Chlorine-Free Synthesis of Organic Alkyl Carbonates and Five- and Six-Membered Cyclic Carbonates

Article abstract of DOI:10.1002/adsc.201500654

This report presents a new, one-pot, facile, selective and green method for methoxycarbonylation of alcohols and synthesis of five- and six-membered cyclic carbonates from corresponding alcohols with dimethyl carbonate (DMC) in the presence of molecular sieves without any additional solvent and catalyst. Syntheses of bifunctional structures comprising a six-membered cyclic carbonate with allyl ether and methacrylate groups, respectively, for different polymerization modes, were also achieved and showed reproducibility on up-scaling the processes.

Full text of DOI:10.1002/adsc.201500654

UPDATES
DOI: 10.1002/adsc.201500654
Chlorine-Free Synthesis of Organic Alkyl Carbonates and Five-
and Six-Membered Cyclic Carbonates
Sang-Hyun Pyoa,* and Rajni Hatti-Kaula
a
Biotechnology, Center for Chemistry and Chemical Engineering, Lund University, Box 124, SE-221 00 Lund, Sweden
Fax: (+46)-46-223-4713; phone: (+46)-46-222-4838; e-mail: sang-hyun.pyo@biotek.lu.se
Received: July 7, 2015; Revised: November 29, 2015; Published online: February 17, 2016
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201500654.
Abstract: This report presents a new, one-pot,
facile, selective and green method for methoxycar-
bonylation of alcohols and synthesis of five- and
six-membered cyclic carbonates from corresponding
alcohols with dimethyl carbonate (DMC) in the
presence of molecular sieves without any additional
solvent and catalyst. Syntheses of bifunctional struc-
tures comprising a six-membered cyclic carbonate
with allyl ether and methacrylate groups, respec-
tively, for different polymerization modes, were also
achieved and showed reproducibility on up-scaling
the processes.
thoxyethoxy)ethanol,[12] and an organocatalyst (1,5,7-
triazabicyclo[4.4.0]dec-5-ene, TBD) to shift the equi-
librium towards the desired product.[9]
The various synthetic routes[13,14] for cyclic carbo-
nates include the reaction of glycerol with DMC, re-
action of epoxides with carbon dioxide catalyzed by
transition metal and metal complex catalysts, and pal-
ladium-catalyzed domino reaction of 4-methoxycarbo-
nyloxy-2-butyn-1-ols with phenols. The majority of
the studies so far report on the synthesis of five-mem-
bered carbonates,[13] while the six-membered cyclic
carbonate is the preferred structure for polymeri-
zation because of being less thermodynamically stable
than its ring-opened polymer and thus retaining CO2,
during the polymerization process.[2,3,15,16] Comparison
of the reactivity of the cyclic carbonates substituted
with allyl and homoallyl groups, 5-(2-propenyl)-1,3-
dioxan-2-one and 4-(3-butenyl)-1,3-dioxolan-2-one
with hexylamine and benzylamine showed the ring
Keywords: alkyl carbonates; chlorine-free reac-
tions; cyclic carbonates; one-pot carbonylation
Organic linear and cyclic carbonates have been draw- opening reaction rates of the six-membered cyclic car-
ing increasing interest for diverse applications, for ex- bonate to be 29 to 62 times faster than those of the
ample, as organic solvents, as useful protecting groups five-membered one at 30–708C.[16c] However, produc-
for alcohols and phenols in organic syntheses, as elec- tion of six-membered cyclic carbonates is not straight-
trolyte solvents in lithium ion batteries, and as mono- forward and/or gives poor product yields using certain
mers for phosgene-free polyurethanes and poly- catalysts and chlorinated carbonylating agents such as
carbonates.[1–3] The latter are especially in demand for phosgene and alkyl chloroformate.[14a–c]
potential use in biomedicine and food applications
Synthesis of a cyclic carbonate from bis(hydroxy-
due to their features of biocompatibility and low tox- methyl)propionic acid (Bis-MPA) has been reported
icity.[3–7] Synthesis of organic carbonates has been typ- using CsF as a catalyst, and bis(pentafluorophenyl)-
ically carried out using phosgene, which, besides carbonate instead of phosgene.[14a] Bis- and tris(cyclic
being highly toxic and corrosive, produces large quan- carbonate)s were prepared using ethyl chloroformate
tities of chloride salts as side products.[8,9] To develop and triethylamine in THF.[14b]
more convenient and environmentally benign process-
In another study, tris- or tetrakis(alkoxycarbony-
es, the organic carbonate interchange reactions using loxy) derivatives obtained from catalytic transesterifi-
