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    • 专利摘要:
    Organocatalysts for obtaining cyclic carbonates. The invention relates to organocatalysts derived from imidazole and their use for the preparation of cyclic carbonates from epoxides and carbon dioxide, which is carried out at a carbon dioxide pressure of 10 bar, 90ºC of temperature, reaction times between 1 and 24 hours and an organocatalyst concentration of 1% in moles, reaching high yields. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2667439A1
    申请号:ES201631419
    申请日:2016-11-07
    公开日:2018-05-10
    发明作者:Antonio Leandro OTERO MONTERO；Juan FERNÁNDEZ BAEZA；Juan TEJEDA SOJO；Agustín LARA SANCHEZ；José Antonio CASTRO OSMA
    申请人:Universidad de Castilla La Mancha；
    IPC主号:
    专利说明:

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    DESCRIPTION
    FIELD OF THE INVENTION
    The present invention belongs 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 (CO2) is the most abundant renewable source of carbon in nature. Therefore, the chemical fixation of CO2 is one of the most important topics in organic synthesis. Several methods for CO2 fixation have been developed despite the low reactivity.
    Catalytic reactions are considered essential for the expansion and deepening of the synthetic utility of CO2. A large number of inorganic and organic metal catalysts has been developed for various chemical conversions of CO2. The synthesis of carbonates or polycarbonates from CO2 and epoxides, carboxylation reactions with CO2, CO2 reduction, and other reactions have been developed and studied extensively and intensively.
    The synthesis of cyclic carbonates normally involves the reaction of epoxides with carbon dioxide, and therefore 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 aprotic polar solvents and as fuel additives.
    Commonly, cyclic carbonates have been synthesized by the phosgene method, which presents some drawbacks, 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
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    It can produce cyclic carbonates profitably on a large scale, the development of environmentally benign methods, such as catalytic methods using CO2 and epoxides under mild reaction conditions, is required. These criteria should reduce the carbon footprint as much as possible, to meet the sustainable conditions of CO2 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 pressures of carbon dioxide are required, the reaction being frequently carried out in supercritical carbon dioxide (Lu, et al., App. Cat. A, 234 (2002), 25-33).
    To optimize the reaction conditions, a wide variety of catalysts for the synthesis of cyclic carbonates has been developed. The most commonly used catalyst systems that operate at room temperature are combinations of Lewis acids and nucleophiles. For example, metal halides such as ZnBr2 (Wu et al., Synth. Commun, 42 (2012), 2564-2573), NbCl5 (Wilhelm et al., Catal. Sci. Technol., 4 (2014), 1638-1643 ) or CoCl2 (Sibaouih et al., Appl. Catal. A, 365 (2009), 1638-1643), as well as metal oxides (Yano et al., Chem. Commun., (1997), 1129-1130), silica modified (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 for obtaining cyclic carbonates have been described in the literature. Complexes of Cr, Co, Al mono- and bimetallic, Co-porphyrin complexes and Cr-sale complexes (exit = imine derived from salicylaldehyde and ethylenediamine) have emerged as highly active catalyst systems in combination with nucleophilic co-catalysts.
    WO2008132474A1 describes the use of aluminum catalysts (exits) dimers 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 at 10 mol% of catalyst and obtaining yields greater than 50%.
    On the other hand, metal-free catalysts for CO2 cycloaddition with epoxides could represent an attractive alternative, since they are generally significantly more
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    Cost effective, easily available, and less toxic. The sustainability of the CO2 coupling reaction 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 CO2 and epoxides into cyclic carbonates. However, a comparison and direct evaluation is difficult. In almost all cases, different reaction conditions apply, which has, to some extent, enormous effects on catalytic performance.
    Ideally, the reference reaction conditions should be based on a process of low temperature and low CO2 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.
    According to one of the conclusions of ChemSusChem 8 (2015) 2436-2454, future research should focus on organocatalysts that can compete with known metal catalysts. The objective is to develop a metal-free catalyst that operates at room temperature, under atmospheric CO2 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 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 greater catalytic activity, with a shorter reaction time, lower catalyst load, lower reaction temperatures and low CO2 pressures, compared to that described in the state of the art.
    The use of organocatalysts allows a large number of cyclic carbonates to be synthesized, thanks to their reaction with epoxides, as well as epoxides derived from products of natural origin.
    It is advisable to copy and paste here all the text of the claims.
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    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 the reaction to be carried out under mild conditions. The organocatalysts have the formula I or II:
    R6
    - vn- nx
    image 1
    image2
    in which Xn-: Cl-, Br-, I-, P-CH3C6H4SO3-, CH3SO3-, CF3SO3-, (C6H5) 4B-, F4B-, CUB-, F6P-, HSO4-, SO42-, NO3-, CO32-, CH3 (CH2) nCO2- (n = 0-20), C6H5-CO2-, CF3CO2-.
    R2, R4, R5, R6, R7, R8 and R9 can be the same or different from each other and equal to: H, CH3 (CH2) n (n = 0-18), (CH3) 2CH, (CH3) 3C, sec -Bu, C6H5, C6H5CH2, OH, CH3 (CH2) nO (n = 0-18), (CH3) 2N, CH2 = CHCH2, CH3CH = CHCH2, 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, o-, m-, p- [sec-Bu] - C6H4, o-, m-, p- [CH3 (CH2) nO] -C6H4 (n = 0-18), o-, m-, P-OH-C6H4, o-, m-, p - [(CH3 ) 2N] -C6H4, o-, m-, P-CF3-C6H4, o-, m-, PF-C6H4, o-, m-, p-Cl-C6H4, o-, m-, p-Br- C6H4, o-, m-, PI-C6H4, o-, m-, P-CHO-C6H4, o-, m-, p-CH3 (CH2) nCO-C6H4 (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-CH3 (CH2) # 2C-C6H4 (n = 0-18).
