Organic Carbonates: Abbas-Alli G. Shaikh

Chem. Rev.
1996, 96, 951−976 951
Organic Carbonates†
Abbas-Alli G. Shaikh
Department of Chemical Sciences, North Maharashtra University, Jalgaon 425 001, India
Swaminathan Sivaram*
Division of Polymer Chemistry, National Chemical Laboratory, Pune 411 008, India
Received June 30, 1995 (Revised Manuscript Received February 27, 1996)
Contents I. Introduction
I. Introduction 951 Carbonic acid which is unstable at room temper-
II. Synthesis, Isolation, and Characterization of 951 ature has been isolated in its pure state at lower
Carbonic Acid temperature and characterized spectroscopically.1,2
III. Carbonates 952 The diesterification of carbonic acid with hydroxy
IV. Classification of Carbonates 953 compounds leads to the formation of stable organic
V. Physical Properties of Carbonates 953 compounds known as organic carbonates. Depending
VI. Methods of Preparation of Organic Carbonates 953 upon the nature of hydroxy compounds, the resulting
A. Phosgenation Technique 953 carbonates are either dialkyl, diaryl, or substituted
B. Oxidative Carbonylation of Alcohols/Phenols 954 dialkyl diaryl carbonates. Among the various types
C. Reaction of Urea with Alcohols/Phenols 955 of organic carbonates, the simplest one is dimethyl
D. Reaction of Oxiranes with Carbon Dioxide 956 carbonate. The production of dimethyl carbonate3,4
E. Use of Metal Carbonate 956 on an industrial scale by catalytic oxycarbonylation
F. Carbonate Interchange Reaction 958 of methanol has provided a great impetus to its use
1. Dialkyl to Dialkyl Carbonates 958 as a safe analog for phosgene or dimethyl sulfate in
2. Dialkyl to Alkyl Aryl Carbonate 960 the manufacture of many useful organic compounds.
3. Dialkyl to Diaryl Carbonates 963 In spite of burgeoning applications, there is no
4. Alkyl Aryl Carbonate to Diaryl Carbonate 964 compilation of the literature on the synthesis and
utility of organic carbonates. The present review,
5. Use of Activated Carbonates 964
therefore, attempts to provide a comprehensive sur-
G. Other Methods of Synthesis of Dialkyl 965 vey of the currently available literature on organic
Carbonates
carbonates.
1. From Halohydrins 965
2. From Alcohols and Carbon Monoxide by 966
Elemental Sulfur II. Synthesis, Isolation, and Characterization of
3. Alicyclic Carbonate from Halogenated 966 Carbonic Acid
Carbonates
Carbonic acid (H2CO3) is of special importance in
4. From Carbon Dioxide 966 nature. It is a key compound in CO2-HCO3/CO32-
5. Alkylation of Alkali Metal Carbonate 967 proton transfer reactions in biological and geochemi-
VII. Applications of Organic Carbonates 967 cal carbonate-containing systems.5-8 Carbonic acid
A. Application of Dimethyl Carbonate as 967 is known to be present to the extent of about 0.4% in
Alkylating Agent under GL-PTC water containing dissolved CO2. The equilibrium
1. Reaction with Phenol and Thiophenol 968 between carbonic acid with carbon dioxide and water
2. Reaction with Primary Aromatic Amines 968 and its significance are well recognized and have
3. Reaction with Arylacetonitriles 968 been thoroughly studied (eq 1).
B. Other Applications of Organic Carbonates 969
1. Dimethyl and Diethyl Carbonates 969 H2O + CO2 h H2CO3 (1)
2. Diphenyl Carbonate 970
3. Allyl Carbonates 970 It is believed that “carbonic acid” cannot exist in
4. Cyclic Carbonates 970 the free state.9 It was not isolated in its pure state
5. Dialkyl Carbonates as Lubricants 972 and characterized spectroscopically until 1960. Later
6. Agriculatural Applications 972 it was possible to prepare the ether adducts of
7. Applications in Medicinal Chemistry 972 carbonic acid H2CO3‚R2O10 (R ) CH3, C2H5) at tem-
8. Miscellaneous Applications 972 perature below -30 °C, and a solid crystal of the
C. Economic Aspects 973 complex was obtained at -78 °C. This was achieved
VIII. Future Perspectives 973 by the addition of an ether solution of anhydrous HCl
IX. Acknowledgement 973 to a suspension of finely divided sodium bicarbonate
X. References 973 in ether at -30 °C. In solution, the adducts decom-
pose into H2O, CO2, and R2O above 5 °C. The
† NCL Communication No. 6191. dissociation constant of carbonic acid is large in
0009-2665/96/0796-0951$25.00/0 © 1996 American Chemical Society
952 Chemical Reviews, 1996, Vol. 96, No. 3 Shaikh and Sivaram
FSO3H SbF5/SO2 –10 to 0 °C

CO32–or HCO3– –80 °C
H3CO3+ CO2 + H3O+ (2)
H+ + + +
H2CO3 HO OH HO OH HO OH (3)
etc.
C C or C +
OH OH OH
Protonated carbonic acid was characterized by 1H-

and 13C-NMR spectroscopy. Olah and co-workers
have recently isolated carbonic acid at low temper-
ature in methanolic solution and characterized it by
13
C-NMR, ab initio, and ILGO studies.1 Simulta-
neously, carbonic acid was synthesized and isolated
by a new cryogenic technique in methanol solvent
and characterized by FTIR spectroscopy.2 This cryo-
Abbas-Alli G. Shaikh received his Bachelor of Science degree in chemistry genic technique is useful for isolation of many other
(1986) followed by his Master of Science in organic chemistry (1988) short-lived intermediates and is suitable for nonvola-
from Shivaji University, Kolhapur, India. He received his Ph.D. degree in tile reactants such as salts which can not be vapor-
polymer chemistry in 1994 from the University of Poona (Pune, India), ized without decomposition.
under the guidance of Dr. S. Sivaram. His thesis was concerned with The reaction of CO2 and H2O in the gas phase has
the synthesis and characterization of poly(aryl carbonate)s and poly(aryl been studied in detail by ab initio calculations.14
ester carbonate)s via carbonate interchange reaction of dialkyl carbonates.
At present he is on the faculty of the Department of Chemical Sciences Several calculations on the gas phase reaction of
at North Maharashtra University, Jalgaon, India, where he teaches polymer carbon dioxide with H2O and hydroxide ion have
chemistry to Master’s degree students. Dr. Shaikh is the author of eight focused mainly on accurate reaction energies.15 These
publications and five patents. predict that a sizeable activation energy (>40 kcal/
mol) is involved in the formation and dissociation of
carbonic acid, and thus the free carbonic acid should
exist as a stable molecule. The existence of a stable
free carbonic acid in the gas phase was evidenced by
mass spectral study of the thermolysis products of
(NH4)HCO3.16 The presence of a stable carbonic acid
radical cation, CH2O3-+ species in the mass spectral
study was observed. This was further confirmed by
collision activation (CA) mass spectroscopy experi-
ments and neutralization reionization (NRMS) ex-
periments (CH2O3+ ion remains intact upon neutral-
ization followed by reionization) (eq 4).
+ – + –
(NH4)HCO3 H2CO3 + NH3 (4)
(m/z = 79) (m/z = 62) (m/z = 17)
(<1%)
Dr. S. Sivaram, Head, Polymer Chemistry Division, National Chemical
Laboratory (NCL), Pune, India, received his Master’s degree in chemistry
from the Indian Institute of Technology, Kanpur, India, and a Ph.D from + – + –
Purdue University, West Lafayette, IN, in 1972, where he worked with H2O + CO2
Professor H. C. Brown. After a stint at the Institute of Polymer Science, (m/z = 18) (m/z = 44)
The University of Akron, Akron, OH, with Professor J. P. Kennedy, he (base peak)
returned to India and began his career at the Indian Petrochemicals Corp.
Ltd., Baroda. In 1988, he joined NCL. Dr. S. Sivaram has wide research Thus the decomposition of carbonic acid to CO2 and
interests in synthetic polymer chemistry. He is the author of over 150 H2O in solution was attributed to the acid/base and
publications and 32 patent applications. He currently holds six U.S. patents also catalysis by solvents. This increases the rate of
and one European patent. Since joining NCL, he has supervised 13 hydration of CO2 and the dissociation of carbonic acid
Ph.D and 9 Master theses in polymer chemistry.
to such an extent that carbonic acid is inaccessible.
comparison with those of the hydrates of other
carbonyl compounds,11 and this has been taken to III. Carbonates
reflect the high stability of the unhydrated species, The monoester of carbonic acid, known as hemi-
CO2. However, an activation energy of 16.5 kcal/mol carbonic acid, is formed by the reaction of alcohol
for the dissociation reaction of carbonic acid to water with carbon dioxide. This is also unstable and
and carbon dioxide suggests that it should be possible decomposes to alcohol and carbon dioxide. Hemicar-
to observe carbonic acid in its free state.12 Olah and bonic acid can only be isolated as salts (with inorganic
White have shown that protonated carbonic acid is metal such as sodium and potassium), simple anhy-
remarkably stable in superacidic media.13 It was drides, or mixed anhydrides with carboxylic acids.17
obtained by simply dissolving carbonates or hydrogen The inorganic salts of hemicarbonic acid are solid,
carbonates in FSO3H-SbF5 (or other superacids). stable, and high-melting compounds. This monosalt
The solutions decompose at about 0 °C to give can be converted to disalt which is known as a metal
hydronium ion and CO2 (eq 2). The protonated carbonate. Hemicarbonic acid upon esterification
carbonic acid is highly resonance stabilized (eq 3). with another molecule of hydroxy compound forms
Organic Carbonates Chemical Reviews, 1996, Vol. 96, No. 3 953
Chart 1
stable organic carbonates. The simplest organic inorganic salts. In many applications, ethylene and
carbonate is dimethyl carbonate. propylene carbonate offer a safe and clean alternative
to more hazardous dipolar aprotic solvents. Inor-
IV. Classification of Carbonates ganic carbonates are white, crystalline compounds,
with high melting points. They are soluble in water
Carbonates can be mainly classified into two and insoluble in most of the organic solvents. They
groups, namely, inorganic (metal) and organic car- easily react with compounds containing acidic proton,
bonates. Depending on the structural variation, e.g., acid, phenol, etc. They are useful in many
organic carbonates can be further subdivided as organic reactions.
shown in Chart 1.
VI. Methods of Preparation of Organic
V. Physical Properties of Organic Carbonates Carbonates
The industrially important dialkyl carbonates are
all colorless liquids. Most of them have a pleasant A. Phosgenation Technique
odor. The aromatic carbonates, on the other hand, In this method, hydroxy compounds (aliphatic,
are solids. Ethylene carbonate is infinitely soluble aromatic) are dissolved in a single or a mixture of
in water. Propylene carbonate is soluble in water inert, anhydrous solvent (dichloromethane, chloro-
only to the extent of 25.0 g of propylene carbonate/ form, benzene, toluene) with excess pyridine and
100 g of water (at 25 °C). Butylene carbonate is less phosgenated at or below room temperature. Pyridine
soluble, yet in water, only 7.0 g of butylene carbonate acts as an acid acceptor and reacts with phosgene,
dissolves in 100 g of water (at 25 °C). Dimethyl and an ionic adduct is formed. The adduct formed
carbonate and diethyl carbonate are sparingly soluble is more reactive than the corresponding chlorocar-
in water. The other carbonates, including aromatic bonic acid esters.19 Pyridine is only one among the
carbonates, are nearly insoluble in water. They are acid acceptors that may be used. Nearly all the
soluble in many organic solvents, particularly polar organic carbonates (except few like ortho- and pyro-
solvents, such as esters, ketones, ethers, alcohols, and carbonate) can be prepared by this method (Scheme
aromatic hydrocarbons. The lower aliphatic carbon- 1). Symmetrical carbonates are obtained in one step,
ates form azeotropic mixtures with several organic whereas unsymmetrical, alkyl aryl, or substituted
solvents.18 Ethylene carbonate finds extensive use alkyl aryl carbonates are obtained by a two-step
as a solvent for aromatic compounds, polymers, and reaction. Aromatic hydroxy compounds20 are much
Scheme 1. Synthesis of Organic Carbonates by Phosgenation Methoda

O
CH2Cl2/Py
2R OH + COCl2 R O C OR + 2Py•HCl
0 °C– room temp
O
+ +
2 N + COCl2 N C N 2Cl–
(adduct)
O
R OH + COCl2 R O C Cl + HCl
O O
+
N+R O C Cl N C O R Cl–
ROH
O
+
R O C OR + N H Cl–
a Where R ) alkyl, aryl, and substituted alkyl and aryl.
Scheme 2. Synthesis of Organic Carbonates by Scheme 3. Synthesis of Organic Carbonates by

