ES2667439B1 - ORGANOCATALIZERS FOR OBTAINING CYCLIC CARBONATES - Google Patents

Description

ORGANOCATALIZERS FOR THE OBTAINING OF CYCLIC CARBONATES

DESCRIPTION

FIELD OF THE INVENTION

The present invention pertains to the technical field of chemistry. The invention relates in particular to an efficient process for synthesizing cyclic carbonates from epoxides and carbon dioxide, using organocatalysts derived from imidazole. In addition, the synthesis of these organocatalysts is reported.

BACKGROUND OF THE INVENTION

Carbon dioxide (CO ² ) is the most abundant source of renewable carbon in nature. Therefore, the chemical fixation of CO ² is one of the most important topics in organic synthesis. Several methods for fixing CO ² have been developed despite the low reactivity.

Catalytic reactions are considered essential for the expansion and deepening of the synthetic utility of CO ² . A large number of inorganic and organic metal catalysts has been developed for several chemical conversions of CO ² . The synthesis of carbonates or polycarbonates from CO ² and epoxides, carboxylation reactions with CO ² , the reduction of CO ² , and other reactions have been developed and studied extensively and intensively.

The synthesis of cyclic carbonates usually involves the reaction of epoxides with carbon dioxide, and thus could be used to capture carbon dioxide, thus reducing greenhouse gas emissions in the atmosphere. In addition, cyclic carbonates have been widely used as raw materials for the preparation of polycarbonates, as electrolytes in secondary lithium ion batteries, as polar aprotic solvents and as fuel additives.

Commonly, cyclic carbonates have been synthesized by the phosgene method, presenting some disadvantages, such as the use of a highly toxic gas (phosgene), the formation of hydrogen chloride (byproduct) and the generation of wastewater containing dichloromethane (solvent) and salts. Although the phosgene method can produce cyclic carbonates profitably on a large scale, requires the development of environmentally benign methods, such as catalytic methods using CO ² and epoxides under mild reaction conditions. These criteria should reduce the carbon footprint as much as possible, to meet the sustainable conditions of CO ² conversion, including easy recycling of the catalyst for reuse.

Catalysts for the synthesis of cyclic carbonates from epoxides and carbon dioxide are already known in the state of the art, although high reaction temperatures and / or high carbon dioxide pressures are required, the reaction being carried out frequently in supercritical carbon dioxide (Lu, et al., App. Cat. A, 234 (2002), 25-33).

To optimize the reaction conditions, a wide variety of catalysts have been developed for the synthesis of cyclic carbonates. The most commonly used catalyst systems operating at room temperature are combinations of Lewis acids and nucleophiles. For example, metal halides such as ZnBr ² (Wu et al., Synth Commun, 42 (2012), 2564-2573), NbCl 5 (Wilhelm et al., Catal. Sci. Technol., 4 (2014), 1638- 1643) or CoCl ² (Sibaouih et al., Appl. Catal. A, 365 (2009), 1638-1643), as well as metal oxides (Yano et al., Chem. Commun., (1997), 1129-1130) , modified silica (Srivastava et al., Tetrahedron Lett. 47 (2006), 4213-4217) and zeolites (Tu et al., J. Catal., 199 (2001), 85-91), can be used as catalysts. The most common is to use them in combination with a suitable nucleophile.

In addition, a wide range of metal complexes that act as catalysts to obtain cyclic carbonates have been described in the literature. Complexes of Cr, Co, Al monoy bimetals, Co-porphyrin complexes and Cr-salen complexes (salen = imine derived from salicylaldehyde and ethylenediamine) have emerged as highly active catalyst systems in combination with nucleophilic co-catalysts.

Patent WO2008132474A1 describes the use of aluminum (salt) dimers catalysts and a cocatalyst, the reaction of different epoxides being carried out with carbon dioxide at room temperature, atmospheric pressure and reaction times between 3 and 24 hours using 0.1 to 10% in moles of catalyst and obtaining yields greater than 50%.

On the other hand, metal-free catalysts for the cycloaddition of CO ² with epoxides could represent an attractive alternative, since they are usually significantly more profitable, easily available, and less toxic. The sustainability of the coupling reaction of CO ² with epoxides to cyclic carbonates could be optimized (Cokoja et al, ChemSusChem 8 (2015) 2436-2454). This document presents a review of a wide range of organocatalysts that can be used for the conversion of CO ² and epoxides into cyclic carbonates. However, a direct comparison and evaluation is difficult. In almost all cases, different reaction conditions are applied, which has, to some extent, enormous effects on the catalytic performance.

Ideally, the reference reaction conditions should be based on a process of low temperature and low CO ² pressure, as well as a short reaction time. However, so far, the reaction time is still too long for these catalysts and has to be further reduced.

Future research should focus on organocatalysts that can compete with known metal catalysts, according to one of the conclusions of ChemSusChem 8 (2015) 2436-2454. The goal is to develop a metal-free catalyst that operates at room temperature, under atmospheric CO ² pressure, and with a low catalyst load. This must be easily recyclable due to the long-term perspective of converting carbon dioxide to a much larger scale than what is currently done.

DESCRIPTION OF THE INVENTION

The present invention provides the use of organocatalysts derived from imidazole, to synthesize cyclic carbonates from epoxides and carbon dioxide. These organocatalysts have a higher catalytic activity, with a shorter reaction time, lower catalyst load, lower reaction temperatures and low CO ² pressures, compared to that described in the state of the art.

The use of organocatalysts makes it possible to synthesize a large number of cyclic carbonates, thanks to the reaction of these with epoxides, as well as epoxides derived from products of natural origin.

It is advisable to copy and paste the entire text of the claims here.

According to a first aspect, the present invention provides a method of synthesis of these organocatalysts, which are very active for the reaction of epoxides with carbon dioxide, to produce cyclic carbonates and allow to carry out the reaction under mild conditions. The organocatalysts have the formula I or II:

where xn: Cl-, Br-, I-, P-CH3C6H4SO3-, CH3SO3-, CF3SO3-, (C ⁶ H ^{5) 4} B-, F4B-, CUB-, F ⁶ P-, HSO4-, SO42-, NO3-, CO32-, CH ³ (CH ²⁾ n CO ² - (n = 0-20), C6H5-CO2-, CF3CO2-.

R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ can be identical or different from each other and equal to: H, CH 3 (CH 2) n (n = 0-18), (CH 3) 2CH , (CH3) 3C, sec-Bu, C6H5, C6H5CH2, OH, CH3 (CH2) nO (n = 0-18), (CH3) 2N, CH2 = CHCH 2, CH ³ CH = CHCH ^2, F, Cl, Br , I, CHO, CN, NO2, CO2H, CH3 (CH2) nCO (n = 0-18), CH3 (CH2) nO2C (n = 0-18), o-, m-, p- [CH3 (CH2) n] -C6H4 (n = 0-18), o-, m-, p - [(CH3) 2CH] -C6H4, o-, m-, p - [(CH ^{3) 3} C] -C ⁶ H ⁴ , o-, m-, p- [sec-Bu] -C ⁶ H ⁴ , o-, m-, p- [CH ³ (CH ² ) nO] -C ⁶ H ⁴ (n = 0-18), o-, m-, P-OH-C6H4, o-, m-, p - [(CH ³ ) ² N] -C ⁶ H ⁴ , o-, m-, P-CF3-C6H4, o-, m -, PF-C6H4, o-, m-, p-Cl-C ⁶ H ⁴ , o-, m-, p-Br-C ⁶ H ⁴ , o-, m-, PI-C6H4, o-, m -, P-CHO-C6H4, o-, m-, p-CH ³ (CH ²⁾ n CO-C ⁶ H ⁴ (n = 0-18), o-, m-, P-CN-C6H4, o- , m-, P-NO2-C6H4, o-, m-, P-HO3S-C6H4, o-, m-, P-HO2C-C6H4, o-, m-, P-CH ³ (CH ² ) nO ² CC ⁶ H ⁴ (n = 0-18).

R ¹ and R ³ can be the same or different from each other and equal to: H, CH 3 (CH 2) n (n = 0-18), (CH 3) 2CH, (CH ³ ) ³ C, sec-Bu, C6H5, C6H5CH2 , CH ³ (CH ² ) nO (n = 0-18), CH ² = CHCH ² , CH ³ CH = CHCH ² , o-, m-, P- [CH ³ (CH ² ) n] -C ⁶ H ⁴ ( n = 0-18), o-, m-, ^p - [(CH3) 2CH] -C6H4, o-, m-, ^p - [(CH3) 3C] -C6H4, o-, m-, P- [ sec-Bu] -C ⁶ H ⁴ , o-, m-, p- [CH ³ (CH ² ) nO] -C ⁶ H ⁴ (n = 0-18), o-, m-, P-OH- C6H4, o-, m-, p - [(CH ^{3) 2} N] -C ⁶ H ^4, o-, m-, P-CF3-C6H4, o-, m-, PF-C6H4, o-, m -, p - Cl-C ⁶ H ⁴ , o-, m-, p-Br-C ⁶ H ⁴ , o-, m-, PI-C6H4, o-, m-, P-CHO-C6H4, o- , m-, p- [CH ³ (CH ² ) nCO] -C ⁶ H ⁴ (n = 0-18), o-, m-, P-CN-C6H4, o-, m-, P-NO2- C6H4, o-, m-, p-CH ³ (CH ² ) nO ² CC ⁶ H ⁴ (n = 0-18).