    R1 and R3 can be the same or different from each other and equal to: H, CH3 (CH2) n (n = 0-18), (CH3) 2CH, (CH3) 3C, sec-Bu, C6H5, C6H5CH2, CH3 (CH2 ) nO (n = 0-18), CH2 = CHCH2, CH3CH = CHCH2, o-, m-, P- [CH3 (CH2) n] -C6H4 (n = 0-18), o-, m-, p - [(CH3) 2CH] -C6H4, o-, m-, p - [(CH3) 3C] -C6H4, o-, m-, P- [sec-Bu] -C6H4, o-, m-, p - [CH3 (CH2) nO] -C6H4 (n = 0-18), o-, m-, P-OH-C6H4, o-, m-, p - [(CH3) 2N] -C6H4, o-, m-, P-CF3-C6H4, o-, m-, PF-C6H4, o-, m-, p-Cl-C6H4, o-, m-, p-Br-C6H4, o-, m-, PI -C6H4, o-, m-, P-CHO-C6H4, o-, m-, p- [CH3 (CH2) nCO] -C6H4 (n = 0-18), o-, m-, P-CN- C6H4, o-, m-, P-NO2-C6H4, o-, m-, p-CH3 (CH2) No2C-C6H4 (n = 0-18).
    A second 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 (I) in combination with a cocatalyst that supplies Xn-, by the following reaction:
    10
    or
    R
    11; v ^ 12 + co2
    d10 K
    (III)
    R
    ■ A
    11 c
    > 10
    R
    (IV)
    Where R10, R11 and R12 are independently selected from H, optionally substituted C1-20 alkyl, optionally substituted C3-20 heterocycle and optionally substituted C5-20 aryl, or R10 and R12 or R11 and R12 form an optionally substituted linker group, between the two carbon atoms to which they are attached respectively. The connecting group, together with the carbon atoms to which they are attached, can form an optionally substituted C5-20 cycloalkyl or C5-20 heterocycle. The C5-20 cycloalkyl or C5-20 heterocycle group may be substituted only at a 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.
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    A possible substituent for the C1-10 alkyl group is a C5-20 aryl group. Another possible group of substituents include, but is not limited to, a C5-20 aryl group (e.g., phenyl, 4-methoxyphenyl), a hydroxy group, a halogen (e.g., Cl), an acetyl group, a ester group, or a C5-20 aryloxy group (eg phenoxy).
    Optional substituents can 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 R11 and R12 = H.
    In some embodiments, optionally substituted C1-4 alkyl and optionally substituted C5-7 aryl are selected. In some of these embodiments R10 is not substituted.
    Preferred epoxides are ethylene oxide (R10 = R11 = R12 = H), propylene oxide (R10 = methyl, R11 = R12 = H), 1,2-butylene oxide (R10 = ethyl, R11 = R12 = H) , and styrene oxide (R10 25 = phenyl, R11 = R12 = H). Other epoxides of interest include 3-hydroxypropylene oxide (R10 =
    CH2OH, R11 = R12 = H), 3-chloropropylene oxide (R10 = CH2C R11 = R12 = H), 3- acetyloxypropylene oxide (R10 = CH2OAc, R11 = R12 = H), 3- (phenylcarbonyloxy) propylene oxide (R10 = CH2OCOPh, R11 = R12 = H), 3-phenoxypropylene oxide (R10 = CH2OPh, R11 = R12 = H) and 4-methoxystyrene oxide (R10 = 4-MeOC6H4, R11 = R12 = 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:
    OR
    R11'V ^ 12 + C02> 10 K
    R '
    (III)
    R
    OR
    . TO
    11 c
    > 10
    R
    12
    (IV)
    5 In which 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 supplies Xn-, where Xn- is: Cl-, Br-, I-, P-CH3C6H4SO3-, CH3SO3-, CF3SO3-,
    (C6H5) 4B-, F4B-, Cl4B-, F6P-, HSO4, SO42-, NO3-, CO32-, CH3 (CH2) nCO2- (n = 0-20), C6H5-CO2-, CF3CO2 "or an 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-, (C6H ^ B-, F4B-, CLB-, F6P-, HSO4-,
    SO42-, NO3-, CO32-, CH3 (CH2) nCO2- (n = 0-20), C6H5-CO2-, CF3CO2-, is carried out from 30 min to 26h.
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    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 at 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:
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    R1V
    R10
    (III)
    R12
    in which 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:
    R
    OR
    TO
    11 c
    > 10
    R
    12
    (IV)
    in which 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 1 to 20 carbon atoms (unless specified otherwise), which can be aliphatic or alicyclic and which can be saturated or unsaturated (partially or totally unsaturated). Therefore, the term "alkyl" includes the alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, etc. subclasses, as discussed below.
    In the context of the alkyl groups, the prefixes (e.g., C1-4, C1-7, C1-20, C2-7, C3-7, etc.) indicate the number of carbon atoms or the range of the number of carbon atoms. For example, the term "C1-4 alkyl", as used herein, refers to an alkyl group having 1 to 4 carbon atoms. Examples of alkyl groups include C1-4 alkyl ("lower alkyl"), C1-7 alkyl and C1-20 alkyl. Note that the first prefix may vary according to other limitations; for example, for unsaturated alkyl groups, 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) . The examples of
    saturated (unsubstituted) branched alkyl groups include isopropyl (C3), isobutyl (C4), sec-butyl (C4), tert-butyl (C4), isopentyl (C5) and neopentyl (C5).
