Synthesis of poly(galactaramides) from alkylene- and substituted alkylenediammonium galactarates

Article abstract of DOI:10.1080/07328300903080749

Polyhydroxypolyamides (PHPAs) represent a class of synthetic polyamides derived from aldaric acid and diamine monomer units. This paper describes the synthesis of some poly(galactaramides), a class of polyhydroxypolyamides, that employs alkylene and subst

Full text of DOI:10.1080/07328300903080749

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Synthesis of Poly(galactaramides)
from Alkylene- and Substituted
Alkylenediammonium Galactarates
Donald E. Kiely a , Arvind Vishwanathan a , Bevan P. Jarman b &
Merilyn Manley-Harris b
a Shafizadeh Rocky Mountain Center for Wood and Carbohydrate
Chemistry , The University of Montana , Missoula, MT, 59812, USA
b Chemistry Department , The University of Waikato , Private Bag
3105, Hamilton, New Zealand
Published online: 24 Jul 2009.
To cite this article: Donald E. Kiely , Arvind Vishwanathan , Bevan P. Jarman & Merilyn Manley-
Harris (2009) Synthesis of Poly(galactaramides) from Alkylene- and Substituted Alkylenediammonium
Galactarates, Journal of Carbohydrate Chemistry, 28:6, 348-368, DOI: 10.1080/07328300903080749
To link to this article: http://dx.doi.org/10.1080/07328300903080749
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Journal of Carbohydrate Chemistry, 28:348–368, 2009
ꢀC
Copyright Taylor & Francis Group, LLC
ISSN: 0732-8303 print / 1532-2327 online
DOI: 10.1080/07328300903080749
Synthesis of Poly
(galactaramides) from
Alkylene- and Substituted
Alkylenediammonium
Galactarates
Donald E. Kiely,1 Arvind Vishwanathan,1 Bevan P. Jarman,2 and
Merilyn Manley-Harris2
1Shafizadeh Rocky Mountain Center for Wood and Carbohydrate Chemistry, The Uni-
versity of Montana, Missoula, MT 59812, USA
2Chemistry Department, The University of Waikato, Private Bag 3105, Hamilton, New
Zealand
Polyhydroxypolyamides (PHPAs) represent a class of synthetic polyamides derived from
aldaric acid and diamine monomer units. This paper describes the synthesis of some
poly(galactaramides), a class of polyhydroxypolyamides, that employs alkylene and
substituted alkylenediammonium galactarate salts, with 1:1 molar equivalency of the
diacid and diamine monomer components, as precursors for the polyamides. The salts
were treated with acid/alcohol and then base in order to initiate the polymerization in
methanol. The polyamides, labeled as prepolyamides, precipitated from solution and
were then subjected to a second polymerization (postpolymerization) in a different sol-
vent to produce a generally larger polyamide, labeled as a postpolyamide.
Keywords Polyamides; Structure-property relationship; Polyhydroxypolyamides;
Poly(galactaramides)
INTRODUCTION
Poly(alkylene galactaramides) are representatives of a class of polyhydrox-
ypolyamides (PHPAs) generated by condensation polymerization of esteri-
fied galactaric acids with appropriate diamines. This polymerization method,
Received December 23, 2008; accepted May 31, 2009.
Address correspondence to D.E. Kiely, Shafizadeh Rocky Mountain Center for Wood
and Carbohydrate Chemistry, The University of Montana, Missoula, MT 59812, USA.
E-mail: donald.kiely@umontana.edu
348

Synthesis of Poly(galactaramides)
349
requiring no pendant hydroxyl group protection, was first described by Ogata
and coworkers,[1–8] and later employed in reports from Hoagland et al.,[9,10]
Hashimoto et al.,[11,12] Kiely et al.,[13,14] and Henkensmeier et al.[15]
PHPAs are of interest because of their origin in part from renewable
carbohydrates and because they are readily degradable in soil,[16] with the
polyamide nitrogens serving as plant nutrients.[17] Additionally, a wide struc-
tural variety of these polyamides can be made using different combinations of
diamine and carbohydrate diacid (aldaric acid) monomers.
In previous studies it was determined that the physical property differ-
ences of poly(alkylene aldaramides) are in part a reflection of the conforma-
tional preferences exhibited by their different aldaric acid monomer units.[14]
Whereas the meso-galactaryl monomer unit is dominated by an extended
conformation,[14] the diastereoisomeric D-glucaryl unit tends toward an aver-
age “bent” conformation.[14,18] The differences in conformational preferences of
the polymer aldaric acid units are reflected in differences in solubility, melt-
ing points, and film-forming ability of the corresponding polyamides.[14,19] For
example, meso-galactaric acid (mucic acid)[20] and its simple ester forms have
high melting points and low water solubilities, properties that are also ob-
served with poly(alkylene galactaramides).
It is well known that in order to make high-molecular-weight condensa-
tion polyamides, molar equivalency of the reactive monomers is required;[21]
for example, the polyamide nylon 6,6 is generated from the 1:1 molar ra-
tio salt of adipic acid:hexamethylenediamine at an elevated temperature of
about 270◦C.[22] Previous preparations of PHPAs involved direct condensation
polymerization of an aldaric acid diester unit with an appropriate primary
diamine, typically using methanol as the solvent.[3,4,12,13] The synthesis of PH-
PAs by this method does not require the high temperatures used to make ny-
lons, temperatures that would decompose aldaric acid ester monomers. How-
ever, a shortcoming of the previously reported syntheses of PHPAs using this
approach is that they do not employ an exact 1:1 molar ratio of diacid and
diamine monomers, due to the difficulty in achieving this ratio by either vol-
umetric or gravimetric methods. Consequently, in order to ultimately prepare
relatively high-molecular-weight poly(galactaramides) under mild polymeriza-
tion conditions, the first goal of this endeavor was to meet the requirement
of equivalent diacid:diamine stoichiometry for polymerization by synthesizing
1:1 galactaric acid:diamine salts as starting monomer precursors. The sec-
ond objective was to convert these salts directly into 1:1 mixtures of esteri-
fied galactaric acid and diammonium salts as precursors for polymerization in
alcohol solution, preferably methanol. The final objective was to subject the
initial polymer, labeled as a prepolyamide, to a second polymerization (post-
polymerization) to obtain a higher-molecular-weight polymer, labeled as a post-
polyamide. It was also reasoned that for successful postpolymerization to occur,
a solvent was required to solubilize the prepolymer better than methanol and

D.E. Kiely et al.
350
allow polymerization to occur at a reasonable rate. A preliminary description
of the results presented here has been reported.[23]
RESULTS AND DISCUSSION
Polyamide Synthesis
The syntheses of the target poly(galactaramides), 7a–j, are outlined in
the Scheme. In the first step meso-galactaric acid (1) was treated with di-
amines (2a–j) in hot aqueous solution to generate the corresponding substi-
tuted diammonium galactarate salts, 3a–j. Typically, within the first few min-
utes, complete dissolution of water-insoluble galactaric acid occurred followed
Scheme. Synthetic steps to prepare poly(alkylene galactaramides) from substituted
diammonium galactarate salts.