Phosgenation Methoda Phosgenation Methoda
O O O
C OCOCl O C
HO OH Cl3CO OCCl3 O O
Py/CH2Cl2
OH
a Where ∼ ) 2,4-dihydroxypentane, 2,4-dihydroxy-2,4-dimeth-
COCl2 cyclization
ylpentane, and cis-8-trans-1,2-dihydroxycyclohexane. X X X
Et3N, CH2Cl2, NaOH
slower to react with phosgene than aliphatic hydroxy

compounds. The more acidic hydroxy compounds are
less reactive toward phosgene. For example, halo- OH OCOCl O
genated phenols react slower than phenol. Substitu- a
Where X ) -C(CH3)2-, -SO2-, -CO-, -O-, -C(O)-O-,
tion in the ortho position also decreases the reactiv- -CO-NH, -O-C(O)-, and -O-C(O)-NH-.
ity. The conversion of hydroxy compounds to car-
bonates can be completed in a short period of time. quires higher temperature (50-150 °C) and results
Therefore, the reaction can be carried out continu- in poor yields of carbonates along with unreacted
ously without any difficulty, and good yields of chlorocarbonates.26 This also leads to the formation
carbonates are obtained. of unwanted products.
The reaction mixture is washed with dilute HCl The advantages of the phosgenation method are (a)
(to neutralize excess pyridine) and then with water high yields of carbonates and (b) functionalized
(to remove salt). Pure organic carbonate is obtained carbonates such as cyclic and activated carbonates
either by distillation or recrystallization from a that can be prepared, which are useful monomers for
suitable solvent or solvent mixtures. Good yields of the preparation of high molecular weight polymers.
5- or 6-membered cyclic carbonates of 1,2- and 1,3- The main drawbacks of this reaction are (a) the
dihydroxy compounds are also obtained by this process involves the use of toxic and hazardous
method.21 Sterically hindered dialkyl carbonates chemicals like pyridine and phosgene, (b) excess
such as di-tert-butyl carbonate can also be prepared pyridine has to be neutralized, and (c) the byproducts
in 50% yield.22 For the preparation of carbonates, salt has to be completely removed and disposed. This
phosgene can be substituted by compounds such as involves additional purification steps.
chloroformic acid trichloromethyl ester (diphosgene)
and bis(trichloromethyl) carbonate. For example, B. Oxidative Carbonylation of Alcohols/Phenols
1,2- and 1,3-diols were easily converted to cyclic
carbonates with triphosgene in CH2Cl2 and pyridine The formation of dialkyl carbonates from the reac-
at 70 °C23 (Scheme 2). tion of alcohols and carbon monoxide has been
Recently, an aromatic dihydroxy compound, namely, reported to be promoted by transition metal com-
bisphenol-A, has been selectively converted to cyclic pounds (in particular palladium, mercury, and cop-
carbonate under pseudo-high-dilution conditions em- per) and post-transition-metal compounds.27 In the
ploying triethylamine-catalyzed hydrolysis/condensa- case of palladium and mercury, however, the reaction
tion reaction of bisphenol-A bis(chloroformate) using does not seem to be selective and involves reduction
CH2Cl2 and NaOH.24 Similarly, functionalized bisphe- to the metal, which can not be reoxidized directly.
nols were converted to functionalized aromatic cyclic The reactivity of copper is of greater interest since
carbonates25 (Scheme 3). through a redox process with oxygen and carbon
In the absence of an organic base, the direct monoxide it gives a system which functions catalyti-
reaction of hydroxy compounds with phosgene re- cally. Romano et al.28 explored the synthesis of
dimethyl carbonate by oxidative carbonylation of were produced. Using catalytic quantities of man-
methanol using a copper salt such as copper chloride ganese salt with palladium, up to 100 mol of diphenyl
as catalyst. The reaction takes place in two steps, carbonate/mol of palladium was achieved. This reac-
in which cuprous chloride is oxidized to cupric meth- tion requires longer time to achieve higher conversion
oxy chloride, and this is reduced with carbon mon- of phenol.
oxide to form dimethyl carbonate and regenerate A number of attempts have been made to produce
cuprous chloride (eq 5). diaryl carbonate by the direct oxidative coupling of
phenols with carbon monoxide or by direct condensa-
2CuCl + 2CH3OH + 1/2O2 f tion with carbon dioxide.35 Oxidation of phenols with
2Cu(OCH3)Cl + H2O carbon monoxide and molecular oxygen is carried out
in the presence of catalysts containing palladium
2Cu(OCH3)Cl + CO f (CH3O)2CO + 2CuCl (5) compounds, alkyl ammonium halide, and an organic
or inorganic base under pressure of 4-30 kg/cm2, at
A number of patents report the synthesis of di- 100-200 °C, for 1-13 h. Diphenyl carbonate is
methyl carbonate by treatment of methanol, CO, and obtained in 4-30% yield with 90-96% selectivity.
oxygen using various catalysts and reaction condi- Use of molecular sieves such as 3 Å is also found to
tions.29 Good conversion to dimethyl carbonate is have favorable effect on yield and selectivity.36 Di-
achieved with high selectivity. Dimethyl carbonate phenyl carbonate in 39.5% yield with 99% selectivity
is also produced by a continuous gas phase reaction is produced by a continuous process in a multistage
of alkyl nitrites (RONO) with CO in the presence of distillation column in which water formed in the
a catalyst comprised of a platinum halide or a reaction is removed as steam by distillation37 (eq 8).
complex with alkali metal or alkaline earth metal
halides.30 Dimethyl carbonate is produced in 70- Et3N, CuBr
2 OH + CO + O2 O CO + H2O (8)
80% yield with a selectivity in the range of 80-90%. Pd(CO)Br 2
CH2Cl2, mol sieves
Dimethyl carbonate is produced industrially by oxi-
dative carbonylation of methanol by Enichem Syn-
thesis,3 Dow Chemical,4 and Ube Industries Ltd. Lower basicities of phenols, expensive catalysts,
Enichem Synthesis has the capacity to produce about low yields, and low catalyst turnover efficiencies have
8800 tons/year dimethyl carbonate.31a precluded a commercial process based on oxidative
The analogous oxidative carbonylation of aromatic carbonylation of phenols. In this context, it is gener-
hydroxy compound has met with less success. Diphen- ally acknowledged that the discovery of a convenient
yl carbonate was formed in moderate yield from and less expensive route to diaryl carbonates would
phenol and carbon monoxide in the presence of a base be a revolutionary development.
and a stoichiometric quantity of a group VIIIb metal
salt.32 Hallgren and Mathews33 reported the reaction C. Reaction of Urea with Alcohols/Phenols
of phenols with carbon monoxide at atmospheric The reaction of urea with alcohols which leads to
pressure and room temperature in the presence of the formation of carbamates using metal salts like
palladium chloride and a tertiary amine to produce zinc acetate and lead acetate was discovered by
a mixture of diaryl carbonates and aryl salicylates Paquin.38 Prolongation of the reaction or the addition
(eq 6, where R ) H, -CH3, -Cl, CH3O-). Only diaryl of triphenylphosphine as a cocatalyst results in the
carbonates were produced when palladium carbonyl formation of carbonate. Isocyanuric acid is a major
chloride was substituted for palladium chloride (eq byproduct of this reaction (eq 9).
7).
CO2 + 2NH3
R OH + CO + Et3N + (PhCN)2PdCl2
–H2O
CH2Cl2
cat.
R OH + H2N C NH2 RO C NH2 + NH3
O O OH
O O
cat. (9)
R O C O R+R O C + R O C O R + NH3
+R OH
R O C NH2 O
–NH3 H
R O R OH + HNCO N C
Et3NHCl + Pd0 + PhCN (6) n
O
2Pd(CO)Cl + 2R OH + 2Et3N
The decomposition of the carbamate to form iso-
CH2Cl2/CO cyanic or isocyanuric acid, which is observed with
catalyst systems such as zinc acetate/triphenylphos-
phine, does not occur if titanium, aluminum, or
R O CO + 2Pd0 + 2Et3NHCl (7)
2 zirconium alkoxides are used in combination with
suitable cocatalysts.39 Besides these, catalysts such
The same reaction was made catalytic34 using an as dibutyltin oxide, dibutyltin dimethoxide, and
oxidation cocatalyst in which the palladium metal triphenyltin chloride have been found to give high
was oxidized to Pd(II) species. A variety of copper, yields of carbonates. Even heterogeneous catalysts
vanadium, cobalt, and manganese salts were effective such as antimony trioxide and aluminum trioxide can
cocatalysts, although in many cases side products be used. This reaction is carried out at 150-195 °C
for 4.5 h and at 195-220 °C for 14 h depending upon agents such as crown ethers or quaternary am-
the catalyst system. monium salts. The reaction gave the corresponding
The yields of carbonates are >99%.40 The am- cyclic carbonates in high yields under high pressure
monia which is liberated during the reaction can be, at 80-120 °C; however, the yield was very small at
in principle, recycled for the synthesis of urea. atmospheric pressure. Ratzenhofer and Kisch45 per-
Primary, secondary, and low-boiling alcohols can be formed the synthesis of cyclic carbonate from the
converted into carbonates. Kinetic studies have reaction of oxirane with carbon dioxide in the pres-
shown that the formation of dialkyl carbonate from ence of mixtures of triphenylphosphine with the
urea and aliphatic hydroxy compound proceeds in two halides of aluminum, molybdenum, or iron at room
steps.40 At a constant temperature of 160 °C, 50% temperature under atmospheric pressure. The yield
of the expected amount of ammonia is formed fast; of cyclic carbonate was not satisfactory.
the urea is completely transformed into carbamate Baba et al.46 found an excellent new catalyst
in the presence of catalyst. Even on raising the system composed of organotin halides with quater-
temperature from 165 to 180 °C, the rate of the nary ammonium or phosphonium salts, in which the
subsequent reaction to dialkyl carbonate remains reaction of oxiranes with carbon dioxide proceeded
much lower than that of the first. The carbamate smoothly to give the corresponding cyclic carbonates
that is formed as intermediate is thermally stable at in high yields at atmospheric pressure at 40-100 °C;
the reaction condition and is transformed into dialkyl however, neither organotin halide nor tetrabutylphos-
carbonate. phonium halide individually showed any catalytic
The reaction of urea with aromatic hydroxy com- activity. This method was also useful for the reaction
pounds was also investigated with temperatures of inactive or acid sensitive oxiranes with carbon
ranging from 150 to 195 °C for 4.5 h using various dioxide to produce cyclic carbonates under neutral
combinations of catalysts. Aryl carbamates are and mild reaction conditions.
formed as intermediates and are thermally unstable. Recently, Nishikubo et al.47 reported the synthesis
They decompose to isocyanuric acid and phenols at of cyclic carbonates by the addition reaction of
the reaction condition (eq 10). The formation and oxiranes with carbon dioxide using insoluble poly-
styrene beads containing pendant quaternary am-
O O monium or phosphonium as catalysts at atmospheric
–NH3
Ar OH + H2N C NH2 ArO C NH2 ArOH + HNCO pressure. The reaction of oxiranes with CO2 pro-
(unstable) ceeded smoothly catalyzed by 1-2 mol % polymer-
(10) supported quaternary onium salts to give the corre-
O O
–
sponding cyclic carbonates in high yields at 80-90
–H+ –
H2N C OAr HN C OAr HNCO + OAr °C. In this reaction system, the catalytic activity of
the polymer-supported quaternary onium salts was
stability of aryl carbamate is also affected by the strongly affected by the following three factors: (i)
nature of substituent, catalysts, and reaction me- degree of ring substitution of the onium salt residues
dium.40 The formation of aryl carbamate is acceler- to the polymer, (ii) degree of cross-linking of the
ated by electron-donating groups and slowed by polystyrene beads and chain length of the alkylene
electron-withdrawing groups. In nonpolar solvents spacer between the polymer backbone and the onium
such as tetralin or dibutyl ether, the decomposition salt, and (iii) hydrophobicity of the alkyl group on
proceeds much more slowly than in polar solvents the onium salts and the kind of onium salts. Thus,
such as DMF, NMP, and HMPA. Decomposition is the polymer-supported quaternary phosphonium salts
enhanced by bases (e.g., triethylamine, pyridine), and with low degree of ring substitution, low degree of
weak acids cause a slow decomposition. The use of cross-linking, and long alkylene spacer chain were
mineral acids results in a fast decomposition. Nev- found to have higher catalytic activity. The polymer-
ertheless, the reaction of phenyl carbamate with supported catalysts can easily be separated at the
phenol under these conditions (similar to aliphatic end of a reaction by filtration and be reused. Kinetic
hydroxy compound) resulted in the formation of only study revealed that the rate of reaction was propor-
1% diphenyl carbonate. tional to the products of catalyst concentration and
oxirane concentration. The mechanism of reaction
D. Reaction of Oxiranes with Carbon Dioxide of oxirane with carbon dioxide catalyzed by the
polymer-supported onium salt is shown in Scheme
The chemistry of carbon dioxide has received much 4.
attention in recent years. It has been considered as
a monomer in polymerization and polycondensation E. Use of Metal Carbonate
reactions.41 The reaction of carbon dioxide with
oxiranes to produce cyclic carbonates has been of Little is known about the transformation of inor-
interest as a useful method for its fixation by a ganic (metal) carbonates to organic carbonates, ex-
chemical process.42 Synthesis of cyclic carbonates cept the reaction of silver carbonate with alkyl
from the reaction of carbon dioxide with oxiranes has iodide.48 This may be due to insolubilities of inor-
been accomplished using Lewis acids, transition- ganic carbonates even in aprotic organic solvents.
metal complexes, organometallic compounds, or poly- Recent work reported in the patent literature de-
(siloxane)-supported metal halides as catalysts under scribes the alkylation of metal carbonate with alkyl
high pressure.43 Rokicki and Kuran44 reported the halides at high temperature and in dipolar aprotic
reaction of oxiranes with carbon dioxide catalyzed by solvents using various catalysts.49 Lissel and Dehm-
alkali metal salts in the presence of phase transfer low50 reported the preparation of dialkyl carbonates
Scheme 4. Reaction Mechanism of Oxiranes with Carbon Dioxide by Polymer-Supported Catalysta

