtOAc/CH2Cl2 as eluent. mp
301-304 °C: IR (CHCl3) 1712, 1666, 1634, 1588 cm-1; 1H NMR (360 MHz, CDCl3) δ 8.77 (d, J = 7.7 Hz,
2H), 8.75 (d, J = 8.3 Hz, 2H), 7.98 (d, J = 7.5 Hz, 2H), 7.82 (d, J = 7.6 Hz, 2H), 7.73 (d, J = 16.0 Hz, 2H),
7.66 (d, J = 8.3 Hz, 4H), 7.55 (s, 4H), 1.10 (m, 4H), 0.83 (m, 4H), 0.09 (s, 18H), -0.02 (s, 18H); 13C NMR
(90 MHz, CDCl3) δ 168.3, 166.8, 163.6, 163.4, 145.8, 143.2, 142.8, 137.9, 135.1, 134.5, 131.5, 130.95,
130.94, 130.0, 129.6, 129.5, 129.0, 128.2, 127.1, 125.0, 122.2, 119.5, 64.4, 62.9, 17.4, 17.0, -1.4, -1.6;
MS m/z (relative intensity) 1250 (M+, 0.8). Anal. Calcd for C70H76N2O12Si4: C, 67.28 ; H, 6.13. Found: C,
66.87; H, 6.12.
Diimide (7b). Following General Procedure A, benzidene and anhydride (5) were combined to afford 7b
as a light yellow solid following silica gel flash chromatography with 30% EtOAc/hexane as eluent. mp
279-282 °C: IR (CHCl3) 1711, 1671, 1638, 1590 cm-1; 1H NMR (300 MHz, CDCl3) δ 8.77 (d, J = 7.3 Hz,
2H), 8.74 (d, J = 7.0 Hz, 2H), 7.98 (d, J = 7.5 Hz, 2H), 7.84 (d, J = 8.3 Hz, 4H), 7.81 (d, J = 7.5 Hz, 2H),
7.73 (d, J = 16.0 Hz, 2H), 7.66 (d, J = 8.3 Hz, 4H), 7.50 (d, J = 8.2 Hz, 4H), 7.46 (d, J = 8.4 Hz, 4H), 6.52
(d, J = 16.0 Hz, 2H), 4.34 (m, 4H), 3.56 (m, 4H), 1.09 (m, 4H), 0.83 (m, 4H), 0.09 (s, 18H), -0.02 (s,
18H); 13C NMR (75 MHz, CDCl3) δ 168.2, 166.8, 163.9, 163.7, 145.8, 143.1, 142.7, 141.1, 137.9, 134.5,
134.4,131.5, 130.93, 130.86, 130.0, 129.5, 129.0, 128.9, 128.5,128.2, 127.0, 124.9, 122.1, 119.5, 64.4,
62.9, 17.3, 17.0, -1.4, -1.6; MS m/z (relative intensity) 1325 (M+, 3.1) 1225 (2.7). HRMS calcd for
C76H80N2O12Si4 1325.4901, found 1325.4867. Anal. Calcd for C76H80N2O12Si4: C, 68.85; H, 6.08. Found:
C, 68.61; H, 6.11.
Diimide (7c). Following General Procedure A, 4,4'-diamino-3,3'-dimethoxybiphenyl and anhydride (5)
were combined to afford 7c as a light yellow solid following silica gel flash chromatography with 1-
6%EtOAc/benzene as eluent. mp 285-288 °C: IR (CHCl3) 1714, 1673, 1635, 1591 cm-1; 1H NMR (300
MHz, CDCl3) δ 8.76 (d, J = 7.5 Hz, 2H), 8.74 (d, J = 7.5 Hz, 2H), 7.97 (d, J = 7.5 Hz, 2H), 7.80 (d, J =
7.6 Hz, 2H), 7.73 (d, J = 16.0 Hz, 2H), 7.66 (d, J = 8.1 Hz, 4H), 7.50 (d, J = 7.4 Hz, 4H), 7.38 (s, 4H),
7.33 (s, 2H), 6.51 (d, J = 16.0 Hz, 2H), 4.34 (m, 4H), 3.88 (s, 6H), 3.56 (m, 4H), 1.09 (m, 4H), 0.83 (m,
4H), 0.09 (s, 18H), -0.02 (s, 18H); 13C NMR (75 MHz, CDCl3) δ 168.3, 166.8, 163.5, 163.3, 155.0, 145.6,
143.7, 143.2, 142.8, 137.7, 134.4, 131.3, 130.8, 130.2, 130.0, 129.5, 129.0, 128.18, 128.17, 127.0, 125.0,

123.2, 122.3, 120.3, 119.4, 111.5, 64.4, 62.9, 55.9, 17.3, 17.0, -1.5, -1.6; MS m/z (relative intensity)
1384 (M+, 100) 1239 (40). HRMS calcd for C78H84N2O14Si4 1385.5087, found 1385.5078. Anal. Calcd
for C78H84N2O14Si4: C, 67.60; H, 6.11. Found: C, 67.50; H, 6.14.
Diimide (7d). Following General Procedure A, 4,4'-diamino-2,2',3,3',5,5',6,6'-octafluorobiphenyl and
anhydride (5) were combined to afford 7d as a light yellow solid following silica gel flash
chromatography with 30%Et2O/hexane → 4:11:35 EtOAc/CH2Cl2/hexane as eluent. mp > 400°C
1
(decomp): IR (KBr) 1722, 1690, 1638, 1590 cm-1; H NMR (360 MHz, CDCl3) δ 8.81 (d, J = 7.7 Hz,
2H), 8.79 (d, J = 7.6 Hz, 2H), 8.01 (d, J = 7.5 Hz, 2H), 7.86 (d, J = 7.6 Hz, 2H), 7.73 (d, J = 16.0 Hz, 2H),
7.67 (d, J = 8.2 Hz, 4H), 7.50 (d, J = 8.2 Hz, 4H), 6.52 (d, J = 16.0 Hz, 2H), 4.34 (m, 4H), 3.57 (m, 4H),
13
1.09 (m, 4H), 0.83 (m, 4H), 0.09 (s, 18H), -0.02 (s, 18H); C NMR (90 MHz, CDCl3) δ 167.9, 166.7,
162.0, 161.8, 146.9, 145.6 (m), 143.0, 142.7 (m), 142.4, 138.9, 134.7, 132.1, 131.6, 131.0, 130.3, 129.5,
129.1, 128.2, 127.4, 123.8, 121.1, 119.7, 116.3 (m), 108.0 (m), 64.6, 62.9, 17.4, 17.0, -1.4, -1.6; MS m/z
(relative intensity) 1468 (M+, 100) 1323 (58). Anal. Calcd for C76H72N2O12F8Si4: C, 62.11; H, 4.94; F,
10.34. Found: C, 61.96; H, 5.11; F, 10.90.
Diimide (7e). Following General Procedure A, trans-1,4-diaminocyclohexane and anhydride (5) were
combined to afford 7e as a light yellow solid following silica gel flash chromatography with CH2Cl2 and
then 5%EtOAc/CH2Cl2 as eluent. mp > 305 °C (decomp, recrystallized from hexane/CHCl3): IR (CHCl3)
1702, 1661, 1638, 1590 cm-1;1H NMR (360 MHz, CDCl3) δ 8.67 (d, J = 7.6 Hz, 2H), 8.65 (d, J = 7.5 Hz,
2H), 7.91 (d, J = 7.5 Hz, 2H), 7.73 (d, J = 7.6 Hz, 2H), 7.69 (d, J = 16.0 Hz, 2H), 7.61 (d, J = 8.3 Hz, 4H),
7.44 (d, J = 8.2 Hz, 4H), 6.48 (d, J = 16.0 Hz, 2H), 5.27 (br s, 2H), 4.31 (m, 4H), 3.51 (m, 4H), 2.87 (m,
13
4H), 1.91 (m, 4H), 1.06 (m, 4H), 0.78 (m, 4H), 0.07 (s, 18H), -0.06 (s, 18H); C NMR (90 MHz, CDCl3)
δ 168.3, 166.8, 164.0, 163.2, 145.0, 143.2, 142.9, 137.2, 134.4, 130.9, 130.8, 130.4, 129.6, 129.4, 128.9,
128.1, 126.7, 125.4, 122.7, 119.5, 64.2, 62.8, 52.8, 28.4, 17.4, 17.0, -1.4, -1.6; MS m/z (relative intensity)
1254 (M+, 3.6) 1154 (0.44). HRMS calcd for C50H28N2O12 1254.4948, found 1254.4945. Anal. Calcd for
C70H82N2O12Si4: C, 66.95; H, 6.58. Found: C, 67.14; H, 6.85.
Diimide (7f). Following General Procedure A, 1,8-diaminooctane and anhydride (5) were combined to
afford 7f as a light yellow solid following silica gel flash chromatography with 40%Et2O/hexane and then
1
4% EtOAc/CH2Cl2 as eluent. mp 203-206 °C: IR (CHCl3) 1704, 1660, 1637, 1591 cm-1; H NMR (360
MHz, CDCl3) δ 8.67 (d, J = 7.7 Hz, 2H), 8.65 (d, J = 8.3 Hz, 2H), 7.91 (d, J = 7.5 Hz, 2H), 7.74 (d, J =
7.7 Hz, 2H), 7.70 (d, J = 16.2 Hz, 2H), 7.62 (d, J = 8.2 Hz, 4H), 7.45 (d, J = 8.2 Hz, 4H), 6.49 (d, J = 16.0