Synthesis of Poly(galactaramides)
351
Table 1: 1H NMR chemical shifts and assignments for compounds 3a–j
Chemical shift, multiplicity, integration, and signal assignmenta
b
3a
3b 4.20, s, 2H
H2, H5
3.90, s, 2H
H3, H4
2.99, t, 4H
N-CH2
1.70, t, 4H
N-CH2-CH2
1.63, m, 4H
N-CH2-CH2
3c 4.22, s, 2H
H2, H5
3.91, s, 2H
H3, H4
2.95, t, 4H
N-CH2
1.38, m, 4H
N-CH2-
CH2-CH2
1.30, bs, 8H
N-CH2-
3d 4.21, s, 2H
3.90, s, 2H
H3, H4
2.93, t, 4H
N-CH2
1.60, m, 4H
N-CH2-CH2
H2, H5
CH2-CH2-
CH2
b
3e
3f
b
3g 4.21, s, 2H
3.90, s, 2H
H3, H4
2.97, t, 4H, 2.57, t, 4H,
N-CH2
2.29, s, 3H
3.18, t, 4H
1.85, m, 4H
CH2-CH2-
CH2
H2, H5
N-CH2-CH2- N-CH3
N-CH3
3h 4.21, s, 2H
3.90, s, 2H
H3, H4
3.74, t, 4H
N-CH2-
CH2-O
3.70, s, 4H
H2, H5
O-CH2-CH2- N-CH2-
O
CH2-O
b
3i
3j 4.21, s, 2H
3.91, s, 2H
H3, H4
3.19, bs, 2H 2.12 d, 4H
H-C-N
1.50, m, 4H
H2, H5
H 2ꢁ, 3ꢁ, 5ꢁ, 6ꢁ H 2ꢁ, 3ꢁ, 5ꢁ,
axial
6ꢁ eq.
a In D2O referenced to t-BuOH at 1.203 ppm.
b Insoluble in any suitable NMR solvent.
by precipitation of the white solid salt shortly thereafter. The exceptions to
this were the water-soluble salts, 3g and 3h, which were made from di-
amines containing heteroatoms (2g and 2h); 3g and 3h were isolated as
solids after the aqueous solution was taken to dryness and the resultant
solid resuspended in methanol. Of the salts made, all but ethylenediammo-
nium (3a), decamethylenediammonium (3e), dodecamethylenediammonium
(3f), and m-xylenyldiammonium (3i) galactarates were soluble enough in D2O
1
for H NMR spectral determination (Table 1). These insoluble salts were also
insoluble in DMSO-d6. Crystal structure studies of salts of galactaric acid
salts[24–28] and of galactaric acid itself[20] indicate that the galactarate unit
is in an extended conformation with strong hydrogen bonding networks that
lead to lack of solubility. These results are supported by a recent x-ray crys-
tal study of the salts 3a, 3b, 3h, 3i, and 3j wherein the meso-galactarate
ion is in the fully extended conformation.[29] In all salts, dimethyl galarac-
tate/dialkylenediammonium mixtures, and pre- and postpolyamides described
in this study, the protons on C-2 and C-5 of the galactaryl moiety are equiv-
1
alent in H NMR spectra as are the protons on C-3 and C-4. The signals for
these two pairs of protons appear as singlets, with the former somewhat down-
field of the latter. The absence of a coupling constant indicates that, at least in
solution, the dihedral angle between H-2 and H-3 and between H-4 and H-5
approaches 90◦ rather than the 60◦ expected for a fully extended conformation.