P cat.
R CH CH2 + O C O R CH CH2
O O O
O
K1
R CH CH2 + Q+X– R CH CH2
–O δ–
O + X
Q
complex I
K2
complex I + CO2 R CH CH2 X δ– R CH CH2
O O– Q+ O O + Q+X–
O O
complex II
a Where R ) PhOCH2-, C4H9-O-CH2-, CH2dCH-O-CH2-, and CH2dCH-CH2-O-CH2Ph-. K1 . K2.
in a phase transfer catalytic reaction from primary Scheme 5. Formation of Dialkyl Carbonate from
alkyl halides (bromides) with a mixture of dry potas- Potassium Carbonate and Alkyl Bromide Using
sium hydrogen carbonate and dry potassium carbon- Organostannyl Catalyst
ate in nonpolar solvents. The yields of organic 2Bu3SnCl + K2CO3 (Bu3Sn)2CO3 + 2KCl
carbonates ranged from 67% to 86%. The reaction
was ineffective in the absence of potassium hydrogen –CO 2
carbonate and a phase transfer catalyst (eq 11, where

(Bu3Sn)2O
R ) n-C5H11, n-C6H13, n-C7H15, n-C4H19, n-C11H23,
C15H31, PhCH2-, (o-Me)PhCH2-, (m-Cl)PhCH2-). A
R13Sn SnR13
(A = O or S)
O O K+O– –OK+
RBr
KHCO3 K2CO3/R–Br C
R Br R O C OH RO C OR (11)
aliquot 336 aliquot 336 organic O O
phase
RO C OR
Fujinami et al.51 reported the preparation of dialkyl A
R13Sn SnR13
carbonates by the heterogeneous reaction of solid
potassium carbonate with alkyl bromides in dimeth- K+O– O–K+ KBr
ylformamide or dimethyl sulfoxide in the presence
solid C
of organostannyl compound such as hexabutyldi- phase
stannoxane or chlorotirbutylstannane as catalyst. O
The reaction of alkyl bromide was studied using
various tin compounds. The reaction was carried out this method was the failure of activated aryl halides
at 40-100 °C for 8-80 h. Dialkyl carbonate was or electronegatively substituted alkyl halides (e.g.,
obtained in 19-89% yield. The alkylation reaction 2,2,2-trifluoroethyl bromide) to produce carbonates
was distinctly accelerated by the addition of a phase due to the labile nature of the intermediate alkoxy
transfer catalyst such as 18-crown-6. The reaction carbonate salts.
was complete in 10 h at 80 °C in less polar solvents A number of carbonates (RCH2O)2CO (R ) CH3,
such as acetonitrile and benzene. This dramatic C2H5, CH2dCH, C3H7, C5H11, C6H5) have been syn-
effect is explained by involving the reaction of trior- thesized by the reaction of alkali metal carbonates
ganotin chloride with metal carbonate to form bis- with the corresponding halogen derivatives in the
(triorganotin) carbonate which is decarboxylated to presence of activating agents such as crown ethers,
hexabutyldistannoxane or hexaalkyldistannthiane. polyglymes, polyamines, and triethylbenzylammo-
This is an efficient catalyst, interacts with the nium chloride. The effects of various parameters
carbonate anion, and forms an organic soluble inter- (type of the halogen derivative, metal carbonate,
mediate. This organotin derivative acts as a solid- activating agent, solvent, and reaction time) on the
liquid phase transfer catalyst. Organostannyl cata- reaction have been studied by Rokicki et al.53 Al-
lyst acts as a Lewis acid and interacts with carbonate though group I and II alkali metal carbonates were
ion and the crown ether as a Lewis base to associate used in alkylation reactions with primary alkyl
with potassium ion. This undergoes efficient reaction halides, K2CO3- with benzyl bromide at 70-80 °C for
with alkyl bromide in organic solvent retaining 24 h using 0.1 mol % 18-crown-6-ether and triethyl-
organic carbonate in the organic phase with separa- benzylammonium chloride as activating agent was
tion of metal bromide (Scheme 5). Cella and Bacon52 found to give >90% yield. Acetonitrile and ethers
prepared dialkyl carbonates by the phase transfer- such as diglyme and dioxane were the best solvents
catalyzed alkylation of alkali metal carbonate and for this reaction. The mechanism proposed for this
bicarbonate salts in nonpolar and polar solvents. The reaction is shown in Scheme 6.
reaction of alkali metal alkyl carbonate salts with Under ordinary conditions, K2CO3 is insoluble even
alkyl halides in dipolar solvents produces mixed alkyl in polar solvents such as DMSO or DMF which
carbonates in good yields. The major limitation of readily solvate cations, and a reaction with benzyl
Scheme 6. Phase Transfer-Catalyzed Reaction of Scheme 7. Carbonate Interchange Reactiona

Alkyl Halides with Metal Carbonatea O O
O
R′O C OR′′ + R1OH R′O C OR1 + R′′OH
activating
R CH2 X + Mt2CO3 R CH2O C OCH2 R + 2Mt X O
agent O
O R′′O C OR1 + R2OH R2O C OR1 + R′′OH
K2CO3 + crown ether KO C O K+ Overall Reaction
O O
O O
R′′O C OR′′ + R1OH + R2OH R2O C OR1 + 2R′′OH
R CH2 Br + KO C O– K+ R CH2O C OK + K+ Br–
a Where R′′ ) alkyl, aryl, or substituted alkyl or aryl; R1, R2 )
O O
alkyl, aryl, same, or different.
K+ Br– + R CH2O C OK KBr + R CH2O C O– K+
O displaces the less nucleophilic compound, and if both

R CH2O C O– K+ +R CH2Br
hydroxy compounds have similar nucleophilicity,
then the less volatile compound displaces the more
O volatile one. Hence, even with lower mass alcohols,
R CH2O C OCH2 R + K+ Br– diaryl carbonates form dialkyl carbonates and the
a Where Mt - K and Na; R ) C H -, -CH dCH, -CH , -C H ,
less nucleophilic phenols, but lower mass dialkyl
6 5 2 3 2 5
-C3H7, and -C5H11, X ) Br and Cl. carbonates react with higher mass alcohols to give
the higher mass dialkyl carbonates; the lower boiling
bromide does not take place. The introduction of alcohol is removed by distillation. In this case
activating agents such as crown ethers results in the carbonate interchange reaction occurs in steps with
formation of a complex of increased liophilicity, and the intermediate formation of a mixed carbonate. The
the “naked” carbonate anion undergoes nucleophilic reaction of dialkyl carbonates with phenols to give
substitution with an alkyl bromide. The reaction of diaryl carbonates occurs contrary to the above rule
alkyl bromides with activated potassium carbonates and can be achieved by using suitable catalysts. It
is reversible, and the yield of alkylpotassium carbon- proceeds, however, at a relatively slow rate. This
ates depends on the amount of excess of bromo reaction is analogous to transesterification reaction
derivatives used and the difference in nucleophilicity involving the reaction of hydroxy compound with an
of the carbonates and bromide anions. The greater ester.55
reactivity of the alkyl bromides compared to the
corresponding chlorides in reactions with K2CO3 is 1. Dialkyl to Dialkyl Carbonates
due to the lower basicity and nucleophilicity of the The carbonate interchange reaction of aliphatic
bromide anion. dihydroxy compounds of the general formula HO-
This method suffers from the following disadvan- (CH2)n-OH, where n ) 1-9, 11-14, and 18, dieth-
tages. (i) Reactions of inorganic carbonates with ylene glycol, trimethylene glycol, and p-xylene glycol
alkyl halides are sluggish even at elevated temper- with diethyl carbonate or dibutyl carbonate was
atures. (ii) This reaction requires a long time, and carried out by Carothers, Van Natta, and Hill.56
yields obtained are also low but can be improved They carried out reactions at temperatures between
under specific reaction conditions. (iii) This reaction 120 and 160 °C, utilizing the catalytic action of
works satisfactorily only with alkyl bromide and K2- sodium alcoholates. They obtained ethylene carbon-
CO3. It is difficult to prepare organic carbonates, ate from ethylene glycol and trimethylene carbonate
using alkyl chloride and iodide with Na2CO3, and from 1,3-trimethylene glycol. However, the aliphatic
other group II metal carbonates. (iv) The solubility dihydroxy compounds in which the -OH groups were
of most metal carbonates in nonpolar solvents is separated by more than three -CH2- groups re-
negligible, and the solubility is not appreciably better sulted in polycarbonates with molecular weight below
in dipolar aprotic solvents. (v) This method is not 3000. Sarel and co-workers57 investigated the influ-
applicable for the preparation of diaryl and activated ence of reaction conditions and structure of the
dialkyl carbonates. (vi) In the preparation of dialkyl aliphatic dihydroxy compounds on the formation of
carbonates by this process, side products such as cyclic carbonates. Peterson58 modified the carbonate
dialkyl ethers are produced. interchange reaction used by Carothrs to eliminate
the influence of alkaline catalyst. He used sodium
F. Carbonate Interchange Reaction alcoholates and an equivalent amount of carboxylic
acid ester as catalysts.
Carbonate interchange reaction can be defined as Therefore, it was concluded that dialkyl carbonates
a process wherein one carbonate is converted to will not undergo carbonate interchange reaction with
another carbonate by which one or both the acyl aliphatic dihydroxy compounds in the absence of
oxygen parts of the parent carbonate are displaced catalysts even at elevated temperatures. The reac-
by an appropriate alkoxide/aryl oxide to produce a tion occurs readily in the presence of basic catalysts
different carbonate with the aid of a suitable catalyst and is a convenient method for the synthesis of
(Scheme 7). dialkyl carbonates and poly(alkyl carbonate)s. Mor-
Carbonate interchange reaction between carbon- gan59 prepared ethylene carbonate by the reaction of
ates and hydroxy compounds adheres to the following ethylene glycol with diethyl carbonate using anhy-
rule:54 The more nucleophilic hydroxy compound drous potassium carbonate as catalyst. Various
Table 1. Carbonate Interchange Reaction of Ethylene Carbonate with Alcohols

