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ward, isocyanate and phosgene-free methods are required for the synthesis of their precursors (mono-
DOI: 10.1039/c3gc40440d
mers) in order to achieve a sustainable production. To foster the discussion with the nal goal to meet
such a sustainable production, this review provides an overview of classic as well as modern and more
www.rsc.org/greenchem
1.
Introduction
Karlsruhe Institute of Technology (KIT), Institute of Organic Chemistry, Fritz-HaberWeg-6, 76131 Karlsruhe, Germany. E-mail: m.a.r.meier@kit.edu;
Fax: (+49)-721-608-46800; Tel: (+49)-721-608-48326
respectively.9 Typical polyols employed for industrial PUR synthesis are diols (i.e. polyester or polyether polyols) or multifunctional polyols, such as glycerol.10
Taking into account the increased importance of polyurethanes for the global market, alternative synthesis routes
avoiding the application of extremely toxic phosgene as well as
toxic isocyanates are mandatory from a sustainability point of
view. Moreover, considering health and safety reasons, polyurethanes with the lowest possible free isocyanate content are
desirable. Furthermore, long-term considerations based on the
availability of petrochemicals due to their depletion make
renewable resources very attractive for a sustainable polyurethane production. Recently, numerous reviews have shown
that the use of renewable resources, which are widely available
and inexpensive, often show reduced environmental impact
and can address some of the main concerns of the petroleumbased chemical industry.11
On the basis of a comprehensive survey of the currently
available literature on polyurethanes and possible new precursors, this review focuses on environmentally friendly and sustainable routes for the production of alternative monomers for
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2.
Isocyanates
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Scheme 2
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In summary, isocyanates are very useful and versatile compounds in organic and polymer chemistry, but nevertheless
they are generally toxic and some of them are classified to be
very toxic (e.g. methyl isocyanate and TDI). Moreover, isocyanates are potentially irritants and cause allergic asthma.24 In
general, it is thus attractive to generate isocyanates in situ and
let them react to the target compounds without isolation.
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gaseous phosgene, derivatives with similar properties like trichloromethyl chloroformate (diphosgene, liquid) and bis-(trichloromethyl) carbonate (triphosgene, solid) are used for
easier handling in laboratory scale synthesis.26 Diphosgene
and triphosgene can be synthesized by chlorination of methyl
formate and dimethyl carbonate (DMC). Nevertheless, in consideration of environmental acceptability and sustainability,
alternative methods are desired that avoid the use of these
highly toxic compounds and the use of chlorine in their
synthesis.
In 1995, Knlker et al. developed a method using di-tertbutyl dicarbonate (Boc2O) in the presence of stoichiometric
amounts of 4-dimethylaminopyridine (DMAP) for the synthesis
of isocyanates from amines (Scheme 3b).27 On a laboratory
scale, this method is a very good alternative to the before mentioned methods, but toxic Boc2O is also obtained by reacting
phosgene with carbon dioxide, tert-butanol and potassium
hydroxide. Moreover, the excess of Boc2O and stoichiometric
quantity of DMAP lead to the formation of large amounts of
waste. Thus, this is a practical procedure for the synthesis of
isocyanates in laboratories, but does not meet the requirements of green chemistry.
Another possibility for the synthesis of isocyanates is the
nucleophilic substitution of alkyl halogenides, tosylates, mesylates or triflates with metal cyanates (Scheme 3c). For this
method, diverse side reactions and polymerisations are
described and, thus, the yields of isocyanates are normally
poor.28 The recent literature showed that alcohols, thiols and
trimethylsilyl ethers can directly be converted to isocyanates by
applying a mixture of triphenylphosphine, 2,3-dichloro-5,6dicyanobenzoquinone (DDQ) and tetrabutylammonium
cyanate.29 High yields can be obtained by this procedure, but
generally, this method is certainly not suited for large-scale
isocyanate synthesis.
Another frequently used method, at least for laboratoryscale isocyanate synthesis, is the Curtius rearrangement of acyl
azides (Scheme 3d).30 Under non-aqueous conditions and
inert solvents, isocyanates can be obtained in high yields. The
Curtius rearrangement is certainly a very useful method, but is
not adequate for industrial applications and in terms of green
chemistry due to the high toxicity and explosive properties of
the needed azides and acyl azides. Alternative procedures such
as the Hofmann rearrangement of amides and the Lossen
rearrangement of hydroxamic acids also aord isocyanates as
intermediates, but usually these are directly degraded to
primary amines in the presence of water or trapped with alcohols to the corresponding carbamates. Nevertheless, modified
procedures of the Hofmann rearrangement as well as Lossen
rearrangement also allow the synthesis of isocyanates.31 Under
classic conditions, these procedures suer from the use of stoichiometric amounts of toxic and corrosive reagents (i.e. Br2 in
the case of the Hofmann rearrangement and acetic anhydride
or acetyl chloride with base in the case of the Lossen
rearrangement) and produce high amounts of waste.
In 1994, Minisci et al. developed a free radical synthesis
procedure of isocyanates in good yields starting from oxalic
2.1.
Scheme 3
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Scheme 4
Scheme 5
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Scheme 6
Scheme 7
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Scheme 9
favored, highly exothermic process. Normally, non-toxic transition metals of groups 810 are applied, but also sulfur, selenium and tellurium catalyze this reaction.38a However,
highly-toxic catalyst residues were detected in the final products and, thus, this route is until now inapplicable for an
industrial poluyurethane synthesis.40 The generally accepted
mechanism starts with the formation of a metallacycle from
the nitroarene in the presence of carbon monoxide and the
catalyst.38a,41 This intermediate fragments by decarboxylation,
but the nitroso group remains bound to the metal. Subsequently, an insertion of carbon monoxide occurs, followed
by decarboxylation. The formed nitrene species, as a key intermediate, can be carbonylated to give the resulting isocyanate.
An even more exothermic reaction is the more often applied
two-step carbonylation to N-phenyl carbamates in the presence
of alcohols, followed by subsequent thermal decomposition to
isocyanates (Scheme 8).16a,17a,38a Numerous catalysts and
ligands are described for this process. Common homogeneous
catalysts are based on ruthenium carbonyl compounds having
chelating ligands,42 palladium(II) compounds with bipyridine
and phenanthroline ligands,43 as well as rhodium carbonyl
compounds.44 Moreover, other catalysts (e.g. cheaper iron catalysts) are described.45 Procedures for the thermal fragmentation of carbamates to isocyanates were already described
above.35a
Other valuable products of reductive carbonylations of aromatic nitro compounds are ureas.38a,46 From a few examples, it
is also known that aryl azides can be converted with carbon
monoxide to aryl isocyanates.47 However, the entry to aryl
azides is an additional non-sustainable step.
Another interesting route to isocyanates starts from isonitriles (isocyanides). Very recently, Le and Ganem published a
mild, ecient and eco-friendly oxidation procedure, with
which isocyanides can be oxidized to isocyanates applying
dimethyl sulfoxide (DMSO) in the presence of catalytic
amounts of trifluoroacetic anhydride (TFAA) (Scheme 9).48 The
oxidation of isonitriles to isocyanates is not a new concept, but
3.