CO2 [1o0r,11]dimethyl carbonate (DMC) synthesized from cation of trimethylolpropane (TMP) and diethyl car-
CO2,
have been proposed as “carbonylation” re- bonate have been subjected to thermal disproportio-
agents to produce asymmetrical and symmetrical car- nation using Aerosil 200 at 200–2208C followed by
bonates.[9] The interchange reaction for synthesis of distillative depolymerization under reduced pressure,
linear carbonate has been characterized by catalyst to give a low yield of the cyclic product 5-ethyl-5-
systems such as the lanthanum(III) complex prepared ethoxyarbonyloxymethyl-1,3-dioxan-2-one.[14c] Recent-
in situ from lanthanum(III) isopropoxide and 2-(2-me- ly many attempts have been made to improve the
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Chlorine-Free Synthesis of Organic Alkyl Carbonates
productivity.[14d–g] A series of substituted six-mem-
bered cyclic carbonates were prepared by catalytic
coupling of oxetane and CO2 using Al(III) and
Fe(III) aminotriphenolate complexes.[14d] Cyclic car-
bonates were also synthesized from CO2 and diols by
a carboxylation–hydration cascade catalytic process
using CeO2 with 2-cyanopyridine.[14e] Carbonate phos-
phonium salts were used to produce five- and six-
membered cyclic carbonates as catalysts for the trans-
esterification of dialkyl carbonates with diols,[14f]
while an allyloxy-functionalized six-membered cyclic
carbonate was synthesized in 63% yield by ring-clos-
ing depolymerization from an oligomer prepared
from trimethylolpropane allyl ether, diethyl carbon-
ate, and NaH.[14g] TMP cyclic carbonate has earlier
been prepared as mixture with a mono(ethoxycarbo-
nyloxy)-TMP cyclic carbonate by transesterification
of polyols with dialkyl carbonates catalyzed by immo-
bilized Candida antarctica lipase B, Novozymꢁ435,
followed by thermal cyclization.[17]
Table 1. Methoxycarbonylation of mono-alcohols with di-
methyl carbonate[a]
In the present study, we demonstrate the alkyl car-
bonylation of various mono-alcohols and polyols with
high selectivity by reaction with DMC in the presence
of molecular sieves and without any additional sol-
vent and catalyst (Scheme 1). The method provides
a new facile and potentially green route for carbony-
lation of alcohols and synthesis of cyclic carbonates.
Especially a new production method for six-mem-
bered cyclic carbonates could provide a useful alter-
native route for the phosgene-free synthesis of polyur-
ethanes and polycarbonates.
[a]
All reactions were carried out using mono-alcohols
(1 mmol), dimethyl carbonate (17.8 mmol) and molecular
sieves (4Š; 0.5 g) in closed vials (4 mL).
[b]
Isolated product yields. All products were confirmed by
1H and 13C NMR.
Reactions between the alcohols and DMC were hols was completed within 2 h at 1108C (Table 1, en-
performed in the presence of molecular sieves 4Š tries 1, 3 and 5), while it took 20 h for the reaction to
only; DMC served also as the solvent and was hence be completed with secondary alcohols (Table 1, en-
used in excess (Table 1). Reaction with primary alco- tries 7 and 9), and no product formation was observed
in the reaction with a tertiary alcohol (Table 1,
entry 11). This difference in the reactivity could be
used for the selective carbonylation of alcohol groups.
The reaction rate was slightly lower at 908C. Reac-
tions performed in the absence of molecular sieves
with n-butanol and 2-butanol (entries 3 and 9)
showed no product formation during a reaction time
of 7 h. This method of trans-carbonylation provides
a mild and useful approach for the synthesis of alkyl
carbonates in high yields in comparison to their syn-
thesis from alkyl haloformates such as methyl, ethyl
and butyl chloroformate that are derived from phos-
gene or triphosgene.[18]
Diol compounds having two alcohol groups at 1,2-
positions such as 1,2-propanediol, 1,2-butanediol and
glycerol can be transformed into 5-membered cyclic
carbonates by methoxycarbonylation of one hydroxy
group with DMC followed by cyclization (Table 2).
There are, however, two possible products with a diol,
carbonated at the 1 (6a) or 2 (6b) hydroxy positions
(Table 2). According to the results in Table 1, methox-
ycarbonylation of the primary alcohol would be ex-
Scheme 1. Synthesis of (A) organic carbonates and (B)
cyclic carbonates from the reaction of monohydric and dihy-
dric alcohols, respectively, with dimethyl carbonate in chlor-
ine- and organic solvent-free medium in the presence of mo-
lecular sieves.
