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Green Chemistry

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Sustainable routes to polyurethane precursors


Cite this: Green Chem., 2013, 15, 1431

Oliver Kreye, Hatice Mutlu and Michael A. R. Meier*


Environmentally friendly products and procedures are being developed both in industry and academia,
mainly due to the depletion of fossil resources and the growing global awareness of the need to protect
the environment. Thus, since polyurethanes represent a highly demanded class of polymers, straightfor-

Received 6th March 2013,


Accepted 4th April 2013

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

sustainable routes towards polyurethanes and their precursors.

1.

Introduction

Since Otto Bayer and co-workers reported the first polyaddition


reaction of diols and diisocyanates to polyurethanes (PUR) in
1947, this class of polymers has found various applications in
all areas of our daily life.1 In light of the benefits that polyurethanes oer through their versatile manufacturing possibilities and overall performance, numerous applications in
dierent fields (i.e. medical,2 automotive and industrial) have
shown high growth rates for a long time.3 Common manifestations of polyurethane formulations are soft or rigid foams,
elastomers, as well as hard solid or flexible plastics.4 In 2011,
the share of polyurethanes within all polymers on the European market was 7.0% (Fig. 1).5 This demand can be attributed
to their light weight, excellent strength to weight ratio, energy
absorbing performance, and comfort features. Their versatility
is instrumental in achieving the mechanical properties
required for specific applications.6
Despite the desirable features of PUR, their industrial synthesis involves highly toxic and hazardous reagents.7,8 The
typical synthesis is carried out by polyaddition reactions of diisocyanates with diols ( polyols) in the presence of tertiary
amines, especially 1,4-diazabicyclo[2.2.2]octane (DABCO), as a
basic catalyst (Scheme 1). Most commonly, diisocyanates are
synthesized by reaction of phosgene with the corresponding
amines. The most frequently used diisocyanates are methylene
diphenyl diisocyanate (MDI) and toluene diisocyanate (TDI),
with demands of 61.3% and 34.1%, respectively. Moreover, aliphatic representatives such as hexamethylene diisocyanate
(HDI) and isophorone diisocyanate (IPDI) are often used,
although with a smaller demand of 3.4% and 1.2%,

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

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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

Fig. 1 Share of major polymer materials in the European plastic market in


2011.5

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Tutorial Review

Scheme 1 Frequently used diisocyanate monomers and their polyaddition


reaction with diols to polyurethanes.

greener polyurethane synthesis avoiding phosgene at any stage


of production. Of exceeding importance is the production of
di- and polyisocyanates, both as commodities and as specialties, for the production of polyurethanes. Thus, in this context,
we summarize classic synthetic routes to isocyanates and carbamates as well as modern and promising possibly ecofriendly ways to these compounds. Finally, some recent developments in the synthesis of renewable polyurethanes are
discussed.

2.

Isocyanates

Isocyanates (RNvCvO) are esters of the unstable isocyanic


acid and are known for their high reactivity towards nucleophilic additions.12 Isocyanates dimerize in an equilibrium reaction to uretidones (Scheme 2). This reaction is catalyzed by
phosphanes as well as tertiary amine bases (e.g. pyridine).
Better known is their trimerisation to isocyanurates ( perhydro1,3,5-triazine-2,4,6-triones) catalyzed by phosphanes, amine
bases, as well as alkali metal salts of formic or acetic acid.
Modern protocols report a very eective cyclotrimerization by
applying alkali metal fluorides, N-heterocyclic carbenes
(NHCs), or diverse other catalysts and methods.13 Isocyanurates play an important role in polymer chemistry for the synthesis of polyisocyanurate foams (PIRs). These foams oer a
high rigidity and are used, for instance, for thermal

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Scheme 2

Common reactions of isocyanates.