Hz, 2H), 4.32 (m, 4H), 4.18 (m, 4H), 3.52 (m, 4H), 1.74 (m, 4H), 1.40 (br s, 8H), 1.08 (m, 4H), 0.80 (m,
4H), 0.08 (s, 18H), -0.05 (s, 18H); 13C NMR (90 MHz, CDCl3) δ 168.3, 166.8, 163.7, 163.4, 145.2, 143.2,
142.9, 137.4, 134.4, 131.0, 130.7, 130.4, 129.6, 129.4, 128.9, 128.1, 126.8, 124.9, 122.2, 119.4, 64.3,
62.9, 40.6, 29.2, 28.0, 27.0, 17.4, 17.0, -1.4, -1.6; MS m/z (relative intensity) 1284 (M+, 100) 994 (26).
HRMS calcd for C72H88N2O12Si4 1284.5440, found 1284.5414.
Diimide (7g). Following General Procedure A, 2,2'-(ethylenedioxy)bis(ethylamine) and anhydride (5)
were combined to afford 7g as a glassy yellow solid following silica gel flash chromatography with 16%
1
EtOAc/CH2Cl2 as eluent. mp 149-152 °C: IR (CHCl3) 1705, 1663, 1638, 1592, 1170, 862, 838 cm-1; H
NMR (400 MHz, CDCl3) δ 8.64 (d, J = 8.6 Hz, 2H), 8.60 (d, J = 7.5 Hz, 2H), 7.90 (d, J = 7.5 Hz, 2H),
7.72 (d, J = 8.6 Hz, 2H), 7.70 (d, J = 16.0 Hz, 2H), 7.62 (d, J = 7.9 Hz, 4H), 7.44 (d, J = 7.9 Hz, 4H), 6.49
(d, J = 16.0 Hz, 2H), 4.39 (br s, 4H), 4.34 (m, 4H), 3.80 (br s, 4H), 3.69 (br s, 4H), 3.54 (m, 4H), 1.09 (m,
4H), 0.81 (m, 4H), 0.10 (s, 18H), -0.04 (s, 18H); 13C NMR (90 MHz, CDCl3) δ 168.5, 167.0, 163.8, 163.6,
145.5, 143.3, 143.0, 137.6, 134.5, 131.2, 130.9, 130.6, 129.8, 129.6, 129.1, 128.3, 127.0, 124.9, 122.2,
119.6, 70.3, 68.0, 64.5, 63.0, 39.4, 17.5, 17.2, -1.2, -1.4; MS m/z (relative intensity) 1328.3 (M+K+, 48)
1311.5 (M+Na+, 100). HRMS calcd for C70H84N2O14NaSi4 1311.4897, found 1311.4797. Anal. Calcd for
C70H84N2O14Si4: C, 65.19; H, 6.56; N, 2.17. Found: C, 64.88; H, 6.53; N, 2.22.
Tetraacid (8a). Following General Procedure B, the diimide (7a) was deprotected to furnish the
tetraacid (8a). mp >360 °C: IR (KBr) 1670, 1589, 1510 cm-1;1H NMR (300 MHz, DMSO-d6) δ 13.2 (br
s, 2H), 12.4 (br s, 2H), 8.63 (d, J = 7.4 Hz, 2H), 8.62 (d, J = 7.4 Hz, 2H), 8.06 (d, J = 7.5 Hz, 2H), 7.91 (d,
J = 7.6 Hz, 2H), 7.81 (d J = 8.1 Hz, 4H), 7.68 (d, J = 15.9 Hz, 2H), 7.60 (s, 4H), 7.74 (d, J = 8.0 Hz, 4H),
13
6.64 (d, J = 16.0 Hz, 2H); C NMR (75 MHz, DMSO-d6) δ 168.8, 167.6, 163.5, 163.3, 145.4, 143.4,
142.7, 138.6, 135.7, 134.1, 130.8, 130.5, 130.3, 129.6, 129.3, 128.7, 128.4, 126.2, 124.7, 122.8, 122.2,
119.7; MS m/z (relative intensity) 849 (M+, 0.08) 769 (1.5). HRMS calcd for C50H28N2O12 849.1720,
found 849.1734.
Tetraacid (8b). Following General Procedure B, the diimide (7b) was deprotected to furnish the tetraacid
(8b). mp >360 °C: IR (KBr) cm-1; 1H NMR (400 MHz, DMSO-d6) δ 12.6 (br s, 4H), 8.58 (d, J = 7.0 Hz,
4H), 8.03 (d, J = 7.1 Hz, 2H), 7.91 (d, J = 8.0 Hz, 4H), 7.88 (d, J = 7.0 Hz, 2H), 7.79 (d, J = 7.4 Hz, 4H),
13
7.67 (d, J = 15.9 Hz, 2H), 7.55 (d, J = 7.6 Hz, 4H), 7.45 (d, J = 7.3 Hz, 4H), 6.63 (d, J = 16.0 Hz, 2H); C
NMR (100 MHz, DMSO-d6) δ 168.9, 167.6, 163.4, 163.3, 145.4, 143.40, 143.36, 142.7, 139.7, 135.4,
134.1, 130.7, 130.4, 130.3, 129.7, 129.5, 129.3, 128.7, 128.4, 127.5, 126.2, 124.6, 122.2, 119.8; MS m/z

(relative intensity) 925 (MH+, 100) 881 (M-CO2, 87). HRMS calcd for C56H33N2O12 925.2034, found
925.2078.
Tetraacid (8c). Following General Procedure B, the diimide (7c) was deprotected to furnish the tetraacid
(8c). mp >360 °C: IR (KBr) 3460, 1710, 1672, 1633, 1590, 1244 cm-1; 1H NMR (360 MHz, DMSO- d6)
δ 12.7 (br s, 4H), 8.63 (d, J = 7.7 Hz, 2H), 8.62 (d, J = 7.3 Hz, 2H), 8.06 (d, J = 7.3 Hz, 2H), 7.91 (d, J =
7.7 Hz, 2H), 7.81 (d, J = 7.7 Hz, 4H), 7.68 (d, J = 15.9 Hz, 2H), 7.55 (m, 6H), 7.49 (d, J = 8.2 Hz, 4H),
13
6.64 (d, J = 15.9 Hz, 2H), 3.88 (s, 6H); C NMR (90 MHz, DMSO-d6) δ 168.8, 167.6, 162.9, 162.8,
155.2, 145.7, 143.5, 142.7, 142.2, 139.2, 138.9, 134.2, 130.9, 130.8, 130.7, 129.5, 129.4, 128.8, 128.4,
126.4, 124.2, 123.8, 121.7, 119.8, 119.5, 111.2, 56.0; MS m/z (relative intensity) 985 (M+, 47) 941 (44).
HRMS calcd for C58H37N2O14 985.2245, found 985.2244.
Tetraacid (8d). Following General Procedure B, the diimide (7d) was deprotected to furnish the
tetraacid (8d). mp >360 °C: IR (KBr) 1719, 1686, 1655, 1637, 1590 cm-1; 1H NMR (300 MHz, DMSO-
d6) δ 12.7 (br s, 4H), 8.69 (d, J = 7.3 Hz, 2H), 8.67 (d, J = 7.4 Hz, 2H), 8.07 (d, J = 7.5 Hz, 2H), 7.93 (d, J
= 7.6 Hz, 2H), 7.79 (d, J = 8.1 Hz, 4H), 7.67 (d, J = 15.9 Hz, 2H), 7.45 (d, J = 7.9 Hz, 4H), 6.64 (d, J =
16.0 Hz, 2H); 13C NMR (75 MHz, DMSO-d6) δ 168.6, 167.6, 161.6, 161.5, 147.0, 145.2 (m), 143.3, 142.4,
141.9 (m), 140.3, 134.3, 131.6, 131.0, 129.8, 129.4, 128.8, 128.5 (m), 128.41, 128.39, 126.6, 122.7, 120.4,
119.9, 116.5 (m); MS m/z (relative intensity) 1069 (M+, 100) 1051 (24). HRMS calcd for C56H24N2O12F8
1069.1283, found 1069.1280.
Tetraacid (8e). Following General Procedure B, the diimide (7e) was deprotected to furnish the tetraacid
(8e). mp >370 °C: IR (KBr) 3448, 1701, 1663 cm-1; 1H NMR (400 MHz, DMSO- d6) δ 13.06 (br s, 2H),
12.50 (br s, 2H), 8.60 (d, J = 7.0 Hz, 2H), 8.58 (d, J = 7.0 Hz, 2H), 7.99 (d, J = 7.0 Hz, 2H), 7.84 (d, J =
7.0 Hz, 2H), 7.77 (d, J = 7.4 Hz, 4H), 7.65 (d, J = 15.8 Hz, 2H), 7.42 (d, J = 7.4 Hz, 4H), 6.62 (d, J = 15.8
Hz, 2H), 5.08 (br s, 2H), 2.69 (br s, 4H), 1.90 (br s, 4H); Tetraacid (8e) was too insoluble to acquire a 13C
NMR spectrum;MS m/z (relative intensity) 855 (M-, 9) 811 (18) 388 (100). HRMS calcd for C50H34N2O12
854.2112, found 884.2110.
Tetraacid (8f). Following General Procedure B, the diimide (7f) was deprotected to furnish the tetraacid
(8f). mp >360 °C: IR (KBr) 1700, 1656, 1590 cm-1; 1H NMR (360 MHz, DMSO- d6) δ 12.7 (br s, 4H),
8.54 (d, J = 7.6 Hz, 2H), 8.54 (d, J = 7.5 Hz, 2H), 7.98 (d, J = 7.5 Hz, 2H), 7.81 (d, J = 7.6 Hz, 2H), 7.76
(d, J = 8.3 Hz, 4H), 7.66 (d, J = 16.0 Hz, 2H), 7.40 (d, J = 8.2 Hz, 4H), 6.61 (d, J = 16.0 Hz, 2H), 4.03 (m,