A second aspect of the invention provides a method for producing cyclic carbonates (IV) comprising contacting an epoxide (III) with carbon dioxide in the presence of an organocatalyst of formula (I) in combination with a cocatalyst that supplies Xn-, by the following reaction:

Wherein R ¹⁰ , R ¹¹ and R ¹² are independently selected from H, optionally substituted C 1-20 alkyl, optionally substituted C 3-20 heterocycle and optionally substituted C 5-20 aryl, or R ¹⁰ and R ¹² or R ¹¹ and R ¹² they form an optionally substituted linking group, between the two carbon atoms to which they are respectively attached. The linking group, together with the carbon atoms to which they are attached, can form a C5-20 cycloalkyl or optionally substituted C5-20 heterocycle. The C5-20 cycloalkyl group or C5-20 heterocycle may be substituted only at one ring position, for example, adjacent to the epoxide. Suitable substituents include optionally substituted C1-10 alkyl, optionally substituted C3-20 heterocycle and optionally substituted C5-20 aryl.

A possible substituent for the C1-10 alkyl group is a C5-20 aryl group. Another possible group of substituents include, but are not limited to, a C5-20 aryl group (e.g., phenyl, 4-methoxyphenyl), a hydroxy group, a halogen (e.g., Cl), an acetyl group, an ester group, or a C5-20 aryloxy group (eg phenoxy).

Optional substituents may be selected from: C1-10 alkyl, C3-20 heterocyclyl, C5-20 aryl, halogen, hydroxy, ether, cyano, nitro, carboxy, ester, amido, amino, acylamido, ureido, acyloxy, thiol, thioether , sulfoxide, sulfonyl, thioamido and sulfonamino.

Preferably, the epoxide is terminal, ie R ¹¹ and R ¹² = H.

In some embodiments optionally substituted C 1-4 alkyl and optionally substituted C 5-7 aryl are selected. In some of these embodiments, R ¹⁰ is unsubstituted.

The preferred epoxides are ethylene oxide (R ¹⁰ = R ¹¹ = R ¹² = H), propylene oxide (R ¹⁰ = methyl, R ¹¹ = R ¹² = H), 1,2-butylene oxide (R ¹⁰ = ethyl , R ¹¹ = R ¹² = H), and styrene oxide (R ¹⁰ = phenyl, R ¹¹ = R ¹² = H). Other epoxides of interest include 3-hydroxypropylene oxide (R ¹⁰ = CH 2 OH, R ¹¹ = R ¹² = H), 3-chloropropylene oxide (R ¹⁰ = CH 2 C R ¹¹ = R ¹² = H), 3-acetyloxypropylene oxide ( R ¹⁰ = CH 2 OAc, R ¹¹ = R ¹² = H), 3- (phenylcarbonyloxy) propylene oxide (R ¹⁰ = CH 2 OCOPh, R ¹¹ = R ¹² = H), 3-phenoxypropylene oxide (R ¹⁰ = CH 2OPh, R ¹¹ = R ¹² = H) and 4-methoxystyrene oxide (R ¹⁰ = 4-MeOC ⁶ H ⁴ , R ¹¹ = R ¹² = H).

A third aspect of the invention provides a process for producing cyclic carbonates ( IV ) comprising contacting an epoxide ( III ) with carbon dioxide in the presence of an organocatalyst of formula ( II ), by the following reaction:

Where R10, R11 and R12 have been defined above.

In another aspect of the invention, the process for producing cyclic carbonates ( IV ) comprising contacting an epoxide ( III ) with carbon dioxide at a pressure of 1 to 10 bar, in the presence of an organocatalyst of formula ( I ) in combination with a cocatalyst that provides xn, xn being: Cl-, Br-, I-, P-CH3C6H4SO3-, CH3SO3-, CF3SO3-, (C ⁶ H ^{5) 4} B-, F4B-, Cl ⁴ B- , F ⁶ P-, HSO4, SO42-, NO3-, CO32-, CH ³ (CH ²⁾ n CO ² - (n = 0-20), C6H5-CO2-, CF ³ CO ² "or organocatalyst of formula ( II) at a temperature range of 20 ° C to 100 ° C.

The process for producing cyclic carbonates of formula ( IV ) comprising contacting an epoxide of formula ( III ) with carbon dioxide in the presence of an organocatalyst of formula ( I ) in combination with a cocatalyst that supplies Xn-, where Xn- : Cl-, Br-, I-, P-CH3C6H4SO3-, CH3SO3-, CF3SO3-, (C ⁶ H ^{5) 4} B-, F4B-, CLB, F ⁶ P-, HSO4-, SO42-, NO3- , CO32-, CH ³ (CH ²⁾ n CO ² - (n = 0-20), C6H5-CO2-, CF3CO2-, takes place from 30 min to 26h.

On the other hand, the process for producing cyclic carbonates of formula ( IV ) comprising contacting an epoxide of formula ( III ) with carbon dioxide in the presence of an organocatalyst of formula ( II ), is carried out for 30 min. 26h

The concentration of the organocatalyst of formula ( I ) or ( II ) is from 0.01 to 1 mol%.

Definitions

Epoxide: The term "epoxide", as used herein, may refer to a compound of the formula:

wherein R10, R11 and R12 have been defined above.

Cyclic carbonate: the term "cyclic carbonate", as used herein, may refer to a compound of the formula:

wherein R10, R11 and R12 have been defined above.

Alkyl: the term "alkyl", as used herein, refers to a monovalent moiety obtained by removing a hydrogen atom from a carbon atom of a hydrocarbon having from 1 to 20 carbon atoms (unless specified another thing), that can be aliphatic or alicyclic and that can be saturated or unsaturated (partially or totally unsaturated). Therefore, the term "alkyl" includes the subclasses alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, etc., as discussed below.

In the context of the alkyl groups, the prefixes (eg, C1-4, C1-7, C1-20, C2-7, C3-7, etc.) indicate the number of carbon atoms or the range of the carbon atoms. number of carbon atoms. For example, the expression "C 1-4 alkyl", as used herein, refers to an alkyl group having 1 to 4 carbon atoms. Examples of alkyl groups include C 1-4 alkyl ( "lower alkyl"), C 1-7 alkyl , and C 1-6 alkyl. Note that the first prefix may vary according to other limitations; for example, for unsaturated alkyl group, the first prefix must be at least 2; for cyclic groups, the first prefix must be at least 3; etc.

Examples of saturated (unsubstituted) alkyl groups include, but are not limited to, methyl (C1), ethyl (C2), propyl (C3), butyl (C4), pentyl (C5), hexyl (Ce) and heptyl (C7) . Examples of saturated (unsubstituted) branched alkyl groups include isopropyl (C3), isobutyl (C4), sec-butyl (C4), tert-butyl (C4), isopentyl (C5) and neopentyl (C5).

Alkenyl: the term "alkenyl", as used herein, refers to an alkyl group having one or more carbon-carbon double bonds. Examples of alkenyl groups include C2-4 alkenyl, C2-7 alkenyl, C2-20 alkenyl.

Examples of (unsubstituted) alkenyl groups include, but are not limited to, ethenyl (vinyl, -CH = CH 2), 1 -propenyl (-CH = CH-CH ³ ), 2-propenyl (allyl, -CH 2 -CH = CH 2 ), isopropenyl (1-methylvinyl, -C (CH ³ ) = CH ² ), butenyl (C 4), pentenyl (C ⁵ ) and hexenyl (C ⁶ ).

Alkynyl: the term "alkynyl", as used herein, refers to an alkyl group having one or more triple bonds. Examples of alkynyl groups include C 2-4 alkynyl, C 2-7 alkynyl, C 2- 20 alkynyl.

Examples of alkynyl groups (unsubstituted) include, but are not limited to, ethynyl (-C CH), 2-propynyl (propargyl, -CH2-CH).