insulation.14 The hydrolysis of isocyanates under acidic or


basic conditions gives unstable carbamic acid derivatives,
which immediately undergo decarboxylation to primary
amines. Unfortunately, in 1984 the uncontrolled reaction of
methyl isocyanate with water led to one of the worst chemical
industry disasters. In the Indian city Bhopal, approximately
8000 people died within two weeks due to gas-related diseases
caused by inhalation of methyl isocyanate and thereof derived
methyl amine.15 The certainly most common reaction of isocyanates is their conversion to carbamates (urethanes) with
alcohols.16 To increase the reaction rate, tertiary amine bases
like 1,4-diazabicyclo[2.2.2]octane (DABCO) or 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) are used as catalysts. With primary or
secondary amines, isocyanates react readily to urea derivatives.17 Furthermore, isocyanates can react to carbodiimides by
applying phospholene 1-oxides as catalysts.18 In modern procedures, the conversion of carboxylic acids or thioacids with
isocyanates to amides under base influence is described.19
Besides this, it is worth noting that during the last few
decades numerous cycloaddition reactions of isocyanates, catalyzed by transition metals, were described.20
The application of isocyanates in polymer chemistry is
focused on the production of polyurethanes, but besides this,
anionic polymerization strategies aord the synthesis of rigid
polyisocyanates.21 Moreover, isocyanate-grafted polymers are
described for additional functionalization and for polymer
conjugation.22 Interesting copolymers were synthesized by
cycloaddition of isocyanates with multifunctionalized alkyne
monomers.23

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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.

Tutorial Review

Conventional synthesis routes to isocyanates.

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

This journal is The Royal Society of Chemistry 2013

Green Chem., 2013, 15, 14311455 | 1433

2.1.

Conventional synthesis of isocyanates

Several dierent strategies for the synthesis of isocyanates are


known.12 The most common and also industrially applied procedure is the treatment of primary amines with phosgene
under release of two equivalents of hydrogen chloride
(Scheme 3a).25 To avoid the application of extremely toxic

Scheme 3

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Tutorial Review

Scheme 4

Free radical synthesis of isocyanates from oxalic acid monoamides.

Scheme 5

Synthesis of isocyanates from formamides.

acid monoamides (Scheme 4).32 With an excess of ammonium


persulfate in the presence of catalytic amounts of silver(I) and
copper(II) salts, carbamoyl radicals are formed, followed by
decarboxylation to isocyanates. Unfortunately, this method is
also limited to small-scale synthesis. The synthesis of oxalic
acid monoamides is extensive and the use of excess
ammonium persulfate makes this process unsustainable.
In 1979, Lesiak and Seyda described a method for the synthesis of isocyanates from formamides.33 After optimization,
they found that the highest yields were obtained if formamides
were heated with an excess of bromine in benzene in the presence of 1,4-diazabicyclo[2.2.2]-octane (DABCO) to obtain isocyanates in moderate yields (Scheme 5). The addition of
DABCO is necessary to bind the released hydrogen bromide.
The applied harsh conditions are limited to non-sensitive formamides and the used halogens are not suitable for a sustainable procedure. However, the idea to use formamides in an
environmentally benign dehydrogenation process for the synthesis of isocyanates is promising, because formamides are
easily accessible in quantitative yields by heating primary
amines in recyclable formic acid or formic acid esters.34 A
challenge is certainly to find a green way for the dehydrogenation of these formamides.
Other procedures for the generation of isocyanates start
from carbamates (urethanes). For detailed synthesis procedures of carbamates, see sections 3.1 and 3.2. The decomposition of carbamates applying temperatures above 250 C in
the presence of dierent catalysts led directly to isocyanates.35
However, this pyrolysis process is limited to N-aryl carbamates
(see Scheme 10 in section 2.2). The thermal fragmentation of
aliphatic carbamates resulted in many side reactions. For this
reason, mild cleavage protocols were developed using silane
and boron compounds in the presence of tertiary amine compounds (Scheme 6). Numerous silanes were investigated and
diiodosilane gave the best results under mildest conditions.36
Also boranes can be used for a rapid and ecient cleavage of
carbamates. First experiments were performed by applying
chlorocatecholborane, but the much cheaper boron trichloride
also eciently cleaves carbamates to isocyanates in nearly
quantitative yields.37 Also these cleavage procedures are
limited to the laboratory scale. Due to the relatively high price
of silanes and toxicity of boron halogenides, their applications

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Scheme 6

Synthesis of isocyanates from carbamates.

in industrial processes are not reasonable and sustainable.