Carbamates
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Scheme 10
Scheme 11
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polyurethanes.1,56 Moreover, some procedures for carbamate
synthesis are described in which carbamoyl chloride, derived
from secondary amines and phosgene, is reacted with alcohols
to give N,N-disubstituted carbamates (Scheme 11c).16a,57
Due to the diculty of handling and the high toxicity of
phosgene, the known alternatives di- and triphosgene as well
as pyrocarbonates can also be used in carbamate synthesis
(Scheme 12a). A common pyrocarbonate reagent is di-tertbutyldicarbonate (Boc2O), used for the introduction of the
Boc-protecting group of amines.52 Due to the importance of
Boc-protection in peptide and related chemistry, several
modern, mild, and ecient procedures are described regarding selectivity and sustainability.58 During the last two
decades, more ecient reagents were developed for the conversions of alcohols or amines to carbamates.16a The use of carbonyl diimidazole (CDI) as a safer and less toxic reagent is an
excellent alternative method for the synthesis of carbamates
starting from alcohols or amines (Scheme 12b and c).59,60
However, also CDI is synthesized from phosgene and large
amounts of by-products are obtained during carbamate synthesis. With carbamoyl-3-nitro-1,2,4-trizole, another highly
reactive carbamate derivative, useful applications in selective
protection of nucleobases are described (Scheme 12d).61 Moreover, methyl N-(triethylammoniumsulfonyl)carbamate, better
known as Burgess reagent, is a versatile reagent in organic synthesis. It is easily prepared by the reaction of chlorosulfonyl
isocyanate with methanol and triethylamine in a two-step procedure.62 It can be used to convert alcohols into olefins and
methyl carbamates, carboxamides into nitriles, formamides
into isonitriles, nitroalkanes into the corresponding nitriloxides, and aldoximes to formamides. Moreover, several applications in the synthesis of heterocycles are known.16a,63 Also
diols can be converted to carbamates using Burgess reagent in
the presence of nucleophiles (Scheme 12e).64
Furthermore, a direct conversion of primary alcohols to
Cbz-protected amines applying the benzyl carbamate derivative of Burgess reagent is described.65 The Burgess reagent can
also be used to synthesize carbamates of -amino acids, which
can be prepared via BaylisHillman reactions.66 Interestingly, a
solvent-free synthesis of primary carbamates can be achieved
directly in a one pot reaction of alcohols with sodium cyanate
(Scheme 12f ). The reaction is performed in the presence of
perchloric acid on silica gel.67 As shown, many procedures
exist for the synthesis of carbamates from alcohols and
amines. However, these methods cannot be considered sustainable for several reasons (see discussion above) and most of
them are limited to lab-scale synthesis.
For the conversions of carboxylic acids to carbamates, three
well-known rearrangement reactions, the Curtius rearrangement of acyl azides, the Homann rearrangement of carboxamides, and the Lossen rearrangement of hydroxamic acids, are
known (Scheme 13).16a As mentioned in section 2.1, the
primary rearrangement products are isocyanates, but in the
presence of alcohols, carbamates are the final products.
Probably the best known of these reactions is the Curtius
rearrangement, although toxic and explosive acyl azides are
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Scheme 13
Scheme 12
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Scheme 15
carbonates.
Scheme 14
3.2.
3.2.1. Organic carbonates as key compounds for sustainable synthesis of carbamates. In general, the application of
organic carbonates for the synthesis of carbamates is certainly
a very promising process for a sustainable and environmentally
benign synthesis of polyurethane precursors. However, to
achieve industrial realization, further developments, both in
terms of eciency (which generally goes along with sustainability) and economic feasibility, of the herein described procedures are certainly necessary. A very promising and
sustainable access to carbamates and also ureas is the catalytic
conversion of primary and secondary amines utilizing dialkyl
or diaryl carbonates (Scheme 15).16a The synthesis of dierent
carbamates applying N,N-disuccinimido carbonate as the activated carbonate was achieved under mild conditions at room
temperature as reported by Ogura et al. in 1983.81 Further reactive carbonates are ortho- or para-substituted bis(nitrophenyl)
carbonates.82 Pentafluorophenyl carbonate derivatives are also
applied for mild conversions to oligopeptidyl carbamates.83
Christensen et al. reported a very useful method to obtain
mono-protected amines in high yields from aliphatic polyamines by the application of alkyl phenyl carbonates. They
demonstrated that tert-butyl, benzyl and allyl phenyl carbonates used in slight excess to the applied di- or polyamine gave
mono-protected Boc-, Cbz- or Alloc-carbamates in yields
between 46 and 98%.84 This oers significant advantages in
terms of less toxic reagents if compared to the above described
classic routes employed for the introduction of the respective
protecting groups.
However, far more attractive with regard to sustainable procedures, several catalysts were described for the formation of
carbamates and ureas from non-activated carbonates. In 2007,
Porco et al. showed that Zr(Ot-Bu)4 (5.0 mol%), in combination
with 2-hydroxypyridine (10 mol%), is an ecient catalytic
system for the reaction of primary and secondary amines with
dialkyl carbonates to obtain variable carbamates and asymmetric ureas.85 Later, Vidal-Ferran et al. observed that 1.0 mol%
zinc acetate is an excellent catalyst to synthesize bis-isocyanate precursors (dimethyl carbamates) of TDI and MDI in
almost quantitative yields from the corresponding anilines via
reaction with DMC.86 Also sodium acetate (20 mol%) is an
eective catalyst for methoxycarbonylation of 1,6-hexanediamine by DMC.87 Moreover, Meier et al. observed that the
strong guanidine base 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD)
catalyzes carbamate formation from primary and renewable
diamines.88 Similarly, TBD (0.5 to 10 mol%, depending on the
alcohol used) can eciently catalyze the formation of symmetric and unsymmetric carbonates from DMC and primary,
secondary, as well as tertiary alcohols.89 Due to the importance
in the development of sustainable and environmentally benign
synthesis procedures of carbamates from amines and DMC,
several other methods and catalysts have also been reported.90
Very promising is the application of enzymes as biocatalysts
for alkoxycarbonylation reactions. Already in 1993, Gotor et al.
showed the synthesis of chiral carbamates by appling CAL
(Candida antarctica lipase immobilized on accurrel) in the
reaction of racemic amines with n-octyl and n-butyl vinyl carbonates.91 Later, the same group showed the CAL catalyzed
alkoxycarbonylation of 1,25-dihydroxyvitamin D3 A-ring precursors with O-[(vinyloxy)carbonyl]oxime to obtain carbamate
derivatives in quite good yields.92 Furthermore, the first regioselective enzymatic alkoxycarbonylation of primary amines to
carbamates of pyrimidine 3,5-diaminonucleoside derivatives
applying CAL-B was described.93 Diallyl or dibenzyl carbonates
are adequate reagents in this alkoxycarbonylation reaction to
obtain allyl and benzyl carbamate derivatives in yields between
Green Chemistry
63% and 72%.94 Moreover, other enzymatic alkoxycarbonylation reactions have also been reported.95
In 2005, Selva et al. reported a catalyst-free synthesis of
methyl carbamates from amines and DMC in supercritical
carbon dioxide.96 At 130 C and a CO2 pressure between 5 and
200 bar, primary aliphatic amines react with DMC selectively
in the presence of anilines and alcohols with conversions up
to 90% after four hours reaction time.
The traditional synthesis of organic carbonates involves the
reaction of phosgene or phosgene derivatives with alcohols.
However, especially for the synthesis of dimethyl and diphenyl
carbonate, eco-friendly industrial processes are described.97
Four well-known synthesis procedures of dimethyl carbonate
(DMC) without applying phosgene received industrial relevance.98 The conversion of carbon dioxide and methanol in
the presence of catalysts is such a well-known method
(Scheme 16a). In 1998, first experiments were described to
investigate the reactivity of carbon dioxide with n-butyl
( phenoxy)-, (alkoxy)- and (oxo)-stannanes and other organic tin
catalysts for the synthesis of DMC.99 Another method reported
about the reaction of methanol with carbon dioxide in the
presence of potassium carbonate to form methyl carbonate
ions as intermediates, which were trapped with methyl iodide
to obtain DMC.100 A general problem of a direct conversion of
methanol with carbon dioxide to DMC is the formed water,
which has to be removed from the equilibrium reaction. In
2009, Tomishige et al. reported a direct conversion of methanol and low pressure carbon dioxide to DMC catalyzed by
CeO2 and promoted by acetonitrile hydration.101 Another synthesis of dimethyl carbonate from methanol and carbon
Scheme 16
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dioxide catalyzed by ZrO2 doped with KCl was investigated by
Murzin and co-workers using chemical traps for water to circumvent thermodynamic limitations.102 Moreover, a catalyst
system of cerium and zirconium oxide in dierent ratios
(CexZr1xO2) supported by ionic liquid [EMIM]Br seems to be a
promising process for the synthesis of DMC.103 Beyond these
mentioned methods, diverse other procedures for the direct
conversion of carbon dioxide with methanol are described.104
Another important industrial process for the synthesis of
DMC is the oxidative carbonylation of methanol (Scheme 16b).
