Method for preparing cyclic carbonate having exocyclic vinylidene group

Abstract

The present invention relates to a method for preparing a cyclic carbonate having an exocyclic vinylidene group by reacting a propargyl alcohol with CO2 in the presence of a silver catalyst having at least one bulky ligand and a lipophilic carboxylate ligand, wherein after the reaction is completed, the catalyst is separated from the cyclic carbonate by using two organic solvents having different polarities and having a miscibility region, wherein the silver catalyst is enriched in the less polar solvent and the cyclic carbonate is enriched in the more polar solvent.

Description

[0001] The present invention relates to a method for preparing a cyclic carbonate having an exocyclic vinylidene group by reacting a propargyl alcohol with CO2 in the presence of a silver catalyst having at least one bulky ligand and a lipophilic carboxylate ligand, wherein after the reaction is completed, the catalyst is separated from the cyclic carbonate by using two organic solvents having different polarities and having a miscibility region, wherein the silver catalyst is enriched in the less polar solvent and the cyclic carbonate is enriched in the more polar solvent. Technical Background

[0002] Cyclic carbonates with exocyclic vinylidene groups are valuable compounds, inter alia, for use in electrolytes for batteries, as described in US 2013 / 0059178, or as monomers in polymer applications, as described in WO 2011 / 157671.

[0003] Cyclic carbonates having no other substituents except the exocyclic vinylidene group (more precisely, no substituents at the 5-position, relative to the 1,3-position of the oxygen ring atom, the 2-position of the oxo group and the 4-position of the vinylidene group) can be obtained by reaction of the corresponding primary propargyl alcohol with CO2 using a silver catalyst with bulky ligands as described in Organic Letters 2019, 21, 1422-1425 or WO 2019 / 034648. The reaction is carried out in an organic solvent such as dichloromethane or acetone. As described in WO2019 / 034648, in the case of volatile products, the product can be separated from the catalyst via distillation and the catalyst can be recycled, which requires simple addition of new solvents and reagents to start a new reaction cycle. However, as also described in WO 2019 / 034648, this method cannot be applied to non-volatile or thermally unstable exo-vinylene carbonates and the product must be separated from the catalyst via column chromatography. For industrial-scale processes, workup of the reaction mixture via column chromatography is uneconomical due to its high costs; moreover, the catalyst cannot be recycled in a simple manner.

[0004] Chem. Commun. 2016, 52, 7830-7833, ACS Sustainable Chem. Eng. 2019, 7, 5614-5619, Green Chem. 2017, 19, 2936-2940 and Journal of CO2 Utilization 2017, 22, 374-381 describe the synthesis of 5,5-disubstituted cyclic carbonates with an exocyclic vinylidene group at the 4-position by reacting tertiary propargyl alcohol with CO2 in the presence of a silver or copper catalyst in the presence of an ionic liquid. The ionic liquid is used as both a solvent and a base. The product is isolated from the reaction mixture by extraction with hexane.

[0005] Although ionic liquids are useful multifunctional reagents on a laboratory scale, they are not suitable for industrial-scale methods in view of their price. In addition, the above method is only effective in the case of non-polar cyclic carbonates that can be fully extracted into the hexane phase. The product with larger polarity is retained in the ionic liquid phase. If these are non-volatile or thermally unstable, they can not be separated from the ionic liquid by distillation. As explained above, for industrial-scale methods, the aftertreatment of the reaction mixture via column chromatography is uneconomical due to its high cost; In addition, the catalyst can not be recycled in a simple manner.

[0006] Therefore, the object of the present invention is to provide an economical process for preparing cyclic carbonates by primary propargyl alcohol and CO2, which allows simple separation of the catalyst from the product and does not require expensive means, such as using ionic liquids as solvents. The process should also allow the economical preparation of non-volatile or thermally unstable external-vinylene carbonates. SUMMARY OF THE INVENTION

[0008] This object is achieved by a process for preparing a cyclic carbonate I selected from the group consisting of compounds of formula Ia, compounds of formula Ib and mixtures thereof:

[0009]

[0010] in

[0011] R 1 It is an organic group;

[0012] The following steps are involved:

[0013] a) reacting a propargyl alcohol of the formula II with carbon dioxide:

[0014]

[0015] Where R 1 As defined above,

[0016] wherein the reaction is carried out in at least one organic solvent L1 or in a solvent mixture containing at least one organic solvent L1 and at least one organic solvent L2; wherein solvent L1 has a higher polarity than solvent L2, and wherein solvents L1 and L2 have a miscibility zone at least between 20-30° C.,

[0017] wherein the reaction is further carried out in the presence of a silver catalyst Ag1 comprising at least one bulky ligand and a carboxylate ligand,

[0018] Wherein the bulky ligand is selected from the ligand of formula III and the ligand of formula IV:

[0019]

[0020] in

[0021] D is P, As or Sb;

[0022] R 2 Each is independently an organic group having 1 to 40 carbon atoms;

[0023] R 3 and R 4 are the same or different and are each an organic group having 1 to 40 carbon atoms,

[0024] R 5 is an organic group having 1 to 40 carbon atoms and can react with R present in ligand IV 2 different or the same; and

[0025] Z is selected from -CR 7 =CR 8 -、-CR 7 =N-, -CR 7 R 9 -CR 8 R 10 -and-CR 7 R 9 -CR 8 R 10 -CR 11 R 12 - a divalent bridging group,

[0026] in

[0027] R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are independently hydrogen or an organic group having 1 to 40 carbon atoms; or

[0028] Two adjacent groups R 7 and R 8 and / or R 10 and R 11 together with the atoms to which they are attached, form a substituted or unsubstituted mono- or polycyclic aliphatic or aromatic ring system having 4 to 40 carbon atoms and which may also contain at least one heteroatom selected from the elements Si, Ge, N, P, O and S as a ring member;

[0029] and wherein the carboxylate ligand is according to Formula V:

[0030]

[0031] in

[0032] R 6is an organic group having 1 to 40 carbon atoms;

[0033] b1) adding a solvent L2 to the reaction mixture obtained in step a), in case step a) has not already been carried out in the presence of at least one solvent L2;

[0034] b2) optionally adding a solvent L2 to the reaction mixture obtained in step a), in case step a) has been carried out in the presence of at least one solvent L2;

[0035] c) phase separation of the reaction mixture obtained in step a) or b1) or step b2) to obtain a product phase containing the cyclic carbonate I and the at least one solvent L1 and a catalyst phase containing the silver catalyst and the at least one solvent L2; and

[0036] d) if necessary separating the cyclic carbonate I from the product phase.

[0037] Of course, the reaction mixture obtained in step a) is subjected to phase separation step c) only if a solvent mixture of L1 and L2 has been used in step a) and if the optional step b2) has not been carried out. If only L1 has been used in step a) (and no L2), the reaction mixture obtained in step b1) is subjected to phase separation step c). If a solvent mixture of L1 and L2 has been used in step a) and if the optional step b2) has been carried out, the reaction mixture obtained in step b2) is subjected to phase separation step c).

[0038] Detailed Description of the Invention

[0039] definition

[0040] If the radical R in compound II is defined above or below 1 (including A in compound II-bis or Poly or Y in II-poly) is "as defined above" (meaning R 1 As defined above and below for compound I), this does not necessarily mean that R 1 Remains unchanged in the reaction of compound II with CO2. 1 Some of the groups in the starting compound II can react with CO2 to give 1 Different groups R 1 Compound I. For example, if R 1 If the oxirane group is present, some or all of these may react with CO2 under ring opening. 1 Inert to the reaction conditions and therefore identical in the starting compound II and in the final compound I.

[0041] In this specification, when the variable R is defined in the formula shown x When used in the context of a compound of the present invention, the term "group" is used interchangeably with the term "radical".

[0042] The term "halogen" denotes in each case fluorine, chlorine, bromine or iodine.

[0043] As used herein, the term "organic group" refers to any group having at least one carbon atom. The group may also contain heteroatoms, such as halogen atoms, N, O, S, Si or Ge. "Contains" means that the organic group may be substituted by a heteroatom-containing group, may be spaced apart by a heteroatom or a heteroatom-containing group and / or may be bonded via a heteroatom or a heteroatom-containing group. However, the organic group is usually bonded to the rest of the molecule via a carbon atom. The organic group is usually derived from a discrete molecule (a discrete molecule is a molecule with a defined molecular weight, as opposed to a molecular weight distribution as in the case of a polymer), but the organic group R 1 It can also be derived from a polymer. In the latter case, if R 1 If the starting compound II is derived from a polymer, then it usually contains more than one -C≡C-CH2OH. This group can be bonded to the polymer backbone directly or via a linking group. By way of example only, a polymer or monomer containing a carboxyl group or a carboxyl derivative that is susceptible to esterification (transesterification) or containing an oxirane ring as present in a glycidyl residue or containing a chlorohydrin residue or an isocyanate group (-NCO) or other groups that can react with an alcohol group in the side chain can be reacted with 1,4-butynediol or another diol having a propargyl alcohol group to obtain a diol in which R 1 (Poly) compounds II derived from polymers containing a large number of -C≡C-CH2OH groups in their side chains. If the monomer is reacted with 1,4-butynediol or another diol having propargyl alcohol groups, this polymer is of course obtained after polymerization of the monomer. In the product I from the reaction of the polymer with CO2, R 1Derived from a polymer containing a plurality of cyclic carbonate groups (more precisely 1,3-dioxolan-2-one-4-yl rings) bonded via exocyclic vinylidene groups. Alternatively, the monomer can first be reacted with CO2 under the reaction conditions described above and below to give a monomer containing an exo-vinylidene bonded cyclic carbonate and then polymerizing the monomer. Merely by way of example, polyacrylic acid or polymethacrylic acid or a polyacrylate or polymethacrylate which is easily transesterified can be esterified with 1,4-butynediol to give a polymer having the repeating unit -[CH2-CH(C(=O)OCH2C≡CH2OH)]- or -[CH2-C(CH3)(C(=O)OCH2C≡CH2OH)]-; or a polyacrylate or polymethacrylate containing -NCO groups in the alcohol-derived portion of the ester (the alcohol-derived portion being derived, for example, from HO-CH2CH2-NCO) can be esterified with 1,4-butynediol to give a polymer having the repeating unit -[CH2-CH(C(=O)OCH2C≡CH2OH)]-; The polymer can be reacted with 1,4-butynediol by an addition reaction to obtain a polymer having a repeating unit -[CH2-CH(C(=O)O-CH2CH2-NH-C(=O)-O-CH2C≡CH2OH)]- or -[CH2-C(CH3)(C(=O)O-CH2CH2-NH-C(=O)-O-CH2C≡CH2OH)]-; or a polyacrylate or polymethacrylate containing a glycidyl residue or a chlorohydrin residue in the alcohol-derived portion of the ester can be reacted with 1,4-butynediol by an addition reaction or a substitution reaction. Alternatively, the corresponding acrylate or methacrylate monomer is first prepared by the above-mentioned esterification / addition / substitution reaction and then polymerized. In another embodiment, the corresponding acrylate or methacrylate monomer (i.e., a (meth)acrylate containing -C≡C-CH2OH in its alcohol-derived portion) can be grafted onto a polymer having a suitable backbone, for example, grafted onto a polyethylene or polypropylene polymer.

[0044] As used herein, the term "organic group having 1 to 40 carbon atoms" refers to any group having at least one carbon atom. The group may also contain heteroatoms, such as halogen atoms, N, O, S, Si or Ge. "Comprising" means that the organic group may be substituted by heteroatom-containing groups, may be interrupted by heteroatoms or heteroatom-containing groups and / or may be bonded via heteroatoms or heteroatom-containing groups. Examples are C1-C 40 Alkyl, Fluorinated C1-C 10 Alkyl, C1-C 12 Alkoxy, saturated, partially unsaturated or maximally unsaturated (including heteroaromatic) heterocyclic radicals containing 3 to 20 carbon atoms and one or more heteroatoms selected from N, O and S as ring members, C6-C 40 Aryl, C6-C 10 Fluoroaryl, C6-C 10 Aryloxy, silyl having 3-24 carbon atoms, C2-C40 Alkenyl, C2-C 40 Alkynyl, C7-C 40 Arylalkyl or C8-C 40 Arylalkenyl. The organic radical is derived in each case from an organic compound. Thus, the organic compound methanol can in principle give three different organic radicals with one carbon atom, namely methyl (H3C-), methoxy (H3C-O-) and hydroxymethyl (HOC(H2)-).

[0045] An aliphatic radical is a radical that does not contain cycloaliphatic, aromatic or heterocyclic components. Examples are alkyl, alkenyl and alkynyl. n -C m ), it means an aliphatic radical generally having 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms, particularly 1 to 20 carbon atoms, especially 1 to 10 or 1 to 6 or 1 to 4 carbon atoms. Of course, alkenyl and alkynyl have at least 2 carbon atoms.

[0046] Cycloaliphatic or alicyclic radicals may contain one or more, for example 1 or 2, alicyclic radicals; however, they do not contain aromatic or heterocyclic components. Examples are cycloalkyl and cycloalkenyl. If the term "cycloaliphatic radical" is used herein without the prefix (C n -C m ), it denotes an aliphatic radical having generally 3 to 40 carbon atoms, preferably 3 to 30 carbon atoms, in particular 3 to 20 carbon atoms, especially 3 to 10 or 3 to 6 carbon atoms.

[0047] An aromatic group or aryl is a monocyclic, bicyclic or polycyclic carbocyclic (i.e. without heteroatoms as ring members) aromatic group. An example of a monocyclic aromatic group is phenyl. In a bicyclic aryl ring, two aromatic rings are fused, i.e. they share two ortho C atoms as ring members. An example of a bicyclic aromatic group is naphthyl. In a polycyclic aryl ring, three or more rings are fused. Examples of polycyclic aromatic groups are phenanthrenyl, anthracenyl, naphthacene, 1H-benzo[a]phenalenyl, pyrenyl, etc. However, for the purposes of the present invention "aryl" also includes bicyclic or polycyclic groups in which not all rings are aromatic, as long as at least one ring is aromatic; in particular if the reactive position is on the aromatic ring (or on a functional group bonded thereto). Examples are indanyl, indenyl, tetrahydronaphthyl, 6,7,8,9-tetrahydro-5H-benzo[7]cycloannulyl, fluorenyl, 9,10-dihydroanthracenyl, 9,10-dihydrophenanthrenyl, 1H-benzo[a]phenanthrenyl and the like, and also ring systems in which not all rings are fused, but are, for example, spiro or bridged, such as benzonorbornenyl. Aryl has in particular 6 to 30, more particularly 6 to 20 and in particular 6 to 10 carbon atoms as ring members.

[0048] Mixed aliphatic-cycloaliphatic radicals contain at least one aliphatic group and also at least one cycloaliphatic group, the point of bonding to the remainder of the molecule being either on the cycloaliphatic group or on the aliphatic group.

[0049] Mixed aliphatic-aromatic radicals contain at least one aliphatic group and also at least one aromatic group, the site of bonding to the remainder of the molecule being either on the aromatic group or on the aliphatic group.

[0050] Mixed cycloaliphatic-aromatic radicals contain at least one cycloaliphatic group and also at least one aromatic group, the point of bonding to the remainder of the molecule being either on the cycloaliphatic group or on the aromatic group.

[0051] Mixed aliphatic-cycloaliphatic-aromatic radicals contain at least one aliphatic group, at least one cycloaliphatic group and also at least one aromatic group, the bonding point to the remainder of the molecule being located on the aliphatic group or on the cycloaliphatic group or on the aromatic group.

[0052] If the aliphatic residue in an aliphatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic and mixed aliphatic-cycloaliphatic-aromatic radical is surrounded by one or more non-adjacent radicals -O-, -S-, -N(R 13 )-, -OC(=O)-, -C(=O)-O-, -N(R 13 )-C(=O)-, -C(=O)-N(R 13 )-, -OC(=O)-O-, -OC(=O)-N(R 13 )-、-N(R 13 )-C(=O)-O- and / or -N(R 13 )-C(=O)-N(R 13 )-interval, this results, for example, in the aliphatic group being replaced by a group -OR x 、-SR x 、-N(R 13 )-R x 、-OC(=O)-R x 、-C(=O)-OR x 、-N(R 13 )-C(=O)-R x 、-C(=O)-N(R 13 )-R x 、-OC(=O)-OR x 、-OC(=O)-N(R 13 )-R x 、-N(R 13 )-C(=O)-OR x and / or -N(R13 )-C(=O)-N(R 13 )-R x Substitution, where R x It is an aliphatic group.

[0053] If the cycloaliphatic radical in a cycloaliphatic, mixed aliphatic-cycloaliphatic, mixed cycloaliphatic-aromatic and mixed aliphatic-cycloaliphatic-aromatic group is surrounded by one or more non-adjacent groups -O-, -S-, -N(R 13 )-, -OC(=O)-, -C(=O)-O-, -N(R 13 )-C(=O)-, -C(=O)-N(R 13 )-, -OC(=O)-O-, -OC(=O)-N(R 13 )-、-N(R 13 )-C(=O)-O- and / or -N(R 13 )-C(=O)-N(R 13 )-, this gives rise to saturated or partially unsaturated heterocyclic rings containing one or more of the abovementioned radicals as ring members. For the purpose of illustrating this type of ring only, if the cycloaliphatic residue is interrupted by a radical -O-, -S- or -N(R 13 )-interrupted, which gives, for example, an oxiranyl, thiirane, aziridinyl, oxetanyl, thietanyl, azetidinyl, furanyl, dihydrofuranyl, tetrahydrofuranyl, thienyl, dihydrothienyl, tetrahydrothienyl, pyrrolidinyl, pyrrolinyl, pyrrolyl, pyranyl, dihydropyranyl, tetrahydropyranyl, thiopyranyl, dihydrothiopyranyl, tetrahydrothiopyranyl, piperidinyl, dihydropyridinyl, tetrahydropyridinyl, pyridyl ring and the like.

[0054] If the aromatic residue in an aromatic, mixed aliphatic-aromatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic and mixed aliphatic-cycloaliphatic-aromatic group is surrounded by one or more non-adjacent groups -O-, -S-, -N(R 13 )-, -OC(=O)-, -C(=O)-O-, -N(R 13 )-C(=O)-, -C(=O)-N(R 13 )-, -OC(=O)-O-, -OC(=O)-N(R 13 )-、-N(R 13 )-C(=O)-O- and / or -N(R 13 )-C(=O)-N(R 13 )-interrupted, this gives partially unsaturated or maximally unsaturated heterocyclic rings, including heteroaromatic rings.

[0055] Aliphatic bridging groups are divalent aliphatic groups. These do not contain any cycloaliphatic, aromatic or heterocyclic components. Examples are alkylene, alkenylene and alkynylene.

[0056] The cycloaliphatic bridging group is a divalent cycloaliphatic group. The divalent cycloaliphatic group may contain one or more, for example 1 or 2, cycloaliphatic groups. The cycloaliphatic groups may be substituted with aliphatic groups, but the bonding position to the rest of the molecule they bridge is on the cycloaliphatic group.

[0057] Aromatic bridging groups are divalent aromatic groups. Divalent aromatic groups may contain one or more, for example 1 or 2 aromatic groups; however, they do not contain cycloaliphatic or heterocyclic components. Aromatic groups may be substituted with aliphatic groups, but the bonding sites to the rest of the molecule are all located on the aromatic groups.

[0058] A mixed aliphatic-cycloaliphatic bridging group contains at least one divalent aliphatic group and at least one divalent cycloaliphatic group, but the two bonding positions to the rest of the molecule are, if possible, both on the cycloaliphatic groups or both on the aliphatic groups or one on the aliphatic group and the other on the cycloaliphatic group.

[0059] Mixed aliphatic-aromatic bridging groups contain at least one divalent aliphatic group and at least one divalent aromatic group, but the two bonding positions to the remainder of the molecule are, if possible, both on the aromatic groups or both on the aliphatic groups or one on the aliphatic group and the other on the aromatic group.

[0060] A mixed aliphatic-cycloaliphatic-aromatic bridging group contains at least one divalent aliphatic group, at least one divalent cycloaliphatic group and at least one divalent aromatic group, but the two bonding positions to the rest of the molecule are, if possible, both on the cycloaliphatic group or both on the aliphatic group or both on the aromatic group or one on the aliphatic group and the other on the cycloaliphatic or aromatic group or one on the cycloaliphatic group and the other on the aromatic group.

[0061] The term "alkyl" refers to a group having generally 1 to 40 carbon atoms ("C1-C 40 alkyl”), preferably 1 to 30 carbon atoms (“C1-C 30 alkyl”), more preferably 1 to 20 carbon atoms (“C1-C 20 alkyl”), especially 1-10 carbon atoms (“C1-C 10C1-C2 alkyl is methyl or ethyl. Examples of C1-C3 alkyl, in addition to those mentioned for C1-C2 alkyl, are propyl and isopropyl. Examples of C1-C4 alkyl, in addition to those mentioned for C1-C3 alkyl, are butyl, 1-methylpropyl (sec-butyl), 2-methylpropyl (isobutyl) or 1,1-dimethylethyl (tert-butyl). Examples of C1-C6 alkyl, in addition to those mentioned for C1-C4 alkyl, are pentyl. C1-C 1-methylbutyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl or 1-ethyl-2-methylpropyl. 10 Examples of the alkyl group include heptyl, octyl, 2-ethylhexyl, nonyl, decyl and positional isomers thereof in addition to those mentioned for the C1-C6 alkyl group. 20 Examples of alkyl groups include C1-C 10 Among the alkyl groups mentioned are n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl and positional isomers thereof. 30 Examples of alkyl groups include C1-C 20 Among the alkyl groups mentioned are also n-henicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-octacosyl, n-nonacosyl, n-triacontyl and positional isomers thereof.

[0062] The term "fluoroalkyl" refers to a fluoroalkyl group generally having 1 to 30 carbon atoms ("fluoro-C1-C 30 alkyl”), preferably 1 to 20 carbon atoms (“fluorinated C1-C 20 alkyl”), especially 1-10 carbon atoms (“fluorinated C1-C 10"Fluorinated C1-C6 alkyl" refers to saturated straight-chain or branched aliphatic hydrocarbon radicals having 1 to 6 ("fluorinated C1-C6 alkyl") or 1 to 4 ("fluorinated C1-C4 alkyl") or 1 or 2 carbon atoms ("fluorinated C1-C2 alkyl"), wherein some or all of the hydrogen atoms in these radicals are replaced by fluorine atoms. "Fluorinated methyl" is a methyl radical in which 1, 2 or 3 hydrogen atoms are replaced by fluorine atoms. "Fluorinated C1-C2 alkyl" relates to alkyl radicals having 1 or 2 carbon atoms (as defined above), wherein some or all of the hydrogen atoms in these radicals are replaced by fluorine atoms. "Fluorinated C1-C3 alkyl" relates to straight-chain or branched alkyl radicals having 1 to 3 carbon atoms ( As described above), wherein some or all of the hydrogen atoms in these groups are replaced by fluorine atoms. "Fluorinated C1-C4 alkyl" refers to straight-chain or branched alkyl groups having 1 to 4 carbon atoms (as described above), wherein some or all of the hydrogen atoms in these groups are replaced by fluorine atoms. "Fluorinated C1-C6 alkyl" refers to straight-chain or branched alkyl groups having 1 to 6 carbon atoms (as described above), wherein some or all of the hydrogen atoms in these groups are replaced by fluorine atoms. "Fluorinated C1-C8 alkyl" refers to straight-chain or branched alkyl groups having 1 to 8 carbon atoms (as described above), wherein some or all of the hydrogen atoms in these groups are replaced by fluorine atoms. "Fluorinated C1-C 10 "Alkyl" refers to straight-chain or branched alkyl groups (as described above) having 1 to 10 carbon atoms, wherein some or all of the hydrogen atoms in these groups are replaced by fluorine atoms; etc. Examples of fluoromethyl are fluoromethyl, difluoromethyl and trifluoromethyl. Examples of fluoro C1-C2 alkyl are fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl or pentafluoroethyl. Examples of fluoro C1-C3 alkyl groups include, in addition to Examples of the fluorinated C1-C2 alkyl group include, in addition to those mentioned for the fluorinated C1-C3 alkyl group, 1-fluoropropyl, 2-fluoropropyl, 3-fluoropropyl, 1,1-difluoropropyl, 2,2-difluoropropyl, 1,2-difluoropropyl, 3,3-difluoropropyl, 3,3,3-trifluoropropyl, heptafluoropropyl, 1,1,1-trifluoroprop-2-yl, heptafluoropropyl, etc. Examples of the fluorinated C1-C4 alkyl group include, in addition to those mentioned for the fluorinated C1-C3 alkyl group, 4-fluorobutyl, nonafluorobutyl, heptadecafluorooctyl, etc.