13
4H), 1.64 (br s, 4H), 1.34 (br s, 8H); C NMR (90 MHz, DMSO-d6) δ 168.7, 167.5, 163.0, 162.9, 145.1,
143.4, 142.6, 138.2, 134.0, 130.7, 130.4, 130.2, 129.2, 129.0, 128.6, 128.3, 126.0, 124.0, 121.6, 120.0,
40.2, 28.6, 27.3, 26.4; MS m/z (relative intensity) 885 (M+, 100) 842 (8). HRMS calcd for C52H40N2O12
885.2676, found 885.2660.
Tetraacid (8g). Following General Procedure B, the diimide (7g) was deprotected to furnish the tetraacid
(8g). mp >360 °C: IR (KBr) 3448, 1702, 1663, 1590 cm-1; 1H NMR (400 MHz, DMSO- d6) δ 12.7 (br s,
4H), 8.50 (d, J = 7.5 Hz, 2H), 8.49 (d, J = 7.5 Hz, 2H), 7.94 (d, J = 7.5 Hz, 2H), 7.75 (d, J = 7.5 Hz, 2H),
7.74 (d, J = 8.3 Hz, 4H), 7.64 (d, J = 16.1 Hz, 2H), 7.35 (d, J = 8.3 Hz, 4H), 6.60 (d, J = 16.1 Hz, 2H),
13
4.14 (m, 4H), 3.61 (m, 4H), 3.53 (m, 4H); C NMR (100 MHz, DMSO-d6) δ 168.7, 167.6, 163.0, 162.8,
145.2, 143.4, 142.6, 138.3, 134.0, 130.7, 130.4, 130.3, 129.2, 129.0, 128.6, 128.3, 126.0, 123.9, 121.4,
119.7, 69.6, 66.8, 38.8; MS m/z (relative intensity) 889 (MH+, 8.4) 845 (15) 476 (100). HRMS calcd for
C50H37N2O14 889.2245, found 889.2237.
N-(3,5-Dinitrophenyl)-n-octanamide (11b). 3,5-Dinitroaniline (300 mg, 1.6 mmol) was dissolved in
o
CH Cl (5 mL). Et N (223 µL, 1.6 mmol) was added via syringe and the solution cooled to 0 C at
2
2
3
which time octanoyl chloride (294 mg, 1.8 mmol) was added via syringe and the solution was allowed to
warm to rt. After 1 h, TLC indicated complete consumption of starting material, so the solution was
diluted with CH Cl (15 mL) and washed with water (20 mL). The organic phase was dried with
2
2
Na SO , filtered, and concentrated in vacuo. The resulting solid was purified by silica gel
2
4
chromatography with 30% EtOAc/hexane as eluent to afford 382 mg (77%) of 11b as a white solid. mp
-1
1
o
86-87 C. IR (CHCl3) 3428, 1711 cm ; H NMR (300 MHz, CDCl3) δ 8.82 (d, J = 2.0 Hz, 2 H), 8.75 (t, J
= 2.0 Hz, 1 H), 7.86 (s, 1 H), 2.49 (t, J = 7.4 Hz, 2 H), 1.82 - 1.70 (m, 2 H), 1.46 - 1.42 (m, 8 H), 0.88 (t, J
13
= 6.8 Hz, 3 H); C NMR (75 MHz, CDCl3) δ 172.1, 148.8, 140.2, 119.1, 113.5, 37.6, 31.6, 29.1, 28.9,
+
25.1, 22.6, 14.0; MS m/z (relative intensity) 310 (M , 2); HRMS calcd for C H N O 310.1403, found
14 19 3 5
310.1409.
N-(3,5-Dinitrophenyl)-2,2-dimethylpropionamide. (11c). Following the procedure used for 11a, 3,5-
dinitroaniline (50 mg, 0.27 mmol) was combined with 2,2-dimethylproprioyl chloride (41 µL 0.33 mmol)
to afford 70 mg (97%) of 11c as a white solid. An analytical sample was prepared by recrystallization
-1
1
o
from EtOAc/hexane. mp 206-210 C. IR (CHCl3) 3446, 1700 cm ; H NMR (200 MHz, CDCl3) δ8.84
13
(s, 2 H), 8.77 (s, 1H), 7.79 (s, 1 H), 1.38 (s, 9 H); C NMR (50 MHz, CDCl3) δ 177.2, 148.7, 140.4,

+
119.4, 113.5, 40.1, 27.4; MS m/z (relative intensity) 267 (M , 3), 57 (100); Anal. Calcd for C H N O ;
11 13 3 5
C, 49.44; H, 4.90; N, 15.72. Found: C, 49.50; H, 4.99; N, 15.59.
N-(3,5-Diaminophenyl)-n-heptanamide (12b). Amide (11b) (100 mg. 0.32 mmol) and 10% Pd/C (10
mg) were mixed and EtOAc (5 mL) was added. The mixture was degassed (freeze, pump, thaw) and the
o
resulting suspension was heated under a hydrogen atmosphere at 80 C for 1 h, at which time TLC
indicated complete consumption of starting material. The mixture was cooled, filtered through Celite,
and the Celite was washed with EtOAc (50 mL). The solution was concentrated in vacuo to afford 80 mg
-1
1
o
(100%) of 12b as a white solid. mp 76-78 C. IR (CHCl3) 3400, 1682 cm ; H NMR (300 MHz, CDCl3)
δ 7.44 (s, 1 H), 6.33 (d, J = 1.3 Hz, 2 H), 5.71 (s, 1 H), 3.54 (s, 4 H), 2.26 (t, J = 7.3, 7.9 Hz, 2 H), 1.67 -
13
1.62 (m, 2 H), 1.28 - 1.26 (m, 8 H), 0.86 (t, J = 6.6, 6.8 Hz, 3 H); C NMR (90 MHz, CDCl3) δ 171.5,
148.0, 140.0, 97.9, 97.4, 37.9, 31.7, 29.2, 29.0, 25.6, 22.6, 14.0; MS m/z (relative intensity) 250 (MH+,
23); HRMS calcd for C H N O 250.1919, found 250.1915.
14 24 3
N-(3,5-Diaminophenyl)-2,2-dimethylpropionamide (12c). Following the procedure used for 12b, amide
(11c) (587 mg, 2.2 mmol) was hydrogenated to produce 380 mg (83%) of 12c as white crystals. mp 214-
-1
1
o
215 C. IR (CHCl3) 3455, 3400 cm ; H NMR (300 MHz, CHCl3) δ 6.38 (d, J = 1.9 Hz, 2 H), 5.80 (t, J =
1.9 Hz, 1 H), 3.57 (s, 4 H), 1.28 (s, 9H); 13C NMR (50 MHz, DMSO-d6) δ 175.6, 148.8, 140.1, 96.3, 95.9,
+
38.9, 27.2; MS m/z (relative intensity) 207 (M , 58), 123 (100); HRMS calcd for C H N O 207.1372,
11 17 3
found 207.1367.
Diimide (13a). Following General Procedure A, diamine(12a)10 and anhydride (5) were combined to
-1
1
o
furnish diimide (13a) as a brown solid. mp 138-144 C. IR (CHCl3) 1712, 1676, 1638, cm ; H NMR
(200 MHz, CDCl3), δ 8.70 (m, 4 H), 7.94 (d, J = 7.4 Hz, 1 H), 7.78 - 7.62 (m, 12 H), 7.47 (d, J = 8.0 Hz,
4 H), 7.11 (s, 1 H), 6.50 (d, J = 15.9 Hz, 2 H), 4.33 (t, J = 8.4 Hz, 4 H), 3.55 (t, J = 8.8 Hz, 4 H), 2.16 (s,
13
3 H), 1.09 (t, J = 8.7 Hz, 4 H), 0.82 (t, J = 8.7 Hz, 4 H), 0.09 (s, 18 H), -0.04 (s, 18 H); C NMR (50
MHz, CDCl3) δ 169.3, 168.1, 166.7, 163.4, 163.2, 145.6, 143.1, 142.7, 140.6, 137.8, 135.6, 134.4, 131.4,
130.90, 130.85, 129.7, 129.4, 129.0, 128.1, 126.8, 124.6, 123.7, 121.9, 119.9, 119.5, 64.3, 62.8, 24.4,
+
17.3, 17.0, -1.5, -1.6; MS m/z (relative intensity) 1306 (MH , 3); HRMS calcd for C H N O Si
72 80 3 13
4
1306.4768, found 1306.4776.
Diimide (13b). Following General Procedure A, diamine (12b) and anhydride (5) were combined to
furnish diimide (13b) as a brown solid following silica gel chromatography with 30% EtOAc/hexane as

