Method for preparing cyclic carbonates having exocyclic vinylidene groups

Abstract

The present invention relates to a method for preparing cyclic carbonates having an exocyclic vinylidene group by reacting 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 complete, the catalyst is separated from the cyclic carbonate by using two organic solvents with different polarities having a solubility gap, and the silver catalyst is enriched in the less polar solvent and the cyclic carbonate is enriched in the more polar solvent.

Description

[Technical Field]

[0001] The present invention relates to a method for preparing cyclic carbonates having an exocyclic vinylidene group by reacting 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 complete, the catalyst is separated from the cyclic carbonate by using two organic solvents with different polarities having a solubility gap, and the silver catalyst is enriched in the less polar solvent and the cyclic carbonate is enriched in the more polar solvent. [Background technology]

[0002] Cyclic carbonates having exocyclic vinylidene groups are useful compounds, particularly compounds useful for use in battery electrolytes, as described in US 2013 / 0059178, or as monomers in polymer applications, as described in WO 2011 / 157671.

[0003] Cyclic carbonates with no other substituents other than the exocyclic vinylidene group (more precisely, no substituents at the 5-position relative to the 1- and 3-position oxygen ring atoms, the 2-position oxo group, and the 4-position vinylidene group) can be obtained by reacting the corresponding primary propargyl alcohol with CO using a silver catalyst with a bulky ligand, 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. In the case of volatile products, as described in WO 2019 / 034648, the product can be separated from the catalyst via distillation, and the catalyst can be recycled; a new reaction cycle can be initiated simply by adding fresh solvent and reagents. However, this method is not applicable to non-volatile or thermally unstable exocyclic vinylidene carbonates; the product must be separated from the catalyst via column chromatography, as also described in WO 2019 / 034648. In engineering scale processes, work-up of the reaction mixture via column chromatography is not economical due to its high cost, and furthermore, 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 bearing an exocyclic vinylidene group at the 4-position by reacting tertiary propargyl alcohol with CO2 in the presence of an ionic liquid in the presence of a silver or copper catalyst. The ionic liquid serves 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 and versatile agents on a laboratory scale, their cost makes them unsuitable for industrial-scale processes. Furthermore, the above-mentioned method only works for non-polar cyclic carbonates that can be sufficiently extracted into the hexane phase. More polar products remain in the ionic liquid phase. If they are non-volatile or thermally unstable, they cannot be separated from the ionic liquid by distillation. As explained above, in industrial-scale processes, workup of the reaction mixture via column chromatography is uneconomical due to its high cost. Furthermore, the catalyst cannot be recycled in a simple manner. Summary of the Invention [Problem to be solved by the invention]

[0006] It was therefore an object of the present invention to provide an economical method for preparing cyclic carbonates from primary propargyl alcohols and CO, which allows for simple separation of the catalyst from the product and does not require resorting to expensive means, such as the use of ionic liquids as solvents. In particular, the method should also allow for the economical preparation of non-volatile or thermally unstable exocyclic vinylidene carbonates. [Means for solving the problem]

[0007] The object is a process for preparing cyclic carbonates I selected from the group consisting of compounds of formula Ia, compounds of formula Ib and mixtures thereof, comprising:

[0008] [ka] [In the formula, R 1 is an organic group] a) Propargyl alcohol of formula II

[0009] [ka] [In the formula, R 1 is as defined above] with carbon dioxide, 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 solvents L1 and L2 have a solubility gap of at least 20-30°C; The reaction is further carried out in the presence of a silver catalyst Ag1 comprising at least one bulky ligand and a carboxylate ligand; The bulky ligand is selected from the group consisting of a ligand of formula III and a ligand of formula IV,

[0010] [ka] [In the formula, D is P, As or Sb; R 2 are each independently an organic group having 1 to 40 carbon atoms, R 3 and R 4 are the same or different and each is an organic group having 1 to 40 carbon atoms, R 5 is an organic group having 1 to 40 carbon atoms, and R present in ligand IV 2 may be different from or the same as Z is -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 - is a divalent bridging group selected from R 7 , R 8 , R 9 , R 10 , R 11 and R 12are each independently hydrogen or an organic group having 1 to 40 carbon atoms, or Two adjacent groups R 7 and R 8 and / or R 10 and R 11 form together with the atoms connecting them a monocyclic or polycyclic substituted or unsubstituted aliphatic or aromatic ring system having 4 to 40 carbon atoms as ring members and which may also contain at least one heteroatom selected from the group consisting of the elements Si, Ge, N, P, O and S, The carboxylate ligand is according to formula V

[0011] [ka] [In the formula, R 6 is an organic group having 1 to 40 carbon atoms. Step, b1) if step a) was not carried out in the presence of at least one solvent L2, adding a solvent L2 to the reaction mixture obtained in step a), b2) if step a) is carried out in the presence of at least one solvent L2, optionally adding solvent L2 to the reaction mixture obtained in step a), c) subjecting the reaction mixture obtained in step a) or step b1) or b2) to phase separation to obtain a product phase containing the cyclic carbonate I and at least one solvent L1 and a catalyst phase containing the silver catalyst and at least one solvent L2; and d) optionally isolating the cyclic carbonate I from the product phase. This is achieved by a method comprising:

[0012] It goes without saying that the reaction mixture obtained in step a) is subjected to the phase separation step c) only if a solvent mixture of L1 and L2 was used in step a) and the optional step b2) was not performed. If only L1 was used in step a) (and not L2), the reaction mixture obtained in step b1) is subjected to the phase separation step c). If a solvent mixture of L1 and L2 was used in step a) and the optional step b2) was performed, the reaction mixture obtained in step b2) is subjected to the phase separation step c). DETAILED DESCRIPTION OF THE INVENTION

[0013] definition R in compound II is equal to or greater than 1 The groups (including A in compounds II-bis or poly or Y in II-poly) are "as defined above" (R 1 means as defined in the context of compound I), this means that R 1 This does not necessarily imply that R remains unchanged in the reaction of compound II with CO2. 1 Some groups that may be present in the starting compound II react with CO to form R 1 Different from R 1 This can result in compounds I having groups such as R 1 If R contains oxiranyl groups, some or all of these may react with CO2 under ring-opening conditions. 1 is inert to the reaction conditions and is therefore the same in the starting compound II and the final compound I.

[0014] As used herein, the term radical refers to a variable R in a given formula. x is used synonymously with the term group when defining

[0015] The term "halogen" means in each case fluorine, chlorine, bromine or iodine.

[0016] 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. "Comprising" means that the organic group may be substituted by, interrupted by, and / or bonded through heteroatoms or heteroatom-containing groups. Generally, however, the organic group is bonded to the remainder of the molecule through a carbon atom. While organic groups are generally derived from discrete molecules (discrete molecules are molecules with defined molecular weights, as opposed to a molecular weight distribution, e.g., a polymer), the organic group R 1 can also be derived from polymers. In the latter case, i.e., R 1 When R is derived from a polymer, the starting compound II generally contains more than one -C≡C-CHOH group. This group may be attached to the polymer backbone directly or via a linking group. By way of example only, a polymer or monomer containing a carboxyl group or carboxyl derivative susceptible to esterification (or transesterification) reactions, or containing an oxiranyl ring, such as that present in a glycidyl residue, or containing a chlorohydrin residue or an isocyanate group (-NCO) or other group in the side chain that can react with an alcohol group, may be reacted with 1,4-butynediol or another diol bearing a propargyl alcohol group to give the (polymeric) compound II, where R 1 can be obtained from a polymer containing a large number of -C≡C-CH2OH groups in its side chains. If the monomer is reacted with 1,4-butynediol or another diol containing a propargyl alcohol group, a polymer is naturally obtained after polymerization of this monomer. In the product I resulting from the reaction of the polymer with CO2, R 1are derived from polymers containing multiple cyclic carbonate groups (more precisely, 1,3-dioxolan-2-on-4-yl rings) linked via exocyclic vinylidene groups. Alternatively, a monomer can first be reacted with CO under the reaction conditions described above and below to obtain a monomer containing an exocyclic vinylidene-linked cyclic carbonate, followed by polymerization of the monomer. By way of example only, polyacrylic or polymethacrylic acid or a polyacrylate or polymethacylate susceptible to transesterification can be esterified with 1,4-butynediol to obtain a polymer having the repeat unit -[CH-CH(C(=O)OCHC≡CHOH)]- or -[CH-C(CH)(C(=O)OCHC≡CHOH)]-, or a polyacrylate or polymethacrylate containing an NCO group in the alcohol-derived portion of the ester (e.g., the alcohol-derived portion derived from HO-CHCH-NCO). Polymethacrylates can be reacted with 1,4-butynediol in an addition reaction to give polymers with the repeating unit -[CH-CH(C(=O)O-CHCH-NH-C(=O)-O-CHC≡CHOH)]- or -[CH-C(CH)(C(=O)O-CHCH-NH-C(=O)-O-CHC≡CHOH)]-, or polyacrylates or polymethacrylates containing glycidyl or chlorohydrin residues in the alcohol-derived portion of the ester can be reacted with 1,4-butynediol in an addition or substitution reaction. Alternatively, the corresponding acrylate or methacrylate monomers can be first prepared by the above esterification / addition / substitution reaction and then polymerized. In yet another alternative, the corresponding acrylate or methacrylate monomer (i.e., a (meth)acrylate containing -C≡C-CHOH in its alcohol-derived moiety) can be grafted onto a polymer having a suitable backbone, such as a polyethylene or polypropylene polymer.

[0017] 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. By "containing," we mean that the organic group may be substituted by a heteroatom-containing group, interrupted by a heteroatom or heteroatom-containing group, and / or bonded via a heteroatom or heteroatom-containing group. Examples include C1-C 40 -Alkyl groups, fluorinated C1-C 10 -Alkyl group, C1-C 12 -alkoxy groups, saturated, partially unsaturated or maximally unsaturated (including heteroaromatic) heterocyclic groups containing 3 to 20 carbon atoms and one or more heteroatoms selected from N, O and S as ring members, C6 to C 40 -aryl group, C6-C 10 -fluoroaryl group, C6-C 10 -aryloxy group, silyl group having 3 to 24 carbon atoms, C2 to C 40 -Alkenyl group, C2-C 40 -Alkynyl group, C7-C 40 -arylalkyl group or C8-C 40 -arylalkenyl groups. The organic group is derived from an organic compound in both cases. Thus, the organic compound methanol can in principle give rise to three different organic groups with one carbon atom: methyl (H3C-), methoxy (H3C-O-), and hydroxymethyl (HOC(H2)-).

[0018] An aliphatic group is a group that does not contain alicyclic, aromatic, or heterocyclic components. Examples include alkyl, alkenyl, and alkynyl groups. As used herein, the term "aliphatic group" is defined by the prefix (C n ~C m When used without a '), it generally refers to an aliphatic group having 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms, especially 1 to 20 carbon atoms, and specifically 1 to 10 or 1 to 6 or 1 to 4 carbon atoms. It will be understood that alkenyl and alkynyl groups have at least 2 carbon atoms.

[0019] A cycloaliphatic or alicyclic group may contain one or more, e.g., one or two, alicyclic groups, but does not contain any aromatic or heterocyclic components. Examples include cycloalkyl and cycloalkenyl groups. As used herein, the term "cycloaliphatic group" is defined by the prefix (C n ~C m When used without a ), it generally refers to an aliphatic group having 3 to 40 carbon atoms, preferably 3 to 30 carbon atoms, especially 3 to 20 carbon atoms, and specifically 3 to 10 or 3 to 6 carbon atoms.

[0020] An aromatic group or aryl (group) is a monocyclic, bicyclic, or polycyclic carbocyclic (i.e., having no 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 vicinal 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 aryl groups include phenanthrenyl, anthracenyl, tetracenyl, 1H-benzo[a]phenalenyl, pyrenyl, etc. However, in the present term, "aryl" also encompasses bicyclic or polycyclic groups in which not all rings are aromatic, as long as at least one ring is aromatic, especially when a reactive site is located on the aromatic ring (or on a functional group attached thereto). Examples include indanyl, indenyl, tetralinyl, 6,7,8,9-tetrahydro-5H-benzo[7]annulenyl, fluorenyl, 9,10-dihydroanthracenyl, 9,10-dihydrophenanthrenyl, 1H-benzo[a]phenalenyl, and the like, as well as ring systems in which not all rings are fused, for example, spiro-linked or bridged, such as benzonorbornyl. In particular, aryl groups have 6 to 30, especially 6 to 20, and particularly 6 to 10 carbon atoms as ring members.

[0021] Mixed aliphatic-aliphatic groups contain at least one aliphatic group and at least one alicyclic group, with the site of attachment to the rest of the molecule being located on the alicyclic or aliphatic group.

[0022] Mixed aliphatic-aromatic groups contain at least one aliphatic group and at least one aromatic group, with the site of attachment to the rest of the molecule being located on either the aromatic or the aliphatic group.

[0023] A mixed alicyclic-aromatic group contains at least one alicyclic group and at least one aromatic group, with the site of attachment to the rest of the molecule being located on either the alicyclic group or the aromatic group.

[0024] Mixed aliphatic-alicyclic-aromatic groups contain at least one aliphatic group, at least one alicyclic group and at least one aromatic group, and the site of attachment to the rest of the molecule is located on the aliphatic or alicyclic or aromatic group.

[0025] The aliphatic residues in the aliphatic group, the mixed aliphatic-alicyclic group, the mixed aliphatic-aromatic group, and the mixed aliphatic-alicyclic-aromatic group are not contiguous with 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 ) -, for example, -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)-ORx , -OC(=O)-N(R 13 )-R x , -N(R 13 )-C(=O)-OR x and / or -N(R 13 )-C(=O)-N(R 13 )-R x group (where R x is an aliphatic group).

[0026] Alicyclic, mixed aliphatic-alicyclic, mixed alicyclic-aromatic, and mixed aliphatic-alicyclic-aromatic groups in which the alicyclic residues are 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 When the alicyclic residue is interrupted by -O-, -S-, or -N(R 13 )-group, the resulting rings include, for example, oxiranyl, thiiranyl, aziridinyl, oxetanyl, thietanyl, azetidinyl, furanyl, dihydrofuranyl, tetrahydrofuranyl, thienyl, dihydrothienyl, tetrahydrothienyl, pyrrolidinyl, pyrrolinyl, pyrrolyl, pyranyl, dihydropyranyl, tetrahydropyranyl, thiopyranyl, dihydrothiopyranyl, tetrahydrothioipyranyl, piperidinyl, dihydropyridinyl, tetrahydropyridinyl, and pyridinyl rings.

[0027] Aromatic, mixed aliphatic-aromatic, mixed aliphatic-aromatic, mixed alicyclic-aromatic and mixed aliphatic-alicyclic-aromatic groups in which the aromatic residues are 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 )-, it becomes a partially unsaturated or maximally unsaturated heterocyclic ring, including heteroaromatic rings.

[0028] Aliphatic bridging groups are divalent aliphatic groups. They do not contain any alicyclic, aromatic, or heterocyclic components. Examples include alkylene, alkenylene, and alkynylene groups.

[0029] Alicyclic bridging groups are divalent alicyclic groups. Divalent alicyclic groups can contain one or more, for example, one or two, alicyclic groups. The alicyclic groups may be substituted by aliphatic groups, but the bonding site to the rest of the molecule they bridge is located on the alicyclic group.

[0030] An aromatic bridging group is a divalent aromatic group. A divalent aromatic group may contain one or more, e.g., one or two, aromatic groups, but does not contain alicyclic or heterocyclic components. The aromatic group may be substituted by an aliphatic group, but both bonding sites to the rest of the molecule are located on the aromatic group(s).

[0031] A mixed aliphatic-alicyclic bridging group contains at least one divalent aliphatic group and at least one divalent alicyclic group, and the two attachment sites to the rest of the molecule can both be located on the alicyclic group(s), or both on the aliphatic group(s), or one on an aliphatic group and the other on an alicyclic group.

[0032] A mixed aliphatic-aromatic bridging group contains at least one divalent aliphatic group and at least one divalent aromatic group, and the two attachment sites to the rest of the molecule can both be located on the aromatic group(s), or both on the aliphatic group(s), or one on an aliphatic group and the other on an aromatic group.

[0033] A mixed aliphatic-alicyclic-aromatic bridging group contains at least one divalent aliphatic group, at least one divalent alicyclic group, and at least one divalent aromatic group, and the two attachment sites to the rest of the molecule can both be located on the alicyclic group(s), or both on the aliphatic group(s), or both on the aromatic group(s), or one on an aliphatic group and the other on an alicyclic or aromatic group, or one on an alicyclic group and the other on an aromatic group.

[0034] The term "alkyl" generally refers to 1 to 40 alkyl groups ("C1 to C 40 -alkyl") carbon atoms, preferably 1 to 30 ("C 30 -alkyl") carbon atoms, more preferably 1 to 20 ("C1 to C 20 -alkyl") carbon atoms, especially 1 to 10 ("C1 to C 10"-alkyl") refers to a linear or branched saturated aliphatic hydrocarbon group having 1 to 6 ("C1-C6-alkyl") or 1 to 4 ("C1-C4-alkyl") or 1 or 2 ("C1-C2-alkyl") carbon atoms. C1-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, 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 C1-C6-alkyl, in addition to those mentioned for C1-C6-alkyl, are heptyl, octyl, 2-ethylhexyl, nonyl, decyl, and positional isomers thereof. 20 Examples of -alkyl include C1-C 10 In addition to those mentioned for -alkyl, there are n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, and their positional isomers. 30 Examples of -alkyl include C1-C 20In addition to those mentioned for -alkyl, there are n-henicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-octacosyl, n-nonacosyl, n-triacontyl, and positional isomers thereof.

[0035] The term "fluorinated alkyl" generally refers to a group having 1 to 30 fluorinated alkyl groups ("fluorinated C1-C 30 -alkyl") carbon atoms, preferably 1 to 20 ("fluorinated C1-C 20 -alkyl") carbon atoms, especially 1 to 10 ("fluorinated C1 to C 10 "Fluorinated C1-C2-alkyl" refers to a straight-chain or branched saturated aliphatic hydrocarbon group having 1 to 6 ("fluorinated C1-C6-alkyl") or 1 to 4 ("fluorinated C1-C4-alkyl") or 1 or 2 ("fluorinated C1-C2-alkyl") carbon atoms, in which some or all of the hydrogen atoms have been replaced by fluorine atoms. "Fluorinated methyl" refers to a methyl in which 1, 2 or 3 hydrogen atoms have been replaced by fluorine atoms. "Fluorinated C1-C2-alkyl" refers to an alkyl group (as described above) having 1 or 2 carbon atoms, in which some or all of the hydrogen atoms have been replaced by fluorine atoms. "Fluorinated C1-C3-alkyl" refers to a straight-chain or branched alkyl group having 1 to 3 carbon atoms (as described above), in which some or all of the hydrogen atoms have been replaced by fluorine atoms. "Fluorinated C1-C4-alkyl" refers to a straight-chain or branched alkyl group having 1 to 4 carbon atoms (as described above), in which some or all of the hydrogen atoms of these groups have been replaced by fluorine atoms. "Fluorinated C1-C6-alkyl" refers to a straight-chain or branched alkyl group having 1 to 6 carbon atoms (as described above), in which some or all of the hydrogen atoms of these groups have been replaced by fluorine atoms. "Fluorinated C1-C8-alkyl" refers to a straight-chain or branched alkyl group having 1 to 8 carbon atoms (as described above), in which some or all of the hydrogen atoms of these groups have been replaced by fluorine atoms. "Fluorinated C1-C10 "-Alkyl" refers to a straight-chain or branched alkyl group having 1 to 10 carbon atoms (as defined above), in which some or all of the hydrogen atoms of these groups have been replaced by fluorine atoms, etc. Examples of fluorinated methyl are fluoromethyl, difluoromethyl and trifluoromethyl. Examples of fluorinated C1-C2-alkyl are fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl or pentafluoroethyl. Examples of fluorinated C1-C3-alkyl, in addition to those mentioned for fluorinated C1-C2-alkyl, 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, heptafluoropropyl, etc. Examples of fluorinated C1-C4-alkyl include, in addition to those mentioned for fluorinated C1-C3-alkyl, 4-fluorobutyl, nonafluorobutyl, heptadecafluorooctyl, etc.

[0036] In perfluorinated alkyls, all hydrogen atoms are replaced by fluorine atoms. Examples include trifluoromethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, and heptadecafluorooctyl.