[0063] In perfluoroalkyl groups, all hydrogen atoms are replaced by fluorine atoms. Examples are trifluoromethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, heptadecafluorooctyl, etc.

[0064] The term "haloalkyl" (also expressed as "partially or fully halogenated alkyl") refers to a alkyl group generally having 1 to 30 carbon atoms ("fluorinated C1-C 30 alkyl”), preferably 1 to 20 carbon atoms (“fluorinated C1-C 20 alkyl”), especially 1-10 carbon atoms (“fluorinated C1-C 10The term "C1-C2-haloalkyl" refers to an alkyl radical having 1 or 2 carbon atoms ("fluorinated C1-C6-alkyl"), in particular a saturated, straight-chain or branched aliphatic hydrocarbon radical having 1 to 6 ("fluorinated C1-C6-alkyl") or 1 to 4 ("fluorinated C1-C4-alkyl") or 1 or 2 carbon atoms ("fluorinated C1-C2-alkyl"), wherein some or all of the hydrogen atoms in these radicals are replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and / or bromine. "C1-C2-haloalkyl" refers to an alkyl radical having 1 or 2 carbon atoms (as mentioned above), wherein some or all of the hydrogen atoms in these radicals are replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and / or bromine. "C1-C3 haloalkyl" relates to straight-chain or branched alkyl groups (as described above) having 1 to 3 carbon atoms, wherein some or all of the hydrogen atoms in these groups are replaced by halogen atoms as described above, in particular fluorine, chlorine and / or bromine. "C1-C4 haloalkyl" relates to straight-chain or branched alkyl groups (as described above) having 1 to 4 carbon atoms, wherein some or all of the hydrogen atoms in these groups are replaced by halogen atoms as described above, in particular fluorine, chlorine and / or bromine. "C1-C6 haloalkyl" relates to straight-chain or branched alkyl groups (as described above) having 1 to 6 carbon atoms, wherein some or all of the hydrogen atoms in these groups are replaced by halogen atoms as described above, in particular fluorine, chlorine and / or bromine. C1-C2 haloalkyl is chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2-dichloro-2-fluoro- Examples of C1-C3 haloalkyl groups include 1-fluoropropyl, 2-fluoropropyl, 3-fluoropropyl, 1,1-difluoropropyl, 2,2-difluoropropyl, 1,2-difluoropropyl, 3,3-difluoropropyl, 3,3,3-trifluoropropyl, heptafluoropropyl, 1,1,1-trifluoroprop-2-yl, 3-chloropropyl, and the like in addition to those mentioned for C1-C2 haloalkyl groups. Examples of C1-C4 haloalkyl groups include 4-chlorobutyl, and the like in addition to those mentioned for C1-C3 haloalkyl groups.

[0065] Strictly speaking, the term "alkenyl" refers to a group generally having 2 to 40 carbon atoms ("C2-C 40 Alkenyl”), preferably 2 to 30 carbon atoms (“C2-C 30 Alkenyl”), more preferably 2 to 20 carbon atoms (“C2-C 20 alkenyl), especially 2-10 carbon atoms ("C2-C 10"alkenyl"), especially a monounsaturated (i.e. containing one C-C double bond), straight-chain or branched aliphatic hydrocarbon radical of 2 to 6 ("C2-C6 alkenyl") or 2 to 4 carbon atoms ("C2-C4 alkenyl"), wherein the C-C double bond may be in any position. However, as used in the present invention, the term also includes "alkanopolyenyl", i.e. a monounsaturated (i.e. containing one C-C double bond), straight-chain or branched aliphatic hydrocarbon radical of usually 4 to 50 carbon atoms ("C4-C6 alkenyl"), 40 Alkanolpolyenyl”), preferably 4 to 30 carbon atoms (“C4-C 30 Alkanolpolyenyl”), more preferably 4 to 20 carbon atoms (“C4-C 20 Alkalkanolpolyenyl”), especially 4-10 carbon atoms (“C4-C 10Examples of C2-C3 alkenyl (only one C-C double bond) are strictly speaking ethenyl, 1-propenyl, 2-propenyl or 1-methylethenyl. Examples of C2-C4 alkenyl (only one C-C double bond) are strictly speaking ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl and 2-methyl-2-propenyl.Examples of C2-C6 alkenyl (only one CC double bond) are strictly speaking ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3- -butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl , 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl C2-C, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl, 1-ethyl-2-methyl-2-propenyl, etc. C2-C. 10 Examples of alkenyl (only one CC double bond) are, strictly speaking, in addition to the examples mentioned for C2-C6-alkenyl, 1-heptenyl, 2-heptenyl, 3-heptenyl, 1-octenyl, 2-octenyl, 3-octenyl, 4-octenyl, 1-nonenyl, 2-nonenyl, 3-nonenyl, 4-nonenyl, 1-decenyl, 2-decenyl, 3-decenyl, 4-decenyl, 5-decenyl and positional isomers thereof.20 Examples of alkenyl (only one CC double bond) are strictly speaking 10 In addition to the examples mentioned for alkenyl, there are 1-undecenyl, 2-undecenyl, 3-undecenyl, 4-undecenyl, 5-undecenyl, 1-dodecenyl, 2-dodecenyl, 3-dodecenyl, 4-dodecenyl, 5-dodecenyl, 6-dodecenyl, 1-tridecenyl, 2-tridecenyl, 3-tridecenyl, 4-tridecenyl, 5-tridecenyl, 6-tridecenyl, 1-tetradecenyl, 1-pentadecenyl, 2-pentadecenyl, 3-pentadecenyl, 4-pentadecenyl, 5-pentadecenyl, 6-pentadecenyl, 7-pentadecenyl, 1-hexadecenyl, 2-hexadecenyl, 3-hexadecenyl, 4-hexadecenyl, 5-hexadecenyl, 6-hexadecenyl, 7-hexadecenyl, 2-pentadecenyl, 3-pentadecenyl, 4-pentadecenyl, 5-pentadecenyl, 6-pentadecenyl, 7-pentadecenyl, 1-hexadecenyl, 2-hexadecenyl, 3-hexadecenyl, 4-hexadecenyl, 5-hexadecenyl, 6-hexadecenyl 1-octadecenyl, 2-octadecenyl, 3-octadecenyl, 4-octadecenyl, 5-octadecenyl, 6-octadecenyl, 7-octadecenyl, 8-octadecenyl, 1-octadecenyl, 2-octadecenyl, 3-octadecenyl, 4-octadecenyl, 5-octadecenyl, 6-octadecenyl, 7-octadecenyl, 8-octadecenyl, 9-octadecenyl The invention further comprises the following: 1-nonadecenyl, 2-nonadecenyl, 3-nonadecenyl, 4-nonadecenyl, 5-nonadecenyl, 6-nonadecenyl, 7-nonadecenyl, 8-nonadecenyl, 9-nonadecenyl, 1-eicosenyl, 2-eicosenyl, 3-eicosenyl, 4-eicosenyl, 5-eicosenyl, 6-eicosenyl, 7-eicosenyl, 8-eicosenyl, 9-eicosenyl, and positional isomers thereof.

[0066] If the terminal CC double bond is in terminal position, ie if the group contains a C═CH 2 group, the alkenyl group is also called vinyl.

[0067] Examples of alkanopolyenyl groups are 1,3-butadien-1-yl, 1,3-butadien-2-yl, 1,3-pentadien-1-yl, 1,3-pentadien-2-yl, 1,3-pentadien-3-yl, 1,3-pentadien-4-yl, 1,3-pentadien-5-yl, 1,4-pentadien-1-yl, 1,4-pentadien-2-yl, 1,4-pentadien-3-yl, and the like.

[0068] The term "alkynyl" as used herein refers to a group generally having 2 to 40 carbon atoms ("C2-C 40 Alkynyl”), preferably 2 to 30 carbon atoms (“C2-C 30alkynyl”), more preferably 2 to 20 carbon atoms (“C2-C 20 Alkynyl"), especially 2-10 carbon atoms ("C2-C 10 C2-C6 alkynyl) and a straight-chain or branched aliphatic hydrocarbon radical having 2 to 6 ("C2-C6 alkynyl") or 2 to 4 carbon atoms ("C2-C4 alkynyl") and a triple bond in any position. Examples of C2-C3 alkynyl are ethynyl, 1-propynyl or 2-propynyl. Examples of C2-C4 alkynyl are ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 4-butylene glycol, 5-butylene glycol, 6-butylene glycol, 7-butylene glycol, 8-butylene glycol, 9-butylene glycol, 10-butylene glycol, 11-butylene glycol, 12-butylene glycol, 13-butylene glycol, 14-butylene glycol, 15-butylene glycol, 16-butylene glycol, 17-butylene glycol, 18-butylene glycol, 19-butylene glycol, 20-butylene glycol, 21-butylene glycol, 22-butylene glycol, 23-butylene glycol, 24-butylene glycol, 25-butylene glycol, 26-butylene glycol, 27-butylene glycol, 28-butylene glycol, 29-butylene glycol, 30-butylene glycol, 31-butylene glycol, 32-butylene glycol, 33-butylene glycol, 34-butylene glycol, 35- , 1-methyl-2-propynyl, etc. Examples of C2-C6 alkynyl are ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl, 4-methyl- 1-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl, 1-ethyl-1-methyl-2-propynyl and the like.

[0069] The term "cycloalkyl" means a cycloalkyl group having 3 to 40 ("C3-C 40 Cycloalkyl”), preferably 3-20 (“C3-C 20 Cycloalkyl”), especially 3-10 (“C3-C 10Examples of cycloalkyl radicals having 3-4 carbon atoms include cyclopropyl and cyclobutyl. Examples of cycloalkyl radicals having 3-5 carbon atoms include cyclopropyl, cyclobutyl and cyclopentyl. Examples of cycloalkyl radicals having 3-6 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Examples of cycloalkyl radicals having 3-8 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Examples of cycloalkyl radicals having 3-10 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl.

[0070] The term "polycyclic cycloalkyl" refers to a group having typically 4 to 40 ("polycyclic C4-C 40 Cycloalkyl”), preferably 4-20 (“polycyclic C4-C 20 Cycloalkyl”), especially 6-20 carbon atoms (“polycyclic C6-C 40 Bicyclic or polycyclic saturated hydrocarbon groups having as ring members a "cycloalkyl" (and of course no heteroatoms); that is, all ring members are carbon atoms. The bicyclic and polycyclic groups may be fused, bridged or spiro rings. Examples of bicyclic fused saturated groups having 6 to 10 carbon atoms include bicyclo[3.1.0]hexyl, bicyclo[3.2.0]heptyl, bicyclo[3.3.0]octyl (1,2,3,3a,4,5,6,6a-octahydropentalenyl), bicyclo[4.2.0]octyl, bicyclo[4.3.0]nonyl (2,3,3a,4,5,6,7,7a-octahydro-1H-indene), bicyclo[4.4.0]decyl (decalinyl) and the like. Examples of bridged bicyclic fused saturated groups having 7 to 10 carbon atoms include bicyclo[2.2.1]heptyl, bicyclo[3.1 .1]heptyl, bicyclo[2.2.2]octyl, bicyclo[3.2.1]octyl, etc. Examples of bicyclic spiro saturated groups are spiro[2.2]pentyl, spiro[2.4]heptyl, spiro[4.4]nonyl, spiro[4.5]decyl, spiro[5.5]undecyl, etc. Examples of saturated polycyclic groups include 2,3,4,4a,4b,5,6,7,8,8a,9,9a-dodecahydro -1H-fluorenyl, 1,2,3,4,4a,5,6,7,8,8a,9,9a,10,10a-tetradecahydroanthracenyl, 1,2,3,4,4a,4b,5,6,7,8,8a,9,10,10a-tetradecahydrophenanthrenyl, 2,3,3a,4,5,6,6a,7,8,9,9a,9b-dodecahydro-1H-phenanthrenyl, adamantyl, and the like.

[0071] The term "cycloalkenyl" unless it is specified as a polycyclic ring generally has 3 to 40 ("C3-C40 cycloalkenyl”), preferably 3-20 (“C3-C 20 Cycloalkenyl"), especially 3-10 ("C3-C 10 C5-C6-cycloalkenyl is a monocyclic partially unsaturated non-aromatic hydrocarbon radical having 3 to 8 ("C3-C8-cycloalkenyl") or more particularly 5 to 7 carbon atoms ("C5-C7-cycloalkenyl") as ring members (and of course no heteroatoms) and one or more, preferably one, non-cumulative CC double bonds in the ring; i.e. all ring members are carbon atoms. Examples of C5-C6-cycloalkenyl are cyclopent-1-en-1-yl, cyclopent-1-en-3-yl, cyclopent-1-en-4-yl, 1,3-cyclopentadien-1-yl, 1,3-cyclopentadien-2-yl, 1,3-cyclopentadien-5-yl, cyclohex-1-en-1-yl, cyclohex-1-en-3-yl, cyclohex-1-en-4-yl, 1,3-cyclohexadien-1-yl, 1,3-cyclohexadien-2-yl, 1,3-cyclohexadien-5-yl, 1,4-cyclohexadien-1-yl and 1,4-cyclohexadien-3-yl. Examples of C5-C7 cycloalkenyl groups include cyclohept-1-en-1-yl, cyclohept-1-en-3-yl, cyclohept-1-en-4-yl, cyclohept-1-en-5-yl, 1,4-cyclohexadien-1-yl and 1,4-cyclohexadien-3-yl in addition to those mentioned above for C5-C6 cycloalkenyl groups. 1,3-cycloheptadien-1-yl, 1,3-cycloheptadien-2-yl, 1,3-cycloheptadien-5-yl, 1,3-cycloheptadien-6-yl, 1,4-cycloheptadien-1-yl, 1,4-cycloheptadien-2-yl, 1,4-cycloheptadien-3-yl and 1,4-cycloheptadien-6-yl. Examples of C3-C8 cycloalkenyl groups include cycloprop-1-en-1-yl, cycloprop-1-en-3-yl, cyclobut-1-en-1-yl, cyclobut-1-en-3-yl, cyclooctane-1-yl, cyclooctane-2-yl, cyclooctane-3-yl, cyclooctane-6 ... -1-en-1-yl, cyclooct-1-en-3-yl, cyclooct-1-en-4-yl, cyclooct-1-en-5-yl, 1,3-cyclooctadien-1-yl, 1,3-cyclooctadien-2-yl, 1,3-cyclooctadien-5-yl, 1,3-cyclooctadien-6-yl, 1,4-cyclooctadien-1-yl, 1,4-cyclooctadien-2-yl, 1,4-cyclooctadien-3-yl, 1,4-cyclooctadien-6-yl, 1,4-cyclooctadien-7-yl, 1,5-cyclooctadien-1-yl and 1,5-cyclooctadien-3-yl.

[0072] The term "polycyclic cycloalkenyl" refers to a group having typically 4 to 40 ("polycyclic C4-C 40 Cycloalkenyl"), preferably 4-20 ("polycyclic C4-C 20 Cycloalkenyl"), especially 6-20 carbon atoms ("polycyclic C6-C 40Bicyclic or polycyclic unsaturated hydrocarbon radicals having as ring members ("cycloalkenyl") (and of course no heteroatoms) and one or more C-C double and / or triple bonds; i.e. all ring members are carbon atoms; wherein the ring is not completely aromatic. These bicyclic and polycyclic radicals may be fused, bridged or spiro rings. Examples of bicyclic fused unsaturated radicals are 1,2,3,4,4a,5,8,8a-octahydronaphthyl, 1,2,3,4,4a,5,6,8a-octahydronaphthyl, 1,2,3,4,4a,5,6,7-octahydronaphthyl, 1,2,3,4,5 , 6,7,8-octahydronaphthyl, 1,2,3,4,5,8-hexahydronaphthyl, 1,4,4a,5,8,8a-hexahydronaphthyl, indanyl, indenyl, hexahydroindenyl such as 2,3,3a,4,7,7a-hexahydro-1H-indenyl or 2,3,3a,4,5,7a-hexahydro-1H-indenyl, tetrahydroindenyl such as 2,3,3a,7a-tetrahydro-1H-indenyl or 2,3,4,7-tetrahydro-1H-indenyl, etc. Examples of the tricyclic condensed unsaturated group are fluorenyl, dihydrofluorenyl, tetrahydrofluorenyl, hexahydrofluorenyl and decahydrofluorenyl.

[0073] "Alkoxy" is an alkyl group as defined above attached to the remainder of the molecule via an oxygen atom; typically a C1-C 30 Alkyl ("C1-C 30 Alkoxy”), preferably C1-C 20 Alkyl ("C1-C 20 Alkoxy”), especially C1-C 12 Alkyl ("C1-C 12"C1-C2 alkoxy" is a C1-C2 alkyl group as defined above which is attached via an oxygen atom. "C1-C3 alkoxy" is a C1-C3 alkyl group as defined above which is attached via an oxygen atom. C1-C2 alkoxy is methoxy or ethoxy. C1-C3 alkoxy is additionally, for example, n-propoxy and 1-methylethoxy (isopropoxy). C1-C4 alkoxy is additionally, for example, butoxy, 1-methylpropoxy (sec-butoxy), 2-methylpropoxy (isobutoxy) or 1,1-dimethylethoxy (tert-butoxy). C1-C6 alkoxy is additionally, for example, pentoxy, 1-methylbutoxy, 2-methylbutoxy, C1-C8-alkoxy is additionally, for example, heptoxy, octyloxy, 2-ethylhexyloxy and positional isomers thereof. 12 Alkoxy is additionally, for example, nonyloxy, decyloxy, undecyloxy, dodecyloxy and positional isomers thereof.

[0074] The substituent "oxo" replaces a CH2 group by a C(=O) group.

[0075] "Aryl" is a monocyclic, bicyclic or polycyclic carbocyclic (i.e., without heteroatoms as ring members) aromatic group. An example of a monocyclic aromatic group is phenyl. In a bicyclic aryl ring, two aromatic rings are fused, i.e., they share two ortho C atoms as ring members. An example of a bicyclic aromatic group is naphthyl. In a polycyclic aryl ring, three or more rings are fused. Examples of polycyclic aryls are phenanthrenyl, anthracenyl, naphthacene, 1H-benzo[a]phenalenyl, pyrenyl, etc. However, for the purposes of the present invention, "aryl" also includes bicyclic or polycyclic groups in which not all rings are aromatic, as long as at least one ring is aromatic; in particular, if the reactive position is on the aromatic ring (or on a functional group bonded thereto). Examples are indanyl, indenyl, tetrahydronaphthyl, 6,7,8,9-tetrahydro-5H-benzo[7]cycloannulyl, fluorenyl, 9,10-dihydroanthracenyl, 9,10-dihydrophenanthrenyl, 1H-benzo[a]phenanthrenyl and the like, and also ring systems in which not all rings are fused, but are, for example, spiro or bridged, such as benzonorbornenyl. Aryl has, in particular, 6 to 40, particularly 6 to 30, more particularly 6 to 20 and in particular 6 to 10 carbon atoms as ring members.

[0076] The rings referred to as heterocycles or heterocyclic radicals or heteroaromatic rings or heteroaryl or heteroaryl groups contain one or more heteroatoms as ring members, i.e. atoms different from carbon. For the purposes of the present invention, these heteroatoms are N, O and S, where N and S can also be present as heteroatom groups, i.e. as NO, SO or SO2. Thus, the rings referred to as heterocycles or heterocyclic radicals or heteroaromatic rings or heteroaryl or heteroaryl groups for the purposes of the present invention contain one or more heteroatoms and / or heteroatom groups selected from N, O, S, NO, SO and SO2 as ring members.

[0077] A heterocycle or heterocyclyl for the purposes of the present invention is a saturated, partially unsaturated or maximum unsaturated heterocycle and includes an aromatic heteromonocyclic, bicyclic or polycyclic ring (if the ring is aromatic, it is also referred to as a heteroaromatic ring or heteroaryl) which contains one or more, in particular 1, 2, 3 or 4, heteroatoms or heteroatom groups independently selected from N, O, S, NO, SO and SO2 as ring members.

[0078] Unsaturated rings contain at least one CC and / or CN and / or NN double bond. The maximum unsaturated ring contains as many conjugated CC and / or CN and / or NN double bonds as the ring size allows. Maximum unsaturated 5- or 6-membered heteromonocyclic rings are usually aromatic. Exceptions are maximum unsaturated 6-membered rings containing O, S, SO and / or SO2 as ring members, such as pyrans and thiopyrans, which are not aromatic. Partially unsaturated rings contain fewer CC and / or CN and / or NN double bonds than the maximum number allowed by the ring size.

[0079] The heterocycle may be attached to the remainder of the molecule via a carbon ring member or via a nitrogen ring member. Of course, the heterocycle contains at least one carbon ring atom. If the ring contains more than one O ring atom, these are not adjacent.

[0080] The heterocycle is especially 3-40-membered, specifically 3-30-membered, more specifically 3-20-membered, especially 3-12-membered or 3-11-membered.

[0081] The heteromonocyclic ring is especially 3-8 membered. Examples of 3, 4, 5, 6, 7 or 8 membered saturated heteromonocyclic rings include oxirane-2-yl, thiirane-2-yl, aziridine-1-yl, aziridine-2-yl, oxetan-2-yl, oxetan-3-yl, thitan-2-yl, thitan-3-yl, 1-oxothietane-2-yl, 1-oxothietane-3-yl, 1,1-dioxothietane-2-yl, 1,1-dioxothietane-3-yl, azetidin-1-yl, azetidin-2-yl, azetidin-3-yl, Cyclobutan-3-yl, tetrahydrofuran-2-yl, tetrahydrofuran-3-yl, tetrahydrothiophen-2-yl, tetrahydrothiophen-3-yl, 1-oxotetrahydrothiophen-2-yl, 1,1-dioxotetrahydrothiophen-2-yl, 1-oxotetrahydrothiophen-3-yl, 1,1-dioxotetrahydrothiophen-3-yl, pyrrolidin-1-yl, pyrrolidin-2-yl, pyrrolidin-3-yl, pyrazolidin-1-yl, pyrazolidin-3-yl, pyrazolidin-4-yl, pyrazolidin-5-yl, imidazolidin-1-yl, imidazolidin-2-yl, imidazolidin-4-yl, Oxazolidin-2-yl, Oxazolidin-3-yl, Oxazolidin-4-yl, Oxazolidin-5-yl, isobutyl Oxazolidin-2-yl, isobutyl Oxazolidin-3-yl, iso Oxazolidin-4-yl, isobutyl oxazolidin-5-yl, thiazolidin-2-yl, thiazolidin-3-yl, thiazolidin-4-yl, thiazolidin-5-yl, isothiazolidin-2-yl, isothiazolidin-3-yl, isothiazolidin-4-yl, isothiazolidin-5-yl, 1,2,4- oxadiazolidine-2-yl, 1,2,4- Oxazolidin-3-yl, 1,2,4- oxadiazolidine-4-yl, 1,2,4- 1,2,4-thiadiazolidin-5-yl, 1,2,4-thiadiazolidin-2-yl, 1,2,4-thiadiazolidin-3-yl, 1,2,4-thiadiazolidin-4-yl, 1,2,4-thiadiazolidin-5-yl, 1,2,4-triazolidin-1-yl, 1,2,4-triazolidin-3-yl, 1,2,4-triazolidin-4-yl, 1,3,4- Oxazolidin-2-yl, 1,3,4- 1,3,4-thiadiazolidin-3-yl, 1,3,4-thiadiazolidin-2-yl, 1,3,4-thiadiazolidin-3-yl, 1,3,4-triazolidin-1-yl, 1,3,4-triazolidin-2-yl, 1,3,4-triazolidin-3-yl, tetrahydropyran-2-yl, tetrahydropyran-3-yl, tetrahydropyran-4-yl, 1,3-di Alk-2-yl, 1,3-di Alk-4-yl, 1,3-di Alk-5-yl, 1,4-diol alkyl-2-yl, piperidin-1-yl, piperidin-2-yl, piperidin-3-yl, piperidin-4-yl, hexahydropyridazin-1-yl, hexahydropyridazin-3-yl, hexahydropyridazin-4-yl, hexahydropyrimidin-1-yl, hexahydropyrimidin-2-yl, hexahydropyrimidin-4-yl, hexahydropyrimidin-5-yl, piperazin-1-yl, piperazin-2-yl, 1,3,5-hexahydrotriazin-1-yl, 1,3,5-hexahydrotriazin-2-yl, 1,2,4-hexahydrotriazin-1-yl, 1,2,4-hexahydrotriazin-2-yl, 1,2,4-hexahydrotriazin-3-yl, 1,2,4-hexahydrotriazin-4-yl, 1,2,4-hexahydrotriazin-5-yl oxazine-5-yl, 1,2,4-hexahydrotriazine-6-yl, morpholin-2-yl, morpholin-3-yl, morpholin-4-yl, thiomorpholin-2-yl, thiomorpholin-3-yl, thiomorpholin-4-yl, 1-oxothiomorpholin-2-yl, 1-oxothiomorpholin-3-yl, 1-oxothiomorpholin-4-yl, 1,1-dioxothiomorpholin-2-yl, 1,1-dioxothiomorpholin-3-yl, 1,1-dioxothiomorpholin-4-yl, azepan-1-, -2-, -3- or -4-yl, oxpan-2-, -3-, -4- or -5-yl, hexahydro-1,3-diazepane Hexahydro-1,4-diazepine Hexahydro-1,3-oxazepine oxazepinyl, hexahydro-1,4-oxaza

[0013] The invention further comprises the following: hexahydro-1,3-dioxepinyl, hexahydro-1,4-dioxepinyl, oxocane, thiocane, azocanyl, [1,3]diazocanyl, [1,4]diazocanyl, [1,5]diazocanyl, [1,5]oxazocanyl, and the like.

