Aminolysis reaction of glycerol carbonate in organic and hydroorganic medium

Article abstract of DOI:10.1007/s11746-011-1995-5

Aminolysis reaction of glycerol carbonate with primary amine in organic and hydroorganic media leads to the formation of two hydroxyurethane isomers and a partial decomposition of glycerol carbonate into glycerol. Aminolysis with a secondary amine promotes the condensation reaction and limits the formation of glycerol. The ratio of α versus β was determined by zgig ¹³C NMR. This technique permits computing the yield of α and β products in the medium. The quantity of glycerol was determined by GC analysis. The ratio of the isomers and the amount of glycerol depend on the amine and the solvent. Kinetic investigations reveal that, in hydroorganic medium, the more the alkyl chain of the amine increased, the less glycerol was formed. On the contrary, in organic medium, the alkyl chain of the amine does not play a major role in the formation of glycerol.

Full text of DOI:10.1007/s11746-011-1995-5

J Am Oil Chem Soc (2012) 89:1125–1133
DOI 10.1007/s11746-011-1995-5
ORIGINAL PAPER
Aminolysis Reaction of Glycerol Carbonate in Organic
and Hydroorganic Medium
•
Bassam Nohra Laure Candy Jean-Franc¸ois Blanco
•
•
•
Yann Raoul Zephirin Mouloungui
Received: 4 October 2011 / Revised: 8 December 2011 / Accepted: 12 December 2011 / Published online: 7 January 2012
Ó AOCS 2012
Abstract Aminolysis reaction of glycerol carbonate with
primary amine in organic and hydroorganic media leads to
the formation of two hydroxyurethane isomers and a partial
decomposition of glycerol carbonate into glycerol. Aminol-
ysis with a secondary amine promotes the condensation
reaction and limits the formation of glycerol. The ratio of a
versus b was determined by zgig 13C NMR. This technique
permits computing the yield of a and b products in the
medium. The quantity of glycerol was determined by GC
analysis. The ratio of the isomers and the amount of glycerol
depend on the amine and the solvent. Kinetic investigations
reveal that, in hydroorganic medium, the more the alkyl
chain of the amine increased, the less glycerol was formed.
On the contrary, in organic medium, the alkyl chain of the
amine does not play a major role in the formation of glycerol.
Introduction
Urethanes are useful compounds having a wide range of
applications in the chemical industry, such as plastic mate-
rials and herbicides [1]. To produce urethanes, the most
common reagent is isocyanate, which is toxic [2–4]. Alter-
natively, hydroxyurethanes are prepared according to non-
isocyanate routes. Hydroxyurethanes are prepared in a
reaction via ring-opening of cyclic carbonates. No volatile or
non-volatile by-products are produced by this reaction [3].
Cyclic carbonates have been explored to develop vari-
ous carbonyl compounds and polymers [5–14]. Glycerol
carbonate is one of the glycerol derivatives that, at present,
captures more academic and industrial attention. Glycerol
carbonate is a green substitute for important petro-deriva-
tive compounds such as ethylene carbonate or propylene
carbonate. It can be prepared using the reaction of glycerol
with carbon dioxide [13, 14, 18], with urea [15] or car-
bonates such as dimethyl carbonate, ethylene carbonate and
propylene carbonate [16, 17]. Cyclic carbonates undergo a
number of reactions with various nucleophiles. The most
explored reaction of cyclic carbonate has been that of
aminolysis, which is the nucleophilic addition of an amine
on the cyclocarbonate function. It provides a hydroxyure-
thane derivative having one hydroxyl group. In the case of
glycerol carbonate, the aminolysis reaction gives rise to
two hydroxyurethane isomers depending on the presence of
the urethane function at the a or b position. Each hy-
droxyurethane isomer has two hydroxyl groups and a
urethane unit on the skeleton of glycerol.
Keywords Aminolysis ꢀ Glycerol carbonate ꢀ Organic
medium ꢀ Hydroorganic medium ꢀ Hydroxyurethane ꢀ
Glycerol
B. Nohra (&) ꢀ L. Candy ꢀ Z. Mouloungui (&)
INP-ENSIACET, LCA (Laboratoire de Chimie
´
Agro-industrielle), INRA, Universite de Toulouse,
UMR 1010 LCAI, 31030 Toulouse, France
e-mail: bassam.nohra@ensiacet.fr
Z. Mouloungui
e-mail: zephirin.mouloungui@ensiacet.fr
L. Candy
e-mail: laure.candy@ensiacet.fr
J.-F. Blanco
INP-ENSIACET, LGC (Laboratoire de Genie Chimique),
´
Universite de Toulouse, 31030 Toulouse, France
Some studies have focused on the effect of the sub-
stituent, the temperature and the solvent in the aminolysis
of the cyclic carbonates. Several substituted cyclic car-
bonates were studied, and the reaction rate with amine was
found to increase as the electron withdrawing character of
´
Y. Raoul
Onidol, 11 rue de Monceau, 75378 Paris, France
e-mail: y.raoul@prolea.com
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J Am Oil Chem Soc (2012) 89:1125–1133
the substituent increased [6, 9]. This is in contradiction with
the conclusions reached by Mikheev et al. [5, 12]. At low
temperature, the aminolysis reaction results in hydroxyure-
thane, whereas at elevated temperatures ([100 °C), another
amine molecule is able to react with the hydroxyurethane
and yields a substituted urea [19]. In the presence of organic
solvents, some authors indicated a somewhat higher ratio of
b versus a hydroxyl [9, 20, 21]. However, the relative iso-
mer ratio is insensitive to the reaction temperature and only
slightly dependent on solvent polarity [9–11]. One study
investigated the condensation reaction of glycerol carbonate
with butylamine in the presence and absence of a solvent in
stoichiometric amounts [22].