[0037] The term "haloalkyl" (also referred to as "partially or fully halogenated alkyl") generally refers to alkyl groups having 1 to 30 fluorinated C1-C 30 -alkyl") carbon atoms, preferably 1 to 20 ("fluorinated C1-C 20 -alkyl") carbon atoms, especially 1 to 10 ("fluorinated C1 to C 10"C1-C2-haloalkyl" refers to an alkyl group (as defined above) having 1 or 2 carbon atoms, in particular 1 to 6 ("fluorinated C1-C6-alkyl") or 1 to 4 ("fluorinated C1-C4-alkyl") or 1 or 2 ("fluorinated C1-C2-alkyl") carbon atoms, in which some or all of the hydrogen atoms have been replaced by the above-mentioned halogen atoms, in particular fluorine, chlorine and / or bromine. "C1-C2-haloalkyl" refers to an alkyl group (as defined above) having 1 or 2 carbon atoms, in which some or all of the hydrogen atoms have been replaced by the above-mentioned halogen atoms, in particular fluorine, chlorine and / or bromine. "C1-C3-haloalkyl" refers to a straight-chain or branched alkyl group (as defined above) having 1 to 3 carbon atoms, in which some or all of the hydrogen atoms have been replaced by the above-mentioned halogen atoms, in particular fluorine, chlorine and / or bromine. "C1-C4-haloalkyl" refers to a straight-chain or branched alkyl group having 1 to 4 carbon atoms (as defined above) in which some or all of the hydrogen atoms have been replaced by halogen atoms as defined above, in particular fluorine, chlorine and / or bromine. "C1-C6-haloalkyl" refers to a straight-chain or branched alkyl group having 1 to 6 carbon atoms (as defined above) in which some or all of the hydrogen atoms have been replaced by halogen atoms as defined above, in particular fluorine, chlorine and / or bromine. Examples of C1-C2-haloalkyl are 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, 2,2,2-trichloroethyl or pentafluoroethyl.Examples of C1-C3-haloalkyl, in addition to those mentioned for C1-C2-haloalkyl, 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, etc. Examples of C1-C4-haloalkyl, in addition to those mentioned for C1-C3-haloalkyl, include 4-chlorobutyl.

[0038] Strictly speaking, the term "alkenyl" generally refers to an alkyl group having 2 to 40 carbon atoms ("C2 to C 40 -alkenyl") carbon atoms, preferably 2 to 30 ("C 30 -alkenyl") carbon atoms, more preferably 2 to 20 ("C 20 -alkenyl") carbon atoms, especially 2 to 10 ("C 10 "C-C-alkenyl" refers to a monounsaturated (i.e., containing one C-C double bond), straight-chain or branched aliphatic hydrocarbon group having from 2 to 6 ("C-C-alkenyl") or from 2 to 4 ("C-C-alkenyl") carbon atoms, specifically from 2 to 6 ("C-C-alkenyl") or from 2 to 4 ("C-C-alkenyl") carbon atoms, where the C-C double bond may be in any position. However, as used in the present invention, the term is also used to refer to "alkapolyenyl" groups, i.e., groups generally having from 4 to 40 ("C-C-alkenyl"). 40 -alkapolyenyl") carbon atoms, preferably 4 to 30 ("C4-C 30 -alkapolyenyl") carbon atoms, more preferably 4 to 20 ("C4-C 20 -alkapolyenyl") carbon atoms, especially 4 to 10 ("C4-C 10It also includes straight-chain or branched aliphatic hydrocarbon groups having one or more conjugated or isolated but non-integrated C-C double bonds ("-alkapolyenyl") carbon atoms and two or more conjugated or isolated C-C double bonds. Examples of C-C-alkenyls in the strict sense (only one C-C double bond) are ethenyl, 1-propenyl, 2-propenyl, and 1-methylethenyl. Examples of C-C-alkenyls in the strict sense (only one C-C double bond) are 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 in the strict sense (only one CC double bond) include 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, and 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-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,Examples include 2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 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, and 1-ethyl-2-methyl-2-propenyl. In the strict sense, C2~C, 10 Examples of -alkenyl (only one CC double bond) include, in addition to the examples given 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. In the strict sense, C2-C 20 Examples of -alkenyl (only one CC double bond) are C2-C 10In addition to the examples given for -alkenyl, examples include 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, 2-tetradecenyl, 3-tetradecenyl, 4-tetradecenyl, 5-tetradecenyl, 6-tetradecenyl, 7-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 , 8-hexadecenyl, 1-heptadecenyl, 2-heptadecenyl, 3-heptadecenyl, 4-heptadecenyl, 5-heptadecenyl, 6-heptadecenyl, 7-heptadecenyl, 8-heptadecenyl, 1-octadecenyl, 2-octadecenyl, 3-octadecenyl, 4-octadecenyl, 5-octadecenyl, 6-octadecenyl, 7-octadecenyl, 8-octadecenyl, 9-octadecenyl, 1-nonadecenyl Nonadecenyl, 2-nonadecenyl, 3-nonadecenyl, 4-nonadecenyl, 5-nonadecenyl, 6-nonadecenyl, 7-nonadecenyl, 8-nonadecenyl, 9-nonadecenyl, 1-eicosadecenyl, 2-eicosadecenyl, 3-eicosadecenyl, 4-eicosadecenyl, 5-eicosadecenyl, 6-eicosadecenyl, 7-eicosadecenyl, 8-eicosadecenyl, 9-eicosadecenyl, and positional isomers thereof.

[0039] When the terminal CC double bond is in a terminal position, ie the group contains a C=CH2 group, the alkenyl group is also called a vinyl group.

[0040] Examples of alkapolyenyl groups include buta-1,3-dien-1-yl, buta-1,3-dien-2-yl, penta-1,3-dien-1-yl, penta-1,3-dien-2-yl, penta-1,3-dien-3-yl, penta-1,3-dien-4-yl, penta-1,3-dien-5-yl, penta-1,4-dien-1-yl, penta-1,4-dien-2-yl, penta-1,4-dien-3-yl, and the like.

[0041] As used herein, the term "alkynyl" generally refers to an alkyl group having 2 to 40 carbon atoms ("C2 to C 40 -alkynyl") carbon atoms, preferably 2 to 30 ("C 30 -alkynyl") carbon atoms, more preferably 2 to 20 ("C 20 -alkynyl") carbon atoms, especially 2 to 10 ("C 10"C-C-alkynyl" refers to a straight-chain or branched aliphatic hydrocarbon group having 2 to 6 ("C-C-alkynyl") carbon atoms, specifically 2 to 4 ("C-C-alkynyl") carbon atoms, and one triple bond at any position. Examples of C-C-alkynyl include ethynyl, 1-propynyl, or 2-propynyl. Examples of C-C-alkynyl include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, and 1-methyl-2-propynyl. Examples of C2-C6 alkynyl include 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- Examples include 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, and 1-ethyl-1-methyl-2-propynyl.

[0042] The term "cycloalkyl" generally refers to a ring containing 3 to 40 ring members ("C3 to C6"), unless specified as polycyclic. 40 -cycloalkyl"), preferably 3 to 20 ("C3 to C 20 -cycloalkyl"), especially 3 to 10 alkyl groups ("C3 to C 10"C-cycloalkyl" refers to a monocyclic saturated hydrocarbon group (but of course no heteroatoms) having 3 to 8 carbon atoms ("C-C-cycloalkyl"), specifically 3 to 8 ("C-C-cycloalkyl") or more specifically 3 to 6 ("C-C-cycloalkyl"), carbon atoms; i.e., all ring members are carbon atoms. Examples of cycloalkyls having 3 to 4 carbon atoms include cyclopropyl and cyclobutyl. Examples of cycloalkyls having 3 to 5 carbon atoms include cyclopropyl, cyclobutyl, and cyclopentyl. Examples of cycloalkyls having 3 to 6 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Examples of cycloalkyls having 3 to 8 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of cycloalkyls having 3 to 10 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl.

[0043] The term "polycyclic cycloalkyl" refers to a group generally having 4 to 40 ring members ("polycyclic C4-C 40 -cycloalkyl"), preferably 4 to 20 ("polycyclic C4 to C 20 -cycloalkyl"), especially 6 to 20 carbon atoms ("polycyclic C6 to C 40"-cycloalkyl" refers to a bicyclic or polycyclic saturated hydrocarbon group having carbon atoms (but of course no heteroatoms). That is, all ring members are carbon atoms. Bicyclic and polycyclic groups can be fused, bridged, or spiro-linked 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-linked saturated groups include 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-phenalenyl, adamantly, and the like.

[0044] The term "cycloalkenyl," unless specified as polycyclic, generally refers to cycloalkenyls having 3 to 40 ring members ("C3 to C4"). 40 -cycloalkenyl"), preferably 3 to 20 ("C3 to C 20 -cycloalkenyl"), especially 3 to 10 carbon atoms ("C3 to C 10"C-C-cycloalkenyl"), specifically having 3 to 8 ("C-C-cycloalkenyl") or more specifically having 5 to 7 ("C-C-cycloalkenyl") carbon atoms (but of course no heteroatoms), i.e., all ring members are carbon atoms, and having one or more, preferably one, non-integrated C-C double bond in the ring. Examples of C5-C6-cycloalkenyl are cyclopent-1-en-1-yl, cyclopent-1-en-3-yl, cyclopent-1-en-4-yl, cyclopenta-1,3-dien-1-yl, cyclopenta-1,3-dien-2-yl, cyclopenta-1,3-dien-5-yl, cyclohex-1-en-1-yl, cyclohex-1-en-3-yl, cyclohex-1-en-4-yl, cyclohexa-1,3-dien-1-yl, cyclohexa-1,3-dien-2-yl, cyclohexa-1,3-dien-5-yl, cyclohexa-1,4-dien-1-yl and cyclohexa-1,4-dien-3-yl. Examples of C5-C7-cycloalkenyl, in addition to those mentioned above for C5-C6-cycloalkenyl, are cyclohept-1-en-1-yl, cyclohept-1-en-3-yl, cyclohept-1-en-4-yl, cyclohept-1-en-5-yl, cyclohepta-1,3-dien-1-yl, cyclohepta-1,3-dien-2-yl, cyclohepta-1,3-dien-5-yl, cyclohepta-1,3-dien-6-yl, cyclohepta-1,4-dien-1-yl, cyclohepta-1,4-dien-2-yl, cyclohepta-1,4-dien-3-yl and cyclohepta-1,4-dien-6-yl.Examples of C3-C8-cycloalkenyl, in addition to those mentioned above for C5-C7-cycloalkenyl, include cycloprop-1-en-1-yl, cycloprop-1-en-3-yl, cyclobut-1-en-1-yl, cyclobut-1-en-3-yl, cyclooct-1-en-1-yl, cyclooct-1-en-3-yl, cyclooct-1-en-4-yl, cyclooct-1-en-5-yl, cycloocta-1,3-dien-1-yl , cycloocta-1,3-dien-2-yl, cycloocta-1,3-dien-5-yl, cycloocta-1,3-dien-6-yl, cycloocta-1,4-dien-1-yl, cycloocta-1,4-dien-2-yl, cycloocta-1,4-dien-3-yl, cycloocta-1,4-dien-6-yl, cycloocta-1,4-dien-7-yl, cycloocta-1,5-dien-1-yl, and cycloocta-1,5-dien-3-yl.

[0045] The term "polycyclic cycloalkenyl" refers to a group having generally 4 to 40 ring members ("polycyclic C4-C 40 -cycloalkenyl"), preferably 4 to 20 ("polycyclic C4 to C 20 -cycloalkenyl"), especially 6 to 20 carbon atoms ("polycyclic C6 to C 40"-cycloalkenyl" refers to a bicyclic or polycyclic unsaturated hydrocarbon group having carbon atoms (but of course no heteroatoms), i.e., all ring members are carbon atoms, and having one or more C-C double and / or triple bonds, and the ring is not aromatic throughout. Bicyclic and polycyclic groups can be fused, bridged, or spiro-linked rings. Examples of bicyclic fused unsaturated groups include 1,2,3,4,4a,5,8,8a-octahydronaphthalenyl, 1,2,3,4,4a,5,6,8a-octahydronaphthalenyl, 1,2,3,4,4a,5,6,7-octahydronaphthalenyl, 1,2,3,4,5,6,7,8-octahydronaphthalenyl, 1,2,3,4,5,8-hexahydronaphthalenyl, 1,4,4a,5,8,8a ... Examples of tricyclic fused unsaturated groups include α-hexahydronaphthalenyl, 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 tricyclic fused unsaturated groups include fluorenyl, dihydrofluorenyl, tetrahydrofluorenyl, hexahydrofluorenyl and decahydrofluorenyl.

[0046] "Alkoxy" refers to an alkyl group, as defined above, attached to the remainder of the molecule through an oxygen atom, generally a C1-C6 alkyl group attached to the remainder of the molecule through an oxygen atom. 30 -Alkyl group (C1-C 30 -alkoxy"), preferably C1-C 20 -Alkyl group (C1-C 20 -alkoxy), especially C1-C 12 -Alkyl group (C1-C 12"C1-C2-alkoxy" is a C1-C2-alkyl group as defined above which is bonded via an oxygen atom. "C1-C3-alkoxy" is a C1-C3-alkyl group as defined above which is bonded 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, 3-methylbutoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy or 1-ethyl-2-methylpropoxy. C1-C8-alkoxy is additionally, for example, heptyloxy, octyloxy, 2-ethylhexyloxy, and positional isomers thereof. 12 -Alkoxy is additionally, for example, nonyloxy, decyloxy, undecyloxy, dodecyloxy, and positional isomers thereof.

[0047] The substituent "oxo" replaces a CH2 group with a C(=O) group.

[0048] "Aryl" refers to a monocyclic, bicyclic, or polycyclic carbocyclic (i.e., having no 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 vicinal 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 aryl groups include phenanthrenyl, anthracenyl, tetracenyl, 1H-benzo[a]phenalenyl, pyrenyl, etc. However, in the present term, "aryl" also encompasses bicyclic or polycyclic groups in which not all rings are aromatic, as long as at least one ring is aromatic, especially when a reactive site is located on the aromatic ring (or on a functional group attached thereto). Examples include indanyl, indenyl, tetralinyl, 6,7,8,9-tetrahydro-5H-benzo[7]annulenyl, fluorenyl, 9,10-dihydroanthracenyl, 9,10-dihydrophenanthrenyl, 1H-benzo[a]phenalenyl, and the like, as well as ring systems in which not all rings are fused, for example, spiro-linked or bridged, such as benzonorbornyl. In particular, aryl groups have 6 to 40, particularly 6 to 30, more particularly 6 to 20, and especially 6 to 10, carbon atoms as ring members.

[0049] A ring referred to as a heterocyclic ring or heterocyclyl or heteroaromatic ring or heteroaryl or hetaryl contains one or more heteroatoms, i.e., atoms other than carbon, as ring members. In the terminology of the present invention, these heteroatoms are N, O and S, which can also be present as heteroatom groups, i.e., NO, SO or SO2. Thus, in the terminology of the present invention, a ring referred to as a heterocyclic ring or heterocyclyl or heteroaromatic ring or heteroaryl or hetaryl contains one or more heteroatoms and / or heteroatom groups selected from the group consisting of N, O, S, NO, SO and SO2 as ring members.

[0050] In the terms of the present invention, heterocyclic ring or heterocyclyl is a saturated, partially unsaturated or maximally unsaturated ring, including aromatic heteromonocyclic, bicyclic or polycyclic rings (also called heteroaromatic rings or heteroaryl or hetaryl when the ring is aromatic) containing one or more, in particular 1, 2, 3 or 4, heteroatoms or heteroatomic groups independently selected from the group consisting of N, O, S, NO, SO and SO2 as ring members.

[0051] An unsaturated ring contains at least one CC and / or CN and / or NN double bond(s). The largest unsaturated ring contains as many conjugated CC and / or CN and / or NN double bonds as allowed by the ring size. The largest 5- or 6-membered unsaturated heteromonocyclic rings are generally aromatic. Exceptions are the largest 6-membered unsaturated rings that are not aromatic and contain O, S, SO, and / or SO as ring members, such as pyran and thiopyran. A partially unsaturated ring contains fewer CC and / or CN and / or NN double bond(s) than the maximum number allowed by the ring size.

[0052] A heterocyclic ring may be attached to the rest of the molecule via a carbon ring member or via a nitrogen ring member. Naturally, a heterocyclic ring contains at least one carbon ring atom. If a ring contains more than one O ring atom, they are not adjacent. The heterocyclic ring is particularly 3 to 40-membered, particularly 3 to 30-membered, more particularly 3 to 20-membered, and particularly 3 to 12-membered or 3 to 11-membered.

[0053] The heteromonocyclic ring is particularly 3- to 8-membered. Examples of 3-, 4-, 5-, 6-, 7-, or 8-membered saturated heteromonocyclic rings include oxiran-2-yl, thiiran-2-yl, aziridin-1-yl, aziridin-2-yl, oxetan-2-yl, oxetan-3-yl, thietan-2-yl, thietan-3-yl, 1-oxothietan-2-yl, 1-oxothietan-3-yl, 1,1-dioxothietan-2-yl, 1,1-dioxothietan-3-yl, azetidin-1-yl, azetidin-2-yl, azetidin-3-yl, tetrahydrofuran-2-yl, tetrahydrofuran-3 ... tetrahydrothien-2-yl, tetrahydrothien-3-yl, 1-oxotetrahydrothien-2-yl, 1,1-dioxotetrahydrothien-2-yl, 1-oxotetrahydrothien-3-yl, 1,1-dioxotetrahydrothien-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 yl, oxazolidin-3-yl, oxazolidin-4-yl, oxazolidin-5-yl, isoxazolidin-2-yl, isoxazolidin-3-yl, isoxazolidin-4-yl, isoxazolidin-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-oxadiazolidin-2-yl, 1,2,4-oxadiazolidin-3-yl yl, 1,2,4-oxadiazolidin-4-yl, 1,2,4-oxadiazolidin-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-oxadiazolidin-2-yl, 1,3,4-oxadiazolidin-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-dioxan-2-yl, 1,3-dioxan-4-yl, 1,3-dioxan-5-yl, 1,4-dioxan-2-yl, piperidin-1-yl, piperidin-2-yl, piperidin-3-yl, piperidin-4-yl, hexahydropyridazin-1-yl 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, 1,2,4-hexahydrotriazin-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, oxepan-2-, -3-, -4- or -5-yl, hexahydro-1,3-diazepinyl, hexahydro-1,4-diazepinyl, hexahydro-1,3-oxazepinyl, hexahydro-1,4-oxazepinyl, hexahydro-1,3-dioxepinyl, hexahydro-1,4-dioxepinyl, oxocane, thiocane, azocanyl, [1,3]diazocanyl, [1,4]diazocanyl, [1,5]diazocanyl, [1,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-dihydrothien-2-yl, 2,3-dihydrothien-3-yl, 2,4-dihydrothien-2-yl, 2,4-dihydrothien-3-yl, 2-pyrrolin-2-yl, 2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 2-isoxazolin-3-yl, 3 ... Isoxazolin-3-yl, 4-isoxazolin-3-yl, 2-isoxazolin-4-yl, 3-isoxazolin-4-yl, 4-isoxazolin-4-yl, 2-isoxazolin-5-yl, 3-isoxazolin-5-yl, 4-isoxazolin-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 Zolin-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-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 3,4-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-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]azepin-1-, -2-, -3-, -4-, -5-, -6- or -7-yl, 3,4,5,6-tetrahydro[2H]azepin-2-, -3-, -4-, -5-, -6- or -7-yl, 2,3,4,7-tetrahydro[1H]azepin-1-, -2-, -3-, -4-, -5-, -6- or -7-yl, 2,3,6,7-tetrahydro[1H]azepin-1-, -2-, -3-, -4-, -5-, -6- or -7-yl, tetrahydrooxy oxepinyl, for example 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-diazepinyl, tetrahydro-1,4-diazepinyl, tetrahydro-1,3-oxazepinyl, tetrahydro-1,3-oxazepinyl, Examples include tetrahydro-1,4-oxazepinyl, tetrahydro-1,3-dioxepinyl, tetrahydro-1,4-dioxepinyl, 1,2,3,4,5,6-hexahydroazocine, 2,3,4,5,6,7-hexahydroazocine, 1,2,3,4,5,8-hexahydroazocine, 1,2,3,4,7,8-hexahydroazocine, 1,2,3,4,5,6-hexahydro-[1,5]diazocine, and 1,2,3,4,7,8-hexahydro-[1,5]diazocine.