[0082] Examples of 3-, 4-, 5-, 6-, 7- or 8-membered partially unsaturated heteromonocyclic rings include 2,3-dihydrofuran-2-yl, 2,3-dihydrofuran-3-yl, 2,4-dihydrofuran-2-yl, 2,4-dihydrofuran-3-yl, 2,3-dihydrothiophen-2-yl, 2,3-dihydrothiophen-3-yl, 2,4-dihydrothiophen-2-yl, 2,4-dihydrothiophen-3-yl, 2-pyrrolin-2-yl, 2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 2-isothiophen-2-yl, 2-isothiophen-2-yl, 2-isothiophen-3 ... Oxazolin-3-yl, 3-iso Oxazolin-3-yl, 4-iso Oxazolin-3-yl, 2-iso Oxazolin-4-yl, 3-iso Oxazolin-4-yl, 4-iso Oxazolin-4-yl, 2-iso Oxazolin-5-yl, 3-iso Oxazolin-5-yl, 4-iso oxazolin-5-yl, 2-isothiazolin-3-yl, 3-isothiazolin-3-yl, 4-isothiazolin-3-yl, 2-isothiazolin-4-yl, 3-isothiazolin-4-yl, 4-isothiazolin-4-yl, 2-isothiazolin-5-yl, 3-isothiazolin-5-yl, 4-isothiazolin-5-yl, 2,3-dihydropyrazol-1-yl, 2,3-dihydropyrazol-2-yl, 2,3-dihydropyrazol- -3-yl, 2,3-dihydropyrazol-4-yl, 2,3-dihydropyrazol-5-yl, 3,4-dihydropyrazol-1-yl, 3,4-dihydropyrazol-3-yl, 3,4-dihydropyrazol-4-yl, 3,4-dihydropyrazol-5-yl, 4,5-dihydropyrazol-1-yl, 4,5-dihydropyrazol-3-yl, 4,5-dihydropyrazol-4-yl, 4,5-dihydropyrazol-5-yl, 2,3-dihydropyrazol-4-yl, Oxazol-2-yl, 2,3-dihydro Oxazol-3-yl, 2,3-dihydro Oxazol-4-yl, 2,3-dihydro Oxazol-5-yl, 3,4-dihydro Oxazol-2-yl, 3,4-dihydro Oxazol-3-yl, 3,4-dihydro Oxazol-4-yl, 3,4-dihydro Oxazol-5-yl, 3,4-dihydro Oxazol-2-yl, 3,4-dihydro Oxazol-3-yl, 3,4-dihydro oxazol-4-yl, 2-, 3-, 4-, 5- or 6-di- or tetrahydropyridinyl, 3-di- or tetrahydropyridazinyl, 4-di- or tetrahydropyridazinyl, 2-di- or tetrahydropyrimidinyl, 4-di- or tetrahydropyrimidinyl, 5-di- or tetrahydropyrimidinyl, di- or tetrahydropyrazinyl, 1,3,5-di- or tetrahydrotriazin-2-yl, 1,2,4-di- or tetrahydrotriazin-3-yl, 2,3,4,5-tetrahydro[1H]azepine -1-, -2-, -3-, -4-, -5-, -6- or -7-yl, 3,4,5,6-tetrahydro[2H]azepine -2-, -3-, -4-, -5-, -6- or -7-yl, 2,3,4,7-tetrahydro[1H]azepine -1-, -2-, -3-, -4-, -5-, -6- or -7-yl, 2,3,6,7-tetrahydro[1H]azepine -1-, -2-, -3-, -4-, -5-, -6- or -7-yl, tetrahydrooxepinyl, such as 2,3,4,5-tetrahydro[1H]oxepin-2-, -3-, -4-, -5-, -6- or -7-yl, 2,3,4,7-tetrahydro[1H]oxepin-2-, -3-, -4-, -5-, -6- or -7-yl, 2,3,6,7-tetrahydro[1H]oxepin-2-, -3-, -4-, -5-, -6- or -7-yl, tetrahydro-1,3-diazepine Tetrahydro-1,4-diazepine Tetrahydro-1,3-oxazepine Tetrahydro-1,4-oxazepine 1,2,3,4,5,6-hexahydroazacyclooctatetraene, 2,3,4,5,6,7-hexahydroazacyclooctatetraene, 1,2,3,4,5,8-hexahydroazacyclooctatetraene, 1,2,3,4,7,8-hexahydroazacyclooctatetraene, 1,2,3,4,5,6-hexahydro[1,5]diazacyclooctatetraene, 1,2,3,4,7,8-hexahydroazacyclooctatetraene, etc.

[0083] Examples of maximally unsaturated (but nonaromatic) heteromonocyclic rings of 3, 4, 5, 6, 7 or 8 members are pyran-2-yl, pyran-3-yl, pyran-4-yl, thiopyran-2-yl, thiopyran-3-yl, thiopyran-4-yl, 1-oxothipyran-2-yl, 1-oxothipyran-3-yl, 1-oxothipyran-4-yl, 1,1-dioxothipyran-2-yl, 1,1-dioxothipyran-3-yl, 1,1-dioxothipyran-4-yl, 2H- Oxazine-2-yl, 2H- Oxazine-3-yl, 2H- Oxazine-4-yl, 2H- Oxazine-5-yl, 2H- Oxazine-6-yl, 4H- Oxazine-3-yl, 4H- Oxazine-4-yl, 4H- Oxazine-5-yl, 4H- Oxazine-6-yl, 6H- Oxazine-3-yl, 6H- Oxazine-4-yl, 7H- Oxazine-5-yl, 8H- Oxazine-6-yl, 2H-1,3- Oxazine-2-yl, 2H-1,3- Oxazine-4-yl, 2H-1,3- Oxazine-5-yl, 2H-1,3- Oxazine-6-yl, 4H-1,3- Oxazine-2-yl, 4H-1,3- Oxazine-4-yl, 4H-1,3- Oxazine-5-yl, 4H-1,3- Oxazine-6-yl, 6H-1,3- Oxazine-2-yl, 6H-1,3- Oxazine-4-yl, 6H-1,3- Oxazine-5-yl, 6H-1,3- Oxazine-6-yl, 2H-1,4- Oxazine-2-yl, 2H-1,4- Oxazine-3-yl, 2H-1,4- Oxazine-5-yl, 2H-1,4- Oxazine-6-yl, 4H-1,4- Oxazine-2-yl, 4H-1,4- Oxazine-3-yl, 4H-1,4- Oxazine-4-yl, 4H-1,4- Oxazine-5-yl, 4H-1,4- Oxazine-6-yl, 6H-1,4- Oxazine-2-yl, 6H-1,4- Oxazine-3-yl, 6H-1,4- Oxazine-5-yl, 6H-1,4- Oxazine-6-yl, 1,4-dioxazine En-2-yl, 1,4-oxathiin-2-yl, 1H-aza 1H-[1,3]-diazepine 1H-[1,4]-diazepine [1,3]diazacyclooctatetraene, [1,5]diazacyclooctatetraene, [1,5]diazacyclooctatetraene, etc.

[0084] The heteroaromatic monocyclic ring is especially 5- or 6-membered. Examples of 5- or 6-membered monocyclic heteroaromatic rings are 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 1-imidazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 2- Azolyl, 4- Azolyl, 5- Azolyl, 3-iso Azolyl, 4-iso Azolyl, 5-iso oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 1,3,4-triazol-1-yl, 1,3,4-triazol-2-yl, 1,3,4-triazol-3-yl, 1,2,3-triazol-1-yl, 1,2,3-triazol-2-yl, 1,2,3-triazol-4-yl, 1,2,5- oxadiazole-3-yl, 1,2,3- oxadiazole-4-yl, 1,2,3- oxadiazole-5-yl, 1,3,4- oxadiazole-2-yl, 1,2,5-thiadiazol-3-yl, 1,2,3-thiadiazol-4-yl, 1,2,3-thiadiazol-5-yl, 1,3,4-thiadiazol-2-yl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 1-oxopyridin-2-yl, 1-oxopyridin-3-yl, 1-oxopyridin-4-yl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazine-2-yl, 1,2,4-triazine-3-yl, 1,2,4-triazine-5-yl, 1,2,3,4-tetrazine-1-yl, 1,2,3,4-tetrazine-2-yl, 1,2,3,4-tetrazine-5-yl, and the like.

[0085] "Heterobicycle" or "heterobicyclyl" contains two rings that have at least one ring atom in common. At least one of the two rings contains as a ring member a heteroatom or heteroatom group selected from N, O, S, NO, SO and SO2. The term includes fused ring systems in which the two rings have two adjacent ring atoms in common, spiro systems in which the rings have only one ring atom in common, and bridged systems in which there are at least three ring atoms in common. For the purposes of the present invention, heterobicycles include fully aromatic bicyclic ring systems; these are also referred to as heteroaromatic bicycles or bicyclic heteroaryls or heterobiaryls. Heterobicycles are preferably 7, 8, 9, 10 or 11 members. Heteroaromatic bicycles are preferably 9, 10 or 11 members. Fully heteroaromatic heterobicycles are 9 or 10 members.

[0086] Examples of fused systems are:

[0087] Examples of 7-, 8-, 9-, 10- or 11-membered saturated heterobicyclic rings containing 1, 2 or 3 (or 4) heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2 as ring members are:

[0088]

[0089]

[0090] Examples of 7-, 8-, 9-, 10- or 11-membered partially unsaturated heterobicyclic rings containing 1, 2 or 3 (or 4) heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2 as ring members are:

[0091]

[0092]

[0093] Examples of 7-, 8-, 9-, 10- or 11-membered maximally unsaturated (but not fully heteroaromatic) heterobicyclic rings containing 1, 2 or 3 (or 4) heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2 as ring members are:

[0094]

[0095]

[0096] Examples of 9- or 10-membered maximally unsaturated fully heteroaromatic heterobicyclic rings containing 1, 2 or 3 (or 4) heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2 as ring members are:

[0097]

[0098] Examples of 7-, 8-, 9-, 10- or 11-membered spiro-heterobicyclic rings containing 1, 2 or 3 (or 4) heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2 as ring members are:

[0099]

[0100]

[0101] Examples of 7-, 8-, 9-, 10- or 11-membered bridged heterobicyclic rings containing 1, 2 or 3 (or 4) heteroatoms or heteroatom groups selected from N, O, S, NO, SO and SO2 as ring members are:

[0102]

[0103] etc.

[0104] In the above structure, # indicates the point of attachment to the rest of the molecule. The point of attachment is not limited to the ring shown above, but can be on either of the two rings, and can be on a carbon ring atom or on a nitrogen ring atom. If the rings carry one or more substituents, these can be bonded to carbon and / or nitrogen ring atoms.

[0105] Polycyclic heterocycles (polyheterocyclyls) contain 3 or more rings, each of which shares at least one ring atom with at least one of the other rings of the polycyclic system. The rings may be fused, spiro-connected or bridged; mixed systems (e.g. one ring spiro-connected to a fused system, or a bridged system fused to another ring) are also possible. Fully aromatic rings are not included in the polycyclic heterocycles (polyheterocyclyls); these are called polycyclic heteroaromatic rings or heteropolyaryls.

[0106] Aryloxy, heterocyclyloxy and heteroaryloxy (also expressed as O-aryl, O-heterocyclyl and O-heteroaryl) are aryl, heterocyclyl and heteroaryl, respectively, as defined above, which are bonded to the remainder of the molecule via an oxygen atom. Examples are phenoxy or pyridyloxy.

[0107] The aryl and heterocyclic groups may be unsubstituted or may carry one or more substituents. Suitable substituents are, for example, linear or branched C1-C 18 Alkyl, C2-C 10 alkenyl or halogen, especially fluorine.

[0108] Examples of natural or synthetic saturated fatty acids having 2 to 41 carbon atoms are acetic acid (2 C atoms in total), propionic acid (3 C atoms in total), butyric acid (4 C atoms in total), isobutyric acid (4 C), valeric acid (5 C), hexanoic acid (6 C), heptanoic acid (7 C), octanoic acid (8 C), 2-ethylhexanoic acid, nonanoic acid (9 C), neononanoic acid (9 C; a branched isomer mixture of n-nonanoic acid), decanoic acid (10 C), 3-propylheptanoic acid (10 C), 2-ethylhexanoic acid, 1-butylhexanoic acid (10 C), ... C), neodecanoic acid (10C; a branched isomer mixture of n-decanoic acid), undecanoic acid (11C), lauric acid (12C), tridecanoic acid (13C), myristic acid (14C), pentadecanoic acid (15C), palmitic acid (16C), heptadecanoic acid (17C), stearic acid (18C), nonadecanoic acid (19C), arachidic acid (20C), heneicosanoic acid (21C) and docosanoic acid (22C). Examples of monounsaturated fatty acids are myristoleic acid (14C), palmitoleic acid (16C), oleic acid (18C), elaidic acid (18C), gandoleic acid (20C); gondoic acid (20C), cetoleic acid (22C) and erucic acid (22C). Examples of polyunsaturated fatty acids are linoleic acid (18C), α-linoleic acid (18C), γ-linoleic acid (18C), α-eleostearic acid (18C), β-eleostearic acid (18C), linoleic acid (18C), arachidonic acid (20C), docosadienoic acid (22C), docosatetraenoic acid (22C), docosapentaenoic acid (22C) and docosahexaenoic acid (22C).

[0109] "(Meth)acrylate" is intended to include acrylates and methacrylates. "Poly(meth)acrylate" relates to polyacrylates, polymethacrylates or copolymers of acrylates and methacrylates.

[0110] For the purposes of the present invention, "acrylate" and "methacrylate" refer to esters of acrylic acid or methacrylic acid (rather than salts thereof), unless expressly stated otherwise. This of course also applies to polymers thereof.

[0111] Embodiments of the present invention

[0112] The following statements regarding preferred definitions of the individual variables and other reaction conditions are valid both individually and in preferred combinations with one another.

[0113] Embodiments of the present invention (Ex)

[0114] Common and preferred embodiments Ex are summarized in the following non-exhaustive list. Other preferred embodiments are apparent from the paragraphs following this list.

[0115] E.1. A method for preparing a cyclic carbonate I selected from a compound of formula Ia, a compound of formula Ib and a mixture thereof:

[0116]

[0117] in

[0118] R 1 It is an organic group;

[0119] The following steps are involved:

[0120] a) reacting a propargyl alcohol of the formula II with carbon dioxide:

[0121]

[0122] Where R 1 has the same meaning as in Formula Ia or Ib,

[0123] wherein the reaction is carried out in at least one organic solvent L1 or in a solvent mixture containing at least one organic solvent L1 and at least one organic solvent L2; wherein solvent L1 has a higher polarity than solvent L2, and wherein solvents L1 and L2 have a miscibility zone at least between 20-30° C.;

[0124] wherein the reaction is further carried out in the presence of a silver catalyst Ag1 comprising at least one bulky ligand and a carboxylate ligand,

[0125] Wherein the bulky ligand is selected from the ligand of formula III and the ligand of formula IV:

[0126]

[0127] in

[0128] D is P, As or Sb;

[0129] R 2 Each is independently an organic group having 1 to 40 carbon atoms;

[0130] R 3 and R 4 are the same or different and are each an organic group having 1 to 40 carbon atoms,

[0131] R 5 is an organic group having 1 to 40 carbon atoms and can react with R present in ligand IV 2 different or the same; and

[0132] Z is selected from -CR 7 =CR 8 -、-CR 7 =N-, -CR 7R 9 -CR 8 R 10 -and-CR 7 R 9 -CR 8 R 10 -CR 11 R 12 - a divalent bridging group,

[0133] in

[0134] R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are independently hydrogen or an organic group having 1 to 40 carbon atoms; or

[0135] Two adjacent groups R 7 and R 8 and / or R 10 and R 11 together with the atoms to which they are attached, form a substituted or unsubstituted mono- or polycyclic aliphatic or aromatic ring system having 4 to 40 carbon atoms and which may also contain at least one heteroatom selected from the elements Si, Ge, N, P, O and S as a ring member;

[0136] and wherein the carboxylate ligand is according to Formula V:

[0137]

[0138] in

[0139] R 6 is an organic group having 1 to 40 carbon atoms;

[0140] b1) adding solvent L2 to the reaction mixture obtained in step a), if step a) has not already been carried out in the presence of at least one solvent L2; or

[0141] b2) optionally adding a solvent L2 to the reaction mixture obtained in step a), in case step a) has been carried out in the presence of at least one solvent L2;

[0142] c) phase separation of the reaction mixture obtained in step a), b1) or b2) to obtain a product phase containing the cyclic carbonate I and the at least one solvent L1 and a catalyst phase containing the silver catalyst and the at least one solvent L2; and

[0143] d) if necessary separating the cyclic carbonate I from the product phase.

[0144] E.2. A method as defined in embodiment 1, wherein R 1 is selected from the group consisting of hydrogen, aliphatic groups, cycloaliphatic groups, aromatic groups, mixed aliphatic-cycloaliphatic groups, mixed aliphatic-aromatic groups, mixed cycloaliphatic-aromatic groups and mixed aliphatic-cycloaliphatic-aromatic groups, wherein the aliphatic, cycloaliphatic and / or aromatic residues in the aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic and mixed aliphatic-cycloaliphatic-aromatic groups may be substituted by one or more halogen atoms; and wherein the aliphatic groups, cycloaliphatic groups and aromatic groups have at least one of the following features (i) and / or (ii) and the mixed aliphatic-cycloaliphatic groups, mixed aliphatic-aromatic groups, mixed cycloaliphatic-aromatic groups and mixed aliphatic-cycloaliphatic-aromatic groups have at least one of the following features (i), (ii) and / or (iii):

[0145] (i) aliphatic, cycloaliphatic and / or aromatic residues in aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic and mixed aliphatic-cycloaliphatic-aromatic groups are bound by one or more non-adjacent groups -O-, -S-, -N(R) 13 )-, -OC(=O)-, -C(=O)-O-, -N(R 13 )-C(=O)-, -C(=O)-N(R 13 )-, -OC(=O)-O-, -OC(=O)-N(R 13 )-、-N(R 13 )-C(=O)-O- and / or -N(R 13 )-C(=O)-N(R 13 )-interval;

[0146] (ii) aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic and mixed aliphatic-cycloaliphatic-aromatic groups carrying one or more radicals selected from -OH, -SH, -N(R) 13 )2, -OC(=O)H, -C(=O)OH, -N(R 13 )-C(=O)H, -C(=O)-NHR 13 , -OC(=O)-OH, -OC(=O)-NHR 13 、-N(R 13 )-C(=O)-OH and -N(R 13 )-C(=O)-NHR 13 Substituents of

[0147] (iii) aliphatic, cycloaliphatic and aromatic residues in mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic and mixed aliphatic-cycloaliphatic-aromatic groups are linked by groups -O-, -S-, -N(R 13 )-, -OC(=O)-, -C(=O)-O-, -N(R 13 )-C(=O)-, -C(=O)-N(R 13 )-, -OC(=O)-O-, -OC(=O)-N(R 13 )-、-N(R 13 )-C(=O)-O- or -N(R 13 )-C(=O)-N(R 13 )-bonded to each other;

[0148] Where R 13 are independently hydrogen or C1-C 10 alkyl.

[0149] E.3. A method as defined in Embodiment 1, wherein the cyclic carbonate is a compound of formula I-poly:

[0150]

[0151] in

[0152] X is a bond or a group -C(=O)-, # -C(=O)-O-* or # -C(=O)-N(R 13 )-*,in # is the point of attachment to O and * is the point of attachment to Y (or to Z if Y is a bond or to poly if Y and Z are a bond);

[0153] Y is a bond or a divalent aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic-aromatic bridging group, wherein the aliphatic, cycloaliphatic and / or aromatic residues in the aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic and mixed aliphatic-cycloaliphatic-aromatic bridging group may be substituted by one or more halogen atoms; and wherein the aliphatic, cycloaliphatic and aromatic bridging group may have at least one of the following features (i) and / or (ii) and the mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic-aromatic bridging group may have at least one of the following features (i), (ii) and / or (iii):

[0154] (i) the aliphatic, cycloaliphatic and / or aromatic residue in the aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic-aromatic bridging group is bound by one or more non-adjacent groups -O-, -S-, -N(R) 13 )-, -OC(=O)-, -C(=O)-O-, -N(R 13 )-C(=O)-, -C(=O)-N(R 13 )-, -OC(=O)-O-, -OC(=O)-N(R 13 )-、-N(R 13 )-C(=O)-O- and / or -N(R 13 )-C(=O)-N(R 13 )-interval;

[0155] (ii) the aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic-aromatic bridging group carries one or more selected from -OH, -SH, -N(R) 13 )2, -OC(=O)H, -C(=O)OH, -N(R 13 )-C(=O)H, -C(=O)-NHR 13 , -OC(=O)-OH, -OC(=O)-NHR 13 、-N(R 13 )-C(=O)-OH and -N(R 13 )-C(=O)-NHR 13 Substituents of

[0156] (iii) aliphatic, cycloaliphatic and / or aromatic residues in mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic-aromatic bridging groups via groups -O-, -S-, -N(R) 13 )-, -OC(=O)-, -C(=O)-O-, -N(R 13 )-C(=O)-, -C(=O)-N(R 13 )-, -OC(=O)-O-, -OC(=O)-N(R 13 )-、-N(R 13 )-C(=O)-O- or -N(R 13 )-C(=O)-N(R 13 )-bonded to each other;

[0157] Where R 13 are independently hydrogen or C1-C 10 alkyl;

[0158] If X and Y are bonds, then Z is a bond or a group -C(=O)-, # -C(=O)-O-* or # -C(=O)-N(R 13 )-*;in # is the point of attachment to Y (or to X if Y is a bond or to O if X and Y are bonds) and * is the point of attachment to Poly; or if Y is a bond and X is a group -C(=O)-, # -C(=O)-O*- or # -C(=O)-N(R 13 )-*, then Z is a bond, where # is the point of attachment to O; or if Y is a divalent aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic-aromatic bridging group, then Z is a bond or the group -O-, -S-, -N(R 13 )-、-C(=O)-、 # -OC(=O)-*、 # -C(=O)-O-*、 # -N(R 13 )-C(=O)-*、 # -C(=O)-N(R 13 )-*、 # -OC(=O)-O-*、 # -OC(=O)-N(R 13 )-*、 # -N(R 13 )-C(=O)-O-* or # -N(R 13 )-C(=O)-N(R 13 )-*,in # is the connection point with Y;

[0159] n is 1-1000; and

[0160] Poly is a residue derived from a polymer having a number average molecular weight of 200 to 10,000; and

[0161] The propargyl alcohol is a compound of II-poly:

[0162]

[0163] wherein X, Y, Z, n and Poly are as defined above.