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Sang-Hyun Pyo and Rajni Hatti-Kaul
Table 2. Synthesis of five-membered cyclic carbonates by re-
bonylation of a diol with DMC and reaction of epox-
ides and oxetanes with carbon dioxide, respectively,
have used catalysts such as transition metals, metal
complexes and enzymes (lipase). Tudorache et al.[13g]
reported that glycerol carbonate was prepared with
59.3% yield from reaction of glycerol with DMC
using lipase extracted from Aspergillus niger as a bio-
catalyst. Meanwhile, we show here that 73.3% of glyc-
erol carbonate could be obtained in the same reaction
without using the lipase but by increasing the temper-
ature to 1108C. The product yield was further in-
creased to 89% by performing the reaction in the
presence of molecular sieves (Table 2).
action of diols and a triol with dimethylcarbonate[a]
Table 3 summarizes the results of reactions between
1,3-diols and DMC to form six-membered cyclic car-
Entry Polyol Temp.
MS
[g]
Time Products Yield[b]
[8C]
[h]
[%]
Table 3. Synthesis of six-membered cyclic carbonates by re-
1
2
3
4
5
6
7
4
4
4
5
5
5
9
110
110
90
110
110
90
0
12
24
24
24
24
24
48
7
7
7
7
7
7
10
11
10
11
10
11
98
99
83
99
89
58
action of diols with dimethyl carbonate.[a]
0.5
0.5
0
0.5
0.5
0
110
73[c]
4[c]
24[c]
76[c]
89[c]
11[c]
8
9
9
9
110
90
0.5
0.5
24
24
[a]
All reactions were carried out using a polyol (1 mmol),
and dimethyl carbonate (17.8 mmol) with or without mo-
lecular sieves (MS; 4Š; 0.5 g) in closed vials (4 mL) at
1108C.
[b]
[c]
Isolated product yields.
Contents of products were determined by gas chromatog-
1
raphy. All products were confirmed by H and 13C NMR
after isolation (silica-flash chromatography using elution
mixture).
pected to occur at a higher reaction rate and with
a higher selectivity.
However, these products were not detected by GC
analysis of the samples taken during the reaction, and
even the linear dicarbonate, 8 was not observed.
These results imply that the cyclization step occurs
soon after the monocarbonate is formed, not allowing
enough time for the dicarbonate (8) formation. Inter-
estingly, the reactions involving 1,2-propanediol and
1,2-butanediol took place rapidly in the absence of
molecular sieves, which is completely in contrast to
the reaction with mono-ols.
It is possible that the position of the 2nd alcohol
group facilitates the reaction of the primary alcohol
group with DMC and subsequent cyclization by some
coordination like intramolecular hydrogen bonding.[19]
The various synthetic routes[13,14] reported so far for
the synthesis of 5-membered cyclic carbonates by car-
[a]
All reactions were carried out using a polyol (0.5 mmol),
dimethyl carbonate (17.8 mmol) and molecular sieves
(MS; 4Š; 0.5 g) at 1208C.
Isolated product yields.
Contents of products were determined by gas chromatog-
raphy. The main side product was the corresponding
linear dicarbonate (P3).
[b]
[c]
[d]
Content for the reaction at 808C. The isolated products
were confirmed by 1H and 13C NMR after isolation
(silica-flash chromatography using elution mixture). En-
tries 6, 7 and 9 showed consistent yields in 60 g, 60 g and
6 kg scale reactions at 1208C, respectively.