hydroxy reaction conditions: product yield
Chem. Abstr. no. (Co. name) compd catalyst temp (°C)/time (h)/pressure (kg/cm2) carbonate (%)
76:99140z C2H5OHa C2H5ONa 175/3/103 DEC 13
(Dow Chem. Co.)
90:168058g CH3OH NaOH reflux/1.5/na DMC na
(Bayer AG)
90:186365j CH3OH ClCH2CO2Na 150/2/na DMC 60
(Bayer AG)
90:186366k CH3OH Tl2O3 150/0.5/na DMC 25
(BayerAG)
92:214901t C4H9OH Ti(OC4H9)4 120/5/na DBC 68
(Nisso Petrochem. Ind. Co. Ltd.)
93:147990k C4H9OH Ph3P 120/5/na DBC 65
93:149791m C2H5OH ZnCl2, Et3N reflux/5/na DEC 70
110:74823g CH3OH anion exchange resin 100/na/7 DMC 48
(Asahi Chem. Ind. Co. Ltd.) (Dowex MSA-1)
116:193723h CH3OH PbO 100/1/na DMC 38
(Asahi Chem. Ind. Co. Ltd.)
118:254406x CH3OH KOH 80/continuous process DMC 45
(Bayer AG)
a Propylene carbonate was used; na ) data not available.
methods are available for the synthesis of ethylene cols such as di-, tri-, and tetraglycols. These reac-
carbonate. It can be conveniently prepared from tions can be prevented by the use of a combination66
carbon dioxide and oxiranes.44-47 of Lewis acid and organic base.
Sakai et al.60 have reported the carbonylation of Carbonate interchange reactions between ethylene
butylstannyl alkoxides with ethylene carbonate un- carbonate and aliphatic hydroxy compounds were
der nitrogen at atmospheric pressure. The corre- also catalyzed by the use of organometallic catalysts
sponding dialkyl carbonates are obtained in 27-73% such as titanium n-butoxide,67 lead oxide,68 thallium
yield (eq 12, where R ) CH3, C2H5, n-C4H9, t-C5H11, oxide69 (Tl2O3), and zinc tetraacetoacetate.70 All the
i-C3H7, i-C4H9, t-C4H9). More emphasis has been reactions are conducted under homogeneous condi-
given to the synthesis of higher alkyl carbonates by tion with or without the use of solvent, and good
carbonate interchange reaction between ethylene yields of corresponding carbonates are obtained.
carbonate and aliphatic hydroxy compounds (eq 13, Recently a process based on the carbonate inter-
where R ) -CH3, -C2H5, n-C4H9, polyhydroxy com- change reaction of ethylene carbonate with methanol
pound, e.g., D-mannitols). Most of the patented producing dimethyl carbonate and ethylene glycol
has been developed by Texaco Chemical Co.71 The
CH2 O CH2 O available patent information of carbonate inter-
40–185 °C
Bu2Sn(OR)2 + O
2–24 h
(RO)2CO + SnBu2 (12) change reaction of ethylene carbonate with hydroxy
CH2 O CH2 O compounds (R-OH) is shown in Table 1.
O Dialkyl carbonates are also prepared by using basic
CH2 O 80–175 °C
CH2 OH
O + 2R OH RO C OR + (13) ion exchange resin72 containing quaternary am-
1–5 h
CH2 O CH2 OH monium groups. For example, dimethyl carbonate
is produced from ethylene carbonate and methanol
information reveals the use of basic inorganic com- by passing the reactants through Dowex MSA-1 at
pounds as catalysts which include alkali metal 100 °C under 7 kg/cm2 gauge in 48% conversion and
derivatives, such as hydroxides,61 alkoxides,62 hy- 99% selectivity. Carbonate interchange reaction of
drides, and alcoholate amides, and alkali metal salts ethylene carbonate with polyhydroxy compounds73
formed from weak acids, such as acetates,63 carbon- such as 1-O-(p-nitrobenzoyl)- and 1-O-benzylglycer-
ates, and bicarbonates. Organic bases such as tri- ols, 1,2:3,4-di-O-isopropylidene-D-mannitols, 1,2-O-
ethylamine63 and triphenylphosphine65 and phase isopropylidene-R-D-glucofuranose, uridine, 1,2:5,6-di-
transfer catalysts such as benzyltrimethylammonium O-isopropylidene-D-mannitol, and D-mannitol was
chloride64 and tetrabutylphosphonium bromide are carried out at 140-160 °C for 15-40 min, 30 mmHg,
also used. All the catalysts are used in the range of and corresponding cyclic carbonates were obtained
0.1-0.01 wt % based on the weight of the reaction in the range of 65-90% yield. Organosilyl carbon-
mixture. Reaction temperature varies from 175 to ates74 (R3SiO-CO-OSiR3), useful as water repel-
225 °C. Lower temperature leads to low yields, even lents, were prepared by reaction of trialkylsilane with
with relatively long reaction times. Some side reac- ethylene carbonate using NiCl2 as catalyst.
tions also take place in the case of alkyl carbonates Dimethyl carbonate and diethyl carbonate can also
which are less stable. They readily split off carbon be used in carbonate interchange reactions with
dioxide and ethers. Such side reactions take place aliphatic hydroxy compounds because the byproduct
between ethylene carbonate and 1,2-glycols. The side formed is a low-boiling point alcohol which can be
products formed are alkyl glycol ethers and polygly- easily removed from the reaction as an azeotrope
with hydrocarbon solvent. Bondav et al.75 have with dimethyl carbonate. The reaction was carried
tabulated the conditions for the carbonate inter- out using inorganic base (cesium carbonate) with
change reaction of diethyl carbonate with R-OH for phase transfer catalyst (PEG-2000) under pressure
C4-10 normal alcohols using metal hydroxides (NaOH, at 125 °C for 5 h. For example, tert-butyl methyl
KOH, Ca(OH)2) as catalysts, and 66-84% yields of carbonate was obtained in 43% yield with 95%
corresponding carbonates were obtained. Dialkyl selectivity from dimethyl carbonate and tert-butyl
carbonates containing allyl double bonds,76 which are alcohol.
useful as materials for optical glasses, are also Recently, the carbonate interchange reaction of
prepared by carbonate interchange reaction between alcohols with dimethyl carbonate has been reported
dimethyl carbonate and allyl alcohol. This is inter- at atmospheric pressure under homogeneous condi-
changed with different diols,77 and double-bond- tions using di-n-butyltin oxide compound as catalyst.81b
containing carbonate compounds are obtained which This reaction does not suffer from severe thermody-
have high refractive index. A variety of simple78 and namic constraints and is therefore more facile. The
substituted79 alkyl carbonates are obtained by car- reaction results in the formation of a mixture of
bonate interchange reaction between dimethyl car- unsymmetrical and symmetrical carbonates in good
bonate/diethyl carbonate and substituted alcohols (eq yields. Alcohols containing bulky groups and electron-
14, where R ) -CH3, -C2H5; R′ ) normal C4-C10 withdrawing groups are unreactive (Table 3). The
alcohols, substituted alcohols, alcohols containing observed reactivities of alcohols and phenols toward
double bonds) (Table 2). carbonate interchange reaction with dimethyl car-
bonate are best understood in terms of a mechanism
O O involving the formation of an alkoxy/aryloxy carbon-
85–144 °C
RO C OR + 2R′ OH
1–12 h
R′O C OR′ + 2ROH (14) ate intermediate (Scheme 8).
Carbonate interchange reaction of dimethyl car- 2. Dialkyl to Alky Aryl Carbonate

bonate with alcohols was also carried out under bas- The reaction of hydroxy compound (aliphatic or
liquid phase transfer catalysis80 (GL-PTC) conditions aromatic) with phosgene results in the formation of
in which potassium carbonate bearing PEGS are able corresponding chloroformate in the presence of an
to catalyze reactions that usually require strong basic acid-binding agent such as organic base. Reaction
media. Under such conditions the hard anions (nu- with another 1 mol of hydroxy compound (aromatic
cleophiles) generated attack the carbonyl carbon or aliphatic) gives alkyl aryl carbonate. Alkyl aryl
according to a BAC2 mechanism (eq 15). carbonate can also be prepared by carbonate inter-
change reaction of phenol with dimethyl carbonate.
OCH3 OCH3
OCH3 This reaction is slow and unfavorable from an equi-
– δ– δ–
Y+ O Y C O Y C O– librium and thermodynamic point of view. Therefore,
OCH3
OCH3 OCH3
it has to be carried out using appropriate catalyst and
reaction conditions. Yamazaki et al.82 have carried
(reagents) (activated complex,
BAC2 mechanism) out the reaction of excess phenol with dibutyl carbon-
OCH3 ate at 220 °C and 550 mmHg pressure for 8 h using
–
Y C O + OCH3 (15) dialkyltin aryl oxide catalyst. It resulted in the
(product) formation of butyl phenyl carbonate in the range of
30-45% with a selectivity of 40-70% (eq 17). In this
It is well known that dimethyl carbonate behaves
as an ester in solution where solvation may be high. O
220 °C/550 mmHg
Therefore, it reacts with nucleophiles according to a C4H9O C OC4H9 + 2PhOH 8h
BAC2 mechanism yielding carbonate interchange
O
product with alcohols. Primary alcohols react better
than secondary ones, and tertiary alcohols are almost PhO C OBu + (PhO)2CO + BuOH (17)
inactive under GL-PTC. Carbonate interchange re- yield = 30–45%
action in GL-PTC is controlled by an alkoxide anion selectivity = 40–70%
intermediate. In fact basicity trends in alkoxides
follow the order tertiary > secondary > primary, so reaction diphenyl carbonate was also formed due to
the first ones are present at equilibrium in lower the reaction of butyl phenyl carbonate with excess
concentrations than the last ones. The steric hin- phenol. In order to obtain higher selectivity of phenol
drance due to the alkyl chain is increased, and the to butyl phenyl carbonate, the reaction has to be
conversion decreases. The yields of dialkyl carbon- carried out at lower temperature, and this can be
ates obtained by this method vary from 27% to 47% achieved by the use of excess dibutyl carbonate.
(eq 16, where R ) -C2H5, n-C3H7, n-C4H9, i-C4H9). Dimethyl carbonate was reacted with phenol in the
presence of titanium tetraphenoxide83 catalyst at 180
O O °C and 6.6 atmospheric pressure with the continuous
K2CO3, PEGs
CH3O C OCH3 + 2ROH RO C OR + 2CH3OH (16) removal of methanol-dimethyl carbonate azeotrope;
180 °C
(27–47%) 53% phenyl methyl carbonate was obtained with 95%
selectivity.
The unsymmetrical81a dialkyl carbonates such as tert- Recently81b the ortho- and meta-substituted phe-
butyl methyl carbonate and tert-amyl methyl carbon- nols were selectively converted to the corresponding
ate, which are useful octane enhancers for gasoline, phenyl methyl carbonate by carbonate interchange
were prepared by carbonate interchange reaction reaction with dimethyl carbonate using di-n-butyltin
Table 2. Carbonate Interchange Reaction of Dimethyl Carbonate/Diethyl Carbonate with Various Hydroxy Compoundsa
Chem. Abstr. no. reaction conditions: yield
(Co. name) DMC/DEC hydroxy compd catalyst temp (°C)/time (h)/pressure (kg/cm2) product carbonate (%)
Organic Carbonates
83:11345f DEC K2CO3 93-120/3/0.4/xylene na

(Chemetron Corp.) CH2OH ( CH2O)2CO
O O
91:38943b DMC C2H5OH KOH 60/1/na DEC + C2H5OCO2Me 70
(BASF AG)
98:142969v DMC CH2dCH-CH2OH + (HOCH2CH2)2O NaOMe reflux/na/na OCOCH2CH2)2O 91
(Anic SPA) O
99:53768g DEC Me2CHC(Me)(OH)C(Me)(OH)Me p-MeC6H4SO3H 110 na/na/na Me Me 93
(Neos Co. Ltd.) (CH3)2 C C Me
O O
O
103:123146a DEC Br CH2dCHCH2ONa 90 na/na/7 Br 83
(Tokuyama Soda Co. Ltd.)
HO(CH2)2O CMe2 OCO(CH2)2 O CMe2
O
Br Br
110:215192q DMC OH 11,4,7,10,13-pentaoxa- reflux/na/na/hexane ( O)2CO 95
(Societe Francaise dorgano) cyclopentadecene
105:42777a DEC 3-(1-pyrrolidino)-1,2-propanediol K2CO3 reflux/3/na CH2 R 97
(Neos Co. Ltd.) O O
O
R = 3-C-pyrrolidino
108:56767w DMC OH + C6H13(CH2)2OH NaOMe 85-130/na/1 84
C6H13(CH2)2OCO2
(Hoechst AG)
110:23867s DEC CF3CH2OCH2CH(OH)CH2OH K2CO3 reflux/1/na CF3CH2O CH2 70
(Neos Co. Ltd.) O O
O
111:23523x DMC Me2CHCH(OH)C(Me)(CH2OH)Me NaOH 144/12/na Me Me 100
(Mitsui Petrochem. Ind. Ltd.) Me2CH CH CH2
O O
O
a na ) data not available.
Chemical Reviews, 1996, Vol. 96, No. 3 961
Table 3. Reaction of Alcohols (R-OH) with Dimethyl Carbonate

reaction conversion dialkyl alkyl methyl selectivity to mol of
sr no. R- time (h) (%) carbonate (%) carbonate (%) dialkyl carbonate (%) product/mol of catalyst
1 Ar-CH2- 8 93 64 29 69 61
2 n-C4H9- 12 84 72 12 86 48
3 s-C4H9- 18 84 55 29 65 56
4 t-C4H9- 24 - - - - -
5 CH2dCH-CH∞- 12 70 41 29 58.5 50
6 CF3-CH2- 24 - - - - -
a
Catalyst: di-n-butyltin oxide, 1 mol % based on alcohol; - ) no reaction.
Scheme 8. Mechanism of Carbonate Interchange Reaction in the Presence of Tin Catalyst