Cycloalkyl: the term "cycloalkyl", as used herein, refers to a cyclic alkyl; that is, a monovalent moiety obtained by elimination of a hydrogen atom from a carbocycle that can be saturated or unsaturated, the remainder of which has 3-20 carbon atoms (unless otherwise specified), including from 3 to 20 atoms in the ring. Therefore, the term "cycloalkyl" includes the cycloalkenyl and cycloalkynyl subclasses. Preferably, each ring has from 3 to 7 atoms in the ring. Examples of cycloalkyl groups include C3-20 cycloalkyl, C3-15 cycloalkyl, C3-10 cycloalkyl, C3-7 cycloalkyl.

Cyclic alkylene: the term "cyclic alkylene " as used herein refers to a divalent moiety obtained by the removal of two hydrogen atoms from two different atoms of a saturated or unsaturated carbocyclic ring, the remainder of which has from 3 to 20 atoms carbon (unless otherwise specified), including 3 to 20 atoms in the ring. Preferably each ring has from 5 to 7 atoms. Examples of cyclic alkylene groups include C3-20 cyclic alkylene, C3-15 cyclic alkylene, C3-10 cyclic alkylene, C3-7 cyclic alkylene.

Examples of alkyl and cyclic alkylene include, but not limited to , those derived from saturated hydrocarbons compounds monocyclic derivatives: cyclopropane (C3), cyclobutane (C4), cyclopentane (C5), cyclohexane (C ^6), cycloheptane (C7), methylcyclopropane (C4), dimethylcyclopropane (C5), methylcyclobutane (C5), dimethylcyclobutane (C ^6), methylcyclopentane (C ^6), dimethylcyclopentane (C7), methylcyclohexane (C7), dimethylcyclohexane (C ^8), menthane (C10); monocyclic unsaturated hydrocarbon compounds: cyclopropene (C3), cyclobutene (C4), cyclopentene (C5), cyclohexene (Ce), methylcyclopropene (C4), dimethylcyclopropene (C5), methylcyclobutene (C5), dimethylcyclobutene (Ce), methylcyclopentene (Ce), dimethylcyclopentene (C7), methylcyclohexene (C7), dimethylcyclohexene (Cs); saturated polycyclic hydrocarbon compounds: tuyan (C10), carano (C10), pinano (C10), bornano (C10), norcaran (C7), norpinano (C7), norbornane (C7), adamantane (C10), decalin (decahydronaphthalene) ( C10); unsaturated polycyclic hydrocarbon compounds: camphene (C10), limonene (C10), pinene (C10); polycyclic hydrocarbon compounds having an aromatic ring: indene (C9), indane (eg, 2,3-dihydro-1H-indene) (C9), tetralin (1,2,3,4-tetrahydronaphthalene) (C10) , acenaphthene (C12), fluoreno (C13), fenaleno (C13), acefenantreno (C15), aceantreno (C16), colantreno (C20).

Heterocyclyl: the term "heterocyclyl", as used herein, refers to a monovalent moiety obtained by elimination of a hydrogen atom from a ring atom of a heterocyclic compound, the remainder of which has from 3 to 20 atoms (except that is specified otherwise), of which from 1 to 10 are heteroatoms. Preferably, each ring has from 3 to 7 atoms, of which from 1 to 4 are heteroatoms.

Heterocyclylene: the term "heterocyclylene", as used herein, refers to a divalent moiety obtained by removing two hydrogen atoms from two different ring atoms of a heterocyclic compound, the remainder of which has from 3 to 20 atoms in the ring (unless otherwise specified), of which 1 to 10 are heteroatoms. Preferably, each ring has from 3 to 7 atoms, of which from 1 to 4 are heteroatoms.

The heterocyclyl or heterocyclylene group may be linked by carbon atoms or ring heteroatoms. Preferably the heterocyclylene group is linked by two carbon atoms.

In relation to the heterocyclyl or heterocyclylene groups, the prefixes (eg, C3-20, C3-7, C5-6, etc.) indicate the number of ring atoms, or the number of ring atoms, are carbon atoms or heteroatoms. For example, the term "heterocyclyl Cs e", as used herein, refers to a heterocyclyl group having 5 ring atoms.Examples of heterocyclyl groups include C3-20 heterocyclyl, C5-20 heterocyclyl, C3-15 heterocyclyl, C5-15 heterocyclyl, C3-12 heterocyclyl, C5-12 heterocyclyl, C3-10 heterocyclyl, C5-10 heterocyclyl, C3-7 heterocyclyl, C5-7 heterocyclyl and C5-6 heterocyclyl.

Likewise, the term "C5-6 heterocyclylene", as used herein, refers to a heterocyclylene group having 5 or 6 ring atoms. Examples of heterocyclylene groups include C3-20 heterocyclylene, C5-20 heterocyclylene, C3-15 heterocyclylene, C5-15 heterocyclylene, C3-12 heterocyclylene, C5-12 heterocyclylene, C3-10 heterocyclylene, C5-10 heterocyclylene, C3-7 heterocyclylene, C5-7 heterocyclylene, and C5-6 heterocyclylene.

Examples of monocyclic heterocyclyl and heterocyclylene groups include, but are not limited to, those derived from:

N1: aziridine (C3), azetidine (C4), pyrrolidine (tetrahydropyrrole) (C5), pyrroline (eg, 3-pyrroline, 2, 5-dihydropyrrole) (C5), 2H-pyrrole or 3H-pyrrole (isopyrrole) , isoazole) (C5), piperidine (C ^6), dihydropyridine (C ^6), tetrahydropyridine (C ^6), azepine (C7);

O 1: oxirane (C3), oxetane (C4), oxolane (tetrahydrofuran) (C5), oxole (dihydrofuran) (C5), oxane (tetrahydropyran) (C ^6), dihydropyran (C ^6), pyran (C ^6), oxepin (C7);

S 1: thiirane (C3), thietane (C4), thiolane (tetrahydrothiophene) (C5), thiane (tetrahydrothiopyran) (C ^6), thiepane (C7);

O2: dioxolane (C5), dioxane (C ^6), and dioxepane (C7);

O3: trioxane (C ⁶ );

N2: imidazolidine (C5), pyrazolidine (diazolidine) (C5), imidazoline (C5), pyrazoline (dihydropyrazole) (C5), piperazine (C ^6);

N1O 1: tetrahydrooxazole (C5), dihydrooxazole (C5), tetrahydroisoxazole (C5), dihydroisoxazole (C5), morpholine (C ^6), tetrahydrooxazine (C ^6), dihydrooxazine (C ^6), oxazine (C ^6);

N1S 1: thiazoline (C5), thiazolidine (C5), thiomorpholine (C ^6);

N2O 1: oxadiazine (C ⁶ )

O 1S 1: oxathiole (C5) and oxathiane (thioxane) (C ^6); Y,

N1O 1S 1: oxathiazine (C ⁶ ).

Examples of substituted monocyclic (non-aromatic) heterocyclylene and heterocyclylene groups include the saccharide derivatives, in cyclic form, for example, furanoses (C ⁶ ), such as arabinofuranosa, lixofuranosa, ribofuranosa and xylofuransa, and pyranose (C ⁶ ), such as alopiranose, altropyranose, glucopyranose, mannopyranose, gulopyranose, idopyranose, galactopyranose, and talopiranose.

C5-20 aryl: the term "C5-20 aryl", as used herein, refers to a monovalent moiety obtained by elimination of a hydrogen atom from an aromatic ring atom C5-20, said compound having one , two or more rings and from 5 to 20 atoms with at least one of said rings, aromatic. Preferably, each ring has from 5 to 7 carbon atoms.

The ring atoms can be all carbon atoms, as in the "carboaryl groups", in which case the group can conveniently be referred to as a "C5-20 carboaryl" group.

C5-20 Arylene: the term "C5-20 arylene", as used herein, refers to a divalent moiety, obtained by elimination of two hydrogen atoms from a C5-20 aromatic ring, said compound having one, or two or more rings, and from 5 to 20 atoms in the ring, with at least one of said rings, aromatic. Preferably, each ring has from 5 to 7 carbon atoms.

The ring atoms can be all carbon atoms, as in the "carboarylene groups" in which case the group can conveniently be referred to as a "C5-20 carboarylene" group.

Examples of C5-20 and C5-20 aryl groups that do not have heteroatoms in the ring (ie, C5-20 carboaryl groups and C5-20 carboarylene) include, but are not limited to, benzene derivatives (ie, phenyl) ) (C ⁶ ), naphthalene (C10), anthracene (C14), phenanthrene (C14), and pyrene (C16).

Alternatively, the ring atoms may include one or more heteroatoms, including, but not limited to, oxygen, nitrogen and sulfur, as in "heteroaryl groups" or "heteroarylene groups". In this case, the group can conveniently be referred to as "C5-20 heteroaryl" or "C5-20 heteroarylene", in which "C5-20" denotes the atoms in the ring, whether carbon atoms or heteroatoms. Preferably, each ring has from 5 to 7 ring atoms, of which from 0 to 4 are heteroatoms.