(Sigma Aldrich, 99.5%), hexylamine (Sigma Aldrich,
99%), octylamine (Sigma Aldrich, 99%), dodecylamine
(Fluka, 99%), hexadecylamine (Fluka, C92%), N-methyl-
butylamine (Sigma, C96%), N-ethylbutylamine (Sigma,
C98%) and O-(2-aminopropyl)-O0-(2-methoxyethyl) poly-
propylene glycol (jeffamineÒ, Aldrich, 99%, Mn = 600)
were used as received. Methanol and acetonitrile (HPLC
grade) were purchased from Merck (Germany).
Synthesis of 3a, a0
A solution of ammonium hydroxide (28%) was added at
50 °C to an equimolar quantity of glycerol carbonate (25 g,
0.2118 mol). After 2 h under mechanical stirring, a homo-
geneous, clear and colorless solution resulted. The reaction
mixture was then distilled under reduced pressure for
The kinetic features of the interaction of cyclocarbonates
with amino groups were studied by Garipov et al. [23]. Studies
of the kinetics of the reaction indicated that the rate of the
reaction of cyclic carbonates with amines depends on the
initial concentration of the amine [12, 24], but is independent
of the substituent on the ring [12, 22]. When using water as a
solvent, side reactions must be considered, such as hydrolysis,
which decreases yields of products compared to those
obtained when using organic solvents. Malkemus et al. [25]
studied the reaction of ethylene carbonate with ammonia at
50 °C to form hydroxyalkylurethane; no formation of a sec-
ondary product has been classified. On the contrary, Ochiai
et al. [26] described the aminolysis reaction of bicyclic car-
bonate. The polyaddition of a hydrophobic bifunctional cyclic
carbonate and hexamethylenediamine effectively gives poly-
urethane with hydroxyl groups in aqueous media, although
accompanied by hydrolysis of bicyclic carbonates into diols.
In this paper, we report the synthesis of hydroxyalky-
lurethanes by the reaction of glycerol carbonate with several
primary (NH2–CnH2n?1; n = 0, 4, 6, 8, 12, 16 or amine-
terminated polypropylene glycol) and secondary amines
(CnH2n?1–NH–C4H9, n = 1–2). a and b isomers were
1
ammonia and water removal. H NMR (DMSO-d6): d in
ppm = 4.13 (m, 1H, –CHOCO), 4.23 (m, 2H, –CH2OCO),
3.90 (quint, 1H, –CHOH), 3.77 (m, 4H, –CH2OH), 3.68 (m,
2H, –CH2OH), .13C NMR (DMSO-d6): d in ppm = 159.30
(a C=O), 159.26 (b C=O), 78.50 (–CHOCO), 74.10
(–CHOH), 67.40 (–CH2OCO), 63.0 (–CH2OH), 66.80
(–CH2OH). IR (KBr): 3,342 cm-1 (t-OH), 1,706 cm-1
(t –OC(=O)NH–), 1,616 cm-1 (–OC=ONH–H). LRMS
(CI): 136 (M ? H?), 153 (M ? NH4?). HRMS (CI):
found M ? H?, 136.0045. C4H9NO4 requires 136.0042.
Synthesis of 3b, b0
N-butylamine (15.49 g, 0.2118 mol) was added at 50 °C to
an equimolar quantity of glycerol carbonate (25 g,
0.2118 mol). The reaction was kept at 50 °C under
1
mechanical stirring for 2 h. H NMR (DMSO-d6): d in
ppm = 5.35–5.20 (m, 2H, –NH), 4.65 (m, 1H, –CHO), 4.1
(m, 2H, –CH2OCO), 3.85 (quint, 1H, –CHOH), 3.70 (m,
4H, –CH2OH), 3.60 (m, 2H, –CH2OH), 3.10 (m, 4H,
–CH2N), 1.45 (m, 4H, –CH2–CH2–CH3), 1.30 (m, 4H,
–CH2–CH3), 1.3 (t, 6H, –CH3).13C NMR (DMSO-d6): d in
ppm = 157.0 (C=O), 79.2 (–CHOCO), 75.0 (–CHOH),
68.0 (–CH2OCO), 65.0 (–CH2OH), 45.0 (–CH2N), 34.0
(–CH2–CH2–CH3), 21.5 (–CH2–CH3), 14.2 (–CH3). IR
(KBr): 3,342 cm-1 (t-OH), 1,697 cm-1 (t –OC(=O)NH–),
1,543 cm-1 (–OC=ONH-R). LRMS (CI): 192 (M ? H?),
209 (M ? NH4?). HRMS (CI): found M ? H?, 192.1228.
C8H18NO4 requires 192.1236.
1
evaluated by the classical 13C or H NMR methods. We
investigated the effects of the solvent, the length of the alkyl
chain and the class of the amine (primary or secondary) on
the selectivity of a versus b isomers. No studies have been
yet reported in the literature describing the kinetics and the
mechanism of the aminolysis reaction and the formation of
glycerol as a by-product in organic and hydroorganic med-
ium. We determined the kinetic constants of glycerol for-
mation during the aminolysis of glycerol carbonate by
different amines in organic and hydroorganic medium.