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    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 alkenyl groups (unsubstituted) include, but are not limited to, ethenyl (vinyl, -CH = CH2), 1-propenyl (-CH = CH-CH3), 2-propenyl (allyl, -CH2-CH = CH2) , isopropenyl (1-methylvinyl, -C (CH3) = CH2), butenyl (C4), pentenyl (C5) and hexenyl (C6).
    Alkynyl: The term "alkynyl," as used herein, refers to an alkyl group having one or more triple bonds. Examples of alkynyl groups include C2-4 alkynyl, C2-7 alkynyl, C2-20 alkynyl.
    Examples of alkynyl groups (unsubstituted) include, but are not limited to, ethynyl (-C ° CH), 2-propynyl (propargyl, -CH2-C ° CH).
    Cycloalkyl: the term "cycloalkyl", as used herein, refers to a cyclic alkyl; that is, a monovalent moiety obtained by removing a hydrogen atom from a carbocycle that can be saturated or unsaturated, the rest of which has 3-20 carbon atoms (unless otherwise specified), including 3 to 20 atoms in the ring. Therefore, the term "cycloalkyl" includes the cycloalkenyl and cycloalkynyl subclasses. Preferably, each ring has 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 removing two hydrogen atoms from two different atoms from a saturated or unsaturated carbocyclic ring, the rest of which has 3 to 20 atoms carbon (unless otherwise specified), including 3 to 20 atoms in the ring. Preferably each ring has 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 are not limited to, those derived from saturated monocyclic hydrocarbon compounds derived from: cyclopropane (C3), cyclobutane (C4), cyclopentane (C5), cyclohexane (C6), cycloheptane (C7), methylcyclopropane ( C4), dimethylcyclopropane (C5), methylcyclobutane (C5), dimethylcyclobutane (C6), methylcyclopentane (C6), dimethylcyclopentane (C7), methylcyclohexane (C7), dimethylcyclohexane (C8), methane (C10); unsaturated monocyclic hydrocarbon compounds: cyclopropene (C3), cyclobutene (C4),
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    cyclopentene (C5), cyclohexene (Ce), methylcyclopropene (C4), dimethylcyclopropene (C5), methylcyclobutene (C5), dimethylcyclobutene (Ce), methylcyclopentene (Ce), dimethylcyclopentene (C7), methylcyclohexene (C7) dimethylcyclohexene (C7); saturated polycyclic hydrocarbon compounds: tuyano (C10), carano (C10), pinano (C10), bornano (C10), norcarano (C7), norpinano (C7), norbornano (C7), adamantano (C10), decalina (decahidronaftaleno) ( C10); unsaturated polycyclic hydrocarbon compounds: canphene (C10), limonene (C10), pinene (C10); polycyclic hydrocarbon compounds having an aromatic ring: indene (C9), indane (e.g., 2,3-dihydro-1H-indene) (C9), tetralin (1,2,3,4-tetrahydronaphthalene) (C10) , acenaphthene (C12), fluorene (C13), phenalene (C13), acefenanthrene (C15), aceantrene (C16), collantrene (C20).
    Heterocyclyl: The term "heterocyclyl," as used herein, refers to a monovalent moiety obtained by removing a hydrogen atom from a ring atom of a heterocyclic compound, the rest of which has 3 to 20 atoms (except otherwise specified), of which 1 to 10 are heteroatoms. Preferably, each ring has 3 to 7 atoms, of which 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 atoms from the ring of a heterocyclic compound, the rest of which has 3 to 20 atoms in the ring (unless otherwise specified), of which 1 to 10 are heteroatoms. Preferably, each ring has 3 to 7 atoms, of which 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 (e.g., C3-20, C3-7, C5-6, etc.) indicate the number of ring atoms, or the range of the number of ring atoms, be carbon atoms or heteroatoms. For example, the term "Cse heterocyclyl," as used herein, refers to a heterocyclyl group having 5 oe ring atoms. Examples of heterocyclyl groups include C3-20 heterocyclyl, C5-20 heterocyclyl, heterocyclyl C3-15, 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.
    Similarly, 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 heterocyclyl groups include, but are not limited to, those derived from:
    5 N1: aziridine (C3), azetidine (C4), pyrrolidine (tetrahydropyrrol) (C5), pyrroline (e.g., 3-pyrroline, 2,
    5-dihydropyrrole) (C5), 2H-pyrrole or 3H-pyrrole (isopyrrole, isoazole) (C5), piperidine (C6), dihydropyridine (C6), tetrahydropyridine (C6), azepine (C7);
    O1: oxirane (C3), oxetane (C4), oxolane (tetrahydrofuran) (C5), oxol (dihydrofuran) (C5), oxano (tetrahydropyran) (C6), dihydropyran (C6), pyrano (C6), oxepine (C7) ;
    S1: thiran (C3), thietane (C4), thiolane (tetrahydrothiophene) (C5), tiano (tetrahydrothiopyran) (C6), tiepane (C7);
    O2: dioxolane (C5), dioxane (C6), and dioxepane (C7);
    O3: trioxane (C6);
    N2: imidazolidine (C5), pyrazolidine (diazolidine) (C5), imidazoline (C5), pyrazoline
    15 (dihydropyrazole) (C5), piperazine (C6);
    N1O1: tetrahydrooxazol (C5), dihydrooxazol (C5), tetrahydroisoxazol (C5), dihydroisoxazol (C5), morpholine (C6), tetrahydrooxazine (C6), dihydrooxazine (C6), oxazine (C6);
    N1S1: thiazoline (C5), thiazolidine (C5), thiomorpholine (C6);
    N2O1: oxadiazine (C6)
    O1S1: oxatiol (C5) and oxatiano (thioxane) (C6); Y,
    N1O1S1: oxathiazine (C6).