The heteroaryl or heteroarylene group may be linked by carbon atoms or ring heteroatoms. Preferably, the heteroarylene group is linked by two carbon atoms.

Examples of C5-20 heteroaryl groups and C5-20 heteroarylene include, but are not limited to, C5 heteroaryl groups and C5 heteroarylene derivatives of furan (oxol), thiophene (thiol), pyrrole (azole), imidazole (1,3-diazole) , pyrazole (1,2-diazole), 1,2,3-triazole, 1,2,4-triazole, oxazole, isoxazole, thiazole, isothiazole, oxadiazole, tetrazole and oxatriazole; and C ⁶ heteroaryl groups derived from isoxazine, pyridine (azine), pyridazine (1,2-diazine), pyrimidine (1,3-diazine, eg, cytosine, thymine, uracil), pyrazine (1,4-diazine) and 1,3,5-triazine.

Examples of C5-20 heteroaryl groups and C5-20 heteroarylene comprising fused rings include, but are not limited to, C9 heteroaryl groups and C9 heteroarylene derivatives of benzofuran, isobenzofuran, benzothiophene, indole, isoindole; C10 heteroaryl groups and C10 heteroarylene derivatives of quinoline, isoquinoline, benzodiazine, pyridopyridine; C14 heteroaryl groups and C14 heteroarylene groups derived from acridine and xanthene.

The alkyl, cyclic alkylene, heterocyclyl, heterocyclylene, aryl and arylene groups which have been indicated, either alone or as part of another substituent, may themselves be substituted with one or more groups selected from themselves and the additional substituents listed below.

Halogen: -F, -Cl, -Br, and -I.

Hydroxy: -OH.

Ether: -OR, wherein R is a substituent of the ether, for example a C 1-7 alkyl group (also referred to as a C 1-7 alkoxy group), a C 3- 20 heterocyclyl group (also referred to as a C 3- 20 heterocyclyloxy group), or a C5-20 aryl group (also referred to as a C5-20 aryloxy group), preferably a C 1-7 alkyl group.

Nitro: -NO2.

Cyan (nitrile, carbonitrile): -CN.

Acyl (keto): -C (O) R, wherein R is an acyl substituent, for example, H, a C 1-7 alkyl group (also referred to as C 1-7 alkyl) -accyl or C 1-7 alkanoyl), a C3-20 heterocyclyl group (also called heterocyclyl (C3-20) acyl), or a C5-20 aryl group (also referred to as aryl (C5-20) acyl), preferably a C1-7 alkyl group. Examples of acyl groups include, but are not limited to, -C (O) CH ³ (acetyl), -C (O) CH ² CH ³ (propionyl), -C (O) C (CH 3) 3 (pivaloyl), and -C (O) Ph (benzoyl, phenone).

Carboxy (carboxylic acid): -COOH.

Ester (carboxylate, carboxylic acid ester, oxycarbonyl): -C (O) OR, where R is a substituent of the ester, for example, a C 1-7 alkyl group, a C 3- 20 heterocyclyl group, or a C ⁵ aryl group - ^20, preferably C ¹ a - ^7. Exemplary ester groups include, but are not limited to, -C (O) OCH3, -C (O) OCH2CH3, -C (O) OC (CH ^, and -C (O) OPh. Amido (carbamoyl, carbamyl, aminocarbonyl , carboxamide): -C (O) NR1R2, wherein R1 and R2 are independently amino substituents group examples of amido groups include, but not limited to , -C (O) NH ^2, -C (O) NHCH3,. -C (O) N (CH ^, -C (O) NHCH2CH3 and -C (O) N (CH2CH3) 2, as well as amido groups in which R1 and R2, together with the nitrogen atom to which they are attached, they form a heterocyclic structure as in, for example, piperidinocarbonyl, morpholinocarbonyl, thiomorpholinocarbonyl, and piperazinylcarbonyl.

Amino: -NR1R2, wherein R1 and R2 are independently amino substituents, for example, hydrogen, C ^1-7 alkyl group (also referred to as C ^1-7 alkylamino or di (C ^1-7) amino), a group heterocyclyl C ^3-20, or C ⁵ aryl group - ^20, preferably H or alkyl C ^1-7, or in the case of a "cyclic" amino group, R1 and R2, taken together with the nitrogen atom to which are joined, form a heterocyclic ring that has 4 to 8 atoms in the ring. Examples of amino groups include, but are not limited to, -NH ² , -NHCH ³ , -NHCH (CH ^ -N (CH ^, -N (CH 3 CH 2) 2, and -NHPh Examples of cyclic amino groups include, but without limitation, aziridinyl, azetidinyl, pyrrolidinyl, piperidino, piperazinyl, perhydrodiazepinyl, morpholino, and thiomorpholino In particular, the cyclic amino groups may be substituted on their ring with any of the substituents defined herein for example carboxy, carboxylate and amido .

Ammonium: -NH ³ +, Z-, in which Z- is a suitable counterion, such as halide (eg Cl-, Br-), nitrate, perchlorate.

Amido (acylamino): -N (R1) C (O) R2, wherein R1 is a substituent of amino, for example, hydrogen, a C ^1-7, a heterocyclyl group C ^3-20, or a group aryl C ^5-20, preferably H or alkyl C ^1-7, most preferably H, and R2 is an acyl substituent, for example, an alkyl C ^1-7, C ^3-20 a heterocyclyl group or a group aryl C ^5-20, preferably an alkyl C ^1-7. Examples of acylamido groups include, but are not limited to, -NHC (O) CH ³ , C (O) NHC (O) CH ² CH ³ and -NHC (O) Ph. R1 and R2 together can form a cyclic structure, as for example in succinimidyl, maleimidyl and phthalimidyl:

Ureido: -N (R1) CONR2R3 wherein R1, R2 and R3 are independently substituents of the amino groups, for example, hydrogen, a C ^1-7, a heterocyclyl group or C ^3-20 aryl group C ⁵ - ^20, preferably hydrogen or alkyl C ^1-7. Examples of ureido groups include, but are not limited to, -NHCONH ² , -NHCONHMe, -NHCONHEt, -NHCONMe ² , - NHCONEt2, -NMeCONH2, - NMeCONHMe, -NMeCONHEt, -NMeCONMe2, - NMeCONEt2 and - NHCONHPh.

Acyloxy: -OC (O) R wherein R can be, for example, a C1-7 alkyl group, a C3-20 heterocyclyl group or a C5-20 aryl group, preferably a C1-7 alkyl group. Examples of acyloxy groups include, but are not limited to, -OC (O) CH ³ (acetoxy), -OC (O) CH ² CH ³ , -OC (O) C (CH 3) 3, -OC (O) Ph, -OC (O) C ⁶ ^ F and -OC (O) CH 2 Ph.

Tiol: -SH.

Thioether (sulfur): -SR, wherein R is a thioether substituent, for example, a C 1-7 alkyl group (also referred to as a C 1-7 alkylthio group), a C 3-20 heterocyclyl group or a C 5 aryl group 20, preferably a C 1-7 alkyl group. Examples of C1-7 alkylthio groups include, but are not limited to, -SCH3 and -SCH2CH3.

Sulfoxide (sulfinyl): -S (O) R, wherein R is a sulfoxide substituent, for example, a C 1-7 alkyl group, a C 3-20 heterocyclyl group or a C 5-20 aryl group, preferably a group C 1-7 alkyl. Examples of sulfoxide groups include, but are not limited to -S (O) CH ³ and -S (O) CH ² CH ³ .

Sulfonyl (sulfone): -S (O) 2R wherein R is a sulfone substituent, for example, a C 1-7 alkyl group, a C 3-20 heterocyclyl group or a C 5- 20 aryl group, preferably a C 1 alkyl group -7. Examples of sulfonyl groups include, but are not limited to -S (O) ² CH ³ (methanesulfonyl, mesyl), -S (O) 2 CF 3, -S (O) ² CH ² CH ³ and -S (O) ² C ⁶ H ⁴ CH ³ (4-methylphenylsulfonyl, tosyl).

Thioamido (thiocarbamyl): -C (S) NR ¹ R ² , wherein R ¹ and R ² are independently substituents of amino, as defined for the amino groups. Examples of thioamido groups, include, but are not limited to, -C (S) NH 2, -C (S) NHCH ³ , -C (S) N (CH ³ ) ² , and -C (S) NHCH ² CH ³ .

Sulfonamido: -NR ¹ S (O) 2R, wherein R ¹ is an amino substituent, as defined for the amino groups, and R is a substituent of the sulfonyl, for example, a C 1-7 alkyl group, a C3-20 heterocyclyl group or a C5-20 aryl group, preferably a C1-7 alkyl group. Examples of sulfonamido groups include, but are not limited to, -NHS (O) 2CH3, -NHS (O) 2Ph and -N (CH ³ ) S (O) ² C ⁶ H ⁵ .

