Method for producing polycarbonates by metal-catalyzed cross-coupling

Abstract

The invention relates to a method for preparing polycarbonate by using metal-catalyzed cross coupling. The method comprises the step of reacting iodinated diaryl carbonate with a structure shown in a formula (I) and terminal alkyne with a structure shown in a formula (IIa) or terminal olefin with a structure shown in a formula (IIb). Furthermore, the present invention relates to a polycarbonate comprising a repeating unit having a structure of formula (IIIa) or (IIIb).

Description

[0001] The present invention relates to a method for preparing a polycarbonate using a metal-catalyzed cross-coupling, the method comprising reacting a diaryl iodide carbonate having a structure of formula (I) as described below with a terminal alkyne having a structure of formula (IIa) or a terminal olefin having a structure of formula (IIb). In addition, the present invention relates to a polycarbonate comprising a repeating unit having a structure of formula (IIIa) or (IIIb) as described below.

[0002] Polycarbonates, particularly aromatic polycarbonates, are known to exhibit improved mechanical and optical properties, heat resistance and weatherability. Due to this property feature, polycarbonates are used in a variety of indoor and outdoor applications. Typically, polycarbonates are prepared by the commonly known interphase phosgenation process or via melt transesterification. Both methods employ the reaction of bisphenols (e.g., bisphenol A [2,2-bis(4-hydroxyphenol)propane]) with phosgene or diaryl carbonate to produce a polymer structure. This means that typically the polymer backbone is defined by the structure of the diol and the carbonate group, which is introduced into the backbone by the polymerization reaction itself. Using aromatic diols, such as bisphenol A, bisphenol B, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol P, bisphenol TMC and bisphenol Z, a backbone comprising carbonate groups on the aromatic ring can be formed. The carbonate group is located in the para position of at least one other substituent on the aromatic ring, depending on the structure of the diol, which connects the carbonate aromatic ring group to the next carbonate group in the polycarbonate backbone.

[0003] However, there is a constant need to improve the properties of conventional aromatic (co)polycarbonates, including the use of bio-based aromatic building blocks. Therefore, the development of alternative synthetic routes to the conventional interphase phosgenation or melt transesterification methods, enabling the attachment of aromatic moieties to carbonate groups, has attracted scientific and economic interest.

[0004] Therefore, an object of the present invention is to provide an alternative method for preparing polycarbonate. Preferably, an object of the present invention is to provide a method for preparing polycarbonate with repeating units, wherein the repeating units comprise two aromatic moieties connected to each other, and - within the repeating units - one of the aromatic moieties is substituted by a carbonate group. More preferably, an object of the present invention is to provide a method for preparing polycarbonate with repeating units, wherein the repeating units comprise two aromatic moieties connected to each other, and - within the repeating units - one of the aromatic moieties is substituted by a carbonate group, wherein the carbonate group is introduced into the repeating units without forming the carbonate group separately. More preferably, an object of the present invention is to provide a method for preparing polycarbonate, comprising a reaction to form a repeating unit, comprising connecting two aromatic moieties to each other. This reaction forces the aromatic moieties to comprise carbonate substituents in order to obtain polycarbonate comprising carbonate groups. Therefore, an object of the present invention is also preferably to provide a method for preparing polycarbonate with repeating units, wherein the repeating units comprise two aromatic moieties connected to each other, and - within the repeating units - one of the aromatic moieties is substituted by a carbonate group, wherein the carbonate group is not affected by the method itself. In this article, the term "affected" preferably means that the carbonate does not decompose.

[0005] In addition to the above, it is an object of the present invention to provide a polycarbonate which can be prepared by the process according to the present invention. Furthermore, it is an object of the present invention to provide a polycarbonate which comprises new chemical and physical properties when compared to the polycarbonates known from the prior art.

[0006] Metal-catalyzed cross-coupling reactions for forming carbon-carbon bonds are well known in synthetic chemistry. For example, the first reaction by Ullmann and Goldberg in the early 20th century involved copper-promoted carbon-carbon bond formation, and copper remained the catalyst of choice until the advent of Nobel Prize-winning work on palladium-catalyzed cross-couplings, such as that performed by Heck, Suzuki, and Negishi. In general, cross-coupling reactions are characterized by a metal-catalyzed coupling of an organic electrophile (usually an organic halide such as an aryl halide) with an (organic) nucleophile (e.g. a terminal alkyne or terminal olefin) in the presence of a base. The following scheme shows an overview of the important metal-catalyzed cross-coupling reactions for forming carbon-carbon bonds.

[0007]

[0008] Organic halides can be based on sp-, sp- 2 - or sp 3 - Hybridized carbon atoms, such as those with sp 2Aryl halides with carbon-halogen bonds. Various reactions have been developed using organometallic carbon nucleophiles, such as in situ generated acetylide anions (Sonogashira coupling). The mechanistic key steps of cross-coupling reactions (such as Sonogashira coupling) usually include oxidative addition of the organohalide, transmetalation of the nucleophilic carbon, and reductive elimination to form the product. As an exception, in the Heck coupling of aryl halides and terminal olefins, the migratory insertion / β-hydride elimination sequence represents the key bond formation step (rather than reductive elimination) to form the product.

[0009] Metal-catalyzed cross-coupling reactions can be homogeneous or heterogeneous catalyzed. For example, the coupling can be carried out using a homogeneous catalyst, which generally involves the use of a traditional organic solvent. In addition, a heterogeneous metal catalyst can also be used for the cross-coupling reaction, and the heterogeneous metal catalyst is composed of a metal dispersed on an inorganic surface or a metal bound to a polymer support through a ligand. For example, palladium on carbon (Pd / C) can be used as a heterogeneous catalyst.