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Chlorine-Free Synthesis of Organic Alkyl Carbonates
bonates. Unlike the reaction of 1,2-diols with DMC ene chemistry for linking allyl ether with thiol group,
(Table 2), the reaction of 1,3-diol showed an inter- and UV curable polymerization of methacrylate
mediate mono-carbonate, implying that the cycliza- group. The reproducibility of the reactions was also
tion rate was slower than the rate of carbonate forma- confirmed with larger amounts of the reactants, i.e.,
tion, and was a rate-determining step. The desired 60 g TMPmMA and 60 g DiTMP, respectively, in a 2
cyclic carbonate product can be produced only via L PARR reactor and 6 kg TMPME in a 200 L pres-
mono-carbonate; formation of di-carbonate prevents sure reactor at 1208C. The syntheses were a straight-
the cyclization reaction, and should hence be mini- forward and green process compared to previous re-
mized. From the results obtained with mono-ols ports.[14,17]
(Table 1), it could be expected that the selectivity for
The presence of molecular sieves was shown to be
mono-carbonate formation from a diol is enhanced by important for the reaction between the alcohol/polyol
introducing substitutes on one of the two alcohol and DMC except in the case of 1,2-diols. Molecular
groups. It is clear from Table 3 that in the reactions sieves 4Š serve to selectively adsorb the reaction by-
with 1,3-propanediol, 1,3-butanediol and 3-methyl- product, methanol, which shifts the equilibrium to-
1,3-butanediol, the resulting content of cyclic carbon- wards the product formation, and preventing the re-
ate in the final product was dependent on the reaction verse reaction from taking place, but required a tem-
rate of primary, secondary and tertiary alcohols. In perature much higher than the boiling point of metha-
the case of 1,3-propanediol, only di-carbonate was nol. Molecular sieves 3Š and 5Š are used for absorp-
formed within 1 h, and in the reaction with 1,3-buta- tion of water and larger molecules (than methanol),
nediol, 67.3% of cyclic carbonate was obtained. On respectively, and were hence not suitable for the reac-
the other hand, a highly selective synthesis of cyclic tion. Whether the molecular sieves also have a catalyt-
carbonate (97.2%) was achieved in the reaction with ic role in the reaction is not clear; they have been
3-methyl-1,3-butanediol having primary and tertiary used as acid and redox heterogeneous catalysts, for
alcohols although at a slower reaction rate due to example, in a variety of selective oxidations, Knoeve-
steric hindrance by the branched diol molecules. The nagel and Henry reactions, and acetalization.[20]
higher reaction selectivity obtained with the branched
The reaction of alkyl carbonylation and cyclic car-
diols could be explained by their stereo-structure bonate synthesis presented here meets the require-
being more favourable to form cyclic intermediate, ments of green chemistry.[21,22] It makes use of non-
due to the shorter distance (3.1–3.4 Š) between the toxic reactants without any additional solvents, or
two hydroxy groups than that (4.2–4.3 Š) in the linear protection or derivatization reagents. DMC is consid-
1,3-diols (see the Supporting Information). The 1,2- ered as an environmentally benign chemical due to its
diols for five-membered cyclic carbonates showed the negligible ecotoxicity, low bioaccumulation, and low
shortest distance (2.7–2.8 Š) to give the highest selec- persistence.[23] Its use in the reaction provides an at-
tivity of cyclic carbonates (see the Supporting Infor- tractive alternative eco-friendly carbonating agent to
mation).
both methyl halides and phosgene. DMC also served
Functionalized cyclic carbonates from branched as a solvent for dissolving the polyol substrates and
diols such as trimethylolpropane monoallyl ether was hence used in excess. It can however be easily re-
(TMPME, Table 3, entry 6), ditrimethylolpropane covered by evaporation (boiling point of 908C), and
(DiTMP, Table 3, entry 7), bis(hydroxymethyl)pro- reused for subsequent reactions. Currently, the main
pionic acid methyl ester (Table 3, entry 8), and trime- limitation to the use of DMC is that the demand sur-
thylolpropane
mono-methacrylate
(TMP-mMA, passes its production. There are lots of ongoing efforts
Table 3, entry 9) were obtained in quite high yields. to develop sustainable phosgene-free routes for DMC
The reaction rate was significantly decreased at lower production directly from CO2 and methanol on large
temperature. For example, in the reaction with scale.[23]
TMPME, 15% yield was obtained at 808C as com-
Different catalysts such as metal complexes and or-
pared to 97% yield at 1208C (Table 3, entry 6). The ganocatalysts have been employed for the carbonyla-
reaction rate was also determined by the presence of tion of alcohols, which besides being costly require
molecular sieves. For example, reaction with 1,3-buta- steps for separation and complete removal from the
nediol (Table 3, entry 4) in the absence of molecular products. Molecular sieves offer an environmental
sieves yielded only 3.5% of the product during a reac- friendly alternative and, although used in excess rela-
tion time of 3 h.
tive to the substrate, they were also recovered without
The functionalized cyclic carbonate products ob- any damage by simple filtration, then reactivated and
tained with DiTMP, TMPME and TMP-mMA would reused at least 10 times with identical reaction rates
provide interesting building blocks for novel polymers and yields ranging between 79–82% in the reaction
with different properties; the respective functionali- with 60 g di-TMP (Supporting Information, Fig-
ties can utilize different polymerization mechanisms ure S1).
such as ROP of cyclic carbonate with diamines, thiol-
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UPDATES
Sang-Hyun Pyo and Rajni Hatti-Kaul
17.8 mmol) and molecular sieves (0 or 0.5 g) at a defined re-
action temperature (90 or 1108C) using a thermomixer. The
products were obtained from the reaction mixture as de-
scribed above by simple filtration of solid particles and
evaporation of excess DMC, followed in some cases by
silica chromatography using mixed solvent of ethyl acetate
and hexane. Quantitative analyses of reaction components
were performed using gas chromatography. The structures
of the products were determined by 1H and 13C NMR.