    Examples of substituted (non-aromatic) monocyclic heterocyclyl and heterocyclylene groups include saccharide derivatives, in cyclic form, for example, furanoses (C6), such as arabinofuranose, lixofuranose, ribofuranose and xylofuran, and pyranose (C6), such as Allopyranose, allotropyranous, glucopyranous, manopyranous, gulopyranous, idopyranous, galactopyranous, and talopyranose.
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    C5-20 aryl: the term "C5-20 aryl", as used herein, refers to a monovalent moiety obtained by removing a hydrogen atom from a C5-20 aromatic ring atom, said compound having one , two or more rings and 5 to 20 atoms with at least one of said rings, aromatic. Preferably, each ring has 5 to 7 carbon atoms.
    The ring atoms may all be carbon atoms, as in the "carboaryl groups", in which case the group may 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 removing two hydrogen atoms from a C5-20 aromatic ring, said compound having one, or two or more rings, and 5 to 20 atoms in the ring, with at least one of said rings, aromatic. Preferably, each ring has 5 to 7 carbon atoms.
    The ring atoms may all be carbon atoms, as in the "carboarylene groups" in which case the group may conveniently be referred to as a "carboarylene group"
    C5-20 ”.
    Examples of C5-20 aryl and C5-20 arylene groups that do not have ring heteroatoms (ie, C5-20 carboaryl and C5-20 carboarylene groups) include, but are not limited to, benzene derivatives (ie, phenyl ) (C6), 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 the "heteroaryl groups" or "heteroarylene groups." In this case, the group may conveniently be referred to as "C5-20 heteroaryl" or "C5-20 heteroarylene", in which "C5-20" indicates the atoms in the ring, whether they are carbon atoms or heteroatoms. Preferably, each ring has 5 to 7 ring atoms, of which 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 and C5-20 heteroarylene groups include, but are not limited to, C5 heteroaryl and C5 heteroarylene groups derived from furan (oxol), thiophene (thiol), pyrrole (azol), imidazole (1,3-diazole) , pyrazole (1,2-diazol), 1,2,3-triazole, 1,2,4-triazole, oxazole, isoxazole, thiazole, isothiazole, oxadiazole, tetrazole and oxatriazole; and C6 heteroaryl groups derived from isoxazine, pyridine (azine),
    pyridazine (1,2-diazine), pyrimidine (1,3-diazine; e.g., cytosine, thymine, uracil), pyrazine (1,4-diazine) and 1,3,5-triazine.
    Examples of C5-20 heteroaryl and C5-20 heteroarylene groups comprising fused rings include, but are not limited to, C9 heteroaryl and C9 heteroarylene groups derived from benzofuran, isobenzofuran, benzothiophene, indole, isoindole; C10 heteroaryl and C10 heteroarylene groups derived from quinoline, isoquinoline, benzodiazine, pyridopyridine; C14 heteroaryl 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, where R is a substituent of the ether, for example a C1-7 alkyl group (also called C1-7 alkoxy group), a C3-20 heterocyclyl group (also called C3-20 heterocyclyloxy group), or a C5-20 aryl group (also called a C5-20 aryloxy group), preferably a C1-7 alkyl group.
    Nitro: -NO2.
    Cyano (nitrile, carbonitrile): -CN.
    Acyl (keto): -C (O) R, wherein R is an acyl substituent, for example, H, a C1-7 alkyl group (also referred to as (C1-7) alkyl-acyl or C1-7 alkanoyl) , a C3-20 heterocyclyl group (also called C3-20 heterocyclyl), or a C5-20 aryl group (also called C5-20) aryl acyl), preferably a C1-7 alkyl group. Examples of acyl groups include, but are not limited to, -C (O) CH3 (acetyl), -C (O) CH2CH3 (propionyl), -C (O) C (CH3) 3 (pivaloyl), and -C (O ) Ph 25 (benzoyl, fenone).
    Carboxy (carboxylic acid): -COOH.
    Ester (carboxylate, carboxylic acid ester, oxycarbonyl): -C (O) OR, wherein R is a substituent of the ester, for example, a C1-7 alkyl group, a C3-20 heterocyclyl group, or a
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    C5-20 aryl group, preferably a C1-7 alkyl group. Examples of 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, in which R1 and R2 are independently substituents of the amino group Examples of amido groups include, but are not limited to, -C (O) NH2, -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, form a heterocyclic structure as in, for example, piperidinocarbonyl, morpholinocarbonyl, thiomorpholinocarbonyl, and piperazinylcarbonyl.
    Amino: -NR1R2, in which R1 and R2 are independently substituents of amino, for example hydrogen, a C1-7 alkyl group (also called C1-7 alkylamino or dialkyl (C1-7) amino), a C3- heterocyclyl group 20, or a C5-20 aryl group, preferably H or a C1-7 alkyl group, or in the case of a "cyclic" amino group, R1 and R2, taken together with the nitrogen atom to which they are attached, form a heterocyclic ring having 4 to 8 atoms in the ring. Examples of amino groups include, but without
    limit, -NH2, -NHCH3, -NHCH (CH ^ -N (CH ^, -N (CH3CH2) 2, and -NHPh. Examples of cyclic amino groups include, but are not limited to, 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: -NH3 +, 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 the amino, for example hydrogen, a C1-7 alkyl group, a C3-20 heterocyclyl group, or a C5 aryl group -20, preferably H or a C1-7 alkyl group, most preferably H, and R2 is an acyl substituent, 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 acylamido groups include, but are not limited to, -NHC (O) CH3, C (O) NHC (O) CH2CH3 and -NHC (O) Ph. R1 and R2 together can form a cyclic structure, such as succinimidyl, maleimidyl and phthalimidyl, for example:
    Ureido: -N (R1) CONR2R3 in which R1, R2 and R3 are independently substituents of the amino groups, for example, hydrogen, a C1-7 alkyl group, a C3-20 heterocyclyl group or a C5-20 aryl group, preferably hydrogen or a C1-7 alkyl group. Examples of ureido groups include, but are not limited to, -NHCONH2, -NHCONHMe, -NHCONHEt, -NHCONMe2,
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    -NHCONEt2, -NMeCONH2, -NMeCONHMe, -NMeCONHEt, -NMeCONMe2, -NMeCONEt2 and -NHCONHPh.