-1
1
o
eluent. mp 148-152 C. IR (CHCl3) 3435, 1713, 1676 cm ; H NMR (300 MHz, CDCl3) δ 8.65 (dd, J =
7.5, 7.6 Hz, 4 H), 7.93 (m, 3 H), 7.81 - 7.69 (m, 6 H), 7.64 (d, J = 8.2 Hz, 4 H), 7.46 (d, J = 8.1 Hz, 4 H),
7.08 (s, 1 H), 6.51 (d, J = 16.0 Hz, 2 H), 4.34 (t, J = 8.3 Hz, 4 H), 3.55 (t, J = 8.9 Hz, 4 H), 2.35 (t, J = 7.5
Hz), 1.87 - 1.67 (m, 2 H), 1.29 - 1.24 (m, 8 H), 1.09 (t, J = 8.2 Hz, 4 H), 0.85 - 0.79 (m, 7 H), 0.09 (s, 18
13
H), -0.03 (s, 18 H); C NMR (75 MHz, CDCl3)δ 171.6, 168.2, 166.8, 163.4, 163.2, 145.7, 143.2, 142.7,
140.2, 137.8, 135.7, 134.5, 131.4, 130.9, 130.8, 129.9, 129.5, 129.0, 128.2, 126.9, 124.8, 123.5, 122.0,
120.0, 119.5, 64.4, 62.9, 37.7, 31.0, 29.2, 29.0, 25.4, 22.6, 17.4, 17.0, 14.0, -1.5, -1.6; m/z (relative
+
intensity) 1390 (MH , 12); HRMS calcd for C H N O Si 1390.5707, found 1390.5688.
78 92 3 13
4
Diimide (13c). Following General Procedure A, diamine (12c) and anhydride (5) were combined to
furnish diimide (13c) as a brown solid following silica gel chromatography with 30% EtOAc/hexane as
-1
1
o
eluent. mp 175-180 C. IR (CHCl3) 1713, 1676, 1638 cm ; H NMR (300 MHz, CDCl3) δ 8.74 (dd, J =
7.6, 7.4 Hz, 4 H), 7.98 (d, J = 7.5 Hz, 2 H), 7.88-7.66 (m, 11 H), 7.52 (d, J = 8.6 Hz, 4 H), 7.17 (s, 1 H),
6.54 (d, J = 15.6 Hz, 2 H), 4.37 (t, J = 8.4 Hz, 4 H), 3.59 (t, J = 8.7 Hz, 4 H), 1.34 (s, 9 H), 1.12 (t, J = 8.4
13
Hz, 4 H), 0.86 (t, J = 8.6 Hz, 4 H), 0.15 (s, 18 H), 0.00 (s, 18 H); C NMR (90 MHz, CDCl3) δ 176.4,
168.2, 166.8, 163.3, 163.1, 145.7, 143.2, 142.8, 139.9, 137.9, 135.9, 134.5, 131.4, 130.89, 130.80, 129.9,
129.5, 129.0, 128.2, 127.0, 124.8, 124.7, 122.1, 120.3, 119.5, 64.4, 62.9, 39.7, 27.5, 17.4, 17.1, -1.4, -1.6;
+
MS m/z (relative intensity) 1348 (M , 100%); HRMS calcd for C H N O Si 1348.5238, found
75 85 3 13
4
1348.5251.
Tetraacid (14a). Following General Procedure B, tetraester (13a) was deprotected to furnish the
-1
1
o
tetraacid (14a) as a yellow solid. mp > 285 C (decomp). IR (KBr) 3568, 1702, 1670 cm ; H NMR
(200 MHz, THF-d8) 9.40 (s, 1 H), 8.61 (d, J = 7.5 Hz, 4 H), 7.99 (d, J = 7.5 Hz, 2 H), 7.81-7.66 (m, 10 H),
13
7.46 (d, J = 7.3 Hz, 4 H), 7.06 (s, 1 H), 6.56 (d, J = 16.1 Hz, 2 H), 2.05 (s, 3 H); C NMR (50 MHz,
THF-d8) δ 173.0, 169.3, 167.7, 163.8, 163.6, 146.7, 144.5, 144.3, 141.5, 139.2, 137.1, 135.5, 133.1, 132.9,
131.4, 131.2, 131.0, 130.5, 129.5, 128.9, 127.9, 126.3, 125.5, 123.7, 120.2; MS m/z (relative intensity)
906 (M+, 16); HRMS calcd for C H N O 906.1935, found 906.1921.
52 32 3 13
Tetraacid (14b). Following General Procedure B, tetraester (13b) was deprotected to furnish the
tetraacid (14b) as a yellow solid following a final trituration with Et2O. mp > 260oC (decomp). IR (KBr)
3448, 1708, 1678 cm-1; 1H NMR (200 MHz, THF-d8) δ 9.28 (s, 1 H), 8.66-8.61 (m, 4 H), 8.00 (d, J = 7.5
Hz, 2 H), 7.83-7.66 (m, 10 H), 7.48 (d, J = 8.1 Hz, 4 H), 7.07 (s, 1 H), 6.57 (d, J = 16.0 Hz, 2 H), 3.58 (s,

13
2 H), 2.33 (m, 2H), 1.33 (m, 8 H), 0.85 (m, 3 H ); C NMR (100 MHz, THF-d ) δ 171.6, 169.3, 167.7,
3
8
163.8, 163.6, 146.6, 144.5, 144.4, 141.5, 139.1, 137.1, 135.5, 131.4, 131.2, 130.9, 130.8, 130.5, 129.6,
128.9, 127.9, 126.3, 125.1, 123.7, 120.4, 120.1, 37.8, 32.8, 30.3, 30.2, 26.4, 23.6, 14.5; MS m/z (relative
intensity) 990 (M+, 100); HRMS calcd for C H N O 990.2874, found 990.2878.
58 44 3 13
Tetraacid (14c). Following General Procedure B, tetraester (13c) was deprotected to furnish the
o
tetraacid (14c) as a yellow solid following a final trituration with Et2O. mp > 325 C (decomp). IR (KBr)
3472, 1708, 1669, 1636, 1589 cm-1; 1H NMR (200 MHz, THF-d8) δ 8.73 (s, 1H), 8.61 (d J = 7.5 Hz, 4H),
7.99 (d, J = 7.5 Hz, 2 H), 7.87 (s, 2 H), 7.79 (d, J = 7.6 Hz, 2 H), 7.73 - 7.66 (m, 6 H), 7.45 (d, J = 8.0 Hz,
13
4 H), 7.0 (s, 1H), 6.56 (d, J = 16.0 Hz, 2 H), 1.29 (s, 9H); C NMR (90 MHz, THF-d8)δ 176.7, 169.3,
167.7, 163.8, 163.3, 146.7, 144.4, 144.2, 141.4, 139.2, 137.0, 135.5, 131.4, 131.2, 130.9, 130.8, 130.5,
129.6, 128.9, 127.9, 126.2, 125.3, 123.6, 121.2, 120.2, 40.3, 27.7; MS m/z (relative intensity) 948
+
(MH ,100); HRMS calcd for C H N O 948.2405, found 948.2412.
55 38 3 13
4-Phenylbutyl 3,5-Dinitrobenzoate (17c). Following General Procedure C, 3,5-dinitrobenzoyl chloride
was combined with 4-phenylbutyl alcohol in toluene to furnish ester (17c) as a yellowish powder
o
1
following chromatography with 7:3 hexane/EtOAc (87%). mp 54-55 C. IR (KBr) 1725 cm-1; H NMR
(360 MHz, CDCl3) δ 9.09 (t, J=2.0 Hz, 1H), 9.15 (d, J=2.0 Hz, 2H), 7.2~7.0 (m, 5H), 4.36 (t, J=6.5 Hz,
2H), 2.60 (t, J=7.0 Hz, 2H), 1.80~1.60 (m, 4H); 13C NMR (75 MHz, acetone-d6) δ 163.9, 150.1, 143.3,
135.0, 130.6, 129.60, 129.56, 127.0, 123.9, 67.7, 36.4, 29.2, 28.9; MS (APCI) m/z (relative intensity) 285
(M+ + 1, 100).
6-Hydroxyhexyl 3,5-Dinitrobenzoate (17e). Following General Procedure C, 3,5-dinitrobenzoyl
chloride was combined with n-hexanol in THF to furnish ester (17e) as a white powder following
chromatography with 6:4 hexane/EtOAc (50%). mp 61-62 oC. IR (KBr) 1735 cm-1; 1H NMR (360 MHz,
CDCl3) δ 9.23 (t, J=2.2 Hz, 1H), 9.16 (d, J=2.2 Hz, 2H), 4.47 (t, J=7.7 Hz, 2H), 3.68 (m, 2H), 1.87 (m,
13
2H), 1.63 (m, 2H), 1.49 (m, 4H); C NMR (75 MHz, acetone-d6) δ 163.9, 150.1, 135.1, 130.2, 123.6,
67.8, 62.7, 34.0, 29.7, 26.9, 26.7; MS (APCI) m/z (relative intensity) 313 (M++1, 22).
2-Hydroxymethyl-3-hydroxypropyl 3,5-Dinitrobenzoate (17f). Following General Procedure C, 3,5-
dinitrobenzoyl chloride was combined with 2-hydroxymethyl-1,3-propanediol in THF to furnish ester
o
(17f) as a yellowish solid following chromatography with 1:1 hexane/EtOAc (39%). mp 83-84 C. IR

(KBr) 3318, 1791 cm-1; 1H NMR (360 MHz, acetone-d6) δ 9.15 (t, J=2.0 Hz, 1H), 9.07 (d, J=2.0 Hz, 2H),
4.56 (d, J=6.2 Hz, 2H), 4.00~3.70 (m, 6H), 2.22 (m, 1H); 13C NMR (90 MHz, acetone-d6) δ 164.0, 150.2,
135.1, 130.1, 124.6, 66.3, 61.5, 44.6; MS (APCI) m/z (relative intensity) 301 (M++1, 9), 283 (100).
Isopropyl 3,5-Diaminobenzoate (18a). Following General Procedure D, 1711 in THF was converted into
the colorless oil (18a) (94%). A sample for spectral characterization was prepared by chromatography
with EtOAc as eluent. IR (neat) 3448, 3354, 1696 cm-1; 1H NMR (300 MHz, acetone-d6) δ 6.61 (d, J=2.0
13
Hz, 2H), 6.19 (t, J=2.1 Hz, 1H), 5.09 (hept, J=6.3 Hz, 1H), 1.27 (t, J=6.2 Hz, 6H); C NMR (75 MHz,
acetone-d6) δ 167.6, 150.4, 133.6, 106.2, 105.7, 68.5, 22.6; MS (APCI) m/z (relative intensity) 195 (M++1,
100).
Cyclohexyl 3,5-Diaminobenzoate (18b). Following General Procedure D, 17b12 in EtOAc was converted
into the colorless oil (18b) (70%). A sample for spectral characterization was prepared by
chromatography with EtOAc as eluent. IR (neat) 3436, 3354, 1696 cm-1; 1H NMR (300 MHz, acetone-d6)
δ 6.63 (d, J=2.1 Hz, 2H), 6.19 (t, J=2.1 Hz, 1H), 4.87 (m, 1H), 1.86 (m, 2H), 1.75 (m, 2H), 1.60~1.30 (m,
6H); 13C NMR (75 MHz, acetone-d6) δ 167.4, 150.4, 133.6, 106.6, 105.7, 73.2, 32.7, 26.6, 24.7; MS (EI)
m/z (relative intensity) 234 (M+, 32), 152 (100).
4-Phenylbutyl 3,5-Diaminobenzoate (18c). Following General Procedure D, 17c in EtOAc was
converted into the gray powder (18c) (95%). A sample for spectral characterization was prepared by
o
1
chromatography with 9:1 EtOAc/MeOH as eluent. mp 84-85 C. IR (KBr) 3448, 3342, 1707 cm-1; H
NMR (360 MHz, CDCl3) δ 7.30~7.10 (m, 5H), 6.79 (d, J=2.0 Hz, 2H), 6.29 (br s, 1H), 4.23 (m, 2H),
13
2.64 (m, 2H), 1.73 (m, 4H); C NMR (75 MHz, acetone-d6) δ 168.1, 150.5, 143.5, 133.1, 129.7, 129.6,
127.0, 106.2, 105.7, 65.2, 36.5, 29.6, 29.1; MS (MALDI) m/z (relative intensity) 285 (M++1, 100).
2-Phenylethyl 3,5-Diaminobenzoate (18d). Following General Procedure D, 17d13 in EtOAc was
converted into the yellow powder (18d) (80%). A sample for spectral characterization was prepared by
o
1
chromatography with 9:1 EtOAc/CH3OH as eluent. mp 66-68 C. IR (KBr) 3448, 3366, 1702 cm-1; H
NMR (300 MHz, acetone-d6) δ 7.35~7.15 (m, 5H), 6.62 (d, J=2.1 Hz, 2H), 6.20 (t, J=2.1 Hz, 1H), 4.39 (t,
13
J=7.0 Hz, 2H), 4.02 (t, J=7.0 Hz, 2H); C HNMR (75 MHz, acetone-d6) δ 170.4, 150.5, 139.7, 133.0,
130.3, 129.7, 127.7, 106.2, 105.8, 66.2, 36.3; MS (MALDI) m/z (relative intensity) 257 (M++1).