Synthesis of 3c, c0
Materials and methods
N-hexylamine (21.43 g, 0.2118 mol) was added at 50 °C
to an equimolar quantity of glycerol carbonate (25 g,
0.2118 mol). The reaction was kept at 50 °C under
mechanical stirring for 2 h. 1H NMR (MeOD): d in
ppm = 4.69 (m, 1H, –CHOCO), 4.06 (m, 2H,–CH2OCO),
Chemicals
Glycerol carbonate (Huntsman, 99.5%), ammonium
hydroxide (Sigma Aldrich, 28% in water), butylamine
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J Am Oil Chem Soc (2012) 89:1125–1133
1127
Synthesis of 3e, e0
3.78 (quint, 1H, –CHOH), 3.66 (m, 4H, –CH2OH), 3.54 (m,
2H, –CH2OH), 3.08 (m, 4H, –CH2NH), 1.48 (m, 4H, –CH2–
CH2–CH3), 1.3 (m, 12H, –CH2–CH2–CH2–CH2–CH3), 0.90
(t, 6H, –CH3). 13C NMR (MeOD): d in ppm = 159.18 (a
C=O), 158.88 (b C=O), 77.06 (–CHOCO), 71.69 (–CHOH),
66.94 (–CH2OCO), 62.12 (b, –CH2OH), 64.21 (a,
–CH2OH), 41.96 (–CH2NH), 33.10 (–CH2–CH2–CH2–CH2–
CH2–CH3), 30.58 (–CH2–CH2–CH2–CH2–CH2–CH3), 31.03
(–CH2–CH2–CH2–CH3), 23.84 (–CH2–CH2–CH3), 14.54
(–CH3). IR (KBr): 3,342 cm-1 (t-OH), 1,697 cm-1 (t –
OC(=O)NH–), 1,543 cm-1 (–OC=ONH-R). LRMS (CI):
220 (M ? H?), 237 (M ? NH4?). HRMS (CI): found
M ? H?, 220.1707. C10H22NO4 requires, 220. 1705.
N-dodecylamine (39.25 g, 0.2118 mol) was added at 50 °C
to an equimolar quantity of glycerol carbonate (25 g,
0.2118 mol). The reaction was kept at 50 °C under
1
mechanical stirring for 2 h. H NMR (DMSO-d6): d in
ppm = 4.52 (m, 1H, –CHOCO), 3.93 (m, 2H,–CH2OCO),
3.57 (quint, 1H,–CHOH), 3.45 (m,4H,–CH2OH), 3.35
(m,2H, –CH2OH), 2.93 (m, 4H,–CH2NH), 1.23 (m,36H,
–CH2–CH2–CH2–CH2–CH2–CH2–CH2–CH2–CH2–CH2–CH3),
1.36 (m, 4H, –CH2–CH2–CH3), 0.85 (t, 6H,–CH3). 13C NMR
(DMSO-d6): d in ppm = 156.41 (a C=O), 156.16 (b C=O),
75.24 (–CHOCO), 69.83 (–CHOH), 65.49 (–CH2OCO), 62.84
(a-CH2OH), 60.14 (b-CH2OH), 40.26 (–CH2NH), 31.36
(–CH2–CH2–CH2–CH2–CH2–CH2–CH2–CH2–CH2–CH2–CH3),
Synthesis of 3d, d0
26.31
(–CH2–CH2–CH2–CH2–CH2–CH2–CH2–CH2–CH2–
CH2–CH3), 29.08 (–CH2–CH2–CH2–CH2–CH2–CH2–CH2–
CH2–CH2–CH2–CH3), 28.78 (–CH2–CH2–CH2–CH2–CH3),
29.48 (–CH2–CH2–CH3), 22.16 (–CH2–CH3), 14.01 (–CH3).
IR (KBr): 3,342 cm-1 (t-OH), 1,697 cm-1 (t –OC(=O)NH–),
1,543 cm-1 (–OC=ONH-R). LRMS (CI): 304 (M ? H?),
321 (M ? NH4?). HRMS (CI): found M ? H?, 304.2483.
C16H34NO4 requires 304.2488.
N-octylamine (27.40 g, 0.2118 mol) was added at 50 °C to
an equimolar quantity of glycerol carbonate (25 g,
0.2118 mol). The reaction was kept at 50 °C under
mechanical stirring for 2 h. 1H NMR (MeOD): d in
ppm = 4.69 (m, 1H, –CHOCO), 4.06 (m, 2H, –CH2OCO),
3.78 (quint, 1H, –CHOH), 3.66 (m, 4H, –CH2OH), 3.54 (m,
2H, –CH2OH), 3.08 (m, 4H, –CH2NH), 1.48 (m, 4H, –CH2–
CH2–CH3), 1.30 (m, 20H, –CH2–CH2–CH2–CH2–CH2–
CH2–CH3), 0.90 (t, 6H,–CH3). 13C NMR (MeOD): d in
ppm = 159.18 (a C=O), 158.88 (b C=O), 77.06 (–CHOCO),
71.69 (–CHOH), 66.94 (–CH2OCO), 64.21 (a, –CH2OH),
62.12 (b, –CH2OH), 41.96 (–CH2NH), 33.15 (–CH2–CH2–
CH2–CH2–CH2–CH2–CH3), 28.02 (–CH2–CH2–CH2–CH2–
CH2–CH3), 30.58 (–CH2–CH2–CH2–CH2–CH3), 30.55
(–CH2–CH2–CH2–CH3), 31.07 (–CH2–CH2–CH3), 23.87
(–CH2–CH3), 14.58 (–CH3). IR (KBr): 3,342 cm-1 (t-OH),
1,697 cm-1 (t –OC(=O)NH–), 1,543 cm-1 (–OC=ONH-R).