Instead, the challenge to find highly ecient catalysts for the
thermal decomposition of aryl- as well as alkylcarbamates to
obtain isocyanates quantitatively should be accepted.
2.2. Modern, sustainable and promising pathways to
isocyanates
A promising and sustainable pathway to aryl isocyanates is the
reductive carbonylation of nitro arenes.16a,38 For the synthesis
of TDI and MDI, this is an excellent alternative method compared to the phosgenation of the corresponding amines.
Already in 1967, Hardy and Benett described the direct conversions of aromatic nitro compounds with carbon monoxide and
Rh/C catalysts at high pressure and temperatures (Scheme 7).39
Several catalysts can be used for this thermodynamically

Scheme 7

Reductive carbonylation of nitro arenes to isocyanates.

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Scheme 9

Scheme 8 Reductive carbonylation of nitro arenes to carbamates followed by


thermal decomposition to isocyanates.

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

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Oxidation of isonitriles to isocyanates.

the earlier described procedures used toxic or non-sustainable


oxidation agents such as mercuric oxide, lead tetraacetate,
ozone as well as halogen- and acid-catalyzed oxidations with
DMSO and pyridine N-oxide.49
A future goal could be to find other mild and environmentally benign oxidation processes to obtain isocyanates from
isonitriles. The drawback is certainly the lack of a sustainable
route to isonitriles. Common procedures to obtain isonitriles
are the dehydration of N-formamides with toxic agents like
phosgene, phosphorous oxychloride, thionyl chloride and
other highly reactive substances in the presence of amine
bases.50 Less applicable methods are nucleophilic substitution
reactions of allyl-, benzyl- and tert-alkylhalogenides with silver
cyanide and the reaction of dichlorocarbene with anilines.51
Thus, an eco-friendly synthesis of isonitriles would be
desirable.

3.

Carbamates

Since carbamates are key intermediates for the synthesis of


isocyanates as well as for direct conversions with diols to nonisocyanate polyurethanes (NIPUs) via transesterification reactions, the following section shall give a closer insight into sustainable routes to carbamates. Carbamates (urethanes) are
formal esters of the instable carbamic acid. In chemistry, carbamates found applications in three main categories: in
polymer chemistry as the functional group of polyurethanes,
in peptide or related chemistry as protective groups of amines,
and in agricultural chemistry as active ingredients of insecticides, fungicides and herbizides. Numerous urethane protecting groups are well-known for the protection of primary and
secondary amines.52 Typical reagents for the protection of
amines are alkyl or aryl chloroformates as well as organic carbonates and pyrocarbonates (Scheme 10). The most commonly
used urethane protecting groups are the tert-butyloxycarbonyl
group (Boc), the benzyloxycarbonyl group (Z or Cbz), the fluorenylmethoxycarbonyl group (Fmoc) and the allyloxycarbonyl
group (Alloc). For each of these groups, dierent conditions
for their cleavage are required. Besides this, numerous other
urethane protecting groups exist for special applications in
peptide chemistry.52 Moreover, carbamates can be transesterified with alcohols in the presence of catalysts (see section 3.2).
Their reaction with primary or secondary amines (aminolysis)
to urea derivatives is also well-established.17a,53
3.1.

Conventional synthesis of carbamates

Carbamates can be obtained via dierent routes from alcohols


and amines using phosgene or one of its derivatives as a

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Scheme 10

Common reaction pathways of carbamates.