    Acyloxy: -OC (O) R wherein R may 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) CH3
    (acetoxy), -OC (O) CH2CH3, -OC (O) C (CH3) 3, -OC (O) Ph, -OC (O) C6 ^ F and -OC (O) CH2Ph.
    Thiol: -SH.
    Thioether (sulfide): -SR, wherein R is a thioether substituent, for example, a C1-7 alkyl group (also called a C1-7 alkylthio group), a C3-20 heterocyclyl group or a C5- aryl group 20, preferably a C1-7 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 substituent of sulfoxide, for example, a C1-7 alkyl group, a C3-20 heterocyclyl group or a C5-20 aryl group, preferably an alkyl group C1-7. Examples of sulfoxide groups include, but are not limited to -S (O) CH3 and -S (O) CH2CH3.
    Sulfonyl (sulfone): -S (O) 2R in which R is a sulfone substituent, for example, a C1-7 alkyl group, a C3-20 heterocyclyl group or a C5-20 aryl group, preferably a C1 alkyl group -7. Examples of sulfonyl groups include, but are not limited to -S (O) 2CH3 (methanesulfonyl, mesyl), -S (O) 2CF3, -S (O) 2CH2CH3 and -S (O) 2C6H4CH3 (4-methylphenylsulfonyl, tosyl).
    Thioamido (thiocarbamyl): -C (S) NR1R2, in which R1 and R2 are independently amino substituents, as defined for the amino groups. Examples of thioamido groups include, but are not limited to, -C (S) NH2, -C (S) NHCH3, -C (S) N (CH3) 2, and -C (S) NHCH2CH3.
    Sulfonamido: -NR1S (O) 2R, in which R1 is an amino substituent, as defined for the amino groups, and R is a sulfonyl substituent, for example, a C1-7 alkyl group, a C3 heterocyclyl group -20 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 (CH3) S (O) 2C6H5.
    As mentioned before, the groups that form the substituent groups listed above, e.g. eg, C1-7 alkyl, C3-20 heterocyclyl and C5-20 aryl, may themselves be substituted. Therefore, the above definitions apply to substituent groups that are substituted.
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    DESCRIPTION OF EMBODIMENTS
    General experimental procedure Elemental analysis
    The elemental analysis was carried out using the Perkin-Elmer 2400 carbon, hydrogen and nitrogen (CHN) analyzer.
    Melting points
    Melting points were recorded using the Stuart Scientific Melting Point Apparatus (SMP10).
    IR spectroscopy
    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 1 H NMR spectra were recorded at 500 MHz and those of 13 C NMR at 100-125 MHz. Coupling constants (J) are expressed in Hertz. The abbreviations used are: s = singlet, d = doublet, t = triplet, dt = triplet doublet, m = multiplet and bs = wide singlet. Chemical shifts are given in ppm relative to TMS using the signals from the residual protons or carbon nuclei of the deuterated solvent.
    Mass spectroscopy
    The spectra by MALDI-TOF were recorded on a Bruker Autoflex II TOF / TOF mass spectrometer using anthralin (1,8,9-Trihydroxyanthracene) as 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. External calibration was carried out using Bruker Peptide Calibration Standard II (mass range: 7003.200 Da) and Protein Calibration Standard I (mass range: 5000-17,500 Da).
    Example 1: Procedure for catalyst synthesis (la)
    According to the general formula (I)
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    image3
    4189; Tejeda, et al., Chem. Commun., 50 (2014), 15313-15315). A mixture of salicidenaniline (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 over, the mixture was allowed to cool to room temperature and concentrated under reduced pressure to a quarter of its initial volume, thus obtaining a brown paste. This paste was washed with water (3X60 mL) forming a brown solid. The product was purified by washing with CH2Cl2 (3x20 mL). 85% yield. 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). 13C NMR (CDCl3, 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 catalyst synthesis (lla)
    According to the general formula (II)
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    Where Xn- = I-, R1 = CeH5, R3 = CH3 (CH2) 3, R5 = OH, R2 = R4 = R6 = R7 = R8 = R9 = H
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    The catalyst (Ila) was synthesized according to the following reaction:
    image5
    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 under vacuum. Yield: 94%. The analysis data are presented below.
    15 Data for the catalyst (Ila): Light brown solid. Melting point: 179-181 ° C. GO
    3100 cm-1- 1H 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, 20 1H, Ar), 9.38 (d, J = 1.5 Hz, 1H , H2 | m). 13C 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. Procedure for the synthesis of cyclic carbonates IV 1-16 from epoxides III 1-16.