D.E. Kiely et al.
352
Table 2: CHN analyses of compounds 3a–j and 4 + 5a–j
Elemental analysis
Calculated Found
Molecular
formula
Molecular
weight
Compound
C
H
N
C
H
N
3a
C8H18N2O8· H2O
288.25
298.29
326.34
354.40
382.45
410.50
373.40
394.37
382.36
324.33
371.21
399.26
427.32
455.37
483.42
511.48
492.82
477.33
447.31
425.31
33.33 6.99 9.72 33.32 7.00 9.69
40.27 7.43 9.39 40.32 7.52 9.40
44.16 8.03 8.58 43.94 8.19 8.54
47.45 8.53 7.90 47.66 8.65 8.04
50.25 8.96 7.32 50.01 8.92 7.24
52.67 9.33 6.82 52.59 9.12 6.82
41.82 8.37 11.25 41.96 8.21 11.17
36.55 7.67 7.10 36.64 7.68 7.13
43.98 6.85 7.33 44.22 6.98 7.28
44.44 7.46 8.64 44.25 7.46 8.53
32.36 6.52 7.55 32.10 6.41 7.53
36.10 7.07 7.02 36.14 7.07 7.02
39.35 7.55 6.56 39.35 7.44 6.01
42.20 7.97 6.15 42.13 7.87 6.23
44.72 8.34 5.79 44.41 8.21 5.54
46.96 8.67 5.48 46.93 8.77 5.39
36.56 7.36 8.53 36.20 7.39 7.97
35.23 7.18 5.87 34.92 6.76 5.54
42.96 6.31 6.26 42.93 6.34 6.42
39.54 7.11 6.59 39.76 6.99 5.81
3b
C
C
10H22N2O8
12H26N2O8
3c
3d
C14H30N2O8
C16H34N2O8
3e
3f
C18H38N2O8
3g
C
13H29N3O8· H2O
3h
C12H26N2O10· 2H2O
3i
C
14H22N2O8· 2H2O
3j
C
12H24N2O8
4 + 5a
4 + 5b
4 + 5c
4 + 5d
4 + 5e
4 + 5f
4 + 5g
4 + 5h
4 + 5i
4 + 5j
C8H14O8+ C2H10Cl2N2
C8H14O8+ C4H14Cl2N2
C8H O8+ C6H18Cl2N2
14
C8H O8+ C8H22Cl2N2
14
C8H O8+ C10H26Cl2N2
14
C8H O8+ C12H30Cl2N2
14
C8H14O8+ C7H22Cl3N3
C8H14O8+ C6H18O2Cl2N2· H2O
C8H14O8+ C8H14Cl2N2
C8H14O8+ C6 H16Cl2N2
The elemental analyses of the salts (Table 2) were consistent with their molec-
ular structures indicating also that salts 3a and 3g are monohydrates while
3h and 3i are dihydrates.
In the next step (Scheme) the salts were converted with methanolic HCl
to 1:1 mixtures of dimethyl galactarate (4)/alkylene- or substituted alkylene-
diammonium dichlorides (5a–j). Each of these diester/disalt mixtures was ob-
1
tained as a white solid in high yield and the H NMR spectral data (Table 3)
and elemental analyses results (Table 2) from each mixture were consistent
with the assigned structures.
The 1:1 dimethyl galactarate (4)/alkylene- or substituted alkylenediammo-
nium dichlorides (5a–j) mixtures were activated for polymerization (Scheme)
by treating them with methanol containing an excess of triethylamine (TEA).
The TEA deprotonates the diammonium salts and also catalyzes lactoniza-
tion of the acylic dimethyl galactarate (4) in methanol, the latter step be-
ing essential for a rapid aminolysis process.[30] The use of TEA in methanol
has previously been reported for the preparation of stereoregular-head, tail-
poly(alkylene D-glucaramides).[31] While it is convenient to employ TEA as the
base to deprotonate the diammonium salts and to promote lactonization of
the ester functions, the monomer primary amines and TEA have compara-
ble base strengths; therefore, a large excess of TEA is needed to adequately
promote polymerization. While methanol has been shown to be an excellent
solvent for polymerizations to make prepolyamides, the relatively low solubil-
ity of the poly(alkylene galactamides) in methanol limits the polymerization

Synthesis of Poly(galactaramides)
353
Table 3: 1H NMR chemical shifts and assignments for the 5a–j moieties of
compounds 4 + 5a–j
Chemical shift, multiplicity, integration and signal assignmenta
5a 8.37, s, 6H
3.08, s, 4H,
N-CH2-CH2-
N
5b 8.07, s, 6H
NH3
2.79, m, 4H,
N-CH2
1.61, m, 4H,
N-CH2-CH2
1.56, t, 4H,
N-CH2-CH2
5c
8.06, s, 6H,
NH3
2.75, m, 4H,
N-CH2-CH2
1.32, m, 4H,
N-CH2-CH2-
CH2
5d 8.04, s, 6H
NH3
2.73, m, 4H,
N-CH2-CH2
1.55, m, 4H,
N-CH2-CH2
1.27,bs, 8H,
N-CH2-CH2-
CH2-CH2
5e
7.99, s, 6H
NH3
2.74, t, 4H,
N-CH2-CH2
1.54, m, 4H,
N-CH2-CH2
1.26, bs, 12H
N-CH2-CH2-
CH2-CH2-CH2
1.25, bs, 16H
N-CH2-CH2-
CH2-CH2-CH2-
CH2
2.71, s, 3H,
N-CH3
2.95, m, 4H,
N-CH2-CH2-O
5f
7.99, s, 6H
NH3
2.74, m, 4H,
N-CH2-CH2
1.54, m, 4H,
N-CH2-CH2
5g 8.21 s, 6H
NH3
3.15, b, 4H,
N-CH2-CH2
3.64, t, 4H,
N-CH2-CH2-
O
7.59 − 7.48,
4H, m−ArH
2.95 s, 2H
N-CH
2.91, bs, 4H,
CH2-N-CH3
3.59, s, 4H,
O-CH2-CH2-
O
4.01, m, 4H
N-CH2
1.99 bs, 4H
H 2ꢁ, 3ꢁ, 5ꢁ, 6ꢁ
axial
2.05, m, 4H
CH2-CH2-CH2
5h
8.11, s, 6H
NH3
5i
5j
8.57 s, 6H
NH3
8.06 s, 6H
NH3
1.39 bs, 4H
H 2ꢁ, 3ꢁ, 5ꢁ, 6ꢁ
eq
In each of these compounds singlet signals each integrating for two protons were found at
approximately 4.98, 4.88, 4.32, and 3.79 ppm, which were assigned as OH-2 and OH-5, OH-3
and OH-4, H-2 and H-5, H-3 and H-4 of 4, respectively; an additional singlet signal integrating
for six protons was found at 3.64 ppm in each spectrum and assigned as H3C-O of 4.
a In DMSO-d6 referenced to TMS at 0.00 ppm.
to preparation of low-molecular-weight materials. By employing a 1:1 molar
ratio of galactaric acid:diamine to prepare the prepolymers in methanol, it was
anticipated that on average, the number of C-terminal ester and N-terminal
amine groups would be the same and allow for further polymerization of the
polymers in solution using an appropriate solvent. Several solvents were eval-
uated for potential use as a general postpolymerization solvent, using prepoly-
mer poly(hexamethylene galactaramide), 6c, as a model for postpolymeriza-
tion. Alcohols as solvents have proven critical for polymerization at reasonable
rates, but do not solubilize the growing polymers very effectively. In contrast,
polar, aprotic dimethyl sulfoxide is a good solvent for PHPAs, but rates of poly-
merization are significantly reduced in this solvent.[30]
The solvents evaluated as postpolymerization solvents were ethy-
lene glycol and the solvent pairs ethylene glycol/dimethyl sulfoxide and
methanol/dimethyl sulfoxide. Ultimately, the prepolymer was first swelled