Scheme 11

Carbamate synthesis by using phosgene and its derivatives.

reagent (Scheme 11). The simplest synthesis procedure to


obtain carbamates is the reaction of primary or secondary
amines with alkyl or aryl chloroformates in the presence of a
base to trap the released hydrogen chloride (Scheme 11a).16a,54
Chloroformates are phosgene derivatives, highly toxic and
thus this method is far from sustainable and not an ecofriendly entry to carbamates. On the laboratory scale,
especially in peptide chemistry, this method is often applied
to introduce amine protecting groups.52 The reaction of
primary amines with phosgene leads to isocyanates
(Scheme 11b). The following addition of alcohols gives carbamates.16a,55 The conversion of diisocyanates with diols is utilized for standard industrial processes for the production of

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Green Chemistry
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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Tutorial Review

Scheme 13

Scheme 12

Phosgene alternatives in the synthesis of carbamates.

the starting materials.30,68 In modern procedures, the acyl


azide is generated in situ by applying CDI, Boc2O, 1-propanephosphonic anhydride (T3P) or diphenylphosphoryl azide

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Carbamates via Curtius, Hofmann and Lossen rearrangements.

(DPPA), followed by rearrangement to carbamates in a one pot


fashion.69 Similarly, the Hofmann rearrangement is often
applied to convert amides to carbamates. Using the traditional
protocol, amides are treated with bromine or chlorine in alkaline solution to obtain primary amines.70 Modern procedures
allow the conversion of amides with hypervalent iodine compounds under mild and neutral conditions to obtain methyl
carbamates.71 Furthermore, N-bromosuccinimide (NBS) can
also be used as a reagent to initiate the rearrangement.72
Recently, some other modifications and also electrochemically
induced Hofmann rearrangements to carbamates are
described.73 The Lossen rearrangement is less often used in
comparison with both the aforementioned methods. One
reason can be the slightly extensive access to hydroxamic
acids. Nevertheless, to date numerous dierent procedures are
described for the synthesis of hydroxamic acids from carboxylic acid derivatives.74 Hydroxamic acids require an activation to undergo the rearrangement under basic
conditions.75 In modern protocols, the activation and
rearrangement occur in a one pot reaction sequence.76
Besides the carbamate synthesis from amines, alcohols and
carboxylic acid derivatives, a few examples describe the conversion of nitriles, aldehydes and ketones to carbamates.16a
Caddick et al. developed a generic approach for the direct
catalytic reduction of nitriles to tert-butyl carbamates applying
catalytic amounts of nickel(II) chloride hexahydrate and an
excess of sodium borohydride and Boc2O (Scheme 14a).77
Also ketones and aldehydes can be directly transformed to
carbamates. In 2007, Seijas et al. observed that substituted
acetophenones and other ketones can be converted with carbamoyl chlorides to enol carbamates in the presence of 2,4,6-collidine as a strong non-nucleophilic base under solvent-free
conditions supported by microwave heating (Scheme 14b).78
Moreover, Tomkinson et al. described the -carbamoylation of
structural diverse ketones and aldehydes by reaction with
N-methyl-O-carbamoyl hydroxylamine hydrochlorides.79 An
interesting synthesis procedure of aromatic acyl carbamates
was reported by Nair and co-workers in which aromatic
aldehydes react with dialkyl diazocarboxylates and triphenyl
phosphine.80

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Scheme 15
carbonates.

Scheme 14

3.2.

Carbamates derived from nitriles, ketones and aldehydes.

Sustainable synthesis procedures of carbamates

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

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Carbamates and ureas by reaction of amines with dialkyl or diaryl

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

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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

Phosgene-free synthesis procedures of dimethyl carbonate (DMC).

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Tutorial Review
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

Transcarbamoylation reactions of carbamates.