[0010] Although the Sonogashira coupling of iodinated aromatic compounds (i.e., existing aromatic compounds without carbonate groups, such as iodinated anisole) with terminal alkynes is generally known, there are only three examples of metal-based cross-coupling of iodinated carbonates with alkynes to date. In all cases, Boc-protected phenolic compounds have been coupled. For example, Ferreira and Costello coupled Boc-protected 4-iodophenol with 4-pentyn-1-ol under Pd / Cu catalysis, using triethylamine as both base and solvent [Costello, JP; Ferreira, EM, Org. Lett. 2019, 21, 9934-9939]. In addition, benzyl propargyl ether has been used as a coupling agent [Bates, RW; Gabel, CJ; Ji, J.; Rama-Devi, T., Tetrahedron 1995, 51, 8199-8212]. Recently, Boc-protected 2-formyl-5-iodo-quinolin-8-ol was also coupled with 4-methoxyphenylacetylene [Ko, M.-S.; Rao, P.S.; Cho, D.-G., Molecules 2021, 26, 917]. However, other couplings with alkynes, as well as polymerization reactions of the corresponding iodinated carbonates, are unknown.

[0011] Along the same lines, the Heck coupling reaction of iodinated active aromatic compounds (i.e., existing aromatic compounds without carbonate groups, such as iodinated anisole) with terminal olefins is known. In contrast, in the context of the cross-coupling reaction of iodinated carbonates with terminal olefins, only one example is known so far. In this example, a Heck-type coupling of iodinated phenolic substrates containing a Boc protecting group was performed [Lu, Y.; Schiller, PW, Synthesis 2001, 1639-1644; Lu, Y.; Weltrowska, G.; Lemieux, C.; Chung, NN; Schiller, PW, Bioorg. Med. Chem. Lett. 2001, 11, 323-325]. Other such couplings of iodinated carbonates with olefins, as well as examples of corresponding polymerization reactions, are unknown.

[0012] Based on this prior art, a further object of the present invention is to provide a process for preparing polycarbonates (in addition to the interphase phosgenation or melt transesterification process), and to provide the polycarbonates themselves, which are based on existing, but also novel aromatic structural units, especially bio-based structural units. Preferably, the process should lead to polycarbonates with improved properties, especially with regard to mechanical and / or optical properties, heat resistance and / or weathering resistance.

[0013] At least one of the above objects, preferably all of these objects, has been solved by the present invention.

[0014] Surprisingly, the inventor has found a method for preparing polycarbonate, which provides an alternative to known methods (such as interphase phosgenation or melt transesterification). More surprisingly, the inventor has found a method for preparing polycarbonate with repeating units, wherein the repeating units include two aromatic moieties connected to each other, and-in the repeating units-one of the aromatic moieties is replaced by carbonate groups. Surprisingly, the inventor has found a method for preparing polycarbonate with repeating units, wherein the repeating units include two aromatic moieties connected to each other, and-in the repeating units-one of the aromatic moieties is replaced by carbonate groups, wherein carbonate groups are introduced into the repeating units without the need to form carbonate groups separately. As mentioned, the inventor can find a method for preparing polycarbonate, including the reaction forming the repeating units, including connecting two aromatic moieties to each other. This reaction forces the aromatic moieties to include carbonate substituents, to form a polymer backbone with repeating units, and each repeating unit includes the carbonate groups replacing one of the aromatic moieties. Faced with this object, the inventors subsequently found a process for preparing polycarbonates having repeating units, the repeating units comprising two aromatic moieties connected to one another and - within the repeating units - one of the aromatic moieties is substituted by a carbonate group, wherein the carbonate group is not affected by the process itself. In this context, the term "affected" preferably means that the carbonate is not decomposed.

[0015] Furthermore, the inventors have found a polycarbonate obtainable by the process according to the invention. Furthermore, the inventors have found a polycarbonate comprising new chemical and physical properties when compared to the polycarbonates known from the prior art.

[0016] The inventors have found a method and a polycarbonate which employs / contains existing, but also novel aromatic structural units, in particular bio-based structural units. The method found by the inventors leads to polycarbonates with improved properties, in particular with regard to mechanical and / or optical properties, heat resistance and / or weathering resistance. The same applies to the polycarbonate itself.

[0017] Surprisingly, it has been found that the metal-catalyzed coupling of the terminal alkynes of the structure of formula (IIa) or the terminal olefins of the structure of formula (IIb) can be used to connect two aromatic moieties with carbonate groups, preferably both of which carry carbonate groups. According to the present invention, this reaction itself can be used to polymerize such aromatic moieties to obtain polycarbonates. This reaction can be used for existing structural units, but can also be used for new, especially bio-based structural units (such as iodinated derivatives of guaiacol carbonate, also referred to as bis(2-methoxyphenyl) carbonate, and derivatives thereof, such as bis(2-methoxy-4-propylphenyl) carbonate). In addition, the resulting polycarbonate obtained from this method is preferably included in properties improved in terms of mechanical and / or optical properties, heat resistance and / or weather resistance.

[0018] Therefore, the present invention provides a method for preparing polycarbonate using metal-catalyzed cross-coupling, which comprises a compound having a structure of formula (I)

[0019]

[0020] and a compound having a structure of formula (IIa) or (IIb)

[0021]

[0022] A reaction in the presence of a metal catalyst and a base, wherein

[0023] a) using the reaction of compound (IIa) to produce a polycarbonate comprising repeating units having a structure of formula (IIIa)

[0024]

[0025] The repeating unit having the structure of formula (IIIa) comprises two aromatic rings, a carbonate group -OC(=O)O- and a connecting group having the structure of formula (IVa)

[0026]

[0027] wherein one of the two aromatic rings is substituted by a carbonate group, the two aromatic rings are connected via a linking group, and the linking group in each repeating unit is independently located at the ortho position, meta position or para position relative to the carbonate group,

[0028] b) using the reaction of compound (IIb) to produce a polycarbonate comprising repeating units having a structure of formula (IIIb)