D.E. Kiely et al.
354
in dimethyl sulfoxide, then diluted with methanol and the reaction mixture
heated for a period of time.
Polyamide Analysis
1
The H NMR chemical shift data for prepolyamides 6a–j are reported in
Table 4, the data from the postpolyamides being essentially the same. The
number average molecular weight (Mn) and the degree of polymerization (DP)
of each polyamide, both prepolyamide and postpolyamide (Table 5), were de-
termined by end-group analysis from 1H NMR spectra by calculating the ratio
of the integrals for methylene protons adjacent to terminal amine groups with
those for methylene protons adjacent to internal amide nitrogens and applying
the formula DP = (Ratio + 1)/2. This formula was derived by plotting a graph
of the theoretical ratio of internal to terminal methylene protons versus DP for
degrees of polymerization 1–20.[32] A convenient gel permeation chromatogra-
phy method to obtain molecular weights and molecular weight distributions
of these polymers that does not use expensive hexafluroisopropanol as eluent
has not yet been established, but work is in progress toward developing such a
method.
The prepolymerizations were carried out in methanol under reflux con-
ditions and, in keeping with previous results, solid was present throughout
the reaction.[14] Dimethyl galactarate has low solubility in the methanol/TEA
medium but gradually dissolves and then rapidly reacts to form polyamide,
which quickly precipitates.
Low polyamide solubility was suspected to be the limiting factor for poly-
mer growth; however, stoichiometric imbalances in previous studies could have
played a role. This study focuses on the effects that stoichiometric equiva-
lency of starting galactaric acid and diamine might offer in producing larger
polyamides than previously prepared where stoichiometric equivalency of
monomers was not employed. As a means to investigate the role of solubility,
a postpolymerization step to make yet larger poly(galactaramides) was inves-
tigated. The results from both the pre- and postpolymerizations are presented
in Table 5.
Inexplicitly, the prepolymerization procedure starting from ethylenedi-
amine was found not to work because the prepolyamide product 6a has a DP
value of only 1, a value that does not change in the postpolymerization process.
The tetramethylenediamine prepolyamide 6b, with a DP = 6.0, is larger than
6a but also suffers from low methanol solubility. However, with the exception
of 6a and 6d, increases in DP of 25% to 50% were obtained as compared to
previously reported values.[14]
In the preparation of 6 and 7 g–i, clear solutions or gels were obtained
during both polymerization processes, and therefore greater degrees of poly-
merization were expected for these polyamides. Indeed, the prepolymer 6g

d
c
c
t
m
d
d
b
b
e
a
b
c
d
e
355

D.E. Kiely et al.
356
Table 5: Degrees of polymerization for pre- and postpolymers and number
average molecular weights (Mn) of postpolymers
% Increase in
DP
Post
DP
DP upon
Mn
Compound prepolymera polymer Postpolymer postpolymerization postpolymer
6a
6b
6c
6d
6e
6f
1.0
6.0
7a
7b
7c
7d
7e
7f
1.0
6.4
0
6.7
2.7
0
234
1677
3277
3816
4671
11.0
12.0
11.4
11.3
12.0
13.5
18.4
0
10.5
10.5
3927
c
c
c
6gb
6hb
6id
6j
7g
7h
7i
10.4
9.1
3.3
14.0
10.7
3.9
51.9
17.6
18.2
5088
3317
1132
7j
a Determined by NMR in TFA-d.
b Determined by NMR in D2O.
c Too great to be determined by this method.
d Determined by NMR in DMSO-d6.
appeared too large for DP determination by the NMR method. A lesser DP
of 26 has been reported for this compound prepared by direct reaction of the
diamine with dimethyl galactarate.[33] In addition, prepolymer 6h underwent
an approximately 50% increase in DP in the postpolymerization process. Pre-
polyamide (6i), derived from the single arylalkylenediamine employed in this
study, had a DP of 9.1, with the postpolyamide 7i showing a small increase
in DP to a value of 10.7. The DP values for polyamides 6i and 7i were com-
parable to those observed with the hexamethylenediamine polyamide 6c (DP
11.0) and 7c (DP 11.3). Prepolyamide 6i, although soluble in TFA-d, did not
yield a spectrum amenable to integration because of overlap of the relevant
signals with the signals for the galactaryl moiety. However, those signals were
resolved when DMSO-d6 was used as the NMR solvent. The location of the ter-
minal methylene protons was verified after preparation in ethanol of a small
DP prepolyamide with a large sharp CH2-NH2 singlet at 3.39 ppm. Both pre-
and postpolyamides 6j and 7j, respectively, were poorly soluble in the pre- and
postpolymerization solvents, and consequently had small DP values (3.3 and
3.9).
SUMMARY AND CONCLUSIONS
An experimental protocol for the preparation of poly(galactaramides) from pre-
cursor polyalkylenediammonium galactarates has been developed. The method
begins with preparation of a 1:1 galactaric acid/diamine salt, to ensure stoi-
chiometric equivalence of the monomer components for subsequent polymer-
ization. The salt is subjected to Fischer esterification in methanolic HCl,

Synthesis of Poly(galactaramides)
357
producing a 1:1 mixture of dimethyl galactarate and the substituted diammo-
nium dichloride. This mixture is then warmed in methanol in the presence of
triethylamine wherein polymerization occurs and the polyamide typically pre-
cipitates. The poly(galactaramide) formed, labeled as a prepolyamide, is then
subjected to a second polymerization in a mixed solvent that allows for greater
polymer solubility than methanol, resulting in a larger poly(galactaramide), la-
beled a postpolyamide. The latter polyamides are larger than those produced
by previous methods where stoichiometric control of monomers was not es-
tablished. Among the alkylenediamines employed, reasonable-size polyamides
(Table 5) were prepared starting with the hexamethylenediamine polyamide
6c and continuing with the (CH2)8, (CH2)10, and (CH2)12 polyamides 6d, 6e,
and 6f, respectively. A similar DP polyamide formed was poly(m−xylenenyl
galactaramide), 6i. It is clear that the nonpolar diamine monomer units and
the poorly soluble galactaryl unit work together to limit the solubility of these
polyamides. In contrast, poly(4-aza-4-methylheptamethylene galactaramide),
6g, has a nitrogen atom and a branching methyl substituent in the alky-
lene chain, both of which make the growing polyamide more methanol solu-
ble and allow polymerization to occur to a greater extent than with the less
methanol-soluble polymers. Postpolymerizations generally resulted in larger
polymers, but again low solubilities of the polymers limited their growth. The
two-stage polymerization strategy was employed because it was determined
that a single polymerization in a typical postpolymerization solvent such as
methanol/dimethylsulfoxide did not yield polyamide that was as large or as
pure as that generated by the method employed here. Overall, the approach
applied to prepare polyamides of this type was effective even with the low sol-
ubility poly(alkylene galactaramides), but has been found to work much bet-
ter with more organic solvent-soluble polyamides of this class, as described
in a preliminary report describing the preparation of a number of poly(D-
glucaramides).[34]
EXPERIMENTAL
General Methods
Reagent-grade chemicals were purchased from commercial vendors and
used without further purification. Deionized water was generated by a Mil-
lipore Simplicity 185 system. Solutions were concentrated under reduced
pressure. 1H NMR spectra were recording using a 400 Varian Unity Plus spec-
trometer in DMSO-d6 referenced to tetramethylsilane (0.00 ppm), in TFA-d
referenced to residual TFA, or in D2O referenced to t-butyl alcohol (1.203 ppm).
Data were processed using ACD/SpecManager software version 9.13, 2006.