The high product yields (97–99%) obtained in
many cases shown in Tables 1–3 suggest that there is
no need for extensive product purification except for
separation from DMC. Atom economy, measured as
the ratio of molecular weight (MW) of the desired
product over the MW of all reactants used in the reac-
tion with TMPME, was relatively high, for example,
75.8%
[=200.23/(174.24+90.08)”100]
(Table 3,
entry 6) and the E-factor, i.e., the mass ratio of waste
to desired product,[24] was only 0.32 [=(32.02”2)/
200.23]. The waste comprises two moles of methanol
formed as a by-product, but considering that metha-
nol can indeed be recovered, these reactions can po-
tentially become waste free. In contrast, the conven-
tional process uses highly toxic raw materials, phos-
gene and alkyl chloroformate and produces corrosive
HCl as a by-product.[8,9] Considering that the E-fac-
tors in various segments of the chemical industry are
in the range of <1–5 for bulk chemicals, 5–50 for fine
chemicals, and 25–100 for the pharmaceutical indus-
try,[24] the reaction presented here can be safely con-
sidered to be more environmentally benign.
In conclusion, a facile, clean, one-step process for
alkyl carbonylation and synthesis of five- and six-
membered cyclic carbonates in high yields is present-
ed. The chlorine-free reaction is a significant improve-
ment over the earlier reports, especially for the syn-
thesis of six-membered cyclic carbonates.[13,14] In com-
General Procedure for the Synthesis of Six-
Membered Cyclic Carbonates
The reactions were performed in 4 mL capped vials using
a thermomixer at 400 rpm. Six-membered cyclic carbonates
were carried out using a polyol (0.5 mmol), DMC (1.5 mL;
17.8 mmol) and molecular sieves (0, 0.5 or 1 g) in the vials
placed in an oil bath at 1208C. The products were then ob-
tained from the reaction mixture by simple filtration of solid
particles and evaporation of excess DMC, followed in some
cases by silica chromatography using mixed solvent of ethyl
acetate and hexane.
Reactions were scaled up for different TMP based sub-
strates. TMPmMA (60 g) and DiTMP (60 g), respectively,
were reacted in DMC (1 L) with molecular sieves (600 g) in
a pressure reactor (2 L), which was heated by an oil bath at
1208C. Samples were withdrawn intermittently for following
the reaction and at the end of the reaction. The reaction
mixture was filtered to remove the solid particles. TMPME
(6 kg) was reacted in DMC (100 L) with molecular sieves
(60 kg) in a pressure reactor (200 L) at 1208C. No stirring
parison to the enzyme-catalyzed reaction, the present was used during the reactions.
Quantitative analyses of reaction components were per-
system is more efficient and cost-effective. The pro-
posed reaction is an important contribution to green
synthetic chemistry, and the products are highly val-
uable for polymer industry and even for biomaterial
industry.
formed using gas chromatography (see the Supporting Infor-
mation for details). The conversion of the substrates and the
product yields were calculated by comparison of peak areas
on the gas chromatograms. The structures of the products
1
were determined by H and 13C NMR (see the Supporting
Information for details).
Experimental Section
General Procedure for the Methoxycarbonylation
Acknowledgements
The reactions were performed in 4 mL capped vials using
a thermomixer at 400 rpm. Methoxycarbonylation was car-
ried out using a mono-alcohol (1 mmol), DMC (1.5 mL;
17.8 mmol) and molecular sieves (4 Š; 0.5 g) at a defined re-
action temperature (90 or 1108C) using a thermomixer.
Samples were withdrawn for GC analysis of the substrates
and products. At the end of the reaction, the products were
obtained from the reaction mixture by simple filtration of
solid particles and evaporation of excess DMC. Quantitative
analyses of reaction components were performed using gas
chromatography. The structures of the products were deter-
The work was supported by VINNOVA (The Swedish
Agency for Innovation System) and Formas (The Swedish
Research Council for Environment, Agricultural Sciences
and Spatial Planning). Mohamed Ismailꢀs contribution to the
calculation of molecular bond distances is highly appreciated.
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