LRMS (CI): 248 (M ? H?), 265 (M ? NH4?). HRMS
(CI): found M ? H?, 248.1859. C12H26NO4 requires, 248.
1862.
Synthesis of 3f, f0
N-hexadecylamine (15.49 g, 0.2118 mol) was added at
50 °C to an equimolar quantity of glycerol carbonate (25 g,
0.2118 mol). The reaction was kept at 50 °C under
mechanical stirring for 2 h. 1H NMR (CDCl3): d in
ppm = 4.91 (m, 1H, –CHOCO), 4.11 (m, 2H,–CH2OCO),
3.87 (quint, 1H,–CHOH), 3.77 (m,4H,–CH2OH), 3.65
(m,2H, –CH2OH), 3.14 (m, 4H,–CH2NH), 1.47 (m,4H,–
CH2–CH2–CH3), 1.23 (m, 52H,–CH2 –CH2–CH2–CH2–
CH2–CH2–CH2–CH2–CH2
–CH2–CH2–CH2–CH2–CH2–
CH2–CH3), 0.86 (t, 6H,–CH3). 13C NMR (CDCl3): d
in ppm = 156.89 (a C=O), 156.92 (b C=O), 76.22
(–CHOCO), 70.88 (–CHOH), 65.95 (–CH2OCO), 63.30
(a-CH2OH), 62.99 (b-CH2OH), 41.41 (–CH2NH), 32.13 (–
CH2– CH2–CH2–NH), 26.96 (–CH2– CH2–CH2–NH), 29.80
(–CH2–CH2–CH2–CH2–CH2–CH2–CH2–CH2–CH2–CH2–
CH2–CH2–CH2–CH2–CH3), 29.57 (–CH2–CH2–CH2–CH2–
CH2–CH2–CH3), 29.49 (–CH2–CH2–CH2–CH2–CH3), 30.04
(–CH2–CH2–CH2–CH3), 22.90 (–CH2–CH2–CH3), 14.34
(–CH3). IR (KBr): 3,342 cm-1 (t-OH), 1,697 cm-1 (t –OC
(=O)NH–), 1,543 cm-1 (–OC=ONH-R). LRMS (CI): 360
(M ? H?), 377 (M ? NH4?). HRMS (CI): found
M ? H?, 360.3114. C20H42NO4 requires, 360.3114.
Synthesis of 3b, b0; 3c, c0 and 3d, d0 in water
A solution of butylamine, hexylamine or octylamine in
water was added to glycerol carbonate in stoechiometric
amount at 50 °C. The reaction was stirred for 2 h. Raw
media were analyzed without purification.
Synthesis for the kinetic study
The kinetics synthesis followed the same protocol as the
synthesis of 3a, a0; 3b, b0 and 3d, d0. The molar ratio was
calculated by assuming that one mole of alkylamine con-
sumes one mole of glycerol carbonate. Sampling was
carried out every 15 min and was analyzed by GC.
Synthesis of 3g, g0
O-(2-aminopropyl)-O0-(2-methoxyethyl)
polypropylene
glycol (12.31 g, 0.106 mol) was added at 50 °C to an
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J Am Oil Chem Soc (2012) 89:1125–1133
equimolar quantity of glycerol carbonate (25 g, 0.2118 mol).
The reaction was kept at 50 °C under mechanical stirring for
4 h. 1H NMR MeOD): d in ppm = 4.69 (m, 1H, –CHOCO),
3.60 (quint, 1H, –CHOH), 4.05 (m, 2H, –CH2O), 3.76 (m,
4H, b, –CH2OH), 3.36 (m, 2H, a, –CH2OH), 3.20 (m, 4H,
–NH–CH–CH2), 7.90 (m, 2H, –NH–CH–CH3), 1.03 (t, 6H,
–NH–CH–CH3), 3.47 (m, 4H*n, –O–CH2–CH–CH3), 3.62
(m, 2H*n, –O–CH2–CH–CH3), 1.13 (m, 6H*n, –O–CH2–
CH–CH3), 3.60 (m, 8H, CH2–CH2–O–CH3), 3.35 (t, 6H, –O–
CH3)..13C NMR (MeOD) d in ppm = 158.53 (a C=O),
158.17 (b C=O), 77.04 (–CHO), 71.65 (–CHOH), 69.86
(–CH2O), 62.10 (b, –CH2OH), 64.24 (a, –CH2OH), 77.73
(–NH–CH–CH2), 47.79 (–NH–CH–CH3),19.28 (–NH–CH–
CH3), 74.51 (–O–CH2–CH–CH3), 76.80 (–O–CH2–CH–
CH3), 17.77 (–O–CH2–CH–CH3), 72.25 (CH2–CH2–O–
CH3), 76.30 (CH2–O–CH3), 59.50 (–O–CH3). IR (KBr):
3,342 cm-1 (t-OH), 1,697 cm-1 (t –OC(=O)NH–), 1,543
cm-1 (–OC=ONH-R). Maldi-TOF: Mn = 700, C7H14NO4–
(C3H6O)n– C3H7O2 with n = 7,72.