D.E. Kiely et al.
358
Ethylenediammonium galactarate (3a)
To a mixture of galactaric acid (1, 97% from Aldrich, 10.00 g, 47.6 mmol)
and deionized water (100 mL) in a round bottom flask was added ethylenedi-
amine (2a, 3.2 mL, 2.88 g, 47.8 mmol) and the solution stirred (75◦C, 20 h).
The solution was allowed to cool to rt and diluted with methanol (100 mL).
The solid that formed was removed by filtration, washed with methanol (2 ×
50 mL), and dried under reduced pressure at rt (16 h) to give ethylenediammo-
nium galactarate (3a, 11.10 g, 81.0%).
Tetramethylenediammonium galactarate (3b)
The procedure for 3a was adapted as follows: galactaric acid (1, 11.9 g,
56.6 mol), deionized water (50 mL), tetramethylenediamine (2b, 5.8 mL, 5.09
g, 57.7 mmol), and stirring at 75◦C for 18 h. The solution was allowed to cool
to rt and diluted with methanol (100 mL). The solid product, tetramethylene-
diammonium galactarate (3b, 15.41 g, 91.2%), was isolated as described for
3a.
Hexamethylenediammonium galactarate (3c)
The procedure for 3a was adapted as follows: galactaric acid (1, 10.00 g,
47.6 mmol), deionized water (50 mL); hexamethylenediamine (2c, 5.54 g, 47.6
mmol) dissolved in deionized water (50 mL) was added to the stirred wa-
ter/galactaric acid mixture, and the reaction mixture stirred at 70◦C (1 h) and
then at rt (20 h). The reaction mixture was diluted with methanol (100 mL)
and the solid product, hexamethylenediammonium galactarate (3c, 14.09 g,
90.8%), isolated as described for 3a.
Octamethylenediammonium galactarate (3d)
The procedure for 3a was adapted as follows: galactaric acid (1, 10.00 g,
47.6 mmol), deionized water (100 mL), octamethylenediamine (2d, 6.90 g, 47.8
mmol), and stirring at 70◦C (1 h) and then at rt (20 h). The reaction mixture
was diluted with methanol (100 mL) and the solid product, octamethylenedi-
ammonium galactarate (3d, 15.78 g, 93.5%), isolated as described for 3a.
Decamethylenediammonium galactarate (3e)
The procedure for 3a was adapted as follows: galactaric acid (1, 10.00 g,
47.6 mmol), deionized water (100 mL), decamethylenediamine (2e, 8.6 g, 49.9
mmol), and stirring at 70◦C (1 h) and then at rt (20 h). The reaction mixture
was diluted with methanol (100 mL) and the solid product, decamethylenedi-
ammonium galactarate (3e, 16.78 g, 92.2%), isolated as described for 3a.

Synthesis of Poly(galactaramides)
359
Dodecamethylenediammonium galactarate (3f)
The procedure for 3a was adapted as follows: galactaric acid (1, 10.00 g,
47.6 mmol), deionized water (100 mL), dodecamethylenediamine (2f, 9.90 g,
49.5 mmol), and stirring at 70◦C (2 h) then at rt (20 h). The reaction mixture
was diluted with methanol (100 mL) and the solid product, dodecamethylene-
diammonium galactarate (3f, 17.41 g, 89.1%), isolated as described for 3a.
4ꢁ-aza-N-methylheptamethylenediammonium galactarate (3g)
The procedure for 3a was adapted as follows: galactaric acid
(1, 10.00 g, 47.6 mmol), deionized water (100 mL), and 4ꢁ-aza-N-
methylheptamethylenediamine (2g, 7.74 mL, 6.97 g, 48.0 mmol) were mixed
together at rt and the resulting solution stirred at 75◦C (2 h) and then at rt
(22 h) with no precipitation occurring. The resulting dark brown solution was
concentrated to an orange-colored syrup and dried under vacuum overnight
to give a pale pink solid. Methanol (100 mL) was added to the solid and the
mixture ground to a slurry with a mortar and pestle. The solid product, 4ꢁ-aza-
N-methylheptamethylenediammonium galactarate (3g, 15.80 g, 88.9%), was
isolated as described for 3a.
3ꢁ,6ꢁ-dioxaoctamethylenediammonium galactarate (3h)
The procedure for 3a was adapted as follows: galactaric acid (1, 10.00 g,
47.6 mmol), deionized water (100 mL), and 3ꢁ,6ꢁ-dioxaoctamethylenediamine
(2h, 7.01 mL, 7.11 g, 47.98 mmol) were stirred together. Upon addition of the
diamine, the galactaric acid immediately dissolved with no precipitation oc-
curring over the course of the reaction. The solution was stirred at rt (18 h)
and then concentrated to give a cream-colored solid. Methanol (125 mL) was
added to the flask and the solid broken up to form a suspension, which was
stirred (40◦C, 1 h). The solid product, 3ꢁ,6ꢁ-dioxaoctamethylenediammonium
galactarate (3h, 16.95 g, 99.3%), was isolated as described for 3a.
m-Xylylenediammonium galactarate (3i)
The procedure for 3a was adapted as follows: galactaric acid (1, 10.00 g,
47.6 mmol), deionized water (100 mL), and m-xylylenediamine (2i, 6.30 mL,
6.50 g, 47.8 mmol) were stirred together at rt for 16 h. Solid remained in the
solution throughout the course of the reaction. The reaction mixture was di-
luted with methanol (100 mL) and the solid product, m-xylylenediammonium
galactarate (3i, 15.48 g, 85.1%), isolated as described for 3a.
trans-1,4-Cyclohexanediammonium galactarate (3j)
The procedure for 3a was adapted as follows: galactaric acid (1, 5.017 g,
23.9 mmol), deionized water (50 mL), and trans-1,4-cyclohexyldiamine (2j,
2.833 g, 24.8 mmol) were stirred together (75◦C, 16 h). Solid remained in