[0164] E.4. A method as defined in embodiment 3, wherein

[0165] X is a bond or a group -C(=O)- or # -C(=O)-N(R 13 )-*,in # is the point of attachment to O and * is the point of attachment to Y (or to Z if Y is a bond or to poly if Y and Z are a bond);

[0166] Y is a bond or a divalent aliphatic or mixed aliphatic-cycloaliphatic bridging group having 1 to 10 carbon atoms, wherein the aliphatic or mixed aliphatic-cycloaliphatic bridging group may be substituted by one or more halogen atoms; and

[0167] wherein the aliphatic bridging group may have at least one of the following features (i) and / or (ii) and the mixed aliphatic-cycloaliphatic bridging group may have at least one of the following features (i), (ii) and / or (iii):

[0168] (i) the aliphatic and / or cycloaliphatic residues in the aliphatic or mixed aliphatic-cycloaliphatic bridging group are interrupted by one or more non-adjacent groups -O-, -OC(=O)-, -C(=O)-O- and / or -OC(=O)-O-;

[0169] (ii) the aliphatic or mixed aliphatic-cycloaliphatic bridging group carries one or more substituents selected from -OH, -OC(=O)H and -C(=O)OH;

[0170] (iii) the aliphatic and / or cycloaliphatic residues in the mixed aliphatic-cycloaliphatic bridging group are bonded to one another via the groups —O—, —OC(═O)—, —C(═O)—O— or —OC(═O)—O;

[0171] If X and Y are a bond then Z is a bond or a group -C(=O)-; or if Y is a bond and X is a group -C(=O)- then Z is a bond; or if Y is a divalent aliphatic or mixed aliphatic-cycloaliphatic bridging group then Z is a bond or a group # -OC(=O)-; and Poly is a residue derived from poly-α-olefin or poly(meth)acrylate.

[0172] E.5. A method as defined in embodiment 4, wherein -XYZ- together is -C(=O)-, # -CH2-CH(OH)-CH2-OC(=O)-* or # -C(=O)-NH-CH2CH2-OC(=O)-*, wherein # is the connection point with O and * is the connection point with Poly.

[0173] E.6. A method as defined in Embodiment 2, wherein the cyclic carbonate is compound Ia, compound Ib or a mixture thereof, wherein R 1 Selected from hydrogen and a group -OR 14 C1-C4 alkyl, wherein

[0174] R 14 is selected from hydrogen, C1-C4 alkyl, C1-C4 haloalkyl, with 1, 2 or 3 radicals R 15 C1-C6 alkyl, with 1, 2 or 3 groups R 15 C1-C6 haloalkyl, -C(=O)R 16 , C3-C6 cycloalkyl, with 1, 2 or 3 radicals R 17 C3-C6 cycloalkyl, phenyl and 3-, 4-, 5- or 6-membered saturated, partially unsaturated or maximally unsaturated heterocycles containing 1, 2 or 3 heteroatoms selected from N, O and S as ring members, wherein the phenyl and heterocycles may carry one or more substituents selected from C1-C4 alkyl and C1-C4 alkoxy;

[0175] in

[0176] R 15 is selected from OH, C1-C6 alkoxy, oxirane, phenyl and a 3-, 4-, 5- or 6-membered saturated heterocyclic ring containing 1 or 2 oxygen atoms as ring members;

[0177] R 16 Selected from C1-C6 alkyl, C2-C6 alkenyl, C1-C4 alkoxy and -NR 18 R 19 , where R 18 is hydrogen or C1-C4 alkyl and R 19 Selected from hydrogen, C1-C4 alkyl, group R 20 Substituted C1-C4 alkyl and phenyl which may have 1, 2, 3, 4 or 5 substituents selected from C1-C4 alkyl and C1-C4 alkoxy;

[0178] in

[0179] R 20 Select from -OR 21 、-N(R 13 )-R 21 、-OC(=O)-R 21 、-C(=O)-OR 21 、-N(R 13 )-C(=O)-R 21 、-C(=O)-N(R 13 )-R 21 、-OC(=O)-OR 21、-OC(=O)-N(R 13 )-R 21 、-N(R 13 )-C(=O)-OR 21 and -N(R 13 )-C(=O)-N(R 13 )-R 21 , where R 21 is hydrogen, C1-C6 alkyl or C2-C6 alkenyl and wherein R 13 are independently hydrogen or C1-C 10 Alkyl; and

[0180] R 17 Select from -OR 21 、-N(R 13 )-R 21 、-OC(=O)-R 21 、-C(=O)-OR 21 、-N(R 13 )-C(=O)-R 21 、-C(=O)-N(R 13 )-R 21 、-OC(=O)-OR 21 、-OC(=O)-N(R 13 )-R 21 、-N(R 13 )-C(=O)-OR 21 and -N(R 13 )-C(=O)-N(R 13 )-R 21 , where R 21 is hydrogen, C1-C6 alkyl or C2-C6 alkenyl and wherein R 13 are independently hydrogen or C1-C 10 alkyl;

[0181] Alternatively, the cyclic carbonate is a compound of formula I-bis:

[0182]

[0183] in

[0184] A is an aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic-aromatic bridging group, wherein the aliphatic, cycloaliphatic and / or aromatic residues in the aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic and mixed aliphatic-cycloaliphatic-aromatic groups may be substituted by one or more halogen atoms; and wherein the aliphatic, cycloaliphatic or aromatic bridging group has at least one of the following features (i) and / or (ii) and the mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic-aromatic bridging group has at least one of the following features (i), (ii) and / or (iii):

[0185] (i) the aliphatic, cycloaliphatic and / or aromatic residue in the aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic-aromatic bridging group is bound by one or more non-adjacent groups -O-, -S-, -N(R) 13 )-, -OC(=O)-, -C(=O)-O-, -N(R 13 )-C(=O)-, -C(=O)-N(R 13 )-, -OC(=O)-O-, -OC(=O)-N(R 13 )-、-N(R 13 )-C(=O)-O- and / or -N(R 13 )-C(=O)-N(R 13 )-interval;

[0186] (ii) the aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic-aromatic bridging group carries one or more selected from -OH, -SH, -N(R) 13 )2, -OC(=O)H, -C(=O)OH, -N(R 13 )-C(=O)H, -C(=O)-NHR 13 , -OC(=O)-OH, -OC(=O)-NHR 13 、-N(R 13 )-C(=O)-OH and -N(R 13 )-C(=O)-NHR 13 Substituents of

[0187] (iii) aliphatic, cycloaliphatic and / or aromatic residues in mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic-aromatic bridging groups via groups -O-, -S-, -N(R) 13)-, -OC(=O)-, -C(=O)-O-, -N(R 13 )-C(=O)-, -C(=O)-N(R 13 )-, -OC(=O)-O-, -OC(=O)-N(R 13 )-、-N(R 13 )-C(=O)-O- or -N(R 13 )-C(=O)-N(R 13 )-bonded to each other;

[0188] Where R 13 are independently hydrogen or C1-C 10 Alkyl; and

[0189] The propargyl alcohol is a compound of formula II, wherein R 1 Selected from hydrogen and a group -OR 14 C1-C4 alkyl, wherein R 14 As defined above, or the propargyl alcohol is a compound of formula II-bis:

[0190]

[0191] wherein A is as defined above.

[0192] E.7. A method as defined in Embodiment 6, wherein the cyclic carbonate is compound Ia, compound Ib or a mixture thereof, wherein R 1 Selected from hydrogen and -CH2-OR 14 ,

[0193] in

[0194] R 14 is selected from hydrogen, with 1, 2 or 3 radicals R 15 C1-C4 alkyl, -C(=O)R 16 and with 1, 2 or 3 groups R 17 C3-C6 cycloalkyl;

[0195] in

[0196] R 15 is selected from OH, C1-C4 alkoxy, phenyl and a 3-, 4-, 5- or 6-membered saturated heterocyclic ring containing 1 or 2 oxygen atoms as ring members;

[0197] R 16 Selected from C1-C6 alkyl, C2-C6 alkenyl, C1-C4 alkoxy and -NR 18 R 19 , where R 18 is hydrogen or C1-C4 alkyl and R 19Selected from hydrogen, C1-C4 alkyl, group R 20 Substituted C1-C4 alkyl and phenyl which may have 1, 2, 3, 4 or 5 substituents selected from C1-C4 alkyl and C1-C4 alkoxy;

[0198] in

[0199] R 20 Select from -OR 21 、-N(R 13 )-R 21 、-OC(=O)-R 21 、-C(=O)-OR 21 、-N(R 13 )-C(=O)-R 21 、-C(=O)-N(R 13 )-R 21 、-OC(=O)-OR 21 、-OC(=O)-N(R 13 )-R 21 、-N(R 13 )-C(=O)-OR 21 and -N(R 13 )-C(=O)-N(R 13 )-R 21 , where R 21 is hydrogen, C1-C6 alkyl or C2-C6 alkenyl and wherein R 13 are independently hydrogen or C1-C 10 Alkyl; and

[0200] R 17 Select from -OR 21 、-N(R 13 )-R 21 、-OC(=O)-R 21 、-C(=O)-OR 21 、-N(R 13 )-C(=O)-R 21 、-C(=O)-N(R 13 )-R 21 、-OC(=O)-OR 21 、-OC(=O)-N(R 13 )-R 21 、-N(R 13 )-C(=O)-OR 21 and -N(R 13 )-C(=O)-N(R 13 )-R 21 , where R 21is hydrogen, C1-C6 alkyl or C2-C6 alkenyl and wherein R 13 are independently hydrogen or C1-C 10 alkyl;

[0201] Or the cyclic carbonate is a compound of formula I-bis as defined in Embodiment 6, wherein A is selected from the following bridging groups: -CH2-O-CH2-1,4-phenylene-CH2-O-CH2-, -CH2-OC(=O)-NH-1,4-tolylene-NH-C(=O)-O-CH2-, -CH2-O-CH2-CH(OH)-CH2-O-(CH2)3-O-CH2-CH(OH)-CH2-O-CH2-, -CH2-O-CH2-CH(OH)-CH2-O-1,4-phenylene-C(CH3)2-1,4-phenylene-O-CH2-CH(OH)-CH2-O-CH2- and -CH2-(OCH2CH2)3-O-CH2-; and

[0202] The propargyl alcohol is a compound of formula II, wherein R 1 Selected from hydrogen and -CH2-OR 14 , where R 14 as defined above, or the propargyl alcohol is a compound of formula II-bis as defined in embodiment 6, wherein A is as defined above.

[0203] E.8. A method as defined in Embodiment 7, wherein the cyclic carbonate is compound Ia, compound Ib or a mixture thereof, wherein R 1 Selected from hydrogen and -CH2-OR 14 ,

[0204] in

[0205] R 14 is selected from hydrogen, with 1, 2 or 3 radicals R 15 C1-C4 alkyl, -C(O)CH3, -C(=O)H and -C(O)OCH3;

[0206] Where R 15 Selected from OH and C1-C4 alkoxy;

[0207] Or the cyclic carbonate is a compound of formula I-bis as defined in Embodiment 6, wherein A is -CH2-O-CH2-CH(OH)-CH2-O-1,4-phenylene-C(CH3)2-1,4-phenylene-O-CH2-CH(OH)-CH2-O-CH2-; and

[0208] The propargyl alcohol is a compound of formula II, wherein R 1 Selected from hydrogen and -CH2-OR14 , where R 14 as defined above, or the propargyl alcohol is a compound of formula II-bis as defined in embodiment 6, wherein A is as defined above.

[0209] E.9. A method as defined in Embodiment 8, wherein the cyclic carbonate is compound Ia, compound Ib or a mixture thereof, wherein R 1 Selected from hydrogen and -CH2-OR 14 ,

[0210] in

[0211] R 14 is selected from hydrogen and carrying 1 or 2 radicals R 15 C1-C4 alkyl;

[0212] Where R 15 Selected from OH and C1-C4 alkoxy;

[0213] Or the cyclic carbonate is a compound of formula I-bis as defined in Embodiment 6, wherein A is -CH2-O-CH2-CH(OH)-CH2-O-1,4-phenylene-C(CH3)2-1,4-phenylene-O-CH2-CH(OH)-CH2-O-CH2-; and

[0214] The propargyl alcohol is a compound of formula II, wherein R 1 Selected from hydrogen and -CH2-OR 14 , where R 14 as defined above, or the propargyl alcohol is a compound of formula II-bis as defined in embodiment 6, wherein A is as defined above.

[0215] E.10. A method as defined in Embodiment 9, wherein the cyclic carbonate is compound Ia, compound Ib or a mixture thereof, wherein R 1 Selected from hydrogen and -CH2-OR 14 , where R 14 is -CH2-CH(OH)-CH2-OC(CH3)3 or -CH2-CH(OH)-CH2-OH; or the cyclic carbonate is a compound of formula I-bis as defined in Embodiment 6, wherein A is -CH2-O-CH2-CH(OH)-CH2-O-1,4-phenylene-C(CH3)2-1,4-phenylene-O-CH2-CH(OH)-CH2-O-CH2-; and the propargyl alcohol is a compound of formula II, wherein R 1 Selected from hydrogen and -CH2-OR 14 , where R 14It is -CH2-CH(OH)-CH2-OC(CH3)3 or -CH2-CH(OH)-CH2-OH; or the propargyl alcohol is a compound of formula II-bis as defined in Embodiment 6, wherein A is -CH2-O-CH2-CH(OH)-CH2-O-1,4-phenylene-C(CH3)2-1,4-phenylene-O-CH2-CH(OH)-CH2-O-CH2-.

[0216] E.11. A method as defined in Embodiment 10, wherein the cyclic carbonate is Compound Ia, Compound Ib or a mixture thereof, wherein R 1 Selected from hydrogen and -CH2-OR 14 , where R 14 is -CH2-CH(OH)-CH2-OC(CH3)3; or the cyclic carbonate is a compound of formula I-bis as defined in Embodiment 6, wherein A is -CH2-O-CH2-CH(OH)-CH2-O-1,4-phenylene-C(CH3)2-1,4-phenylene-O-CH2-CH(OH)-CH2-O-CH2-; and the propargyl alcohol is a compound of formula II, wherein R 1 Selected from hydrogen and -CH2-OR 14 , where R 14 It is -CH2-CH(OH)-CH2-OC(CH3)3; or the propargyl alcohol is a compound of formula II-bis as defined in Embodiment 6, wherein A is -CH2-O-CH2-CH(OH)-CH2-O-1,4-phenylene-C(CH3)2-1,4-phenylene-O-CH2-CH(OH)-CH2-O-CH2-.

[0217] E.12. A method as defined in Embodiment 11, wherein the cyclic carbonate is Compound Ia, Compound Ib or a mixture thereof, wherein R 1 Selected from hydrogen and -CH2-OR 14 , where R 14 is -CH2-CH(OH)-CH2-OC(CH3)3; and the propargyl alcohol is a compound of formula II, wherein R 1 Selected from hydrogen and -CH2-OR 14 , where R 14 It is -CH2-CH(OH)-CH2-OC(CH3)3.

[0218] E.13. A method as defined in embodiment 12, wherein the cyclic carbonate is compound Ia, compound Ib or a mixture thereof, wherein R 1 is hydrogen, and wherein the propargyl alcohol is a compound of formula II, wherein R 1It's hydrogen.

[0219] E.14. A method as defined in any of the preceding embodiments, wherein the bulky ligand is a ligand of formula III, wherein

[0220] D is P or As,

[0221] R 2 is selected from monocyclic or polycyclic C3-C 40 Cycloalkyl, monocyclic or polycyclic C3-C 40 Cycloalkenyl, C6-C 40 aryl and 3-40 membered saturated, partially unsaturated or maximally unsaturated monocyclic or polycyclic heterocyclic cyclic groups, wherein the cyclic group may be bonded to D via an oxygen atom and wherein the cyclic group may carry one or more substituents selected from the group consisting of C1-C6 alkyl, C1-C6 alkoxy, optionally substituted by 1, 2, 3, 4 or more substituents R 22 Substituted phenyl, optionally substituted by 1, 2, 3, 4 or more substituents R 22 Substituted naphthyl, containing 1, 2, 3 or 4 heteroatoms selected from N, O and S as ring members and optionally substituted by 1, 2 or 3 or more substituents R 23 A substituted monocyclic 5- or 6-membered heteroaromatic ring and containing 1, 2, 3 or 4 heteroatoms selected from N, O and S as ring members and optionally substituted by 1, 2 or 3 or more substituents R 23 Substituted fused bicyclic 8-10 membered heteroaromatic ring system,

[0222] in

[0223] R 22 Each independently selected from C1-C6 alkyl, C1-C6 alkoxy, NR 24 R 25 , where R 24 and R 25 are independently hydrogen or C1-C 12 alkyl; phenyl, naphthyl and monocyclic saturated, partially unsaturated or maximum unsaturated 5- or 6-membered heterocycles containing 1, 2, 3 or 4 heteroatoms selected from N, O and S as ring members, wherein the last three cyclic radicals may in turn carry 1, 2, 3, 4 or 5 substituents selected from halogen, C1-C4-alkyl and C1-C4-alkoxy; and

[0224] R 23 Each independently has a 22 one of the given meanings; and

[0225] R 3 and R 4 independently selected from C1-C6 alkyl, monocyclic or polycyclic C3-C 40 Cycloalkyl, monocyclic or polycyclic C3-C40 Cycloalkenyl and C6-C 10 Aryl.

[0226] E.15. A method as defined in embodiment 14, wherein

[0227] D is P;

[0228] R 2 is optionally substituted by 1, 2, 3, 4 or more substituents R 22 Substituted phenyl, optionally substituted by 1, 2, 3, 4 or more substituents R 22 Substituted o-biphenyl, optionally substituted by 1, 2, 3, 4 or more substituents R 22 Substituted naphthyl, optionally substituted by 1, 2, 3, 4 or more substituents R 22 o-binaphthyl, containing 1, 2 or 3 nitrogen atoms as ring members and optionally substituted by 1, 2 or 3 substituents R 23 A substituted monocyclic 5- or 6-membered heteroaromatic ring system and containing 1, 2, 3 or 4 nitrogen atoms as ring members and optionally substituted by 1, 2 or 3 or more substituents R 23 Substituted fused bicyclic 8-10 membered heteroaromatic ring system,

[0229] in

[0230] R 22 Each independently selected from C1-C4 alkyl, C1-C4 alkoxy, NR 24 R 25 , where R 24 and R 25 are independently hydrogen or C1-C 10 alkyl; phenyl optionally substituted by 1, 2, 3, 4 or 5 substituents selected from halogen, C1-C4 alkyl and C1-C4 alkoxy; and monocyclic saturated, partially unsaturated or maximum unsaturated 5- or 6-membered heterocyclic ring containing 1, 2 or 3 heteroatoms selected from N and O as ring members; and

[0231] R 23 are each independently phenyl optionally substituted with 1, 2, 3, 4 or 5 substituents selected from halogen, C1-C4 alkyl and C1-C4 alkoxy; and

[0232] R 3 and R 4 are independently selected from branched C3-C6 alkyl groups, monocyclic C3-C6 cycloalkyl groups, adamantyl groups and phenyl groups.

[0233] E.16. A method as defined in embodiment 15, wherein

[0234] D is P;

[0235] R 2It was NR 24 R 25 Substituted phenyl, wherein R 24 and R 25 are independently hydrogen or C1-C 10 Alkyl; or substituted by 1, 2, 3 or 4 groups R 22 Substituted o-biphenyl,

[0236] in

[0237] R 22 Each independently selected from C1-C4 alkyl and NR 24 R 25 , where R 24 and R 25 are independently hydrogen or C1-C 10 alkyl.

[0238] E.17. A method as defined in embodiment 16, wherein R 24 and R 25 Independently of each other are C3-C 10 alkyl.

[0239] E.18. A method as defined in embodiment 14, wherein the bulky ligand is selected from compounds of formula AW and mixtures thereof, wherein AW is as defined below.

[0240] E.19. A method as defined in embodiment 18, wherein the bulky ligand is selected from compounds of formula D, V, W, and mixtures thereof.

[0241] E.20. A method as defined in embodiment 19, wherein the bulky ligand is a compound of formula D (XPhos).

[0242] E.21. A method as defined in any one of embodiments 1-13, wherein the bulky ligand is a ligand of formula IV, wherein R 2 and R 5 are independently C6-C6 alkyl, C1-C6 alkoxy and C3-C6 cycloalkyl. 10 Aryl, and Z is -CR 7 =CR 8 -, where R 7 and R 8 are independently hydrogen or C1-C6 alkyl.

[0243] E.22. A method as defined in embodiment 21, wherein R 2 and R 5 is 2,6-diisopropylphenyl and Z is -CH=CH-.

[0244] E.23. A method as defined in any one of the preceding embodiments, wherein R 6 Selected from C1-C 40 Alkyl, C2-C 40 Alkenyl with C3-C 10 A C1-C6 alkyl group of a cycloalkyl ring, wherein C3-C 10 The cycloalkyl ring may have 1, 2, 3, 4 or 5 C1-C6 alkyl substituents. 10 C1-C4 alkyl of aryl ring, wherein C6-C 10 The aryl ring may have 1, 2, 3, 4 or 5 substituents selected from C1-C6 alkyl and C1-C6 alkoxy, and the C6-C6 alkyl ring may have 1, 2, 3, 4 or 5 substituents selected from C1-C6 alkyl and C1-C6 alkoxy. 10 Aryl.

[0245] E.24. A method as defined in embodiment 23, wherein R 6 Selected from C1-C 30 Alkyl, C6-C 30 Alkenyl and C1-C4 alkyl having a C3-C6 cycloalkyl ring.

[0246] E.25. A method as defined in embodiment 24, wherein R 6 Selected from C1-C 22 Alkyl and C1-C4 alkyl with a C5-C6 cycloalkyl ring.

[0247] E.26. A method as defined in embodiment 25, wherein R 6 Selected from C1-C 20 Alkyl and C2-C4 alkyl with a cyclohexyl ring.

[0248] E.27. A method as defined in embodiment 26, wherein R 6 Selected from C8-C 18 Alkyl and C2-C4 alkyl with a cyclohexyl ring.

[0249] E.28. A method as defined in any one of embodiments 1-22, wherein R 6 Selected from C2-C 40 Alkyl, C2-C 40 Alkenyl with C3-C 10 A C1-C6 alkyl group of a cycloalkyl ring, wherein C3-C 10 The cycloalkyl ring may have 1, 2, 3, 4 or 5 C1-C6 alkyl substituents. 10 C1-C4 alkyl of aryl ring, wherein C6-C 10The aryl ring may have 1, 2, 3, 4 or 5 substituents selected from C1-C6 alkyl and C1-C6 alkoxy, and the C6-C6 alkyl ring may have 1, 2, 3, 4 or 5 substituents selected from C1-C6 alkyl and C1-C6 alkoxy. 10 Aryl.

[0250] E.29. A method as defined in embodiment 28, wherein R 6 Selected from C6-C 30 Alkyl, C6-C 30 Alkenyl and C1-C4 alkyl having a C3-C6 cycloalkyl ring.

[0251] E.30. A method as defined in embodiment 29, wherein R 6 Selected from C6-C 22 Alkyl and C1-C4 alkyl with a C5-C6 cycloalkyl ring.

[0252] E.31. A method as defined in embodiment 30, wherein R 6 Selected from C8-C 20 Alkyl and C2-C4 alkyl with a cyclohexyl ring.

[0253] E.32. A method as defined in embodiment 31, wherein R 6 Selected from C8-C 18 Alkyl and C2-C4 alkyl with a cyclohexyl ring.

[0254] E.33. A method as defined in any of the preceding embodiments, wherein the silver catalyst Ag1 is a preformed catalyst or is formed in situ by reacting a silver precatalyst, which is a silver compound or silver salt that does not contain the bulky ligand, with a compound of formula III, a carbene of formula IV, or a precursor of a carbene of formula IV; wherein in the case where the silver precatalyst does not contain a carboxylate ligand V, the silver precatalyst is also reacted with a corresponding acid R of the carboxylate ligand V. 6 -C(=O)OH or formula R 6 -C(=O)O - M + Its salt reaction, where M + It is a cation equivalent;

[0255] In the case where the silver catalyst Ag1 is formed in situ, the compound of formula III, the carbene of formula IV or the precursor of the carbene of formula IV is used in an amount of 0.2-1.8 mol / mol of silver present in the silver precatalyst.