[0054] Examples of maximally unsaturated (but not aromatic) heteromonocyclic rings that are 3, 4, 5, 6, 7 or 8 membered include pyran-2-yl, pyran-3-yl, pyran-4-yl, thiopryran-2-yl, thiopyran-3-yl, thiopyran-4-yl, 1-oxothiopyran-2-yl, 1-oxothiopyran-3-yl, 1-oxothiopyran-4-yl, 1,1-dioxothiopyran-2-yl, 1,1-dioxothiopyran-3-yl, 1,1-dioxothiopyran-4-yl, 2H-oxazolidin ... 2H-oxazin-3-yl, 2H-oxazin-4-yl, 2H-oxazin-5-yl, 2H-oxazin-6-yl, 4H-oxazin-3-yl, 4H-oxazin-4-yl, 4H-oxazin-5-yl, 4H-oxazin-6-yl, 6H-oxazin-3-yl, 6H-oxazin-4-yl, 7H-oxazin-5-yl, 8H-oxazin-6-yl, 2H-1,3-oxazin-2-yl, 2H-1,3-oxazin-4-yl, 2H-1,3-oxazin-5-yl, 2H-1,3-oxazin-6-yl yl, 4H-1,3-oxazin-2-yl, 4H-1,3-oxazin-4-yl, 4H-1,3-oxazin-5-yl, 4H-1,3-oxazin-6-yl, 6H-1,3-oxazin-2-yl, 6H-1,3-oxazin-4-yl, 6H-1,3-oxazin-5-yl, 6H-1,3-oxazin-6-yl, 2H-1,4-oxazin-2-yl, 2H-1,4-oxazin-3-yl, 2H-1,4-oxazin-5-yl, 2H-1,4-oxazin-6-yl, 4H-1,4-oxazin-2-yl, 4H-1,4- Examples include oxazin-3-yl, 4H-1,4-oxazin-4-yl, 4H-1,4-oxazin-5-yl, 4H-1,4-oxazin-6-yl, 6H-1,4-oxazin-2-yl, 6H-1,4-oxazin-3-yl, 6H-1,4-oxazin-5-yl, 6H-1,4-oxazin-6-yl, 1,4-dioxin-2-yl, 1,4-oxathiin-2-yl, 1H-azepine, 1H-[1,3]-diazepine, 1H-[1,4]-diazepine, [1,3]diazocine, [1,5]diazocine, and [1,5]diazocine.

[0055] The heteroaromatic monocyclic ring is particularly 5- or 6-membered. Examples of 5- or 6-membered monocyclic heteroaromatic rings include 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-oxazolyl, 4-oxazolyl, 5-oxazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-Isoxazolyl, 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-oxadiazol-4-yl, 1,2,3-oxadiazol-5-yl, 1,3,4-oxadiazol-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-pyridinyl, 3-pyridinyl, 4-pyridinyl, 1-oxopyridin-2-yl, 1-oxopyridin Examples include 1,3,5-triazin-3-yl, 1-oxopyridin-4-yl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl, 1,2,4-triazin-5-yl, 1,2,3,4-tetrazin-1-yl, 1,2,3,4-tetrazin-2-yl, and 1,2,3,4-tetrazin-5-yl.

[0056] A "heterobicyclic ring" or "heterobicyclyl" contains two rings that share at least one common ring atom. At least one of the two rings contains a heteroatom or heteroatom group selected from the group consisting of N, O, S, NO, SO, and SO2 as a ring member. The term includes fused (fused) ring systems in which two rings share two adjacent common ring atoms, as well as spiro systems in which the rings share only one common ring atom, and bridged systems in which the rings share at least three common ring atoms. In the context of this invention, heterobicyclic rings include aromatic bicyclic ring systems throughout. These are also referred to as heteroaromatic bicyclic rings or bicyclic (bicycyclic) heta-(or hetero)aryls or heterobiaryls. Heterobicyclic rings are preferably 7-, 8-, 9-, 10-, or 11-membered. Heteroaromatic bicyclic rings are preferably 9-, 10-, or 11-ring. Heteroaromatic heterobicyclic rings are generally 9-, 10-, or 11-ring.

[0057] Examples of condensed systems: Examples of 7-, 8-, 9-, 10- or 11-membered saturated heterobicyclic rings containing 1, 2 or 3 (or 4) heteroatoms or heteroatomic groups as ring members selected from the group consisting of N, O, S, NO, SO and SO2 include:

[0058] [ka] There is TIFF0007778699000006.tif75153.

[0059] 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 the group consisting of N, O, S, NO, SO, and SO2 as ring members include:

[0060] [ka] There is TIFF0007778699000008.tif146158.

[0061] Examples of maximally unsaturated (but not heteroaromatic as a whole) heterobicyclic rings containing 1, 2 or 3 (or 4) heteroatoms or heteroatom groups selected from the group consisting of N, O, S, NO, SO and SO2 as ring members include:

[0062] [ka] There is TIFF0007778699000010.tif156160.

[0063] Examples of maximally unsaturated 9- or 10-membered heteroaromatic heterobicyclic rings containing as ring members 1, 2 or 3 (or 4) heteroatoms or heteroatom groups selected from the group consisting of N, O, S, NO, SO and SO2 include:

[0064] [ka] There is TIFF0007778699000012.tif123155.

[0065] Examples of 7-, 8-, 9-, 10-, or 11-membered spiro-linked heterobicyclic rings containing 1, 2, or 3 (or 4) heteroatoms or heteroatomic groups selected from the group consisting of N, O, S, NO, SO, and SO2 as ring members include:

[0066] [ka] There is TIFF0007778699000014.tif49157.

[0067] 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 the group consisting of N, O, S, NO, SO, and SO2 as ring members include:

[0068] [ka] etc.

[0069] In the above structure, # represents the point of attachment to the rest of the molecule. The point of attachment is not limited to the ring in which it is shown, but may be on either of the two rings and on a carbon or nitrogen ring atom. When a ring has one or more substituents, these may be attached to a carbon and / or nitrogen ring atom.

[0070] Polyheterocyclic rings (polyheterocyclyls) contain three or more rings, each of which has at least one ring atom shared with at least one of the other rings in the polycyclic ring system. The rings may be fused, spiro-linked, or bridged. Mixed systems (e.g., one ring spiro-linked to a fused system, or a bridged system fused to another ring) are also possible. Aromatic rings are not included throughout polyheterocyclic rings (polyheterocyclyls). These are called polyheteroaromatic rings or heteropolyaryls.

[0071] Aryloxy, heterocyclyloxy, and heteroaryloxy (also designated O-aryl, O-heterocyclyl, and O-heteroaryl) are aryl, heterocyclyl, and heteroaryl, respectively, as defined above, attached to the remainder of the molecule via an oxygen atom. Examples include phenoxy or pyridyloxy.

[0072] The aryl and heterocyclic rings may be unsubstituted or may carry one or more substituents. Suitable substituents include, for example, linear or branched C1-C 18 -Alkyl, C2-C 10 -alkenyl or halogen, in particular fluorine.

[0073] Examples of natural or synthetic saturated fatty acids having 2 to 41 carbon atoms include 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), caproic acid (6 C), enanthic acid (7 C), caprylic acid (8 C), 2-ethylhexanoic acid, pelargonic acid (9 C), neononanoic acid (9 C; a mixture of branched isomers of n-nonanoic acid), capric acid (10 C), 3-propylheptanoic acid (10 C), neodecanoic acid (10 C; a mixture of branched isomers of n-decanoic acid). Examples of monounsaturated fatty acids include undecanoic acid (11 C), lauric acid (12 C), tridecanoic acid (13 C), myristic acid (14 C), pentadecanoic acid (15 C), palmitic acid (16 C), margaric acid (17 C), stearic acid (18 C), nonadecanoic acid (19 C), arachidic acid (20 C), heneicosylic acid (21 C), and behenic acid (22 C). Examples of monounsaturated fatty acids include myristoleic acid (14 C), palmitoleic acid (16 C), oleic acid (18 C), elaidic acid (18 C), gadoleic acid (20 C); gondonic acid (20 C), spermaceti acid (22 C), and erucic acid (22 C). Examples of polyunsaturated fatty acids are linoleic acid (18 C), α-linoleic acid (18 C), γ-linoleic acid (18 C), α-eleostearic acid (18 C), β-eleostearic acid (18 C), stearidonic acid (18 C), arachidonic acid (20 C), docosadienoic acid (22 C), docosatetraenoic acid (22 C), docosapentaenoic acid (22 C), and docosahexaenoic acid (22 C).

[0074] "(Meth)acrylate" is meant to encompass acrylates and methacrylates. "Poly(meth)acrylate" refers to polyacrylates, polymethacrylates, or copolymers of acrylates and methacrylates.

[0075] For the purposes of this invention, unless otherwise specified, "acrylate" and "methacrylate" refer to esters of acrylic acid or methacrylic acid (but not to salts thereof), and this of course also applies to their polymers.

[0076] Embodiments of the present invention The following remarks regarding preferred definitions of variables and other reaction conditions are valid alone and are also preferred in combination with one another.

[0077] Embodiment (Ex) of the present invention General and preferred embodiments Ex are summarized in the following non-exhaustive list: Further preferred embodiments will become apparent from the paragraphs following this list.

[0078] E.1. A process for preparing cyclic carbonates I selected from the group consisting of compounds of formula Ia, compounds of formula Ib and mixtures thereof, comprising:

[0079] [ka] [In the formula, R 1 is an organic group] a) Propargyl alcohol of formula II

[0080] [ka] [In the formula, R 1 has the same meaning as in formula Ia or Ib. with carbon dioxide, 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 solvents L1 and L2 have a solubility gap of at least 20-30°C; The reaction is further carried out in the presence of a silver catalyst Ag1 comprising at least one bulky ligand and a carboxylate ligand; The bulky ligand is selected from the group consisting of a ligand of formula III and a ligand of formula IV

[0081] [ka] [In the formula, D is P, As or Sb; R 2 are each independently an organic group having 1 to 40 carbon atoms, R 3 and R 4 are the same or different and each is an organic group having 1 to 40 carbon atoms, R 5 is an organic group having 1 to 40 carbon atoms, and R present in ligand IV 2 may be different from or the same as Z is -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 - is a divalent bridging group selected from R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently hydrogen or an organic group having 1 to 40 carbon atoms, or Two adjacent groups R 7 and R 8 and / or R 10 and R 11 together with the atoms connecting them form a monocyclic or polycyclic substituted or unsubstituted aliphatic or aromatic ring system having 4 to 40 carbon atoms as ring members and which may also contain at least one heteroatom selected from the group consisting of the elements Si, Ge, N, P, O and S. The carboxylate ligand is according to formula V

[0082] [ka] [In the formula, R 6 is an organic group having 1 to 40 carbon atoms. Step, b1) if step a) was not carried out in the presence of at least one solvent L2, adding a solvent L2 to the reaction mixture obtained in step a), or b2) if step a) is carried out in the presence of at least one solvent L2, optionally adding solvent L2 to the reaction mixture obtained in step a), c) subjecting the reaction mixture obtained in step a), b1) or b2) to phase separation to obtain a product phase containing the cyclic carbonate I and at least one solvent L1 and a catalyst phase containing the silver catalyst and at least one solvent L2; and d) optionally isolating the cyclic carbonate I from the product phase. A method comprising:

[0083] E.2.R 1 is selected from the group consisting of hydrogen, an aliphatic group, an alicyclic group, an aromatic group, a mixed aliphatic-alicyclic group, a mixed aliphatic-aromatic group, a mixed alicyclic-aromatic group, and a mixed aliphatic-alicyclic-aromatic group; the aliphatic, alicyclic and / or aromatic residues in the aliphatic, alicyclic, aromatic, mixed aliphatic-alicyclic, mixed aliphatic-aromatic, mixed alicyclic-aromatic and mixed aliphatic-alicyclic-aromatic groups may be substituted by one or more halogen atoms; The aliphatic, cycloaliphatic and aromatic groups have at least one of the following characteristics (i) and / or (ii); and the mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic and mixed aliphatic-cycloaliphatic-aromatic groups have at least one of the following characteristics (i), (ii) and / or (iii): (i) The aliphatic, alicyclic, aromatic, mixed aliphatic-alicyclic, mixed aliphatic-aromatic, mixed alicyclic-aromatic, and mixed aliphatic-alicyclic-aromatic groups are each independently selected from the group consisting of 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 )- is interrupted by, (ii) Aliphatic, alicyclic, aromatic, mixed aliphatic-alicyclic, mixed aliphatic-aromatic, mixed alicyclic-aromatic, and mixed aliphatic-alicyclic-aromatic groups are defined as -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 having one or more substituents selected from the group consisting of (iii) The aliphatic, alicyclic and aromatic residues in the mixed aliphatic-alicyclic, mixed aliphatic-aromatic, mixed alicyclic-aromatic and mixed aliphatic-alicyclic-aromatic radicals are not limited to the 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 )-, R 13are each independently hydrogen or C1 to C 10 - alkyl, 2. The method defined in embodiment 1.

[0084] E.3. The cyclic carbonate is a compound of formula I-Poly;

[0085] [ka] [In the formula, X is a bond or a group -C(=O)-; # -C(=O)-O-* or # -C(=O)-N(R 13 )-*, where: # is the point of attachment to O, * is the point of attachment to Y (or to Z if Y is a bond, or to poly if Y and Z are bonds), Y is a bond, or a divalent aliphatic bridging group, alicyclic bridging group, aromatic bridging group, aliphatic-alicyclic mixed bridging group, aliphatic-aromatic mixed bridging group, alicyclic-aromatic mixed bridging group, or aliphatic-alicyclic-aromatic mixed bridging group, in which the aliphatic, alicyclic and / or aromatic residues in the aliphatic bridging group, alicyclic bridging group, aromatic bridging group, aliphatic-alicyclic mixed bridging group, aliphatic-aromatic mixed bridging group, alicyclic-aromatic mixed bridging group, and aliphatic-alicyclic-aromatic mixed bridging group are optionally substituted with one or more halogen atoms; The aliphatic, cycloaliphatic or aromatic bridging group may have at least one of the following characteristics (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 characteristics (i), (ii) and / or (iii): (i) The aliphatic, alicyclic and / or aromatic residues in the aliphatic bridging group, alicyclic bridging group, aromatic bridging group, mixed aliphatic-alicyclic bridging group, mixed aliphatic-aromatic bridging group, mixed alicyclic-aromatic bridging group, or mixed aliphatic-alicyclic-aromatic bridging group are not separated by one or more non-adjacent groups -O-, -S-, -N(R 13 )-, -OC(=O)-, -C(=O)-O-, -N(R13 )-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 )- is interrupted by, (ii) An aliphatic bridging group, an alicyclic bridging group, an aromatic bridging group, a mixed aliphatic-alicyclic bridging group, a mixed aliphatic-aromatic bridging group, a mixed alicyclic-aromatic bridging group, or a mixed aliphatic-alicyclic-aromatic bridging group is not an -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 having one or more substituents selected from the group consisting of (iii) The aliphatic, alicyclic and / or aromatic residues in the aliphatic-alicyclic mixed bridging group, the aliphatic-aromatic mixed bridging group, the alicyclic-aromatic mixed bridging group or the aliphatic-alicyclic-aromatic mixed bridging group are not represented by the 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 )-, R 13 are each independently hydrogen or C1 to C 10 -alkyl, Z is a bond or a group -C(=O)- when X and Y are bonds; # -C(=O)-O-* or # -C(=O)-N(R 13)-*, where: # 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 Z is a group in which Y is a bond and X is a group -C(=O)-; # -C(=O)-O*- or # -C(=O)-N(R 13 )-*, where: # is the point of attachment to O, or Z is a bond or a 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 )-*, where: # is the point of attachment to Y, n is 1 to 1000, Poly is a residue derived from a polymer having a number average molecular weight of 200 to 10,000. Propargyl alcohol is a compound of formula II-poly

[0086] [ka] wherein X, Y, Z, n and poly are as defined above. 2. The method defined in embodiment 1.

[0087] E.4. X is a bond or a group -C(=O)- or # -C(=O)-N(R 13 )-*, where: # is the point of attachment to O, * is the point of attachment to Y (or to Z if Y is a bond, or to poly if Y and Z are bonds), Y is a bond, or a divalent aliphatic bridging group or a mixed aliphatic-alicyclic bridging group having 1 to 10 carbon atoms, the aliphatic bridging group or the mixed aliphatic-alicyclic bridging group being optionally substituted with one or more halogen atoms; The aliphatic bridging group may have at least one of the following characteristics (i) and / or (ii), and the mixed aliphatic-alicyclic bridging group may have at least one of the following characteristics (i), (ii) and / or (iii): (i) the aliphatic-aliphatic and / or alicyclic residues in the aliphatic bridging group or the mixed aliphatic-alicyclic bridging group are interrupted by one or more non-adjacent groups -O-, -O-C(=O)-, -C(=O)-O-, and / or -O-C(=O)-O-; (ii) the aliphatic bridging group or mixed aliphatic-alicyclic bridging group has one or more substituents selected from the group consisting of -OH, -OC(=O)H, and -C(=O)OH; (iii) the aliphatic and / or alicyclic residues in the mixed aliphatic-alicyclic bridging group are bonded to each other via the groups -O-, -OC(=O)-, -C(=O)-O-, or -OC(=O)-O; Z is a bond or a group —C(═O)— when X and Y are bonds; Z is a bond when Y is a bond and X is a group -C(=O)-; or Z is a bond or a group when Y is a divalent aliphatic bridging group or a mixed aliphatic-alicyclic bridging group. # -OC(=O)-, Poly is a residue derived from a poly-α-olefin or a poly(meth)acrylate; 4. The method defined in embodiment 3.

[0088] E.5. -XYZ- together form -C(=O)-, # -CH2-CH(OH)-CH2-OC(=O)-* or # -C(=O)-NH-CH2CH2-OC(=O)-*, where # is the point of attachment to O and * is the point of attachment to poly; 5. The method defined in embodiment 4.

[0089] E.6. The cyclic carbonate is compound Ia, compound Ib, or a mixture thereof; In the formula, R 1 is hydrogen, and the group -OR 14 and C1-C4-alkyl having the formula R 14 is hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, 1, 2 or 3 R 15 C1-C6-alkyl having a group; 1, 2 or 3 R 15 C1-C6-haloalkyl having a group; -C(=O)R 16 , C3-C6-cycloalkyl, 1, 2 or 3 R 17 C3-C6-cycloalkyl having a group; phenyl and 3-, 4-, 5- or 6-membered saturated, partially unsaturated or maximally unsaturated heterocyclic rings containing 1, 2 or 3 heteroatoms selected from N, O and S as ring members, wherein phenyl and the heterocyclic ring may carry one or more substituents selected from the group consisting of C1-C4-alkyl and C1-C4-alkoxy, R 15 is selected from the group consisting of OH, C1-C6-alkoxy, oxyranly, phenyl, and 3-, 4-, 5-, or 6-membered saturated heterocyclic rings containing one or two oxygen atoms as ring members, R 16 is C1-C6-alkyl, C2-C6-alkenyl, C1-C4-alkoxy and -NR 18 R 19 and R 18 is hydrogen or C1-C4-alkyl, and R 19 is hydrogen, C1-C4 alkyl, R20 C1-C4-alkyl substituted by groups, and phenyl which may have 1, 2, 3, 4 or 5 substituents selected from the group consisting of C1-C4-alkyl and C1-C4-alkoxy, R 20 -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 and R 21 is hydrogen, C1-C6-alkyl or C2-C6-alkenyl, R 13 are each independently hydrogen or C1 to C 10 -alkyl, R 17 -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 , and R is selected from the group consisting of21 is hydrogen, C1-C6-alkyl or C2-C6-alkenyl, R 13 are each independently hydrogen or C1 to C 10 -alkyl, Or the cyclic carbonate is a compound of formula I-bis

[0090] [ka] [In the formula, A is an aliphatic bridging group, an alicyclic bridging group, an aromatic bridging group, a mixed aliphatic-alicyclic bridging group, a mixed aliphatic-aromatic bridging group, a mixed alicyclic-aromatic bridging group, or a mixed aliphatic-alicyclic-aromatic bridging group; the aliphatic, alicyclic and / or aromatic residues in the aliphatic, alicyclic, aromatic, mixed aliphatic-alicyclic, mixed aliphatic-aromatic, mixed alicyclic-aromatic and mixed aliphatic-alicyclic-aromatic groups may be substituted by one or more halogen atoms; The aliphatic, cycloaliphatic or aromatic bridging group has at least one of the following characteristics (i) and / or (ii); 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): (i) The aliphatic, alicyclic and / or aromatic residues in the aliphatic bridging group, alicyclic bridging group, aromatic bridging group, mixed aliphatic-alicyclic bridging group, mixed aliphatic-aromatic bridging group, mixed alicyclic-aromatic bridging group, or mixed aliphatic-alicyclic-aromatic bridging group are not separated 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 )- is interrupted by, (ii) An aliphatic bridging group, an alicyclic bridging group, an aromatic bridging group, a mixed aliphatic-alicyclic bridging group, a mixed aliphatic-aromatic bridging group, a mixed alicyclic-aromatic bridging group, or a mixed aliphatic-alicyclic-aromatic bridging group is not an -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 having one or more substituents selected from the group consisting of (iii) The aliphatic, alicyclic and / or aromatic residues in the aliphatic-alicyclic mixed bridging group, the aliphatic-aromatic mixed bridging group, the alicyclic-aromatic mixed bridging group or the aliphatic-alicyclic-aromatic mixed bridging group are not represented by the 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 )-, R 13 are each independently hydrogen or C1 to C 10 -alkyl] Propargyl alcohol is a compound of formula II, where R 1 is hydrogen and -OR 14 C1-C4-alkyl having a group, R 14 is as defined above, or the propargyl alcohol is a compound of formula II-bis

[0091] [ka] wherein A is as defined above. 3. The method defined in embodiment 2.