(–CH2OH), 66.80 (–CH2OH), 42.10 (–N–CH2–CH3), 13.10
(–N–CH2–CH3), 48.70 (–N–CH2–), 31.61 (–CH2–CH2–CH3),
20.52 (–CH2–CH3), 13.70 (–CH3). IR (KBr): 3,401 cm-1
(t-OH), 1,684 cm-1 (t –OC(=O)N–). LRMS (CI): 220
(M ? H?), 238 (M ? NH4?). HRMS (CI): found M ? H?,
220.1545. C10H22NO4 requires 220.1549.
Characterization
1H and 13C nuclear magnetic resonance (NMR) spectra
were achieved on a Bruker AvanceÒ 300-MHz instrument
using tetramethylsilane (TMS) as an internal standard and
equipped with a QNP probe (1H, 19F, 31P, 13C). A pre-
1
liminary study of H (zg30), J-mod and dept135 signals
completed with 2D studies (COSY, HSQC) led to the
attribution of the NMR signals. The ratio of a/b isomers is
determinated at 293.2 K, with the zgig 13C pulse program.
In the most recent experiments, the delay time D1 is greater
than or equal to 30 s in order to permit the full relaxation of
all nuclei concerned in the assay.
Synthesis of 3h, h0
Fourier transform infrared (FT-IR) spectra were mea-
sured on a PerkinElmer Spectrum 65 spectrometer. Low
resolution mass spectrometry analyses were performed on a
triple quadruple instrument TSQ 700 (thermoquest). Mass
calibration was conveniently carried out using the precur-
N-methylbutylamine (18.46 g, 0.2118 mol) was added at
50 °C to an equimolar quantity of glycerol carbonate (25 g,
0.2118 mol). The reaction was kept at 50 °C under
mechanical stirring for 2 h. 1H NMR (DMSO-d6): d in
ppm = 4.13 (m, 1H, –CHOCO), 4.23 (m, 2H,–CH2OCO),
3.90 (quint, 1H,–CHOH), 3.77 (m,4H,–CH2OH), 3.68 (m,2H,
–CH2OH), 2.90 (m, 6H,–CH3N), 2.96 (m, 4H,–CH2N), 1.55
(m,4H,–CH2–CH2–CH3), 1.33 (m, 4H,–CH2–CH3), 0.96
(t, 6H,–CH3).13C NMR (DMSO-d6): d in ppm = 156.18
(a C=O), 156.39 (b C=O), 79.07 (–CHOCO), 68.00
(–CH2OCO), 74.08 (–CHOH), 62.98 (–CH2OH), 66.78
(–CH2OH), 34.40 (–N–CH3), 51.20 (–N–CH2–), 31.30
(–CH2–CH2–CH3), 20.50 (–CH2–CH3), 13.7 (–CH3). IR
(KBr): 3,401 cm-1 (t-OH), 1,684 cm-1 (t –OC(=O)N–).
LRMS (CI): 206 (M ? H?), 223 (M ? NH4?). HRMS
(CI): found M ? H?, 206.1493. C9H20NO4 requires
206.1501.
?
sor ion NH4 (m/z = 18). High-resolution mass spec-
trometry was obtained using the ionization method; CI
refers to chemical ionization.
Gas chromatography (GC) analyses were performed
with Varian 3900 using
a BP20 (SGE) column
(12 m 9 0.53 mm 9 1 lm) in a temperature range of
60–230 °C at 30 °C/min and 20 min at 230 °C, with
methanol as the dilution solvent. The injector and FID
detector temperatures were set at 250 °C. The injection
volume was 1 ll. Chromatograms were treated by a Star
Chromatography Workstation t0.6.4. Software. O-(2-ami-
nopropyl)-O0-(2-methoxyethyl) polypropylene glycolhydro-
xyurethane MALDI-TOF spectra were recorded on a
MicroMX Waters MALDI apparatus equipped with a
337-nm nitrogen laser with 4-ns pulse duration. The sam-
ples were dissolved in MeOH and mixed with a solution of
the MALDI-TOF matrix (2,5-dihydroxybenzoic acid, NaI).
Synthesis of 3i, i0
N-ethylbutylamine (21.43 g, 0.2118 mol) was added at 50 °C
to an equimolar quantity of glycerol carbonate (25 g,
0.2118 mol). The reaction was kept at 50 °C under mechan-
ical stirring for 2 h. 1H NMR (DMSO-d6): d in ppm = 4.13
(m, 1H, –CHOCO), 4.23 (m, 2H,–CH2OCO), 3.90 (quint,
1H,–CHOH), 3.77 (m,4H,–CH2OH), 3.68 (m,2H, –CH2OH),
3.00 (m, 4H, –N–CH2–CH3), 1.20 (m, 6H, –N–CH2–CH3),
2.96 (m, 4H,– N–CH2–), 1.55 (m,4H,–CH2–CH2–CH3), 1.33
(m, 4H,–CH2–CH3), 0.96 (t, 6H,–CH3).13C NMR (DMSO-
d6): d in ppm = 156.19 (a C=O), 156.41 (b C=O), 79.10
(–CHOCO), 68.03 (–CH2OCO), 74.10 (–CHOH), 63.00
Results and Discussion
Aminolysis reaction of glycerol carbonate in organic
medium
Aminolysis reaction with primary amine
Aminolysis reaction of glycerol carbonate 1 with different
amines 2 was carried out at 50 °C for 2 h to afford the
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J Am Oil Chem Soc (2012) 89:1125–1133
1129
corresponding a and b hydroxyurethanes isomers 3 and the
secondary product glycerol 4 (Fig 1). The reaction was
conducted by infrared spectroscopy until the complete
disappearance of the lC=O bond of the carbonate function
(1786 cm-1) and the appearance of the l(OC(=O)–NHR)
bond of the urethane unit (1697 cm-1). The urethane unit
also gives two other bands. The high frequency at
1543 cm-1 corresponds to the (–OC(=O)NH-R), and the
low frequency at 1250 cm-1 is attributed to l(C(=O)–O–
C) of the glycerol unit.