RO O OR
2ROH + 2Bu2Sn O Sn Sn + H2O
Bu Bu
Bu Bu
(I)
Bu
Bu
OR OCH3
O Sn C
OCH3
(I) + H3CO OCH3 O O
Sn
Bu OR
Bu
(1a)
RO OR
Bu Sn O C OCH3 + Bu2Sn O
Bu OCH3
H2O
O O
RO C OCH3 RO C OR
Bu Sn O + Bu Sn O
Bu Bu
(2) (5) + ROH + CH3OH
–CO2 O O –CO2
RO RO
RO C OCH3 RO C OR
Bu Sn OCH3 + (3) + (6) Bu Sn OR
Bu2SnO Bu2SnO
Bu (4) Bu (7)
Table 4. Reaction of Phenol and Substituted Phenols with Dimethyl Carbonatea

conversion diaryl aryl methyl selectivity to mol of
sr no. substituent (%) carbonate (%) carbonate (%) diaryl carbonate (%) product/mol of catalyst
1 H 37 33 4 90 20
2 p-CH3 39 30 9 77 24
3 p-OCH3 63 52 11 82 36
4 p-Cl 51 45 6 88 28
5 m-CH3 25 - 25 0 25
6 m-OCH3 25 - 25 0 25
7 o-CH3 11 - 11 0 11
8 o-Cl 9 - 9 0 9
9 -CHO - - - - -
10 -COOCH3 - - - - -
a Catalyst: di-n-butyltin oxide (1 mol % catalyst based on phenol and substituted phenols). Reaction time: 12 h (for sr no.
1-8), 24 h (for sr no. 9); - ) no reaction.
oxide as catalyst at atmospheric pressure (Table 4, methyl carbonate. The detailed information about
entries 5-8). catalysts, time, percent conversion, and selectivity to
A large number of patents84 have appeared in the phenyl methyl carbonate is shown in Table 5. Phenol
literature which report the preparation of phenyl is converted to phenyl methyl carbonate in 12-48%
Table 5. Preparation of Phenyl Methyl Carbonate (PhMeC) by Carbonate Interchange Reaction of Dimethyl
Carbonate with Phenol
reaction conditions:
temp (°C)/time (h)/pressure PhMeC DPC selectivity
Chem. Abstr. no. (Co. name) catalyst (kg/cm2)/solvent (%) (%) to PhMeC (%)
90:186577e Ti(OC4H9)4 160/45/na/heptane na na 94
(Bayer AG)
90:186578f (n-C4H9)2Sn(OPh)2 155/na/na/heptane na na 98
(Bayer AG)
91:92272va (n-C4H9)2Sn(OBu)2 150/na/vacuum/na 40 2.3 95
(Mitsubishi Chem. Ind. Co. Ltd.)
95:42628c TiCl3 98/na/na/na na na 100
(Snam Progetti SPA)
98:106994r Zr(acac)4 130/10/na/na 47.8 2.2 95
98:125616k Pb(OH)2PbCO3 + LiCl 130/4/na/na 27.2 na 100
99:213037y (C8H17)2SnO + Ti(OC3H7)4 + 100/na/na/na 20 na 100
(Gen. Elec. Co.) 5 Å mol sieves
104:50646bb (n-C4H9)2Sn(C2H2O2)2 + 180/1-7/na/na 14 7 67
(Gen. Elec. Co.) CH3SO3H
112:157845h Ti(OC3H7)4 280/0.5/na/na 18 2 88
(Mitsui Petrochem. Ind. Ltd.)
112:178360m (AcOSnBu2)2O 250/0.5/na/na 11 na 100
119:203159g YbCl3 170/1.5-7/na/na 16 0.7 95
(Ube Industries)
119:270820d Ti(OC3H7)4 reflux/4/na/na 12 4 75
(Bayer AG)
a Dibutyl carbonate was used. b DEC was used; na ) data not available.
yield and in >90% selectivity (eq 18). for the preparation of diaryl carbonate are organo-
metallic compounds such as titanium, tin,85 silicon,86
O lead, iron,87 lithium,88 and aluminum89 which are
98–180 °C
H3CO C OCH3 + 2PhOH used as alkoxides, oxides, and acetates. Tin com-
1–7–10 h
pounds are used as stannoxane,90 and polymeric tin
O
compounds such as poly(oxydioctylstannylene)91 are
PhO C OCH3 + (PhO)2CO + CH3OH (18) also used. A wide temperature range is reported
yield = 12–47% (150-250 °C) for the carbonate interchange reaction
selectivity = 95–100% between dialkyl carbonate and aromatic hydroxy
compound. Byproduct formed in the reaction is
3. Dialkyl to Diaryl Carbonates removed in the form of azeotrope with the hydrocar-
bon solvent, or it is removed as azeotrope with dialkyl
The oxidative carbonylation of phenol with carbon carbonate. Therefore, in this reaction dialkyl carbon-
monoxide and carbon dioxide is not an effective ate is used in excess. A number of patents are extant
method to prepare diphenyl carbonate. The best on the catalytic carbonate interchange reaction of
method as of now appears to be through the carbon- phenol with dimethyl carbonate. They reveal the use
ate interchange reaction between dialkyl carbonate of titanium and organotin catalysts. A maximum
and aromatic hydroxy compound, in spite of the fact conversion of phenol to diphenyl carbonate is ob-
that this reaction is slow and possesses unfavorable tained in the range of 34-36% with 100% selectivity.
equilibrium and thermodynamics. This reaction The use of specific catalysts, temperature, yield of
takes place in two steps. In the first step dialkyl the product, and selectivity to diphenyl carbonate is
carbonate reacts with 1 mol of aromatic hydroxy given in Table 6.
compound to form alkyl aryl carbonate. Reaction
The carbonate interchange reaction of various
with another 1 mol of hydroxy compound leads to the
para-substituted phenols with dimethyl carbonate
formation of diaryl carbonate (eq 19). This reaction
was studied at atmospheric pressure using di-n-
O
butyltin oxide as catalyst. Para substituent gave
90–180–250 °C predominantly diaryl carbonate with a low percent-
H3CO C OCH3 + 2PhOH
1–24–32 age of para-substituted phenyl methyl carbonate.
(h)
Electronic effects of the substituents appeared im-
O O portant in obtaining good conversion and selectivity
PhO C OPh + PhO C OCH3 + CH3OH (19) to product carbonate. Phenols possessing electron-
yield = 12–45% withdrawing groups were unreactive, and higher
selectivity = 50–100% nucleophilic phenols were found to be more reactive
in this reaction81b (Table 4, entries 9, 10, 1-4).
is carried out in the liquid phase under homogeneous A continuous process is also described for the
condition with soluble catalysts. Catalysts employed preparation of diphenyl carbonate from dimethyl
Table 6. Preparation of Diphenyl Carbonate by Carbonate Interchange Reaction of Dimethyl Carbonate with
Phenol
reaction conditions:
temp (°C)/time (h)/pressure DPC PhMeC selectivity
Chem. Abstr. no. (Co. name) catalyst (kg/cm2)/solvent (%) (%) to DPC (%)
92:58427K Si-Ti complex 250/3/4/N2 12.5 6.3 66
(Mitsubishi Chem. Ind. Co. Ltd.)
95:80505t Li2O3a 150-220/10/na/na 17.2 12.7 57
104:50647c poly(oxydioctylstannylene)a 180/1-24/na/na 32.2 9.1 78
(Gen. Elec. Co.)
106:67825y Fe(OAc)3 155-185/8/na/benzene 34.3 na 100
(Daicel Chem. Ind. Ltd.)
109:210720e (BuSn(OAc)2)O reflux/8/na/na 5.3 na 100
116:193904t Al(OPh)3 or Al(OMe)3 85-90/8/na/na 36.5 na 100
119:162809y MgCl2-Ti(OBu)4-organotin 190/32/na/benzene 36.4 na 100
(Tianrangi Huagong)
119:180523e (n-C4H9)2Sn(OBu)2 reflux/8/na/benzene 45 42 51
a DEC was used; na ) data not available.
carbonate. Reaction is carried out in the presence butoxide, sodium hydrogen titanium butoxide, stron-
of catalyst such as titanium phenoxide92 and in three tium methoxide, magnesium methoxide, aluminum
successive reaction zones. Conditions were selected isopropoxide, tetraethyl tin, lead borate, and sodium
to maximize the formation of aryl alkyl carbonate in phenoxide. Usually diethyl carbonate was formed,
the first two zones, while conversion to diphenyl and other symmetrical carbonates were isolated.
carbonate was favored in the third zone. The vapors However, the loss of CO2 and other side reactions
from the first two zones were separated by distillation were also observed. The course of the reaction was
to give recyclable streams. A similar continuous dependent upon the structure of the carbonates and
process is also described for the preparation of on the catalyst. The more alkaline catalysts such as
diphenyl carbonate using PbO93 catalyst; 885 g/kg/h sodium methoxide and lithium aluminum ethoxide
diphenyl carbonate with 99% selectivity is obtained. promoted more side reactions. Titanium butoxide
It is reported that Enichem Synthesis (Italy) pro- was reported to be the best catalyst for this reaction.
duces 4000 tons of diphenyl carbonate per year by Phenyl methyl carbonate was converted to diphenyl
carbonate interchange reaction of dimethyl carbonate carbonate using aluminum-based Lewis acid cata-
with phenol.31 This process has been licenced to GE lysts, and anisole was also formed due to decarboxy-
Plastics in Japan.31b lation reaction.95b It is evident from the patent
literature96,84j,k that phenyl methyl carbonate is con-
4. Alkyl Aryl Carbonate to Diaryl Carbonate verted to diphenyl carbonate using various Lewis acid
catalysts at 180-195 °C with or without the use of
Alkyl aryl carbonate can be converted to diaryl
hydrocarbon solvent to remove dialkyl carbonate (eq
carbonate by reaction with another molecule of
21). A summary of available information is pre-
aromatic hydroxy compound using a suitable catalyst.
sented in Table 7.
This reaction is slow and thermodynamically unfa-
vorable. Only one patent reports the reaction of
O O O
phenyl methyl carbonate with phenol in benzene 180–200 °C
solvent in the presence of catalyst, and byproduct 2PhO C OCH3 PhO C OPh + H3CO C OCH3 (21)
1–5 h
methanol was removed as an azeotrope. In this
reaction phenyl methyl carbonate was converted to 5. Use of Activated Carbonates
diphenyl carbonate in 48.4% yield and 95% selectiv-
ity.94 Alkyl aryl carbonates can be conveniently In the case of esters, transesterification is acceler-
converted to diaryl carbonate by self-condensation or ated due to the electron-withdrawing substituents on
disproportion reaction in presence of Lewis acid either the alkyl or alkoxy group of the ester. Like-
catalysts. Williams et al.95a have studied the dispro- wise carbonate interchange reaction can also be
portion of various unsymmetrical carbonates by accelerated by the presence of electron-withdrawing
heating in the presence of different catalysts (eq 20, groups in dialkyl and diaryl carbonates. Dialkyl
where R, R′ ) alkyl, aryl). carbonates containing fluorine groups and diaryl
carbonates containing -NO2, -Cl, or -CN in the
O O O ortho position with respect to the carbonate linkage
2RO C OR′
Catalyst
RO C OR + R′O C OR′ (20)
are more reactive in carbonate interchange reaction.
190–200 °C These carbonates are known as activated carbonates.
(unsymmetrical) (symmetrical) Diaryl carbonates such as bis(4-nitrophenyl) carbon-
ate, bis(2,4-dinitrophenyl) carbonate, and bis(2,4,6-
Mixed ethyl and aryl or aryl alkyl carbonates dis- trichlorophenyl) carbonate are also activated carbon-
proportionate in the presence of catalysts such as ates but are less reactive than bis(2-nitrophenyl)
sodium methoxide, titanium tetrachloride, titanium carbonate.
Table 7. Self-Condensation of Phenyl Methyl Carbonate to Diphenyl Carbonate

reaction conditions: conversion selectivity
Chem. Abstr. no. (Co. name) catalyst temp (°C)/time (h)/solvent (%) to DPC (%)
85:46222g Ti(OPh)4 180/4/ethylcyclohexane 70 95
(Anic SPA)
87:5655y Ti(OPh)4 180/4/na 40 95
(Anic SPA)
112:178360m Mn2(CO)10 200/1/na na na
117:130915x Na2WO4 195/5/na 74 93
117:192542g Ti(OBu)4 80/na/na na 99
(Idemitsu Kosan Co. Ltd.)
118:105312m PbO 180/3/na 89 99
(Asahi Kasei Kogyo KK)
a na ) data not available.
Scheme 9. Synthesis of Dialkyl and Diaryl Carbonates by Carbonate Interchange Reaction with Activated
Dialkyl and Diaryl Carbonates
toluene, heptane
(CF3CH2O)2CO + 2R OH (RO)2CO + 2CF3CH2OH
NaOMe
CH2
where R =
, , and CH3 (CH2)5 ; yield = 97–100%.
R= , , and ; yield = 70–85%.

H3C
NO2 NO2 OH
O
NO2
CH2Cl2/250 °C/2 h
O C O + 2R OH (RO)2CO + 2
DMAP (1 mol %)
where R = , etc.; yield = 99–100%.

, Cl
NO2
O
CH2Cl2/48 h
NO2 O C O NO2 (RO)2CO +
DMAP (1 mol %)
OH
where R = , etc.; yield = 23–52%.