[0092] E.7. The cyclic carbonate is compound Ia, compound Ib, or a mixture thereof; In the formula, R 1 is hydrogen and -CH2-OR 14 is selected from the group consisting of R 14 is hydrogen, 1, 2 or 3 R 15 C1-C4-Alkyl with a group; -C(=O)R 16 and 1, 2 or 3 R 17 is selected from the group consisting of C3-C6-cycloalkyl having a group, R 15 is selected from the group consisting of OH, C1-C4-alkoxy, phenyl, and 3-, 4-, 5-, or 6-membered saturated heterocyclic rings containing one or two oxygen atoms as ring members, R 16 is C1-C6-alkyl, C2-C6-alkenyl, C1-C4-alkoxy and -NR 18 R 19 and R 18 is hydrogen or C1-C4-alkyl, and R 19 is hydrogen, C1-C4 alkyl, R 20 C1-C4-alkyl substituted by groups, and phenyl which may have 1, 2, 3, 4 or 5 substituents selected from the group consisting of C1-C4-alkyl and C1-C4-alkoxy, R 20 -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)-OR21 and -N(R 13 )-C(=O)-N(R 13 )-R 21 and R 21 is hydrogen, C1-C6-alkyl or C2-C6-alkenyl, R 13 are each independently hydrogen or C1 to C 10 -alkyl, R 17 -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 , and R is selected from the group consisting of 21 is hydrogen, C1-C6-alkyl or C2-C6-alkenyl, R 13 are each independently hydrogen or C1 to C 10 -alkyl, or the cyclic carbonate is a compound of formula I-bis as defined in embodiment 6; wherein A is a bridging group: -CH2-O-CH2-1,4-phenylene-CH2-O-CH2-; -CH2-OC(=O)-NH-1,4-toluylene-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- is selected from Propargyl alcohol is a compound of formula II, where R 1 is hydrogen and -CH2-OR 14 and R 14 is 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. 7. The method defined in embodiment 6.

[0093] E.8. The cyclic carbonate is compound Ia, compound Ib, or a mixture thereof; In the formula, R 1 is hydrogen and -CH2-OR 14 is selected from the group consisting of R 14 is hydrogen, 1, 2 or 3 R 15 C1-C4-alkyl having the group; -C(O)CH3, -C(=O)H and -C(O)OCH3; R 15 is selected from the group consisting of OH and C1-C4-alkoxy, or the cyclic carbonate is a compound of formula I-bis as defined in embodiment 6; wherein A is —CH—O—CH—CH(OH)—CH—O-1,4-phenylene-C(CH)—1,4-phenylene-O—CH—CH(OH)—CH—O—CH—; Propargyl alcohol is a compound of formula II, where R 1 is hydrogen and -CH2-OR 14 and R 14 is 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. 8. The method defined in embodiment 7.

[0094] E.9. The cyclic carbonate is compound Ia, compound Ib, or a mixture thereof; In the formula, R 1is hydrogen and -CH2-OR 14 is selected from the group consisting of R 14 is a hydrogen atom and one or two R 15 is selected from the group consisting of C1-C4-alkyl having a group, R 15 is selected from the group consisting of OH and C1-C4-alkoxy, or the cyclic carbonate is a compound of formula I-bis as defined in embodiment 6; wherein A is —CH—O—CH—CH(OH)—CH—O-1,4-phenylene-C(CH)—1,4-phenylene-O—CH—CH(OH)—CH—O—CH—; Propargyl alcohol is a compound of formula II, where R 1 is hydrogen and -CH2-OR 14 and R 14 is 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. 9. The method defined in embodiment 8.

[0095] E.10. The cyclic carbonate is compound Ia, compound Ib, or a mixture thereof, wherein R 1 is hydrogen and -CH2-OR 14 and R 14 is —CH—CH(OH)—CH—OC(CH) or —CH—CH(OH)—CH—OH, or the cyclic carbonate is a compound of formula I-bis as defined in embodiment 6, wherein A is —CH—O—CH—CH(OH)—CH—O-1,4-phenylene-C(CH)-1,4-phenylene-O—CH—CH(OH)—CH—O—CH—; and the propargyl alcohol is a compound of formula II, wherein R 1 is hydrogen and -CH2-OR 14 and R 14is —CH—CH(OH)—CH—OC(CH) or —CH—CH(OH)—CH—OH, or the propargyl alcohol is a compound of formula II-bis as defined in embodiment 6, wherein A is —CH—O—CH—CH(OH)—CH—O-1,4-phenylene-C(CH)-1,4-phenylene-O—CH—CH(OH)—CH—O—CH—; 10. The method defined in embodiment 9.

[0096] E.11. The cyclic carbonate is compound Ia, compound Ib, or a mixture thereof, wherein R 1 is hydrogen and -CH2-OR 14 and R 14 is —CH—CH(OH)—CH—OC(CH), or the cyclic carbonate is a compound of formula I-bis as defined in embodiment 6, wherein A is —CH—O—CH—CH(OH)—CH—O-1,4-phenylene-C(CH)—1,4-phenylene-O—CH—CH(OH)—CH—O—CH—; and the propargyl alcohol is a compound of formula II, wherein R 1 is hydrogen and -CH2-OR 14 and R 14 is —CH—CH(OH)—CH—OC(CH), or the propargyl alcohol is a compound of formula II-bis as defined in embodiment 6, where A is —CH—O—CH—CH(OH)—CH—O-1,4-phenylene-C(CH)-1,4-phenylene-O—CH—CH(OH)—CH—O—CH—.

[0097] E.12. The cyclic carbonate is compound Ia, compound Ib, or a mixture thereof, wherein R 1 is hydrogen and -CH2-OR 14 and R 14 is —CH—CH(OH)—CH—OC(CH), and propargyl alcohol is a compound of formula II, where R 1 is hydrogen and -CH2-OR14 and R 14 12. The method defined in embodiment 11, wherein is —CH—CH(OH)—CH—OC(CH)

[0098] E.13. 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 The method defined in embodiment 12, wherein is hydrogen.

[0099] E.14. The bulky ligand is a ligand of formula III, During the ceremony, D is P or As; R 2 is a monocyclic or polycyclic C3-C 40 -cycloalkyl, monocyclic or polycyclic C3-C 40 -Cycloalkenyl, C6-C 40 - a cyclic group selected from the group consisting of aryl and 3-40 membered saturated, partially unsaturated or maximally unsaturated monocyclic or polycyclic heterocyclic rings, which may be linked to D via an oxygen atom, and which may be C1-C6-alkyl, C1-C6-alkoxy, 1, 2, 3 or 4 R 22 phenyl optionally substituted by a substituent, 1, 2, 3 or 4 R 22 naphthyl optionally substituted by substituents, containing 1, 2, 3 or 4 heteroatoms selected from the group consisting of N, O and S as ring members, and 1, 2 or 3 R 23 a monocyclic 5- or 6-membered heteroaromatic ring optionally substituted by a substituent and containing 1, 2, 3, or 4 heteroatoms selected from the group consisting of N, O, and S as ring members, and 1, 2, or 3 R 23 and optionally substituted fused bicyclic 8- to 10-membered heteroaromatic ring systems, R 22 are each independently C1-C6-alkyl, C1-C6-alkoxy, NR 24 R25 [where R 24 and R 25 are each independently hydrogen or C1-C 12 -alkyl], phenyl, naphthyl and monocyclic saturated, partially unsaturated or maximally unsaturated 5- or 6-membered heterocyclic rings containing as ring members 1, 2, 3 or 4 heteroatoms selected from the group consisting of N, O and S, the last three mentioned ring groups optionally bearing 1, 2, 3, 4 or 5 substituents selected from the group consisting of halogen, C1-C4-alkyl and C1-C4-alkoxy, R 23 are each independently, R 22 has one of the meanings described for R 3 and R 4 are each independently C1-C6-alkyl, monocyclic or polycyclic C3-C 40 -cycloalkyl, monocyclic or polycyclic C3-C 40 -Cycloalkenyl and C6-C 10 -aryl, 10. The method as defined in any one of the preceding embodiments.

[0100] E.15. D is P, R 2 but 1, 2, 3 or 4 R 22 phenyl optionally substituted by a substituent, 1, 2, 3 or 4 R 22 ortho-biphenyl optionally substituted by a substituent, 1, 2, 3 or 4 R 22 naphthyl optionally substituted by a substituent, 1, 2, 3 or 4 R 22 ortho-binaphthyl optionally substituted by substituents, containing 1, 2 or 3 nitrogen atoms as ring members and 1, 2 or 3 R 23 monocyclic 5- or 6-membered heteroaromatic rings optionally substituted by substituents and containing 1, 2, or 3, or 4 nitrogen atoms as ring members and 1, 2, or 3 R 23 a fused bicyclic 8- to 10-membered heteroaromatic ring system optionally substituted by substituents; R 22 each independently represents C1-C4 alkyl, C1-C4 alkoxy, NR 24 R 25 [where R 24 and R 25 are each independently hydrogen or C1-C 10 -alkyl], phenyl optionally substituted by 1, 2, 3, 4 or 5 substituents selected from the group consisting of halogen, C1-C4-alkyl and C1-C4-alkoxy, and monocyclic saturated, partially unsaturated or maximally unsaturated 5- or 6-membered heterocyclic rings containing as ring members 1, 2 or 3 heteroatoms selected from the group consisting of N and O, R 23 are each independently phenyl optionally substituted by 1, 2, 3, 4 or 5 substituents selected from the group consisting of halogen, C1-C4-alkyl and C1-C4-alkoxy, R 3 and R 4 are independently selected from the group consisting of branched C3-C6-alkyl, monocyclic C3-C6-cycloalkyl, adamantyl and phenyl, 15. The method defined in embodiment 14.

[0101] E.16. D is P, R 2 But NR 24 R 25 phenyl substituted by 24 and R 25 are each independently hydrogen or C1-C 10 -alkyl], or 1, 2, 3 or 4 R 22 ortho-biphenyl substituted by a substituent, R 22 are each independently C1-C4 alkyl and NR 24 R 25 [where R 24 and R 25 are each independently hydrogen or C1-C 10 -alkyl; 16. The method defined in embodiment 15.

[0102] E.17.R 24 and R 25 are independent of each other, C3~C 10 The method as defined in embodiment 16, wherein - is alkyl.

[0103] E.18. The method defined in embodiment 14, wherein the bulky ligand is selected from compounds of formulae A through W and mixtures thereof, where A through W are as defined below.

[0104] E.19. The method defined in embodiment 18, wherein the bulky ligand is selected from compounds of formula D, V, W, and mixtures thereof.

[0105] E.20. The method defined in embodiment 19, wherein the bulky ligand is a compound of formula D (XPhos).

[0106] E.21. The bulky ligand is a ligand of formula IV, wherein R 2 and R 5 are each independently a C6-C alkyl group optionally substituted by 1, 2, 3, 4 or 5 substituents selected from the group consisting of C1-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 each independently hydrogen or C1-C6-alkyl.

[0107] E.22.R 2 and R 5 22. The process defined in embodiment 21, wherein is 2,6-diisopropylphenyl and Z is -CH=CH-.

[0108] E.23.R 6 However, C1~C 40 -Alkyl, C2-C 40-Alkenyl, C3-C 10 -C1-C6-alkyl having a cycloalkyl ring [wherein C3-C 10 - the cycloalkyl ring may have 1, 2, 3, 4 or 5 C1-C6-alkyl substituents], C6-C 10 -C1-C4-alkyl having an aryl ring [wherein C6-C 10 - the aryl ring may have 1, 2, 3, 4 or 5 substituents selected from the group consisting of C1-C6-alkyl and C1-C6-alkoxy], and C6-C alkyl and C1-C6-alkoxy. 10 The method as defined in any one of the preceding embodiments, wherein the aryl is selected from the group consisting of:

[0109] E.24.R 6 However, C1~C 30 -Alkyl, C6-C 30 The method defined in embodiment 23, wherein the alkyl group is selected from the group consisting of: -alkenyl, and C1-C4-alkyl having a C3-C6-cycloalkyl ring.

[0110] E.25.R 6 However, C1~C 22 25. The method as defined in embodiment 24, wherein the alkyl group is selected from the group consisting of C1-C4-alkyl having a C5-C6-cycloalkyl ring.

[0111] E.26.R 6 However, C1~C 20 26. The method defined in embodiment 25, wherein the C2-C4-alkyl having a cyclohexyl ring is selected from the group consisting of -alkyl, and C2-C4-alkyl having a cyclohexyl ring.

[0112] E.27.R 6 But C8~C 18 27. The method defined in embodiment 26, wherein the alkyl is selected from the group consisting of C2-C4-alkyl having a cyclohexyl ring, and C2-C4-alkyl having a cyclohexyl ring.

[0113] E.28.R 6But C2~C 40 -Alkyl, C2-C 40 -Alkenyl, C3-C 10 -C1-C6-alkyl having a cycloalkyl ring [wherein C3-C 10 - the cycloalkyl ring may have 1, 2, 3, 4 or 5 C1-C6-alkyl substituents], C6-C 10 -C1-C4-alkyl having an aryl ring [wherein C6-C 10 - the aryl ring may have 1, 2, 3, 4 or 5 substituents selected from the group consisting of C1-C6-alkyl and C1-C6-alkoxy], and C6-C alkyl and C1-C6-alkoxy. 10 23. The method defined in any one of embodiments 1 to 22, wherein the aryl is selected from the group consisting of:

[0114] E.29.R 6 But C6~C 30 -Alkyl, C6-C 30 The method as defined in embodiment 28, wherein the alkyl group is selected from the group consisting of: -alkenyl, and C1-C4-alkyl having a C3-C6-cycloalkyl ring.

[0115] E.30.R 6 But C6~C 22 The method defined in embodiment 29, wherein the alkyl is selected from the group consisting of C1-C4-alkyl having a C5-C6-cycloalkyl ring.

[0116] E.31.R 6 But C8~C 20 The method defined in embodiment 30, wherein the alkyl group is selected from the group consisting of C2-C4-alkyl having a cyclohexyl ring, and C2-C4-alkyl having a cyclohexyl ring.

[0117] E.32.R 6 But C8~C 18 32. The method defined in embodiment 31, wherein the alkyl is selected from the group consisting of C2-C4-alkyl having a cyclohexyl ring, and C2-C4-alkyl having a cyclohexyl ring.

[0118] E.33. The silver catalyst Ag1 is a preformed catalyst or is formed in situ by reaction of a silver precatalyst, which is a silver compound or silver salt that does not contain bulky ligands, with a compound of formula III, a carbene of formula IV or a precursor of a carbene of formula IV; If the silver pre-catalyst does not contain a carboxylate ligand V, the silver pre-catalyst may be treated with a corresponding acid R of the carboxylate ligand V. 6 -C(=O)OH or formula R 6 -C(=O)O - M + a salt thereof [wherein M + is a cation equivalent], 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 0.2 to 1.8 mol per mol of silver present in the silver precatalyst, 10. The method as defined in any one of the preceding embodiments.

[0119] E.34. The precursor of the carbene of formula IV is a compound of formula VI,

[0120] [ka] [In the formula, R 2 , R 5 and Z are as defined in any one of embodiments 1, 21, or 22; and X - is the anion equivalent] When compound VI is used, it is used together with a base, 34. The method defined in embodiment 33.

[0121] E.35. The process as defined in embodiment 33 or 34, wherein in the case of the 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 to 1.5 mol per mol of silver present in the silver pre-catalyst.

[0122] E.36. The process as defined in embodiment 35, wherein in the case of the 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 to 1.2 mol per mol of silver present in the silver pre-catalyst.

[0123] E.37. The process as defined in embodiment 36, wherein in the case of the 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 to 1.2 mol per mol of silver present in the silver pre-catalyst.

[0124] E.38. The process as defined in any one of the preceding embodiments, wherein the silver catalyst Ag1 is used in step a) in an amount of 0.001 to 50 mol % relative to the amount of propargyl alcohol of formula II.

[0125] E.39. The process defined in embodiment 38, wherein the silver catalyst Ag1 is used in step a) in an amount of 0.001 to 20 mol % relative to the amount of propargyl alcohol of formula II.

[0126] E.40. The process as defined in embodiment 39, wherein the silver catalyst Ag1 is used in step a) in an amount of 0.005 to 10 mol % relative to the amount of propargyl alcohol of formula II.

[0127] E.41. The 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 % relative to the amount of propargyl alcohol of formula II.

[0128] E.42. The process defined in embodiment 41, wherein the silver catalyst Ag1 is used in step a) in an amount of 0.5 to 3 mol % relative to the amount of propargyl alcohol of formula II.

[0129] E.43. Solvent L1 is at least 10 × 10 -30 The method as defined in any one of the preceding embodiments, wherein the solvent is a polar aprotic solvent having a dipole moment of C m.

[0130] E.44. Solvent L1 is at least 11 × 10 -30 44. The method defined in embodiment 43, wherein the solvent is a polar aprotic solvent having a dipole moment of C m.

[0131] E.45. Solvent L2 is at most 2 × 10 -30 The method as defined in any one of the preceding embodiments, wherein the solvent is a non-polar solvent having a dipole moment of C m.

[0132] E.46. Solvent L2 is at most 1 × 10 -30 46. ​​The method defined in embodiment 45, wherein the solvent is a non-polar solvent having a dipole moment of C m.

[0133] E.47. The method defined in embodiment 46, wherein the solvent L2 is a non-polar solvent having a dipole moment of 0 C·m.

[0134] E.48. Solvent L1 is selected from the group consisting of amides, ureas, nitriles, sulfoxides, sulfones, ethers, esters, carbonates, nitro compounds and mixtures thereof, and solvent L2 is selected from the group consisting of alkanes, cycloalkanes, and C 12 ~C 20 The method as defined in any one of the preceding embodiments, wherein the alkyl group is selected from the group consisting of C1-C2-alkyl esters of fatty acids.

[0135] E.49. The process as defined in embodiment 48, wherein solvent L1 is a polar aprotic solvent selected from the group consisting of formamide, N-methylformamide, N,N-dimethylformamide, N,N-dimethylacetamide, tetramethylurea, N,N-dimethylimidazolinone, N,N-dimethylpropyleneurea, acetonitrile, propionitrile, benzonitrile, dimethyl sulfoxide, sulfolane, dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, nitromethane, nitrobenzene, and mixtures thereof.

[0136] E.50. Solvent L2 is C5-C15 -alkanes, C5-C8-cycloalkanes which may have C1-C2-alkyl substituents, C 12 ~C 20 The method as defined in embodiment 48 or 49, wherein the alkyl ester is selected from the group consisting of C1-C2-alkyl esters of fatty acids and mixtures thereof.

[0137] E.51. - Solvent L1 is acetonitrile and solvent L2 is C5-C 14 -alkanes, C5-C8-cycloalkanes which may have C1-C2-alkyl substituents, and saturated C 12 ~C 20 selected from the group consisting of C1-C2-alkyl esters of fatty acids, or - Solvent L1 is dimethylformamide, and solvent L2 is C5-C 14 -alkanes, C5-C8-cycloalkanes which may have C1-C2-alkyl substituents, and saturated C 12 ~C 20 selected from the group consisting of C1-C2-alkyl esters of fatty acids; 51. The method defined in any one of embodiments 48 to 50.