In 1998, the Bayer AG described a process for the oxycarbonylation of methanol to DMC using molten salts as catalysts.105
The catalyst system consists of a eutectic mixture of copper
chloride and potassium chloride. In 2003, Itoh et al. reported
the synthesis of DMC by vapor phase oxidative carbonylation
of methanol applying CuCl2/NaOH/activated carbon catalysts.106 The application of CuY zeolite supported on silicon
carbide as an improved catalytic system for the vapor phase
oxidative carbonylation was reported by Keller and co-workers
in 2008.107 Moreover, Li et al. developed an ecient and recyclable catalyst (Schi base/zeolite) for the oxidative carbonylation.108 In addition to these mentioned methods for the
oxidative carbonylation of methanol to DMC, several other processes have been reported.109
During the last few years, the catalytic conversion of urea to
DMC has gained more and more interest (Scheme 16c). In
2003, Arai et al. described the conversion of urea and ethylene
glycol to ethylene carbonate catalyzed by ZnO.110 Followed by
the before mentioned transesterification procedures with
methanol, this method is an important step for the urea based
synthesis of DMC. Later on, Sun et al. reported the direct synthesis of DMC from urea and methanol over a ZnO catalyst.111
In 2007, the same group described a high-yielding direct synthesis of DMC by urea methanolysis applying a catalytic distillation process over a Zn-based catalyst.112 One year later, Sun
and co-workers investigated the optimal conditions for the synthesis of DMC from methyl carbamate (intermediate from urea
methanolysis) and methanol with zinc compounds as catalysts.113 Very recently, Cai et al. reported the selective synthesis
of DMC from urea and methanol applying a Fe2O3/HMCM-49
catalytic system in a batch reactor.114
Probably the most frequently employed method to prepare
carbonates is the two step conversion of ethylene or propylene
oxide with carbon dioxide to ethylene carbonate or propylene
carbonate, followed by transesterification with methanol to
DMC (Scheme 16d). In 2003, Arai et al. reported the direct synthesis of DMC and glycols from epoxides, methanol and
carbon dioxide using heterogeneous Mg containing smectite
catalysts.115 At the same time, Wang and co-workers described
the application of KI and K2CO3 as a catalyst mixture for the
synthesis of DMC from ethylene oxide under supercritical conditions.116 CaO/carbon composites are also described to catalyze the transesterification of ethylene and propylene oxide
with methanol to DMC.117 In 2006, He et al. described the
application of recyclable inorganic base/phosphonium halidefunctionalized polyethylene glycol as a catalyst for the
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Scheme 17
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Scheme 19
alcohols.
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Scheme 21
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82%. The conversion is strongly dependent on the applied formanilides, alcohols, the kind of ruthenium catalyst as well as
the solvent. Fully substituted formanilides did not react under
these conditions. To convert fully substituted formamides into
carbamates, Reddy et al. recently demonstrated a copper-catalyzed oxidative CO coupling by direct CH bond activation of
formamides (Scheme 22b).156 The coupling of N,N-dialkyl formamides with dierent -ketoesters and 2-carbonyl substituted phenol derivatives aorded enol carbamates and
substituted phenol carbamates. Formamides can be easily synthesized in high yields from the corresponding primary or secondary amine by reaction with sustainable formic acid or its
esters.34 In combination with catalytic oxidation or reductive
dehydrogenation processes, this access to carbamates meets
the requirements of green chemistry.
4.
Polyurethane synthesis
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obtained by the reaction of diisocyanate with di- or multi-functional polyols. A large range of polyurethanes can be prepared
with specific physico-chemical properties, depending on the
nature of the polyol and the diisocyanate. Thus, various polyurethanes have been developed for more than 70 years based
on numerous possible structural variations. The polyol segments, which nowadays are easily derived from diverse
biomass feedstocks, are often biocompatible and biodegradable. The manifold approaches to obtain such renewable
polyols will not be discussed here, since they are described in
many review articles and are discussed there in detail.157
Despite the use of renewable polyols, toxic polyisocyanates
obtained from the reaction between an amine and phosgene,
remain an important issue to be overcome in the chemistry of
polyurethanes. The design of an ideal commercially applicable
method, combining sustainability and high mechanical/physical properties, is the main aim of ongoing research, both in
academia and industry. While aiming at sustainable polyurethane synthesis, alternative and environmentally friendly
routes that either use non-isocyanate pathways and/or employ
renewable resources derived diisocyanates at best synthesized
by the above discussed sustainable methods are certainly
required. The most interesting developments on isocyanatefree and non-phosgene routes to polyurethane can be summarized as shown in Scheme 23.
An alternative, green and isocyanate-free route is the ring
opening of cyclic carbonates with amines yielding urethane
linkages. The step-growth polyaddition of bifunctional fivemembered cyclic carbonates and diamines, reported as early
as 1957158 and recently reviewed by Mller et al.159
(Scheme 23a), is an example of this type of reaction. The resulting product contains additional hydroxyl groups and appears
as non-porous polyurethane with a pore-free surface since
neither volatile nor non-volatile by-products are produced by
this reaction. One of the advantages of this method is that the
dicyclocarbonates can be obtained in a sustainable manner, as
also discussed above.160 For instance, recent research was
focused on the synthesis of the dicyclocarbonate reactants
directly from renewable resources such as glycerol.161 The
ecient and atom economic thiolene coupling of allyl-cyclocarbonate with a dithiol yielded the corresponding dicarbonate precursor for polyurethanes. Additionally, the resulting
non-isocyanate polyurethanes show better thermal stability
than conventional polyurethanes due to the absence of thermally unstable biurets and allophanates.162 Moreover, the
lower toxicity, the biodegradability of the cyclic carbonates,
and their high reactivity towards amines make them very
attractive in the field of isocyanate-free PUs, as has been
reviewed by Guan et al.163 Since the polymers obtained possess
molar masses in the range of 1020 kDa, this approach is
usually employed in the synthesis of prepolymers163 or thermosetting coatings.164 Recently, this method was modified by
Guillaume and co-workers in order to be able to synthesize
higher molecular weight polymers.165 Their strategy was based
on the synthesis of ,-bis(cyclic carbonate) telechelic polycarbonate precursors by ring-opening polymerization of
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Tutorial Review
Scheme 23 Polyurethane synthesis via isocyanate- and phosgene-free routes: (a) the polyaddition of bifunctional cyclic carbonate and diamine; (b) the polycondensation of ethylene carbonate, diamines and diols; (c) the cationic ring-opening polymerization of cyclic urethane; (d) the copolymerization of substituted aziridines with carbon dioxide.
polymerisation (ROP) of aliphatic cyclic urethanes or diurethanes (Scheme 23c).169 It is worth mentioning that the fiveand six-membered cyclic urethanes can be prepared in a sustainable manner by reactions of alkylene diamines or amino
alcohols with reagents, such as dialkyl carbonates,170 or with
pressurized carbon dioxide in the absence catalysts.171
However, the drawback of this approach is that not all of the
cyclic urethanes are easy to synthesise, and the ones that are
easily formed are thermodynamically stable and thus less reactive for polymerization.