As mentioned before, the groups forming the substituent groups listed above, e.g. C.sub.1-7 alkyl, C3-20 heterocyclyl and C5-20 aryl, may themselves be substituted. Therefore, the above definitions apply to substituent groups that are substituted.

DESCRIPTION OF MODES OF REALIZATION

General experimental procedure

Elemental analysis

The elemental analysis was carried out using the Perkin-Elmer 2400 carbon, hydrogen and nitrogen (CHN) analyzer.

Melting points

The melting points were recorded using the Stuart Scientific Melting Point Apparatus (SMP10).

IR spectroscopy

The IR spectra of pure solids were recorded on a Shimadzu IRPrestige-21 FTIR spectrometer equipped with an attenuated total reflectance (ATR) accessory.

NMR

All NMR spectra were recorded at room temperature on a Varian spectrometer. The 1H NMR spectra were recorded at 500MHz and those of 13C NMR at 100-125MHz. The coupling constants (J) are expressed in Hertz. The abbreviations used are: s = singlet, d = doublet, t = triplet, dt = doublet of triplets, m = multiplet and bs = singlet width. Chemical shifts are given in ppm relative to TMS using signals from the residual protons or carbon nuclei of the deuterated solvent.

Mass spectroscopy

The MALDI-TOF spectra were recorded on a Bruker Autoflex II TOF / TOF mass spectrometer using anthralin (1,8,9-Trihydroxyanthracene) as a matrix and sodium acetate as an additive. The samples were co-crystallized with the matrix and the additive in a 5: 250: 1 ratio in the probe and were ionized with a positive mode reflector. The external calibration was carried out using Bruker Peptide Calibration Standard II (mass range: 700 3,200 Da) and Protein Calibration Standard I (mass range: 5000-17,500 Da).

Example 1: Process for the synthesis of the catalyst ( la )

4189; Tejeda, et al., Chem. Commun., 50 (2014), 15313-15315). A mixture of salicylimaniline (3.02 g, 15.3 mmol), p-tosylmethylisonitrile (3.87 g, 19.82 mmol), K2CO3 (6.32 g, 45.73 mmol) and methanol (60 mL) was refluxed under vigorous stirring for 3 hours. After the reaction was complete, the mixture was allowed to cool to room temperature and concentrated under reduced pressure to a quarter of its initial volume, thereby obtaining a brown colored paste. This paste was washed with water (3X60 mL) forming a brown solid. The product was purified by washing with CH2Cl2 (3x20 mL). Performance 85%. The analytical data are presented below.

Data for the catalyst ( la ): Orange solid. Melting point 223-224 ° C. IR 3059 cm ^-1 .

¹ H NMR (CDCl 3, 500 MHz) 5 (ppm) = 6.20-6.60 (OH), 6.79 (t, J = 7.7 Hz, 1H, Ar), 6.91 (dd, J = 7.2 Hz, J = 1.8 Hz, 1H, Ar), 6.94 (d, J = 8 Hz, 1H, Ar), 7.15-7.17 (m, 2H, Ar), 7 , 22 (dt, J = 7.7 Hz, 1.3 Hz, 1H, Ar), 7.28 (s, 1H, H5Im), 7.33-7.37 (m, 3H, Ar), 7, 79 (s, 1H, H2Im). 13 C NMR (CDCl 3, 125 MHz) 5 (ppm) = 115.6, 116.0, 120.2, 124.9, 127.6, 128.1, 129.4, 129.8, 130.3, 131 , 3, 136.2, 138.9, 154.2.

Example 2: Procedure for the synthesis of the catalyst ( lla )

Where Xn- = I-, R1 = CeH5, R3 = CH3 (CH2) 3, R5 = OH, R2 = R4 = R6 = R7 = R8 = R9 = H

The catalyst ( Ila ) was synthesized according to the following reaction:

it was heated at 100 ° C under vigorous stirring for 7 h. After cooling the reaction mixture to room temperature, the mixture was filtered to obtain a residue. The product was purified by washing with ethyl acetate and drying in vacuo. Yield: 94%. The data of the analyzes are presented below.

Data for the catalyst ( Ila ): Light brown solid. Melting point: 179-181 ° C. IR 3100 cm-1- ¹ H NMR (500 MHz, CDCh) (ppm) = 1.02 (t, J = 7.5 Hz, 3H, CH3), 1.50 (sext, J = 7.6, 2H , CH2), 2.02 (qint, J = 7.6 Hz, 2H, CH2), 4.44 (t, J = 7.5 Hz, 2H, CH2), 6.82 (dt, J = 7, 5 Hz, J = 1.2 Hz, 1H, Ar), 6.98 (dd, J = 7.7 Hz, J = 1.8 Hz, 1H, Ar), 7.16 (d, J = 7, 5 Hz, 1H, Ar), 7.26-7.29 (m, 1H, Ar), 7.34-7.38 (m, 2H, Ar), 7.42-7.45 (m, 3H, Ar), 7.47 (d, J = 1.5 Hz, 1H, Ar), 7.49 (d, J = 1 Hz, 1H, Ar), 9.38 (d, J = 1.5 Hz, 1H, H2 | m). ¹³ C NMR (125 MHz, CDCb) (ppm) 13.8, 19.4, 31.6, 49.5, 112.7, 116.9, 117.4, 121.6, 125.6, 129, 9, 130.2, 131.8, 132.1, 132.9, 135.1, 136.8, 158.8.

Example 3. Process for the synthesis of cyclic carbonates IV 1-16 from epoxides III 1-16 .

OR

OR

^{> 11} iy ^, ^> 12+ co 2. 0 ^ 0

> 10 K

R i-i "':} C

(III) R1 ° R 12

(IV)

An epoxide ( III ) (10.0 mmol), and a combination of a catalyst ( la ) and tetrabutylammonium iodide (0.01-0.1 mmol) or a catalyst ( lla ) (0.01-0.1 mmol) ) were introduced into a stainless steel reactor with a magnetic stir bar. The autoclave was sealed, pressurized to 5 bar with CO2, heated to the desired temperature and then pressurized to 10 bar with CO2. The reaction mixture was stirred at 90 ° C for 24 h.

The conversion of epoxide ( III ) to cyclic carbonate ( IV ) was then determined by analysis of a sample using 1 H NMR spectroscopy. The remaining sample was filtered on silica gel, eluting with CH ² Cl ² to remove the catalyst. The eluent was evaporated under reduced pressure to give the cyclic carbonate, both pure and a mixture of cyclic carbonate and unreacted epoxide. In the latter case, the mixture was purified by flash chromatography using a solvent gradient of first hexane, and subsequently a Hexane: Ethyl Acetate (9: 1) mixture, then readjusting the ratio with Hexane: Ethyl Acetate (3: 1). ), and finally with ethyl acetate to give the pure cyclic carbonate. The results are shown below:

Table 1

Reacted Catalyst

R11 R12 ^river epoxide (% Ta Rend P ^co2 Time. _N

moles) (° C) (bar) (h) (%) 1 ^{III 1} C ⁶ H ⁵ HH _IIa (1) 90 10 1 87

2 ^{III 2} CH ³ HH _IIa (1) 90 10 1 82

3 ^{III 3} C ⁸ H ¹⁷ HH _IIa (1) 90 10 1 88

4 ^{III 4} CH ² CH ³ HH _IIa (1) 90 10 1 84

5 ^{III 5} (CH2) 3CH3 HH _IIa (1) 90 10 1 83

6 ^{III 6} C6H4Cl HH _IIa (1) 90 10 1 92

7 ^{III 7} C6H4Br HH _IIa (1) 90 10 1 95

8 ^{III 8} CH ² OH HH _IIa (1) 90 10 1 99

9 ^{III 9} CH2Cl HH _IIa (1) 90 10 1 88

10 ^{III 10} CH2OC6H4 HH _IIa (1) 90 10 1 94

11 ^{III 11} (CH2) 4 H _IIa (1) 90 10 24 84

12 ^{III 12} (CH2) 3 H _IIa (1) 90 10 24 92

13 ^{III 13} CH3 CH3 H _IIa (1) 90 10 24 52

14 ^{III 14} H CH3 CH3 _IIa (1) 90 10 24 63

15 ^{III 15} H C6H5 C6H5 _IIa (1) 90 10 24 78

16 ^{III 16} H CH3 C6H5 _IIa (1) 90 10 24 75

Detailed results for example 3

Next, the data of the analyzes for the cyclic carbonates IV 1-16, synthesized in the following conditions are given:

Temperature 90 ° C.

Pressure: 10 bar. Reaction time: 1-24 h.

Catalyst: 1% in moles.