[0138] E.52. - Solvent L1 is acetonitrile and solvent L2 is C5-C 12 -alkanes and C6-C8-cycloalkanes, or - Solvent L1 is dimethylformamide, and solvent L2 is C5-C 12 -alkanes and C5-C8-cycloalkanes, 52. The method defined in embodiment 51.

[0139] E.53. The process 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.

[0140] E.54. The process defined in embodiment 53, wherein solvent L1 is acetonitrile and solvent L2 is cyclohexane or decane.

[0141] E.55. The process as defined in any one of the preceding embodiments, wherein in step a), propargyl alcohol is present in an amount of 0.1 to 25% by weight, based on the total weight of all solvents used in step a).

[0142] E.56. The process defined in embodiment 55, wherein in step a), propargyl alcohol is present in an amount of 0.5 to 20% by weight, based on the total weight of all solvents used in step a).

[0143] E.57. The process defined in embodiment 56, wherein in step a), propargyl alcohol is present in an amount of 1 to 20% by weight, based on the total weight of all solvents used in step a).

[0144] E.58. The process defined in embodiment 57, wherein in step a), propargyl alcohol is present in an amount of 1 to 15% by weight, based on the total weight of all solvents used in step a).

[0145] E.59. The method as defined in any one of the preceding embodiments, wherein step a) is carried out at a pressure in the range of 0.1 to 200 bar.

[0146] E.60. The method defined in embodiment 59, wherein step a) is carried out at a pressure in the range of 1 to 100 bar.

[0147] E.61. The method defined in embodiment 60, wherein step a) is carried out at a pressure in the range of 5 to 80 bar.

[0148] E.62. The method as defined in any one of the preceding embodiments, wherein step a) is carried out at a temperature in the range of 0 to 100°C.

[0149] E.63. The method defined in embodiment 62, wherein step a) is carried out at a temperature in the range of 10 to 80°C.

[0150] E.64. The method defined in embodiment 63, wherein step a) is carried out at a temperature in the range of 10 to 40°C.

[0151] E.65. The method as defined in any one of the preceding embodiments, wherein in step a), no solvent L2 is used and step b1) is performed.

[0152] E.66. The process as defined in any one of the preceding embodiments, wherein in step c), solvent L1 and solvent L2 are present in an overall weight ratio of 80:20 to 20:80.

[0153] E.67. The process defined in embodiment 66, wherein in step c), solvent L1 and solvent L2 are present in an overall weight ratio of 70:30 to 30:70.

[0154] E.68. The process as defined in embodiment 67, wherein in step c), solvent L1 and solvent L2 are present in an overall weight ratio of 60:40 to 40:60.

[0155] E.69. The process as defined in any one of the preceding embodiments, wherein the product phase obtained in step c) contains more than 50 wt. % of the cyclic carbonate I formed in step a) and the catalyst phase contains more than 50 wt. % of the silver catalyst.

[0156] E.70. The process as defined in embodiment 69, wherein the product phase obtained in step c) contains more than 66.7 wt.% of the cyclic carbonate I formed in step a) and the catalyst phase contains more than 66.7 wt.% of the silver catalyst.

[0157] E.71. The process as defined in embodiment 70, wherein the product phase obtained in step c) contains more than 83.3 wt.% of the cyclic carbonate I formed in step a) and the catalyst phase contains more than 83.3 wt.% of the silver catalyst.

[0158] R 1 base In compounds I and II, R 1is an organic group. As explained above, this group may be derived from a separate molecule or from a polymer. R 1 When R is derived from a polymer, the starting compound II generally contains more than one -C≡C-CHOH group (logically the final product will contain more than one cyclic carbonate group, typically attached via a vinylidene group). As already explained above, this group may be attached 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 susceptible to esterification (or transesterification) reactions, or containing an oxiranyl ring, such as present in a glycidyl residue, or containing a chlorohydrin residue or an isocyanate group (-NCO) or other group in the side chain that can react with an alcohol group, may be reacted with 1,4-butynediol or another diol containing a propargyl alcohol group to give the (polymeric) compound II, where R 1 can be obtained from a polymer containing a large number of -C≡C-CH2OH groups in its side chains. If the monomer is reacted with 1,4-butynediol or another diol, a polymer is naturally obtained after polymerization of this monomer. In the product I resulting from the reaction of the polymer with CO2, R 1is derived from a polymer containing multiple cyclic carbonate groups (more precisely, 1,3-dioxolan-2-on-4-yl rings) linked via exocyclic vinylidene groups. Alternatively, a monomer can first be reacted with CO under the reaction conditions described above and below to obtain a monomer containing an exocyclic vinylidene-linked cyclic carbonate, followed by polymerization of the monomer. Alternatively, a monomer can first be reacted with CO under the reaction conditions described above and below to obtain a monomer containing an exocyclic vinylidene-linked cyclic carbonate, followed by polymerization of the monomer. By way of example only, polyacrylic or polymethacrylic acid or transesterification-prone polyacrylates or polymethacylates can be esterified with 1,4-butynediol to give polymers having the repeating unit -[CH2-CH(C(=O)OCH2C≡CH2OH)]- or -[CH2-CCH3(C(=O)OCH2C≡CH2OH)]-, or polyacrylates containing NCO groups in the alcohol-derived portion of the ester (e.g., alcohol-derived portion derived from HO-CH2CH2-NCO). Polyacrylates or polymethacrylates can be reacted with 1,4-butynediol in an addition reaction to obtain polymers having the 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 polyacrylates or polymethacrylates containing glycidyl or chlorohydrin residues can be reacted with 1,4-butynediol in an addition or substitution reaction. Alternatively, the corresponding acrylate or methacrylate monomers can be first prepared by the above-mentioned esterification / addition / substitution reaction and then polymerized. In yet another alternative, the corresponding acrylate or methacrylate monomers can be grafted onto a polymer having a suitable backbone, such as a polyethylene or polypropylene polymer. However, the polymer residues are not limited to these few examples.The polymer residues can be derived from very different polymer types, such as polymers with polyolefin backbones, poly(meth)acrylates, polyesters, polyethers, polyurethanes, polyureas, polyamides, polycarbonates, and the like.

[0159] Simply for the avoidance of any doubt, R 1 are derived from separate molecules, the starting compound may nevertheless naturally contain more than one —C≡C—CHOH group (logically the final compound will also contain more than one cyclic carbonate group attached via the vinylidene group).

[0160] In a preferred embodiment, the cyclic carbonate is compound Ia, compound Ib, or a mixture thereof, wherein R 1 is selected from the group consisting of hydrogen, an aliphatic group, an alicyclic group, an aromatic group, a mixed aliphatic-alicyclic group, a mixed aliphatic-aromatic group, a mixed alicyclic-aromatic group, and a mixed aliphatic-alicyclic-aromatic group; the aliphatic, alicyclic and / or aromatic residues in the aliphatic, alicyclic, aromatic, mixed aliphatic-alicyclic, mixed aliphatic-aromatic, mixed alicyclic-aromatic and mixed aliphatic-alicyclic-aromatic groups may be substituted by one or more halogen atoms; The aliphatic, cycloaliphatic and aromatic groups have at least one of the following characteristics (i) and / or (ii), and the mixed aliphatic-cycloaliphatic, mixed aliphatic-aromatic, mixed cycloaliphatic-aromatic and mixed aliphatic-cycloaliphatic-aromatic groups have at least one of the following characteristics (i), (ii) and / or (iii). (i) The aliphatic, alicyclic, aromatic, mixed aliphatic-alicyclic, mixed aliphatic-aromatic, mixed alicyclic-aromatic, and mixed aliphatic-alicyclic-aromatic groups are each independently selected from the group consisting of 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 )- is interrupted by, (ii) Aliphatic, alicyclic, aromatic, mixed aliphatic-alicyclic, mixed aliphatic-aromatic, mixed alicyclic-aromatic, and mixed aliphatic-alicyclic-aromatic groups are defined as -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 having one or more substituents selected from the group consisting of (iii) The aliphatic, alicyclic and aromatic residues in the mixed aliphatic-alicyclic, mixed aliphatic-aromatic, mixed alicyclic-aromatic and mixed aliphatic-alicyclic-aromatic radicals are not limited to the 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 )-, R 13 are each independently hydrogen or C1 to C 10 - alkyl.

[0161] In a more preferred embodiment, the cyclic carbonate is compound Ia, compound Ib, or a mixture thereof; In the formula, R 1 is hydrogen and -OR 14 is selected from the group consisting of C1-C4-alkyl having a group, R 14is hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, 1, 2 or 3 R 15 C1-C6-alkyl having a group, 1, 2 or 3 R 15 C1-C6-haloalkyl having a group; -C(=O)R 16 , C3-C6-cycloalkyl, 1, 2 or 3 R 17 C3-C6-cycloalkyl having a group; phenyl and 3-, 4-, 5- or 6-membered saturated, partially unsaturated or maximally unsaturated heterocyclic rings containing 1, 2 or 3 heteroatoms selected from N, O and S as ring members, wherein phenyl and the heterocyclic ring may carry one or more substituents selected from the group consisting of C1-C4-alkyl and C1-C4-alkoxy, R 15 is selected from the group consisting of OH, C1-C6-alkoxy, oxiranyl, phenyl, and 3-, 4-, 5-, or 6-membered saturated heterocyclic rings containing one or two oxygen atoms as ring members; R 16 is C1-C6-alkyl, C2-C6-alkenyl, C1-C4-alkoxy and -NR 18 R 19 and R 18 is hydrogen or C1-C4-alkyl, and R 19 is hydrogen, C1-C4 alkyl, R 20 C1-C4-alkyl substituted by groups, and phenyl which may have 1, 2, 3, 4 or 5 substituents selected from the group consisting of C1-C4-alkyl and C1-C4-alkoxy, R 20 -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 )-R21 , -N(R 13 )-C(=O)-OR 21 and -N(R 13 )-C(=O)-N(R 13 )-R 21 and R 21 is hydrogen, C1-C6-alkyl or C2-C6-alkenyl, R 13 are each independently hydrogen or C1 to C 10 -alkyl, R 17 -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 and R 21 is hydrogen, C1-C6-alkyl or C2-C6-alkenyl, R 13 are each independently as defined above (i.e., hydrogen or C1-C 10 -alkyl), Or the cyclic carbonate is a compound of formula I-bis

[0162] [ka] [In the formula, A is an aliphatic bridging group, an alicyclic bridging group, an aromatic bridging group, a mixed aliphatic-alicyclic bridging group, a mixed aliphatic-aromatic bridging group, a mixed alicyclic-aromatic bridging group, or a mixed aliphatic-alicyclic-aromatic bridging group; the aliphatic, alicyclic and / or aromatic residues in the aliphatic, alicyclic, aromatic, mixed aliphatic-alicyclic, mixed aliphatic-aromatic, mixed alicyclic-aromatic and mixed aliphatic-alicyclic-aromatic groups may be substituted by one or more halogen atoms; The aliphatic, cycloaliphatic or aromatic bridging group has at least one of the following characteristics (i) and / or (ii); 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): (i) The aliphatic, alicyclic and / or aromatic residues in the aliphatic bridging group, alicyclic bridging group, aromatic bridging group, mixed aliphatic-alicyclic bridging group, mixed aliphatic-aromatic bridging group, mixed alicyclic-aromatic bridging group, or mixed aliphatic-alicyclic-aromatic bridging group are not separated 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 )- is interrupted by, (ii) An aliphatic bridging group, an alicyclic bridging group, an aromatic bridging group, a mixed aliphatic-alicyclic bridging group, a mixed aliphatic-aromatic bridging group, a mixed alicyclic-aromatic bridging group, or a mixed aliphatic-alicyclic-aromatic bridging group is not an -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 having one or more substituents selected from the group consisting of (iii) The aliphatic, alicyclic and / or aromatic residues in the aliphatic-alicyclic mixed bridging group, the aliphatic-aromatic mixed bridging group, the alicyclic-aromatic mixed bridging group or the aliphatic-alicyclic-aromatic mixed bridging group are not represented by the 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 )-, R 13 are each independently hydrogen or C1 to C 10 -alkyl].

[0163] As a result, the propargyl alcohol is preferably a compound of formula II, where R 1 is hydrogen and -OR 14 C1-C4-alkyl having a group, R 14 is as defined in the above preferred embodiment of the cyclic carbonate, or the propargyl alcohol is a compound of formula II-bis

[0164] [ka] wherein A is as defined in the above preferred embodiment of the cyclic carbonate I-bis.

[0165] More preferably, the cyclic carbonate is compound Ia, compound Ib, or a mixture thereof, wherein R 1 is hydrogen and -CH2-OR 14 is selected from the group consisting of R 14 is hydrogen, 1, 2 or 3 R 15 C1-C4-Alkyl with a group; -C(=O)R 16 , and 1, 2 or 3 R 17is selected from the group consisting of C3-C6-cycloalkyl having a group, R 15 is selected from the group consisting of OH, C1-C4-alkoxy, phenyl, and 3-, 4-, 5-, or 6-membered saturated heterocyclic rings containing one or two oxygen atoms as ring members, R 16 is C1-C6-alkyl, C2-C6-alkenyl, C1-C4-alkoxy and -NR 18 R 19 and R 18 is hydrogen or C1-C4-alkyl, and R 19 is hydrogen, C1-C4 alkyl, R 20 C1-C4-alkyl substituted by groups, and phenyl which may have 1, 2, 3, 4 or 5 substituents selected from the group consisting of C1-C4-alkyl and C1-C4-alkoxy, R 20 -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 and R 21 is hydrogen, C1-C6-alkyl or C2-C6-alkenyl, R 13 are each independently hydrogen or C1 to C 10 -alkyl, R 17 -OR 21 , -N(R 13 )-R 21 , -OC(=O)-R21 , -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 and R 21 is hydrogen, C1-C6-alkyl or C2-C6-alkenyl, R 13 are each independently hydrogen or C1 to C 10 -alkyl, or the cyclic carbonate is a compound of formula I-bis as defined above, wherein A is a bridging group: -CH2-O-CH2-1,4-phenylene-CH2-O-CH2-; -CH2-OC(=O)-NH-1,4-toluylene-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-, the result, The propargyl alcohol is more preferably a compound of formula II, wherein R 1 is hydrogen and -CH2-OR 14 and R 14 is as defined in the above more preferred embodiments of the cyclic carbonate, or the propargyl alcohol is a compound of formula II-bis, where A is as defined in the above more preferred embodiments of the cyclic carbonate.

[0166] 1,4-Toluylene is a divalent group of the formula:

[0167] [ka] # represents the point of attachment (to NH in the above formula).

[0168] Even more preferably, the cyclic carbonate is compound Ia, compound Ib, or a mixture thereof, wherein R 1 is hydrogen and -CH2-OR 14 is selected from the group consisting of R 14 is hydrogen, 1, 2 or 3 R 15 C1-C4-alkyl having a group; -C(O)CH3, -C(=O)H and -C(O)OCH3, R 15 is selected from the group consisting of OH and C1-C4-alkoxy, or the cyclic carbonate is a compound of formula I-bis as defined above, wherein A is —CH—O—CH—CH(OH)—CH—O-1,4-phenylene-C(CH)—1,4-phenylene-O—CH—CH(OH)—CH—O—CH—; the result, Propargyl alcohols are in particular compounds of formula II, in which R 1 is hydrogen and -CH2-OR 14 and R 14 is as defined in the above specific embodiments of the cyclic carbonate, or the propargyl alcohol is a compound of formula II-bis, where A is as defined in the above specific embodiments of the cyclic carbonate.

[0169] In particular, the cyclic carbonate is compound Ia, compound Ib or a mixture thereof, wherein R 1 is hydrogen and -CH2-OR 14 is selected from the group consisting of R 14 is a hydrogen atom and one or two R 15is selected from the group consisting of C1-C4-alkyl having a group, R 15 is selected from the group consisting of OH and C1-C4-alkoxy, or the cyclic carbonate is a compound of formula I-bis as defined in embodiment 6, wherein A is —CH—O—CH—CH(OH)—CH—O-1,4-phenylene-C(CH)—1,4-phenylene-O—CH—CH(OH)—CH—O—CH—; the result, Propargyl alcohol is a compound of formula II, where R 1 is hydrogen and -CH2-OR 14 and R 14 is as defined above, or the propargyl alcohol is a compound of formula II-bis as defined in embodiment 6, where A is as defined above.

[0170] In particular, the cyclic carbonate is compound Ia, compound Ib, or a mixture thereof, wherein R 1 is hydrogen and -CH2-OR 14 and R 14 is —CH—CH(OH)—CH—OC(CH) or —CH—CH(OH)—CH—OH, or the cyclic carbonate is a compound of formula I-bis as defined in embodiment 6, wherein A is —CH—O—CH—CH(OH)—CH—O-1,4-phenylene-C(CH)-1,4-phenylene-O—CH—CH(OH)—CH—O—CH—; the result, Propargyl alcohol is a compound of formula II, where R 1 is hydrogen and -CH2-OR 14 and R 14is —CH—CH(OH)—CH—OC(CH) or —CH—CH(OH)—CH—OH, or the propargyl alcohol is a compound of formula II-bis as defined in embodiment 6, where A is —CH—O—CH—CH(OH)—CH—O-1,4-phenylene-C(CH)-1,4-phenylene-O—CH—CH(OH)—CH—O—CH—.

[0171] In more particular embodiments, the cyclic carbonate is compound Ia, compound Ib, or a mixture thereof, wherein R 1 is hydrogen and -CH2-OR 14 and R 14 is —CH—CH(OH)—CH—OC(CH) or the cyclic carbonate is a compound of formula I-bis as defined above, wherein A is —CH—O—CH—CH(OH)—CH—O-1,4-phenylene-C(CH)-1,4-phenylene-O—CH—CH(OH)—CH—O—CH—; As a result, propargyl alcohols are, inter alia, compounds of formula II, in which R 1 is hydrogen and -CH2-OR 14 and R 14 is -CH2-CH(OH)-CH2-OC(CH3)3, or the propargyl alcohol is a compound of formula II-bis as defined above, where 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-.

[0172] This latter bridging group A has the formula:

[0173] [ka] where # is the point of attachment to the exocyclic vinylidene group in I-bis and the triple bond in II-bis.

[0174] Specifically, the cyclic carbonate is compound Ia, compound Ib, or a mixture thereof, wherein R 1 is hydrogen, and propargyl alcohol is a compound of formula II, where R 1 is hydrogen.

[0175] In an alternative embodiment, R 1 is derived from the polymer.

[0176] Suitable polymers are, for example, polyolefins (more precisely, polymers with a polyolefin backbone), poly(meth)acrylates, polyesters, polyethers, polyurethanes, polyureas, polyamides, polycarbonates, and mixed forms thereof, i.e. polymers containing, in polymerized form, monomers characteristic of different types of said polymers, such as polyolefins grafted with (meth)acrylates, resulting in polymers with a polyolefin backbone and poly(meth)acrylate side chains, or block copolymers with blocks derived from different polymer types, or polymers resulting from the reaction of isocyanates with both amines and alcohols, etc. In particular, the polymer is a poly(meth)acrylate, in particular a polymethacrylate.