D.E. Kiely et al.
360
the solution throughout the course of the reaction. The reaction mixture
was cooled and methanol (100 mL) added. The solid product, trans-1,4-
cyclohexanediammonium galactarate (3j, 7.18 g, 92.7%), was isolated as de-
scribed for 3a.
Dimethyl Galactarate/Alkylenediammonium Dichloride Salts
1:1 Dimethyl galactarate/ethylenediammonium dichloride (4 + 5a)
Acetyl chloride (3.0 mL) was added drop-wise to a stirred solution
of methanol (100 mL) in an ice bath. Ethylenediammonium galactarate
(3a, 4.00 g, 13.88 mmol) was added to the solution and the reaction
mixture heated at reflux with stirring (4 h) and then concentrated to a
white powder, which was dried under vacuum at rt (16 h) to give solid
1:1 dimethyl galactarate/ethylenediammonium dichloride (4 + 5a, 4.91 g,
95.3%).
1:1 Dimethyl galactarate/tetramethylenediammonium dichloride (4 + 5b)
The procedure for 4 + 5a was adapted as follows: methanol (200 mL),
acetyl chloride (6.0 mL), and tetramethylenediammonium galactarate (3b,
4.00 g, 13.41 mmol) were stirred at reflux (4 h). The solid product, 1:1 dimethyl
galactarate/tetramethylenediammonium dichloride (4 + 5b, 4.79 g, 89.5%),
was isolated as described for 4 + 5a.
1:1 Dimethyl galactarate/hexamethylenediammonium dichloride (4 + 5c)
The procedure for 4 + 5a was adapted as follows: methanol (100 mL),
acetyl chloride (3.0 mL), and hexamethylenediammonium galactarate (3c, 4.00
g, 12.27 mmol) were stirred at reflux (4 h). The solid product, 1:1 dimethyl
galactarate/hexamethylenediammonium dichloride (4 + 5c, 4.90 g, 93.2%),
was isolated as described for 4 + 5a.
1:1 Dimethyl galactarate/octamethylenediammonium dichloride (4 + 5d)
The procedure for 4 + 5a was adapted as follows: methanol (100 mL),
acetyl chloride (3.0 mL), and octamethylenediammonium galactarate (3d,
4.00 g, 11.29 mmol) were stirred at reflux (4 h). The solid product, 1:1 dimethyl
galactarate/octamethylenediammonium dichloride (4 + 5d, 4.93 g, 95.9%), was
isolated as described for 4 + 5a.
1:1 Dimethyl galactarate/decamethylenediammonium dichloride (4 + 5e)
The procedure for 4 + 5a was adapted as follows: methanol (100 mL),
acetyl chloride (3.0 mL), and decamethylenediammonium galactarate (3e,
4.00 g, 10.46 mmol) were stirred at reflux (4 h). The solid product, 1:1 dimethyl

Synthesis of Poly(galactaramides)
361
galactarate/decamethylenediammonium dichloride (4 + 5e, 4.81 g, 95.0%), was
isolated as described for 4 + 5a.
1:1 Dimethyl galactarate/dodecamethylenediammonium dichloride (4 + 5f)
The procedure for 4 + 5a was adapted as follows: methanol (100 mL),
acetyl chloride (3.0 mL), and dodecamethylenediammonium galactarate (3f,
4.00 g, 9.74 mmol) were stirred at reflux (4 h). The solid product, 1:1 dimethyl
galactarate/dodecamethylenediammonium dichloride (4 + 5f, 4.57 g, 91.6%),
was isolated as described for 4 + 5a.
1:1 Dimethyl galactarate/4ꢁ-aza- N-methylheptamethylenetriammonium
trichloride (4 + 5g)
The procedure for 4 + 5a was adapted as follows: methanol (100 mL),
acetyl chloride (8.0 mL), and 4ꢁ-aza-N-methylheptamethylenediammonium
galactarate (3g, 4.00 g, 10.71 mmol) were stirred at reflux (4 h). The solid prod-
uct, 1:1 dimethyl galactarate/4ꢁ-aza-N-methylheptamethylenetriammonium
trichloride (4 + 5g, 4.58 g, 86.7%), was isolated as described for 4 + 5a.
1:1 Dimethyl galactarate/3ꢁ,6ꢁ-dioxaoctamethylenediammonium dichloride
(4 + 5h)
The procedure for 4 + 5a was adapted as follows: methanol (100 mL),
acetyl chloride (3.0 mL), and 3ꢁ,6ꢁ-dioxaoctamethylenediammonium galac-
tarate (3h, 4.00 g, 11.16 mmol) were stirred at reflux (4 h). The solid product,
1:1 dimethyl galactarate/3ꢁ ,6ꢁ-dioxaoctamethylenediammonium dichloride (4
+ 5h, 4.38 g, 82.1%), was isolated as described for 4 + 5a.
1:1 Dimethyl galactarate/m-xylylenediammonium dichloride (4 + 5i)
The procedure for 4 + 5a was adapted as follows: methanol (100 mL),
acetyl chloride (3.0 mL), and m-xylylenediammonium galactarate (3i, 4.00
g, 10.47 mmol) were stirred at reflux (4 h). The solid product, 1:1 dimethyl
galactarate/m-xylylenediammonium dichloride (4 + 5i, 4.36 g, 93.2%), was iso-
lated as described for 4 + 5a.
1:1 Dimethyl galactarate/trans-1,4-cyclohexanediammonium dichloride
(4 + 5j)
The procedure for 4 + 5a was adapted as follows: methanol (100 mL),
acetyl chloride (3.0 mL), and trans-1,4-cyclohexyldiammonium galactarate (3j,
4.00 g, 12.32 mmol) were stirred at reflux (4 h). The solid product, 1:1 dimethyl
galactarate/trans-1,4-cyclohexyldiammonium dichloride (4 + 5j, 4.76 g, 90.9%),
was isolated as described for 4 + 5a. 1H NMR (D2O) 4.56, s, 2H (H2,H5), 4.06,
s, 2H (H3, H4), 3.77, s, 6H (O-CH3), 3.20, bs, 2H (H1ꢁ, H4ꢁ), 2.13, d, 4H (H2ꢁ,
H3ꢁ, H5ꢁ, H6ꢁ axial), 1.51, m, 4H (H2ꢁ, H3ꢁ, H5ꢁ, H6ꢁ equatorial).