Data for styrene carbonate ( IV 1 ): Yield 87%. White solid purified by washing with ethyl acetate. Mp: 49-51 ° C; 1 H NMR (500 MHz, CDCh, 298 K): 87.3-7.5 (5H, m, ArH), 5.70 (1H, t J 8.0 Hz, CHO), 4.82 (1H, t J 8.4 Hz, OCH ² ), 4.36 (1H, t J 8.6 Hz, OCH ² ); 13 C {1 H} NMR (125 MHz, CDCh, 298 K) 8154.8, 135.8, 129.7, 129.2, 125.8, 76.7, 71.2; IR (neat, cm-1): v 3060, 3029, 2961, 2903, 1791, 1599; HRMS (ESI +): calcd. m / z 187.0366 [M + Na] +; found: 187.0369.

Data for propylene carbonate ( IV 2 ): Yield 82%. Colorless liquid.1H NMR (500 MHz, CDCl ³ , 298 K): 84.8-4.9 (1H, m, OCH), 4.57 (1H, t J 8.3 Hz, OCH ² ), 4, 04 (1H, dd J 8.3, 7.4 Hz, OCH ² ), 1.50 (3H, d J 6.3 Hz, CH ³ ); 13 C {1 H} NMR (125 MHz, CDCh, 298 K) 8154.7, 73.2, 70.5, 19.2; IR (neat, cm-1): v 2961, 2902, 1781; HRMS (ESI +): calcd. m / z 125.0209 [M + Na] + found: 125.0215.

Data for 1-decene carbonate ( IV 3 ): Yield 88%. COLORLESS LIQUID 1 H NMR (500 MHz, CDCl ³ , 298 K): 84.8-4.6 (1H, m, OCH), 4.50 (1H, dd J 8.4, 7.8 Hz, OCH ² ), 4 , 04 (1H, dd J 8.4, 7.2 Hz, OCH ² ), 1.6-1.9 (2H, m, CH ² ), 1.1-1.6 (12H, m, 6 x CH ² ), 0.86 (3H, t J 6.8 Hz, CH ³ ); 13 C {1 H} NMR (125 MHz, CDCl 3, 298 K) 8155.2, 77.1, 69.5, 34.0, 31.9, 29.4, 29.2, 29.1, 24.5, 22.7, 14.2; IR (neat, cm-1): v 2916, 2851, 1800; HRMS (ESI +): calcd. m / z 201.1485 [M + H] +; found: 201.1493.

Data for 1,2-butylene carbonate ( IV 4 ): Yield 84%. COLORLESS LIQUID 1 H NMR (500 MHz, CDCl 3, 298 K): 8 4.5-4.7 (1H, m, OCH), 4.49 (1H, t J 8.1 Hz, OCH ² ), 4.05 (1H , dd J 6.3, 5.3 Hz, OCH ² ), 1.6-1.9 (2H, m, CH ² ) 1.00 (3H, t J 7.1, Hz, CH ³ ). 13 C {1 H} NMR (125 MHz, CDCl ³ , 298 K) 8155.2, 78.1.69.1.27.0, 8.6. IR (neat, cm-1): v 2938, 2917, 1801; HRMS (ESI +): calcd. m / z 139.0366 [M + Na] +; found: 139.0364.

Data for 1,2-hexylene carbonate ( IV 5 ): Yield 83%. Colorless liquid.1H NMR (500 MHz, CDCl ³ , 298 K): 8 4.68 (1H, qd J 7.5, 5.4 Hz, OCH), 4.52 (1H, t J 8.1 Hz, OCH ² ), 4.06 (1H, dd J 8.4, 7.2 Hz, OCH ² ), 1.6-1.9 (2H, m, CH ² ), 1.2-1.6 (4H , m, 2 x CH ² ), 0.91 (3H, t J 7.1 Hz, CH ³ ); 13 C {1 H} NMR (125 MHz, CDCh, 298 K) 8154.8, 77.0, 69.2, 33.4, 26.3, 22.1, 13.5; IR (neat, cm-1): v 2941.2922, 2899, 1796; HRMS (ESI +): calcd. m / z 167.0679 [M + Na] +; found: 167.0682.

Data for 4-chlorostyrene carbonate ( IV 6 ): Yield 92%. Solid white. Mp: 66-69 ° C; 1 H NMR (500 MHz, CDCl ³ , 298 K): 87.42 (2H, d J 8.5 Hz, ArH), 7.32 (2H, d J 8.5 Hz, ArH), 5.68 (1H , t J 7.9 Hz, OCH), 4.82 (1H, t J 8.4 Hz, OCH), 4.31 (1H, t J 7.8 Hz, OCH ² ); 13 C {1 H} NMR (125 MHz, CDCh, 298 K) 8154.6, 135.9, 134.4, 129.6, 127.3, 76.8, 71.1; IR (neat, cm-1): v 2973, 2698, 2121, 2017, 1971, 1793; HRMS (ESI +): calcd. m / z 220.9976 [M + Na] +; found: 220.9977.

Data for 4-bromostyrene carbonate ( IV 7 ): 95% yield. Solid white. Mp: 72-75 ° C; 1 H NMR (500 MHz, CDCh, 298 K): 87.58 (2H, dd J 8,1,2.0 Hz, ArH), 7.25 (2H, dd J 8.4, 1.8 Hz, ArH ), 5.68 (1H, t J 7.9 Hz, OCH), 4.82 (1H, t J 8.4 Hz, OCH ² ), 4.31 (1H, t J 7.8 Hz, OCH ² ); 13 C {1 H} NMR (125 MHz, CDCh, 298 K) 8154.5, 134.8, 132.5, 127.5, 123.9, 76.8, 70.9; IR (neat, cm-1): v 2951, 2522, 2161, 2017, 1981, 1801, 1771; HRMS (ESI +): calcd. m / z 264.9471 [M + Na] +; found: 264.9460.

Data for glycerol carbonate ( IV 8 ): Yield 99%. Colorless liquid.1H NMR (500 MHz, DMSO-d6, 298 K): 85.22 (1H, t J 5.5, OH), 4.7-4.8 (1 H, m, OCH), 4, 45 (1H, t J 8.3 Hz, CH ² O), 4.24 (1H, dd J 8.1, 5.8 Hz, CH ² O), 3.62 (1H, ddd J 12.5, 5.5, 2.6 Hz, CH ² OH), 3.46 (1H, ddd J 12.6, 5.6, 3.3 Hz, CH ² OH); 13 C {1 H} NMR (125 MHz, DMSO-d 6, 298 K) 8155.7, 77.5, 66.4, 61.1; IR (neat, cm-1): v 3382, 2901, 1799; HRMS (ESI +): calcd. m / z 141.0158 [M + Na] +; found: 141.0156.

Data for 3-chloropropylene carbonate ( IV 9 ): Yield 88%. COLORLESS LIQUID 1 H NMR (500 MHz, CDCl, 298 K): 84.98 (1 H, m, OCH), 4.59 (1 H, t J 8.5 Hz, CH ² CO, 4.41 (1 H, dd J 9.0, 8.7 Hz, CH ² CO, 3.79 (1H, dd J 12.0, 6.5 Hz, CH ² O), 3.73 (1H, dd J 12.5, 4.0 Hz, CH ² O); 13C {1H} NMR (125 MHz, CDCh, 298 K) 8154.2, 74.3, 67.0, 43.7, IR (neat, cm-1): 3451, 1971, 1803; HRMS (ESI +): calcd, m / z 158.9819 [M + Na] +, found: 158.9815.

Data for 3-phenoxypropylene carbonate ( IV 10 ): Yield 94%. Solid white. Mp: 94-97 ° C; 1 H NMR (500 MHz, CDCh, 298 K): 87.2-7.5 (2H, m, 2 x ArH), 7.04 (1H, t J 7.5 Hz, ArH), 6.9-7 , 0 (2H, m, 2 x ArH), 5.0-5.1 (1H, m, OCH), 4.5-4.7 (2H, m, O CH ² ), 4.26 (1H, dd J 10.6, 4.2 Hz, CH ² OPh), 4.16 (1H, dd J 10.6, 3.6 Hz, CH ² OPh); 13 C {1 H} NMR (125 MHz, CDCh, 298 K) 8158.1, 154.5, 129.7, 122.0, 114.6, 74.1.66.9, 66.2; IR (neat, cm-1): 3429, 3061.2989, 2924, 2328, 1791; HRMS (ESI +): calcd. m / z 217.0471 [M + Na] +; found: 217.0482.