[0177] R 1 When derived from a polymer, the cyclic carbonate is preferably a compound of formula I-poly

[0178] [ka] [In the formula, X is a bond or a group -C(=O)-; # -C(=O)-O-* or # -C(=O)-N(R 13 )-*, where: # is the point of attachment to O, * is the point of attachment to Y (or to Z if Y is a bond, or to poly if Y and Z are bonds), Y is a bond, or a divalent aliphatic bridging group, alicyclic bridging group, aromatic bridging group, aliphatic-alicyclic mixed bridging group, aliphatic-aromatic mixed bridging group, alicyclic-aromatic mixed bridging group, or aliphatic-alicyclic-aromatic mixed bridging group, in which the aliphatic, alicyclic and / or aromatic residues in the aliphatic bridging group, alicyclic bridging group, aromatic bridging group, aliphatic-alicyclic mixed bridging group, aliphatic-aromatic mixed bridging group, alicyclic-aromatic mixed bridging group, and aliphatic-alicyclic-aromatic mixed bridging group are optionally substituted with one or more halogen atoms; The aliphatic, cycloaliphatic or aromatic bridging group may have at least one of the following characteristics (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 characteristics (i), (ii) and / or (iii): (i) The aliphatic, alicyclic and / or aromatic residues in the aliphatic bridging group, alicyclic bridging group, aromatic bridging group, mixed aliphatic-alicyclic bridging group, mixed aliphatic-aromatic bridging group, mixed alicyclic-aromatic bridging group, or mixed aliphatic-alicyclic-aromatic bridging group are not separated 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 )- is interrupted by, (ii) An aliphatic bridging group, an alicyclic bridging group, an aromatic bridging group, a mixed aliphatic-alicyclic bridging group, a mixed aliphatic-aromatic bridging group, a mixed alicyclic-aromatic bridging group, or a mixed aliphatic-alicyclic-aromatic bridging group is not an -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 having one or more substituents selected from the group consisting of (iii) The aliphatic, alicyclic and / or aromatic residues in the aliphatic-alicyclic mixed bridging group, the aliphatic-aromatic mixed bridging group, the alicyclic-aromatic mixed bridging group or the aliphatic-alicyclic-aromatic mixed bridging group are not represented by the 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 )-, R 13 are each independently hydrogen or C1 to C 10 -alkyl, Z is a bond or a group -C(=O)- when X and Y are bonds; # -C(=O)-O-* or # -C(=O)-N(R 13 )-*, where: # 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 Z is a group in which Y is a bond and X is a group -C(=O)-; # -C(=O)-O*- or # -C(=O)-N(R 13 )-*, where: # is the point of attachment to O, or Z is a bond or a 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 )-*, where: # is the point of attachment to Y, n is 1 to 1000, Poly is a residue derived from a polymer having a number average molecular weight of 200 to 10,000. Propargyl alcohol is a compound of formula II-poly.

[0179] [ka] wherein X, Y, Z, n and poly are as defined above. More preferably, X is a bond or a group -C(=O)- or # -C(=O)-N(R 13 )-*, where: # is the point of attachment to O, * is the point of attachment to Y (or to Z if Y is a bond, or to poly if Y and Z are bonds), Y is a bond or a divalent aliphatic bridging group or a mixed aliphatic-alicyclic bridging group having 1 to 10 carbon atoms, the aliphatic bridging group or the mixed aliphatic-alicyclic bridging group optionally being substituted with one or more halogen atoms; The aliphatic bridging group may have at least one of the following characteristics (i) and / or (ii), and the mixed aliphatic-alicyclic bridging group may have at least one of the following characteristics (i), (ii) and / or (iii): (i) the aliphatic-aliphatic and / or alicyclic residues in the aliphatic bridging group or the mixed aliphatic-alicyclic bridging group are interrupted by one or more non-adjacent groups -O-, -O-C(=O)-, -C(=O)-O-, and / or -O-C(=O)-O-; (ii) the aliphatic bridging group or mixed aliphatic-alicyclic bridging group has one or more substituents selected from the group consisting of -OH, -OC(=O)H, and -C(=O)OH; (iii) the aliphatic and / or alicyclic residues in the mixed aliphatic-alicyclic bridging group are bonded to each other via the groups -O-, -OC(=O)-, -C(=O)-O-, or -OC(=O)-O; Z is a bond or a group -C(=O)- when X and Y are bonds; or Z is a bond when Y is a bond and X is a group -C(=O)-; or Z is a bond or a group when Y is a divalent aliphatic bridging group or a mixed aliphatic-alicyclic bridging group. # -OC(=O)-, Poly is a residue derived from a poly-α-olefin or from a poly(meth)acrylate, in particular from a poly(meth)acrylate, particularly from a polymethacrylate.

[0180] In particular, -XYZ- together form -C(=O)-, # -CH2-CH(OH)-CH2-OC(=O)-* or # -C(=O)-NH-CH2CH2-OC(=O)-*, where # is the point of attachment to O, and * is the point of attachment to poly. In this case, when poly is derived from poly(meth)acrylate, the polymer I-poly contains [-CH-CH-(ZYXO-CH-CH=(1,3-dioxolan-2-one-4-diyl)] or [-CH-C(CH)-(ZYXO-CH-CH=(1,3-dioxolan-2-one-4-diyl)] repeating units.

[0181] Separate molecule- and polymer-derived R 1of which R are derived from distinct molecules, in particular R derived from distinct molecules as defined above 1 is preferred.

[0182] catalyst In one preferred embodiment, the bulky ligand in the silver catalyst is a ligand of formula III: In another preferred embodiment, the bulky ligand in the silver catalyst is a ligand of formula IV: Of these, ligand III is more preferred.

[0183] Preferably, in the bulky ligand of formula III: D is P or As; R 2 is a monocyclic or polycyclic C3-C 40 -cycloalkyl, monocyclic or polycyclic C3-C 40 -Cycloalkenyl, C6-C 40 - a cyclic group selected from the group consisting of aryl and 3-40 membered saturated, partially unsaturated or maximally unsaturated monocyclic or polycyclic heterocyclic rings, which may be linked to D via an oxygen atom, and which may be C1-C6-alkyl, C1-C6-alkoxy, 1, 2, 3 or 4 R 22 phenyl optionally substituted by a substituent, 1, 2, 3 or 4 R 22 naphthyl optionally substituted by substituents, containing 1, 2, 3 or 4 heteroatoms selected from the group consisting of N, O and S as ring members, and 1, 2 or 3 R 23 monocyclic 5- or 6-membered heteroaromatic rings optionally substituted by substituents and containing 1, 2, 3, or 4 heteroatoms selected from the group consisting of N, O, and S as ring members, and 1, 2, or 3 R 23 and optionally substituted fused bicyclic 8- to 10-membered heteroaromatic ring systems, R 22 are each independently C1-C6-alkyl, C1-C6-alkoxy, NR 24 R 25 [where R 24 and R 25 are each independently hydrogen or C1-C12 -alkyl], phenyl, naphthyl and monocyclic saturated, partially unsaturated or maximally unsaturated 5- or 6-membered heterocyclic radicals containing as ring members 1, 2, 3 or 4 heteroatoms selected from the group consisting of N, O and S, the last three mentioned cyclic radicals optionally bearing 1, 2, 3, 4 or 5 substituents selected from the group consisting of halogen, C1-C4-alkyl and C1-C4-alkoxy, R 23 are each independently, R 22 has one of the meanings described for R 3 and R 4 are each independently C1-C6-alkyl, monocyclic or polycyclic C3-C 40 -cycloalkyl, monocyclic or polycyclic C3-C 40 -Cycloalkenyl and C6-C 10 -aryl.

[0184] More preferably, D is P, R 2 is 1, 2, 3 or 4 R 22 phenyl optionally substituted by a substituent, 1, 2, 3 or 4 R 22 ortho-biphenyl optionally substituted by a substituent, 1, 2, 3 or 4 R 22 naphthyl optionally substituted by a substituent, 1, 2, 3 or 4 R 22 ortho-binaphthyl optionally substituted by substituents, containing 1, 2 or 3 nitrogen atoms as ring members and 1, 2 or 3 R 23 monocyclic 5- or 6-membered heteroaromatic rings optionally substituted by substituents and containing 1, 2, or 3, or 4 nitrogen atoms as ring members and 1, 2, or 3 R 23 a fused bicyclic 8- to 10-membered heteroaromatic ring system optionally substituted by substituents; R 22 are each independently C1-C4 alkyl, C1-C4 alkoxy, NR 24 R 25[where R 24 and R 25 are each independently hydrogen or C1-C 10 -alkyl], phenyl optionally substituted by 1, 2, 3, 4 or 5 substituents selected from the group consisting of halogen, C1-C4-alkyl and C1-C4-alkoxy, and monocyclic saturated, partially unsaturated or maximally unsaturated 5- or 6-membered heterocyclic rings containing as ring members 1, 2 or 3 heteroatoms selected from the group consisting of N and O, R 23 are each independently phenyl optionally substituted by 1, 2, 3, 4 or 5 substituents selected from the group consisting of halogen, C1-C4-alkyl and C1-C4-alkoxy, R 3 and R 4 are independently selected from the group consisting of branched C3-C6-alkyl, monocyclic C3-C6-cycloalkyl, and adamantylphenyl.

[0185] in particular, D is P, R 2 is NR 24 R 25 phenyl substituted by 24 and R 25 are each independently hydrogen or C1-C 10 -alkyl, preferably C3 to C 10 -alkyl], or 1, 2, 3 or 4 R 22 ortho-biphenyl substituted by a substituent, R 22 are each independently C1-C4 alkyl and NR 24 R 25 [where R 24 and R 25 are each independently hydrogen or C1-C 10 -Alkyl, preferably C3-C 10 -alkyl.

[0186] In particular, the bulky ligand is selected from compounds of formulae A to W and mixtures thereof:

[0187] [ka] TIFF0007778699000032.tif125153 [wherein Me is methyl, Cy is cyclohexyl, i-Pr is isopropyl, Ph is phenyl, and t-Bu is tert-butyl]

[0188] The above ligands are known as Buchwald ligands, many of which 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).

[0189] In a specific embodiment, XPhos (a compound of formula D), a ligand of formula V, a ligand of formula W, or a mixture of V and W, is used as ligand III. Very specifically, a compound of formula D (XPhos) is used.

[0190] In the ligand of formula IV, the double dot indicates that the ligand is a carbene. Therefore, ligand IV is also called an N-heterocyclic carbene ligand, or NHC-ligand for short. A silver catalyst containing NHC ligand IV can be depicted as follows:

[0191] [ka]

[0192] Preferably, in the ligand of formula IV, R 2 and R 5are each independently a C6-C alkyl group optionally substituted by 1, 2, 3, 4 or 5 substituents selected from the group consisting of C1-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 each independently hydrogen or C1-C6-alkyl. In particular, R 2 and R 5 is 2,6-diisopropylphenyl and Z is -CH=CH-.

[0193] R 6 is preferably C1 to C 40 -Alkyl, C2-C 40 -Alkenyl, C3-C 10 -C1-C6-alkyl having a cycloalkyl ring [wherein C3-C 10 - the cycloalkyl ring may have 1, 2, 3, 4 or 5 C1-C6-alkyl substituents], C6-C 10 -C1-C4-alkyl having an aryl ring [wherein C6-C 10 - the aryl ring may have 1, 2, 3, 4 or 5 substituents selected from the group consisting of C1-C6-alkyl and C1-C6-alkoxy], and C6-C alkyl and C1-C6-alkoxy. 10 -aryl. More preferably, R 6 is C1~C 40 -Alkyl, C2-C 40 -alkenyl, and C1-C4-alkyl with a C3-C6-cycloalkyl ring. Even more preferably, R 6 is C1~C 30 -Alkyl, C6-C 30 from the group consisting of alkenyl and C1-C4-alkyl with a C3-C6-cycloalkyl ring, in particular C1-C 22-alkyl and C1-C4-alkyl having a C5-C6-cycloalkyl ring, specifically C1-C 20 -alkyl and C2-C4-alkyl with a cyclohexyl ring, very particularly C8-C 18 -alkyl, and C2-C4-alkyl having a cyclohexyl ring.

[0194] R 6 is an alkyl group, the carboxylate R 6 -COO - is derived from a natural or synthetic saturated fatty acid having more preferably 2 to 41 carbon atoms, even more preferably 2 to 31 carbon atoms, in particular 2 to 23 carbon atoms, particularly 2 to 21 carbon atoms, and very particularly 9 to 19 carbon atoms; R 6 is an alkenyl group, the carboxylate R 6 -COO - R is derived from a natural or synthetic unsaturated fatty acid, more preferably having 3 to 41 carbon atoms, even more preferably having 7 to 31 carbon atoms. 6 is an alkyl group, the carboxylate R 6 -COO - are derived in particular from natural or synthetic saturated fatty acids having 2 to 23 carbon atoms, particularly saturated fatty acids having 2 to 21 carbon atoms, very particularly saturated fatty acids having 9 to 19 carbon atoms.

[0195] In specific embodiments, R 6 is lipophilic and therefore preferably has at least 2 carbon atoms. In view of the above, in this case, R 6 is preferably C2 to C 40 -Alkyl, C2-C 40 -Alkenyl, C3-C 10 -C1-C6-alkyl having a cycloalkyl ring [wherein C3-C 10 - the cycloalkyl ring may have 1, 2, 3, 4 or 5 C1-C6-alkyl substituents], C6-C 10 -C1-C4-alkyl having an aryl ring [wherein C6-C10 - the aryl ring may have 1, 2, 3, 4 or 5 substituents selected from the group consisting of C1-C6-alkyl and C1-C6-alkoxy], and C6-C alkyl and C1-C6-alkoxy. 10 -aryl. More preferably, in this case, R 6 is C2~C 40 -Alkyl, C2-C 40 -alkenyl, and C1-C4-alkyl with a C3-C6-cycloalkyl ring. Even more preferably, R 6 C6~C 30 -Alkyl, C6-C 30 from the group consisting of alkenyl and C1-C4-alkyl with a C3-C6-cycloalkyl ring, in particular C6-C 22 -alkyl and C1-C4-alkyl having a C5-C6-cycloalkyl ring, specifically C8-C 20 -alkyl and C2-C4-alkyl with a cyclohexyl ring, very particularly C8-C 18 -alkyl, and C2-C4-alkyl having a cyclohexyl ring.

[0196] 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 the group of ligands consisting of compounds of formula III and compounds of formula IV, preferably compounds of formula III, and a lipophilic carboxylate ligand according to formula V shown above.

[0197] Alternatively, the silver catalyst Ag1 can be formed in situ in a reaction medium by combining a silver pre-catalyst, which is a silver compound or silver salt that does not contain a bulky ligand, with a compound of formula III, a carbene of formula IV, or a precursor of a carbene of formula IV to form a catalytically active silver complex Ag1 in the reaction medium. If the silver pre-catalyst does not contain a lipophilic carboxylate ion V, the silver pre-catalyst can be formed in situ by combining the silver pre-catalyst with the corresponding acid R of the carboxylate V. 6-C(=O)OH or formula R 6 -C(=O)O - M + a salt thereof [wherein M + is a cation equivalent].

[0198] A suitable precursor to the carbene of formula IV is its protonated form in combination with a base and represented by formula VI.

[0199] [ka] [In the formula, R 2 , R 5 and Z are as defined above, and X - is the anion equivalent]

[0200] Suitable bases for deprotonating the protonated form of various NHC ligands according to formula VI are described by de Fremont et al., Coordination Chemistry Reviews 253 (2009) 876-881. Deprotonation of the protonated form of the NHC ligand can be carried out in ammonia or in an aprotic solvent such as THF or ether. Deprotonation requires anhydrous conditions and a pK a It requires the use of a strong base with a value above 14. Potassium or sodium hydride is usually used with a catalytic amount of tert-butoxide, 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 efficient alternatives.

[0201] Silver compounds useful as precatalysts include, for example, Ag(OAc) (OAc = acetate), AgF, AgNO, silver trifluoroacetate, AgO, AgCO, and Ag(OOCR). 6) is any silver salt having a lipophilic carboxylate ion according to Formula V, which is written as follows: When Ag(OAc), AgF, AgNO3, silver trifluoroacetate, Ag2O, or Ag2CO3 is used as a precatalyst, the lipophilic carboxylate ligand also reacts with the free acid HOOCR 6 or any salt R 6 -C(=O)O - M + of the form [where M + is the cation equivalent]. Suitable cation equivalents are metal cations, such as alkali metal cations, e.g., Li + , Na + , K. + , Cs + or Rb + , or alkaline earth metal cations, e.g., Ca 2+ , Mg 2+ , Sr 2+ Or Ba 2+ or ammonium cation NR4 + [wherein R is independently hydrogen, C1 to C 10 -Alkyl or C1-C 10 -alkoxy]. Thus, salts can be, for example, M1(OOCR 6 ) [where M1 is Li + , Na + , K. + , Cs + , Rb + or NR4 + ], or M2(OOCR 6 )2 [where M2 is Ca 2+ , Mg 2+ , Sr 2+ or Ba 2+ Preferably, the pre-catalyst is Ag(OOCR 6 )

[0202] 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 per mol of silver present in the silver pre-catalyst. 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 to 1.8 mol, preferably 0.3 to 1.5 mol, particularly 0.4 to 1.2 mol, specifically 0.8 to 1.2 mol per mol of silver present in the silver pre-catalyst, and very particularly in an amount approximately equimolar to the amount of silver present in the silver pre-catalyst.

[0203] Preferably, for practical and economic reasons, the catalyst is formed in situ in step a).

[0204] The amount of silver catalyst Ag1 used in process step a) relative to the amount of propargyl alcohol of formula II can vary within a wide range. Usually, silver catalyst Ag1 is used in a substoichiometric amount relative to the amount of propargyl alcohol of formula II. Typically, the amount of silver catalyst Ag1 is 50 mol % or less, frequently 20 mol % or less, particularly 10 mol % or less, or 5 mol % or less, or 3 mol % or less, relative to the amount of propargyl alcohol of formula II. Silver catalyst Ag1 is preferably used in step a) in an amount of 0.001 to 50 mol %, more preferably 0.001 to 20 mol %, particularly 0.005 to 10 mol %, specifically 0.01 to 5 mol %, and very specifically 0.05 to 3 mol %, relative to the amount of propargyl alcohol of formula II. The catalyst amount is related to the amount of silver contained therein.

[0205] solvent In the method of the present invention, solvents L1 and L2 are used. A "solvent" is a substance that dissolves a solute (chemically different liquid, solid, or gas) to form a solution. A solution is a homogeneous mixture in which a gaseous, liquid, or solid solute is dissolved in the solvent. A homogeneous mixture is composed of two or more substances, solute particles are not visible to the naked eye, and light is not scattered. In this context, solvents L1 and L2 are liquid at 20°C. Solvents L1 and L2 have different polarities and therefore different solvating powers for different solutes. Solvent L1 has weak solvating power for non-polar starting materials or products, while solvent L2 has weak solvating power for polar starting materials or products. Therefore, in this context, the term "solvent" is not limited to a compound or medium that strictly dissolves all starting materials, catalyst components, and products. A solvent is more generally understood as a dispersion medium that strictly dissolves only a portion of the starting materials, catalyst components, or products.

[0206] The solvents L1 and L2 used in the method of the present invention have a solubility gap at 1013 mbar at least between 20 and 30°C. The "solubility gap" means that a mixture of solvents L1 and L2 is not stable but demixes to form two distinct phases. One of the two phases consists essentially of solvent L1, and the other consists essentially of solvent L2. "Essentially" means that the phase contains less than 10% by weight, preferably less than 5% by weight, of the other solvent, i.e., the minor solvent, relative to the total weight of solvents L1 and L2. At 20°C, solvent L1 has a solubility in solvent L2 of less than 5 g per liter of L2, preferably less than 2 g per liter of L2, and in particular less than 1 g per liter of L2. Solvent L2 has a solubility in solvent L1 of less than 5 g per liter of L1, preferably less than 2 g per liter of L1, and in particular less than 1 g per liter of L1. Solubility is related to the formation of a homogeneous mixture without phase separation.

[0207] Preferably, the solvents L1 and L2 used in the process of the present invention have a solubility gap of at least 20-80°C at 1013 mbar, more preferably at least 15-100°C at 1013 mbar, in particular over the entire temperature range in which the solvent is liquid at 1013 mbar.

[0208] Preferably, the solvent L1 is at least 10×10 -30 C m, especially at least 11 × 10 -30 It is a polar aprotic solvent with a dipole moment of C m.

[0209] Preferably, the solvent L2 is at most 2×10 -30 C m, preferably at most 1 × 10 -30 It is a nonpolar solvent with a dipole moment of C·m, ​​especially 0 C·m.

[0210] Preferably, the solvent L1 is at least 10×10 -30 A polar aprotic solvent with a dipole moment of C m, solvent L2 is at most 2 × 10 -30 It is a nonpolar solvent with a dipole moment of C m.

[0211] More preferably, the solvent L1 has a concentration of at least 11×10 -30 A polar aprotic solvent with a dipole moment of C m, solvent L2 is at most 1 × 10 -30 It is a nonpolar solvent with a dipole moment of C m.

[0212] In particular, the solvent L1 has a concentration of at least 11 × 10 -30 is a polar aprotic solvent with a dipole moment of 0 C m, and solvent L2 is a nonpolar solvent with a dipole moment of 0 C m.

[0213] Solvent L1 is preferably selected from the group consisting of amides, ureas, nitriles, sulfoxides, sulfones, carbonates, nitro compounds and mixtures thereof.

[0214] Examples of suitable amides include formamide, N-methylformamide, N,N-dimethylformamide and N,N-dimethylacetamide.