6-Hydroxylhexyl 3,5-Diaminobenzoate (18e). Following General Procedure D, 17e in MeOH was
converted into 18e (87%, gray needles). A sample for spectral characterization was prepared by
o
1
chromatography with EtOAc as eluent. mp 70-71 C. IR (KBr) 3413, 1702 cm-1; H NMR (360 MHz,
acetone-d6 +D2O) δ 6.63 (d, J=2.0 Hz, 2H), 6.22 (t, J=2.0 Hz, 1H), 4.18 (t, J=6.6 Hz, 2H), 3.51 (t, J=6.4
13
Hz, 2H), 2.04 (m, 2H), 1.80~1.30 (m, 6H); C NMR (75 MHz, acetone-d6) δ 168.1, 150.5, 133.2, 106.2,
105.7, 65.3, 62.8, 34.0, 29.5, 27.1, 26.8; MS (MALDI) m/z (relative intensity) 253 (M++1, 100).
2-(Hydroxymethyl)-3-hydroxypropyl 3,5-Diaminobenzoate (18f). Following General Procedure D,
17f in MeOH was converted into the off-white powder (18f) (88%). A sample for spectral
o
characterization was prepared by chromatography with 6:4 EtOAc/MeOH as eluent. mp 104-106 C. IR
1
(KBr) 3392, 3345, 1706 cm-1; H NMR (360 MHz, acetone-d6+D2O) δ 6.62 (d, J=2.2 Hz, 2H), 6.22 (t,
13
J=2.0 Hz, 1H), 4.26 (d, J=5.9 Hz, 2H), 3.66 (d, J=5.5 Hz, 4H), 2.08 (m, 1H); C NMR (75 MHz,
acetone-d6) δ 168.9, 150.2, 150.1, 132.7, 106.9, 64.1, 61.0, 44.4; MS (APCI) m/z (relative intensity) 241
(M++1, 100).
4-Methylphenyl 3,5-Diaminobenzoate (18g). Following General Procedure D, 17g14 in THF was
converted into the off-white powder (18g) (86%). A sample for spectral characterization was prepared by
1
chromatography with 4:1 EtOAc/hexane as eluent. mp 100-101 oC. IR (KBr) 3399, 1735 cm-1; H NMR
(360 MHz, acetone-d6) δ 7.22 (d, J=8.6 Hz, 2H), 7.06 (d, J=8.6 Hz, 2H), 6.76 (d, J=1.8 Hz, 2H), 6.29 (t,
J=1.8 Hz, 1H), 4.65 (br s, 4H), 2.33 (s, 3H); 13C NMR (75 MHz, acetone-d6) δ 166.9, 150.7, 150.6, 136.3,
132.2, 131.1, 122.9, 106.6, 106.2, 21.3; MS (APCI) m/z (relative intensity) 243 (M++1, 100).
4-Methoxyphenyl 3,5-Diaminobenzoate (18h). Following General Procedure D, 17h15 in THF was
converted into the yellow powder (18h) (98%). A sample for spectral characterization was prepared by
o
1
chromatography with 4:1 EtOAc/hexane as eluent. mp 80-81 C. IR (KBr) 3378, 1719 cm-1; H NMR
(360 MHz, acetone-d6) δ 7.10 (d, J=9.1 Hz, 2H), 6.90 (d, J=9.1 Hz, 2H), 6.76 (d, J=1.8 Hz, 2H), 6.28 (t,
13
J=1.8 Hz, 1H), 4.60 (br s, 4H), 3.80 (s, 3H); C NMR (75 MHz, acetone-d6) δ 167.2, 158.6, 150.7,
146.1,132.2, 123.9, 115.6, 106.6, 106.3, 56.3; MS (APCI) m/z (relative intensity) 259 (M++1, 100).
Diimide(19a). Following General Procedure A with the modification that 20 equiv of triethylamine was
substituted for the zinc acetate, diamine (18a) in THF was converted into diimide (19a) as a yellow
powder following chromatographic purification with 7:3 hexane/EtOAc as eluent (44%). mp 160-162 oC.
IR (KBr) 1713, 1672 cm-1; 1H NMR (360 MHz, acetone-d6) δ 8.71 (d, J=7.6 Hz, 2H), 8.69 (d, J=7.6 Hz,

2H), 8.28 (d, J=2.0 Hz, 2H), 8.05 (d, J=7.6 Hz, 2H), 7.94 (d, J=7.6 Hz, 2H), 7.87 (t, J=2.2 Hz, 1H), 7.85
(d, J=7.9 Hz, 4H), 7.75 (d, J=16.2 Hz, 2H), 7.54 (d, J=7.9 Hz, 4H), 6.66 (d, J=15.8 Hz, 2H), 5.28 (m,
1H), 4.32~4.29 (m, 4H), 3.60~3.55 (m, 4H), 1.38 (d, J=6.5 Hz, 6H), 1.12~1.07 (m, 4H), 0.91~0.86 (m,
13
4H), 0.10 (s, 18H), -0.03 (s, 18H); C NMR (90 MHz, acetone-d6) δ 168.5, 166.8, 165.1, 163.9, 163.7,
146.5, 144.04, 144.02,138.8, 137.4, 135.6, 135.4, 133.3, 131.7, 131.4, 131.06, 130.96 130.93, 130.5,
129.8, 129.2, 127.9, 126.4, 123.7, 120.3, 69.4, 64.5, 62.9, 22.2, 18.2, 17.6, -1.3, -1.4; MS (MALDI) m/z
(relative intensity) 1357 (M++Na, 100).
Diimide(19b). Following General Procedure A with the modification that 20 equiv of triethylamine was
substituted for the zinc acetate, diamine (18b) in xylene was converted into diimide (19b) as a yellow
powder following chromatographic purification with 4:1 hexane/EtOAc as eluent (24%). mp 162-164 oC.
IR (KBr) 1713, 1672 cm-1; 1H NMR (360 MHz, acetone-d6) δ 8.69 (d, J=7.7 Hz, 2H), 8.68 (d, J=7.5 Hz,
2H), 8.30 (d, J=2.0 Hz, 2H), 8.03 (d, J=7.5 Hz, 2H), 7.93 (d, J=7.5 Hz, 2H), 7.86 (t, J=1.8 Hz, 1H), 7.84
(d, J=8.2 Hz, 4H), 7.75 (d, J=15.9 Hz, 2H), 7.53 (d, J=8.4 Hz, 4H), 6.64 (d, J=15.9 Hz, 2H), 5.05 (m,
1H), 4.31 (m, 4H), 3.56 (m, 4H), 1.96 (m, 2H), 1.77 (m, 2H), 1.58 (m, 4H), 1.42 (m, 2H), 1.09 (m, 4H),
0.87 (m, 4H), 0.10 (s, 18H), -0.04 (s, 18H); 13C NMR (75 MHz, acetone-d6) δ 168.6, 166.9, 165.1, 164.2,
164.1, 146.5, 144.12, 144.10,143.8, 138.8, 137.8, 135.4, 133.4, 131.8, 131.6, 131.3, 131.1, 130.9, 130.5,
129.8, 129.3, 127.8, 126.3, 123.7, 120.3, 74.3, 64.7, 62.9, 32.3, 26.1, 24.3, 19.3, 18.8, -1.3, -1.4; MS
(MALDI) m/z (relative intensity) 1397 (M++Na, 100).
Diimide(19c). Following General Procedure A with the modification that 20 equiv of triethylamine was
substituted for the zinc acetate, diamine (18c) in xylene was converted into diimide (19c) as a yellow
powder following chromatographic purification with 4:1 hexane/EtOAc as eluent (34%). mp 122-124 oC.
IR (KBr) 1713, 1678 cm-1; 1H NMR (360 MHz, acetone-d6) δ 8.69 (d, J=7.7 Hz, 2H), 8.67 (d, J=7.5 Hz,
2H), 8.29 (d, J=2.0 Hz, 2H), 8.02 (d, J=7.5 Hz, 2H), 7.91 (d, J=7.5 Hz, 2H), 7.86 (t, J=2.0 Hz, 1H), 7.83
(d, J=8.2 Hz, 4H), 7.74 (d, J=16.0 Hz, 2H), 7.52 (d, J=8.2 Hz, 4H), 7.25~7.05 (m, 5H), 6.64 (d, J=16.2
Hz, 2H), 4.32 (m, 4H), 3.57 (m, 4H), 2.67 (t, J=7.1 Hz, 2H), 1.80 (m, 4H), 1.10 (m, 4H), 0.88 (m, 4H),
13
0.10 (s, 18H), -0.02 (s, 18H); C NMR (90 MHz, acetone-d6) δ 168.5, 166.9, 165.7, 164.1, 163.9, 146.4,
144.0, 143.8, 143.0,138.7, 137.6, 135.6, 135.3, 132.8, 132.3, 131.7, 131.6, 131.2, 131.1, 130.8, 130.5,
129.8, 129.2, 129.0, 127.7, 126.5, 126.2, 123.5, 120.2, 65.9, 64.6, 62.9, 35.9, 29.0, 28.5, 17.9, 17.4; MS
(MALDI) m/z (relative intensity) 1447 (M++Na, 85).
Diimide(19d). Following General Procedure A with the modification that 20 equiv of triethylamine was
substituted for the zinc acetate, diamine (18d) in THF was converted into diimide (19d) as a yellow