The replacement of phosgene by CO2, which is abundant,
renewable and environmentally friendly,172 is another emerging non-isocyanate route. Aziridines, nitrogen analogues of
epoxides, can react in supercritical CO2 (scCO2) to give cyclic
urethanes, and polymers consisting of urethane and amine
units (Scheme 23d).173 Thus, substituted aziridines were copolymerized with carbon dioxide to give random copolymers of
polyurethane in the presence or absence of catalysts. This does
not only avoid phosgene and isocyanates, but also highlights
the potential applications of CO2 in the synthesis of industrially useful chemicals as the alternative carbon source. Ihata
et al. reported the reaction of 2-methylaziridine and scCO2 to
give a polymer with a high content of urethane units, which
exhibited a thermoresponsive behaviour (i.e. lower critical
solution temperature, LCST) in water, undergoing a sharp
phase change over a broad range of 4185 C.174 It was
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Scheme 26
New AB-type condensable monomers from various fatty acid derivatives for bio-based polyurethanes synthesis.182
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The cycloaddition of CO2 to epoxides, as discussed in
section 3.2, produces cyclic carbonates and is one of the few
industrial processes that utilize CO2 as a raw material. Within
this concept, the reaction of epoxidized soybean oil with
carbon dioxide has been studied intensively and some
research groups have synthesized PU networks by reacting this
carbonated soybean oil with dierent diamines adopting the
method (a) in Scheme 23.176 Moreover, a wide variety of crosslinked terpene-based renewable polyurethanes were synthesized by curing novel limonene dicarbonates with polyfunctional amines, such as citric aminoamides.177 The limonene
dicarbonates were obtained from limonene dioxide with a
chemical fixation of 34 wt% CO2. Additionally, recently a new
bio-based non-isocyanate urethane was obtained by the reaction of a cyclic carbonate synthesized from a modified linseed
oil and an alkylated phenolic polyamine from cashew nut shell
liquid.178 On the other hand, only a few reports are focused on
the carbonation of vegetable-based precursors with the objective to prepare linear non-isocyanate polyurethanes. For
instance, Cramail and co-workers have synthesized linear nonisocyanate polyurethanes with moderate molar masses by polyaddition of various diamines with linear bis-carbonates,
obtained by the carbonation of bis-epoxidized fatty acid diesters from methyl oleate in scCO2.179
Scheme 28
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As a current trend, fully bio-based thermoplastic polyurethanes with comparable properties to those derived from
commercially available diisocyanates have been synthesized
employing diisocyanates obtained from azelaic and oleic acid
via the Curtius rearrangement (see also section 2.1), thus
avoiding the direct exposure to isocyanates.180 The self-metathesis of oleic acid yielded 1,18-octadec-9-enedioic acid, which
was converted into the necessary diisocyanate derivative by
the aforementioned Curtius rearrangement (Scheme 24b).
Scheme 27 Biobased polyureas synthesis via the metal-free catalysed isocyanate-free route.184
Synthesis of (R)-(+)- and (S)-()-limonene based polyurethanes with various renewable diols in a sustainable manner.88
Scheme 29 (A) Nucleophilic amine-thiol-ene conjugation: aminolysis of the thiolactone ring (a), followed by thia-Michael addition (b). EWG = electron-withdrawing group. (B) Representative AB-monomer, containing a thiolactone and an acrylate group as reactive entities and its subsequent in situ polymerization to yield isocyanate-free functionalized polyurethanes.186
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Scheme 30
A phosgene-free method based on a diacyl hydrazide intermediate was employed in the transformation of fatty acid
derivatives into diisocyanates (Scheme 25), which subsequently
were reacted with commercially available and fatty acid based
diols to obtain partially or fully bio-based polyurethanes with
thermo-mechanical properties close to polyethylene.181
Cramail and co-workers have recently discussed the synthesis of isocyanate-free, fully-biobased polyurethanes via a
one-pot AB-type polyaddition method, either by self-
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catalyst, was carried out either in bulk or in solution to yield
the desired polyurethanes. However, rather low molar mass
polyurethanes were obtained for AB-monomers presented in
Scheme 26A, especially for the carbamate derivative, due to the
presence of secondary hydroxyl functions and the formation of
cyclic structures. Polyurethanes based on methyl oleate and
ricinoleic acid were of amorphous nature due to the pendent
alkyl chains, but displayed well-defined glass transition temperatures, while polyurethanes from AB-type monomers based
on methyl 10-undecenoate displayed semi-crystalline behaviour with well-defined melting transitions.
As a sustainable starting material for polyurethanes synthesis, dicarbamates can also be employed. Dicarbamates can
be synthesized from diamines by reacting them with dicarbonates, such as dimethyl carbonate (see also section 3.2) in an
eco-friendly manner. For instance, Deepa et al. reported that
polyurethanes can be obtained by melt polycondensation of
dicarbamates with diols (or diamines) in the presence of a
metal based catalyst (titanium tetrabutoxide).183 It was
observed that only in the presence of the catalyst high conversions of 97% were achieved. With the aim to propose a more
sustainable method for isocyanate-free polyurethanes/polyureas, Koning and co-workers adopted the aforementioned
procedure (Scheme 27).184 In the corresponding work, TBD
was applied for the first time to prepare polyureas, avoiding
the use of metal catalysts (see also section 3.2).
Along the same idea, Meier and co-workers synthesized
terpene based dicarbamates and studied their behavior in
polycondensation with various renewable diols for the synthesis of renewable polyurethanes with molecular weights up
to 12.6 kDa in a non-isocyanate and phosgene-free manner
(Scheme 28).88 The addition of cysteamine hydrochloride to
(R)-(+)- and (S)-()-limonene was described as an eective way
to obtain the amine functionalized renewable monomers,
which were easily transformed into dicarbamates via a phosgene-free route employing dimethyl carbonate and TBD as a
catalyst.
Other renewable polyurethanes containing carbohydratederived units have also been prepared. For instance, relatively
high molecular weight, linear, stereoregular and optically
active polyurethanes were synthesized by polymerization of a
conveniently substituted 1-amino-1-deoxyalditol prepared from
185
D-galactono-1,4-lactone.
Very recently, nucleophilic aminethiolene conjugation
(Scheme 29) was developed to enable the one-pot, additive-free
synthesis of isocyanate-free polyurethanes.186 According to this
procedure, AB-type monomers containing both an acrylate
and a thiolactone unit are undergoing aminolysis and the
resulting intermediate thiolacrylate reacts in situ via Michael
addition to yield polyurethanes with a large structural variety.
5.
Conclusions
As mentioned in the introduction, a major concern in polyurethane chemistry is the high toxicity of the precursors used,
Tutorial Review
namely phosgene and isocyanate. Thus, research both in
industry and academia is facing increasing demand for environmentally benign and safe processes for the synthesis of
these compounds. Scheme 30 summarized the herein discussed sustainable strategies for phosgene-free polyurethane
synthesis. Obviously, carbon dioxide and monoxide as well as
organic carbonates play an important role in these processes.
In principle, the production of these sustainably prepared
polyurethane precursors is technologically feasible and these
routes are capable of substituting hazardous phosgene.
However, more research and development is certainly necessary before the transition to a greener production of isocyanates, carbamates and thereof derived polyurethanes becomes
reality. With this review we thus aimed to provide a basis for
the discussion and further development of sustainable and
green synthesis routes to carbamates, isocyanates and polyurethanes and of course illustrate the very recent progress in
this field.
Tutorial Review
14
15
16
17
18
19
20
21
Green Chemistry
22
23
24
25
26
817829; (e) K. Liou, K. C. Khemani and F. Wudl, Macromolecules, 1991, 24, 22172220; (f) T. E. Patten and
B. M. Novak, J. Am. Chem. Soc., 1991, 113, 50655066;
(g) T. E. Patten and B. M. Novak, Macromolecules, 1993, 26,
436439; (h) T. E. Patten and B. M. Novak, J. Am. Chem.
Soc., 1996, 118, 19061916; (i) M. S. Rahman, S. Samal
and J.-S. Lee, Macromolecules, 2006, 39, 50095014;
( j) M. S. Rahman, H.-S. Yoo, M. Changez and J.-S. Lee,
Macromolecules, 2009, 42, 39273932.