[0215] Examples of suitable ureas include tetramethylurea, N,N-dimethylimidazolinone, and N,N-dimethylpropyleneurea.

[0216] Examples of suitable nitriles include acetonitrile, propionitrile and benzonitrile.

[0217] An example of a suitable sulfoxide is dimethyl sulfoxide.

[0218] An example of a suitable sulfene is sulfolane.

[0219] Examples of suitable carbonates include dimethyl carbonate, diethyl carbonate, ethylene carbonate and propylene carbonate.

[0220] Examples of suitable nitro compounds include nitromethane and nitrobenzene.

[0221] L1 is more preferably selected from the group consisting of formamide, N-methylformamide, N,N-dimethylformamide (DMF), N,N-dimethylacetamide, tetramethylurea, N,N-dimethylimidazolinone, N,N-dimethylpropyleneurea, acetonitrile, propionitrile, benzonitrile, dimethyl sulfoxide, sulfolane, dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, nitromethane, nitrobenzene, and mixtures thereof.

[0222] In a specific embodiment, L1 is acetonitrile or DMF, more specifically acetonitrile.

[0223] The solvent L2 is preferably an alkane, a cycloalkane, a C 12 ~C20 - selected from the group consisting of C1-C2-alkyl esters of fatty acids and mixtures thereof.

[0224] Suitable examples of alkanes include C5-C 15 - alkanes, such as pentane, hexane, heptane, octane, nonane, decane, dodecane, tetradecane, pentadecane, their structural isomers and mixtures thereof;

[0225] Examples of suitable cycloalkanes are C5-C8-cycloalkanes which may have C1-C2-alkyl substituents, such as cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, cyclooctane, and the like.

[0226] 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.

[0227] More preferably, the solvent L2 is a C5-C 14 -alkanes, C5-C8-cycloalkanes which may have C1-C2-alkyl substituents, C 12 ~C 20 Even more preferably, the solvent L2 is selected from the group consisting of C1-C2-alkyl esters of fatty acids, C6-C 12 -alkanes, C5-C6-cycloalkanes which may have methyl substituents, C 16 ~C 20 - methyl esters of fatty acids, and mixtures thereof. In particular, the solvent L2 is selected from the group consisting of pentane, hexane, heptane, octane, nonane, decane, dodecane, cyclopentane, cyclohexane, and mixtures thereof.

[0228] In specific embodiments, L2 is cyclohexane, hexane or decane, more specifically cyclohexane or decane, and most specifically cyclohexane.

[0229] In certain embodiments, - Solvent L1 is acetonitrile and solvent L2 is C5-C 14 -alkanes, C5-C8-cycloalkanes which may have C1-C2-alkyl substituents, and saturated C 12 ~C 20 selected from the group consisting of C1-C2-alkyl esters of fatty acids, or - Solvent L1 is dimethylformamide, and solvent L2 is C5-C 14 -alkanes, C5-C8-cycloalkanes which may have C1-C2-alkyl substituents, and saturated C 12 ~C 20 It is selected from the group consisting of C1-C2 alkyl esters of fatty acids.

[0230] In particular, - Solvent L1 is acetonitrile and solvent L2 is C5-C 12 -alkanes, C5-C8-cycloalkanes which may have methyl substituents, and saturated C 16 ~C 20 methyl esters of fatty acids; or - Solvent L1 is dimethylformamide, and solvent L2 is C5-C 12 -alkanes, C5-C8-cycloalkanes which may have methyl substituents, and saturated C 16 ~C 20 The fatty acid methyl esters are selected from the group consisting of:

[0231] In particular, - Solvent L1 is acetonitrile and solvent L2 is C5-C 12 -alkanes and C6-C8-cycloalkanes, or - Solvent L1 is dimethylformamide, and solvent L2 is C5-C 12-alkanes and C5-C8-cycloalkanes.

[0232] in particular, solvent L1 is acetonitrile and solvent L2 is cyclohexane, or - solvent L1 is acetonitrile and solvent L2 is hexane; - solvent L1 is acetonitrile and solvent L2 is octane, or - solvent L1 is acetonitrile and solvent L2 is decane, or - solvent L1 is acetonitrile and solvent L2 is dodecane, or solvent L1 is dimethylformamide and solvent L2 is cyclohexane, or - solvent L1 is dimethylformamide and solvent L2 is hexane, or - solvent L1 is dimethylformamide and solvent L2 is octane, or solvent L1 is dimethylformamide and solvent L2 is decane, or - Solvent L1 is dimethylformamide and solvent L2 is dodecane.

[0233] Very specifically, solvent L1 is acetonitrile and solvent L2 is cyclohexane, or - solvent L1 is acetonitrile and solvent L2 is decane, or - Solvent L1 is dimethylformamide and solvent L2 is hexane.

[0234] Of these, it is preferred that the solvent L1 is acetonitrile and the solvent L2 is cyclohexane or decane.

[0235] In step a), the propargyl alcohol is preferably present in an amount of 0.1 to 25% by weight, more preferably 0.5 to 20% by weight, in particular 1 to 20% by weight, for example 1 to 15% by weight, based on the total weight of all solvents used in step a).

[0236] The CO2 used in the carboxylation-cyclization reaction can be used in pure form or, if desired, in admixture with other gases, preferably inert gases such as nitrogen or argon. It is preferred to use CO2 in undiluted form.

[0237] The reaction is typically carried out at a CO2 pressure in the range of 0.1 to 200 bar, preferably in the range of 1 to 100 bar, more preferably in the range of 5 to 80 bar, and especially in the range of 10 to 70 bar. If the CO2 is in undiluted form, the pressure is applied by CO2. In this case, the reaction is typically carried out at a CO2 pressure in the range of 0.1 to 200 bar, preferably in the range of 1 to 100 bar, more preferably in the range of 5 to 80 bar, and especially in the range of 10 to 70 bar.

[0238] If the reaction conditions are such that CO2 is liquid (e.g., pressures above 57.3 bar at 20°C) or in its supercritical phase (pressures above 73.8 bar at temperatures above 31°C), CO2 can under certain conditions also act as an additional solvent or solubilizer for the two liquid phases formed by solvents L1 and L2 (if step a) is carried out in the presence of solvent L2).

[0239] Process step a) can be carried out over a wide temperature range: the reaction can be carried out at a temperature in the range of 0 to 150°C, although it is understood that high temperatures are not required, and the reaction is preferably carried out at a temperature in the range of 0 to 100°C, more preferably 10 to 80°C, especially 10 to 40°C.

[0240] The reaction can be carried out primarily continuously, semi-continuously or discontinuously, with continuous processes being preferred.

[0241] The reaction can be carried out in all reactors known by those skilled in the art for this type of reaction, and the reactor is selected accordingly.Suitable reactors are described and summarized in the relevant prior art, such as appropriate monographs and references, for example, US Pat. No. 6,639,114, column 16, lines 45-49.Preferably, an autoclave is used for the reaction, which may have an internal stirrer and an internal lining.

[0242] The composition obtained in the carboxylation-cyclization reaction of the present invention comprises an unsubstituted exocyclic vinylidene carbonate, i.e., a cyclic carbonate of formula Ia or Ib.

[0243] After step a) is completed, the pressure is released before steps b1) (if performed), b2) (if performed) and c) are continued.

[0244] If in step a) solvent L2 is not used, step b1) must be carried out.

[0245] If a solvent mixture containing L1 and L2 is used in step a), it may be advantageous in some circumstances to also carry out step b2). For example, if the mixture contains too little L2, making efficient phase separation impossible, it may be advantageous to add additional solvent L2. The ideal mixing ratio of solvents L1 and L2 depends on the specific solvents L1 and L2, the specific starting materials, catalyst, their respective concentrations, and the phase separation method, and can be determined by those skilled in the art.

[0246] 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 an overall weight ratio of preferably 80:20 to 20:80, more preferably 70:30 to 30:70, in particular 60:40 to 40:60.

[0247] In one embodiment of the present invention, in step a), no solvent L2 is used and step b1) is carried out (in which case step b2) is of course skipped).

[0248] In another embodiment of the present invention, in step a), a solvent mixture containing L1 and L2 is used, and step b2) can be skipped as long as the amount of L2 is too small to prevent efficient phase separation, in which case step b2) is performed.

[0249] In step c), the two organic liquid phases can be separated from each other and the non-polar organic phase, enriched in silver catalyst, can be recycled as catalyst in the carboxylation reaction of step a).

[0250] The two liquid phases are typically separated by gravity phase separation, which can be carried out using, for example, standard equipment and methods, as described, for example, in E. Muller 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, "Apparatus."

[0251] On a laboratory scale, the phase separation can be carried out, for example, in a separatory funnel. On an industrial scale, countercurrent extraction devices such as mixer-settler devices, extraction columns, stirred extraction columns, continuous packed bed liquid-liquid extractors, etc. are suitable.

[0252] 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 achieve more complete extraction of the catalyst Ag1. However, the separation is generally so efficient that it is not necessary to repeat steps b1) / b2) and c).

[0253] According to the invention, in step c) the catalyst is separated from the cyclic carbonate by using two organic solvents with a solubility gap: the silver catalyst Ag1 is enriched in the less polar solvent and the cyclic carbonate is enriched in the more polar solvent.

[0254] The silver catalyst Ag1 enriched in the less polar solvent is P = [concentration of silver catalyst Ag1 in the non-polar organic phase] / [concentration of silver catalyst Ag1 in the polar organic phase] means that the partition coefficient is >1. The partition coefficient is preferably >2, particularly preferably >5.

[0255] The product Ia or Ib or a mixture thereof enriched in the polar solvent phase is determined by the partition coefficient of the product Ia or Ib or a mixture thereof. P = [concentration of product Ia or Ib in the polar organic phase] / [concentration of product Ia or Ib in the non-polar organic phase] means that the partition coefficient is >1. The partition coefficient is preferably >2, particularly preferably >5.

[0256] The product phase obtained in step c) therefore contains more than 50 wt. %, preferably more than 66.7 wt. %, in particular more than 83.3 wt. % of the cyclic carbonate I formed in step a), and the catalyst phase contains more than 50 wt. %, preferably more than 66.7 wt. %, in particular more than 83.3 wt. % of the silver catalyst.

[0257] Optionally, the cyclic carbonate I can be isolated from the product phase [step d)]. For example, the product can be obtained by evaporating the solvent from the polar organic phase, and if desired, the solvent can be recycled to the carboxylation reaction. This isolation method is particularly advantageous for synthesis carried out on an industrial scale. A polar organic solvent can also be used to further reduce the amount of product in the non-polar phase by countercurrent extraction. Conversely, a certain amount of non-polar solvent can be removed from the non-polar organic solvent phase by evaporation and used to recycle more of the silver catalyst, thereby reducing the silver content in the polar organic phase by countercurrent extraction.

[0258] The recycled silver catalyst can be reused in step a), and the conversion rate after the first turnover is satisfactory. Even after several turnovers, the catalytic activity is still satisfactory.

[0259] Although the workup of the polar organic phase of the process of the present invention and the isolation of the cyclic carbonate of formula Ia or Ib can of course be carried out in other conventional ways, such as by filtration or aqueous extraction workup, isolation via evaporation of the polar solvent is the most economical and simple route, at least on an industrial scale. The cyclic carbonate of formula Ia or Ib or a mixture thereof is generally obtained in sufficient purity by applying such measures or a combination thereof, eliminating the need for additional purification steps. Alternatively, further purification can be achieved by methods commonly used in the art, such as recrystallization.

[0260] The invention is illustrated by the following examples.

[0261] [Example] Unless otherwise specified, each percentage is based on weight percent.

[0262] General All chemicals and solvents were purchased from Sigma-Aldrich or ABCR and used without further purification.

[0263] 1 H and 13 C NMR spectra were obtained using Bruker Avance 200 MHz and 400 MHz spectrometers. Z The residual protons of the solvent ( 1 H) or carbon ( 13 C) Resonance peaks were used as reference. Chemical shifts (δ) are reported in ppm. Abbreviations used: XPhos = 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl THF = tetrahydrofuran DMF = N,N-dimethylformamide Et2O = diethyl ether

[0264] I. Synthesis of Ligands V and W The title compound was obtained via a modified synthesis 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 sealed and heated at 120 °C for 48 h. 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% aqueous Na2CO3 (100 mL), and brine (100 mL) and dried over Na2SO4. The solution was evaporated to dryness and purified by silica column chromatography using petroleum ether as the eluent. The product was obtained as a colorless oil (2.63 g; 64%). 1 H NMR (300 MHz, CDCl3): δ = 7.55 (dd, J = 7.9, 1.5 Hz, 1H, H Ar ), 7.22 (ddd, J = 8.1, 7.6, 1.9, 1H, H Ar ), 7.09 (dd, J = 8.0, 1.6 Hz, 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). 13 C NMR (75 MHz, CDCl3): δ 149.8, 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. HRMS (ESI): m / z C 22 H 38 Calculated value of BrN: 396.2260 [M+H] + ; The measured value is 396.2261.

[0265] 2. Synthesis of リガンドVの The title compound was obtained via a modified synthesis described in J. Org. Chem., 2000, 65, 5334-5341. To a 25 mL oven-dried, three-necked flask equipped with a stir bar and reflux condenser under argon was added Mg turnings (126 mg; 5.17 mmol), 2-bromo-N,N-dioctylaniline (991 mg, 2.50 mmol) from Example 1, and THF (5 mL). 1,2-Dibromoethane (38 μL; 0.44 mmol) in THF (1 mL) was added dropwise via cannula over 5 min, and the mixture was heated to 50 °C for 5 min and then at reflux for an additional 16 h. The mixture was cooled to 60 °C. 1-Bromo-2-chlorobenzene (252 μL; 2.85 mmol) was added dropwise over 10 min, and the mixture was heated at 60 °C for 2 h. After cooling to room temperature, CuCl (282 mg; 2.59 mmol) was added, followed by the dropwise addition of a solution of chlorodicyclohexylphosphine (0.57 mL; 2.59 mmol) in THF (1 mL). After stirring the mixture for an additional 16 h, 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 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 columned on silica using a hexane / diethyl ether solvent gradient (hexane / Et2O 1:0 to 19:1). The resulting pale yellow viscous oil (553 mg; 43% crude yield) contained the desired ligand V as the major product, ligand W, and an unidentified phosphine complex in a ratio of approximately 1:0.24:0.12. After further purification by gradient silica column chromatography using dichloromethane / acetone as the eluent, the pure product (94 mg; 7%) was obtained. 1H NMR (300 MHz, CDCl3): δ 7.60–7.47 (m, 1H), 7.34–7.17 (m, 4H), 7.05–6.96 (m, 2H), 6.95–6.87 (m, 1H–), 2.092 (2.4–2.47). 46H), 0.87 (m, 6H). 13 C NMR (75 MHz, CDCl3): δ δ 149.6 (d, J CP = 30.7 Hz), 149.6, 136.2 (d, J CP = 5.8 Hz), 135.1 (d, J CP = 20.2 Hz), 133.4 (d, J CP = 3.8 Hz), 132.7 (d, J CP = 3.2 Hz), 131.3 (d, J CP = 5.9 Hz), 127.9, 127.6, 125.9, 120.0, 120.0, 52.6, 37.1 (d, J CP = 16.3 Hz), 33.9 (d, J CP = 14.1 Hz), 31.9, 30.7 (d, J CP = 11.3 Hz), 30.6 (d, J CP = 17.5 Hz), 30.2 (d, J CP = 12.7 Hz), 30.0 (d, J CP = 8.5 Hz), 29.6, 29.4, 28.0 (d, J CP = 7.5 Hz), 27.8 (d, J CP = 10.5 Hz), 27.5, 27.4 (d, J CP = 9.3 Hz), 27.3 (d, J CP = 11.7 Hz), 27.2, 26.7, 26.6, 22.8, 14.2.. 31 P NMR (122 MHz, CDCl3): δ-11.3. HRMS (ESI): m / z C 40 H 64Calculated value for NP: 590.4849 [M+H] + ; Actual value: 590.4850.

[0266] 3. Synthesis of Ligand W To a 25 mL oven-dried, three-necked flask equipped with a stir bar and reflux condenser under argon were added Mg turnings (39 mg; 1.60 mmol), 2-bromo-N,N-dioctylaniline (496 mg, 1.25 mmol), and THF (8 mL). 1,2-Dibromoethane (19 μL; 0.22 mmol) in THF (1 mL) was added dropwise via cannula over 5 min, and the mixture was heated to 50 °C for 5 min and then at reflux for an additional 3 h. The mixture was cooled to room temperature, and CuCl (141 mg; 1.43 mmol) was added, followed by the dropwise addition of a solution of chlorodicyclohexylphosphine (0.29 mL; 1.30 mmol) in THF (1 mL). After stirring the mixture for an additional 16 hours, 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 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 over Na2SO4. The solvent was removed in vacuo, and the residue was columned on silica using a dichloromethane / acetone solvent gradient (CHCl2 / acetone 1:0 to 19:1). The product was isolated as a colorless viscous oil (221 mg; 34%). The oxidized phosphine was also 31 Detected by P NMR and HRMS (<4% of sample). 1H NMR (500 MHz, CDCl3): δ 7.38 (d, J = 7.3 Hz, 1H), 7.24 (t, J = 7.5 Hz, 1H), 7.11-7.04 (m, 1H), 7.01 (t, J = 7.2 Hz, 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). 13 C NMR (75 MHz, CDCl3): δ 157.8 (d, J CP = 19.4 Hz), 133.4 (d, J CP = 3.5 Hz), 133.2 (d, J CP = 16.9 Hz), 128.6, 122.7 (d, J CP = 3.6 Hz), 122.6, 54.7 (d, J CP = 5.8 Hz), 34.9 (d, J CP = 15.1 Hz), 31.9, 30.5 (d, J CP = 16.5 Hz), 29.8 (d, J CP = 11.0 Hz), 29.6, 29.3, 27.5, 27.5-27.3 (m), 26.6, 26.4, 22.7, 14.1. 31 P NMR (122 MHz, CDCl3): δ-13.2.

[0267] II. Synthesis of Cyclic Carbonates General Reaction Procedure A. Addition of solvent L2 after the carboxylation reaction: An 80 mL steel autoclave was charged with propargyl alcohol (II) (5.0 mmol), a silver salt, a bulky donor ligand, and a polar organic solvent L1.

[0268] 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 a non-polar organic solvent, L2. After phase separation, the conversion of propargyl alcohol and product formation were measured in both phases. 1 The silver content in both phases was determined by ICP-MS.

[0269] [Example 1] Alkynol: Propargyl alcohol (R 1 =H); 280 mg (5 mmol) Silver salt: Silver neodecanoate [Ag(CH 19 C(O)O)]; 14 mg (0.05 mmol) Bulky donor ligand: XPhos; 23.8 mg (0.05 mmol) Polar organic solvent L1: acetonitrile; 10 mL Non-polar organic solvent: cyclohexane CO2 pressure: 20 bar After the reaction, the conversion of the propargyl alcohol to the corresponding exocyclic vinylidene carbonate was determined to be 99% by NMR. The reaction mixture was extracted with cyclohexane (10 mL) as a nonpolar organic solvent L2. The solvent fraction 1 H-NMR showed that the exocyclic vinylidene carbonate remained in the acetonitrile phase. The silver content in the nonpolar organic phase was 370 mg / kg, and in the polar organic phase was 55 mg / kg (P = 6.7).

[0270] [Example 2] Alkynol: Propargyl alcohol (R 1 =H); 280 mg (5 mmol) Silver salt: Silver neodecanoate [Ag(CH 19 C(O)O)]; 14 mg (0.05 mmol) Bulky donor ligand: XPhos; 23.8 mg (0.05 mmol) Polar organic solvent L1: acetonitrile; 10 mL Non-polar organic solvent: cyclohexane CO2 pressure: 20 bar After the reaction, the conversion of the propargyl alcohol to the corresponding exocyclic vinylidene carbonate was determined to be 99% by NMR. The reaction mixture was extracted with cyclohexane (2×5 mL) as a nonpolar organic solvent L2. 1 By H-NMR, the exocyclic vinylidene carbonate remained in the acetonitrile phase. All volatiles were removed from the combined cyclohexane fractions, and the remaining catalyst residue was redissolved in acetonitrile (10 ml) and reused in the carboxylation under the same conditions as above after the addition of fresh propargyl alcohol (but without further addition of silver or bulky ligand). 1 Conversion to exocyclic vinylidene carbonate by 1 H-NMR spectroscopy was also 99%.