[0256] E.34. A method as defined in Embodiment 33, wherein the precursor of the carbene of Formula IV is a compound of Formula VI:

[0257]

[0258] Where R 2 , R 5 and Z is as defined in any one of Embodiments 1, 21 or 22 and X- is an anion equivalent, wherein in the case of using compound VI, this is used together with a base;

[0259] E.35. A method as defined in embodiment 33 or 34, wherein, in the case of in situ formation of the silver catalyst Ag1, the compound of formula III, the carbene of formula IV or the precursor of the carbene of formula IV is used in an amount of 0.3-1.5 mol / mol of silver present in the silver precatalyst.

[0260] E.36. A process as defined in embodiment 35, wherein, in the case of in situ formation of the silver catalyst Ag1, the compound of formula III, the carbene of formula IV or the precursor of the carbene of formula IV is used in an amount of 0.4-1.2 mol / mol of silver present in the silver precatalyst.

[0261] E.37. A process as defined in embodiment 36, wherein, in the case of in situ formation of the silver catalyst Ag1, the compound of formula III, the carbene of formula IV or the precursor of the carbene of formula IV is used in an amount of 0.8-1.2 mol / mol of silver present in the silver precatalyst.

[0262] E.38. A process as defined in any of the preceding embodiments, wherein the silver catalyst Ag1 is used in step a) in an amount of 0.001 to 50 mol %, based on the amount of propargyl alcohol of formula II.

[0263] E.39. A process as defined in embodiment 38, wherein the silver catalyst Ag1 is used in step a) in an amount of 0.001 to 20 mol %, based on the amount of propargyl alcohol of the formula II.

[0264] E.40. A process as defined in embodiment 39, wherein the silver catalyst Ag1 is used in step a) in an amount of 0.005-10 mol %, based on the amount of propargyl alcohol of formula II.

[0265] E.41. A process as defined in embodiment 40, wherein the silver catalyst Ag1 is used in step a) in an amount of 0.01 to 5 mol %, based on the amount of propargyl alcohol of the formula II.

[0266] E.42. A process as defined in embodiment 41, wherein the silver catalyst Ag1 is used in step a) in an amount of 0.5 to 3 mol %, based on the amount of propargyl alcohol of the formula II.

[0267] E.43. A method as defined in any of the preceding embodiments, wherein the solvent L1 is a solvent having a dipole moment of at least 10·10 -30Polar aprotic solvent for C·m.

[0268] E.44. A method as defined in embodiment 43, wherein the solvent L1 is a solvent having a dipole moment of at least 11·10 -30 Polar aprotic solvent for C·m.

[0269] E.45. A method as defined in any of the preceding embodiments, wherein the solvent L2 is a solvent having a dipole moment of at most 2·10 -30 C·m nonpolar solvent,

[0270] E.46. A method as defined in embodiment 45, wherein the solvent L2 is a solvent having a dipole moment of at most 1·10 -30 C·m non-polar solvent.

[0271] E.47. A method as defined in embodiment 46, wherein solvent L2 is a non-polar solvent having a dipole moment of 0 C·m.

[0272] E.48. A method as defined in any of the preceding embodiments, wherein the solvent L1 is selected from amides, ureas, nitriles, sulfoxides, sulfones, ethers, esters, carbonates, nitro compounds and mixtures thereof, and L2 is selected from paraffins, cycloalkanes and C 12 -C 20 C1-C2 alkyl esters of fatty acids;

[0273] E.49. A method as defined in embodiment 48, wherein solvent L1 is a polar aprotic solvent and is selected from formamide, N-methylformamide, N,N-dimethylformamide, N,N-dimethylacetamide, tetramethylurea, N,N-dimethylimidazolidinone, N,N-dimethylpropylene urea, acetonitrile, propionitrile, benzonitrile, dimethyl sulfoxide, cyclopentane, dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, nitromethane, nitrobenzene and mixtures thereof.

[0274] E.50. A method as defined in embodiment 48 or 49, wherein the solvent L2 is selected from C5-C 15 Alkanes, C5-C8 cycloalkanes which may have C1-C2 alkyl substituents, 12 -C 20 C1-C2 alkyl esters of fatty acids and mixtures thereof.

[0275] E.51. A method as defined in any one of embodiments 48-50, wherein

[0276] - solvent L1 is acetonitrile and solvent L2 is selected from C5-C 14 Alkanes, C5-C8 cycloalkanes which may have C1-C2 alkyl substituents, and saturated C 12 -C 20C1-C2 alkyl esters of fatty acids; or

[0277] - solvent L1 is dimethylformamide and solvent L2 is selected from C5-C 14 Alkanes, C5-C8 cycloalkanes which may have C1-C2 alkyl substituents, and saturated C 12 -C 20 C1-C2 alkyl esters of fatty acids.

[0278] E.52. A method as defined in embodiment 51, wherein

[0279] - solvent L1 is acetonitrile and solvent L2 is selected from C5-C 12 Alkanes and C6-C8 cycloalkanes; or

[0280] - solvent L1 is dimethylformamide and solvent L2 is selected from C5-C 12 Chain alkanes and C5-C8 cycloalkanes.

[0281] E.53. A process as defined in embodiment 52, wherein solvent L1 is acetonitrile and solvent L2 is cyclohexane or decane, or solvent L1 is dimethylformamide and solvent L2 is hexane.

[0282] E.54. A process as defined in embodiment 53, wherein solvent L1 is acetonitrile and solvent L2 is cyclohexane or decane.

[0283] E.55. A process as defined in any of the preceding embodiments, wherein in step a) the propargyl alcohol is present in an amount of 0.1-25 wt. % relative to the total weight of all solvents used in step a).

[0284] E.56. A process as defined in embodiment 55, wherein in step a) the propargyl alcohol is present in an amount of 0.5-20% by weight relative to the total weight of all solvents used in step a).

[0285] E.57. A process as defined in embodiment 56, wherein in step a) the propargyl alcohol is present in an amount of 1-20% by weight relative to the total weight of all solvents used in step a).

[0286] E.58. A process as defined in embodiment 57, wherein in step a) the propargyl alcohol is present in an amount of 1-15% by weight relative to the total weight of all solvents used in step a).

[0287] E.59. A method as defined in any of the preceding embodiments, wherein step a) is carried out at a pressure in the range of 0.1-200 bar.

[0288] E.60. A process as defined in embodiment 59, wherein step a) is carried out at a pressure in the range of 1-100 bar.

[0289] E.61. A process as defined in embodiment 60, wherein step a) is carried out at a pressure in the range of 5-80 bar.

[0290] E.62. A method as defined in any of the preceding embodiments, wherein step a) is carried out at a temperature in the range of 0-100°C.

[0291] E.63. A process as defined in embodiment 62, wherein step a) is carried out at a temperature in the range of 10-80°C.

[0292] E.64. A process as defined in embodiment 63, wherein step a) is carried out at a temperature in the range of 10-40°C.

[0293] E.65. A process as defined in any of the preceding embodiments, wherein no solvent L2 is used in step a) and step b1) is performed.

[0294] E.66. A process as defined in any of the preceding embodiments, wherein in step c) solvent L1 and solvent L2 are present in a total weight ratio of 80:20 to 20:80.

[0295] E.67. A process as defined in embodiment 66, wherein in step c) solvent L1 and solvent L2 are present in a total weight ratio of 70:30 to 30:70.

[0296] E.68. A process as defined in embodiment 67, wherein in step c) solvent L1 and solvent L2 are present in a total weight ratio of 60:40 to 40:60.

[0297] E.69. A process as defined in any of the preceding embodiments, wherein the product phase obtained in step c) contains greater than 50% by weight of the cyclic carbonate I formed in step a) and the catalyst phase contains greater than 50% by weight of the silver catalyst.

[0298] E.70. A process as defined in embodiment 69, wherein the product phase obtained in step c) contains greater than 66.7% by weight of the cyclic carbonate I formed in step a) and the catalyst phase contains greater than 66.7% by weight of the silver catalyst.

[0299] E.71. A process as defined in embodiment 70, wherein the product phase obtained in step c) contains greater than 83.3% by weight of the cyclic carbonate I formed in step a) and the catalyst phase contains greater than 83.3% by weight of the silver catalyst.

[0300] Group R 1

[0301] In compounds I and II, R 1 is an organic group. As explained above, this group can be derived from a discrete molecule or a polymer. 1 If the starting compound II is derived from a polymer, then it usually contains more than one group -C≡C-CH2OH (and logically the end product usually contains more than one cyclic carbonate bonded via a vinylidene group). As explained above, this group can be bonded to the polymer backbone directly or via a linking group. Merely by way of example, a polymer or monomer containing a carboxyl group or a carboxyl derivative susceptible to esterification (transesterification) or containing an oxirane ring as present in a glycidyl residue or containing a chlorohydrin residue or an isocyanate group (-NCO) or other groups that can react with an alcohol group in the side chain can be reacted with 1,4-butynediol or another diol containing a propargyl alcohol group to obtain a carboxyl group in which R 1 (Poly) compounds II derived from polymers containing a large number of -C≡C-CH2OH groups in their side chains. If the monomer is reacted with 1,4-butynediol or another diol, the polymer is of course obtained after the polymerization of the monomer. In the product I from the reaction of the polymer with CO2, R 1Derived from a polymer containing a plurality of cyclic carbonate groups (more precisely 1,3-dioxolane-2-one-4-yl rings) bonded via exocyclic vinylidene groups. Alternatively, the monomer may first be reacted with CO2 under the reaction conditions described above and below to obtain a monomer containing an exo-vinylidene bonded cyclic carbonate and then polymerized. Alternatively, the monomer may first be reacted with CO2 under the reaction conditions described above and below to obtain a monomer containing an exo-vinylidene bonded cyclic carbonate and then polymerized. By way of example only, polyacrylic acid or polymethacrylic acid or a polyacrylate or polymethacrylate which is easily transesterified can be esterified with 1,4-butynediol to give a polymer having the repeating unit -[CH2-CH(C(=O)OCH2C≡CH2OH)]- or -[CH2-C(CH3)(C(=O)OCH2C≡CH2OH)]-; or a polyacrylate or polymethacrylate containing an -NCO group in the alcohol-derived portion of the ester (the alcohol-derived portion is derived, for example, from HO-CH2CH2-NCO) can be esterified with 1,4-butynediol to give a polymer having the repeating unit -[CH2-CH(C(=O)OCH2C≡CH2OH)]-; The acrylate is reacted with 1,4-butynediol in an addition reaction to obtain a polymer having a repeating unit -[CH2-CH(C(=O)O-CH2CH2-NH-C(=O)-O-CH2C≡CH2OH)]- or -[CH2-C(CH3)(C(=O)O-CH2CH2-NH-C(=O)-O-CH2C≡CH2OH)]-; or a polyacrylate or polymethacrylate containing a glycidyl residue or a chlorohydrin residue can be reacted with 1,4-butynediol in an addition or substitution reaction. Alternatively, the corresponding acrylate or methacrylate monomer is first prepared by the above-mentioned esterification / addition / substitution reaction and then polymerized. In another embodiment, the corresponding acrylate or methacrylate monomer can be grafted onto a polymer having a suitable backbone, for example, grafted onto a polyethylene or polypropylene polymer. However, the polymer residue is not limited to these few examples; it can be derived from very different polymer types, such as polymers with a polyolefin backbone, poly(meth)acrylates, polyesters, polyethers, polyurethanes, polyureas, polyamides, polycarbonates, and the like.

[0302] However, just to avoid any doubt, in R 1 In the case of derivation from discrete molecules, the starting compound may of course contain more than one group -C≡C-CH2OH (and the final compound will logically also contain more than one cyclic carbonate group bonded via a vinylene group).

[0303] In a preferred embodiment, the cyclic carbonate is compound Ia, compound Ib or a mixture thereof, wherein R 1is selected from the group consisting of hydrogen, aliphatic groups, cycloaliphatic groups, aromatic groups, mixed aliphatic-cycloaliphatic groups, mixed aliphatic-aromatic groups, mixed cycloaliphatic-aromatic groups and mixed aliphatic-cycloaliphatic-aromatic groups; wherein the aliphatic, cycloaliphatic and / or aromatic residues in the aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic and mixed aliphatic-cycloaliphatic-aromatic groups may be substituted by one or more halogen atoms; and wherein the aliphatic groups, cycloaliphatic groups and aromatic groups have at least one of the following features (i) and / or (ii) and the mixed aliphatic-cycloaliphatic groups, mixed aliphatic-aromatic groups, mixed cycloaliphatic-aromatic groups and mixed aliphatic-cycloaliphatic-aromatic groups have at least one of the following features (i), (ii) and / or (iii):

[0304] (i) aliphatic, cycloaliphatic and / or aromatic residues in aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic and mixed aliphatic-cycloaliphatic-aromatic groups are bound by one or more non-adjacent groups -O-, -S-, -N(R) 13 )-, -OC(=O)-, -C(=O)-O-, -N(R 13 )-C(=O)-, -C(=O)-N(R 13 )-, -OC(=O)-O-, -OC(=O)-N(R 13 )-、-N(R 13 )-C(=O)-O- and / or -N(R 13 )-C(=O)-N(R 13 )-interval;

[0305] (ii) aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic and mixed aliphatic-cycloaliphatic-aromatic groups carrying one or more radicals selected from -OH, -SH, -N(R) 13 )2, -OC(=O)H, -C(=O)OH, -N(R 13 )-C(=O)H, -C(=O)-NHR 13 , -OC(=O)-OH, -OC(=O)-NHR 13 、-N(R 13 )-C(=O)-OH and -N(R 13 )-C(=O)-NHR 13 Substituents of

[0306] (iii) aliphatic, cycloaliphatic and aromatic residues in mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic and mixed aliphatic-cycloaliphatic-aromatic groups are linked by groups -O-, -S-, -N(R 13)-, -OC(=O)-, -C(=O)-O-, -N(R 13 )-C(=O)-, -C(=O)-N(R 13 )-, -OC(=O)-O-, -OC(=O)-N(R 13 )-、-N(R 13 )-C(=O)-O- or -N(R 13 )-C(=O)-N(R 13 )-bonded to each other;

[0307] Where R 13 are independently hydrogen or C1-C 10 alkyl.

[0308] In a more preferred embodiment, the cyclic carbonate is compound Ia, compound Ib or a mixture thereof, wherein R 1 Selected from hydrogen and a group -OR 14 C1-C4 alkyl,

[0309] in

[0310] R 14 is selected from hydrogen, C1-C4 alkyl, C1-C4 haloalkyl, with 1, 2 or 3 radicals R 15 C1-C6 alkyl, with 1, 2 or 3 groups R 15 C1-C6 haloalkyl, -C(=O)R 16 , C3-C6 cycloalkyl, with 1, 2 or 3 radicals R 17 C3-C6 cycloalkyl, phenyl and 3-, 4-, 5- or 6-membered saturated, partially unsaturated or maximally unsaturated heterocycles containing 1, 2 or 3 heteroatoms selected from N, O and S as ring members, wherein the phenyl and heterocycles may carry one or more substituents selected from C1-C4 alkyl and C1-C4 alkoxy;

[0311] in

[0312] R 15 is selected from OH, C1-C6 alkoxy, oxirane, phenyl and a 3-, 4-, 5- or 6-membered saturated heterocyclic ring containing 1 or 2 oxygen atoms as ring members;

[0313] R 16 Selected from C1-C6 alkyl, C2-C6 alkenyl, C1-C4 alkoxy and -NR 18 R 19 , where R 18 is hydrogen or C1-C4 alkyl and R 19 Selected from hydrogen, C1-C4 alkyl, group R 20Substituted C1-C4 alkyl and phenyl which may have 1, 2, 3, 4 or 5 substituents selected from C1-C4 alkyl and C1-C4 alkoxy;

[0314] in

[0315] R 20 Select from -OR 21 、-N(R 13 )-R 21 、-OC(=O)-R 21 、-C(=O)-OR 21 、-N(R 13 )-C(=O)-R 21 、-C(=O)-N(R 13 )-R 21 、-OC(=O)-OR 21 、-OC(=O)-N(R 13 )-R 21 、-N(R 13 )-C(=O)-OR 21 and -N(R 13 )-C(=O)-N(R 13 )-R 21 , where R 21 is hydrogen, C1-C6 alkyl or C2-C6 alkenyl and wherein R 13 are independently hydrogen or C1-C 10 Alkyl; and

[0316] R 17 Select from -OR 21 、-N(R 13 )-R 21 、-OC(=O)-R 21 、-C(=O)-OR 21 、-N(R 13 )-C(=O)-R 21 、-C(=O)-N(R 13 )-R 21 、-OC(=O)-OR 21 、-OC(=O)-N(R 13 )-R 21 、-N(R 13 )-C(=O)-OR 21 and -N(R 13 )-C(=O)-N(R 13 )-R 21 , where R 21 is hydrogen, C1-C6 alkyl or C2-C6 alkenyl and wherein R 13Each independently as defined above (i.e. hydrogen or C1-C 10 alkyl);

[0317] Alternatively, the cyclic carbonate is a compound of formula I-bis:

[0318]

[0319] in

[0320] A is an aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic-aromatic bridging group, wherein the aliphatic, cycloaliphatic and / or aromatic residues in the aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic and mixed aliphatic-cycloaliphatic-aromatic groups may be substituted by one or more halogen atoms; and wherein the aliphatic, cycloaliphatic or aromatic bridging group has the following characteristics (i) and / or

[0321] or (ii) and the mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic-aromatic bridging group has at least one of the following characteristics (i), (ii) and / or (iii):

[0322] (i) the aliphatic, cycloaliphatic and / or aromatic residue in the aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic-aromatic bridging group is bound by one or more non-adjacent groups -O-, -S-, -N(R) 13 )-, -OC(=O)-, -C(=O)-O-, -N(R 13 )-C(=O)-, -C(=O)-N(R 13 )-, -OC(=O)-O-, -OC(=O)-N(R 13 )-、-N(R 13 )-C(=O)-O- and / or -N(R 13 )-C(=O)-N(R 13 )-interval;

[0323] (ii) the aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic-aromatic bridging group carries one or more selected from -OH, -SH, -N(R) 13 )2, -OC(=O)H, -C(=O)OH, -N(R 13 )-C(=O)H, -C(=O)-NHR 13 , -OC(=O)-OH, -OC(=O)-NHR 13 、-N(R13 )-C(=O)-OH and -N(R 13 )-C(=O)-NHR 13 Substituents of

[0324] (iii) aliphatic, cycloaliphatic and / or aromatic residues in mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic-aromatic bridging groups via groups -O-, -S-, -N(R) 13 )-, -OC(=O)-, -C(=O)-O-, -N(R 13 )-C(=O)-, -C(=O)-N(R 13 )-, -OC(=O)-O-, -OC(=O)-N(R 13 )-、-N(R 13 )-C(=O)-O- or -N(R 13 )-C(=O)-N(R 13 )-bonded to each other;

[0325] Where R 13 are independently hydrogen or C1-C 10 alkyl.

[0326] Therefore, the propargyl alcohol is preferably a compound of formula II, wherein R 1 Selected from hydrogen and a group -OR 14 C1-C4 alkyl, wherein R 14 As defined in the above preferred embodiments of the cyclic carbonate, or the propargyl alcohol is a compound of formula II-bis:

[0327]

[0328] wherein A is as defined in the above preferred embodiments of the cyclic carbonate I-bis.

[0329] More preferably, the cyclic carbonate is compound Ia, compound Ib or a mixture thereof, wherein R 1 Selected from hydrogen and -CH2-OR 14 ,

[0330] in

[0331] R 14 is selected from hydrogen, with 1, 2 or 3 radicals R 15 C1-C4 alkyl, -C(=O)R 16 and with 1, 2 or 3 groups R 17 C3-C6 cycloalkyl;

[0332] in

[0333] R 15 is selected from OH, C1-C4 alkoxy, phenyl and a 3-, 4-, 5- or 6-membered saturated heterocyclic ring containing 1 or 2 oxygen atoms as ring members;

[0334] R 16 Selected from C1-C6 alkyl, C2-C6 alkenyl, C1-C4 alkoxy and -NR 18 R 19 , where R 18 is hydrogen or C1-C4 alkyl and R 19 Selected from hydrogen, C1-C4 alkyl, group R 20 Substituted C1-C4 alkyl and phenyl which may have 1, 2, 3, 4 or 5 substituents selected from C1-C4 alkyl and C1-C4 alkoxy;

[0335] in

[0336] R 20 Select from -OR 21 、-N(R 13 )-R 21 、-OC(=O)-R 21 、-C(=O)-OR 21 、-N(R 13 )-C(=O)-R 21 、-C(=O)-N(R 13 )-R 21 、-OC(=O)-OR 21 、-OC(=O)-N(R 13 )-R 21 、-N(R 13 )-C(=O)-OR 21 and -N(R 13 )-C(=O)-N(R 13 )-R 21 , where R 21 is hydrogen, C1-C6 alkyl or C2-C6 alkenyl and wherein R 13 are independently hydrogen or C1-C 10 Alkyl; and

[0337] R 17 Select from -OR 21 、-N(R 13 )-R 21 、-OC(=O)-R 21 、-C(=O)-OR 21 、-N(R 13 )-C(=O)-R 21 、-C(=O)-N(R 13 )-R 21、-OC(=O)-OR 21 、-OC(=O)-N(R 13 )-R 21 、-N(R 13 )-C(=O)-OR 21 and -N(R 13 )-C(=O)-N(R 13 )-R 21 , where R 21 is hydrogen, C1-C6 alkyl or C2-C6 alkenyl and wherein R 13 are independently hydrogen or C1-C 10 alkyl;

[0338] Or the cyclic carbonate is a compound of formula I-bis as defined above, wherein A is selected from the following bridging groups: -CH2-O-CH2-1,4-phenylene-CH2-O-CH2-, -CH2-OC(=O)-NH-1,4-tolylene-NH-C(=O)-O-CH2-, -CH2-O-CH2-CH(OH)-CH2-O-(CH2)3-O-CH2-CH(OH)-CH2-O-CH2-, -CH2-O-CH2-CH(OH)-CH2-O-1,4-phenylene-C(CH3)2-1,4-phenylene-O-CH2-CH(OH)-CH2-O-CH2- and -CH2-(OCH2CH2)3-O-CH2-; and therefore the propargyl alcohol is more preferably a compound of formula II, wherein R 1 Selected from hydrogen and -CH2-OR 14 , where R 14 as defined in the above more preferred embodiments of the cyclic carbonate, or the propargyl alcohol is a compound of formula II-bis, wherein A is as defined in the above more preferred embodiments of the cyclic carbonate.

[0339] 1,4-Tolylene is a divalent radical of the formula:

[0340]

[0341] # indicates the connection point (in the above formula, it is the connection point with NH).

[0342] Even more preferably, the cyclic carbonate is compound Ia, compound Ib or a mixture thereof, wherein R 1 Selected from hydrogen and -CH2-OR 14 ,

[0343] in

[0344] R 14 is selected from hydrogen, with 1, 2 or 3 radicals R15 C1-C4 alkyl, -C(O)CH3, -C(=O)H and -C(O)OCH3;

[0345] in

[0346] R 15 Selected from OH and C1-C4 alkoxy;

[0347] or the cyclic carbonate is a compound of formula I-bis as defined above, wherein A is -CH2-O-CH2-CH(OH)-CH2-O-1,4-phenylene-C(CH3)2-1,4-phenylene-O-CH2-CH(OH)-CH2-O-CH2-;

[0348] And thus the propargyl alcohol is especially a compound of formula II, wherein R 1 Selected from hydrogen and -CH2-OR 14 , where R 14 as defined in the above specific embodiments of the cyclic carbonate, or the propargyl alcohol is a compound of formula II-bis, wherein A is as defined in the above specific embodiments of the cyclic carbonate.