, Cl
Brunelle synthesized bis(2,2,2-trifluoroethyl) car- carbonate.101 These activated carbonates are also
bonate97 and bis(2-nitrophenyl) carbonate98 by the useful in the synthesis of high molecular weight
reaction of corresponding hydroxy compounds with polycarbonates in the presence of 4-(dimethylamino)-
phosgene. Other di- or trisubstituted carbonates pyridine as catalyst.99
were synthesized by reaction with triphosgene.99
These activated carbonates reacted with various G. Other Methods of Synthesis of Dialkyl
hydroxy compounds, and the corresponding carbon- Carbonates
ates were obtained in good yields. The carbonate
interchange reaction of activated dialkyl carbonate100 1. From Halohydrins
was carried out with alcohols and phenols using
hydrocarbon solvent at the reflux temperature in the Alicyclic carbonates were prepared from vic-halo-
presence of base (Scheme 9). Carbonate interchange hydrins using sodium hydrogen carbonate102 and
reactions of bis(2-nitrophenyl)carbonate101 and bis- sodium alkyl carbonates.103 These methods require
(4-nitrophenyl)carbonate with various phenols were high temperature and pressures to obtain good yields
carried out at room temperature using an organic of the carbonates. Alicyclic carbonates can be pre-
base such as triethylamine, and the rate of reaction pared in high yields, in short reaction times, under
was accelerated by the use of hypernucleophilic mild conditions and without the above-mentioned
4-(dimethylamino)pyridine as catalyst (Scheme 9). drawbacks by simply stirring the corresponding vic-
Bis(4-nitrophenyl) carbonate was found to be less halohydrins with tetramethylammonium104 hydrogen
effective in carbonate interchange reaction for pre- carbonate in acetonitrile. Tetramethylammonium
paring diaryl carbonates. Bis(2-nitrophenyl) carbon- hydrogen carbonate was easily obtained by saturat-
ate in the presence of 4-(dimethylamino)pyridine as ing the commercially available methanol solution of
a catalyst shows a unique reactivity. This was tetramethylammonium hydroxide with carbon diox-
mainly attributed to the unusual stabilization of the ide (eq 22, where R1, R2, R3 ) -H, -CH3, -C6H5; X
tetrahedral intermediate formed by the attack of ) -Cl, -Br). Bromohydrins react faster than the
4-(dimethylamino)pyridine on the bis(2-nitrophenyl) corresponding chlorohydrins.
R2 H K2CO3 (anhydrous)
C6H5CH2Cl + n-C4H9OH
CO2/ acetonitrile DMAC, 80 °C/4h
R1 C C R3 + (CH3)4NHCO3 CO2 atm
20 °C
OH X 10-75 min C6H5CH2O C OC4H9 + HCl
R2 H
O
R1 R3 + (CH3)4NX + H2O (22) (82%)
O O (25)
O O
base
ROH + CO2 ROCOOH + R1X RO C OR1 + HX
K2CO3
2. From Alcohols and Carbon Monoxide by Elemental
Sulfur
This method is useful for the preparation of sym-
Several cyclic and acyclic carbonates were synthe- metrical and unsymmetrical dialkyl carbonates in
sized from the corresponding alcohols using carbon good yields. The reaction is efficient with primary
monoxide in good to excellent yields. Carbonates are and secondary alcohols and primary butyl bromides
formed by carbonylation of alcohol with carbon and iodides.
monoxide and elemental sulfur105 in the presence of b. From CO2, Alcohol, and Triphenylphosphine. In
triethylamine or 1-methylpyrolidine at 30 kg/cm2, 80 this reaction, an alcohol reversibly adds to carbon
°C, for 4 h to afford the corresponding ammonium dioxide, and hemicarbonic acid is formed. This reacts
salts of O-alkyl thiocarbonates followed by treatment with triphenylphosphine-diethyl azodicarboxylate
with copper(II) chloride at room temperature (eq 23, complex, and further reaction of another 1 mol of
where R ) -CH2-CH-Ph, -CH2-CH2-, -CH2- alcohol results in the formation of dialkyl carbonate
CH(CH3)-, n-C6H13-, n-C4H9-, i-C4H9-, Ph-CH2-). with the liberation of triphenylphosphine oxide and
dicarbethoxyhydrazine. This reaction is character-
N Me/THF, 4 h
O ized by mildness, simplicity, and good yield under
R OH + CO + S RO C S N
H
(23)
ambient conditions (eq 26a, where R ) i-C4H9-,
30 kg/cm2, 80 °C Me C5H11-, CH3-CH(CH3)-(CH2)4-, CH2dCH-
CH2-).109a
CuCl2/ROH
RT/18 h
THF, 180 °C
2R OH + CO2 + Ph3P: + EtO2CN NCO2Et
O RT
(26a)
RO C OR
EtO2CNHNHCO2Et + Ph3P O + ROCO2R
3. Alicyclic Carbonate from Halogenated Carbonates Dixneuf and Bruneau1091b have reported a one-step
Mono-106 or dihalogenated107 alkyl carbonates were transformation of substituted propargyl alcohols with
heated with or without catalyst at 180-200 °C for CO2 and a phosphine catalyst to a cyclic carbonate
1-4 h. Cyclic carbonates were obtained in 82-90% in 98% yield (eq 26b, where R1 ) -CH3; R2 ) -CH3,
yields with the formation of alkyl halide byproduct -C2H5, -C6H5, -n-C4H9, -CHdCH2). The reaction
(eq 24). occurs with tertiary alcohols. The R-methylene cyclic
carbonates are useful intermediates for the synthesis
Me Me
of β-oxopropyl carbonates and oxazolidinones.
180 °C
Cl CH2 CH O C OC2H5 CH2 CH + C2H5Cl
Hg(OAc)2 R1
R1
O O O R2
n-Bu3P
(24) HC C C OH + CO2 O O (26b)
O 100 °C/8 h or
50 °C/20 h
180 °C R2 O
Br CH2 CH CH2O C OC2H5 Br + EtBr
O O
Br O c. From CO2, Alcohol, and Dialkoxydibutyltin.
O Reactions of carbon dioxide with dibutyltin dialkox-
(88%) ides have been studied by Sakai et al.110 This method
was also studied by Yamazaki et al.82 who showed
4. From Carbon Dioxide the preparation of dialkyl carbonates from CO2 and
alcohols in the presence of dialkoxydibutyltin. The
Recent interest in the utilization of carbon dioxide reactions were carried out under pressure of CO2. It
as a synthetic building block has prompted investiga- is assumed that carbon dioxide is inserted into the
tions toward preparation of carbonates from carbon Sn-O bond of Bu2Sn(OR)2 followed by alcoholysis
dioxide. yielding carbonate and Bu2Sn(OH)2, which is again
a. From CO2, Alcohol, and Alkyl Halide.108 In this esterified by alcohol, so that the tin catalyst is reused.
reaction alcohol and carbon dioxide reversibly react Removal of most of the water produced from the
to form monoalkylcarbonic acid, which in turn affords reaction mixture is necessary to give higher yields
monoalkyl carbonate in the presence of potassium of carbonates (eq 27,where R′ ) -CH3, -C2H5,
carbonate. The monoalkyl carbonate thus formed -C4H9, -C5H11).
reacts with alkyl halide to produce carbonate. The
key to this reaction is the use of K2CO3 as base (eq Bu2Sn(OR′)2
25). 2R′OH + CO2 9
100-170 °C/24 h
8 (R′O)2CO + H2O (27)
d. Fixation of CO2 by Metal Salt.111 Ethanol is reagent through a solid bed bearing a liquid catalyst
added to a reactor filled with CO2, and the reaction (SL-PTC).119-122 Several reactions of industrial im-
is catalyzed by Hg(OAc)2. Diethyl carbonate is portance are carried out under such conditions.
obtained in 58% yield. Reaction of a mixture of Examples of such reactions are the oxidation of SO2
alcohols with CO2 is also catalyzed by nitronium salt. to SO3, aromatic alkylation, and oxychlorination.
For example, propargyl alcohol and methanol are However, activated anions were never allowed to
reacted with CO2 in the presence of Ru(CO)12 and react in classical organic synthesis under SL-PTC.
triethylamine for 120 h at room temperature. Pro- The second method involves the flow of gaseous
pargyl methyl carbonate was obtained in 76% yield. reagents through a molten phase transfer catalyst
supported on a solid. This is known as gas-liquid
5. Alkylation of Alkali Metal Carbonate112 phase transfer catalysis (GL-PTC). This new method
Alkali metal carbonate, e.g., ethyl potassium car- was extensively studied by Tundo et al.123
bonate, was obtained by passing CO2 through an GL-PTC technique has many advantages over the
alcoholic solution of potassium ethanolate. Alkyla- classical PTC technique. (i) A continuous process can
tion with alkyl halide gives dialkyl carbonate (eq 28, be carried out in a gas phase. (ii) It is useful for
where R′ ) -CH3, -C2H5, -C4H9, -C5H11). highly selective synthesis, and gas phase reactions
occur at a high rate due to the absence of solvation
O
– + 2 h/150 °C
of the anions. For example, nucleophilic substitution
RO COOK + R X RO C OR + KX (28) reaction occurs around 107 times faster in the gas
(92%) phase than in solution. (iii) Activated anions have
high free energy in the unsolvated state. (iv) No
VIII. Applications of Organic Carbonates solvent is used in this reaction. In GL-PTC reactions,
both reagents and products, which are in gaseous
A. Application of Dimethyl Carbonate as phase, are reversibly adsorbed on liquid film. This
Alkylating Agent under GL-PTC in turn is supported on a solid. The liquid film
Even though dimethyl carbonate can be used to constitutes the phase in which the reaction occurs
introduce a carbonate linkage by carbonate inter- because the liquid actually is a molten phase transfer
change reaction, it is also a useful chemical for a catalyst. It allows the activation of anions.
variety of synthetic and industrial applications under Catalysts able to provide reactions under GL-PTC
different reaction conditions. The various applica- conditions include both ionic substances such as
tions of dimethyl carbonate and other organic car- quaternary onium salts and neutral ligands like
bonates are detailed in this section. crown ethers, cryptands, or poly(ethylene glycol)s. In
Dimethyl carbonate is an intermediate whose GL-PTC, poly(ethylene glycol)s (PEGs) are exten-
reactivity makes it useful as a substitute for phos- sively used because PEGs are thermally stable upto
gene and dimethyl sulfate. These are used as inter- 200 °C and they have a high adjustable vapor
mediates in several industrial applications. In many pressure depending on their mean molecular weight.
organic chemical transformations, dimethyl carbon- Finally, PEGs are cheap and nontoxic substances.
ate offers a safe and cleaner reaction, free of solid In GL-PTC some problems can arise from the
wastes. limited stability with time and/or temperature be-
Dimethyl carbonate, under appropriate operating cause gas phase processes are usually performed at
conditions, is active toward various substrates in high temperatures in order to volatilize the organic
carbonylation113 and methylation.114,115 The potential reagents and speed up the reaction. Under such
areas of utilization are numerous, and it covers a conditions, decomposition or partial volatilization of
large part of the present industrial uses of phosgene the catalyst may take place. Therefore an important
and dimethyl sulfate. The use of dimethyl carbonate prerequisite for a GL-PTC catalyst is that it must
as an alkylating agent has been thoroughly studied have high thermal stability at the reaction conditions.
using various catalysts and conditions and appears The GL-PTC technique has been extensively used
to be the reagent of choice for the methylation of for a variety of organic reactions. This includes
phenols. alkylation of weak acidic compounds such as phenols
Phase transfer catalysis (PTC) has been used for and mercaptans with alkyl halides using K2CO3 as
a long time by organic chemists to catalyze many a base,124 transhalogenations in alkyl halides,125,126
organic reactions. PTC has become in recent years and production of primary alkyl halides from primary
one of the most widely used techniques in organic alcohols.127
synthesis and is applied to a great number of organic As dimethyl carbonate is a low-boiling (bp 90 °C)
reactions.116,117 Alkylation of phenols and substituted compound, it can be easily volatilized at lower tem-
phenols with dimethyl carbonate is also carried out perature and is thermally stable. Therefore dimethyl
under PTC using K2CO3 and crown ethers.118 But carbonate meets the conditions of GL-PTC technique.
the yields of the product obtained were low (eq 29). Dimethyl carbonate is used in GL-PTC for alkylation
K2CO3/18-crown-6
of weakly acidic compounds such as phenols, thiophe-
R1-PhOH 9 8 R1-PhOR (29) nols, aromatic amines, malonic acid esters, and
180 °C
DMC arylacetonitriles. Under GL-PTC conditions the an-
ions generated attack the saturated carbon of di-
where R1 ) alkyl. methyl carbonate. In this reaction a broader delo-
PTC reactions can be carried out by different calization results during the transition state, and the
methods. The first method involves flow of a gaseous corresponding ether is formed by a base-catalyzed
bimolecular alkyl-oxygen fission (BAL2) mechanism because the leaving group (SO42- or Hal-) can not
(eq 30). be removed from the reaction medium.
δ– 2. Reaction with Primary Aromatic Amines