synthesis of DMC from propylene oxide.118 Furthermore,


MgOCeO2 mixed oxide catalysts were established by Yoo and
co-workers.119 Garca and co-workers found that gold nanoparticles promote the catalytic activity of ceria for the transesterification of propylene carbonate to DMC.120 Recently, Cai et al.
showed an electrochemical synthesis of DMC from methanol,
CO2 and propylene oxide in ionic liquids.121 Besides this,
numerous other sustainable and eco-friendly processes are
described for the insertion of carbon dioxide to epoxides and
for the transesterification of cyclic carbonates to DMC.122 As
summarized, several sustainable alternatives for the synthesis
of DMC have been developed and, thus, DMC appeared to be a
readily available and sustainable alternative, being regarded as
a non-toxic phosgene substitute for the eco-friendly and safe
synthesis of carbamates, ureas and polyurethanes.
Several catalytic systems are able to catalyze the exchange
reaction of alcohols in carbamates (transcarbamoylation reactions, Scheme 17). Jousseaume et al. reported that bismuth triflate in amounts of only 1.0 mol% is a highly ecient catalyst
for the transcarbamoylation of N-hexyl O-methyl carbamates to
N-hexyl O-octyl carbamates at a temperature of 160 C.123
Lanthanum(III) isopropoxide is also reported to catalyze the
transcarbamoylation of methyl carbamates in an excellent
manner.124 Moreover, Lewis acids such as titanium(IV) isopropoxide and tin(II) 2-ethylhexanoate gave similar results.125
Very recently, Meier et al. reported a sustainable way to carbamates from hydroxamic acids. In the introduced eco-friendly
Lossen rearrangement, dialkyl and diaryl carbonates are able
to activate the hydroxamic acids in situ in the presence of catalytic amounts of tertiary amine bases (0.10.4 eq.) to initiate
the rearrangement by heating for one day (Scheme 18).126 First
investigations were carried out with DMC, but also several
other dialkyl carbonates as well as diphenyl carbonate could
be employed in the catalytic Lossen rearrangements of

Scheme 18 New base catalyzed Lossen rearrangements of hydroxamic acids


with organic carbonates.

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Scheme 19
alcohols.

Oxidative carbonylation of primary amines in the presence of

aliphatic hydroxamic acids to the corresponding alkyl and aryl


carbamates in good yields. The application of these conditions
to aromatic hydroxamic acids aorded the direct synthesis of
anilines in yields up to 83%. In consideration of the aspects of
green chemistry, the solvent/activation mixture can be recycled
several times and, thus, the production of chemical waste can
be minimized. For the synthesis of carbamates from carboxylic
acids, this method seems to be a promising sustainable and
eco-friendly process.
3.2.2. Miscellaneous sustainable synthesis procedures of
carbamates. Another access to carbamates is the metal catalyzed oxidative carbonylation of amines and anilines
(Scheme 19).16a In 1984, Fukuoka et al. reported a novel catalytic synthesis of carbamates by oxidative alkoxycarbonylation of
primary amines and anilines with alcohols in the presence of
palladium and iodides.127 The obtained yields of methyl and
ethyl carbamates were in most cases above 90%. Moreover, the
same group mentioned that this reaction was also catalyzed in
the presence of other platinum group metals and alkali metal
halides.128 One year later, Alper and Hartstock showed a mild,
catalytic alternative for the conversion of amines into carbamates.129 Anilines were converted to methyl and ethyl carbamates applying a catalytic mixture of PdCl2 (10 mol%), CuCl2
(20 mol%) and traces of hydrochloric acid at room temperature. The obtained yields ranged from 16% in the case of sterically hindered anilines up to 99% for unsubstituted aniline. In
1992, Leung and Dombek reported that metallomacrocyclic
compounds, such as metalloporphyrins, are excellent catalysts
for the oxidative carbonylation of amines to carbamates.130 A
cobalt porphyrin complex (1.0 mol%) promoted by sodium
iodide (10 mol%) showed the highest activity and full conversion was observed after three hours at 180 C under high
pressure in the case of the synthesis of ethyl carbamates of
tert-butyl amine and aniline in the presence of ethanol.
Schwartz and co-workers reported that elemental iodine represents a good promoter for palladium catalyzed oxidative
carbonylation in the presence of potassium carbonate.131
Methyl and ethyl carbamates were obtained in yields between
24 and 90% from anilines and aliphatic amines performing
the oxidative carbonylation in the presence of methanol or
ethanol. A polymer supported palladiumcopper catalyst for
the oxidative carbonylation of aniline was developed by Liao
and co-workers.132 Moreover, a PdCl2/ZrO2SO42 catalyst
system was shown to be highly ecient for the oxidative
carbonylation of amines.133 Deng et al. developed a highly
ecient ionic liquid-mediated palladium complex catalyst
system for the oxidative carbonylation of amines.134 High conversions and selectivity for the synthesis of methyl N-phenylcarbamate were achieved with low catalyst loadings. The same