[0029]

[0030] The repeating unit having the structure of formula (IIIb) comprises two aromatic rings, a carbonate group -OC(=O)O- and a linking group having the structure of formula (IVb)

[0031]

[0032] wherein one of the two aromatic rings is substituted by a carbonate group, the two aromatic rings are connected by a connecting group, and the connecting group in each repeating unit is independently located at the ortho position, meta position or para position relative to the carbonate group,

[0033] And among them

[0034] - each m is independently 0 to 4, preferably 1 to 3,

[0035] - Each R 1 and R 2 R 1 Substituents and R 2 a substituent which is capable of activating the aromatic ring it replaces by mesenchymal and / or inductive effects,

[0036] -R 3 express

[0037] o optionally substituted alkyl, alkenyl or alkynyl, wherein the optionally substituted alkyl, alkenyl or alkynyl is optionally interrupted by at least one heteroatom,

[0038] o optionally substituted cycloalkyl or cycloalkenyl, or

[0039] o optionally substituted phenyl,

[0040] -R 4 express

[0041] o optionally substituted alkyl or alkenyl,

[0042] o optionally substituted cycloalkyl or cycloalkenyl, or

[0043] o optionally substituted aryl,

[0044] - Each R 5 Independently express

[0045] o Hydrogen atoms, or

[0046] o optionally substituted alkyl or alkenyl, wherein the optionally substituted alkyl or alkenyl is optionally interrupted by an ester group, and

[0047] -n is the number of repeating units.

[0048] The polycarbonate in the context of the present invention may be a homopolycarbonate or a copolycarbonate; the polycarbonate may be linear or branched or cyclic, depending on the type of monomer used in the present invention. For the purposes of the present invention, the expression "bio-based" should be understood in the following sense as the relevant chemical compound being available and / or obtainable via renewable and / or sustainable raw materials at the date of application and / or preferably being such renewable and / or sustainable raw materials. Renewable and / or sustainable raw materials are preferably understood to mean raw materials that are regenerated by natural processes at a rate comparable to their consumption rate (see CEN / TS16295:2012). This expression is particularly useful for distinguishing it from raw materials produced from fossil raw materials, which, according to the present invention, are also referred to as petroleum-based raw materials. Whether a raw material is bio-based or petroleum-based can be determined by measuring the carbon isotopes in the raw materials, since the carbon isotopes C in fossil raw materials are preferably 1.5-2.0. 14 The relative amount is low. For example, this can be carried out according to ASTM D6866-18 (2018) or ISO16620-1 to -5 (2015) or DIN SPEC 912362011-07. Exemplary bio-based carbonates are guaiacol carbonate and bis (2-methoxy-4-propylphenyl) carbonate. In addition, iodination of bio-based carbonates with an electrophilic iodinating agent (e.g., iodine monochloride in a halogenated solvent such as dichloromethane) can provide iodinated bio-based carbonate diaryl esters of formula (I) in the sense of the present invention. Exemplary iodinated bio-based carbonate diaryl esters of formula (I) are bis (5-iodo-2-methoxyphenyl) carbonate and bis (5-iodo-2-methoxy-4-propylphenyl) carbonate.

[0049] In the context of the present invention, reference is made to the mechanism of the palladium-catalyzed Sonogashira and Heck cross-coupling reactions representing metal-catalyzed cross-coupling reactions, for example, an aryl halide reacts with a terminal alkyne or a terminal olefin, respectively, in the presence of a palladium catalyst and a base, which reactions are known to those skilled in the art and are described in various textbooks on organic chemistry. The method according to the invention may be based on the Sonogashira or Heck cross-coupling reactions, but also includes modifications of the classic reactions. Therefore, reference is more precisely made to the more general metal-catalyzed cross-coupling reactions. However, those skilled in the art know and understand the concept of the Sonogashira and Heck cross-couplings and, once the present invention is understood, the principle of this general concept can be transferred to modifications of the method of the invention.

[0050] Further reference has been made to the substituent (substituent of aromatic ring) that can activate its substituted aromatic ring by mediating effect and / or inductive effect.Those skilled in the art are known to activate the substituent of its substituted aromatic ring by mediating effect and / or inductive effect.Under this background, diaryl carbonate can carry out electrophilic iodination reaction with electrophilic iodination agent, to obtain the iodinated diaryl carbonate of formula (I) as the starting material of the reaction according to the method according to the invention.For example, iodination agent can be the iodine monochloride (ICl) used in halogenated solvent (for example methylene chloride).Because the iodinated diaryl carbonate with the structure of formula (I) as the reaction starting material of the method according to the invention may not be commercially available usually, therefore before according to the method according to the invention, can provide by carrying out described iodination to diaryl carbonate.

[0051]