[0271] [Example 3] Alkynol: Propargyl alcohol (R 1 =H); 280 mg (5 mmol) Silver salts: Silver stearate [Ag(C 17 H 35C (O)O)]; 19.6 mg (0.05 mmol) Bulky donor ligand: XPhos; 23.8 mg (0.05 mmol) Polar organic solvent L1: acetonitrile; 10 mL Non-polar organic solvent: decane CO2 pressure: 20 bar After the reaction, the conversion of propargyl alcohol to the corresponding exocyclic vinylidene carbonate was determined by NMR to be 99%. A 2 mL aliquot of the reaction solution was extracted with decane (2 mL) as the nonpolar solvent L2. The silver content in the nonpolar organic phase was 390 mg / kg, and the silver content in the polar organic phase was 50 mg / kg (P = 7.8).

[0272] [Example 4] Alkynol: Propargyl alcohol (R 1 =H); 280 mg (5 mmol) Silver salt: Silver cyclohexanebutyrate [Ag(cyclohexyl-(CH2)3-C(O)O)]; 13.9 mg (0.05 mmol) Bulky donor ligand: XPhos; 23.8 mg (0.05 mmol) Polar organic solvent L1: acetonitrile; 10 mL Non-polar organic solvent: cyclohexane CO2 pressure: 20 bar After the reaction, the conversion of propargyl alcohol to the corresponding exocyclic vinylidene carbonate was determined by NMR to be 99%. A 2 mL aliquot of the reaction solution was extracted with cyclohexane (2 mL) as the nonpolar solvent L2. The silver content in the nonpolar organic phase was 390 mg / kg, and the silver content in the polar organic phase was 65 mg / kg (P = 6.0).

[0273] [Example 5] Alkynol: Compound II [wherein R 1 =-CH2-O-CH2-CH(OH)-CH2-OC(CH3)3];1.08g(5mmol) Silver salt: Silver neodecanoate [Ag(CH 19 C(O)O)]; 27.9 mg (0.10 mmol) Bulky donor ligand: XPhos; 47.7 mg (0.10 mmol) Internal standard: Mesitylene 232μL (1.67mmol) Polar organic solvent L1: acetonitrile; 10 mL Non-polar organic solvent: cyclohexane CO2 pressure: 20 bar After all the reagents and L1 have been added, a certain amount of the mixture is taken and diluted in CDCl3, 1 t was determined by H NMR. Cyclohexane was used as the non-polar solvent L2 according to the procedure described for Example 2. After the reaction, the conversion of the propargyl alcohol to the corresponding exocyclic vinylidene carbonate was determined to be 76% by NMR. Upon recycling, 1 Conversion to exocyclic vinylidene carbonate was determined to be 67% by 1 H NMR.

[0274] The silver content in the non-polar organic phase was 1200 mg / kg, and the silver content in the polar organic phase was 310 mg / kg (P=43.9).

[0275] [Example 6] Alkynol: Compound II [wherein R 1 = 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, where A has the formula:

[0276] [ka] 500mg (0.97mmol) Silver salt: Silver neodecanoate [Ag(CH 19 C(O)O)]; 14 mg (0.05 mmol) Bulky donor ligand: XPhos; 23.8 mg (0.05 mmol) Polar organic solvent L1: acetonitrile; 10 mL Non-polar organic solvent: cyclohexane CO2 pressure: 20 bar After the reaction, the conversion of the propargyl alcohol to the corresponding bis-exocyclic vinylidene carbonate was determined to be 99% by NMR. The reaction mixture was extracted with cyclohexane (2×5 mL) as a nonpolar organic solvent L2. 1 H-NMR showed that the exocyclic vinylidene carbonate remained in the acetonitrile phase. The silver content in the nonpolar organic phase was 100 mg / kg, and the silver content in the polar organic phase was 35 mg / kg (P = 2.9).

[0277] [Example 7] Alkynol: Compound II [wherein R 1= 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) Silver salt: Silver neodecanoate [Ag(CH 19 C(O)O)]; 14 mg (0.05 mmol) Bulky donor ligand: XPhos; 23.8 mg (0.05 mmol) Polar organic solvent L1: dimethylformamide; 10 mL Non-polar organic solvent: hexane CO2 pressure: 20 bar After the reaction, the conversion of propargyl alcohol to the corresponding bis-exocyclic vinylidene carbonate was determined by NMR to be 56%. The reaction mixture was extracted with hexane (2×5 mL) as a non-polar organic solvent L2. The solvent fraction 1 According to 1 H-NMR, the exocyclic vinylidene carbonate remained in the acetonitrile phase.

[0278] B. Addition of solvent L2 in the carboxylation reaction: An 80 mL steel autoclave was charged with propargyl alcohol (II) (5.0 mmol), silver salt, bulky donor ligand, polar organic solvent L1, and nonpolar organic solvent L2. In the case of recycle experiments, the nonpolar organic solvent L2 phase containing the silver catalyst from a previous reaction was charged 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 h. The CO2 overpressure was then carefully released. After phase separation, the conversion of propargyl alcohol and product formation were monitored in both phases. 1 The silver content in both phases was determined by ICP-MS.

[0279] [Example 8] Alkynol: Propargyl alcohol (R 1 =H); 280 mg (5 mmol) Silver salts: Silver neodecanoate [Ag(C 10H 19 O2]; 14 mg (0.05 mmol) Bulky donor ligand: XPhos; 23.8 mg (0.05 mmol) Polar organic solvent: acetonitrile; 5 mL Non-polar organic solvent: cyclohexane; 5 mL CO2 pressure: 20 bar After the reaction, the conversion of propargyl alcohol to the corresponding exocyclic vinylidene carbonate was determined to be 91% by NMR. 1 By H-NMR, exocyclic vinylidene carbonate could only be detected in the acetonitrile phase. After phase separation, the cyclohexane phase containing the silver catalyst was reused after adding 280 mg of propargyl alcohol and 5 mL of acetonitrile under the same conditions as above for carboxylation. 1 By H-NMR spectroscopy, the conversion to exocyclic vinylidene carbonate in the second run using recycled catalyst was 96%.

[0280] [Example 9] Alkynol: Propargyl alcohol (R 1 =H); 280 mg (5 mmol) Silver salt: Silver neodecanoate [Ag(CH 19 C(O)O)]; 14.0 mg (0.05 mmol) Bulky donor ligand: compound of formula V (actually a mixture of V and W and an unknown phosphine ligand, obtained in I.2, in a ratio of about 1.0:0.24:0.12); 29.5 mg (0.05 mmol) Polar organic solvent L1: acetonitrile; 10 mL Nonpolar organic solvent L2: cyclohexane; 10 mL CO2 pressure: 20 bar After the reaction, the conversion of propargyl alcohol to the corresponding exocyclic vinylidene carbonate was determined by NMR to be 30%. Extraction was performed with additional cyclohexane (3 x 10 mL). The silver content in the nonpolar organic phase was 480 mg / kg, and the silver content in the polar organic phase was 30 mg / kg (P = 16.0) after the first extraction and 5 mg / kg after the third extraction.

[0281] [Example 10] Alkynol: Propargyl alcohol (R 1 =H); 280 mg (5 mmol) Silver salt: Silver acetate [Ag(CH3C(O)O)]; 8.3 mg (0.05 mmol) Bulky donor ligand: compound of formula V (actually a mixture of V and W and an unknown phosphine ligand, obtained in I.2, in a ratio of about 1.0:0.24:0.12); 29.5 mg (0.05 mmol) Polar organic solvent L1: acetonitrile; 10 mL Nonpolar organic solvent L2: cyclohexane; 10 mL CO2 pressure: 20 bar After the reaction, the conversion of propargyl alcohol to the corresponding exocyclic vinylidene carbonate was determined by NMR to be 50%. Extraction was performed with additional cyclohexane (3 x 10 mL). The silver content in the nonpolar organic phase was 310 mg / kg, and the silver content in the polar organic phase was 90 mg / kg (P = 3.4) after the first extraction and 32 mg / kg after the third extraction.

[0282] [Example 11] Alkynol: Propargyl alcohol (R 1 =H); 280 mg (5 mmol) Silver salt: Silver neodecanoate [Ag(CH 19 C(O)O)]; 14.0 mg (0.05 mmol) Bulky donor ligand: Compound of formula W; 29.5 mg (0.05 mmol) Polar organic solvent L1: acetonitrile; 10 mL Nonpolar organic solvent L2: cyclohexane; 10 mL CO2 pressure: 20 bar After the reaction, the conversion of propargyl alcohol to the corresponding exocyclic vinylidene carbonate was determined by NMR to be 36%. Extraction was performed with additional cyclohexane (3 x 10 mL). The silver content in the nonpolar organic phase was 600 mg / kg, and the silver content in the polar organic phase was 21 mg / kg (P = 28.6) after the first extraction and 2 mg / kg after the third extraction.

[0283] [Example 12] Alkynol: Propargyl alcohol (R 1 =H); 280 mg (5 mmol) Silver salt: Silver neodecanoate [Ag(CH 19 C(O)O)]; 14.0 mg (0.05 mmol) Bulky donor ligand: Compound of formula W; 29.5 mg (0.05 mmol)* Polar organic solvent L1: acetonitrile; 10 mL Nonpolar organic solvent L2: cyclohexane; 10 mL CO2 pressure: 50 bar After the reaction, the conversion of propargyl alcohol to the corresponding exocyclic vinylidene carbonate was determined to be 81% by NMR. 1 Conversion to exocyclic vinylidene carbonate was determined to be 70% by 1 H NMR.

[0284] C. Substrate screening by adding solvent L2 in the carboxylation reaction: An 80 mL steel autoclave was charged with propargyl alcohol (II), a silver salt, a bulky donor ligand, the polar organic solvent CHCN, and the nonpolar organic solvent cyclohexane. The reaction mixture was pressurized with CO and stirred at room temperature for 18 h. The CO overpressure was then carefully released. After phase separation, the conversion of propargyl alcohol and product formation were monitored in both phases. 1 The silver content in both phases was determined by ICP-MS.

[0285] [Table 1]

[0286] D. Recycling of carboxylation reaction with the addition of solvent L2 [Example 21] Alkynol: Compound II [wherein R 1 =-CH2-O-CH2-CH(OH)-CH2-OC(CH3)3];0.54g(2.5mmol) Silver salt: Silver neodecanoate [Ag(CH 19 C(O)O)]; 7.0 mg (0.025 mmol) Bulky donor ligand: V; 14.7 mg (0.025 mmol) Polar organic solvent L1: acetonitrile; 5 mL Nonpolar organic solvent L2: cyclohexane; 2.5 mL CO2 pressure: 20 bar In a glovebox, the alkynol, silver(I) neodecanoate, ligand V, acetonitrile, and cyclohexane were placed in a Premex autoclave equipped with a Teflon insert. The autoclave was sealed and charged with 50 bar of CO. After stirring at room temperature for 18 h, the CO pressure was carefully released, and the autoclave was purged with argon before being reintroduced into the glovebox. 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 x 5 mL). The combined cyclohexane washes were concentrated to approximately 2.5 mL and reintroduced into the autoclave with additional substrate and acetonitrile for the subsequent run. The workup after the second run was the same as after the first run, and the entire procedure was repeated for the third run. The acetonitrile phase was treated with 1.25 M methanolic HCl (50 μL), filtered through a short Celite pad, and the solvent was removed under reduced pressure to give the product. Product yields were determined using mesitylene as an internal standard. 1 Determined by H-NMR. Yield of exo-vinylenecarbonate after the first run: 90% Yield of exocyclic vinylene carbonate after first recycle: 81% Yield of exocyclic vinylene carbonate after first recycling: 71% Aspects of the present disclosure include the following. [1] A method for preparing a cyclic carbonate I selected from the group consisting of compounds of formula Ia, compounds of formula Ib, and mixtures thereof, comprising: [ka] [In the formula, R 1 is -CH 2 -OR 14 and R 14 is hydrogen, 1, 2 or 3 R 15 C with group 1 ~C 4 -Alkyl, -C(=O)R 16 , and 1, 2 or 3 R 17 C with group 3 ~C 6 -cycloalkyl, R 15 OH, C 1 ~C 4 - is selected from the group consisting of alkoxy, phenyl, and 3-, 4-, 5-, or 6-membered saturated heterocyclic rings containing 1 or 2 oxygen atoms as ring members, R 16 is C 1 ~C 6 -Alkyl, C 2 ~C 6 -Alkenyl, C 1 ~C 4 -alkoxy and -NR 18 R 19 and R 18 is hydrogen or C 1 ~C 4 -alkyl, and R 19 is hydrogen, C 1 ~C 4 -Alkyl, R 20 C substituted by a group 1 ~C 4 -alkyl, and C 1 ~C 4 -alkyl and C 1 ~C 4 -phenyl, which may have 1, 2, 3, 4 or 5 substituents selected from the group consisting of alkoxy; R 20 -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 and R 21 are each independently hydrogen, C 1 ~C 6 -alkyl or C 2 ~C 6 -alkenyl, and R 13 are each independently hydrogen or C 1 ~C 10 -alkyl, R 17 -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(R13 )-C(=O)-OR 21 and -N(R 13 )-C(=O)-N(R 13 )-R 21 and R 21 are each independently hydrogen, C 1 ~C 6 -alkyl or C 2 ~C 6 -alkenyl, and R 13 are each independently hydrogen or C 1 ~C 10 -alkyl] a) Propargyl alcohol of formula II

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[10] The method of any one of aspects 1 to 9, wherein in step c), solvent L1 and solvent L2 are present in a total weight ratio of 80:20 to 20:80.

Claims

1. A method for preparing cyclic carbonates I, comprising the steps a) to d) The cyclic carbonate I is a compound of formula Ia, a compound of formula Ib 【Chemistry 1】 [In the formula, R 1 is -CH 2 -OR 14 and R 14 is hydrogen, 1, 2 or 3 R 15 C with group 1 ~C 4 -Alkyl, -C(=O)R 16 , and 1, 2 or 3 R 17 C with group 3 ~C 6 -cycloalkyl, R 15 OH, C 1 ~C 4 - is selected from the group consisting of alkoxy, phenyl, and 3-, 4-, 5-, or 6-membered saturated heterocyclic rings containing 1 or 2 oxygen atoms as ring members, R 16 is C 1 ~C 6 -Alkyl, C 2 ~C 6 -Alkenyl, C 1 ~C 4 -alkoxy and -NR 18 R 19 and R 18 is hydrogen or C 1 ~C 4 -alkyl, and R 19 is hydrogen, C 1 ~C 4 -Alkyl, R 20 C substituted by a group 1 ~C 4 -alkyl, and C 1 ~C 4 -alkyl and C 1 ~C 4 -phenyl, which may have 1, 2, 3, 4 or 5 substituents selected from the group consisting of alkoxy; R 20 -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 and R 21 are each independently hydrogen, C 1 ~C 6 -alkyl or C 2 ~C 6 -alkenyl, and R 13 are each independently hydrogen or C 1 ~C 10 -alkyl, R 17 -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 and R 21 are each independently hydrogen, C 1 ~C 6 -alkyl or C 2 ~C 6 -alkenyl, and R 13 are each independently hydrogen or C 1 ~C 10 -alkyl] and mixtures thereof, wherein the process comprises, as step a), a) Propargyl alcohol of formula II 【Chemistry 2】 [In the formula, R 1 is as defined above] with carbon dioxide, or Or, the cyclic carbonate I is a compound of the formula I-bis 【Transformation 3】 wherein A is a bridging group: -CH 2 -O-CH 2 -1,4-phenylene-CH 2 -O-CH 2 -; -CH 2 -OC(=O)-NH-1,4-toluylene-NH-C(=O)-O-CH 2 -; -CH 2 -O-CH 2 -CH(OH)-CH 2 -O-(CH 2 ) 3 -O-CH 2 -CH(OH)-CH 2 -O-CH 2 -; -CH 2 -O-CH 2 -CH(OH)-CH 2 -O-1,4-phenylene-C(CH 3 ) 2 -1,4-phenylene-O-CH 2 -CH(OH)-CH 2 -O-CH 2 -; and -CH 2 -(AND 2 CH 2 ) 3 -AND 2 - Select from wherein the method comprises, as step a) a) Compounds of formula II-bis 【Chemistry 4】 wherein A is as defined above. with carbon dioxide, in step a), 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, solvent L1 being more polar than solvent L2, and solvents L1 and L2 having a solubility gap at 1013 mbar and at least 20-30° C., where "solubility gap" means that the mixture of solvents L1 and L2 demixes to form two distinct phases, one of the two phases consisting essentially of solvent L1 and the other of the two phases consisting essentially of solvent L2, "essentially" meaning that the phases contain less than 10% by weight of the other solvent, i.e. the minor solvent, relative to the total weight of solvents L1 and L2, Solvent L1 is at least 10 × 10 -30 A polar aprotic solvent with a dipole moment of C m, and the solvent L2 is at most 2 × 10 -30 It is a non-polar solvent with a dipole moment of C m solvent L1 is a polar aprotic solvent selected from the group consisting of formamide, N-methylformamide, N,N-dimethylformamide, N,N-dimethylacetamide, tetramethylurea, N,N-dimethylimidazolinone, N,N-dimethylpropyleneurea, acetonitrile, propionitrile, benzonitrile, dimethyl sulfoxide, sulfolane, dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, nitromethane, nitrobenzene and mixtures thereof; the solvent L2 is selected from the group consisting of C5-C15-alkanes, C5-C8-cycloalkanes which may have C1-C2-alkyl substituents, C1-C2-alkyl esters of C12-C20 fatty acids and mixtures thereof, The reaction in step a) is further carried out in the presence of a silver catalyst Ag1 comprising at least one bulky ligand and a carboxylate ligand, The bulky ligand is a compound of formula A-W 【Transformation 5】 【change】 wherein Me is methyl, Cy is cyclohexyl, i-Pr is isopropyl, Ph is phenyl, and t-Bu is tert-butyl. and mixtures thereof; The carboxylate ligand is represented by formula V 【Transformation 6】 [In the formula, R 6 is C 8 ~C 18 -C with alkyl and cyclohexyl rings 2 ~C 4 -alkyl] This is due to The method further comprises, as step b), b1) if step a) was not carried out in the presence of at least one solvent L2, adding a solvent L2 to the reaction mixture obtained in step a), or b2) optionally adding solvent L2 to the reaction mixture obtained in step a) if step a) was carried out in the presence of at least one solvent L2 Including, The method further comprises steps c) and d) c) subjecting the reaction mixture obtained in step a), b1) or b2) to phase separation to obtain a product phase containing the cyclic carbonate I and at least one solvent L1 and a catalyst phase containing the silver catalyst and at least one solvent L2; and d) optionally isolating the cyclic carbonate I from the product phase. A method comprising:

2. The cyclic carbonate is compound Ia, compound Ib, or a mixture thereof, wherein R 1 Ha-CH 2 -OR 14 and R 14 Ha-CH 2 -CH(OH)-CH 2 -OC(CH 3 ) 3 and the propargyl alcohol is a compound of formula II, wherein R 1 Ha-CH 2 -OR 14 and R 14 Ha-CH 2 -CH(OH)-CH 2 -OC(CH 3 ) 3 The method of claim 1, wherein

3. 3. The method according to claim 1, wherein the silver catalyst Ag1 is used in step a) in an amount of 0.001 to 50 mol % relative to the amount of propargyl alcohol of formula II.

4. Solvent L1 is at least 11 × 10 -30 It is a polar aprotic solvent with a dipole moment of C m, Solvent L2 is at most 1 × 10 -30 The method according to any one of claims 1 to 3, wherein the solvent is a non-polar solvent having a dipole moment of C m.

5. Solvent L1 is acetonitrile and solvent L2 is C 5 ~C 14 -Alkanes, C 1 ~C 2 -C, which may have alkyl substituents 5 ~C 8 -cycloalkanes, and saturated C 12 ~C 20 C in fatty acids 1 ~C 2 -alkyl esters, or solvent L1 is dimethylformamide and solvent L2 is C 5 ~C 14 -Alkanes, C 1 ~C 2 -C, which may have alkyl substituents 5 ~C 8 -cycloalkanes, and saturated C 12 ~C 20 C in fatty acids 1 ~C 2 - alkyl esters.

6. 5. The process according to claim 1, wherein the solvent L1 is acetonitrile and the solvent L2 is cyclohexane or decane.

7. 7. The method according to any one of claims 1 to 6, 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.

8. 8. The method according to claim 1, wherein in step c) solvent L1 and solvent L2 are present in an overall weight ratio of 80:20 to 20:80.

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