[0349] Specifically, the cyclic carbonate is compound Ia, compound Ib or a mixture thereof, wherein R 1 Selected from hydrogen and -CH2-OR 14 ,

[0350] in

[0351] R 14 is selected from hydrogen and carrying 1 or 2 radicals R 15 C1-C4 alkyl;

[0352] in

[0353] R 15 Selected from OH and C1-C4 alkoxy;

[0354] or the cyclic carbonate is a compound of formula I-bis as defined in Embodiment 6, wherein A is -CH2-O-CH2-CH(OH)-CH2-O-1,4-phenylene-C(CH3)2-1,4-phenylene-O-CH2-CH(OH)-CH2-O-CH2-;

[0355] And thus the propargyl alcohol is a compound of formula II, wherein R 1 Selected from hydrogen and -CH2-OR 14 , where R 14 as defined above, or the propargyl alcohol is a compound of formula II-bis as defined in embodiment 6, wherein A is as defined above.

[0356] More specifically, the cyclic carbonate is compound Ia, compound Ib or a mixture thereof, wherein R 1 Selected from hydrogen and -CH2-OR 14 , where R 14 is -CH2-CH(OH)-CH2-OC(CH3)3 or -CH2-CH(OH)-CH2-OH; or the cyclic carbonate is a compound of formula I-bis as defined in Embodiment 6, wherein A is -CH2-O-CH2-CH(OH)-CH2-O-1,4-phenylene-C(CH3)2-1,4-phenylene-O-CH2-CH(OH)-CH2-O-CH2-;

[0357] And thus the propargyl alcohol is a compound of formula II, wherein R 1 Selected from hydrogen and -CH2-OR 14 , where R 14 It is -CH2-CH(OH)-CH2-OC(CH3)3 or -CH2-CH(OH)-CH2-OH; or the propargyl alcohol is a compound of formula II-bis as defined in Embodiment 6, wherein A is -CH2-O-CH2-CH(OH)-CH2-O-1,4-phenylene-C(CH3)2-1,4-phenylene-O-CH2-CH(OH)-CH2-O-CH2-.

[0358] In more specific embodiments, the cyclic carbonate is Compound Ia, Compound Ib, or a mixture thereof, wherein R 1 Selected from hydrogen and -CH2-OR 14 , where R 14 is -CH2-CH(OH)-CH2-OC(CH3)3; or the cyclic carbonate is a compound of formula I-bis as defined above, wherein A is -CH2-O-CH2-CH(OH)-CH2-O-1,4-phenylene-C(CH3)2-1,4-phenylene-O-CH2-CH(OH)-CH2-O-CH2-;

[0359] And therefore the propargyl alcohol is more specifically a compound of formula II, wherein R 1 Selected from hydrogen and -CH2-OR 14 , where R 14 It is -CH2-CH(OH)-CH2-OC(CH3)3; or the propargyl alcohol is a compound of formula II-bis as defined above, wherein A is -CH2-O-CH2-CH(OH)-CH2-O-1,4-phenylene-C(CH3)2-1,4-phenylene-O-CH2-CH(OH)-CH2-O-CH2-.

[0360] The latter bridging group A has the formula:

[0361]

[0362] where # is the point of attachment to the exo-vinylene group in I-bis and the triple bond in II-bis.

[0363] Specifically, the cyclic carbonate is compound Ia, compound Ib or a mixture thereof, wherein R 1 is hydrogen, and the propargyl alcohol is a compound of formula II, wherein R 1 It's hydrogen.

[0364] In an alternative embodiment, R 1 Derived from polymers.

[0365] Suitable polymers are, for example, polyolefins (more precisely, polymers with a polyolefin backbone), poly(meth)acrylates, polyesters, polyethers, polyurethanes, polyureas, polyamides, polycarbonates and mixtures thereof; i.e. polymers which contain in polymerized form the monomers which are characteristic of the various types of the abovementioned polymers, for example in polyolefins grafted with (meth)acrylates, which give polymers with a polyolefin backbone and poly(meth)acrylate side chains, or in block copolymers with blocks derived from different polymer types or polymers obtained by reaction of isocyanates with both amines and alcohols, etc. The polymers are in particular poly(meth)acrylates, in particular polymethacrylates.

[0366] In R 1 In the case of being derived from a polymer, the cyclic carbonate is preferably a compound of formula I-poly:

[0367]

[0368] in

[0369] X is a bond or a group -C(=O)-, # -C(=O)-O-* or # -C(=O)-N(R 13 )-*,in # is the point of attachment to O and * is the point of attachment to Y (or to Z if Y is a bond or to poly if Y and Z are a bond);

[0370] Y is a bond or a divalent aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic-aromatic bridging group, wherein the aliphatic, cycloaliphatic and / or aromatic residues in the aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic and mixed aliphatic-cycloaliphatic-aromatic bridging group may be substituted by one or more halogen atoms; and wherein the aliphatic, cycloaliphatic and aromatic bridging group may have at least one of the following features (i) and / or (ii) and the mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic-aromatic bridging group may have at least one of the following features (i), (ii) and / or (iii):

[0371] (i) the aliphatic, cycloaliphatic and / or aromatic residue in the aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic-aromatic bridging group is bound by one or more non-adjacent groups -O-, -S-, -N(R) 13 )-, -OC(=O)-, -C(=O)-O-, -N(R 13 )-C(=O)-, -C(=O)-N(R 13 )-, -OC(=O)-O-, -OC(=O)-N(R 13 )-、-N(R 13 )-C(=O)-O- and / or -N(R 13 )-C(=O)-N(R 13 )-interval;

[0372] (ii) the aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic-aromatic bridging group carries one or more selected from -OH, -SH, -N(R) 13 )2, -OC(=O)H, -C(=O)OH, -N(R 13 )-C(=O)H, -C(=O)-NHR 13 , -OC(=O)-OH, -OC(=O)-NHR 13 、-N(R 13 )-C(=O)-OH and -N(R 13 )-C(=O)-NHR 13 Substituents of

[0373] (iii) aliphatic, cycloaliphatic and / or aromatic residues in mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic-aromatic bridging groups via groups -O-, -S-, -N(R) 13)-, -OC(=O)-, -C(=O)-O-, -N(R 13 )-C(=O)-, -C(=O)-N(R 13 )-, -OC(=O)-O-, -OC(=O)-N(R 13 )-、-N(R 13 )-C(=O)-O- or -N(R 13 )-C(=O)-N(R 13 )-bonded to each other;

[0374] Where R 13 are independently hydrogen or C1-C 10 alkyl;

[0375] If X and Y are bonds, then Z is a bond or a group -C(=O)-, # -C(=O)-O-* or # -C(=O)-N(R 13 )-*;in # is the point of attachment to Y (or to X if Y is a bond or to O if X and Y are bonds) and * is the point of attachment to Poly; or if Y is a bond and X is a group -C(=O)-, # -C(=O)-O*- or # -C(=O)-N(R 13 )-*, then Z is a bond, where # is the point of attachment to O; or if Y is a divalent aliphatic, cycloaliphatic, aromatic, mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic or mixed aliphatic-cycloaliphatic-aromatic bridging group, then Z is a bond or the group -O-, -S-, -N(R 13 )-、-C(=O)-、 # -OC(=O)-*、 # -C(=O)-O-*、 # -N(R 13 )-C(=O)-*、 # -C(=O)-N(R 13 )-*、 # -OC(=O)-O-*、 # -OC(=O)-N(R 13 )-*、 # -N(R 13 )-C(=O)-O-* or # -N(R 13 )-C(=O)-N(R 13 )-*,in # is the connection point with Y;

[0376] n is 1-1000; and

[0377] Poly is a residue derived from a polymer having a number average molecular weight of 200 to 10,000; and

[0378] The propargyl alcohol is a compound of II-poly:

[0379]

[0380] wherein X, Y, Z, n and Poly are as defined above.

[0381] More preferably,

[0382] X is a bond or a group -C(=O)- or # -C(=O)-N(R 13 )-*,in # is the point of attachment to O and * is the point of attachment to Y (or to Z if Y is a bond or to poly if Y and Z are a bond);

[0383] Y is a bond or a divalent aliphatic or mixed aliphatic-cycloaliphatic bridging group having 1 to 10 carbon atoms, wherein the aliphatic or mixed aliphatic-cycloaliphatic bridging group may be substituted by one or more halogen atoms; and wherein the aliphatic bridging group may have at least one of the following features (i) and / or (ii) and the mixed aliphatic-cycloaliphatic bridging group may have at least one of the following features (i), (ii) and / or (iii):

[0384] (i) the aliphatic and / or cycloaliphatic residues in the aliphatic or mixed aliphatic-cycloaliphatic bridging group are interrupted by one or more non-adjacent groups -O-, -OC(=O)-, -C(=O)-O- and / or -OC(=O)-O-;

[0385] (ii) the aliphatic or mixed aliphatic-cycloaliphatic bridging group carries one or more substituents selected from -OH, -OC(=O)H and -C(=O)OH;

[0386] (iii) the aliphatic and / or cycloaliphatic residues in the mixed aliphatic-cycloaliphatic bridging group are bonded to one another via the groups —O—, —OC(═O)—, —C(═O)—O— or —OC(═O)—O;

[0387] If X and Y are a bond then Z is a bond or a group -C(=O)-; or if Y is a bond and X is a group -C(=O)- then Z is a bond; or if Y is a divalent aliphatic or mixed aliphatic-cycloaliphatic bridging group then Z is a bond or a group # -OC(=O)-; and

[0388] Poly is a residue derived from a poly-α-olefin or a poly(meth)acrylate, especially a poly(meth)acrylate, specifically a polymethacrylate.

[0389] Specifically, -XYZ- together means -C(=O)-, # -CH2-CH(OH)-CH2-OC(=O)-* or # -C(=O)-NH-CH2CH2-OC(=O)-*, wherein # is the point of attachment to O and * is the point of attachment to Poly. If in this case Poly is derived from a poly(meth)acrylate, the polymer I-poly contains repeating units of [-CH2-CH-(ZYXO-CH2-CH=(1,3-dioxolane-2-one-4-ylidene)] or [-CH2-C(CH3)-(ZYXO-CH2-CH=(1,3-dioxolane-2-one-4-ylidene)].

[0390] In R derived from discrete molecules and polymers 1 Preferably, R is derived from a discrete molecule, especially a discrete molecule as defined above. 1 .

[0391] catalyst

[0392] In a preferred embodiment, the bulky ligand in the silver catalyst is a ligand of Formula III.

[0393] In another preferred embodiment, the bulky ligand in the silver catalyst is a ligand of formula IV.

[0394] Among them, ligand III is more preferred.

[0395] Preferably, in the bulky ligand of formula III,

[0396] D is P or As,

[0397] R 2 is selected from monocyclic or polycyclic C3-C 40 Cycloalkyl, monocyclic or polycyclic C3-C 40 Cycloalkenyl, C6-C 40 aryl and 3-40 membered saturated, partially unsaturated or maximally unsaturated monocyclic or polycyclic heterocyclic cyclic groups, wherein the cyclic group may be bonded to D via an oxygen atom and wherein the cyclic group may carry one or more substituents selected from the group consisting of C1-C6 alkyl, C1-C6 alkoxy, optionally substituted by 1, 2, 3, 4 or more substituents R 22 Substituted phenyl, optionally substituted by 1, 2, 3, 4 or more substituents R 22Substituted naphthyl, containing 1, 2, 3 or 4 heteroatoms selected from N, O and S as ring members and optionally substituted by 1, 2 or 3 or more substituents R 23 A substituted monocyclic 5- or 6-membered heteroaromatic ring system and containing 1, 2, 3 or 4 heteroatoms selected from N, O and S as ring members and optionally substituted by 1, 2 or 3 or more substituents R 23 A substituted fused bicyclic 8-10 membered heteroaromatic ring system wherein

[0398] R 22 Each independently selected from C1-C6 alkyl, C1-C6 alkoxy, NR 24 R 25 , where R 24 and R 25 are independently hydrogen or C1-C 12 alkyl; phenyl, naphthyl and monocyclic saturated, partially unsaturated or maximum unsaturated 5- or 6-membered heterocycles containing 1, 2, 3 or 4 heteroatoms selected from N, O and S as ring members, wherein the last three cyclic radicals may in turn carry 1, 2, 3, 4 or 5 substituents selected from halogen, C1-C4-alkyl and C1-C4-alkoxy; and R 23 Each independently has a 22 one of the given meanings; and

[0399] R 3 and R 4 independently selected from C1-C6 alkyl, monocyclic or polycyclic C3-C 40 Cycloalkyl, monocyclic or polycyclic C3-C 40 Cycloalkenyl and C6-C 10 Aryl.

[0400] More preferred

[0401] D is P;

[0402] R 2 is optionally substituted by 1, 2, 3, 4 or more substituents R 22 Substituted phenyl, optionally substituted by 1, 2, 3, 4 or more substituents R 22 Substituted o-biphenyl, optionally substituted by 1, 2, 3, 4 or more substituents R 22 Substituted naphthyl, optionally substituted by 1, 2, 3, 4 or more substituents R 22 o-binaphthyl, containing 1, 2 or 3 nitrogen atoms as ring members and optionally substituted by 1, 2 or 3 substituents R 23 A substituted monocyclic 5- or 6-membered heteroaromatic ring system and containing 1, 2, 3 or 4 nitrogen atoms as ring members and optionally substituted by 1, 2 or 3 or more substituents R 23 Substituted fused bicyclic 8-10 membered heteroaromatic ring system,

[0403] in

[0404] R 22 Each independently selected from C1-C4 alkyl, C1-C4 alkoxy, NR 24 R 25 , where R 24 and R 25 are independently hydrogen or C1-C 10 alkyl; phenyl optionally substituted by 1, 2, 3, 4 or 5 substituents selected from halogen, C1-C4 alkyl and C1-C4 alkoxy; and monocyclic saturated, partially unsaturated or maximum unsaturated 5- or 6-membered heterocyclic ring containing 1, 2 or 3 heteroatoms selected from N and O as ring members; and

[0405] R 23 are each independently phenyl optionally substituted with 1, 2, 3, 4 or 5 substituents selected from halogen, C1-C4 alkyl and C1-C4 alkoxy; and

[0406] R 3 and R 4 are independently selected from branched C3-C6 alkyl groups, monocyclic C3-C6 cycloalkyl groups, adamantyl groups and phenyl groups.

[0407] Specifically,

[0408] D is P;

[0409] R 2 It was NR 24 R 25 Substituted phenyl, wherein R 24 and R 25 are independently hydrogen or C1-C 10 Alkyl, preferably C3-C 10 Alkyl; or substituted by 1, 2, 3 or 4 groups R 22 Substituted o-biphenyl,

[0410] in

[0411] R 22 Each independently selected from C1-C4 alkyl and NR 24 R 25 , where R 24 and R 25 are independently hydrogen or C1-C 10 Alkyl, preferably C3-C 10 alkyl.

[0412] The bulky ligand is especially selected from compounds of formula AW and mixtures thereof:

[0413]

[0414]

[0415] wherein Me is methyl, Cy is cyclohexyl, i-Pr is isopropyl, Ph is phenyl and t-Bu is tert-butyl.

[0416] The above ligands are known as Buchwald ligands. Many of them are commercially available, such as DavePhos (A), MePhos (B), XPhos (D), tBuDavePhos (E), JohnPhos (G), PhDavePhos (J), CyJohnPhos (M), SPhos (O), RuPhos (Q), CPhos (R), BrettPhos (S), AlPhos (T) and RockPhos (U).

[0417] In a specific embodiment, XPhos (compound of the formula D), a ligand of the formula V, a ligand of the formula W or a mixture of V and W is used as ligand III. Very particularly the compound of the formula D (XPhos) is used.

[0418] In the ligand of formula IV, the double dot indicates that the ligand is a carbene. Therefore, ligand IV is also called N-heterocyclic carbene ligand or NHC-ligand for short. Silver catalysts containing NHC ligand IV can be represented as follows:

[0419]

[0420] Preferably, in the ligand of formula IV, R 2 and R 5 are independently C6-C6 alkyl, C1-C6 alkoxy and C3-C6 cycloalkyl. 10 Aryl, and Z is -CR 7 =CR 8 -, where R 7 and R 8 are independently hydrogen or C1-C6 alkyl. 2 and R 5 is 2,6-diisopropylphenyl and Z is -CH=CH-.

[0421] R 6 Preferably selected from C1-C 40 Alkyl, C2-C 40 Alkenyl with C3-C 10 The C1-C6 alkyl group of the cycloalkyl ring, wherein the C3-C 10 The cycloalkyl ring may have 1, 2, 3, 4 or 5 C1-C6 alkyl substituents. 10 C1-C4 alkyl of aryl ring, wherein C6-C10 The aryl ring may have 1, 2, 3, 4 or 5 substituents selected from C1-C6 alkyl and C1-C6 alkoxy, and the C6-C6 alkyl ring may have 1, 2, 3, 4 or 5 substituents selected from C1-C6 alkyl and C1-C6 alkoxy. 10 More preferably R 6 Selected from C1-C 40 Alkyl, C2-C 40 Alkenyl and C1-C4 alkyl with a C3-C6 cycloalkyl ring. Even more preferably R 6 Selected from C1-C 30 Alkyl, C6-C 30 Alkenyl and C1-C4 alkyl with a C3-C6 cycloalkyl ring, especially C1-C 22 C1-C4 alkyl and C5-C6 cycloalkyl ring-bearing C1-C4 alkyl, especially C1-C 20 C2-C4 alkyl and C8-C4 alkyl with a cyclohexyl ring, very particularly selected from 18 Alkyl and C2-C4 alkyl with a cyclohexyl ring.

[0422] In R 6 In the case of an alkyl group, the carboxylate R 6 -COO - It is therefore more preferably derived from a natural or synthetic saturated fatty acid having 2 to 41 carbon atoms, even more preferably 2 to 31 carbon atoms, particularly 2 to 23 carbon atoms, especially 2 to 21 carbon atoms, very particularly 9 to 19 carbon atoms; and in R 6 In the case of an alkenyl group, the carboxylate group R 6 -COO - It is therefore more preferred to be derived from natural or synthetic unsaturated fatty acids having 3 to 41 carbon atoms, even more preferably 7 to 31 carbon atoms. 6 In the case of an alkyl group, the carboxylate R 6 -COO - In particular, they are derived from natural or synthetic saturated fatty acids having 2 to 23 carbon atoms, in particular from saturated fatty acids having 2 to 21 carbon atoms, very particularly from saturated fatty acids having 9 to 19 carbon atoms.

[0423] In a specific embodiment, R 6 is lipophilic and therefore preferably has at least 2 carbon atoms. Thus, in this case R 6 Preferably selected from C2-C 40 Alkyl, C2-C 40 Alkenyl with C3-C 10 The C1-C6 alkyl group of the cycloalkyl ring, wherein the C3-C 10The cycloalkyl ring may have 1, 2, 3, 4 or 5 C1-C6 alkyl substituents. 10 C1-C4 alkyl of aryl ring, wherein C6-C 10 The aryl ring may have 1, 2, 3, 4 or 5 substituents selected from C1-C6 alkyl and C1-C6 alkoxy, and the C6-C6 alkyl ring may have 1, 2, 3, 4 or 5 substituents selected from C1-C6 alkyl and C1-C6 alkoxy. 10 More preferably in this case R 6 Selected from C2-C 40 Alkyl, C2-C 40 Alkenyl and C1-C4 alkyl with a C3-C6 cycloalkyl ring. Even more preferably R 6 Selected from C6-C 30 Alkyl, C6-C 30 Alkenyl and C1-C4 alkyl with a C3-C6 cycloalkyl ring, especially C6-C 22 C1-C4 alkyl and C5-C6 cycloalkyl ring, especially C8-C 20 C2-C4 alkyl and C8-C4 alkyl with a cyclohexyl ring, very particularly selected from 18 Alkyl and C2-C4 alkyl with a cyclohexyl ring.

[0424] The silver catalyst Ag1 of the process of the present invention can be used in the form of a preformed metal complex comprising silver, at least one bulky ligand selected from compounds of formula III and IV, preferably compounds of formula III, and a lipophilic carboxylate ligand according to formula V shown above.

[0425] Alternatively, the silver catalyst Ag1 is formed in situ in the reaction medium by combining a silver precatalyst which is a silver compound or silver salt which does not contain the bulky ligand with a compound of formula III, a carbene of formula IV or a precursor of a carbene of formula IV in the reaction medium to form a catalytically active silver complex Ag1. In the case where the silver precatalyst does not contain a lipophilic carboxylate ion V, the silver precatalyst is also reacted with the corresponding acid R of the carboxylate V. 6 -C(=O)OH or formula R 6 -C(=O)O - M + Its salt reaction, where M + It is a cationic equivalent.

[0426] A suitable precursor of the carbene of formula IV is its protonated form as shown in formula VI in combination with a base:

[0427]

[0428] Where R 2 , R 5and Z are as defined above and X- is an anionic equivalent.

[0429] Bases suitable for deprotonating the protonated forms of the various NHC ligands according to formula VI are described by de Frémont et al., Coordination Chemistry Reviews 253 (2009) 876-881. The deprotonation of the protonated forms of the NHC ligands can be carried out in ammonia or in aprotic solvents such as THF or ethers. The deprotonation requires anhydrous conditions and uses a pK a A strong base with a value greater than 14. Potassium hydride or sodium hydride with a catalytic amount of tert-butoxide is usually used, but tert-butoxide itself, lithium aluminum hydride, n-butyllithium, methyllithium, tert-butyllithium, potassium hexamethyldisilazide (KHMDS), and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) are also effective alternatives.

[0430] Silver compounds which can be used as precatalysts are, for example, Ag(OAc) (OAc=acetate), AgF, AgNO3, silver trifluoroacetate, Ag2O, Ag2CO3 and any silver salt with a lipophilic carboxylate ion according to formula V - as Ag(OOCR 6 ). If Ag(OAc), AgF, AgNO3, silver trifluoroacetate, Ag2O or Ag2CO3 are used as the precatalyst, a lipophilic carboxylate ligand must also be added to the reaction medium, either as a free acid HOOCR 6 in the form of any salt R 6 -C(=O)O - M + In the form of + is a cation equivalent. Suitable cation equivalents are metal cations, such as alkali metal cations, for example Li + 、Na + , K + , Cs + or Rb + , or alkaline earth metal cations such as Ca 2+ Mg 2+ , Sr 2+ Or Ba 2+ ; or ammonium cation NR4 + , wherein R is independently hydrogen, C1-C 10 Alkyl or C1-C 10 Thus, the salt may be, for example, M1(OOCR 6 ), where M1 can be Li + 、Na + , K + , Cs + , Rb +or NR4 + , or M2(OOCR 6 )2, where M2 can be Ca 2+ Mg 2+ , Sr 2+ Or Ba 2+ Preferably the precatalyst is Ag(OOCR 6 ).

[0431] In the case of in situ formation of the silver catalyst Ag1, the compound of formula III, the carbene of formula IV or the precursor of the carbene of formula IV is suitably used in an amount of less than 2 mol / mol of the silver present in the silver precatalyst. Preferably, the compound of formula III, the carbene of formula IV or the precursor of the carbene of formula IV is used in an amount of 0.2-1.8 mol, preferably 0.3-1.5 mol, in particular 0.4-1.2 mol, especially 0.8-1.2 mol / mol of the silver present in the silver precatalyst, very particularly in an amount approximately equimolar to the silver present in the silver precatalyst.

[0432] For practical and economic reasons it is preferred to form the catalyst in situ in step a).

[0433] The amount of the silver catalyst Ag1 used in process step a) can vary within a wide range, based on the amount of propargyl alcohol of formula II. The silver catalyst Ag1 is usually used in a substoichiometric amount relative to the propargyl alcohol of formula II. The amount of the silver catalyst Ag1 is usually not more than 50 mol%, often not more than 20 mol%, in particular not more than 10 mol% or not more than 5 mol% or not more than 3 mol%, based on the amount of propargyl alcohol of formula II. The silver catalyst Ag1 is preferably used in step a) in an amount of 0.001-50 mol%, more preferably 0.001-20 mol%, in particular 0.005-10 mol%, especially 0.01-5 mol%, very specifically 0.05-3 mol%, based on the amount of propargyl alcohol of formula II. The amount of catalyst given above relates to the amount of silver contained therein.