[0052] In this context, by selecting R on the aromatic ring(s) of the diaryl carbonate 1 and / or R 2 Substituents, those skilled in the art can affect the structure of the resulting iodinated diaryl carbonate of formula (I), and therefore can also affect the structure of the polycarbonate produced by the metal-catalyzed cross-coupling reaction of the iodinated diaryl carbonate of formula (I). This is because in the metal-catalyzed cross-coupling reaction of the iodinated diaryl carbonate of formula (I) with the terminal alkyne of structure (IIa) or the terminal olefin of structure (IIb), the iodine atom in the iodinated diaryl carbonate of formula (I) is respectively and independently replaced by the linking group of formula (IVa) or (IVb) in the repeating unit of the corresponding polycarbonate of formula (IIIa) or (IIIb) obtained as the product of the method according to the present invention (i.e., coupled at the same position). In other words, by affecting the position of the iodine atom on the aromatic ring of the diaryl carbonate of formula (I), those skilled in the art can determine the corresponding position of the linking group in the resulting polycarbonate repeating unit. For example, if the iodine atom in the iodinated diaryl carbonate of formula (I) is located in the meta position relative to the carbonate group already present, then the linking group in the polycarbonate repeating unit produced by the metal-catalyzed cross-coupling reaction of the iodinated diaryl carbonate of formula (I) with the terminal alkyne of structure (IIa) or the terminal olefin of structure (IIb) is also located in the meta position relative to the carbonate group in the repeating unit (IIIa) or (IIIb), respectively. A person skilled in the art who understands the concept of metal-catalyzed cross-coupling reactions will be able to understand and transfer this concept to modifications of the above examples. Along those lines, by selecting R on the (one or more) aromatic rings of the iodinated diaryl carbonate of formula (I), the linking group in the polycarbonate repeating unit produced by the metal-catalyzed cross-coupling reaction of the iodinated diaryl carbonate of formula (I) will be located in the meta position relative to the carbonate group in the repeating unit (IIIa) or (IIIb), respectively. 1 and / or R 2 substituents, wherein each substituent R 1 and / or R 2The substituted aromatic ring can be activated by the mediating effect and / or the inductive effect, and the metal-catalyzed cross-coupling reaction of the diaryl iodide carbonate of formula (I) with the unsaturated compound having the structure of formula (IIa) or (IIb) can be promoted. 1 and / or R 2 In the case where the substituent represents a methoxy group capable of activating the aromatic ring it replaces by a positive mesomeric effect (+M-effect) as described below, it has been found that R 1 and / or R 2 This choice of substituent is advantageously to include the substituent R 1 and / or R 2 In this context, the term "beneficial" is understood in the following sense: in the absence of the substituent R 1 and / or R 2 In the case of the presence of the above beneficial activation R 1 and / or R 2 In this context, however, it should also be noted that the number "m" in formula (I) may also be 0, wherein each m is independently a substituent R on the substituted (or unsubstituted) aromatic ring thereof. 1 and / or R 2 In other words, the corresponding aromatic rings independently may also not be substituted by R at all. 1 and / or substituent R 2 Substitution. In this context, in the reaction using compound (IIa), each m in formula (I) may be independently 0 to 4. Preferably, in the reaction using compound (IIa), each m in formula (I) is independently 1 to 3. More preferably, in the reaction using compound (IIa), each m in formula (I) is independently 1 or 2. Most preferably, in the reaction using compound (IIa), each m in formula (I) is 1, or each m in formula (I) is 2. In the reaction using compound (IIb), each m in formula (I) may be independently 0 to 4. Preferably, in the reaction using compound (IIb), each m in formula (I) is independently 1 to 3. More preferably, in the reaction using compound (IIb), each m in formula (I) is independently 1 or 2. Most preferably, in the reaction using compound (IIb), each m in formula (I) is 1, or each m in formula (I) is 2. In this context, when each m is independently 0, i.e. the corresponding aromatic ring is not substituted by any substituent R at all 1 and / or substituent R 2Substitution, the positive meso-effect (+M-effect) of the carbonate group -OC(=O)O- already present in the diaryl carbonate can be decisive for the structure of the corresponding iodinated diaryl carbonate of formula (I) produced by electrophilic iodination of the diaryl carbonate with an electrophilic iodination agent (such as iodine monochloride used in dichloromethane).

[0053] Preferably, the term "mediation effect" or M effect refers to the known resonance effect. More preferably, the term refers to the delocalization of electrons in a molecule through the interaction between two π bonds or a π bond and a lone pair of electrons present on an adjacent atom. The term is preferably used to describe the electronic effect of a substituent on an aromatic moiety based on a related resonance structure. It is usually represented by the letter M. When a substituent extracts electrons from an aromatic ring through a π bond, which is called resonance electron extraction, the mediation effect can be negative (-M). When a substituent donates electrons to an aromatic ring through a π bond, the effect can also be positive (+M, called resonance electron donation).

[0054] Preferably, the term "inductive effect" or I effect refers to the movement of electrons via a sigma bond to a more electronegative atom. Due to the inductive effect, one end of the bond acquires a partial positive charge, while the other end acquires a partial negative charge. The relative inductive effects of substituents bonded to an aromatic ring are described with reference to hydrogen. For example, a substituent with a +I effect (electron-donating property) is more capable of donating its sigma electrons to the aromatic ring than hydrogen. Conversely, a substituent with a -I effect (electron-withdrawing property) is more capable of absorbing or accepting sigma electrons than hydrogen.

[0055] The M and I effects are known to those skilled in the art. It is known that existing substituents on the aromatic ring can affect the overall reaction rate or have a directing effect on the positional isomers of the formed product. Here, the electron-donating or electron-withdrawing group is preferably an atom or functional group that supplies or withdraws part of its electron density to the conjugated π system via a mediating effect or an inductive effect, respectively. This makes the π system more nucleophilic. In terms of regioselectivity, some existing substituent groups on the aromatic ring promote further substitutions in the ortho or para position relative to itself. Other groups are conducive to further substitutions in the meta position. Those groups are known to those skilled in the art. Substituents that exhibit a +I or +M effect can be directed to the ortho and / or para position relative to itself. Substituents that exhibit an -I or -M effect can be directed to the meta position. As known to those skilled in the art, the M effect of a substituent is in principle more important than the I effect. This means that the +M effect can suppress the small -I effect.