NMR. Figure 2 depicts the zgig 13C NMR of a and b
N-octylhydroxyurethanes (3d and 3d0) and shows the 65/35
ratio of the former and the latter. We verified the ratio of
the selectivity on the signals assignable to the carbonyl
carbon signals (i and i0) that appeared at 159.18 and
158.88 ppm, at the a-methine carbon signals (k and k0) at
71.69 and 77.06 ppm, but also at the b-methine carbon
signals (l and l0) at 64.21 and 62.12 ppm of the glycerol
skeleton. These results were confirmed by HPLC analysis.
With a 1:1 molar ratio (glycerol carbonate: amine) and a
number of carbons of the alkyl chain of the amine less than
or equal to 12, the conversion of glycerol carbonate and the
yield of hydroxyurethanes was more than 87%. For longer
alkyl chains, the conversion of glycerol carbonate was
weaker and the yield of hydroxyurethanes decreased (runs
In the literature, the ratio of a versus b hydroxyure-
thanes is generally established in a post-reactional phase by
1
spectroscopic methods more particularly by H NMR [9,
10, 22]. The structures of the compounds and the ratio of a
versus b hydroxyurethanes were determined by zgig 13C
OH
OH
OH
OH
OH
O
O
OH
OH
O
T=50°C, t =2h
+
+
NH4-OH
NH2-R
O
N
H
R
+
O
O
A) Without solvent
B) Water
N
R
OH
H
O
1
2
3
4
Fig. 1 Aminolysis reaction of glycerol carbonate (3a and 3a0: a and b
hydroxyurethane with R=H; 3b and 3b0: a and b N-butylhydroxy-
urethane with R=C4H9; 3c and 3c0: a and b N-hexylhydroxyurethane
with R=C6H13; 3d and 3d0: a and b N-octylhydroxyurethane with
R=C8H17; 3e and 3e0: a and b N-dodecylhydroxyurethane with
R=C12H25
;
3f and 3f0:
a
and
b
N-hexadecylhydroxyurethane
R=C16H33; 3 g and 3 g0: a and b O-(2-aminopropyl)-O0-(2-methoxy-
ethyl) polypropylene glycolhydroxyurethane with R=O-(2-aminopro-
pyl)-O0-(2-methoxyethyl) polypropylene glycol
13
Fig. 2 Zgig C NMR (300 MHz, MeOD) of a and b N-octylhydroxyurethanes (3d and 3d0) obtained from glycerol carbonate and octylamine
(asterisk indicates glycerol)
123

1130
J Am Oil Chem Soc (2012) 89:1125–1133
OH
R'-NH-R
long alkyl chain of the amine seems to be the main factor
responsible for the modification of the rate constants of the
ring-opening and so the modification of the selectivity of a
versus b. The ratios of a and b isomers were almost
dependent on amines as suggested by prior studies [11], but
independent of the reaction temperature (runs 2–3; 7 and
10; 12–13; 14–17).
OHO
O
OH
OH
O
N
R
+
+
O
O
OH
R'
N
R
O
O
R'
1
2
3
Fig. 3 Aminolysis reaction of glycerol carbonate with secondary
amine (3h and h0: a and b N-methylbutylhydroxyurethane with
R=CH3 and R0=C4H9; 3i and 3i0: a and b N-ethylbutylhydroxyure-
thane with R=C2H5 and R0=C4H9)
A surprising experimental fact is the presence of glyc-
erol. This by-product derives from the aminolysis reaction
of glycerol carbonate, more particularly in hydroorganic
medium. The presence of glycerol in the medium was
conducted by GC analysis. Gas chromatography is an
analytical tool that affords simultaneous analysis of the
conversion of glycerol carbonate, the formation of
hydroxyurethanes and glycerol. Kinetic investigations of the
aminolysis reaction were of value in order to evaluate the
percentage of glycerol present in the reaction. This type of
reaction is fast, and the formation of glycerol is significant.
As shown in Table 1, in organic medium, the yield of
glycerol was stable at around 10% whatever amine was
12, 14). However, increasing the reaction temperature (runs
13, 15) and the amine ratio (runs 16–17) favored the yield
of the reaction. The conversion of glycerol carbonate and
the yield of hydroxyurethanes were affected by the reaction
temperature and the ratio of glycerol carbonate: amine.