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     , IV  1: R10 = C6H5, R11 = R12 = H;
     , IV  2: R10 = CH3, R11 = R12 = H;
     , IV  3: R10 = C8H17, R11 = R12 = H;
     , IV  4: R10 = CH2CH3, R11 = R12 = H;
     , IV  5: R10 = (CH2) 3CH3, r11 = r12 = h
     , IV  6: R10 = C6H4Cl, R11 = R12 = H;
     , IV  7: R10 = C6H4Br, R11 = R12 = H;
     , IV  8: R10 = CH2OH, R11 = R12 = H;
     , IV  9: R10 = CH2Cl, R11 = R12 = H;
     , IV  10: R10 = CH2OC6H4, R11 = R12 =
     , IV  11: R10-R12 = (CH2) 4, R11 = H;
     , IV  12: R10-R12 = (CH2) 3, R11 = H;
     , IV  13: R10 = R12 = CH3, R11 = H;
     , IV  14: R10 = H, R11 = R12 = CH3;
     , IV  15: R10 = H, R11 = R12 = C6H5;
     , IV  16: R10 = H, R11 = C6H5, R12 = CH3
    An epoxide (III) (10.0 mmol), and a combination of a catalyst (la) and iodide of
    Tetrabutylammonium (0.01-0.1 mmol) or a catalyst (lla) (0.01-0.1 mmol) was introduced into a stainless steel reactor with a magnetic stir bar. The autoclave was sealed, pressurized at 5 bar with CO2, heated to the desired temperature and then pressurized at 10 bar with CO2. The reaction mixture was stirred at 90 ° C for 24h.
    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 CH2Cl2 to remove the catalyst. The eluent was evaporated under reduced pressure to give the cyclic carbonate, both pure and a mixture of unreacted cyclic carbonate and epoxide. In the latter case, the mixture was purified by flash chromatography using a solvent gradient of first hexane, and subsequently a mixture Hexane: Ethyl acetate (9: 1), then readjusting the ratio with Hexane: Ethyl acetate (3: 1) ), and finally with ethyl acetate to give pure cyclic carbonate. The results are shown below:
    Table 1
    He recovered Epoxide
    River
    R12
    R11
    Catalyst (mol%)
    Ta
    (° C)
    Pco2 Yield Time
    (bar) (h) (%)
     one  III 1 C6H5 H H IIa (1) 90 10 1 87
     2  III 2 CH3 H H IIa (1) 90 10 1 82
     3  III 3 C8H17 H H IIa (1) 90 10 1 88
     4  III 4 CH2CH3 H H IIa (1) 90 10 1 84
     5  III 5 (CH2) 3CH3 H H IIa (1) 90 10 1 83
     6  III 6 C6H4Cl H H IIa (1) 90 10 1 92
     7  III 7 C6H4Br H H IIa (1) 90 10 1 95
     8  III 8 CH2OH H H IIa (1) 90 10 1 99
     9  III 9 CH2Cl H H IIa (1) 90 10 1 88
     10  III 10 CH2OC6H4 H H IIa (1) 90 10 1 94
     eleven  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
     fifteen  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
    The analysis data for the cyclic carbonates IV 1-16, synthesized under the following conditions, are given below:
    Temperature 90 ° C
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    Pressure: 10 bar. Reaction time: 1-24 h. Catalyst: 1 mol%
    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, OCH2), 4.36 (1H, t J 8.6 Hz, OCH2); 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. 1 H NMR (500 MHz, CDCl 3, 298 K): 84.8-4.9 (1H, m, OCH), 4.57 (1H, t J 8.3 Hz, OCH2), 4.04 ( 1H, dd J 8.3, 7.4 Hz, OCH2), 1.50 (3H, d J 6.3 Hz, CH3); 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 (1 H, m, OCH), 4.50 (1 H, dd J 8.4, 7.8 Hz, OCH 2), 4.04 (1H, dd J 8.4, 7.2 Hz, OCH2), 1.6-1.9 (2H, m, CH2), 1.1-1.6 (12H, m, 6 x CH2), 0 , 86 (3H, t J 6.8 Hz, CH3); 13C {1H} NMR (125 MHz, CDCl3, 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 1H NMR (500 MHz, CDCl3, 298 K): 8 4.5-4.7 (1H, m, OCH), 4.49 (1H, t J 8.1 Hz, OCH2), 4.05 (1H, dd J 6.3, 5.3 Hz, OCH2), 1.6-1.9 (2H, m, CH2) 1.00 (3H, t J 7.1 Hz, CH3). 13C {1H} NMR (125 MHz, CDCl3, 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. 1 H 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, OCH2 ), 4.06 (1H, dd J 8.4, 7.2 Hz, OCH2), 1.6-1.9 (2H, m, CH2), 1.2-1.6 (4H, m, 2 x CH2), 0.91 (3H, t J 7.1 Hz, CH3); 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.
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    Data for 4-chlorostyrene carbonate (IV 6): Yield 92%. White solid. Mp: 66-69 ° C; 1H NMR (500 MHz, CDCls, 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, OCH2); 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-bromo-styrene carbonate (IV 7): Yield 95%. White solid. 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, OCH2), 4.31 (1H, t J 7.8 Hz, OCH2); 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): 99% yield. Colorless liquid. 1 H NMR (500 MHz, DMSO-d6, 298 K): 85.22 (1 H, t J 5.5, OH), 4.7-4.8 (1 H, m, OCH), 4, 45 (1H, t J 8.3 Hz, CH2O), 4.24 (1H, dd J 8.1, 5.8 Hz, CH2O), 3.62 (1H, ddd J 12.5, 5.5, 2.6 Hz, CH2OH), 3.46 (1H, ddd J 12.6, 5.6, 3.3 Hz, CH2OH); 13 C {1 H} NMR (125 MHz, DMSO-d6, 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, 8.7 Hz, CH2CO, 3.79 (1H, dd J 12.0, 6.5 Hz, CH2O), 3.73 (1H, dd J 12.5, 4.0 Hz, CH2O); 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%. White solid. 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 CH2), 4.26 (1H, dd J 10.6, 4.2 Hz, CH2OPh), 4.16 (1H, dd J 10.6, 3.6 Hz, CH2OPh); 13C {1H} 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%. White solid. 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, CH2), 1.3-1.4 (2H, m, CH2); 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%. White solid. 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, 5 CH2), 1.50-1.90 (4H, m, CH2); 13 C {1 H} NMR (100 MHz, CDCh, 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 cis and trans isomers. 1 H NMR (400 MHz, CDCh, 298 K): d4.82 (m, 2H, 10 CH), 1.35 (6, d J 6.2 Hz, CH3); 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): Yield 63%. White solid. Mp: 30-32 ° C; 1H NMR (400 MHz, CDCl3.298 K): d4.32 (m, 2H, CH), 1.44 (6, d J5.9 Hz, CH3); 13C {1H} 15 NMR (100 MHz, CDCh, 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%. White solid. 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); 13C {1H} NMR (100 MHz, CDCh, 298 K) d154.4, 135.1, 129.8, 129.3, 20 126.1, 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%. White solid. Mp: 112-115 ° C; 1 H NMR (400 MHz, CDCh, 298 K): d 7.30-7.50 (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, CH3); 13 C {1 H} NMR (100 MHz, CDCh, 25 298 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.