[0056] It has been found that the process according to the invention can be used to obtain regular polymer backbones having a linking group of formula (IVa) or (IVb) between two linked aromatic moieties

[0057]

[0058] The linking group is located at the ortho position, meta position or para position relative to the carbonate group. According to the present invention, if not otherwise specified, the ortho position, meta position or para position always refers to the position on the aromatic ring relative to the mandatory carbonate group on the same ring. Existing carbonate groups have a small +M effect and can be able to direct electrophilic iodine to the para position relative to the carbonate group. However, this effect can be suppressed by the additional substituents on the aromatic ring. According to the present invention, each R in formula (I) and / or (IIIa) and / or (IIIb) 1 and R 2 Each independently represents an additional R 1 and R 2 Substituents that are capable of activating the aromatic ring they replace through mesotropic and / or inductive effects. For example, all additional R 1 and / or R 2 The substituents may exhibit a +M or +I effect. In addition, each m in formula (I) and formula (IIIa) or (IIIb) is independently 0 to 4, preferably 1 to 3. This means that one or more additional substituents R 1 and / or R 2 may be attached to the aromatic ring (m is 1 to 4). Alternatively, no additional substituent R may be attached to the aromatic ring. 1 and / or R 2 (m is 0). In this context, in the reaction using compound (IIa), each m can be independently 0 to 4. Preferably, in the reaction using compound (IIa), each m is independently 1 to 3. More preferably, in the reaction using compound (IIa), each m is independently 1 or 2. Most preferably, in the reaction using compound (IIa), each m is 1, or each m is 2. In the reaction using compound (IIb), each m can be independently 0 to 4. Preferably, in the reaction using compound (IIb), each m is independently 1 to 3. More preferably, in the reaction using compound (IIb), each m is independently 1 or 2. Most preferably, in the reaction using compound (IIb), each m is 1, or each m is 2. In this context, it has been found that additional R 1 and R 2 The substituents can suppress the para-directing effect of the carbonate group, allowing very selective iodination reactions to occur, and regular polycarbonate polymers can be found to have meta-linkages relative to the carbonate groups, resulting from metal-catalyzed cross-coupling of iodinated diaryl carbonates of formula (I) (obtainable by electrophilic iodination reactions).

[0059] For example, if R 1 and / or R 2The substituent has a para-directing effect (i.e., R 1 and / or R 2 The substituents are capable of directing the electrophilic iodine to the aromatic ring relative to R 1 and / or R 2 The substituent is located at the para position), and the R 1 and / or R 2 The substituent is located in the ortho position relative to the carbonate group substituting the same aromatic ring, then in the polycarbonate produced by coupling the terminal alkyne of formula (IIa) or the terminal olefin of formula (IIb) with the iodinated diaryl carbonate of formula (I), a meta-linkage relative to the carbonate group is obtained, thereby directing the para-directed R 1 and / or R 2 The substituent is incorporated in the ortho position relative to the carbonate group substituting the same aromatic ring. Thus, selective coupling can occur, wherein the resulting polycarbonate contains primarily meta linkages. However, in this context, it should be noted that the "para-directed" R 1 and / or R 2 Substituents are generally understood to be ortho-directed and para-directed substituents (as opposed to substituents that are only meta-directed). The skilled person knows that substituents can be para / ortho-directed or meta-directed. Turning to the present case, "para-directed" R 1 and / or R 2 Substituents are primarily directed at the para and ortho positions. If this “para-directed” R 1 and / or R 2 Substituents (which are usually para- and ortho-directed) are present in the ortho position relative to the carbonate group (substituting the same aromatic ring), then steric hindrance may lead to completely para-selective substitution (resulting in meta-linkage). In this case, ortho-substitution may not be observed. Examples of such para-directed substituents are alkoxy groups, such as methoxy.

[0060] R 1 and / or R 2 Substituents may also be located in the meta or para position relative to the carbonate group on the same aromatic ring. 1 and / or R 2 How the substituents and their directing effects on the position of the aromatic ring relative to the carbonate group substituting the same aromatic ring can affect the resulting iodination position and thus the linkage in the polycarbonate resulting from the cross-coupling at the same position of the aromatic ring. 1 and / or R 2 The effect of the selective reaction is even more pronounced if the polycarbonate is a polyisocyanate, a polyisocyanate, or a polyisocyanate. These substituents, due to their chemical nature, are able to direct the electrophilic iodine to exactly the same carbon atom. Those skilled in the art know how different substituents attached to the aromatic ring(s) affect the resulting polycarbonate.

[0061] Furthermore, the compound of formula (IIa) or (IIb) respectively determines the structure of the linking group of formula (IVa) or (IVb) respectively in the repeating unit of formula (IIIa) or (IIIb) respectively of the polycarbonate produced by the process according to the invention.

[0062]

[0063] The compound of formula (IIa) is a compound having R 3 Substituents of the terminal alkyne, the R 3 The substituent may be an optionally substituted alkyl, alkenyl or alkynyl group, wherein the optionally substituted alkyl, alkenyl or alkynyl group is optionally interrupted by at least one heteroatom. 3 represents an optionally substituted cycloalkyl or cycloalkenyl group. 3 represents an optionally substituted phenyl group. Therefore, R in the linking group of formula (IVa) and the repeating unit of formula (IIIa) 3 is any of the above groups, depending on R 3 In the compound of formula (IIa), what does it mean? Conversely, the compound of formula (IIb) is a compound with R 4 Substituents and R 5 Substituents of terminal olefins. 4 represents an optionally substituted alkyl or alkenyl group. 4 represents an optionally substituted cycloalkyl or cycloalkenyl group. 4 represents an optionally substituted aryl group. 5 represents a hydrogen atom. Alternatively, R 5 represents an optionally substituted alkyl or alkenyl group, wherein the optionally substituted alkyl or alkenyl group is optionally interrupted by an ester group. 4 and / or R 5 is any of the above groups, depending on the R 4 and / or R 5 What does R mean? 3 , R 4 and / or R 5 The carbon atoms of the substituent may be straight-chain or branched. 3 , R 4 and / or R 5 represents an alkenyl group, the alkenyl group may contain one or more double bonds. Thus, if R 3 represents an alkynyl group, the alkynyl group may contain one or more triple bonds. In general, by selecting the substituent R of the compound of formula (IIa) or (IIb) 3 , R 4 and / or R5 , those skilled in the art are able to adjust the structure of the resulting linking group in the repeating unit having the structure of formula (IIIa) or (IIIb), and thus those skilled in the art are able to adjust the structure of the entire polycarbonate.