(a) S. R. Gaonkar, K. Srinivasan and G. Sudesh Kumar,
J. Polym. Sci., Part A: Polym. Chem., 1992, 30, 19111916;
(b) W. Mormann and K. Schmalz, Macromolecules, 1994,
27, 71157120; (c) W. Mormann, K. Schmalz and
A. Grimm, Macromol. Chem. Phys., 1997, 198, 419429;
(d) R. R. Thomas, D. R. Anton, W. F. Graham,
M. J. Darmon and K. M. Stika, Macromolecules, 1998, 31,
45954604; (e) W. Mormann and A. Grimm, J. Polym. Sci.,
Part A: Polym. Chem., 1998, 36, 611616; (f) K. R. Brzezinska,
S. A. Curtin and T. J. Deming, Macromolecules, 2002, 35,
29702976; (g) M. E. Wright, S. Fallis, A. J. Guenthner
and L. C. Baldwin, Macromolecules, 2005, 38, 10014
10021; (h) H. T. T. Duong, V. T. Huynh, P. de Souza
and M. H. Stenzel, Biomacromolecules, 2010, 11, 2290
2299; (i) F. Biedermann, E. A. Appel, J. del Barrio,
T. Gruendling, C. Barner-Kowollik and O. A. Scherman,
Macromolecules, 2011, 44, 48284835; ( j) G. Gody,
C. Rossner, J. Moraes, P. Vana, T. Maschmeyer and
S. Perrier, J. Am. Chem. Soc., 2012, 134, 1259612603.
(a) T. Tsuda and H. Hokazono, Macromolecules, 1993, 26,
17961797; (b) T. Tsuda and A. Tobisawa, Macromolecules,
1994, 27, 59435947; (c) T. Tsuda and A. Tobisawa, Macromolecules, 1995, 28, 13601363.
Toxicity of isocyanates: (a) T. Tsuda and H. Hokazono,
Chem. Res. Toxicol., 1991, 4, 503509; (b) P. Lind,
M. Dalene, V. Lindstrm, A. Grubb and G. Skarping,
Analyst, 1997, 122, 151154; (c) D. Bradley, Anal. Chem.
News Features, 1997, 339A; (d) D. C. Allport, D. S. Gilbert
and S. M. Outterside, in MDI and TDI: Safety, Health and
the Environment: A Source Book and Practical Guide, WileyVCH, Weinheim, 2003; (e) C. Riedlich, Risk of Isocyanate
Exposure in the Construction Industry, CPWR Technical
Report, Yale University, School of Medicine, 2010.
For a review about the synthesis of isocyanates via phosgenation of amines see: (a) H. J. Twitchett and J. Zhang,
Chem. Soc. Rev., 1974, 3, 209230; for selected synthesis
procedures see: (b) R. L. Shriner, W. H. Horne and
R. F. B. Cox, Org. Synth., 1943, Coll. Vol. 2, 453; 1934, 14,
72; (c) R. J. Slocombe, E. E. Hardy, J. H. Saunders and
R. L. Jenkins, J. Am. Chem. Soc., 1950, 72, 18881891;
(d) J. S. Nowick, N. A. Powell, T. M. Nguyen and
G. Noronha, J. Org. Chem., 1992, 57, 73647366;
(e) J. S. Nowick, D. L. Holmes, G. Noronha, E. M. Smith,
T. M. Nguyen and S.-L. Huang, J. Org. Chem., 1996, 61,
39293934.
For a review about diphosgene and triphosgene see:
(a) W. Su, W. Zhong, G. Bian, X. Shi and J. Zhang, Org.
Green Chemistry
27
28
29
30
31
32
33
34
35
Prep. Proced. Int., 2004, 36, 499547; for synthesis procedures see: (b) K. Kurita and Y. Iwakura, Org. Synth.,
1988, Coll. Vol. 6, 715; 1979, 59, 195 (c) S. Th. Sigurdsson,
B. Seeger, U. Kutzke and F. Eckstein, J. Org. Chem., 1996,
61, 38833884; (d) J. H. Tsai, L. R. Takaoka, N. A. Powell
and J. S. Nowick, Org. Synth., 2004, Coll. Vol. 10, 544;
2002, 78, 220.
(a) H.-J. Knlker, T. Braxmeier and G. Schlechtingen,
Angew. Chem., Int. Ed. Engl., 1995, 34, 24972500;
(b) H.-J. Knlker and T. Braxmeier, Synlett, 1997, 925928.
(a) A. Wurtz, Liebigs Ann., 1849, 71, 326342;
(b) A. W. Hofmann, Liebigs Ann., 1850, 74, 133;
(c) K. H. Slotta and L. Lorenz, Chem. Ber., 1925, 58, 1320
1323.
B. Akhlaghinia, Synthesis, 2005, 19551958.
(a) C. F. H. Allen and A. Bell, Org. Synth., 1955, Coll. Vol.
3, 846; 1944, 24, 94; (b) C. Kaiser and J. Weinstock, Org.
Synth., 1988, Coll. Vol. 6, 95; 1979, 59, 1; (c) P. J. Jessup,
C. B. Petty, J. Roos and L. E. Overman, Org. Synth., 1988,
Coll. Vol. 6, 910; 1971, 51, 48; (d) J. W. Gilman and
Y. A. Otonari, Synth. Commun., 1993, 23, 335341;
(e) L. Marinescu, J. Thinggaard, I. B. Thomsen and
M. Bols, J. Org. Chem., 2003, 68, 94539455;
(f ) E. A. Englund, H. N. Gopi and D. H. Appella, Org. Lett.,
2004, 6, 213215; (g) V. V. Sureshbabu, B. S. Patil and
R. Venkataramanarao, J. Org. Chem., 2006, 71, 76977705.
(a) R. G. Arnold, J. A. Nelson and J. J. Verbanc, J. Chem.
Educ., 1957, 34, 158165; (b) T. Mukaiyama and
H. Nohira, J. Org. Chem., 1961, 26, 782784;
(c) V. I. Gorbatenko and L. I. Samarai, Synthesis, 1980, 85
110; (d) W. J. Middleton, J. Org. Chem., 1984, 49, 4541
4543; (e) P. Dub, N. F. Fine Nathel, M. Vetelino,
M. Couturier, C. Larrive Aboussafy, S. Pichette,
M. L. Jorgensen and M. Hardink, Org. Lett., 2009, 11,
56225625.
(a) F. Minisci, F. Coppa and F. Fontana, J. Chem. Soc.,
Chem. Commun., 1994, 679679; (b) F. Minisci, F. Fontana,
F. Coppa and Y. M. Yan, J. Org. Chem., 1995, 60, 5430
5433.
T. Lesiak and K. Seyda, J. Prakt. Chem., 1979, 321, 161
163.
(a) T. Chancellor and C. Morton, Synthesis, 1994, 1023
1025; (b) K. Kobayashi, K. Yoneda, T. Mizumoto,
H. Umakoshi, O. Morikawa and H. Konishi, Tetrahedron
Lett., 2003, 44, 47334736; (c) D. Prosperi, S. Ronchi,
L. Lay, A. Rencurosi and G. Russo, Eur. J. Org. Chem.,
2004, 395405; (d) B. Westermann, D. Michalik, A. Schaks,
O. Kreye, Ch. Wagner, K. Merzweiler and L. A. Wessjohann,
Heterocycles, 2007, 73, 863872.
For a review about interconversion of carbamates/isocyanates see: (a) E. Delebecq, J.-P. Pascault, B. Boutevin and
F. Ganachaud, Chem. Rev., 2013, 113, 80118; selected
thermolysis procedures of aryl carbamates to isocyanates:
(b) Y. Wang, X. Zhao, F. Li, S. Wang and J. Zhang, J. Chem.
Technol. Biotechnol., 2001, 76, 857861; (c) X. Zhao,
Y. Wang, S. Wang, H. Yang and J. Zhang, Ind. Eng. Chem.
Tutorial Review
36
37
38
39
40
41
42
43
Tutorial Review
44
45
46
47
48
49
Green Chemistry
50
51
52
53
54
Green Chemistry
55
56
57
58
59
60
61
Tutorial Review
62 E. M. Burgess, H. R. Penton Jr., E. A. Taylor and
W. M. Williams, Org. Synth., 1988, Coll. Vol. 6, 788; 1977,
56, 40.
63 (a) S. Khapli, S. Dey and D. Mal, J. Indian Inst. Sci., 2001,
81, 461476; (b) G. M. Atkins Jr. and E. M. Burgess, J. Am.