[0434] Solvents

[0435] Solvents L1 and L2 are used in the process of the present invention. "Solvent" is a substance that dissolves a solute (chemically different liquids, solids or gases) to obtain a solution. A solution is a homogeneous mixture in which a gaseous, liquid or solid solute is dissolved in a solvent. A homogeneous mixture is composed of two or more substances, in which the particles of the solute cannot be seen by the naked eye and do not scatter light. In this context, solvents L1 and L2 are liquids at 20°C. Solvents L1 and L2 differ in their polarity and therefore have different solvating powers for different solutes. Solvent L1 has a weak solvating power for non-polar raw materials or products, while solvent L2 has a weak solvating power for polar raw materials or products. Therefore, in this context, the term "solvent" is not limited to a compound or medium that dissolves all raw materials, catalyst components and products in an appropriate sense. A solvent should more generally be understood as a dispersion medium that dissolves only a portion of the raw materials, catalyst components or products (in an appropriate sense).

[0436] The solvents L1 and L2 used in the process according to the invention have a miscibility zone at least between 20 and 30° C. at 1013 mbar. “Miscibility zone” means that the mixture of solvents L1 and L2 is not stable, but separates to form two independent phases. One of the two phases consists essentially of solvent L1 and the other phase consists essentially of solvent L2. “Essentially” means that the phase contains less than 10% by weight, preferably less than 5% by weight of another solvent, i.e. a solvent that is not a main component, relative to the total weight of solvents L1 and L2. At 20° C., solvent L1 has a miscibility of less than 5 g / l L2, preferably less than 2 g / l L2, in particular less than 1 g / l L2 in solvent L2, and solvent L2 has a miscibility of less than 5 g / l L1, preferably less than 2 g / l L1, in particular less than 1 g / l L1 in solvent L1. Miscibility relates to the formation of a homogeneous mixture in which no phase separation occurs.

[0437] Preferably, the solvents L1 and L2 used in the process of the present invention have a miscibility zone at least between 20 and 80° C. at 1013 mbar, more preferably at least between 15 and 100° C. at 1013 mbar, and especially over the entire temperature range in which the solvents are liquid at 1013 mbar.

[0438] Preferably, the solvent L1 has a dipole moment of at least 10·10 -30 C·m, especially at least 11·10 -30 Polar aprotic solvent for C·m.

[0439] Preferably, the solvent L2 has a dipole moment of at most 2·10 -30 C·m, preferably at most 1·10 -30 C·m, especially non-polar solvents of 0C·m.

[0440] Preferably, the solvent L1 has a dipole moment of at least 10·10-30 C·m polar aprotic solvent and solvent L2 is a solvent with a dipole moment of at most 2·10 -30 C·m non-polar solvent.

[0441] More preferably, the solvent L1 has a dipole moment of at least 11·10 -30 C·m polar aprotic solvent and solvent L2 is a solvent with a dipole moment of at most 1·10 -30 C·m non-polar solvent.

[0442] Specifically, the solvent L1 is a solvent having a dipole moment of at least 11·10 -30 C·m is a polar aprotic solvent and solvent L2 is a nonpolar solvent with a dipole moment of 0 C·m.

[0443] The solvent L1 is preferably selected from the group consisting of amides, ureas, nitriles, sulfoxides, sulfones, carbonates, nitro compounds and mixtures thereof.

[0444] Examples of suitable amides are formamide, N-methylformamide, N,N-dimethylformamide and N,N-dimethylacetamide.

[0445] Examples of suitable ureas are tetramethylurea, N,N-dimethylimidazolidinone and N,N-dimethylpropyleneurea.

[0446] Examples of suitable nitriles are acetonitrile, propionitrile and benzonitrile.

[0447] An example of a suitable sulfoxide is dimethyl sulfoxide.

[0448] An example of a suitable sulfone is sulfolane.

[0449] Examples of suitable carbonates are dimethyl carbonate, diethyl carbonate, ethylene carbonate and propylene carbonate.

[0450] Examples of suitable nitro compounds are nitromethane and nitrobenzene.

[0451] L1 is more preferably selected from formamide, N-methylformamide, N,N-dimethylformamide (DMF), N,N-dimethylacetamide, tetramethylurea, N,N-dimethylimidazolidinone, N,N-dimethylpropylene urea, acetonitrile, propionitrile, benzonitrile, dimethyl sulfoxide, sulfolane, dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, nitromethane, nitrobenzene and mixtures thereof.

[0452] In specific embodiments, L1 is acetonitrile or DMF, more specifically acetonitrile.

[0453] The solvent L2 is preferably selected from alkanes, cycloalkanes, C 12 -C 20 C1-C2 alkyl esters of fatty acids and mixtures thereof.

[0454] Examples of suitable alkanes are C5-C 15 Chain alkanes, such as pentane, hexane, heptane, octane, nonane, decane, dodecane, tetradecane, pentadecane, their structural isomers and mixtures thereof.

[0455] Examples of suitable cycloalkanes are C5-C8 cycloalkanes which may carry C1-C2 alkyl substituents, such as cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, cyclooctane and the like.

[0456] Suitable C 12 -C 20 Examples of C1-C2 alkyl esters of fatty acids are methyl laurate, ethyl laurate, methyl myristate, ethyl myristate, methyl palmitate, ethyl palmitate, methyl stearate, ethyl stearate, methyl arachidate and ethyl arachidate.

[0457] More preferably, the solvent L2 is selected from C5-C 14 Alkanes, C5-C8 cycloalkanes which may have C1-C2 alkyl substituents, 12 -C 20 C1-C2 alkyl esters of fatty acids and mixtures thereof. Even more preferably, solvent L2 is selected from C6-C 12 Alkanes, C5-C6 cycloalkanes which may have methyl substituents, C 16 -C 20 Methyl esters of fatty acids and mixtures thereof. The solvent L2 is especially selected from pentane, hexane, heptane, octane, nonane, decane, dodecane, cyclopentane, cyclohexane and mixtures thereof.

[0458] In a specific embodiment, L2 is cyclohexane, hexane or decane, more specifically cyclohexane or decane, very specifically cyclohexane.

[0459] In certain embodiments,

[0460] - solvent L1 is acetonitrile and solvent L2 is selected from C5-C 14 Alkanes, C5-C8 cycloalkanes which may have C1-C2 alkyl substituents, and saturated C 12 -C 20 C1-C2 alkyl esters of fatty acids; or

[0461] - solvent L1 is dimethylformamide and solvent L2 is selected from C5-C 14 Alkanes, C5-C8 cycloalkanes which may have C1-C2 alkyl substituents, and saturated C 12 -C 20 C1-C2 alkyl esters of fatty acids.

[0462] More specifically,

[0463] - solvent L1 is acetonitrile and solvent L2 is selected from C5-C 12 Alkanes, C5-C8 cycloalkanes which may have methyl substituents, and saturated C 16 -C 20 Methyl esters of fatty acids; or

[0464] - solvent L1 is dimethylformamide and solvent L2 is selected from C5-C 12 Alkanes, C5-C8 cycloalkanes which may have methyl substituents, and saturated C 16 -C 20 Methyl esters of fatty acids.

[0465] Even more specifically,

[0466] - solvent L1 is acetonitrile and solvent L2 is selected from C5-C 12 Alkanes and C6-C8 cycloalkanes; or

[0467] - solvent L1 is dimethylformamide and solvent L2 is selected from C5-C 12 Chain alkanes and C5-C8 cycloalkanes.

[0468] In particular,

[0469] - solvent L1 is acetonitrile and solvent L2 is cyclohexane; or

[0470] - solvent L1 is acetonitrile and solvent L2 is hexane;

[0471] - solvent L1 is acetonitrile and solvent L2 is octane; or

[0472] - solvent L1 is acetonitrile and solvent L2 is decane; or

[0473] - solvent L1 is acetonitrile and solvent L2 is dodecane; or

[0474] - solvent L1 is dimethylformamide and solvent L2 is cyclohexane; or

[0475] - solvent L1 is dimethylformamide and solvent L2 is hexane; or

[0476] - solvent L1 is dimethylformamide and solvent L2 is octane; or

[0477] - solvent L1 is dimethylformamide and solvent L2 is decane; or

[0478] - Solvent L1 is dimethylformamide and solvent L2 is dodecane.

[0479] Very especially,

[0480] - solvent L1 is acetonitrile and solvent L2 is cyclohexane; or

[0481] - solvent L1 is acetonitrile and solvent L2 is decane; or

[0482] - Solvent L1 is dimethylformamide and solvent L2 is hexane.

[0483] It is preferred that solvent L1 is acetonitrile and solvent L2 is cyclohexane or decane.

[0484] In step a), the propargyl alcohol is preferably present in an amount of 0.1-25% by weight, more preferably 0.5-20% by weight, especially 1-20% by weight, for example 1-15% by weight, relative to the total weight of all solvents used in step a).

[0485] The CO2 used in the carboxylation-cyclization reaction can be used in pure form or, if desired, in a mixture with other gases, preferably inert gases, such as nitrogen or argon. Preference is given to using CO2 in undiluted form.

[0486] The reaction is usually carried out at a CO pressure in the range of 0.1-200 bar, preferably 1-100 bar, more preferably 5-80 bar, especially 10-70 bar. If CO is in undiluted form, the pressure is applied by CO. In this case, the reaction is usually carried out at a CO pressure in the range of 0.1-200 bar, preferably 1-100 bar, more preferably 5-80 bar, especially 10-70 bar.

[0487] Under certain conditions, CO2 can also be used as an additional solvent or as a solubilizer for the two liquid phases formed by solvents L1 and L2 (if step a) is carried out in the presence of solvent L2), if the reaction conditions are such that CO2 is liquid (for example, at a pressure greater than 57.3 bar at 20°C) or in its supercritical phase (at a pressure greater than 73.8 bar at a temperature above 31°C).

[0488] Process step a) can be carried out in a wide temperature range. The reaction can be carried out at a temperature in the range of 0-150°C, but high temperatures are not necessary, and the reaction is preferably carried out at a temperature in the range of 0-100°C, more preferably 10-80°C, and especially 10-40°C.

[0489] The reaction can in principle be carried out continuously, semi-continuously or discontinuously. A continuous process is preferred.

[0490] The reaction can in principle be carried out in all reactors known to the person skilled in the art for such reactions and the reactor is therefore selected accordingly. Suitable reactors are described and reviewed in the relevant prior art, for example in suitable monographs and references as mentioned in US 6,639,114, column 16, lines 45-49. Preferably an autoclave which may have an internal stirrer and an inner lining is used for the reaction.

[0491] The composition obtained in the carboxylation-cyclization reaction of the present invention comprises unsubstituted exo-vinylene carbonate, ie, a cyclic carbonate of formula Ia or Ib.

[0492] After completion of step a), the pressure is released before proceeding to steps b1) (if performed), b2) (if performed) and c).

[0493] If no solvent L2 is used in step a), step b1) must be carried out.

[0494] If a solvent mixture containing L1 and L2 has been used in step a), it may be advantageous in some cases to carry out step b2); i.e. to add further solvent L2, for example if the mixture contains too little L2 to allow effective phase separation. The ideal mixing ratio of solvents L1 and L2 depends on the specific solvents L1 and L2, the specific starting materials, the catalyst, their respective concentrations and the phase separation method and can be determined by the person skilled in the art.

[0495] A suitable amount of solvent L2 added in step b1) or b2) is such that in step c) solvent L1 and solvent L2 are present in a total weight ratio of preferably 80:20 to 20:80, more preferably 70:30 to 30:70, especially 60:40 to 40:60.

[0496] In one embodiment of the invention, no solvent L2 is used in step a) and step b1) is carried out (step b2) is of course skipped in this case).

[0497] In another embodiment of the present invention, a solvent mixture containing L1 and L2 is used in step a) and step b2) can be skipped; unless the amount of L2 is too small to allow effective phase separation; in which case step b2) is performed.

[0498] The two organic liquid phases can be separated from one another in step c) and the nonpolar organic phase enriched in the silver catalyst can be recycled as catalyst in the carboxylation reaction in step a).

[0499] The two organic phases are usually separated by gravity phase separation. This can be carried out, for example, using standard equipment and standard methods such as described in E. Müller et al., "Liquid-Liquid Extraction", Ullmann's Encyclopedia of Industrial Chemistry, 2005, Wiley-VCH Verlag GmbH & Co KGaA, DOI: 10.1002 / 14356007.b03_06, Chapter 3 "Equipment".

[0500] On a laboratory scale, phase separation can be carried out, for example, in a separating funnel; on an industrial scale, countercurrent extraction equipment, such as mixer-settler equipment, extraction columns, stirred extraction columns, continuous packed bed liquid-liquid extraction equipment, etc. are suitable.

[0501] Steps b1) / b2) and c) can be repeated once or several times. For example, after the phase separation in step c), L2 can be added to the separated phase containing L1 to obtain a more complete extraction of the catalyst Ag1. However, the separation is usually so complete that it is not necessary to repeat steps b1) / b2) and c).

[0502] According to the invention, step c) results in the separation of the catalyst from the cyclic carbonate by using two organic solvents having a miscibility zone. The silver catalyst Ag1 is enriched in the less polar solvent and the cyclic carbonate is enriched in the more polar solvent.

[0503] The silver catalyst Ag1 is enriched in the solvent with a smaller polarity, which means that the distribution coefficient of the silver catalyst Ag1 is greater than 1:

[0504] P = [concentration of silver catalyst Ag1 in non-polar organic phase] / [concentration of silver catalyst Ag1 in polar organic phase]

[0505] The partition coefficient is preferably >2, particularly preferably >5.

[0506] Product Ia or Ib or a mixture thereof is enriched in the polar solvent phase means that the distribution coefficient of product Ia or Ib or a mixture thereof is >1:

[0507] P = [Concentration of product Ia or Ib in the polar organic phase] / [Concentration of product Ia or Ib in the non-polar organic phase]

[0508] The partition coefficient is preferably >2, particularly preferably >5.

[0509] Thus, the product phase obtained in step c) contains more than 50% by weight, preferably more than 66.7% by weight, in particular more than 83.3% by weight of the cyclic carbonate I formed in step a) and the catalyst phase contains more than 50% by weight, preferably more than 66.7% by weight, in particular more than 83.3% by weight of the silver catalyst.

[0510] If necessary, this cyclic carbonate I can be separated from this product [step d)]. For example, this product can be obtained by evaporating solvent from this polar organic phase, and this solvent can be recycled to this carboxylation reaction if necessary. This separation method is especially favourable for the synthetic that carries out on an industrial scale. This polar organic solvent can also be used for further reducing the product amount in this non-polar phase by countercurrent extraction. Vice versa, can be mutually removed a certain amount of non-polar solvent from this non-polar organic solvent by evaporation and can also be used for reducing the silver content in this polar organic phase by countercurrent extraction to recycle more this silver catalyst.

[0511] After the first cycle, the recycled silver catalyst can be reused in step a) with satisfactory conversion. Even after several cycles, the catalytic activity remains satisfactory.

[0512] The separation of the aftertreatment of this polar organic phase of the inventive method and the cyclic carbonate of formula Ia or Ib certainly also can be carried out in another conventional manner, for example by filtration or water extraction aftertreatment, but the separation via the evaporation of this polar solvent is the most economical and simple approach, at least on an industrial scale.By using such measures or its combination, the cyclic carbonate of formula Ia or Ib or its mixture are obtained with enough purity usually, and this has gotten rid of extra purification steps.Alternately, can be further purified as recrystallization by the method commonly used in this area.

[0513] The invention is illustrated by the following examples. Example

[0514] Figures expressed in percentages are each based on % by weight, unless expressly stated otherwise.

[0515] summary

[0516] All chemicals and solvents were purchased from Sigma-Aldrich or ABCR and used without further purification.

[0517] 1 H and 13 C NMR spectra were recorded on Bruker Avance 200 MHz and 400 MHz spectrometers and were based on the residual protons of the solvent ( 1 H) or carbon ( 13 C) Resonance peaks are used as reference. Chemical shifts (δ) are reported in ppm.

[0518] Abbreviations used:

[0519] XPhos=2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl

[0520] THF = Tetrahydrofuran

[0521] DMF=N,N-dimethylformamide

[0522] Et2O = ether

[0523] I. Synthesis of Ligands V and W

[0524] The title compound was synthesized via a modification as described in Synlett, 2017, 28, 2891-2895 (SI). 2-Bromoaniline (1.17 mL; 10.35 mmol), N,N-diisopropylethylamine (5.41 mL; 31.04 mmol) and 1-bromooctane (5.36 mL; 31.05 mmol) were added to anhydrous DMF (10 mL) in a pressure tube. The tube was tightly sealed and heated at 120 ° C for 48 hours. The reaction was cooled to room temperature and diluted with petroleum ether / ethyl acetate (1:1 v / v; 100 mL). The organic phase was washed with water (3×100 mL), 10% Na2CO3 aqueous solution (100 mL) and brine (100 mL) and dried over Na2SO4. The solution was evaporated to dryness and purified by silica gel column chromatography with petroleum ether as eluent. The product (2.63 g; 64%) was obtained as a colorless oil.

[0525] 1 H NMR (300MHz, CDCl3): δ=7.55 (dd, J=7.9, 1.5Hz, 1H, H Ar ), 7.22 (ddd, J=8.1, 7.6, 1.9, 1H, H Ar ), 7.09 (dd, J=8.0, 1.6Hz, 1H, H Ar ), 6.92-6.83 (m, 1H, H Ar ), 3.06-2.95 (m, 4H, CH2N), 1.50-1.35 (m, 4H, CH2), 1.35-1.16 (m, 20H, CH2), 0.91-0.79 (m, 6H, CH3).

[0526] 13 C NMR (75MHz, CDCl3): δ149.8, 133.7, 127.5, 124.2, 124.2, 122.3, 53.5, 31.9, 29.5, 29.3, 27.2, 27.0, 22.7, 14.1.

[0527] HRMS(ESI):C 22 H 38 m / z calculated for BrN: 396.2260 [M+H] + ; Measured value: 396.2261.

[0528] 2. Synthesis of Ligand V

[0529] The title compound was obtained via a modified synthesis as described in J. Org. Chem., 2000, 65, 5334-5341. Magnesium turnings (126 mg; 5.17 mmol), 2-bromo-N,N-dioctylaniline (991 mg, 2.50 mmol) obtained from Example 1 and THF (5 mL) were added to a dried 25 mL three-necked flask equipped with a stirring bar and a reflux condenser under argon. 1,2-Dibromoethane (38 μL; 0.44 mmol) in THF (1 mL) was added dropwise via cannula over 5 minutes, and the mixture was heated to 50° C. for 5 minutes, then heated to reflux temperature for a further 16 hours. The mixture was cooled to 60° C. 1-Bromo-2-chlorobenzene (252 μL; 2.85 mmol) was added dropwise over 10 minutes and the mixture was heated at 60° C. for 2 hours. After cooling to room temperature, CuCl (282 mg; 2.59 mmol) was added, followed by a solution of chlorodicyclohexylphosphine (0.57 mL; 2.59 mmol) in THF (1 mL) was added dropwise. After the mixture was stirred for another 16 hours, the suspension was diluted with petroleum ether / ethyl acetate (1:1; 70 mL), 30% NH4OH (25 mL) and brine (25 mL) and the mixture was stirred for 10 minutes. The organic phase was collected and washed repeatedly with 5 mL portions of 30% NH4OH until the aqueous phase was colorless. The organic phase was further washed with water (10 mL) and brine (5 mL) and dried on Na2SO4. The solvent was removed in vacuo and the residue was subjected to column chromatography on silica gel using a hexane / ether solvent gradient (1:0 hexane / Et2O to 19:1). The obtained light yellow viscous oil (553 mg; 43% crude yield) contained the desired ligand V as the main product, and the ratio of ligand W and unidentified phosphine complex was about 1:0.24:0.12. The pure product was obtained after further purification by gradient silica gel column chromatography using dichloromethane / acetone as eluent (94 mg; 7%).

[0530] 1 H NMR (300MHz, CDCl3): δ7.60-7.47(m, 1H), 7.34-7.17(m, 4H), 7.05-6.96(m, 2H), 6.95-6.87(m, 1H), 2.82-2.67(m, 4H), 2.09-0.94(m, 46H), 0.87(m, 6H).

[0531] 13 C NMR (75MHz, CDCl3): δ149.6 (d, J CP =30.7Hz), 149.6, 136.2 (d, J CP =5.8Hz), 135.1(d, JCP =20.2Hz), 133.4(d, J CP =3.8Hz), 132.7(d, J CP =3.2Hz), 131.3(d, J CP =5.9Hz), 127.9, 127.6, 125.9, 120.0, 120.0, 52.6, 37.1 (d, J CP =16.3Hz), 33.9(d, J CP =14.1Hz), 31.9, 30.7 (d, J CP =11.3Hz), 30.6(d, J CP =17.5Hz), 30.2(d, J CP =12.7Hz), 30.0(d, J CP =8.5Hz), 29.6, 29.4, 28.0 (d, J CP =7.5Hz), 27.8(d, J CP =10.5Hz), 27.5, 27.4 (d, J CP =9.3Hz), 27.3(d, J CP =11.7Hz), 27.2, 26.7, 26.6, 22.8, 14.2.

[0532] 31 P NMR (122MHz, CDCl3): δ-11.3.

[0533] HRMS(ESI):C 40 H 64 Calculated m / z of NP: 590.4849 [M+H] + ; Measured value: 590.4850.

[0534] 3. Synthesis of Ligand W

[0535] Magnesium turnings (39 mg; 1.60 mmol), 2-bromo-N,N-dioctylaniline (496 mg, 1.25 mmol) and THF (8 mL) were added to an oven-dried 25 mL three-necked flask equipped with a stirring bar and a reflux condenser under argon. 1,2-Dibromoethane (19 μL; 0.22 mmol) in THF (1 mL) was added dropwise via cannula over 5 min, the mixture was heated to 50° C. for 5 min, then heated to reflux temperature for a further 3 h. The mixture was cooled to room temperature and CuCl (141 mg; 1.43 mmol) was added, followed by a solution of chlorodicyclohexylphosphine (0.29 mL; 1.30 mmol) in THF (1 mL) was added dropwise. After the mixture was stirred for a further 16 h, the suspension was diluted with petroleum ether / ethyl acetate (1:1; 40 mL), 30% NH4OH (10 mL) and brine (10 mL) and the mixture was stirred for 10 min. The organic phase was collected and washed repeatedly with 5 mL portions of 30% NH4OH until the aqueous phase was colorless. The organic phase was further washed with water (10 mL) and brine (5 mL) and dried over Na2SO4. The solvent was removed in vacuo and the residue was column chromatographed on silica gel using a dichloromethane / acetone solvent gradient (1:0 CH2Cl2 / acetone to 19:1). The product was isolated as a colorless viscous oil (221 mg; 34%). 31 Phosphine oxide was detected by P NMR and HRMS (< 4% of the sample).

[0536] 1 H NMR (500MHz, CDCl3): δ7.38 (d, J=7.3Hz, 1H), 7.24 (t, J=7.5Hz, 1H), 7.11-7.04 (m, 1H), 7.01(t, J=7.2Hz, 1H), 3.10-3.02(m, 4H), 1.94-1.85(m, 2H), 1.84-1.71(m, 4H), 1.65(br s, 4H), 1.58-1.52 (m, 2H), 1.40 (br s, 2H), 1.33-1.00 (m, 30H), 0.86 (t, J=6.7Hz, 6H).

[0537] 13 C NMR (75MHz, CDCl3): δ157.8 (d, J CP =19.4Hz), 133.4(d, J CP =3.5Hz), 133.2(d, J CP =16.9Hz), 128.6, 122.7 (d, J CP =3.6Hz), 122.6, 54.7 (d, J CP =5.8Hz), 34.9(d, JCP =15.1Hz), 31.9, 30.5 (d, J CP =16.5Hz), 29.8(d, J CP =11.0Hz), 29.6, 29.3, 27.5, 27.5-27.3 (m), 26.6, 26.4, 22.7, 14.1. 31 P NMR (122MHz, CDCl3): δ-13.2.

[0538] II. Synthesis of Cyclic Carbonates

[0539] General reaction procedure

[0540] A. Add solvent L2 after the carboxylation reaction:

[0541] To a 80 mL steel autoclave were added propargyl alcohol (II) (5.0 mmol), silver salt, bulky donor ligand and polar organic solvent L1. The reaction mixture was pressurized with CO2 and stirred at room temperature for 18 hours. The CO2 overpressure was then carefully released and the catalyst was extracted with non-polar organic solvent L2. After phase separation, the conversion of the propargyl alcohol and the formation of the product were carried out in two phases by 1 The silver content in the two phases was determined by ICP-MS.