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Scheme 20 Carbamates by reaction of primary amines with carbon dioxide


and electrophilic agents.

group also showed that a gold(I)-complex acts as an ecient


catalyst for the oxidative carbonylation.135 Yamanaka et al.
demonstrated an electro-organic approach for the synthesis of
N-hexyl carbamate by carbonylation of methanol and hexylamine over a gold supported carbon anode.136 Furthermore,
other methods, also in the synthesis of cyclic carbamates,
applying oxidative carbonylations are described.137
A very simple, eective and environmentally benign access
to carbamates can be achieved by a three component reaction
of a primary or secondary amine with carbon dioxide to obtain
an instable carbamic acid derivative in an equilibrium reaction, which can be trapped by electrophiles to form carbamates (Scheme 20). Numerous procedures describe that
electrophiles, such as alkyl halogenides, tosylates, epoxides,
alkynes, Michael acceptors and also alcohols, can be
applied.16a
In an early example, Katchalski et al. reported the reaction
of ethylene diamine with carbon dioxide, followed by reaction
with diazomethane to obtain the dimethyl carbamate derivative.138 In 1977, Yoshida and Inoue showed that carbamic acid
derivatives can react with ethyl vinyl ether to obtain 1-ethoxy
ethyl carbamates.139 The same group reported also that epoxides can react with carbamic acids to obtain monocarbamic
esters from 1,2-diols.140 Later, Inoue and co-workers described
a conversion of epoxides by the application of aluminum porphyrin as a catalyst for the fixation and activation of carbon
dioxide, followed by reaction with secondary amines to obtain
N,N-dialkyl carbamates.141 In 1984, Yoshida et al. reported the
synthesis of carbamates by the reaction of amines, carbon
dioxide and alkyl halides.142 To promote this reaction, Cs2CO3
is an ecient additive.143 Moreover, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) is very useful for the fixation of carbon
dioxide as the DBUCO2 complex.144 Instead of applying alkyl
halides as electrophiles, tosylates react in the same manner.145
The direct use of alcohols is also possible by activation with
dialkyl azodicarboxylates and triphenyl phosphine (Mitsunobu
reagent).146 Sakakura et al. reported the direct application of
alcohols in the presence of 2.0 mol% dibutyl tin oxide as a
catalyst for the synthesis of carbamates.147 Moreover, ortho
esters can react as electrophiles with carbamic acids to the corresponding carbamates.148 Inesi et al. developed electrogenerated systems for direct synthesis of carbamate esters from
carbon dioxide, amines and alkyl halides.149
Furthermore, it has been shown that carbamic acids
derived from amines and carbon dioxide can also react with
alkyne derivatives mediated by ruthenium catalysts. In 1987,
Sasaki and Dixneuf reported the reaction of acetylenic alcohols

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Scheme 21

Carbamates derived from oximes.