H H O
O
–
Y + H3CO C
δ– Under GL-PTC conditions aromatic amines pro-
Y C O C (30)
OCH3 duce selectively N-methylanilines. The overall pro-
H CH3 cess is described as follows (eq 33).
(reagent)
(activated complex)
PEGs, K2CO3
ArNH2 + CH3OCOOCH3 98
ArNHCH3 + CH3OH + CO2 (33)
–
O
YCH3 + O C
CH3 The reaction does not occur in the absence of PEGs.
(products)
Besides, in the absence of K2CO3, the reaction
produces only urethane (ArNHCOOCH3). Therefore,
it is the base that promotes the subsequent alkylation
1. Reaction with Phenol and Thiophenol reaction. At 90% conversion and a dimethyl carbon-
ate/aniline molar ratio of 10, <1% N,N-dimethyl-
Under GL-PTC conditions when a mixture of aniline is produced. N-Methylaniline is produced
dimethyl carbonate and phenols or mercaptans flows industrially by the monoalkylation of aniline with
through a catalytic bed of K2CO3/PEGs, only anisole methanol in gas phase. High temperatures (up to
is produced128 (eqs 31 and 32). 400 °C), high pressures, or long contact times are
needed. This results in the formation of a mixture
PEGs, K2CO3
ArOH + CH3OCOOCH3 98 of mono- and dimethylanilines and unreacted aniline.
ArOCH3 + CH3OH + CO2 (31) 3. Reaction with Arylacetonitriles
PEGs, K2CO3 Very high selectivities in monoalkylation arise
RSH + CH3OCOOCH3 98 when dimethyl carbonate is reacted with carbanions,
RSCH3 + CH3OH + CO2 (32) under GL-PTC condition. Arylacetonitriles and ma-
lonic acid esters give only methylation, through a
BAL2 mechanism. Moreover, only mono-C-alkylation
In GL-PTC potassium carbonate-bearing PEGs as
occurs (eq 34).
catalysts are able to catalyze reactions that usually
require strong basic media. Under these conditions, PEGs, K2CO3
reactions of soft nucleophiles like ArO- and RS- are ArCH2CN + CH3OCOOCH3 9
conv ) 97.5%
8
strongly promoted. Mercaptans are more easily select ) 99.5%
obtained than alkoxides by reaction with a base and ArCH(CH3)CN + CH3OH + CO2 (34)
so undergo a faster nucleophilic displacement. On
the other hand, the nucleophilic strength of anions When arylacetonitriles are reacted with alkyl halides
is enhanced under GL-PTC conditions as they attack in the presence of strong bases, alkylation is not quite
the methyl group rather than the carbonyl one. The as selective and yields large amounts of dialkyl
overall reaction pathway is as follows: derivatives as byproducts under classical or PTC
conditions.
PhOH + B f BH+ + PhO- Owing to anion activation and presumably due to
their microenvironmental effects, dimethyl carbonate
PhO- + CH3OCOOCH3 f reacts differently in batch and in continuous flow
conditions. The results are as follows:
PhOCH3 + CH3OCOO-
products
reagents batch GL-PTC
BH+ + CH3OCOO- f B + CO2 + CH3OH ArOH ArOCOOCH3 ArOCH3
ArSH (RSH) ArSCH3(-) ArSCH3 (RSCH3)
ArNH2 ArNHCOOCH3 ArNHCH3
Overall reaction: PhOH + CH3OCOOCH3 f ROH ROCOOCH3 + (RO)2CO ROCOOCH3 + (RO)2CO
PhOCH3 + CO2 + CH3OH ArCH2CN ArCH(CN)COOCH3 ArCH(CN)CH3
Such differences might be attributed not only to

Anion activation and deficiency in solvation during anion activation but also to temperature effects. GL-
the transition state enables ArO- anions to shift the PTC derives different products from reactions carried
nucleophilic attack forward to the methyl group out in solution often in a very selective way. Thus
according to the BAL2 mechanism. The leaving the results attest that dimethyl carbonate can readily
group, namely, the methoxycarbonate anion, is not replace the highly toxic dimethyl sulfate as safe
stable and spontaneously decomposes into CO2. The methylating agent when the reactions are carried out
acidity is removed from the reaction environment, the under GL-PTC conditions in a continuous flow pro-
base is regenerated, and the process continues. cess. The detailed information based on this aspect
Alkylation with dimethyl sulfate or alkyl halides (GL-PTC) is described by Tundo et al. in a review
requires the use of a base in stoichiometric amounts article.129
Dimethyl carbonate can be used under GL-PTC for O OCH3

Pd(0)
Ar O
C (38)
alkylation of various compounds containing acidic ArOH + THF, 60 °C
52-92%
hydrogen. The reaction, however, takes place in the O
gaseous phase. Dimethyl carbonate can also be used O OCH3 (30%) (39)
in solution to carry out the alkylation reaction using HO R OH + C
(dimethylamino)pyridine,130 Lewis acids such as Al- O
(III) compounds,131 quaternary ammonium salts,132 +
and guanidine bases133 as catalysts at 100-180 °C. O
C
O
(70%)
Alkylation reactions can be carried out using lower
temperatures and neutral conditions using palladium- O
(0) as catalyst.
Pd(0), THF
Lakhmiri et al.134 converted primary and secondary 80-85%
alcohols of the carbohydrate series into allyl ethers