[0542] Embodiment 1:

[0543] Alkynol: propargyl alcohol (R 1 =H); 280 mg (5 mmol)

[0544] Silver salt: Silver neodecanoate [Ag(C9H 19 C(O)O)]; 14 mg (0.05 mmol)

[0545] Bulky donor ligand: XPhos; 23.8 mg (0.05 mmol)

[0546] Polar organic solvent L1: acetonitrile; 10mL

[0547] Non-polar organic solvent: cyclohexane

[0548] CO2 pressure: 20 bar

[0549] After the reaction, the conversion of the propargyl alcohol to the corresponding exo-vinylene carbonate was determined to be 99% by NMR. The reaction mixture was extracted with cyclohexane (10 mL) as the non-polar organic solvent L2. 1H-NMR, the exo-vinylene carbonate remained in the acetonitrile phase. The silver content was 370 mg / kg in the nonpolar organic phase and 55 mg / kg in the polar organic phase (P=6.7).

[0550] Embodiment 2:

[0551] Alkynol: propargyl alcohol (R 1 =H); 280 mg (5 mmol)

[0552] Silver salt: Silver neodecanoate [Ag(C9H 19 C(O)O)]; 14 mg (0.05 mmol)

[0553] Bulky donor ligand: XPhos; 23.8 mg (0.05 mmol)

[0554] Polar organic solvent L1: acetonitrile; 10mL

[0555] Non-polar organic solvent: cyclohexane

[0556] CO2 pressure: 20 bar

[0557] After the reaction, the conversion of the propargyl alcohol to the corresponding exo-vinylene carbonate was determined to be 99% by NMR. The reaction mixture was extracted with cyclohexane (2*5 mL) as the non-polar organic solvent L2. 1 H-NMR, the exo-vinylene carbonate remained in the acetonitrile phase. All volatiles were removed from the combined cyclohexane fractions, the remaining catalyst residue was redissolved in acetonitrile (10 ml) and reused in the carboxylation under the same conditions as described above after addition of fresh propargyl alcohol (but no further silver or bulky ligands). The conversion to the exo-vinylene carbonate was calculated according to 1 H-NMR spectroscopy was again 99%.

[0558] Embodiment 3:

[0559] Alkynol: propargyl alcohol (R 1 =H); 280 mg (5 mmol)

[0560] Silver salt: Silver stearate [Ag(C 17 H 35C (O)O)]; 19.6 mg (0.05 mmol)

[0561] Bulky donor ligand: XPhos; 23.8 mg (0.05 mmol)

[0562] Polar organic solvent L1: acetonitrile; 10mL

[0563] Non-polar organic solvent: decane

[0564] CO2 pressure: 20 bar

[0565] After the reaction, the conversion of the propargyl alcohol to the corresponding exo-vinylene carbonate was determined by NMR to be 99%. A 2 mL aliquot of the reaction solution was extracted with decane (2 mL) as the non-polar solvent L2, and the silver content was 390 mg / kg in the non-polar organic phase and 50 mg / kg in the polar organic phase (P=7.8).

[0566] Embodiment 4:

[0567] Alkynol: propargyl alcohol (R 1 =H); 280 mg (5 mmol)

[0568] Silver salt: Silver cyclohexanebutyrate [Ag(cyclohexyl-(CH2)3-C(O)O)]; 13.9 mg (0.05 mmol)

[0569] Bulky donor ligand: XPhos; 23.8 mg (0.05 mmol)

[0570] Polar organic solvent L1: acetonitrile; 10mL

[0571] Non-polar organic solvent: cyclohexane

[0572] CO2 pressure: 20 bar

[0573] After the reaction, the conversion of the propargyl alcohol to the corresponding exo-vinylene carbonate was determined to be 99% by NMR. A 2 mL aliquot of the reaction solution was extracted with cyclohexane (2 mL) as the non-polar solvent L2, and the silver content was 390 mg / kg in the non-polar organic phase and 65 mg / kg in the polar organic phase (P=6.0).

[0574] Embodiment 5:

[0575] Alkynol: R 1 = Compound II of -CH2-O-CH2-CH(OH)-CH2-OC(CH3)3; 1.08 g (5 mmol)

[0576] Silver salt: Silver neodecanoate [Ag(C9H 19 C(O)O)]; 27.9 mg (0.10 mmol)

[0577] Bulky donor ligand: XPhos; 47.7 mg (0.10 mmol)

[0578] Internal Standard: 232μL (1.67mmol)

[0579] Polar organic solvent L1: acetonitrile; 10mL

[0580] Non-polar organic solvent: cyclohexane

[0581] CO2 pressure: 20 bar

[0582] When all reagents and L1 have been added, take an aliquot of this mixture and dilute in CDCl3 to pass through 1 H NMR determination of t0. The procedure described for Example 2 was followed with cyclohexane as nonpolar solvent L2. After the reaction, the conversion of the propargyl alcohol to the corresponding exo-vinylene carbonate was determined by NMR to be 76%. In the case of recycling, the conversion to the exo-vinylene carbonate was determined according to 1 H NMR determined 67%.

[0583] The silver content was 1200 mg / kg in the non-polar organic phase and 310 mg / kg in the polar organic phase (P=43.9).

[0584] Embodiment 6:

[0585] Alkynol: R 1 = Compound II of 4,4′-((((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(2-hydroxypropane-3,1-diyl))bis(oxy))bis(but-2-yn-1-ol) (= compound of formula II-bis, wherein A has the following formula):

[0586]

[0587] 500mg(0.97mmol)

[0588] Silver salt: Silver neodecanoate [Ag(C9H 19 C(O)O)]; 14 mg (0.05 mmol)

[0589] Bulky donor ligand: XPhos; 23.8 mg (0.05 mmol)

[0590] Polar organic solvent L1: acetonitrile; 10mL

[0591] Non-polar organic solvent: cyclohexane

[0592] CO2 pressure: 20 bar

[0593] After the reaction, the conversion of the propargyl alcohol to the corresponding di-exo-vinylene carbonate was determined to be 99% by NMR. The reaction mixture was extracted with cyclohexane (2*5 mL) as the non-polar organic solvent L2. 1H-NMR, the exo-vinylene carbonate remained in the acetonitrile phase. The silver content was 100 mg / kg in the nonpolar organic phase and 35 mg / kg in the polar organic phase (P=2.9).

[0594] Embodiment 7:

[0595] Alkynol: R 1 = Compound II of 4,4'-((((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(2-hydroxypropane-3,1-diyl))bis(oxy))bis(but-2-yn-1-ol); 500 mg (0.97 mmol)

[0596] Silver salt: Silver neodecanoate [Ag(C9H 19 C(O)O)]; 14 mg (0.05 mmol)

[0597] Bulky donor ligand: XPhos; 23.8 mg (0.05 mmol)

[0598] Polar organic solvent L1: dimethylformamide; 10 mL

[0599] Non-polar organic solvent: hexane

[0600] CO2 pressure: 20 bar

[0601] After the reaction, the conversion of the propargyl alcohol to the corresponding di-exo-vinylene carbonate was determined to be 56% by NMR. The reaction mixture was extracted with hexane (2*5 mL) as the non-polar organic solvent L2. 1 H-NMR, the exo-vinylene carbonate remains in the acetonitrile phase. B. Addition of solvent L2 to the carboxylation reaction:

[0602] To an 80 mL steel autoclave were added propargyl alcohol (II) (5.0 mmol), silver salt, bulky donor ligand, polar organic solvent L1 and non-polar organic solvent L2. In the case of a recycle run, the non-polar organic solvent L2 phase containing the silver catalyst from the previous reaction was added to the autoclave and fresh polar organic solvent and propargyl alcohol were added. The reaction mixture was pressurized with CO2 and stirred at room temperature for 18 hours. The CO2 overpressure was then carefully released. After phase separation, the conversion of the propargyl alcohol and the formation of the product were carried out in two phases by 1 The silver content in the two phases was determined by ICP-MS.

[0603] Embodiment 8:

[0604] Alkynol: propargyl alcohol (R 1 =H); 280 mg (5 mmol)

[0605] Silver salt: Silver neodecanoate [Ag(C 10 H 19 O2]; 14 mg (0.05 mmol)

[0606] Bulky donor ligand: XPhos; 23.8 mg (0.05 mmol)

[0607] Polar organic solvent: acetonitrile; 5mL

[0608] Non-polar organic solvent: cyclohexane; 5 mL

[0609] CO2 pressure: 20 bar

[0610] After the reaction, the conversion of the propargyl alcohol to the corresponding exo-vinylene carbonate was determined by NMR to be 91%. 1 H-NMR, the exo-vinylene carbonate can only be detected in the acetonitrile phase. After phase separation, the cyclohexane phase containing the silver catalyst was reused in the carboxylation under the same conditions as described above after adding 280 mg of propargyl alcohol and 5 mL of acetonitrile. The conversion to the exo-vinylene carbonate in the second run using the recycled catalyst was calculated according to 1 H-NMR spectroscopy: 96%.

[0611] Embodiment 9:

[0612] Alkynol: propargyl alcohol (R 1 =H); 280 mg (5 mmol)

[0613] Silver salt: Silver neodecanoate [Ag(C9H 19 C(O)O)]; 14.0 mg (0.05 mmol)

[0614] Bulky donor ligand: compound of formula V (actually a mixture of V and W obtained in I.2 and an unknown phosphine ligand, in a ratio of about 1.0:0.24:0.12); 29.5 mg (0.05 mmol)

[0615] Polar organic solvent L1: acetonitrile; 10mL

[0616] Non-polar organic solvent L2: cyclohexane; 10 mL

[0617] CO2 pressure: 20 bar

[0618] After the reaction, the conversion of the propargyl alcohol to the corresponding outer-vinylene carbonate was 30% by NMR determination. Extraction was performed with additional cyclohexane (3*10 mL). The silver content was 480 mg / kg in the non-polar organic phase and 30 mg / kg (P=16.0) in the polar organic phase after the first extraction and 5 mg / kg after the third extraction.

[0619] Embodiment 10:

[0620] Alkynol: propargyl alcohol (R 1 =H); 280 mg (5 mmol)

[0621] Silver salt: silver acetate [Ag(CH3C(O)O)]; 8.3 mg (0.05 mmol)

[0622] Bulky donor ligand: compound of formula V (actually a mixture of V and W obtained in I.2 and an unknown phosphine ligand, in a ratio of about 1.0:0.24:0.12); 29.5 mg (0.05 mmol)

[0623] Polar organic solvent L1: acetonitrile; 10mL

[0624] Non-polar organic solvent L2: cyclohexane; 10 mL

[0625] CO2 pressure: 20 bar

[0626] After the reaction, the conversion of the propargyl alcohol to the corresponding outer-vinylene carbonate was 50% by NMR determination. Extraction was performed with additional cyclohexane (3*10 mL). The silver content was 310 mg / kg in the non-polar organic phase and 90 mg / kg (P=3.4) in the polar organic phase after the first extraction and 32 mg / kg after the third extraction.

[0627] Embodiment 11:

[0628] Alkynol: propargyl alcohol (R 1 =H); 280 mg (5 mmol)

[0629] Silver salt: Silver neodecanoate [Ag(C9H 19 C(O)O)]; 14.0 mg (0.05 mmol)

[0630] Bulky donor ligand: Compound of formula W; 29.5 mg (0.05 mmol)

[0631] Polar organic solvent L1: acetonitrile; 10mL

[0632] Non-polar organic solvent L2: cyclohexane; 10 mL

[0633] CO2 pressure: 20 bar

[0634] After the reaction, the conversion of the propargyl alcohol to the corresponding exo-vinylene carbonate was 36% by NMR determination. Extraction was performed with additional cyclohexane (3*10 mL). The silver content was 600 mg / kg in the non-polar organic phase and 21 mg / kg (P=28.6) in the polar organic phase after the first extraction and 2 mg / kg after the third extraction.

[0635] Embodiment 12:

[0636] Alkynol: propargyl alcohol (R 1 =H); 280 mg (5 mmol)

[0637] Silver salt: Silver neodecanoate [Ag(C9H 19 C(O)O)]; 14.0 mg (0.05 mmol)

[0638] Bulky donor ligand: Compound of formula W; 29.5 mg (0.05 mmol)*

[0639] Polar organic solvent L1: acetonitrile; 10mL

[0640] Non-polar organic solvent L2: cyclohexane; 10 mL

[0641] CO2 pressure: 50 bar

[0642] After the reaction, the conversion of the propargyl alcohol to the corresponding exo-vinylene carbonate was determined by NMR to be 81%. In the case of recycling, the conversion to the exo-vinylene carbonate was determined according to 1 H NMR analysis: 70%.

[0643] C. Substrate screening by adding solvent L2 in the carboxylation reaction:

[0644] To an 80 mL steel autoclave were added propargyl alcohol (II), silver salt, bulky donor ligand, polar organic solvent CH3CN and non-polar organic solvent cyclohexane. The reaction mixture was pressurized with CO2 and stirred at room temperature for 18 hours. The CO2 overpressure was then carefully released. After phase separation, the conversion of the propargyl alcohol and the formation of the product were carried out in two phases by 1 The silver content in the two phases was determined by ICP-MS.

[0645]

[0646] [a] Propargyl alcohol 1 (2.5 mmol) or di-propargyl alcohol (2, 3 or 4; 1.0 mmol) in CH3CN / cyclohexane (5:2.5 mL), nd = not determined. [b] Used after adding acetone (5 mL) (1, 2 and 4) or 1,3,5-trimethoxybenzene (3) as internal standard 1 H NMR determination. [c] The acetonitrile product phase was washed three times with cyclohexane and filtered on celite, then acidified with 1.25 M methanolic HCl. The isolated yield of EVC after column chromatography is in parentheses. [d] Ag partition coefficient, P = 10.4. [e] Ag partition coefficient, P = 4.8.

[0647] D. Recycle in the carboxylation reaction with addition of solvent L2:

[0648] Embodiment 21:

[0649] Alkynol: R 1 = Compound II of -CH2-O-CH2-CH(OH)-CH2-OC(CH3)3; 0.54 g (2.5 mmol)

[0650] Silver salt: Silver neodecanoate [Ag(C9H 19 C(O)O)]; 7.0 mg (0.025 mmol)

[0651] Bulky donor ligand: V; 14.7 mg (0.025 mmol)

[0652] Polar organic solvent L1: acetonitrile; 5 mL

[0653] Non-polar organic solvent L2: cyclohexane; 2.5 mL

[0654] CO2 pressure: 20 bar

[0655] In a glove box, alkynol, silver (I) neodecanoate, ligand V, acetonitrile and cyclohexane were placed in a Premex autoclave with a Teflon plug. The autoclave was sealed and 50 bar CO2 was added. After stirring at room temperature for 18 hours, the CO2 pressure was carefully released and the autoclave was purged with argon before being reintroduced into the glove box. Cyclohexane (2.5 mL) was added and the organic layer was separated in a separatory funnel. The acetonitrile layer was further washed with cyclohexane (2×5 mL). The combined cyclohexane washes were concentrated to approximately 2.5 mL and reintroduced into the autoclave along with other substrates and acetonitrile for subsequent operations. The post-treatment after the second round of operation was the same as after the first round of operation and the entire procedure was repeated in the third round of operation. The acetonitrile phase was treated with 1.25 M methanolic HCl (50 μL), filtered through a short pad of diatomaceous earth and the solvent was removed under reduced pressure to give the product. The product yield was 2.5%. As an internal standard1 H-NMR determination.

[0656] Yield of exo-vinylene carbonate after the first operation: 90%

[0657] Yield of exo-vinylene carbonate after the first recycle: 81%

[0658] Yield of exo-vinylene carbonate after the first recycle: 71%

Claims

1. A method for preparing a cyclic carbonate I selected from the group consisting of a compound of formula Ia, a compound of formula Ib and mixtures thereof: in R 1 Yes -CH2-OR 14 , in R 14 is selected from hydrogen, with 1, 2 or 3 radicals R 15 C1-C4 alkyl, -C(=O)R 16 and with 1, 2 or 3 groups R 17 C3-C6 cycloalkyl; in R 15 is selected from OH, C1-C4 alkoxy, phenyl and a 3-, 4-, 5- or 6-membered saturated heterocyclic ring containing 1 or 2 oxygen atoms as ring members; R 16 Selected from C1-C6 alkyl, C2-C6 alkenyl, C1-C4 alkoxy and -NR 18 R 19 ,in R 18 is hydrogen or C1-C4 alkyl and R 19 Selected from hydrogen, C1-C4 alkyl, group R 20 Substituted C1-C4 alkyl and phenyl which may have 1, 2, 3, 4 or 5 substituents selected from C1-C4 alkyl and C1-C4 alkoxy; in R 20 Select from -OR 21 、-N(R 13 )-R 21 、-OC(=O)-R 21 、-C(=O)-OR 21 , -N(R 13 )-C(=O)-R 21 、-C(=O)-N(R 13 )-R 21 、-O-C(=O)-O-R 21 、-O- C(=O)-N(R 13 )-R 21 、-N(R 13 )-C(=O)-O-R 21 和-N(R 13 )-C(=O)- N(R 13 )-R 21 , where R 21 are each independently hydrogen, C1-C6 alkyl or C2-C6 alkenyl and wherein R 13 are independently hydrogen or C1-C 10 Alkyl; and R 17 Select from -OR 21 、-N(R 13 )-R 21 、-OC(=O)-R 21 、-C(=O)-OR 21 、-N(R 13 )- C(=O)-R 21 、-C(=O)-N(R 13 )-R 21 、-O-C(=O)-O-R 21 、-O-C(=O)- N(R 13 )-R 21 , -N(R 13 )-C(=O)-OR 21 Sum-N(R 13 )-C(=O)-N(R 13 )-R 21 , among them R 21 are each independently hydrogen, C1-C6 alkyl or C2-C6 alkenyl and wherein R 13 are independently hydrogen or C1-C 10 alkyl; The following steps are involved: a) reacting a propargyl alcohol of the formula II with carbon dioxide: Where R 1 As defined above, Alternatively, the cyclic carbonate is a compound of formula I-bis: Wherein A is selected from the following bridging groups: -CH2-O-CH2-1,4-phenylene-CH2-O-CH2-, -CH2-OC(=O)-NH-1,4-tolylene-NH-C(=O)-O-CH2-, -CH2-O-CH2-CH(OH)-CH2-O-(CH2)3-O-CH2-CH(OH)-CH2-O-CH2-, -CH2-O-CH2-CH(OH)-CH2-O-1,4-phenylene-C(CH3)2-1,4-phenylene-O-CH2-CH(OH)-CH2-O-CH2- and -CH2-(OCH2CH2)3-O-CH2-; Wherein 1,4-tolylphenylene is a divalent radical of the formula: # indicates the connection point with NH; and the propargyl alcohol is wherein R 1 Yes -CH2-OR 14 A compound of formula II, wherein R 14 As defined above, or the propargyl alcohol is a compound of formula II-bis: wherein A is as defined above; The reaction is carried out in a solvent mixture containing at least one organic solvent L1 and at least one organic solvent L2; wherein the solvent L1 is a solvent having a dipole moment of at least 10·10 -30 C·m polar aprotic solvent; and solvent L2 is a solvent with a dipole moment of at most 2·10 -30 C·m nonpolar solvent, wherein the reaction is further carried out in the presence of a silver catalyst Ag1 comprising at least one bulky ligand and a carboxylate ligand, Wherein the bulky ligand is selected from the group consisting of compounds of formula AW and mixtures thereof: wherein Me is methyl, Cy is cyclohexyl, i-Pr is isopropyl, Ph is phenyl and t-Bu is tert-butyl; and wherein the carboxylate ligand is according to Formula V: in R 6 Selected from C8-C 18 Alkyl and C2-C4 alkyl with a cyclohexyl ring; b1) adding solvent L2 to the reaction mixture obtained in step a), if step a) has not already been carried out in the presence of at least one solvent L2; or b2) optionally adding a solvent L2 to the reaction mixture obtained in step a), in case step a) has been carried out in the presence of at least one solvent L2; c) phase separation of the reaction mixture obtained in step a), b1) or b2) to obtain a product phase containing the cyclic carbonate I and the at least one solvent L1 and a catalyst phase containing the silver catalyst and the at least one solvent L2; and d) if necessary separating the cyclic carbonate I from the product phase.

2. The method as claimed in claim 1, wherein the cyclic carbonate is compound Ia, compound Ib or a mixture thereof, wherein R 1 Yes -CH2-OR 14 , where R 14 is -CH2-CH(OH)-CH2-OC(CH3)3; and the propargyl alcohol is a compound of formula II, wherein R 1 Yes -CH2-OR 14 , where R 14 It is -CH2-CH(OH)-CH2-OC(CH3)3.

3. The process as claimed in claim 1, wherein the silver catalyst Ag1 is used in step a) in an amount of 0.001 to 50 mol %, based on the amount of propargyl alcohol of formula II.

4. The process as claimed in claim 2, wherein the silver catalyst Ag1 is used in step a) in an amount of 0.001 to 50 mol %, based on the amount of propargyl alcohol of formula II.

5. A process as claimed in any one of claims 1 to 4, wherein the solvent L1 is a solvent having a dipole moment of at least 11.10 - 30 C·m polar aprotic solvent; and solvent L2 is a solvent with a dipole moment of at most 1·10 -30 C·m non-polar solvent.

6. A process as claimed in any one of claims 1 to 4, wherein the solvent L1 is selected from amides, ureas, nitriles, sulfoxides, sulfones, carbonates, nitro compounds and mixtures thereof, and the solvent L2 is selected from alkanes, cycloalkanes and C 12 -C 20 C1-C2 alkyl esters of fatty acids.

7. A process as claimed in claim 6, wherein the solvent L1 is acetonitrile and the solvent L2 is selected from C5-C 14 Alkanes, C5-C8 cycloalkanes which may have C1-C2 alkyl substituents, and saturated C 12 -C 20 C1-C2 alkyl esters of fatty acids; or solvent L1 is dimethylformamide and solvent L2 is selected from C5-C 14 Alkanes, C5-C8 cycloalkanes which may have C1-C2 alkyl substituents, and saturated C 12 -C 20 C1-C2 alkyl esters of fatty acids.

8. A process as claimed in claim 6, wherein the solvent L1 is a polar aprotic solvent and is selected from formamide, N-methylformamide, N,N-dimethylformamide, N,N-dimethylacetamide, tetramethylurea, N,N-dimethylimidazolidinone, N,N-dimethylpropyleneurea, acetonitrile, propionitrile, benzonitrile, dimethyl sulfoxide, sulfolane, dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, nitromethane, nitrobenzene and mixtures thereof; and wherein the solvent L2 is selected from C5-C 15 Alkanes, C5-C8 cycloalkanes which may have C1-C2 alkyl substituents, 12 -C 20 C1-C2 alkyl esters of fatty acids and mixtures thereof.

9. A process as claimed in claim 8, wherein solvent L1 is acetonitrile and solvent L2 is cyclohexane or decane.

10. A process as claimed in any one of claims 1 to 4 and 7 to 9, wherein step a) is carried out at a pressure in the range of 0.1 to 200 bar and at a temperature in the range of 0 to 100°C.

11. A process as claimed in claim 5, wherein step a) is carried out at a pressure in the range of 0.1-200 bar and at a temperature in the range of 0-100°C.

12. A process as claimed in claim 6, wherein step a) is carried out at a pressure in the range of 0.1-200 bar and at a temperature in the range of 0-100°C.

13. A process as claimed in any one of claims 1 to 4, 7 to 9 and 11 to 12, wherein in step c) solvent L1 and solvent L2 are present in a total weight ratio of 80:20 to 20:

80.

14. A process as claimed in claim 5, wherein in step c) solvent L1 and solvent L2 are present in a total weight ratio of 80:20 to 20:

80.

15. A process as claimed in claim 6, wherein in step c) solvent L1 and solvent L2 are present in a total weight ratio of 80:20 to 20:

80.

16. A process as claimed in claim 10, wherein in step c) solvent L1 and solvent L2 are present in a total weight ratio of 80:20 to 20:80.

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