[0064] "Alkyl" in the context of the present invention, for example and if not mentioned differently, refers to a saturated straight-chain or branched hydrocarbon, and therefore, it contains only carbon-carbon (CC) single bonds. Preferably, the alkyl group according to the present invention has 1 to 20 carbon atoms. In addition, the alkyl group according to the present invention may be interrupted by at least one heteroatom, or an ester group -C(=O)O-, or a combination of these. If the present invention defines the carbon atoms of the alkyl group in a different way, the choice of alkyl structure may be limited. The heteroatom may, for example, be selected from a nitrogen atom or an oxygen atom. In this context, it should be noted that if the heteroatom is a nitrogen atom, the nitrogen can be further substituted by a substituent (except a hydrogen atom) in addition to interrupting the alkyl group, which means that the nitrogen atom can represent a trisubstituted nitrogen atom as part of a tertiary amine.

[0065] "Alkenyl" in the context of the present invention, for example and if not mentioned differently, refers to an unsaturated straight-chain or branched hydrocarbon, and which contains one or more carbon-carbon (C=C) double bonds in addition to single bonds. Preferably, the alkenyl according to the present invention has 1 to 20 carbon atoms. In addition, the alkenyl according to the present invention may be interrupted by at least one heteroatom, or an ester group -C(=O)O-, or a combination of these. If the present invention defines the carbon atoms of the alkenyl in a different way, the choice of these structures may be limited. The heteroatom may, for example, be selected from a nitrogen atom or an oxygen atom. In this context, it should be noted that if the heteroatom is a nitrogen atom, the nitrogen, in addition to interrupting the alkenyl, may also be further substituted by a substituent (except a hydrogen atom), which means that the nitrogen atom may represent a trisubstituted nitrogen atom as part of a tertiary amine.

[0066] "Alkynyl" in the context of the present invention, for example and if not mentioned differently, refers to an unsaturated straight-chain or branched hydrocarbon, and which contains one or more carbon-carbon (C≡C) triple bonds in addition to single bonds. Preferably, the alkynyl according to the invention has 1 to 20 carbon atoms. In addition, the alkynyl according to the invention may be interrupted by at least one heteroatom. If the present invention defines the carbon atoms of the alkynyl in a different way, the choice of these structures may be limited. The heteroatom may, for example, be selected from a nitrogen atom or an oxygen atom. In this context, it should be noted that if the heteroatom is a nitrogen atom, the nitrogen, in addition to interrupting the alkynyl, may be further substituted by R 6 (except hydrogen atoms) substitution, which means that the nitrogen atom can represent a trisubstituted nitrogen -N (R 6 )-. For example, the alkynyl groups according to the present invention may be trisubstituted nitrogen-N(R 6)-interrupted, wherein the further substituent R 6 represents an alkynyl group as defined above. Preferably, R 6 represents a straight chain or branched alkynyl group having 1 to 20 carbon atoms. More preferably, R 6 represents a straight-chain or branched alkynyl group having 3 carbon atoms. Most preferably, R 6 It represents a straight-chain alkynyl group having 3 carbon atoms.

[0067] "Cycloalkyl" in the context of the present invention, for example and if not mentioned differently, refers to a saturated carbocyclic hydrocarbon and, therefore, it contains only carbon-carbon (C-C) single bonds. Preferably, the cycloalkyl groups according to the present invention have 6 to 12 carbon atoms. They may be monocyclic or polycyclic. C6 to C 12 Preferred examples of cycloalkyl are cyclohexane, cycloheptane, cyclooctane, cyclodecane, cycloundecane or cyclododecane. Most preferred is cyclohexane.

[0068] "Cycloalkenyl" in the context of the present invention, for example and if not mentioned differently, refers to an unsaturated carbocyclic hydrocarbon and which, in addition to single bonds, contains one or more carbon-carbon (C=C) double bonds. Preferably, the cycloalkenyl groups according to the invention have 6 to 12 carbon atoms. They may be monocyclic or polycyclic. C6 to C 12 Preferred examples of cycloalkyl are cyclohexene, cycloheptene, cyclooctene, cyclodecene, cycloundecene or cyclododecene. Most preferred is cyclohexene.

[0069] "Alkoxy" in the context of the present invention, for example and if not mentioned differently, refers to a straight-chain or branched alkyl group (-OR) which is bonded solely to oxygen. Preferably, the alkoxy group according to the invention has 1 to 6 carbon atoms and thus includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, neopentoxy, 1-ethylpropoxy, cyclohexyloxy, cyclopentyloxy, n-hexyloxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 1,2-dimethylpropoxy, 1-methylpentyloxy, 2-methylpentyloxy, The present invention also includes 1,2-dimethylbutyloxy, 1,3-dimethylbutyloxy, 2,2-dimethylbutyloxy, 2,3-dimethylbutyloxy, 3,3-dimethylbutyloxy, 1-ethylbutyloxy, 2-ethylbutyloxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy, 1-ethyl-2-methylpropoxy or 1-ethyl-2-methylpropoxy. If the present invention defines the carbon atoms of the alkoxy group in different ways, the selection of these structures can be limited.

[0070] The above list should be understood as examples and not as limitations.

[0071] "Aryl" in the context of the present invention, for example and if not mentioned differently, refers to an organic group derived by removing at least one hydrogen atom from an aromatic hydrocarbon. Preferably, the aryl group according to the present invention comprises at least one phenyl group. In this context, "phenyl" in the context of the present invention, for example and if not mentioned differently, refers to an aryl group derived by removing at least one hydrogen atom from benzene (C6H6). Preferably, the phenyl group according to the present invention has 6 to 12 carbon atoms in total. For example, the phenyl group according to the present invention can be an aryl group derived by removing two hydrogen atoms from benzene (C6H6), i.e. the organic group -C6H4-.