powder following chromatographic purification with 7:3 hexane/EtOAc as eluent (48%). mp 118-120 oC.
IR (KBr) 1713, 1672 cm-1; 1H NMR (360 MHz, acetone-d6) δ 8.72 (d, J=7.5 Hz, 2H), 8.70 (d, J=7.5 Hz,
2H), 8.28 (d, J=2.2 Hz, 2H), 8.05 (d, J=7.5 Hz, 2H), 7.95 (d, J=7.5 Hz, 2H), 7.88 (t, J=2.2 Hz, 1H), 7.85
(d, J=8.6 Hz, 4H), 7.76 (d, J=15.8 Hz, 2H), 7.55 (d, J=7.9 Hz, 4H), 7.40~7.10 (m, 5H), 6.66 (d, J=16.2
Hz, 2H), 4.58 (t, J=7.2 Hz, 2H), 4.39~4.29 (m, 4H), 3.60~3.55 (m, 4H), 3.11 (t, J=7.2 Hz, 2H),
13
1.12~1.09 (m, 4H), 0.91~0.86 (m, 4H), 0.11 (s, 18H), -0.02 (s, 18H); C NMR (90 MHz, acetone-d6) δ
168.5, 166.9, 165.5, 164.1, 163.9, 146.4, 144.0, 143.7, 138.8, 138.7, 137.5, 135.4,135.3, 132.6, 131.7,
131.6, 131.2, 131.1, 130.7, 130.5,129.8, 129.7, 129.3, 129.2, 127.6, 127.2, 126.1, 123.4, 120.2, 66.6, 64.6,
62.9, 35.7, 17.9, 17.4, -1.4, -1.5; MS (MALDI) m/z (relative intensity) 1419 (M++Na).
Diimide(19e). Following General Procedure A with the modification that 20 equiv of triethylamine was
substituted for the zinc acetate, diamine (18e) in xylene was converted into diimide (19e) as a yellow
powder following chromatographic purification with 1:1 hexane/EtOAc as eluent (25%). mp 119-122 oC.
IR(KBr), 1713, 1672 cm-1; 1H NMR (360 MHz, acetone-d6) δ 8.70 (d, J=7.7 Hz, 2H), 8.69 (d, J=7.5 Hz,
2H), 8.30 (d, J=1.8 Hz, 2H), 8.04 (d, J=7.5 Hz, 2H), 7.93 (d, J=7.7 Hz, 2H), 7.87 (t, J=1.8 Hz, 1H), 7.84
(d, J=8.2 Hz, 4H), 7.74 (d, J=16.0 Hz, 2H), 7.53 (d, J=8.4 Hz, 4H), 6.64 (d, J=16.2 Hz, 2H), 4.38 (t,
J=6.6 Hz, 2H), 4.31 (m, 4H), 3.57 (m, 4H), 3.49 (t, J=5.7 Hz, 2H), 1.79 (m, 2H), 1.53~1.41 (m, 6H), 1.09
13
(m, 4H), 0.87 (m, 4H), 0.08 (s, 18H), -0.05 (s, 18H); C NMR (90 MHz, acetone-d6) δ 168.5, 166.9,
165.7, 164.1, 164.0, 146.4, 144.1, 143.7, 138.7, 137.6, 135.6,135.3, 132.9, 131.7, 131.6, 131.2, 131.1,
130.7, 130.5, 129.8, 129.2, 127.6, 126.1, 123.4, 120.2, 66.1, 64.7, 62.9, 62.3, 33.6, 29.4, 26.6, 26.3, 17.9,
17.4, -1.3, -1.4; MS (MALDI) m/z (relative intensity) 1415 (M++Na, 90).
Diimide(19f). Following General Procedure A with the modification that 20 equiv of triethylamine was
substituted for the zinc acetate, diamine (18f) in xylene was converted into diimide (19f) as a yellow
powder following chromatographic purification with 1:4 hexane/EtOAc as eluent (30%). mp 188-190 oC;
1
IR (KBr) 3450, 1707, 1672 cm-1; H NMR (360 MHz, acetone-d6) δ 8.71 (d, J=7.7 Hz, 2H), 8.69 (d,
J=7.5 Hz, 2H), 8.31 (d, J=1.8 Hz, 2H), 8.05 (d, J=7.5 Hz, 2H), 7.94 (d, J=7.5 Hz, 2H), 7.88 (t, J=1.8 Hz,
1H), 7.85 (d, J=8.2 Hz, 4H), 7.76 (d, J=16.0 Hz, 2H), 7.54 (d, J=8.2 Hz, 4H), 6.65 (d, J=16.0 Hz, 2H),
4.49 (d, J=6.2 Hz, 2H), 4.31 (m, 4H), 3.73 (d, J=5.7 Hz, 4H), 3.57 (m, 4H), 2.15(m, 1H), 1.09 (m, 4H),
0.88 (m, 4H), 0.09 (s, 18H), -0.03 (s, 18H); 13C NMR (90 MHz, acetone-d6) δ 168.5, 166.9, 165.8, 164.1,
164.0, 146.4, 144.1, 143.7, 138.7, 137.6, 135.6, 135.3, 132.9, 131.8, 131.6, 131.24,131.16,130.8, 130.5,
129.8, 129.2, 127.7, 126.1, 123.5, 120.2, 64.7, 64.4, 62.9, 61.1, 44.3, 18.0, 17.4, -1.3, -1.4; MS (MALDI)
m/z (relative intensity) 1403 (M++Na, 90).

Diimide(19g). Following General Procedure A with the modification that 20 equiv of triethylamine was
substituted for the zinc acetate, diamine (18g) in THF was converted into diimide (19g) as a yellow
powder following chromatographic purification with 7.5:2.5 hexane/EtOAc as eluent (51%). mp 108-111
oC. IR (KBr) 1707, 1672 cm-1; 1H NMR (360 MHz, acetone-d6) δ 8.71 (d, J=7.7 Hz, 2H), 8.69 (d, J=7.5
Hz, 2H), 8.43 (d, J=1.8 Hz, 2H), 8.04 (d, J=7.5 Hz, 2H), 7.95 (t, J=2.1 Hz, 1H), 7.93 (d, J=7.7 Hz, 2H),
7.83 (d, J=8.4 Hz, 4H), 7.75 (d, J=16.2 Hz, 2H), 7.53 (d, J=8.4 Hz, 4H), 7.30~7.20 (m, 4H), 6.64(d,
J=16.2 Hz, 2H), 4.31 (m, 4H), 3.57 (m, 4H), 2.35 (s, 3H), 1.09 (m, 4H), 0.87 (m, 4H), 0.10 (s, 18H),
-0.03 (s, 18H); 13C NMR (90 MHz, acetone-d6) δ 168.5, 166.8, 164.4, 163.9, 163.8, 150.1, 146.6, 144.06,
144.02, 138.9, 137.6, 136.1,135.6, 132.5, 132.3, 131.9, 131.7, 131.5, 131.0, 130.59, 130.57, 129.9, 129.2,
127.9, 126.4, 123.7, 122.4, 120.3, 108.4, 64.5, 62.9, 29.9, 18.2, 17.6, -1.4, -1.5; MS (MALDI) m/z
(relative intensity) 1405 (M++Na, 100).
Diimide(19h). Following General Procedure A with the modification that 20 equiv of triethylamine was
substituted for the zinc acetate, diamine (18h) in xylene was converted into diimide (19h) as a yellow
powder following chromatographic purification with 7:3 hexane/EtOAc as eluent (37%). mp 102-104 oC.
IR (KBr), 1708, 1672 cm-1; 1H NMR (300 MHz, acetone-d6) δ 8.73 (d, J=7.5 Hz, 2H), 8.72 (d, J=7.6 Hz,
2H), 8.44 (d, J=1.8 Hz, 2H), 8.06 (d, J=7.5 Hz, 2H), 7.96 (t, J=1.8 Hz, 1H), 7.95 (d, J=7.7 Hz, 2H), 7.85
(d, J=8.5 Hz, 4H), 7.76 (d, J=15.6 Hz, 2H), 7.54 (d, J=8.1 Hz, 4H), 7.29 (d, J=9.2 Hz, 2H), 7.00 (d,
J=9.2 Hz, 2H), 6.65 (d, J=16.0 Hz, 2H), 4.30 (m, 4H), 3.82 (s, 3H), 3.57 (m, 4H), 1.08 (m, 4H), 0.87 (m,
13
4H), 0.10 (s, 18H), -0.02 (s, 18H); C NMR (75 MHz, acetone-d6) δ 168.5, 166.9, 164.6, 164.0, 163.9,
158.3, 146.3, 145.3, 144.0, 143.6, 138.5, 137.5, 136.1, 135.2, 132.1, 131.74, 131.69, 131.67, 131.2, 130.6,
130.4, 129.7, 129.1, 127.5, 125.9, 123.4, 123.2, 120.1, 115.1, 64.6, 62.9, 55.8, 17.9, 17.4, -1.3, -1.5;
MS (MALDI) m/z (relative intensity) 1405 (M++Na, 45).
Tetraacid (20a). Following General procedure B, the tetra(silylethyl)ester (19a) was converted to the
o
tetraacid (20a) (88%, light yellow needles). mp > 350 C (decomp). IR (KBr) 3424, 2931, 1707, 1672
cm-1;1H NMR (360 MHz, THF-d8): δ 8.69 (d, J=7.2 Hz, 2H), 8.67 (d, J=7.2 Hz, 2H), 8.14 (d, J=1.8 Hz,
2H), 8.03 (d, J=7.2 Hz, 2H), 7.85 (d, J=7.2 Hz, 2H), 7.73~7.68 (m, 7H), 7.51 (d, J=7.2 Hz, 2H), 6.58 (d,
13
J=16.2 Hz, 2H), 5.27 (hept, J=6.1 Hz, 1H), 1.37 (d, J=6.1 Hz, 6H); C NMR (90 MHz, THF-d8 +
DMSO-d6): δ 170.2, 168.6, 164.4, 164.3, 164.2, 147.2, 144.27, 144.26, 137.8, 136.2,135.5, 134.1,133.3,
131.2, 131.0, 130.5, 129.9,129.6, 129.2, 128.3, 125.6, 123.4, 123.3, 120.7, 114.4, 70.0, 22.4; MS
(MALDI) m/z (relative intensity) 957 (M++Na, 100).