using allyl ethyl carbonate in the presence of Pd(0)
at 60-80 °C (eqs 35 and 36). Anomeric hydroxyl as
O R O
well as functionalized compounds like hydroxyl esters
were also allylated (eq 37). O O O
CH3 C CH2 C OC2H5 + C C2H5 (40)
O O
O O
O O 80% °C, N–methylpiperidine, Ru
Pd(0) (35)
HO O O OC2H5
+ C 60-80 °C O O O O
O O O CH3 C CH C OC2H5
O O
O
The reaction presumably involves an oxidative ad-
O O OC2H5 Pd(0) dition followed by dicarboxylation.
OH + C 60-80 °C
HO O
O O
K2CO3
O CH3O C CH CN + CH3O C OCH3
O O Ar
O CH3
O
O (36) CH3O C C CN (41)
O
O Ar
O CH3 O
K2CO3
H C2H5 C NOH + CH3 OC OCH3
O CO2CH3 180-190 °C
Pd(0) CH3
H 1:4 H3C N
HO CO2CH3 O CO2CH3
H O (42)
O OC2H5 O
+ C (37) H3C
H
HO CO2CH3 O O CO2CH3 O
H Pd(0) Pd(0)
1:2 + CH3 C O O C2H5
C C CH3
HO CO2CH3
H O O
(43)
Substituted phenols can also be converted to allyl aryl
ethers in the presence of Pd(0) catalysts135 (eq 38, B. Other Applications of Organic Carbonates
where Ar ) -C6H5, p-CH3O-C6H4-, 2,6-(CH3)2-
C6H3-, p-Cl-C6H4-, p-NO2-C6H4-). This reaction 1. Dimethyl and Diethyl Carbonates
has been extended to bisphenols recently (eq 39, The carbonate linkage plays a dominant role in
where R ) -C(CH3)2).136 Bisallyl ethers of bisphe- determining the chemical properties of dimethyl and
nol-A are important intermediates and find use in a diethyl carbonate. The carbonate interchange reac-
variety of polymer-forming reactions. Allyl carbon- tion can be used to obtain higher symmetrical and
ates can be used to alkylate ethyl acetoacetate in the unsymmetrical alkhl aryl and diaryl carbonates using
presence of a catalytic amount of ruthenium in suitable reaction conditions.
N-methylpiperidine137 (eq 40). Diethyl carbonate is an excellent solvent in the
Phenyl acetonitriles and ketone oximes react with midboiling range. This has been used as a medium
dimethyl carbonate in the presence of a base like K2- evaporating solvent for cellulose nitrate and finds
CO3 to yield the corresponding monoalkylated prod- applications where a pure neutral/acquer solvent is
uct and cyclic oxazolin-2-ones respectively138,139 (eqs required. Diethyl carbonate finds substantial use as
41 and 42). Reaction of norbornene with acetyl ethyl an intermediate for various pharmaceuticals, notably
carbonate gave a cyclopropane derivative140 (eq 43). phenobarbital where it is used to prepare diethyl
phenylmalonate. Diethyl and dimethyl carbonate are (acrylonitrile).161 They are also important for the
used in the production of urethanes, ureas,141,142 and extractive separation of mixtures162 and as additives
other aliphatic carbonic acid esters such as alkyl for hydraulic fluids.163 They are often used in oxy-
carbonates,143 cyclic carbonates,144 and oxetanes.145 alkylation reactions of -OH, -SH, or aromatic -NH
Carbonate interchange reaction with N-acylated groups in place of oxiranes, which are more difficult
2-aminoethanols followed by elimination of carbon to handle.162,164 They readily react with carboxylic
dioxide leads to polymerizable N-vinyl compounds.146 acids to form 2-hydroxyethyl esters,165 e.g., bis(2-
Dimethyl carbonate has been reacted with rice hull hydroxylethyl) terephthalate, which is a monomer for
ash using 5 wt % alkali at 352 °C to obtain tet- poly(ethylene terephthalate). Primary and secondary
ramethoxysilane.147 Dimethyl carbonate can be used amines are converted into urethanes166 or ureas.167
to introduce a carbonate linkage in a polymer by Polymerization of ethylene carbonates yields poly-
suitable carbonate interchange reaction. For ex- (ether carbonate)s because of the partial elimination
ample, diphenyl carbonate81b can be produced from of carbon dioxide.168 The hydrolysis of 5-membered
dimethyl carbonate (eq 19) which in turn can be used cyclic carbonates produces high yields of very pure
for the manufacture of an engineering polymer such 1,2-diols.169 Some specific applications of cyclic car-
as poly(aryl carbonate)s based on bisphenol-A. The bonates are described in the following sections.
latter reaction is thermodynamically favorable and a. Curing of Phenol-Formaldehyde Resins.170 Phe-
has been extensively studied during the past few nol-formaldehyde (PF) resins are used as thermoset-
years8 (eq 2). Considerable research efforts have ting wood adhesives and foundary core binders.
gone into the synthesis of poly(aryl carbonate)s by Cyclic carbonates accelerate the curing of alkaline PF
direct carbonate interchange reaction of bisphenol-A resins. PF resin curing, which is believed to be
or its diesters with dimethyl carbonate149 (eq 3). accelerated by the formation of phenate ions, is
Poly(alkyl carbonate)s can also be prepared by car- instead slowed down by increasingly alkaline pHs
bonate interchange reaction of aliphatic dihydroxy and accelerates in the presence of esters and carbon-
compounds with dimethyl carbonate using suitable ates. This has been attributed to the strength and
catalysts.150 dissociation of the acid involved in the ester which
determines the rate of curing of the resin. This
2. Diphenyl Carbonate correspondence between rate of cure and pKa of the
Diphenyl carbonate is used as an intermediate for acid ester is the first clear indication of some sort of
the synthesis of low molecular weight aliphatic acid-base mechanism. The cure acceleration of PF
monoisocynates starting from the corresponding ure- resins is faster in the presence of carbonates com-
as or allophenates.151 Dicarboxylic acids react with pared with esters. This was due to the fact that the
diphenyl carbonate to eliminate carbon dioxide and cyclic carbonate gives more functionality on the
form diphenyl esters, which are the starting materi- phenolic nuclei. Esters are monoprotic acids, whereas
als for the production of high molecular weight carbonates are diprotic, similar to carbonic acid. A
aromatic polyesters.152,153 Diphenyl carbonate can be mechanism has been proposed for cure acceleration
used to increase the viscosity of polycondensates such by cyclic carbonates.170 The cure acceleration of PF
as polyamides and polyesters.154 The reaction of resins using cyclic carbonate is widely used by
pentaerythritol phosphate alcohol with diphenyl plywood and chipboard industry.
carbonate in the presence of imidazole catalyst at 204 b. Accelerators for Curing Silicate Systems Used
°C in an isopropylated triphenyl phosphate solvent as Foundry Sand Binders. Silica sand is widely used
at 70 mmHg with distillation of phenol gave an 87% in foundries to produce molds and cores. If the sand
yield of bis(pentaerythritol phosphate) carbonate155 has to be reclaimed successfully, then the reclamation
(eq 44). process must not only restore the condition of the
O
sand by breaking down agglomerates and removing
O metal particles but also enable the sand to be reused
C OH + PhO C OPh with the same type of binding agent as before. It is
2O P O
O imidazole reported that sand bonded with aqueous sodium
204 °C (44) silicate and hardened with cyclic alkylene carbonate
O can be reclaimed to provide an acceptable reclaimed
O O sand by means of an attrition process.171 Typically,
C O C O C
O P O O P O dry sand is mixed with 3.5 wt % of a 45-50% aqueous
O O sodium silicate solution and 0.35 wt % propylene
carbonate. The sand hardens, presumably due to the
3. Allyl Carbonates formation of SiO2 gel (eq 45).
Plastics having excellent optical clarity and useful-
ness in lens applications are obtained by polymer- CH3
izing a bis(allyl carbonate) such as diethylene glycol Na2SiO3 + + H2O
bis(allyl carbonate).156,157 Allyl carbonates can be O O
used to modify other vinyl polymers.158,159 Diallyl O
carbonate is effective as a blossom-thinning agent for Na2CO3 + SiO2 (gel) + HO CH CH2 OH (45)
fruit trees.160
CH3
4. Cyclic Carbonates
Five-membered cyclic carbonates are polar and, for c. Acceleration of Epoxy Resin Curing. Use of
this reason, are excellent solvents, e.g., for poly- cyclic carbonates as reactive diluents for epoxy resins
has been reported.172-174 Studies have shown that hydroxyl group. This reaction take place in aqueous
use of cyclic carbonate results in decrease in gel time solution. The resulting urethane-containing oligo-
due to the lower viscosity and higher polarity of the mers with amine end groups can serve as amine
medium.175,176 Furthermore the reaction of amine solidifiers for epoxy resins and as solidifiers for other
with carbonates is exothermic, and this evolved heat compounds, which have the ability to react with
also increases the cure rate. The carbonates also amine or hydroxyl end groups.
significantly influence the cured resin’s thermal and By this method the end user can mix the urethane
mechanical properties. Amines reacts with carbon- oligomer with epoxy resins, apply it on a substrate,
ates to form carbonates or urethanes (eq 46) which and allow the cross-linking to occur on site, in the
O
pores of substrate so that the resulting polyurethane
fills the pores of substrate. This results in a strong
NH2 N N NH2 +
O O bond between the polyurethane and the substrate.
H H This method provides a material that has a combina-
(46) tion of all the advantages of known epoxy resins plus
the hardness, strength, and flexibility of polyure-
O
thane.
C OH
H2N N N N O f. Flexible Polyurethanes for Coating.179 Polyiso-
H H H cyanates have been used successfully as chipboard
binders. Since in this process absorption of polyiso-
result in the replacement of some of the epoxy
cyanates occurs on the wood particles, the quantity
reactive groups with unreactive groups. These ma-
of polyisocyanates needed to bind a certain amount
terials do, however, provide physical cross-link sites
of wood chips is relatively high. The efficiency of
because of their association through hydrogen bond-
polyisocyanates is greatly improved by using a poly-
ing and thus give cured resins with better room
temperature mechanical properties. isocyanate composition containing an organoclay and
d. Reactive Doluents/Compatibilizers in Polyure- a cyclic alkylene carbonate. The cyclic alkylene
thanes.177 Reaction injection molded (RIM) polyure- carbonate acts as a polar activator. This composition
thanes are made from relatively high molecular provides excellent adhesion to the wood particles,
weight polyethers which contain amine groups, di- exhibits a desirable regel time, and can be easily
amine chains extensively, and isocyanates. Several sprayed.
advantages are seen in using cyclic carbonates such g. Thermosetting Resins.180 Thermosetting resins
as propylene carbonates in RIM polyurethanes: Cy- can be obtained by polymerization of a cyclic carbon-
clic carbonate causes significant lowering of viscosity ate with a polyvalent isocyanate compound in the
of the product. Excellent heat sag properties are also presence of potassium fluoride as the catalyst. Poly-
realized. The highly polar carbonate dissolves in the (ethylene oxide), cryptands, or quarternary am-
hard block phase causing a significant decrease in monium salts are additionally used to activate the
the stiffness at elevated temperatures. It is also reaction. It is possible to complete the hardening
found that the systems containing propylene carbon- reaction within several minutes without producing
ate react slowly. This property is desirable because any appreciable amount of gas. The resulting ther-
it allows for the complete filling of larger RIM parts. mosetting resins have relatively high transparency
e. Synthesis of Polyurethanes.178 The synthesis of and excellent impact strength.
urethanes and polyurethanes is carried out without h. Hot Melt Polyurethane Composition.181 Hot
using diisocyanates. In this method an epoxide resin melt polyurethane compositions are prepared from
or polyfunctional epoxy compound is reacted with poly(butylenediol adipate), tosyl isocyanate, methyl-
carbon dioxide in the presence of quarternary am- enediphenyl diisocyanate (MDI), and propylene car-
monium salt as catalyst (eq 47). It is desirable for bonate by heating in the presence of dibutyltin
benzyldimethylammonium chloride
dilaurate as catalyst. This composition is useful as
CH2 CH Pn CH CH2 + CO2 a bonding agent in the footwear industry.
100 °C, water, 10 kg/Cm2
O O i. Superior Cleaning Solvent.182 Solvent composi-
CH2 CH Pn CH CH2 tions having superior cleaning power can be formu-
O O O O lated using cyclic carbonate as one of the key com-
ponents. Such solvents exhibit low toxicity are
O O
IPDI
nonflammable, pH neutral, essentially nonvolatile,
water and aprotic. For example, a solvent composition
60 °C
comprising of ethylene carbonate, ethylene diacetate,
triethanolamine, and/or N-methyl-2-pyrrolidone ex-
O O
hibit superior cleaning for a wide range of residues
NH2–R–HN–C–O–CH2–CH–Pn–CH–CH2–O–C–N–R–NH2 (47) and are environmentally and physiologically safe.
H
OH OH These may be diluted with water for cleaning tasks
that are insensitive to corrosion. Such a solvent
at least some of the molecules in the epoxide resin effectively removes residues such as oils, greases,
to have more than two epoxy groups. The helps to epoxy resins, organic adhesives, waxes, photoresist,
promote cross-linking in the final product. The inks, fingernail enamel, and nonpolymeric paints and
oligomer is further reacted with a diamine to form a coatings. These are also useful for removing evapo-
urethane oligomer which contains a urethane and a rative drying finishes like lacquer or varnish from
solid substrates including wood, plastic, metal, and with metal soap.189 Various complex carbonates are
ceramics. especially useful as components of greases and
j. Thermal Recording Materials.183 Cyclic carbon- lubricating oils because they do not form corrosive
ate compounds having an electron-donating com- acids when pyrolyzed.190 Addition of carbonates to
pound and an electron-accepting compound are useful fuels and lubricating oils is a means of reducing the
as thermal recording materials. These materials accumulation of engine deposits.191 Applications of
show high thermal response and good storage stabil- dialkyl carbonates in the fields of synthetic lubricants
ity for colored images. have been reviewed by Fisicaro and Gerbar in a
k. Electrolytes.184 Propylene carbonate is widely recent review.192
employed as an organic solvent in electrolytes for
high-energy density batteries and electrolytic capaci- 6. Agricultural Applications
tors, due to its good solvent properties, high dielectric Various mixed alkyl chlorinated aryl carbonates
constant, low pour point, and high boiling point. find use as herbicides and seed disinfectants. Car-
Mixtures of propylene carbonate and ethylene carbonates active as herbicides are customarily obtained
bonate are also used. Use of cyclic carbonates from alkynols,193 and those active as acaricides,
extends capacitor life and is often superior to the fungicides, and insecticides are obtained from (dini-
conventional glycol-based dielectrics. troalkyl)phenols.194,195 Dihalogenocyanophenyl alkyl
l. Extraction of Metals.184 Propylene carbonate is carbonates196,197 and alkyl phenyl carbonates pos-
used for the extraction of metals. The metals are sessing a fluorinated aliphatic group can also be used
extracted from acidic solutions as salts or complexes to make pesticides.198 Alkyl carbonates containing
formed with propylene carbonate. Metals that can the oxime functional group are active as fungicides.199
be extracted include bismuth, cadmium, cerium,
cobalt, copper, gold, iridium, iron, lead, mercury, 7. Applications in Medicinal Chemistry
molybdenum, palladium, rhodium, uranium, vana- Alkoxy carbonylation of amines is of considerable
dium, and zinc. interest in medicinal chemistry. Di(2-pyridyl) car-
m. Cosmetics and Personal Care.184 Propylene bonate is used for the synthesis of various protected
carbonate is an excellent polar additive for monto- carbonates.200 N,N′-Disuccinimidyl carbonate has
morillonite or bentonite clay gellants. These gellants been reorganized as versatile reagent for active ester
are widely used as gel bases for lipstick, skin clean- synthesis.201 N,N′-Disuccinimidyl carbonate has been
ers, antiperspirants, eye shadow, mascara, hair found to be a highly effective alkoxy-carbonylating
conditioners, and other cosmetic products. agent for a variety of primary and even sterically
n. Miscellaneous.184 Ethylene carbonate is used hindered secondary alcohols and are subsequently
in photosensitive compositions for preparing litho- converted to functionalized carbonates.202 These are
graphite plates. Plasticizers for thin acrylic films pharmacologically important organic molecules.203
also incorporate ethylene carbonate. Ethylene car- Iodoalkyl carbonates204 are useful as esterification
bonate may be employed as a liquid fuel for jet or agents for cephalosporin, penicillin, β-lactam, etc.
turboprop engines, either alone or in combination
with ethylene oxide and nitroalkanes. A propylene 8. Miscellaneous Applications
carbonate-methanol-amine mixture is an effective Higher dialkyl carbonates are useful as lubricants,
detergent for bearing components. Propylene car- solvents for cellulosic compounds, and additives.205
bonate is used in fire extinguishing compounds and Unsymmetrical carbonates such as methyl tert-butyl
antifoam agents for antifreeze. Either propylene or carbonate and methyl tert-amyl carbonate are useful
ethylene carbonate may be used in hydraulic brake as octane enhancers for gasoline.81a Salts of carbonic
fluids having low hydroscopicity and low viscosity at acid monoesters can be used to carboxylate com-
reduced temperatures. Ethylene carbonate can be pounds such as ketones.206,207
utilized as a solvent in the separation of different Some carbonates are suitable for use as flavor and
aromatic amines. Propylene carbonate is used as a fragrance sources, e.g., 4-isopropyl-5,5-dimethyl-2-
pretreatment in metal-plating processes and as a oxo-1,3-dioxane which is used to enhance the aroma
plating medium. It can also be used in the bleaching of foods, perfumes, and cosmetic and provides the
of wood. Other applications of ethylene carbonate in product with an aroma like that of coumarin or
reactions such as hydroxyethylation, hydroxyethyl tobacco.208 Mixed aromatic and aliphatic carbonates
carbonate formation, and polymerization by both are used to produce a softer poly(vinyl chloride).209
condensation and ionic methods have been described They also serve as aids in the dyeing of textiles.210
in a technical brochure published by Dow Chemical Biodegradable compositions containing dialkyl car-
Co.185 bonates are used as textile softners.211 Dialkyl
carbonates are useful as oil components for cosmetics
5. Dialkyl Carbonates as Lubricants
and pharmaceuticals.212 Ethoxylated carbonates can
Aliphatic carbonates possessing ether groups are be used as rolling oil in the manufacture of rolling
used as lubricants and hydaulic fluid.186 Oligocar- sheets.213 Some special carbonates have acquired
bonates containing ether groups are also useful as importance as protecting groups in peptide synthesis,
lubricant compositions for refrigerators. These oli- e.g., bis(pentafluorophenyl) carbonate214 is used for
gomers have low hygroscopicity, high detergency, and the synthesis of several pentafluorophenyl esters of
good compatibility with non-ozone-destroying halo- amino acids. Di-tert-butyl iminodicarbonates are
fluorocarbons.187,188 Lubricating greases useful at low useful for the introduction of protected amino func-
temperatures are made from carbonates thickened tionalities.215 Acrylate-terminated carbonates having
molecular weight in the range of 720-1500 are useful (8) Literature up to 1973 is reviewed in Gmelin Handbuch der
anorganischen Chemie: “Kohlenstoff”; Pietsch, E. H. E., Ko-
for the preparation of cross-linked carbonate-contain- towski, A., Eds.; Verlag Chemie: Weinheim Teil, 1973; Part C3,
ing polymers.216 p 14.
(9) (a) Beyer, H.; Warter, W. Lehrbuch fur Organische Chemie, 20th
Esters of carboxylic acids were readily synthesized ed.; Hirzel: Stuttgart, 1984; p 328. (b) Gmelin Handbuch der
from alkyl or aryl halides by reacting the correspond- anorganischen Chemie: “Kohlenstoff”, 8th ed.; Verlag Chemie:
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9735e. CR950067I

Organic Carbonates: Abbas-Alli G. Shaikh

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Chem. Rev.

1996, 96, 951−976 951

FSO3H SbF5/SO2 –10 to 0 °C

Protonated carbonic acid was characterized by 1H-

Scheme 1. Synthesis of Organic Carbonates by Phosgenation Methoda

a Where R ) alkyl, aryl, and substituted alkyl and aryl.

Scheme 2. Synthesis of Organic Carbonates by Scheme 3. Synthesis of Organic Carbonates by

slower to react with phosgene than aliphatic hydroxy

Scheme 4. Reaction Mechanism of Oxiranes with Carbon Dioxide by Polymer-Supported Catalysta

carbonate and a phase transfer catalyst (eq 11, where

Scheme 6. Phase Transfer-Catalyzed Reaction of Scheme 7. Carbonate Interchange Reactiona

O displaces the less nucleophilic compound, and if both

Table 1. Carbonate Interchange Reaction of Ethylene Carbonate with Alcohols

Carbonate interchange reaction of dimethyl car- 2. Dialkyl to Alky Aryl Carbonate

83:11345f DEC K2CO3 93-120/3/0.4/xylene na

Table 3. Reaction of Alcohols (R-OH) with Dimethyl Carbonate

Scheme 8. Mechanism of Carbonate Interchange Reaction in the Presence of Tin Catalyst

Table 4. Reaction of Phenol and Substituted Phenols with Dimethyl Carbonatea

1-8), 24 h (for sr no. 9); - ) no reaction.

Table 7. Self-Condensation of Phenyl Methyl Carbonate to Diphenyl Carbonate

R= , , and ; yield = 70–85%.

where R = , etc.; yield = 99–100%.

where R = , etc.; yield = 23–52%.

δ– 2. Reaction with Primary Aromatic Amines

Such differences might be attributed not only to

Dimethyl carbonate can be used under GL-PTC for O OCH3

alcohols of the carbohydrate series into allyl ethers

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