[0072] In the context of the present invention, "I" refers to an iodine substituent. However, in this context, it should be noted that the iodinated diaryl carbonate of formula (I) may also contain a substituent "I q ” (rather than the substituent “I”), wherein I refers to an iodine atom, and q is I q The number of iodine atoms on the substituted aromatic ring, and wherein q can be a number greater than 1. For example, each q can be 2, so that in the compound of formula (I), each aromatic ring is substituted with two iodine atoms. For example, if each q is 2, then the two iodine atoms of the two aromatic rings in the compound of formula (I) can each independently be attached to the meta position on the corresponding aromatic ring relative to the carbonate group already present in the compound of formula (I), thereby producing multiple meta-links in the resulting branched polycarbonate.

[0073] In addition, "n" is listed as the number of repeating units in formula (IIIa) and (IIIb). Preferably, n is 6 to 60, more preferably 10 to 55, even more preferably 20 to 50, even more preferably 25 to 45, and most preferably 30 to 40. Depending on the length of the polycarbonate produced (and therefore on the number of repeating units n), the physical, chemical and mechanical properties of the polycarbonate may be different. Depending on the number of repeating units, the microscopic and / or macroscopic structure of the polycarbonate may also be changed. By the preferred number of repeating units n, an optimal balance between the processability and mechanical properties of the polycarbonate produced can be established. Therefore, those skilled in the art can select the number of n to adjust the specific properties of the polycarbonate.

[0074] According to the present invention, the cross-coupling reaction of the diaryl iodide carbonate of formula (I) and the terminal alkyne of formula (IIa) or the terminal olefin of formula (IIb) requires a metal catalyst. The term "metal catalyst" is known to those skilled in the art. Generally, a catalyst refers to a substance that increases the rate of a chemical reaction without undergoing any permanent chemical change itself. If the catalyst and the reactant are in the same phase (liquid / solid or gas), the catalyst is referred to as a homogeneous catalyst. Metal compounds, such as palladium (II) compounds used in traditional organic solvents, are examples of homogeneous catalysts. In contrast, if the catalyst and the reactant are in different phases, the catalyst is referred to as a heterogeneous catalyst. An example of a heterogeneous catalyst is a pure metal, such as palladium (Pd) representing a non-supported heterogeneous catalyst. When a heterogeneous catalyst is attached to a material with a high surface area (such as carbon), it represents a supported heterogeneous catalyst, such as palladium on carbon (Pd / C). The carrier provides stability for the heterogeneous metal catalyst. In particular, transition metals are suitable metals for use as metal catalysts because they can exist in various oxidation states, transform between oxidation states, form complexes with organic ligands, and serve as good electron sources. In the context of the present invention, metal catalysts are necessary for the key steps of performing metal-catalyzed cross couplings. Depending on reaction conditions, the key steps of metal-catalyzed cross couplings may involve oxidative addition of organic halides, transmetallation of nucleophilic carbons and reduction elimination or migration insertion / β-hydride elimination sequences to form products. In addition to enabling and accelerating cross coupling reactions, metal catalysts may also be able to apply regioselectivity and / or stereoselectivity in the polycarbonate produced by the method according to the present invention.

[0075] In addition, according to the present invention, the cross-coupling reaction of the diaryl iodide carbonate of formula (I) and the terminal alkyne of formula (IIa) or the terminal olefin of formula (IIb) requires a base. The term "base" is known to those skilled in the art. In particular, the definition of the term "base" has been given by Arrhenius, Bronsted-Lowry and Lewis. According to Bronsted-Lowry, an acid is a proton (hydrogen nucleus) donor, while a base is a proton (hydrogen nucleus) acceptor, and an acid and a corresponding base are referred to as a conjugate acid-base pair. According to Lewis' definition, an acid is an electron pair acceptor, while a base is an electron pair donor. These bases are referred to as "Lewis acids" and "Lewis bases", and are electrophiles and nucleophiles, respectively, in organic chemistry, and "Lewis bases" are ligands in coordination chemistry. In the context of the present invention, for example, in a palladium-catalyzed Heck cross-coupling reaction, a base can be crucial for the regeneration of the palladium (0) species as part of the catalytic cycle by the reduction elimination of the palladium (II) species. The regenerated palladium(0) species may then be able to undergo oxidative addition and begin a new catalytic cycle. In another example, in a Sonogashira cross-coupling reaction, a base may be required for the deprotonation of a terminal alkyne in the presence of a copper co-catalyst and the generation of the corresponding acetylide anion, which may then be transmetallated to a palladium catalytic species to enable further catalytic steps and ultimately generate an alkyne-substituted cross-coupling product.

[0076] In a preferred embodiment of the present invention, a method is provided, wherein at least one R 1 Substituents and / or at least one R 2 The substituent is located in the ortho position relative to the carbonate group substituting the same aromatic ring. Preferably, at least one R 1 and R 2 The substituents are all located in the ortho or para position relative to the carbonate group.

[0077] In addition, in a preferred embodiment of the present invention, a method is provided, wherein each R 1 The substituent and each R 2 The substituents independently represent alkyl or alkoxy groups, more preferably alkyl or alkoxy groups having 1 to 6 carbon atoms. They may be straight chain or branched. Alkyl groups exhibit a +I effect, and alkoxy groups exhibit a +M effect. For steric reasons, substituents having 1 to 6 carbon atoms are preferred. Therefore, preferably each R 1 The substituent and each R 2The substituents independently represent methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, neopentyl, 1-ethylpropyl, cyclohexyl, cyclopentyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1,2-dimethylpropyl, 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, 1-ethyl-2-methylpropyl, 1-ethyl-2-methylpropyl, methoxy, ethoxy, n-propoxy, isopropyl Propoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, neopentoxy, 1-ethylpropoxy, cyclohexyloxy, cyclopentyloxy, n-hexyloxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 1,2-dimethylpropoxy, 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, 1-ethyl-2-methylpropoxy or 1-ethyl-2-methylpropoxy.