The selectivity of the reaction favored the a isomer [7,
11, 12]. However, the length of the alkyl chain of the amine
affects the regioselectivity of the ring-opening. Herewith,
the more the alkyl chain increased, the more the ratio of the
b isomer increased (Fig. 3). The steric hindrance due to the
Table 1 Aminolysis reaction of glycerol carbonate with amines
c
Run
T °C
t (h)
Solvent
Ratioa
Conversionb
a/b
Yieldd (%)
Yield of ae
Yield of bf
Yield of 4g
Compounds
1
50
25
50
50
50
2
2
water
1:1
1:1
1:1
100
78
95/5
69
73
91
79
90
86
90
88
83
89
87
73
90
18
42
58
98
49
95
29
69
94
65
55
68
62
64
65
63
62
43
63
49
36
44
9
3
31
5
3a, a0
3b, b0
2
–
75/25
75/25
78/22
71/29
75/25
65/35
70/30
55/45
65/35
57/43
49/51
18
23
17
26
22
27
26
43
27
37
37
46
9
3
–
100
9
4
water
21
9
5
2
2
–
1:1
1:1
100
3c, c0
3d,d0
6
water
14
10
11
12
11
11
7
7
50
50
50
60
50
50
80
50
80
80
90
50
80
50
80
90
–
100
100
95
8
water
9
DMSO
10
11
12
13
14
15
16
17
18
19
21
22
23
a
–
–
–
100
98
2
2
2
2
2
2
4
2
4
2
4
4
1:1
1:1
3e, e0
3f, f0
80
100
20
10
2
–
1:1
51/49
3g, g0
1:1
44
21
29
50
29
58
15
36
49
21
28
48
21
42
13
32
43
1:1.4
1:1.4
1:1
60
100
50
–
–
58/42
52/46
1
1
3h, h0
3i, i0
1:1.4
1:1
95
30
1:1.4
1:1.8
70
95
Molar ratio of glycerol carbonate versus amine
b
Conversion of glycerol carbonate determined by GC analysis
Selectivity of a versus b by zgig 13C NMR
Yield of hydroxyurethanes
c
d
e,f
g
Yield of a and b calculated
Yield of glycerol determined by GC analysis
123

J Am Oil Chem Soc (2012) 89:1125–1133
1131
used (runs 3, 5, 7, 11 and 13). However, this yield
decreases depending on the reactivity of the amine (runs
14–17). A primary amine on a secondary carbon reacts
faster than a primary amine on a tertiary carbon. The
probable reason for this phenomenon is that the amine
plays the roles of both catalyst and reagent, affording the
ring-opening of the glycerol carbonate to form glycerol and
hydroxyurethane isomers. Moreover, because of forming
an intramolecular bond and blockage of carbonyl oxygen,
it considerably lowers the susceptibility of the whole
hydroxyalkylurethane group to hydrolysis.
favored in the presence of bases [27]. The nucleophilic
addition of the amine on the cyclocarbonate competes with
the chemical instability of the reagent in the presence of
aqueous amines.
As shown in Fig. 4, the more the alkyl chain increases,
the less glycerol is formed. Moreover, the ratio in the b
isomer increases with the number of carbon atoms. Indeed,
the differing hydrophobicity of the amine is a probable
reason for this clear difference. Octylamine containing a
considerable degree of hydrophobic structure may have
excluded water from the carbonate moieties to prevent its
solvatation effect and then limited the decomposition of
glycerol carbonate.
Aminolysis reaction with secondary amine
The formation of the by-product glycerol as a function
of reaction time was investigated for different aminolysis
reactions. Its formation was monitored by GC analysis. We
have found some differences in the rate of the reaction and
the formation of glycerol as a by-product between the
different nitrogen nucleophiles. The reaction in the pres-
ence of ammonium hydroxide is very fast. It leads to a
quick and total conversion of glycerol carbonate in about
15 min into glycerol along with the formation of short
chain hydroxyurethane. At 5 min reaction time, glycerol
was calculated to be 15%. After this time, the hydrolysis of
urethane function takes place, and the percentage of glyc-
erol increases progressively as a function of time. At 2 h,
the hydrolysis product was 30%. For longer alkyl chain
primary amines, it is readily apparent that the rate of for-
mation of glycerol is slower. At 15 min reaction time, the
decomposition of residual glycerol carbonate had started
already, and the glycerol yield was calculated to be 6.5%
for butylamine, 5.8% for hexylamine and 5.5% for octyl-
amine. At the end of the reaction time, the glycerol yield
was calculated to be 21% (run 4), 14% (run 6) and 11%
(run 8) for reactions with butylamine, hexylamine and
octylamine, respectively. The reaction was complete after
2 h, leading to a total consumption of glycerol carbonate
(Fig. 5). For short chain amines, the competition between
aminolysis and decomposition of glycerol carbonate
favored the decomposition as water easily reached the
cyclocarbonate, which is not the case for longer hydro-
phobic amines. Even if the nucleophilic addition of amines
remains the principal reaction, the presence of water in
basic conditions enhances the parallel decomposition
reaction of glycerol carbonate into glycerol.
The reaction of 1 with secondary amine 2 (Fig. 3) was
carried out in the same conditions as for primary amines.
The reaction was monitored by infrared spectroscopy until
the complete disappearance of the lC=O bond of the car-
bonate function (1786 cm-1) and the appearance of the
l(OC(=O)–N–) bond of the carbamoyle unit (1684 cm-1).