D.E. Kiely et al.
362
Poly(alkylene galactaramide) Prepolymers
Prepolymer Poly(ethylene galactaramide) (6a)
1:1 Dimethyl galactarate (4)/ethylenediammonium dichloride (5a, 2.50 g,
6.73 mmol) was added to methanol (100 mL) with stirring. Triethylamine (20
mL) was added and the stirred mixture was heated (70◦C, 16 h). The reaction
mixture was cooled to rt and diluted with methanol (100 mL). The solid prod-
uct was removed by filtration, washed with methanol (2 × 50 mL), and dried
under vacuum at rt (16 h) to give prepolymer poly(ethylene galactaramide)
(6a, 1.39 g, 88.5%). NMR in TFA-d showed that the degree of polymerization
was 1 and that only the dimer had formed.
Prepolymer poly(tetramethylene galactaramide) (6b)
The procedure for 6a was adapted as follows: dimethyl galactarate
(4)/tetramethylenediammonium dichloride (5b), 2.50 g, 6.26 mmol), methanol
(80 mL), and triethylamine (20 mL) were stirred (70◦C, 16 h). The reaction mix-
ture was cooled to rt and diluted with methanol (100 mL) and the solid prod-
uct was isolated as described for 6a to give prepolymer poly(tetramethylene
galactaramide) (6b, 1.41 g, 69.5%). NMR in TFA-d showed that the degree of
polymerization was 6.0.
Prepolymer poly(hexamethylene galactaramide) (6c)
The procedure for 6a was adapted as follows: 1:1 dimethyl galactarate
(4)/hexamethylenediammonium dichloride (5c) (2.00 g, 4.68 mmol), methanol
(80 mL), and triethylamine (13.2 mL) were stirred (70◦C, 16 h). The re-
action mixture was cooled to rt and diluted with methanol (100 mL) and
the solid product was isolated as described for 6a to give prepolymer
poly(hexamethylene galactaramide) (6c, 1.06 g, 78.1%). NMR in TFA-d showed
that the degree of polymerization was 11.0.
Prepolymer poly(octamethylene galactaramide) (6d)
The procedure for 6a was adapted as follows: 1:1 dimethyl galactarate
(4)/octamethylenediammonium dichloride (5d) (2.50 g, 5.49 mmol), methanol
(100 mL), and triethylamine (13.2 mL) were stirred (70◦C, 16 h). The reaction
mixture was cooled to rt and diluted with methanol (100 mL) and the solid
product was isolated as described for 6a to give prepolymer poly(octamethylene
galactaramide) (6d, 1.108 g, 63.5%). NMR in TFA-d showed that the degree of
polymerization was 12.0.
Prepolymer poly(decamethylene galactaramide) (6e)
The procedure for 6a was adapted as follows: 1:1 dimethyl galactarate
(4)/decamethylenediammonium dichloride (5e) (2.50 g, 5.17 mmol), methanol

Synthesis of Poly(galactaramides)
363
(100 mL), and triethylamine (15 mL) were stirred (70◦C, 16 h). The re-
action mixture was cooled to rt and diluted with methanol (100 mL) and
the solid product was isolated as described for 6a to give prepolymer
poly(decamethylene galactaramide) (6e, 1.17 g, 65.3%). NMR in TFA-d showed
that the degree of polymerization was 11.4.
Prepolymer poly(dodecamethylene galactaramide) (6f)
The procedure for 6a was adapted as follows: 1:1 dimethyl galactarate
(4)/dodecamethylenediammonium dichloride (5f) (2.54 g, 4.97 mmol), methanol
(120 mL), and triethylamine (14 mL) were stirred (70◦C, 16 h). The re-
action mixture was cooled to rt and diluted with methanol (100 mL) and
the solid product was isolated as described for 6a to give prepolymer
poly(dodecamethylene galactaramide) (6f, 1.37 g, 74.0%). NMR in TFA-d
showed that the degree of polymerization was 10.5.
Prepolymer poly(4ꢁ-aza-N-methylheptamethylene galactaramide) (6g)
The procedure for 6a was adapted as follows: 1:1 dimethyl galactarate
(4)/4ꢁ-aza-N-methylheptamethylenetriammonium trichloride (5g) (2.50 g, 5.07
mmol), methanol (90 mL), and and triethylamine (15.5 mL) were stirred (70◦C,
16 h). The reaction mixture was cooled to rt and diluted with methanol (100
mL) and the solid product was isolated as described for 6a to give prepolymer
poly(4ꢁ-aza-N-methylheptamethylene galactaramide) (6g, 1.08 g, 66.8%). NMR
in D2O showed that the degree of polymerization was too great to measure by
this method.
Prepolymer poly[3ꢁ,6ꢁ-dioxaoctamethylene galactaramide] (6h)
The procedure for 6a was adapted as follows: 1:1 dimethyl galactarate
(4)/3ꢁ,6ꢁ-dioxaoctamethylenediammonium dichloride (5h), (2.50 g, 5.24 mmol),
methanol (100 mL), and triethylamine (16 mL) were stirred (70◦C, 16 h). The
reaction mixture was cooled to rt and diluted with methanol (100 mL) and the
solid product was isolated as described for 6a to give prepolymer poly(3ꢁ,6ꢁ-
dioxaoctamethylene galactaramide) (6h, 0.659 g, 39.0%). NMR in D2O showed
that the degree of polymerization was 10.4.
Prepolymer poly(m-xylylene galactaramide) (6i)
The procedure for 6a was adapted as follows: 1:1 dimethyl galactarate
(4)/m-xylylenediammonium dichloride (5i) (3.00 g, 6.71 mmol), methanol
(120 mL), and triethylamine (19.0 mL) were stirred (70◦C, 16 h). The reaction
mixture was cooled to rt and diluted with methanol (100 mL) and the solid
product was isolated as described for 6a to give prepolymer poly(m-xylylene
galactaramide) (6i, 1.77 g, 85.1%). NMR in DMSO-d6 showed that the degree
of polymerization was 9.1.