with secondary amines and carbon dioxide catalyzed with


0.4 mol% Ru3(CO)12 to obtain 2-oxoalkyl N,N-diethylcarbamates in moderate yields.150 Moreover, the same group mentioned that numerous ruthenium complexes catalyze the
synthesis of vinyl carbamates from carbon dioxide, terminal
alkynes and secondary amines.151 At the same time, Mitsudo
et al. found that [Ru(COD)(COT)], in the presence of phosphines, catalyzes the reaction of terminal alkynes with secondary amines and carbon dioxide to obtain enol carbamates in
yields up to 80%.152 The direct use of carbon dioxide for the
synthesis of carbamates as discussed above seems very promising in view of a sustainable process to polyurethane
precursors.
Modern procedures with promising aspects regarding sustainable and environmentally friendly entries to carbamates
employ oximes and formamides. Cardona et al. developed the
first catalytic oxidation procedure to convert aromatic aldoximes in the presence of alcohols to the corresponding carbamates (Scheme 21).153 The oxidation is performed with
catalytic quantities of methyl trioxorhenium (MTO) and an
excess of urea hydrogen peroxide as the oxidant. Long reaction
times (48 days) at room temperature are required to obtain
the carbamates in moderate yields ranging from 35 to 72%.
This method seems to be a promising approach for the conversion of aromatic aldehydes into carbamates making use of
urea hydrogen peroxide as a sustainable oxidation agent. Furthermore, Elghamry showed an unexpected synthesis of N-aryl
carbamates by heating 2-oximinoacetoacetates as ketoxime
derivatives with anilines at 130 C for a few minutes under
solvent-free conditions.154 The N-aryl carbamates were
obtained in good yields between 70 and 75%.
Other interesting starting materials for the synthesis of carbamates are formamides. In 1993, Kotachi et al. reported a
ruthenium-catalyzed synthesis of carbamates by dehydrogenation of formamides with alcohols (Scheme 22a).155 The reaction of substituted formanilides with various alcohols in the
presence of dierent ruthenium catalysts in refluxing mesitylene aorded N-aryl carbamates in yields ranging from 23% to

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Scheme 22 Carbamates derived from formamide couplings with alcohols,


enols and phenols.

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

As mentioned in the introduction, polyurethanes (PUs) are a


class of polymers that contain urethane linkages and are

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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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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.

trimethylene carbonate using a glycerol carbonate as a chain


transfer agent, followed by the ring-opening polyaddition of
the terminal cyclic carbonate with a diamine. Thus, poly(carbonate-hydroxyurethanes) with dierent molecular weights
could be achieved.
The related reaction of ethylene carbonate with diamines
and diols can also be considered as a possibility for the preparation of linear polyurethanes in a phosgene-free way
(Scheme 23b).166 Thus, a transcarbamoylation of dihydroxyurethanes, obtained via the nucleophilic addition of diamines to
ethylene carbonate, with diols using Bu2SnO as a catalyst was
reported by Rokicki et al.166 Furthermore, ethylene carbonate
was used in the synthesis of urethane containing diols or
hydroxy acids using amino alcohols or amino acids, respectively, which in turn were enzymatically polymerized.167 Alternatively, aliphatic polyurethanes were obtained in high yields
via the self-polycondensation of dihydroxyurethanes without
using diols.168 The addition of a diamine to ethylene carbonate gives the respective urethane derivatives with hydroxylethyl
carbamates (hydroxyurethanes). A two-step polycondensation,
consisting of polycondensation performed under a nitrogen
atmosphere followed by that under reduced pressure, was
eective in yielding polymers with molecular weights up to
10 kDa.
Another method for polyurethane preparation is a chain
growth polymerisation procedure employing ring-opening

This journal is The Royal Society of Chemistry 2013

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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observed that an increased CO2 pressure can be a reason for a


significant decrease in the lower critical solution temperature
of the polymers, possibly due to an increase in their urethane
contents.175

Scheme 24 Synthesis of saturated (a) and unsaturated (b) diisocyanate from


oleic acid.180

Scheme 26

Scheme 25 Thiol-ene additions onto double bonds as an approach for the


synthesis of fatty acid based diisocyanates.181

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

Tutorial Review
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

Overview of sustainable synthesis procedures to polyurethane precursors reported in this review.

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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condensation or transcarbamoylation.182 Fatty acid derivatives,


namely, ricinoleic acid, methyl oleate and methyl 10-undecenoate, were transformed to AB-type monomers containing
hydroxyl-acyl azide or hydroxyl-methyl urethane functionalities
(Scheme 26).
A thiolene addition onto the double bonds of either
methyl oleate or methyl 10-undecenoate was the key step to
obtain more reactive AB-type monomers (Scheme 26B). The
polyaddition of these AB-type monomers, with or without a

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Green Chemistry
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,

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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.

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