Chem. Soc., 1968, 90, 47444745; (c) E. M. Burgess,
H. R. Penton Jr. and E. A. Taylor, J. Org. Chem., 1973, 38,
2631; (d) S. Burckhardt, Synlett, 2000, 559559.
64 K. C. Nicolaou, X. Huang, S. A. Snyder, P. Bheema Rao,
M. Bella and M. V. Reddy, Angew. Chem., Int. Ed., 2002, 41,
834838.
65 M. R. Wood, J. Y. Kim and K. M. Books, Tetrahedron Lett.,
2002, 43, 38873890.
66 M. Mamaghani and A. Badrian, Tetrahedron Lett., 2004,
45, 15471550.
67 A. R. Modarresi-Alam, F. Khamooshi, M. Nasrollahzadeh
and H. A. Amirazizi, Tetrahedron, 2007, 63, 87238726.
68 (a) E. F. Scriven and K. Turnbull, Chem. Rev., 1988, 88,
297366; (b) W. F. Gilmore and H.-J. Lin, J. Org. Chem.,
1978, 43, 45354537; (c) P. J. Jessup, C. B. Petty, J. Roos
and L. E. Overman, Org. Synth., 1988, Coll. Vol. 6, 95;
1979, 59, 1; (d) L. S. Richter and S. Andersen, Tetrahedron
Lett., 1998, 39, 87478750; (e) T. Tada, Y. Ishida and
K. Saigo, Synlett, 2007, 235238; (f ) P. H. Dussault and
C. Xu, Tetrahedron Lett., 2004, 45, 74557457.
69 (a) H. Lebel and O. Leogane, Org. Lett., 2005, 7, 4107
4110; (b) D. Sawada, S. Sasayama, H. Takahashi and
S. Ikegami, Tetrahedron Lett., 2006, 47, 72197223;
(c) H. Lebel and O. Leogane, Org. Lett., 2006, 8, 5717
5720; (d) D. Sawada, S. Sasayama, H. Takahashi and
S. Ikegami, Tetrahedron, 2008, 64, 87808788;
(e) O. Leogane and H. Lebel, Org. Synth., 2009, 86, 113
120; (f) O. Leogane and H. Lebel, Synthesis, 2009, 1935
1940; (g) J. K. Augustine, A. Bombrun, A. B. Mandal,
P. Alagarsamy, R. N. Atta and P. Selvam, Synthesis, 2011,
14771483.
70 E. W. Wallis and J. F. Lane, Org. React., 1946, 3, 267306.
71 (a) M. R. Almond, J. B. Stimmel, E. A. Thompson and
G. M. Loudon, Org. Synth., 1993, Coll. Vol. 8, 132; 1988,
66, 132; (b) R. M. Moriarty, C. J. Chany II, R. K. Vaid,
O. Prakash and S. M. Tuladhar, J. Org. Chem., 1993, 58,
24782482; (c) A. A. Zagulyaeva, C. T. Banek,
M. S. Yusubov and V. V. Zhdankin, Org. Lett., 2010, 12,
46444647; (d) A. Yoshimura, M. W. Luedtke and
V. V. Zhdankin, J. Org. Chem., 2012, 77, 20872091.
72 (a) X. Huang, M. Seid and J. W. Keillor, J. Org. Chem.,
1997, 62, 74957496; (b) X. Huang and J. W. Keillor, Tetrahedron Lett., 1997, 38, 313316; (c) J. W. Keillor and
X. Huang, Org. Synth., 2004, Coll. Vol. 10, 549; 2002, 78,
234; (d) A. Palmieri, S. V. Ley, K. Hammond, A. Polyzos
and I. R. Baxendale, Tetrahedron Lett., 2009, 50, 3287
3289.
73 (a) J. Yamaguchi, K. Hoshi and T. Takeda, Chem. Lett.,
1993, 12731274; (b) Y. Matsumura, T. Maki and Y. Satoh,
Tetrahedron Lett., 1997, 38, 88798882; (c) G. A. Hiegel and
T. J. Hogenauer, Synth. Commun., 2005, 35, 20912098;
Tutorial Review
74
75
76
77
78
79
Green Chemistry
80 V. Nair, S. C. Mathew, A. T. Bijua and E. Suresh, Tetrahedron Lett., 2007, 48, 90189020.
81 (a) K. Takeda, Y. Akagi, A. Saiki, T. Tsukahara and
H. Ogura, Tetrahedron Lett., 1983, 24, 45694572;
(b) A. K. Ghosh, T. T. Duong, S. P. McKee and
W. J. Thompson, Tetrahedron Lett., 1992, 33, 27812784.
82 M. Simon, C. Csunderlik, L. Cotarca, M. T. Cproiu,
I. Neda, M. C. Turoczi and R. Volpicelli, Synth. Commun.,
2005, 35, 14711479.
83 V. V. Sureshbabu and H. P. Hemantha, Synth. Commun.,
2009, 39, 35553566.
84 M. Pittelkow, R. Lewinsky and J. B. Christensen, Synthesis,
2002, 21952202.
85 C. Han and J. A. Porco Jr., Org. Lett., 2007, 9, 15171520.
86 E. Reixach, N. Bonet, F. X. Rius-Ruiz, S. Wershofen and
A. Vidal-Ferran, Ind. Eng. Chem. Res., 2010, 49, 63626366.
87 D.-L. Sun, S.-J. Xie, J.-R. Deng, C.-J. Huang, E. Ruckenstein
and Z.-S. Chao, Green Chem., 2010, 12, 483490.
88 M. Firdaus and M. A. R. Meier, Green Chem., 2013, 15,
370380.
89 H. Mutlu, J. Ruiz, S. C. Solleder and M. A. R. Meier, Green
Chem., 2012, 14, 17281735.
90 (a) I. Vauthey, F. Valot, C. Gozzi, F. Fache and M. Lemaire,
Tetrahedron Lett., 2000, 41, 63476350; (b) Y. Wang,
X. Zhao, F. Li, S. Wang and J. Zhang, J. Chem. Technol. Biotechnol., 2001, 76, 857861; (c) N. Nagaraju and
G. Kuriakose, Green Chem., 2002, 4, 269271;
(d) M. Curini, F. Epifano, F. Maltese and O. Rosati, Tetrahedron Lett., 2002, 43, 48954897; (e) T. Sima, S. Guo,
F. Shi and Y. Deng, Tetrahedron Lett., 2002, 43, 81458147;
(f ) M. Distaso and E. Quaranta, Tetrahedron, 2004, 60,
15311539; (g) T. Baba, A. Kobayashi, Y. Kawanami,
K. Inazu, A. Ishikawa, T. Echizenn, K. Murai, S. Aso and
M. Inomata, Green Chem., 2005, 7, 159165; (h) F. Li,
J. Miao, Y. Wang and X. Zhao, Ind. Eng. Chem. Res., 2006,
45, 48924897; (i) S. Wang, G. Zhang, X. Ma and J. Gong,
Ind. Eng. Chem. Res., 2007, 46, 68586864; ( j) D. W. Kim,
E. S. Huh, S. D. Park, L. V. Nguyen, M. D. Nguyen,
H. S. Kim, M. Cheong and D. Q. Nguyen, Adv. Synth.
Catal., 2010, 352, 440446; (k) Y. Pei, H. Li, H. Liu and
Y. Zhang, Ind. Eng. Chem. Res., 2011, 50, 19551961.
91 M. Pozo and V. Gotor, Tetrahedron, 1993, 49, 43214326.
92 V. Gotor-Fernndez, M. Ferrero, S. Fernndez and
V. Gotor, J. Org. Chem., 1999, 64, 75047515.
93 I. Lavandera, S. Fernndez, M. Ferrero and V. Gotor,
J. Org. Chem., 2004, 69, 17481751.
94 R. Morn-Ramallal, V. Gotor-Fernndez, P. Laborda,
F. J. Sayago, C. Cativiela and V. Gotor, Org. Lett., 2012, 14,
16961699.