Tetraacid (20b). Following General procedure B, the tetra(silylethyl)ester (19b) was converted to the
tetraacid (20b) (52%, yellow needles). mp 340 oC (decomp). IR (KBr) 3436, 1707, 1672 cm-1; 1H NMR
(360 MHz, THF-d8) δ 8.69 (d, J=7.7 Hz, 2H), 8.67 (d, J=7.7 Hz, 2H), 8.16 (d, J=1.8 Hz, 2H), 8.03 (d,
J=7.7 Hz, 2H), 7.85 (d, J=7.5 Hz, 2H), 7.72 (d, J=8.2 Hz, 4H), 7.70 (d, J=16.2 Hz, 2H) 7.68 (t, J=1.8
Hz, 1H), 7.51 (d, J=8.4 Hz, 4H), 6.58 (d, J=15.8 Hz, 2H), 5.05 (m, 1H), 2.0~1.0 (m, 10H); 13C NMR (75
MHz, THF-d8+ DMSO-d6) δ 170.3, 168.7, 165.2, 164.4, 164.3, 147.3, 144.2, 144.1, 137.8, 135.5, 133.1,
131.6, 131.43, 131.40, 131.36, 131.0, 130.50, 130.48, 129.5, 129.2, 127.7, 125.5, 123.4, 121.17, 121.16,
74.2, 32.4, 30.4, 24.5; MS (MALDI) m/z (relative intensity) 997 (M++Na, 45).
Tetraacid (20c). Following General procedure B, the tetra(silylethyl)ester (19c) was converted to the
tetraacid (20c) (100%, yellow powder). mp 240 oC (decomp). IR (KBr) 3424, 2954, 1707, 1672 cm-1; 1H
NMR (360 MHz, THF-d8) δ 8.68 (d, J=7.7 Hz, 2H), 8.66 (d, J=8.0 Hz, 2H), 8.16 (d, J=2.0 Hz, 2H), 8.02
(d, J=7.5 Hz, 2H), 7.84 (d, J=7.5 Hz, 2H), 7.71 (d, J=15.7 Hz, 2H), 7.70 (d, J=7.5 Hz, 4H), 7.69 (t,
J=2.0 Hz, 1H), 7.50 (d, J=8.1 Hz, 4H), 7.20~7.00 (m, 5H), 6.57 (d, J=15.9 Hz, 2H), 4.37 (t, J=6.2 Hz,
13
2H), 2.67 (t, J=6.7 Hz, 2H), 1.79 (m, 4H); C NMR (75 MHz, THF-d8) δ169.9, 168.6, 165.8, 164.3,
164.1, 147.0, 144.2, 143.0, 140.1, 137.7, 135.9, 135.6, 132.7, 131.6, 131.4, 131.20, 131.18, 131.0, 130.5,
129.7, 129.3, 129.23, 129.21, 129.1, 127.8, 126.5, 125.9, 123.5, 121.1, 65.9, 36.1, 29.2, 28.6; MS
(MALDI) m/z (relative intensity) 1047 (M++Na, 100).
Tetraacid (20d). Following General procedure B, the tetra(silylethyl)ester (19d) was converted to the
tetraacid (20d) (28%, yellow needles). mp 320 oC (decomp). IR (KBr) 3433, 1711, 1678 cm-1; 1H NMR
(360 MHz, THF-d8) δ 8.72 (d, J=7.2 Hz, 2H), 8.70 (d, J=7.2 Hz, 2H), 8.18 (d, J=3.6 Hz, 2H), 8.06 (d,
J=7.2 Hz, 2H), 7.87 (d, J=7.2 Hz, 2H), 7.75~7.71 (m, 7H), 7.53 (d, J=7.2 Hz, 4H), 7.33~7.17 (m, 5H),
6.60 (d, J=14.4 Hz, 2H), 4.55 (t, J=7.2 Hz, 2H), 3.10 (t, J=7.2 Hz, 2H); 13C NMR (90 MHz, DMSO-d6) δ
169.8, 168.9, 164.4, 164.2, 164.0, 153.7, 149.2, 144.7, 143.6, 139.6, 139.1, 138.7, 135.1, 131.9, 131.6,
131.59, 131.55, 130.4, 130.3, 129.7, 129.3, 129.2, 129.18, 127.3, 127.2, 125.0, 122.4, 121.4, 119.4, 64.0,
35.4; MS (MALDI) m/z (relative intensity) 1019 (M++Na, 90).
Tetraacid (20e). Following General procedure B, the tetra(silylethyl)ester (19e) was converted to the
tetraacid (20e) (57%, yellow powder). mp 340 oC (decomp). IR (KBr) 3436, 1709, 1672 cm-1; 1H NMR
(360 MHz, THF-d8) δ 8.69 (d, J=7.7 Hz, 2H), 8.66 (d, J=7.9 Hz, 2H), 8.16 (d, J=2.0 Hz, 2H), 8.02 (d,
J=7.5 Hz, 2H), 7.84 (d, J=7.7 Hz, 2H), 7.71 (d, J=15.7 Hz, 2H), 7.70 (d, J=8.2 Hz, 4H), 7.69 (t, J=2.0
Hz, 1H), 7.50 (d, J=8.2 Hz, 4H), 6.57 (d, J=15.9 Hz, 2H), 4.35 (t, J=6.5 Hz, 2H), 3.46 (t, J=6.1 Hz, 2H),

1.77 (m, 2H), 1.50~1.40 (m, 6H); 13C NMR (90 MHz, THF-d8) δ 169.3, 167.7, 165.7, 163.9, 163.8, 146.9,
144.4, 144.3, 139.5, 137.4, 135.6, 132.8, 132.4, 131.5, 131.3, 131.1, 131.0, 130.9, 130.6, 129.6, 128.9,
127.9, 126.2, 123.6, 120.3, 66.0, 62.4, 33.9, 30.6, 26.9, 26.6; MS (MALDI) m/z (relative intensity) 1015
(M++Na, 100).
Tetraacid (20f). Following General procedure B, the tetra(silylethyl)ester (19f) was converted to the
tetraacid (20f) (100%, yellow powder). mp 270 oC (decomp). IR (KBr) 3424, 3072, 2954, 1713 cm-1; 1H
NMR (360 MHz, THF-d8) δ 8.69 (d, J=7.7 Hz, 2H), 8.67 (d, J=8.0 Hz, 2H), 8.17 (d, J=2.0 Hz, 2H),
8.03 (d, J=7.5 Hz, 2H), 7.85 (d, J=7.5 Hz, 2H), 7.71 (d, J=8.4 Hz, 4H), 7.70 (t, J=2.0 Hz, 1H), 7.69 (d,
J=16.2 Hz, 2H), 7.50 (d, J=8.2 Hz, 4H), 6.57 (d, J=16.0 Hz, 2H), 4.43 (d, J=6.1 Hz, 2H), 3.66 (d, J=5.7
13
Hz, 4H), 2.06 (m, 1H); C NMR (90 MHz, THF-d8) δ 167.9, 166.5, 164.5, 162.6, 162.5, 145.6, 143.02,
142.97, 138.2, 136.0, 134.2, 130.1, 130.0, 129.73, 129.70, 129.3, 129.2, 128.2, 127.58, 127.56 126.6,
124.7, 122.2, 119.9, 118.9, 66.2, 59.8, 29.0; MS (MALDI) m/z (relative intensity) 1003 (M++Na, 45).
Tetraacid (20g). Following General procedure B, the tetra(silylethyl)ester (19g) was converted to the
tetraacid (20g) (61%, yellow powder). mp 200 oC (decomp). IR (KBr) 3424, 3060, 1707, 1672 cm-1; 1H
NMR (360 MHz, THF-d8) δ 8.70 (d, J=7.7 Hz, 2H), 8.68 (d, J=7.7 Hz, 2H), 8.32 (d, J=1.8 Hz, 2H),
8.03 (d, J=7.5 Hz, 2H), 7.85 (d, J=7.7 Hz, 2H), 7.78 (d, J=1.8 Hz, 1H), 7.72 (d, J=8.4 Hz, 4H), 7.70 (d,
J=15.9 Hz, 2H), 7.50 (d, J=8.2 Hz, 4H), 7.18 (d, J=6.1 Hz, 4H), 6.58 (d, J=16.1 Hz, 2H), 2.34 (s, 3H);
13C NMR (90 MHz, THF-d8) δ 169.3, 167.8, 164.0, 163.9, 163.8, 147.0, 146.9, 144.45, 144.42, 144.39,
139.55, 139.47, 137.6, 136.0, 135.6, 135.59, 131.4, 131.0, 130.59, 130.54, 130.49, 129.7, 129.0, 128.9,
128.0, 126.2, 123.6, 122.4, 120.3, 21.0; MS (MALDI) m/z (relative intensity) 1005 (M++Na, 40).
Tetraacid (20h). Following General procedure B, the tetra(silylethyl)ester (19h) was converted to the
tetraacid (20h) (61%, yellow clusters). mp 350 oC (decomp). IR (KBr) 3436, 1707, 1672 cm-1; 1H NMR (360
MHz, THF-d8) δ 8.70 (d, J=7.5 Hz, 2H), 8.68 (d, J=7.7 Hz, 2H), 8.31 (d, J=1.8 Hz, 2H), 8.04 (d, J=7.5
Hz, 2H), 7.85 (d, J=7.5 Hz, 2H), 7.77 (d, J=1.8 Hz, 1H), 7.71 (d, J=8.2 Hz, 4H), 7.70 (d, J=15.9 Hz, 2H),
7.51 (d, J=8.4 Hz, 4H), 7.20 (d, J=9.1 Hz, 2H), 6.93 (d, J=9.1 Hz, 2H), 6.58 (d, J=16.1 Hz, 2H), 3.78 (s,
13
3H); C NMR (90 MHz, THF-d8 + DMSO-d6) δ 170.1, 168.7, 165.0, 164.5, 164.3, 158.5, 147.2, 145.4,
144.3, 144.1, 140.7, 138.1, 135.5, 131.9, 131.7, 131.5, 131.4, 131.0, 130.53, 130.51, 129.7, 129.35,
129.29, 127.7, 125.7, 123.6, 123.4, 121.1, 115.5, 56.2; MS (MALDI) m/z (relative intensity) 1021
(M++Na, 45).