Data for cis-1,2-cyclohexene carbonate ( IV 11 ): yield 84%. Solid white. Mp: 35-37 ° C; 1 H NMR (400 MHz, CDCh, 298 K): 84.6-4.7 (m, 2H, CHO), 1.8-2.0 (4H, m, 2xCH2CHO), 1.5-1.7 ( 2H, m, CH ² ), 1.3-1.4 (2H, m, CH ² ); 13C {1H} NMR (100 MHz, CDCh, 298 K) d 155.2, 75.7, 26.7, 19.2; IR (neat, cm'1): 2933, 2861, 1784; HRMS (ESI +): calcd. m / z 165.0522 [M + Na] +; found: 165.0522.

Data for cis-1,2-cyclopentene carbonate ( IV 12 ): Yield 92%. Solid white. Mp: 30-33 ° C; 1 H NMR (400 MHz, CDCh, 298 K): d5.00-5.20 (m, 2H, CHO), 2.00-2.20 (2H, m, CH ² ), 1.50-1.90 (4H, m, CH ² ); 13 C {1 H} NMR (100 MHz, CDC h, 298 K) d155.6, 81.9, 32.3, 21.6; IR (neat, cm-1): 2967, 2871, 1789; HRMS (ESI +): calcd. m / z 151.0366 [M + Na] +; found: 151.0360.

Data for cis-2,3-butene carbonate ( IV 13 ): Yield 52%. Colorless liquid of a 94: 6 mixture of the cis and trans isomers. 1 H NMR (400 MHz, CDCh, 298 K): d 4,82 (m, 2 H, CH), 1.35 (6, d J 6.2 Hz, CH ³ ); 13 C {1 H} NMR (100 MHz, CDCl, 298 K) d154.7, 76.1, 14.5; IR (neat, cm-1): 2960, 2899, 1787; HRMS (ESI +): calcd. m / z 139.0366 [M + Na] +; found: 139.0365.

Data for trans-2,3-butene carbonate ( IV 14 ): 63% yield. Solid white. Mp: 30-32 ° C; 1 H NMR (400 MHz, CDCl ³ , 298 K): d 4,32 (m, 2 H, CH), 1.44 (6, d J 5.9 Hz, CH ³ ); 13 C {1 H} NMR (100 MHz, CDC h, 298 K) d154.6, 80.0, 18.5; IR (neat, cm-1): 2955, 2871, 1776; HRMS (ESI +): calcd. m / z 139.0366 [M + Na] +; found: 139.0369.

Data for trans-1,2-diphenylethylene carbonate ( IV 15 ): Yield 78%. Solid white. Mp: 109-110 ° C; 1 H NMR (400 MHz, CDCh, 298 K): d7.35-7.45 (m, 6H, ArH), 7.25-7.35 (m, 4H, ArH), 5.42 (s, 2H, CH); 13 C {1 H} NMR (100 MHz, CDCh, 298 K) d154.4, 135.1, 129.8, 129.3, 126.1, 85.0, 80.8, 18.4; IR (neat, cm-1): 3051, 2977, 1812, 1458; HRMS (ESI +): calcd. m / z 263.0679 [M + Na] +; found: 263.0676.

Data for trans-1-phenyl-2-methylethylene carbonate ( IV 16 ): Yield 75%. Solid white. Mp: 112-115 ° C; 1 H NMR (400 MHz, CDCh, 298 K): d7.30-7.50 (5H, m, ArH) 5.12 (1H, d, J 8.0 Hz, CH), 4.59 (1H, m , CH), 1.55 (3H, d, J 8.0 Hz, CH ³ ); 13 C {1 H} NMR (100 MHz, CDCh, 298 K) d 154.4, 135.1, 129.8, 129.3, 126.1.85.0, 80.8, 18.4; IR (neat, cm-1): 3010, 2950, 1800, 1459; HRMS (ESI +): calcd. m / z 201.0522 [M + Na] +; found: 201.0529.

Claims (5)

A catalyst for producing cyclic carbonates, characterized in that said catalyst is of formula I or II:

where xn is selected from the group consisting of Cl-, Br-, I-, P-CH3C6H4SO3-, CH3SO3-, CF3SO3-, (C ⁶ H ^{5) 4} B-, F4B-, Cl ⁴ B-, F ⁶ P-, HSO4-, SO42-, NO3-, CO32-, CH ³ (CH ²⁾ n CO ² - (n = 0-20), C ⁶ H ⁵ -CO ² -y CF3CO2-, R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ may be the same or different from each other and are selected from the group consisting of H, CH 3 (CH 2) n (n = 0-18), ( CH3) 2CH, (CH3) 3C, sec-Bu, C6H5, C6H5CH2, OH, CH3 (CH2) nO (n = 0-18), (CH3) 2N, CH2 = CHCH 2, CH ³ CH = CHCH ² F, Cl, Br, I, CHO, CN, NO2, CO2H, CH3 (CH2) nCO (n = 0-18), CH3 (CH2) nO2C (n = 0-18), o-, m- , p- [CH3 (CH2) n] -C6H4 (n = 0-18), o-, m-, p - [(CH3) 2CH] -C6H4, o-, m-, p - [(CH3) 3C] -C6H4, or -, m-, p ^- [sec-Bu] -C6H4, o-, m-, p- [CH ³ (CH ²⁾ nO] -C ⁶ H ⁴ (n = 0-18), o-, m- , P-C6H4-OH, o-, m-, p - [(CH ^{3) 2} N] -C ⁶ H ^4, o-, m-, P-CF3-C6H4, o-, m-, P ^- F -C6H4, o-, m-, p-Cl-C ⁶ H ⁴ , o-, m-, p-Br-C ⁶ H ⁴ , o-, m-, P ^- I-C6H4, o-, m- , P-CHO-C6H4, o-, m-, p-CH ³ (CH ² ) nCO-C ⁶ H ⁴ (n = 0-18), o-, m-, p-CN-C ⁶ H ⁴ , o-, m-, p-NO ² -C ⁶ H ⁴ , o-, m-, P-HO3S-C6H4, o-, m-, P-HO2C-C6H4, o-, m-, and p-CH ³ (CH ² ) nO ² CC ⁶ H ⁴ (n = 0-18), R ¹ and R ³ may be the same or different from each other and are selected from the group consisting of H, CH 3 (CH 2) n (n = 0-18), (CH 2 CH, (CH 3) 3 C, sec-Bu, C 6 H 5, C6H5CH2, CH3 (CH2) nO (n = 0-18) CH 2 = CHCH 2, CH ³ CH = CHCH ^2, o-, m -, p- [CH ³ (CH ²⁾ n] -C ⁶ H ⁴ (n = 0-18), o-, m -, p - [(CH ^{3) 2} CH] -C ⁶ H ^4, o-, m-, p - [(CH ^{3) 3} C] -C ⁶ H ^4, o-, m-, p- [sec-Bu] -C ⁶ H ⁴ , o-, m-, p- [CH ³ (CH ² ) nO] -C ⁶ H ⁴ (n = 0-18), or -, m-, P-C6H4-OH, o-, m-, p - [(CH ^{3) 2} N] -C ⁶ H ^4, o-, m-, P-CF3-C6H4, o-, m- , PF-C6H4, o-, m-, p-Cl-C ⁶ H ⁴ , o-, m-, p-Br-C ⁶ H ⁴ , o-, m-, PI-C6H4, o-, m- , P-CHO-C6H4, o-, m-, p- [CH ³ (CH ²⁾ nCO] -C ⁶ H ⁴ (n = 0-18), o-, m-, P-CN-C6H4, or -, m-, P ^- NO2-C6H4, o-, m and p-CH3 (CH2) nO2C-C6H4 (n = 0-18). 2. A process for producing cyclic carbonates according to the reaction

wherein each of the substituents R ¹⁰ , R ¹¹ and R ¹² are selected from H, C 1-20 alkyl optionally substituted by C 1-10 alkyl, C 3-20 heterocyclyl, C 5-20 aryl, halogen, hydroxy, ether, cyano, nitro , carboxy, ester, amido, amino, acylamido, ureido, acyloxy, thiol, thioether, sulfoxide, sulfonyl, thioamido, and sulfonamido, C3-20 heterocycle optionally substituted by C1-10 alkyl, C3-20 heterocyclyl, C5-20 aryl, halogen , hydroxy, ether, cyano, nitro, carboxy, ester, amido, amino, acylamido, ureido, acyloxy, thiol, thioether, sulfoxide, sulfonyl, thioamido and sulfonamino and C5-20 aryl optionally substituted by C1-10 alkyl, C3 heterocyclyl 20, C5-20 aryl, halogen, hydroxy, ether, cyano, nitro, carboxy, ester, amido, amino, acylamido, ureido, acyloxy, thiol, thioether, sulfoxide, sulfonyl, thioamido and sulfonamido, or R ¹⁰ and R ¹² or R ¹¹ and R ¹² form an optionally substituted linking group, between the two carbon atoms to which they are respectively attached, where e the linking group, together with the carbon atoms to which they are attached, can form a C5-20 cycloalkyl or C5-20 heterocycle optionally substituted by C1-10 alkyl, C3-20 heterocyclyl, C5-20 aryl, halogen, hydroxy , ether, cyano, nitro, carboxy, ester, amido, amino, acylamido, ureido, acyloxy, thiol, thioether, sulfoxide, sulfonyl, thioamido and sulfonamido, characterized by contacting an epoxide with carbon dioxide in the presence of a catalyst having the formula I:

where R 2, R 4, R 5, R 6, R 7, R ⁸ and R ⁹ can be the same or different from each other and are selected from the group consisting of H, CH ³ (CH ² ) n (n = 0-18), (CH ³ ) ² CH, (CH ³ ) ³ C, sec-Bu, C ⁶ H ⁵ , C ⁶ H ⁵ CH ² , OH, CH 3 (CH 2) n O (n = 0-18), (CH 2 N, CH 2 = CH 2 , CH ³ CH = CHCH ² , F, Cl, Br, I, CHO, CN, NO 2, CO 2 H, CH 3 (CH 2) nCO (n = 0-18), CH 3 (CH 2) n O 2 C (n = 0-18), o-, m- , p- [CH ³ (CH ² ) n] -C ⁶ H ⁴ (n = 0-18), o-, m-, p - [(CH ³ ) ² CH] -C ⁶ H ⁴ , o-, m-, p - [(CH ³ ) ³ C] -C ⁶ H ⁴ , o-, m-, p- [sec-Bu] -C ⁶ H ⁴ , o-, m-, p - [CH ³ (CH ² ) nO] -C ⁶ H ⁴ (n = 0-18), o-, m-, P-OH-C6H4, o-, m-, p - [(CH ³ ) ² N ] -C ⁶ H ⁴ , o-, m-, P-CF3-C6H4, o-, m-, PF-C6H4, o-, m-, p-Cl-C ⁶ H ⁴ , o-, m-, p-Br-C ⁶ H ⁴ , o-, m-, PI-C6H4, o-, m-, P-CHO-C6H4, o-, m-, p-CH ³ (CH ² ) nCO-C ⁶ H ⁴ (n = 0-18), o-, m-, p-CN-C ⁶ H ⁴ , o-, m-, p-NO ² -C ⁶ H ⁴ , o-, m-, P-HO3S-C6H4, o-, m-, P-HO2C-C6H4, o-, m-, p-CH ³ (CH ² ) nQ ² C-OeH ⁴ (n = 0-18 ), R ¹ is selected from the group consisting of H, CH3 (CH2) n (n = 0-18), (CH3) 2CH, (CH3) 3C, sec-Bu, C6H5, C6H5CH2, CH ³ (CH ²⁾ nO (n = 0-18) CH 2 = CHCH 2, CH ³ CH = CHCH ^2, o-, m-, p- [CH ³ (CH ²⁾ n] -C ⁶ H ⁴ (n = 0-18), or -, m-, p - [(CH ³ ) ² CH] -C ⁶ H ⁴ , o-, m-, p - [(CH ³ ) ³ C] -C ⁶ H ⁴ , o-, m-, p - [sec-Bu] -C ⁶ H ⁴ , o-, m-, p- [CH ³ (CH ² ) nO] -C ⁶ H ⁴ (n = 0-18), o-, m-, P- OH-C6H4, o-, m-, p - [(CH ^{3) 2} N] -C ⁶ H ^4, o-, m-, P-CF3-C6H4, o-, m-, PF-C6H4, o- , m-, p-Cl-C ⁶ H ⁴ , o-, m-, p-Br-C ⁶ H ⁴ , o-, m-, PI-C6H4, o-, m-, P-CHO-C6H4, o-, m-, p- [CH ³ (CH ² ) nCO] -C ⁶ H ⁴ (n = 0-18), o-, m-, P-CN-C6H4, o-, m-, p- NO ² -C ⁶ H ⁴ , o-, m-, p-CH ³ (CH ² ) nO ² CC ⁶ H ⁴ (n = 0-18), in combination with a cocatalyst that supplies Xn-, where Xn-: Cl-, Br-, I-, P-CH3C6H4SO3-, CH3SO3-, CF3SO3-, (C ⁶ H ^{5) 4} B-, F4B-, CUB-, F ⁶ P-, HSO4-, SO42-, NO3-, CO32-, CH ³ (CH ² ) nCO ² - (n = 0-20), C6H5-CO2- and CF3CO2-, or of an organocatalyst of formula II:

where X n- is selected from the group consisting of Cl-, Br-, I-, P-CH3C6H4SO3-, CH3SO3-, CF3SO3-, (C ⁶ H ^{5) 4} B-, F4B-, Cl ⁴ B-, F ⁶ P-, HSO4-, SO42-, NO3-, CO32-, CH ³ (CH ²⁾ n CO ² - (n = 0-20), C6H5-CO2- and CF3CO2-, R ^2, R ^4, R ^5, R ⁶ , R ⁷ , R ⁸ and R ⁹ may be the same or different from each other and are selected from the group consisting of H, CH 3 (CH 2) n (n = 0-18), (CH 3) 2CH, (CH 3) 3C, sec -Bu, C6H5, C6H5CH2, OH, CH ³ (CH ²⁾ nO (n = 0-18), (CH ^{3) 2} N, CH 2 = CHCH 2, CH ³ CH = CHCH ^2, F, Cl, Br, I, CHO, CN, NO2, CO2H, CH3 (CH2) nCO (n = 0-18), CH3 (CH2) nO2C (n = 0-18), o-, m-, p- [CH ³ (CH ² ) n ] -C ⁶ H ⁴ (n = 0-18), o-, m-, p - [(CH ³ ) ² CH] -C ⁶ H ⁴ , o-, m-, p - [(CH ³ ) ³ C] -C ⁶ H ⁴ , o-, m-, p- [sec-Bu] -C ⁶ H ⁴ , o-, m-, p- [CH ³ (CH ² ) nO] -C ⁶ H ⁴ ( n = 0-18), o-, m-, P-OH-C6H4, o-, m-, p - [(CH ³ ) ² N] -C ⁶ H ⁴ , o-, m-, P-CF3 -C6H4, o-, m-, PF-C6H4, o-, m-, p-Cl-C ⁶ H ⁴ , o-, m-, p-Br-C ⁶ H ⁴ , o-, m-, PI -C6H4, o-, m-, P-CHO-C6H4, o-, m-, p-CH ³ (CH ²⁾ n CO-C ⁶ H ⁴ (n = 0-18), o-, m-, P -CN-C6H4, o-, m-, P-NO2-C 6H4, o-, m-, P-HO3S-C6H4, o-, m-, P-HO2C-C6H4, o-, m- and p-CH ³ (CH ² ) nO ² CC ⁶ H ⁴ (n = 0 -18), R ¹ and R ³ may be the same or different from each other and are selected from the group consisting of H, CH 3 (CH 2) n (n = 0-18), (CH 3) 2CH, (CH 3) 3C, sec- Bu, C6H5, C6H5CH2, CH ³ (CH ²⁾ nO (n = 0-18) CH 2 = CHCH 2, CH ³ CH = CHCH ^2, o-, m-, p- [CH ³ (CH ²⁾ n] - C ⁶ H ⁴ (n = 0-18), o-, m-, p - [(CH ³ ) ² CH] -C ⁶ H ⁴ , o-, m-, p - [(CH ³ ) ³ C] -C ⁶ H ⁴ , o-, m-, p- [sec-Bu] -C ⁶ H ⁴ , o-, m-, p- [CH ³ (CH ² ) nO] -C ⁶ H ⁴ (n = 0-18), o-, m-, P-OH-C6H4, o-, m-, p - [(CH ³ ) ² N] -C ⁶ H ⁴ , o-, m-, P-CF3-C6H4 , o-, m-, PF-C6H4, o-, m-, p-Cl-C ⁶ H ⁴ , o-, m-, p-Br-C ⁶ H ⁴ , o-, m-, pi-CeH ⁴ , o-, m-, p-CHO-CeH ^ o-, m-, p- [CH ³ (CH ² ) nOO] -OeH ⁴ (n = 0-18) , o-, m-, p-CN-CeH ⁴ , o-, m-, p-NO ² -CeH ⁴ , o-, m- and p-CH ³ (CH ² ) nO ² C-CeH ⁴ (n = 0-18). 3. The process according to claim 2, characterized in that the reaction temperature is in the range between 20 and 100 ° C. 4. The process according to claim 2 to 3, characterized in that the reaction pressure is in the range between 1 and 10 bar. 5. The process according to any of claims 2 to 4, characterized in that the reaction time in reaction III ^ IV is in the range between 30 min and 2e hours. and. The process according to any of claims 2 to 5, characterized in that the concentration of catalyst is in the range between 0.01 and 1% in moles.