D.E. Kiely et al.
364
Prepolymer poly(trans-1,4-cyclohexane galactaramide) (6j)
The procedure for 6a was adapted as follows: 1:1 dimethyl galactarate
(4)/trans-1,4-cyclohexanediammonium dichloride (5j) (2.00 g, 4.70 mmol),
methanol (100 mL), and triethylamine (15.0 mL) were stirred (70◦C, 24 h). The
reaction mixture was cooled to rt and diluted with methanol (100 mL) and the
solid product was isolated as described for 6a to give prepolymer poly(trans-
1,4-cyclohexane galactaramide) (6j, 0.582 g 42.9%). NMR in TFA-dshowed that
the degree of polymerization was 3.3.
Procedures evaluated for optimization of postpolymerization of prepolymers
using prepolymer 6c
Procedure (a) 1:2 DMSO:Ethylene Glycol: 6c (28.0 mg) in DMSO (280 µL), ethy-
lene glycol (560 µL), and triethylamine (75 µL) was heated with stirring
(60◦C, 2 h). Excess methanol was added to precipitate the polymer, which
was separated by vacuum filtration, washed with methanol, and dried un-
der vacuum. Yield 19.5 mg, 69.6%; DP 8.0.
Procedure (b) 1:2 DMSO:Methanol: as for procedure (a) above but using 6c
(26.8 mg), DMSO (268 µL), methanol (536 µL), and triethylamine (72 µL).
Yield 17.6 mg, 65.7%; DP 8.0.
Procedure (c) 2:1 DMSO:Ethylene Glycol: as for procedure (a) above but using
6c (34.1 mg), DMSO (682 µL), ethylene glycol (341 µL), and triethylamine
(91 µL). Yield 21.76 mg, 63.6%; DP 9.7.
Procedure (d) 2:1 DMSO:Methanol: as for procedure (a) above but using 6c
(26.4 mg), DMSO (528 µL), methanol (264 µL), and triethylamine (71 µL).
Yield 13.9 mg, 52.6%; DP 8.0.
Procedure (e) 1:1 DMSO:Methanol with preswelling: 6c (100 mg) was
preswelled (50◦C, 2 h) in DMSO (2 mL); methanol (2 mL) and triethylamine
(100 µL) were added and the mixture was heated with stirring (60◦C, 24 h).
The mixture was cooled, methanol (4 mL) was added, and the resultant mix-
ture stirred at rt (2 h). The solid product was collected by vacuum filtration
and resuspended in methanol (5 mL) with stirring (15 min). The solid prod-
uct was again collected by vacuum filtration and dried in a vacuum oven
(25◦C, 24 h). Yield 74.0 mg, 74%; DP 11.2.
Procedure (f) 1:2 DMSO: Methanol with preswelling: Exactly as for procedure
(e) above except that DMSO (1 mL) was used for the preswelling step. Yield
77.6 mg, 77.6%; DP 11.3.
General Method for Preparation of Postpolymers
Prepolymer (100.0 mg) was preswelled in DMSO (1.00 mL) with stirring
(120 min, 50◦C), methanol (2.00 mL) and triethylamine (100 mL) were added,

Synthesis of Poly(galactaramides)
365
and the resultant mixture was stirred (25 h, 60◦C). After cooling, methanol
(4.00 mL) was added and the mixture stirred (120 min, 25◦C). The solid product
was collected by vacuum filtration and resuspended in methanol (5 mL) with
stirring (15 min). The solid product was again collected by vacuum filtration
and dried in a vacuum oven (25◦C, 24 h).
Postpolymer poly(ethylene galactaramide) (7a)
Upon swelling, the prepolymer formed a suspension. Recovery was 73.3%.
NMR in TFA-d showed that the DP was 1 and the prepolymer was unchanged
from the postpolymer.
Postpolymer poly(tetramethylene galactaramide) (7b)
Upon swelling, the prepolymer formed a stiff gel, which required breaking
up to mix with the methanol. Recovery was 78.2%. NMR in TFA-d showed that
the DP was 6.4.
Postpolymer poly(hexamethylene galactaramide) (7c)
Upon swelling the prepolymer formed a suspension. Recovery was 77.6%.
NMR in TFA-d showed that the DP was 11.3.
Postpolymer poly(octamethylene galactaramide) (7d)
Upon swelling the prepolymer formed a suspension. Recovery was 92.0.6%.
NMR in TFA-d showed that the DP was 12.0.
Postpolymer poly(decamethylene galactaramide) (7e)
Upon swelling the prepolymer formed a suspension. Recovery was 83.4%.
NMR in TFA-d showed that the DP was 13.5.
Postpolymer poly(dodecamethylene galactaramide) (7f)
Upon swelling the prepolymer formed a suspension. Recovery was 87.9%.
NMR in TFA-d showed that the DP was unchanged at 10.5.
Postpolymer poly(4ꢁ-aza-N-methylheptamethylene galactaramide) (7g)
Upon swelling the prepolymer formed a clear gel that became cloudy upon
addition of methanol. Recovery was 42.1%. NMR in D2O showed that the de-
gree of polymerization was too large to be measured by this method.
Postpolymer poly(3ꢁ,6ꢁ-dioxaoctamethylene galactaramide) (7h)
Upon swelling the prepolymer formed a clear solution that became cloudy
some time after addition of methanol. Recovery was 57.7%. NMR in D2O
showed that the DP was 14.

D.E. Kiely et al.
366
Postpolymer poly(m-xylylene galactaramide) (7i)
Upon swelling the prepolymer formed a clear solution that became cloudy
upon addition of methanol. Recovery was 62.1%. NMR in DMSO-d6 showed
that the DP was 10.7.
Postpolymer poly(trans-1,4-cyclohexane galactaramide) (7j)
Upon swelling the prepolymer formed a clear solution that became cloudy
upon addition of methanol. Recovery was 70.3%. NMR in TFA-d showed that
the DP was 3.9.
ACKNOWLEDGMENTS
Significant financial support for this research was from the U.S. Department of
Agriculture (USDA-CREES Grant Nos. 2004-364463, 2005-34463-11561, and
2006-34463-16886) and is gratefully acknowledged.
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