    权利要求:
    Claims (6)
    [1]
    5
    1. A catalyst for producing cyclic carbonates, characterized in that said catalyst is of formula I or II:
    image 1
    in which Xn- is selected from the group consisting of Cl-, Br-, I-, p-CHsCe ^ SOs-, CH3SO3-, CF3SO3-, (CeH5) 4B-, F4B-, Cl4B-, FeP-, HSO4- , SO42-, NO3-, CO32-, CH3 (CH2) nCO2- (n = 0-20),
    CeH5-CO2-and CF3CO2-,
    R2, R4, R5, Re, R7, R8 and R9 can be the same or different from each other and are selected from the group consisting of H, CH3 (CH2) n (n = 0-18), (CH3) 2CH, (CH3 ) 3C, sec-Bu, CeH5, C6H5CH2, OH, CH3 (CH2) nO (n = 0-18), (CH3) 2N, CH2 = CHCH2, CH3CH = CHCH2, 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) nj-CeH (n = 0-18), o-, m-, p - [(CH3) 2CHj-CeH4, o-, m-, p - [(CH3) 3Cj-CeH4, o-, m-, p- [sec-Buj- CeH4, o-, m-, p- [CH3 (CH2) nOj-CeH4 (n = 0-18), o-, m-, p-OH-CeH4, o-, m-, p - [(CH3) 2Nj-CeH4, o-, m-, 15 p-CF3-CeH4, o-, m-, pF-CeH4, o-, m-, p-Cl-Ce ^, o-, m-, p-Br- CeH4, o-, m-, pI-Ce ^, o-, m-,
    p-CHO-CeH4, o-, m-, p-CH3 (CH2) nCO-CeH4 (n = 0-18), o-, m-, p-CN-Ce ^, o-, m-, p- NO2-CeH4, o-, m-, p-HO3S-CeH4, o-, m-, p-HO2C-CeH4, o-, m-, and p-CH3 (CH2) No2C-CeH4 (n = 0-18 ),
    R1 and R3 may be the same or different from each other and are selected from the group consisting of H, CH3 (CH2) n (n = 0-18), (CH ^ CH, (CH3) 3C, sec-Bu, CeH5, CeH5CH2, CH3 (CH2) nO (n = 0-18), CH2 = CHCH2, CH3CH = CHCH2, o-, m-, p- [CH3 (CH2) nj-CeH4 (n = 0-18), o-, m -, p - [(CH3) 2CHj-CeH4,
    o-, m-, p - [(CH3) 3Cj-CeH4, o-, m-, p- [sec-Buj-CeH4, o-, m-, p- [CH3 (CH2) nOj-CeH4 (n = 0-18), o-, m-, p-OH-CeH4, o-, m-, p - [(CH3) 2Nj-CeH4, o-, m-, p-CF3-CeH4, o-, m- , pF-CeH4, o-, m-, p-Cl-CeH4, o-, m-, p-Br-CeH4, o-, m-, pI-CeH4, o-, m-, p-CHO-CeH4 , o-, m-,
    p- [CH3 (CH2) nCOj-CeH4 (n = 0-18), o-, m-, p-CN-CeH4, o-, m-, p-NO2-CeH4, o-, m-y
    25 p-CH3 (CH2) nO2C-CeH4 (n = 0-18).