Triimide (23). Following General Procedure A, anhydride (5) and 1,3,5-triaminobenzene (22)5 were
combined to furnish triimide (23) as a yellow solid following silica gel flash chromatography with 40%
-1
1
o
EtOAc/hexane as eluent. mp 182-188 C. IR (CHCl3) 1714, 1681, 1638 cm ; H NMR (360 MHz,
CDCl3) δ 8.77 (overlapping doublets, J = 7.8, 8.5 Hz, 6 H), 7.96 (d, J = 7.5 Hz, 3 H), 7.79 (d, J = 7.6 Hz,
3 H), 7.72 (d, J = 16.0 Hz, 3 H), 7.66 - 7.63 (m, 9H), 7.49 (d, J = 8.1 Hz, 6 H), 6.50 (d, J = 16.0 Hz, 3 H),
4.33 (t, J = 8.4 Hz, 6 H), 3.56 (t, J = 8.5 Hz, 6 H), 1.09 (t, J = 8.4 Hz, 6 H), 0.83 (t, J = 9.1 Hz, 6 H), 0.10
13
(s, 27 H), 0.09 (s, 27H); C NMR (90 MHz, CDCl3) δ 168.2, 166.8, 163.1, 162.9, 145.7, 143.2, 142.8,
137.9, 135.2, 134.5, 131.6, 131.1, 130.9, 129.9, 129.8, 129.5, 129.1, 128.2, 127.0, 124.9, 122.2, 119.5,
+
64.4, 62.9, 17.4, 17.1, -1.4, -1.6; MS m/z (relative intensity) 1835 (MH , 80); HRMS calcd for 1834.6557,
found 1834.6638.
Hexaacid (24). Following General Procedure B, triimide (23) was deprotected to yield hexaacid (24) as a
-1
1
o
yellow solid. mp > 360 C (decomp). IR (KBr) 3448, 1711, 1676 cm ; H NMR (200 MHz, THF-d8) δ
8.71 - 8.65 (overlapping doublets, 6 H), 8.01 (d, J = 7.4 Hz, 3 H), 7.82 (d, J = 7.5 Hz, 3 H), 7.73 - 7.62 (m,
12 H), 7.49 (d, J = 8.0 Hz, 6 H), 6.56 (d, J = 16.1 Hz, 3 H); 13C NMR (90 MHz, THF-d8) δ 169.2, 167.6,
163.6, 163.5, 146.6, 144.5, 144.4, 139.2, 138.1, 136.5, 135.5, 131.4, 131.3, 130.9, 130.8, 129.6, 128.8,
+
127.9, 126.3, 125.9, 123.7, 120.2; MS m/z (relative intensity) 1234 (M , 100); HRMS calcd for
C H N O 1234.2307, found 1234.2312.
72 40 3 18
Tetraimide (29a). Following General Procedure A, tetraamine (28a) and anhydride (5) were combined in
mesitylene to afford 29a as an orange solid following silica gel flash chromatography with CH2Cl2 as
1
eluent (34%). mp 186-188°C; IR (CDCl3) 1700, 1658, 1639, 1591 cm-1; H NMR (CDCl3) δ 8.75 - 8.69
(m, 8H,), 7.94 (d, J = 7.6 Hz, 4H), 7.77 (m, 6H), 7.69 - 7.63 (m, 10H), 7.49 (d, J = 8.1 Hz, 8H), 6.51 (d, J
= 16.0 Hz, 4H), 4.75 (m, 8H), 4.33 (t, J = 8.4 Hz, 8H), 3.55 (t, J = 8.9 Hz, 8H), 2.18 (m, 8H), 1.09 (t, J =
8.4 Hz, 8H), 0.83 (t, J = 8.9 Hz, 8H), 0.09 (s, 36 H), -0.03 (s, 36H); 13C NMR (75 MHz, CDCl3) δ 168.5,
166.9, 163.8, 163.6, 145.3, 143.3, 143.0, 137.5, 134.4, 131.2, 130.8, 130.6, 129.8, 129.5, 129.0, 128.2,
126.9, 125.0, 122.3, 119.4, 64.4, 62.9, 36.9, 35.0, 29.7, 17.4, 17.1, -1.4, -1.5; MS m/z (relative intensity)
2469 (M+, 100); HRMS Calcd for C137H160N4O24Si8 2469.9655, found 2469.9549.
Tetraimide (29b). Following General Procedure A, tetraamine (28b) and anhydride (5) were combined
in mesitylene to afford 29b as an orange solid following silica gel flash chromatography with CH2Cl2 to
20% EtOAc/hexane as eluent (27%). mp 131-133°C. IR (CDCl3) 1702, 1659 cm-1; 1H NMR (200 MHz,
CDCl3) δ 8.57 (d, J = 7.6 Hz, 8H), 7.90 (d, J = 7.5 Hz, 4H), 7.76 - 7.67 (m, 16H), 7.43 (d, J = 8.1 Hz, 8H),

6.51 (d, J = 16.0 Hz, 4H), 4.35 (t, J = 8.5 Hz, 8H), 4.15 (m, 8H), 3.54 (t, J = 8.9 Hz, 8H), 1.72 (m, 8H),
1.42 (s, 8H), 1.10 (t, J = 8.5 Hz, 8H), 0.81 (t, J = 8.9 Hz, 8H), 0.10 (s, 36H), -0.03 (s, 36H); 13C NMR (75
MHz, CDCl3) δ 168.3, 166.7, 163.5, 163.3, 145.0, 143.2, 142.9, 137.2, 134.3, 130.9, 130.6, 130.3, 129.6,
129.4, 128.8, 128.1, 126.7, 124.9, 122.2, 119.4, 64.2, 62.8, 41.1, 37.3, 33.4, 21.9, 17.3, 17.0, -1.4, -1.6;
HRMS Calcd for C141H168N4O24Si8 2525.0262, found 2525.0203.
Octaacid (30a). Following General Procedure B, 83 mg (0.03 mmol) of the tetraimide (29a) was
deprotected to furnish octaacid (30a). This crude solid was dissolved in 1:1 THF:EtOAc (20 mL) and
then washed with 0.5 N HCl. The organic layer was then washed with 0.5 N NaOH. The aqueous layer
was extracted with 1:1 THF:EtOAc (3 x 10 mL) to remove any organic impurities and then it was
acidified to pH 2 with 0.5 N HCl, at which point a precipitate deposited. The precipitate was extracted
from the aqueous layer with 1:1 THF:EtOAc (3 x 15 mL). The combined organic layers were washed
with H2O (3 x 10 mL), then dried over Na2SO4, filtered, and concentrated in vacuo to afford 44 mg (78%)
of octaacid (30a) as a bright yellow solid. mp >310°C; IR (KBr) 3448, 2958, 1701, 1655, 1637, 1591 cm-1;
1H NMR (360 MHz, DMSO-d6) δ 12.6 (br s, 8H), 8.49-8.44 (m, 8H), 7.97 (d, J = 7.3 Hz, 4H), 7.78-
7.74 (m, 12H), 7.66 (d, J = 16.0 Hz, 4H), 7.40 (d, J = 8.0 Hz, 8H), 6.61 (d, J = 15.3 Hz, 4H), 4.47-4.41
13
(m, 8H), 2.03-2.00 (m, 8H); C NMR (90 MHz, DMSO-d6) δ 168.9, 167.6, 163.1, 162.9, 151.5, 145.1,
143.4, 142.7, 139.2, 138.3, 134.0, 130.7, 129.3, 128.7, 128.0, 126.1, 124.9, 124.3, 121.8, 119.7, 34.4,
30.4, 21.1; MS m/z (relative intensity) 1669 (MH+, 100); HRMS Calcd for C97H65N4O24 1669.3989, found
1669.3976.
Octaacid (30b). Following General Procedure B, 126 mg (0.05 mmol) of the tetraimide (29b) was
deprotected to furnish the octaacid (30b). The crude yellow-green solid was dissolved in 1:1 THF:EtOAc
(30 mL) and then washed with 0.5 N HCl. The separated organic layer was then washed with 0.5 N
NaOH. The aqueous layer was extracted with 1:1 THF:EtOAc (3 x 15 mL) then acidified to pH 2 with
0.5 N HCl, at which point a precipitate deposited. The precipitate was removed from the aqueous layer
with 1:1 THF:EtOAc (3 x 20 mL). The combined organic layers were washed with H2O (3 x 10 mL),
dried over Na2SO4, filtered, and concentrated in vacuo to afford 69 mg (80%) of yellow solid. mp
1
>310°C. IR (KBr) 3448, 1702, 1655, 1631, 1591 cm-1; H NMR (300 MHz, DMSO-d6) δ 12.7 (bs, 8H),
8.36 (dd, J = 7.3 Hz, 4H), 8.30 (dd, J = 7.3 Hz, 4H), 7.89 (d, J = 7.8 Hz, 4H), 7.70 - 7.60 (m, 16H), 7.25
(d, J = 8.2 Hz, 8H), 6.60 (d, J = 16.4 Hz, 4H), 3.92 (m, 8H), 1.48 (m, 8H,), 1.21 (m, 8H); 13C NMR (90
MHz, DMSO-d6) δ 168.8, 167.6, 162.9, 162.8, 151.5, 145.0, 143.4, 142.6, 139.2, 138.2, 134.0, 130.6,

128.9, 128.3, 128.0, 125.9, 124.9, 123.9, 121.5, 119.7, 34.4, 30.4, 21.2, 21.0; HRMS Calcd for
C101H73N4O24 1725.4615, found 1725.4741.
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