95 (a) L. F. Garca-Alles, F. Mors and V. Gotor, Tetrahedron
Lett., 1993, 34, 63376338; (b) M. Soledad de Castro,
P. Domnguez and J. V. Sinisterra, Tetrahedron Lett., 1993,
34, 63376338.
96 (a) M. Selva, P. Tundo and A. Perosa, Tetrahedron Lett.,
2002, 43, 12171219; (b) M. Selva, P. Tundo, A. Perosa and
F. DallAcqua, J. Org. Chem., 2005, 70, 27712777.
Green Chemistry
97 (a) J. E. Hallgren, G. M. Lucas and R. O. Matthews, J. Organomet. Chem., 1981, 204, 135138; (b) A.-A. G. Shaikh and
S. Sivaram, Ind. Eng. Chem. Res., 1992, 31, 11671170;
(c) Z.-h. Fu and Y. Ono, J. Mol. Catal. A: Chem., 1997, 118,
293299; (d) W. B. Kim and J. S. Lee, Catal. Lett., 1999, 59,
8388; (e) Z. Weiqing, Z. Xinqiang, W. Yanji and Z. Jiyan,
Appl. Catal., A, 2004, 260, 1924; (f ) G. Fan, S.-i. Fujita,
B. Zou, M. Nishiura, X. Meng and M. Arai, Catal. Lett.,
2009, 133, 280287; (g) G. Fan, Z. Wang, B. Zou and
M. Wang, Fuel Process. Technol., 2011, 92, 10521055;
(h) L. Wei, D. Zhiping, Y. Hua, T. Qifeng and W. Yuanxin,
Chin. J. Chem. Eng., 2013, 21, 813.
98 For reviews about the synthesis of organic carbonates see:
(a) A.-A. G. Shaikh and S. Sivaram, Chem. Rev., 1996, 96,
951976; (b) Y. P. Patil, P. J. Tambade, S. R. Jagtap and
B. M. Bhanage, Front. Chem. Eng. China, 2010, 4, 213
235.
99 (a) T. Sakakura, Y. Saito, M. Okano, J.-C. Choi and T. Sako,
J. Org. Chem., 1998, 63, 70957096; (b) M. Selva, P. Tundo,
A. Perosa and F. DallAcqua, Organometallics, 2000, 19,
45634567; (c) J.-C. Choi, L.-N. He, H. Yasuda and
T. Sakakura, Green Chem., 2002, 4, 230234.
100 (a) S.-ichiro. Fujita, B. M. Bhanage, Y. Ikushima and
M. Arai, Green Chem., 2001, 3, 8791; (b) Z. Hou, B. Han,
Z. Liu, T. Jiang and G. Yang, Green Chem., 2002, 4, 467
471.
101 M. Honda, A. Suzuki, B. Noorjahan, K. Fujimoto,
K. Suzuki and K. Tomishige, Chem. Commun., 2009, 4596
4598.
102 V. Eta, P. Mki-Arvela, A.-R. Leino, K. Kords, T. Salmi,
D. Y. Murzin and J.-P. Mikkola, Ind. Eng. Chem. Res., 2010,
49, 96099617.
103 Z.-F. Zhang, Z.-W. Liu, J. Lu and Z.-T. Liu, Ind. Eng. Chem.
Res., 2011, 50, 19811988.
104 (a) K. Kohno, J.-C. Choi, Y. Ohshima, H. Yasuda and
T. Sakakura, ChemSusChem, 2008, 1, 186188; (b) B. Fan,
H. Li, W. Fan, J. Zhang and R. Li, Appl. Catal., A, 2010,
372, 94102; (c) D. Ballivet-Tkatchenko, F. Bernard,
F. Demoisson, L. Plasseraud and S. R. Sanapureddy,
ChemSusChem, 2011, 4, 13161322.
105 Z. Kricsfalussy, H. Waldmann and H.-J. Traenckner, Ind.
Eng. Chem. Res., 1998, 37, 865866.
106 H. Itoh, Y. Watanabe, K. Moric and H. Umino, Green
Chem., 2003, 5, 558562.
107 G. Rebmann, V. Keller, M. J. Ledoux and N. Keller, Green
Chem., 2008, 10, 207213.
108 D. Zhu, F. Mei, L. Chen, T. Li, W. Mo and G. Li, Energy
Fuels, 2009, 23, 23592363.
109 (a) S. A. Anderson and T. W. Root, J. Mol. Catal. A: Chem.,
2004, 220, 247255; (b) M. Richter, M. J. G. Fait, R. Eckelt,
E. Schreier, M. Schneider, M.-M. Pohl and R. Fricke, Appl.
Catal., B, 2007, 73, 269281; (c) W.-S. Dong, X. Zhou,
C. Xin, C. Liu and Z. Liu, Appl. Catal., A, 2008, 334, 100
105; (d) L. Zhong, W. Ruiyu, Z. Huayan and X. Kechang,
Fuel, 2010, 89, 13391343; (e) J. Engeldinger, C. Domke,
M. Richter and U. Bentrup, Appl. Catal., A, 2010, 382,
Tutorial Review
110
111
112
113
114
115
116
117
118
119
120
121
122
123
124
Tutorial Review
125 G. Shapiro and M. Marzi, J. Org. Chem., 1997, 62, 7096
7097.
126 O. Kreye, S. Wald and M. A. R. Meier, Adv. Synth. Catal.,
2013, 355, 8186.
127 S. Fukuoka, M. Chono and M. Kohno, J. Chem. Soc.,
Chem. Commun., 1984, 399400.
128 S. Fukuoka, M. Chono and M. Kohno, J. Org. Chem., 1984,
49, 14581460.
129 H. Alper and F. W. Hartstock, J. Chem. Soc., Chem.
Commun., 1985, 11411142.
130 T. W. Leung and B. D. Dombek, J. Chem. Soc., Chem.
Commun., 1992, 205206.
131 I. Pri-Bar and J. Schwartz, J. Org. Chem., 1995, 60, 8124
8125.
132 B. Wan, S. Liao and D. Yu, React. Funct. Polym., 2000, 45,
5559.
133 F. Shi, Y. Deng, T. SiMa and H. Yang, J. Catal., 2001, 203,
525528.
134 F. Shi, J. Peng and Y. Deng, J. Catal., 2003, 219, 372375.
135 (a) F. Shi and Y. Deng, Chem. Commun., 2001, 443444;
(b) F. Shi and Y. Deng, J. Catal., 2002, 211, 548551.
136 R. G. de Leon, I. Yamanaka and K. Otsuka, Chem. Lett.,
2002, 764765.
137 (a) T. Mizuno, J. Takahashi and A. Ogawa, Tetrahedron,
2002, 58, 78057808; (b) A. Orejn, A. M. Masdeu-Bult,
P. Salagre, S. Castilln, C. Claver, A. Padilla, B. Almena
and F. Luis Serrano, Ind. Eng. Chem. Res., 2008, 47, 8032
8036; (c) G. Li, L. Chen, J. Bao, T. Li and F. Mei, Appl.
Catal., A, 2008, 346, 134139; (d) P. Giannoccaro,
A. Dibenedetto, M. Gargano, E. Quaranta and M. Aresta,
Organometallics, 2008, 27, 967975; (e) X. Zhang, H. Jing
and G. Zhang, Synth. Commun., 2010, 40, 16141624.
138 E. Katchalski, C. Berliner-Klibanski and A. Berger, J. Am.
Chem. Soc., 1951, 73, 18291831.
139 Y. Yoshida and S. Inoue, Chem. Lett., 1977, 13751376.
140 (a) Y. Yoshida and S. Inoue, Chem. Lett., 1978, 139140;
(b) T. Asano, N. Saito, S. Ito, K. Hatakeda and T. Toda,
Chem. Lett., 1978, 311312; (c) Y. Yoshida and S. Inoue,
Bull. Chem. Soc. Jpn., 1978, 51, 559560; (d) T. Iwasaki,
N. Kihara and T. Endo, Bull. Chem. Soc. Jpn., 2000, 73,
713719.