    [2]
    2. A procedure to produce cyclic carbonates according to the reaction
    5
    10
    fifteen
    twenty
    25
    image2
    wherein each of the substituents R10, R11 and R12 are selected from H, C1-20 alkyl 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, 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, C3-20 heterocyclyl, aryl C5-20, halogen, hydroxy, ether, cyano, nitro, carboxy, ester, amido, amino, acylamido, ureido, acyloxy, thiol, thioether, sulfoxide, sulfonyl, thioamido and sulfonamido, or R10 and R12 or R11 and R12 form a optionally substituted connector group, between the two carbon atoms to which they are attached respectively, where the gru The connector, 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:
    image3
    where R2, R4, R5, R6, R7, R8 and R9 can be the same or different from each other and are selected from the group consisting of H, CH3 (CH2) n (n = 0-18), (CH3) 2CH, (CH3 ) 3C, sec-Bu, C6H5, C6H5CH2,
    OH, CH3 (CH2) nO (n = 0-18), (CH ^ N, CH2 = CHCH2, CH3CH = CHCH2, 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, o-, m-, p- [sec-Bu] -C6H4, o-, m-, p- [CH3 (CH2) nO] -C6H4 (n = 0-18), o-, m-, P-OH-C6H4, o-, m-, p - [( CH3) 2N] -C6H4, o-, m-, P-CF3-C6H4, o-, m-, PF-C6H4, o-, m-, p-Cl-C6H4, o-, m-, p-Br -C6H4, o-, m-, PI-C6H4, o-, m-, P-CHO-C6H4, o-, m-, p-CH3 (CH2) nCO-C6H4 (n = 0-18), or- , m-, p-CN-C6H4, o-, m-, p-NO2-C6H4,
    5
    10
    fifteen
    twenty
    25
    30
    o-, m-, P-HO3S-C6H4, o-, m-, P-HO2C-C6H4, o-, m-, p-CH3 (CH2) nQ2C-OeH4 (n = 0-18), R1 is selected from the group consisting of H, CH3 (CH2) n (n = 0-18), (CH3) 2CH, (CH3) 3C, sec-Bu, C6H5, C6H5CH2, CH3 (CH2) nO (n = 0-18), CH2 = CHCH2, CH3CH = CHCH2, o-, m-,
    p- [CH3 (CH2) n] -C6H4 (n = 0-18), o-, m-, p - [(CH3) 2CH] -C6H4, o-, m-, p - [(CH3) 3C] -C6H4, o-, m-, p- [sec-Bu] -C6H4, o-, m-, p- [CH3 (CH2) nO] -C6H4 (n = 0-18), o-, m-, P-OH-C6H4, o-, m-, p - [(CH3) 2N] -C6H4, o-, m-, P-CF3-C6H4, o-, m-, PF-C6H4, o-, m- , p-Cl-C6H4, o-, m-, p-Br-C6H4, o-, m-, PI-C6H4, o-, m-, P-CHO-C6H4, o-, m-, p- [ CH3 (CH2) nCO] -C6H4 (n = 0-18), o-, m-, P-CN-C6H4, o-, m-, p-NO2-C6H4, o-, m-, p-CH3 ( CH2) nO2C-C6H4 (n = 0-18), in combination with a cocatalyst that supplies Xn-, with Xn-: Cl-, Br-, I-, P-CH3C6H4SO3-, CH3SO3-, CF3SO3-, (C6H5) 4B-, F4B-, CUB-, F6P-, HSO4-, SO42-, NO3-, CO32-, CH3 (CH2) nCO2- (n = 0-20), C6H5-CO2- and CF3CO2-,
    or of an organocatalyst of formula II:
    image4
    where Xn- is selected from the group consisting of Cl-, Br-, I-, P-CH3C6H4SO3-, CH3SO3-, CF3SO3-, (C6H5) 4B-, F4B-, Cl4B-, F6P-, HSO4-, SO42-, NO3-, CO32-, CH3 (CH2) nCO2- (n = 0-20),
    C6H5-CO2- and CF3CO2-, R2, R4, R5, R6, R7, R8 and R9 can be the same or different from each other and are selected from the group consisting of H, CH3 (CH2) n (n = 0-18), (CH3) 2CH, (CH3) 3C, sec-Bu, C6H5, C6H5CH2, OH, CH3 (CH2) nO (n = 0-18), (CH3) 2N, CH2 = CHCH2, CH3CH = CHCH2, 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, o-, m-, p- [sec-Bu] -C6H4, o-, m-, p- [CH3 (CH2) nO] -C6H4 (n = 0-18), o-, m-, P-OH-C6H4, o-, m-, p - [(CH3) 2N] -C6H4, o-, m-, P-CF3-C6H4, o-, m-, PF-C6H4, o-, m-, p-Cl-C6H4 , o-, m-, p-Br-C6H4, o-, m-, PI-C6H4, o-, m-, P-CHO-C6H4, o-, m-, p-CH3 (CH2) nCO-C6H4 (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- and p-CH3 (CH2) nO2C-C6H4 (n = 0-18), R1 and R3 may be the same or different from each other and are selected from the group consisting of H, CH3 ( CH2) n (n = 0-18), (CH3) 2CH, (CH3) 3C, sec-Bu, C6H5, C6H5CH2, CH3 (CH2) nO (n = 0-18), CH2 = CHCH2, CH3CH = CHCH2, o-, m-,
    p- [CH3 (CH2) n] -C6H4 (n = 0-18), o-, m-, p - [(CH3) 2CH] -C6H4, o-, m-, p - [(CH3) 3C] -C6H4, o-, m-, p- [sec-Bu] -C6H4, o-, m-, p- [CH3 (CH2) nO] -C6H4 (n = 0-18), o-, m-, P-OH-C6H4, o-, m-, p - [(CH3) 2N] -C6H4, o-, m-, P-CF3-C6H4, o-, m-, PF-C6H4, o-, m- , p-Cl-C6H4, o-, m-, p-Br-C6H4,
    o-, m-, pi-CeH4, o-, m-, p-CHO-CeH ^ o-, m-, p- [CH3 (CH2) nOO] -OeH4 (n = 0-18), o-, m-, p-CN-CeH4, o-, m-, P-NO2-C6H4, o-, m- and p-CH3 (CH2) nO2C-CeH4 (n = 0-18).
    5
    10
    [3]
    3. The method according to claim 2, characterized in that the reaction temperature is in the range between 20 and 100 ° C.
    [4]
    4. The method according to claim 2 to 3, characterized in that the reaction pressure is in the range between 1 and 10 bar.
    [5]
    5. The method 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 26 hours. 6
    [6]
    6. The process according to any of claims 2 to 5, characterized in that the catalyst concentration is in the range between 0.01 and 1 mol%.
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2008132474A1|2007-04-25|2008-11-06|University Of Newcastle Upon Tyne|Synthesis of cyclic carbonates in the presence of dimeric aluminium catalysts|
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