As summarized in Table1, the conversion reached respec-
tively 50% and 30% with N-methyl (run 18) and N-eth-
ylbutylamine (run 21). The probable reason for this lower
conversion of glycerol carbonate is the weaker nucleophi-
licity of the secondary amine and the hydrophobic char-
acter of the alkyl chain. The conversion of glycerol
carbonate was improved by increasing either the reaction
temperature or the reagent concentration. The reaction of
glycerol carbonate with a secondary amine was dependent
on the reaction temperature, the ratio of the reagents and
the amine. Furthermore, the use of a secondary amine
instead of a primary amine improved the selectivity toward
the b isomer and limited the hydrolysis side reaction. This
is probably due to the lower basicity (pKb butyl-
amine = 3.55; pKb N-methylbutylamine = 3.1) and the
higher steric hindrance of the secondary amine.
Aminolysis reaction of glycerol carbonate
in hydroorganic medium
Aminolysis of the glycerol carbonate with several amines 2
in water at 50 °C affords hydroxyurethanes 3 and the by-
product glycerol 4 (Fig. 1). The hydroorganic medium is
initially made of glycerol carbonate, aliphatic amine and
water, representing two competitive nucleophiles, the one
being weaker than the other. Reagents are miscible with
water to the extent that aliphatic amines have fewer than 12
carbon atoms. When using water as a solvent, side reac-
tions must be considered, such as the decomposition of
glycerol carbonate into glycerol that decreases yields of
products. Glycerol carbonate is susceptible to glycerol and
carbon dioxide formation at low temperature in the pres-
ence of 5% water under stirring. This decomposition is
In the progress of the aminolysis reaction of glycerol
carbonate, the rates of the reaction were in the order of
2a > 2b > 2d, indicating the lesser reactivity of 2d and 2b
toward 2a. Since the reactivity of 2a was higher than that
of 2b and 2d, we calculated the reaction rate constants k in
order to evaluate the difference in reactivity. The kinetic
disappearance of the amine and cyclic carbonate (i.e.,
glycerol carbonate) was studied by several authors [19, 22,
123

1132
J Am Oil Chem Soc (2012) 89:1125–1133
100
carbonate, and the rate of formation of glycerol is much
faster.
90
80
70
60
50
40
30
20
10
0
Next, we studied the aminolysis reaction of glycerol
carbonate with octylamine in solvent medium (runs 8 and
9) in order to study the effect of the solvent on the ratio of a
versus b and the amount of glycerol formed. We found that
the presence of glycerol is affected by the solvent polarity.
In the case of water, the selectivity of a versus b is
affected by water presence (runs 4, 6, 8). However, with
organic solvents the selectivity of a versus b is slightly
dependent on solvent polarity [11, 21, 22].
W
Wo
W
Wo
W
Wo
W
Wo
W
Wo
W
Wo
0
4
6
8
12
16
beta
alpha
Glycerol
Conclusion
Fig. 4 Yield of a, b and glycerol in the function of the number of
carbon atoms of the primary amine determined by GC analysis and
13C NMR (W water, Wo without water)
We have investigated the aminolysis reaction of glycerol
carbonate in organic and hydroorganic media, giving two
hydroxyurethane isomers and the by-product glycerol. We
elucidated the ratio and the structures of a and b hydrox-
yalkylurethane isomers obtained by the reaction of 1 with
amines. The conversion of glycerol carbonate and the yield
of hydroxyurethanes were dependent on the reaction tem-
perature and the ratio of the amine added. The ratio of the
isomers was determined by zgig 13C NMR, giving the same
results as those determined by gas chromatography. The
ratio in a hydroxyalkylurethane was higher than that of the
b isomer using a primary amine and approximately the
same with a secondary amine. Moreover, the selectivity of
a versus b was independent of the reaction temperature, but
dependent on the solvents and amines structures. We also
demonstrated the non-negligible formation of glycerol as a
by-product. The quantity of glycerol depends on the reac-
tivity of the amine and the presence of water in the med-
ium. The presence of water affects the formation of b
isomer and increases the formation of glycerol. This effect
is reduced with longer alkyl chains. Finally, the aminolysis
reaction of glycerol carbonate with a secondary amine
28, 29]. However, the kinetic formation of glycerol as a by-
product of the aminolysis reaction has never been
demonstrated.
The reaction rates are expressed by Eq. (1).
ꢁdC=dt = kC2ðC : concentration of 1Þ
Equation (1) can be transformed to Eq. (2).
ð1Þ
ð2Þ
1=Cꢁ1=C0 = kt
Figure 6 illustrates the correlation between reaction time
and 1/C–1/C0, where linear relationships through the origin
can be observed, demonstrating the validity of the premise
above. The slopes of the lines provided the reaction rate
constants: k2a = 4.5035 (g g min-1), k2b = 1.054
(g g min-1) and k2d = 0.6223 (g g min-1), respectively.
These results confirm the reactivity of every amine used in
the aminolysis of glycerol carbonate. In conclusion, the use
of water as a solvent enhances the by-product forma-
tion significantly, i.e., the decarboxylation of glycerol
100
160
2a
140
80
2b
120
2a
2d
60
100
2b
80
60
40
20
0
2d
40
20
0
0
15
30
45
60
75
90
105 120 135 150
0
20
40
60
80
100
120
140
160
Reaction time (min)
time(min)
Fig. 5 Disappearance of glycerol carbonate in the aminolysis reac-
tion of glycerol carbonate with ammonia (2a), butylamine (2b) and
octylamine (2d) at 50 °C in water
Fig. 6 Time-(1/C-1/C0) relationships in the aminolysis reaction of
glycerol carbonate with ammonia (2a), butylamine (2b) and octyl-
amine (2d) at 50 °C in water
123

J Am Oil Chem Soc (2012) 89:1125–1133
1133
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123