141 F. Kojima, T. Aida and S. Inoue, J. Am. Chem. Soc., 1986,
108, 391395.
142 (a) Y. Yoshida, S. Ishii and T. Yamashita, Chem. Lett.,
1984, 15711572; (b) Y. Yoshida, S. Ishii, M. Watanabe
and T. Yamashita, Bull. Chem. Soc. Jpn., 1989, 62, 1534
1538; (c) M. Yoshida, N. Hara and S. Okuyama, Chem.
Commun., 2000, 151152; (d) R. Srivastava, D. Srinivas and
P. Ratnasamy, Appl. Catal., A, 2005, 289, 128134;
(e) D. Chaturvedi and S. Ray, Monatsh. Chem., 2006, 137,
201206.
143 (a)
K.
J.
Butcher,
Synlett,
1994,
825826;
(b) R. N. Salvatore, V. L. Flanders, D. Ha and K. W. Jung,
Org. Lett., 2000, 2, 27972800; (c) R. N. Salvatore,
J. A. Ledger and K. W. Jung, Tetrahedron Lett., 2001, 42,
60236025; (d) R. N. Salvatore, S. I. Shin, A. S. Nagle and
Green Chemistry
144
145
146
147
148
149
150
151
152
153
154
155
156
157
158
Green Chemistry
159 C. Hahn, H. Keul and M. Mller, Polym. Int., 2012, 61,
10481060.
160 S.-H. Pyo, P. Persson, M. A. Mollaahmad, K. Srensen,
S. Lundmark and R. Hatti-Kau, Pure Appl. Chem., 2012, 84,
637661.
161 S. Benyahya, M. Desroches, R. Auvergne, S. Carlotti,
S. Caillol and B. Boutevin, Polym. Chem., 2011, 2, 2661
2667.
162 O. L. Figovsky and L. D. Shapovalov, Macromol. Symp.,
2002, 187, 325332.
163 J. Guan, Y. H. Song, Y. Lin, X. Z. Yin, M. Zuo, Y. H. Zhao,
X. L. Tao and Q. Zheng, Ind. Eng. Chem. Res., 2011, 50,
65176527.
164 D. C. Webster and A. L. Crain, Prog. Org. Coat., 2000, 40,
275282.
165 M. Helou, J.-F. Carpentier and S. M. Guillaume, Green
Chem., 2011, 13, 266271.
166 G. Rokicki and A. Piotrowska, Polymer, 2002, 43, 2927
2935.
167 Y. Yanagishita, M. Kato, K. Toshima and S. Matsumura,
ChemSusChem, 2008, 1, 133142.
168 B. Ochiai and T. Utsuno, J. Polym. Sci., Part A: Polym.
Chem., 2013, 51, 525533.
169 Examples of ROP of cyclic aliphatic urethanes/diurethanes: (a) H. K. Hall and A. K. Schneider, J. Am. Chem.
Soc., 1958, 80, 64096412; (b) H. K. Hall and A. Elshekeil,
Polym. Bull., 1980, 3, 233239; (c) S. Negen, H. Keul and
H. Hocker, Macromol. Rapid Commun., 1996, 17, 373382;
(d) S. Negen, H. Keul and H. Hocker, Macromolecules,
1997, 30, 12891297; (e) S. Negen, H. Keul and
H. Hocker, Macromol. Chem. Phys., 1998, 199, 197206;
(f ) F. Bachmann, J. Reimer, M. Ruppenstein and
J. Thiem, Macromol. Rapid Commun., 1998, 19, 2126;
(g) F. Schmitz, H. Keul and H. Hcker, Macromol.
Chem. Phys., 1998, 199, 3948; (h) S. Negen,
J. Kuan, T. Fey, H. Keul and H. Hcker, Macromol.
Chem. Phys., 2000, 201, 21082114.
170 (a) J. Kuan, H. Keul and H. Hcker, Macromolecules,
2001, 34, 389395; (b) E. Fischer and H. Koch, Justus
Liebigs Ann. Chem., 1886, 232, 222228; (c) F. F. Ebetino,
US Pat., 3 254 075, 1966; (d) Y. Fu, T. Baba and Y. Ono,
J. Catal., 2001, 197, 9197; (e) T. Baba, A. Kobayashi,
T. Yamauchi, H. Tanaka, S. Aso, M. Inomata and
Y. Kawanami, Catal. Lett., 2002, 82, 193197;
(f ) V. S. N. Parimi, A. S. Chida, R. Srinivasan,
M. Chandrasekharam and A. K. Singh, Synth. Commun.,
2001, 31, 20432046.
Tutorial Review
171 B. M. Bhanage, S. Fujita, Y. Ikushima and M. Arai, Green
Chem., 2003, 5, 340342.
172 T. Sakakura, J.-C. Choi and H. Yasuda, Chem. Rev., 2007,
107, 23652387.
173 R. D. Lundberg, S. Albans and D. R. Montgomery, US Pat.,
3 523 924, 1970.
174 O. Ihata, Y. Kayaki and T. Ikariya, Angew. Chem., Int. Ed.,
2004, 43, 717719.
175 O. Ihata, Y. Kayaki and T. Ikariya, Kobunshi Ronbunshu,
2005, 62, 196199.
176 (a) I. Javni, P. H. Doo and Z. S. Petrovic, J. Appl. Polym.
Sci., 2008, 108, 38673875; (b) B. Tamami, S. Sohn and
G. L. Wilkes, J. Appl. Polym. Sci., 2004, 92, 883891;
(c) G. L. Wilkes, S. Sohn and B. Tamami, US Pat.,
2004230009 (A1), 2004; (d) Z. Li, Y. Zhao, S. Yan, X. Wang,
M. Kang, J. Wang and H. Xiang, Catal. Lett., 2008, 123,
246251; (e) O. Trn, N. Kayaman-Apohan, M. Kahraman,
Y. Menceloglu and A. Gngr, J. Sol-Gel Sci. Technol., 2008,
47, 290299.
177 M. Bhr, A. Bitto and R. Mlhaupt, Green Chem., 2012, 14,
14471454.
178 A. R. Mahendran, N. Aust, G. Wuzella, U. Mller and
A. Kandelbauer, J. Polym. Environ., 2012, 20, 926931.
179 A. Boyer, E. Cloutet, T. Tassaing, B. Gadenne, C. Alfos and
H. Cramail, Green Chem., 2010, 12, 22052213.
180 (a) L. Hojabri, X. Kong and S. S. Narine, J. Polym. Sci., Part
A: Polym. Chem., 2010, 48, 33023310; (b) L. Hojabri,
X. Kong and S. S. Narine, Biomacromolecules, 2009, 10,
884891; (c) L. Hojabri, X. Kong and S. S. Narine, Biomacromolecules, 2010, 11, 911918.
181 A. S. More, T. Lebarb, L. Maisonneuve, B. Gadenne,
C. Alfos and H. Cramail, Eur. Polym. J., 2013, 49, 823833.
182 (a) D. V. Palaskar, A. Boyer, E. Cloutet, C. Alfos and
H. Cramail, Biomacromolecules, 2010, 11, 12021211;
(b) A. S. More, B. Gadenne, C. Alfos and H. Cramail, Green
Chem., 2012, 3, 15941605; (c) A. S. More, L. Maisonneuve,
T. Lebarbe, B. Gadenne, C. Alfos and H. Cramail,
Eur. J. Lipid Sci. Technol., 2013, 115, 6175.
183 P. Deepa and M. Jayakannan, J. Polym. Sci., Part A: Polym.
Chem., 2008, 46, 24452458.
184 D. Tang, D.-J. Mulder, B. A. J. Noordover and
C. E. Koning, Macromol. Rapid Commun., 2011, 32, 1379
1385.
185 R. V. Gomez and O. Varela, Macromolecules, 2009, 42,
81128117.
186 P. Espeel, F. Goethals, F. Driessen, L.-T. T. Nguyen and
F. E. DuPrez, Polym. Chem., 2013, 4, 24492456.