[0078] In general, the skilled person will know how the selection of any compound of formula (I) affects the resulting polycarbonate comprising repeating units having the structure of formula (IIIa) or (IIIb). Thus, the skilled person will be able to predict the structural impact of the compound of formula (I). Preferably, the compound of formula (I) is selected from iodinated bio-based diaryl carbonates, such as iodinated guaiacol carbonate or iodinated bis(2-methoxy-4-propylphenyl) carbonate. In the case of iodinated guaiacol carbonate, for R 1 And for R 2 , m are all 1, and R 1 and R 2 Each of the substituents is a methoxy group, each located at an ortho position relative to the carbonate group substituting the same aromatic ring. For iodinated bis(2-methoxy-4-propylphenyl) carbonate, for R 1 And for R 2 , m are both 2, one of them is R 1 and an R 2The substituents are each methoxy, each located at an ortho position relative to the carbonate group substituting the same aromatic ring, and one R 1 and an R 2 The substituents are each n-propyl, each located in the para position relative to the carbonate group substituting the same aromatic ring. The exemplary bio-based carbonates mentioned, namely guaiacol carbonate or bis(2-methoxy-4-propylphenyl) carbonate, are each substituted with R exhibiting a +M effect. 1 and R 2 Substitution with substituents (here: methoxy) - where these methoxy substituents are located in the ortho position relative to the carbonate group substituting the same aromatic ring and are all capable of directing electrophilic iodine to the position para relative to itself and meta relative to the carbonate group on the aromatic ring - can be successfully iodinated at said position relative to the carbonate group. In addition, in model reactions, iodinated bio-based diaryl carbonates of formula (I) (such as bis(5-iodo-2-methoxyphenyl) carbonate or bis(5-iodo-2-methoxy-4-propylphenyl) carbonate) have been successfully coupled with terminal alkynes of formula (IIa) or terminal olefins of formula (IIb) (at the same position).

[0079] The resulting polycarbonate comprises repeating units having a structure of formula (IIIa) or (IIIb). In formula (IIIa), R 3 represents an optionally substituted alkyl, alkenyl or alkynyl group, wherein the optionally substituted alkyl, alkenyl or alkynyl group is optionally interrupted by at least one heteroatom. 3 represents an optionally substituted cycloalkyl or cycloalkenyl group. 3 In a preferred embodiment, R 3 represents an alkyl group having 1 to 20 carbon atoms, wherein the alkyl group is optionally interrupted by at least one heteroatom, and wherein at least one heteroatom is preferably selected from an oxygen atom or a nitrogen atom. In another preferred embodiment, R 3 represents phenyl, or a substituted phenyl having a total of 6 to 12 carbon atoms. Even more preferably, R 3 represents an alkyl group which is not interrupted and has 1 to 8 carbon atoms, most preferably 4 carbon atoms. A person skilled in the art knows how the selection of any compound of formula (IIa) affects the resulting polycarbonate comprising repeating units having the structure of formula (IIIa). Therefore, a skilled person is able to predict the effect of the structure of the compound of formula (IIa). In a most preferred embodiment of the present invention, a method is provided, wherein the compound of formula (IIa) is 1,7-octadiyne, wherein R 3represents an uninterrupted straight-chain alkyl radical having 4 carbon atoms. It has been found that this compound can be successfully used as a coupling partner for iodinated bio-based diaryl carbonates of formula (I) (such as bis(5-iodo-2-methoxyphenyl) carbonate or bis(5-iodo-2-methoxy-4-propylphenyl) carbonate) in a model reaction. In formula (IIIb), R 4 represents an optionally substituted alkyl or alkenyl group. 4 represents an optionally substituted cycloalkyl or cycloalkenyl group. 4 Preferably, R 4 represents an alkyl group having 1 to 20 carbon atoms. In addition, in formula (IIIb), R 5 represents a hydrogen atom. Alternatively, R 5 represents an optionally substituted alkyl or alkenyl group, wherein the optionally substituted alkyl or alkenyl group is optionally interrupted by an ester group. Preferably, R 5 Represents a hydrogen atom, or an alkyl group having 1 to 20 carbon atoms, wherein the alkyl group is optionally interrupted by an ester group. Again, the skilled person knows how the selection of any compound of formula (IIb) affects the resulting polycarbonate comprising repeating units having the structure of formula (IIIb). Therefore, the skilled person is able to predict the effect of the structure of the compound of formula (IIb). In a preferred embodiment of the present invention, a method is provided, wherein the compound of formula (IIb) is ethane-1,2-diyl diacrylate. Therefore, R 4 represents a straight chain alkyl group having 2 carbon atoms, and R 5 In a model reaction, such compounds react successfully with diaryl iodinated carbonates such as bis(5-iodo-2-methoxy-4-propylphenyl) carbonate.

[0080] In the context of the present invention, the linking groups of formula (IVa) and (IVb) in the repeating units of each formula (IIIa) and (IIIb) of the polycarbonate produced by the reaction of the iodinated diaryl carbonate of formula (I) with the terminal alkyne of formula (IIa) or the terminal olefin of structure (IIb) are independently located at the ortho position, meta position or para position relative to the carbonate group replacing the same aromatic ring. In a preferred embodiment of the present invention, the linking groups of formula (IVa) and / or (IVb) in the repeating units of each formula (IIIa) and / or formula (IIIb) of the obtained polycarbonate are independently located at the meta position relative to the carbonate group replacing the same aromatic ring. In this case, each iodine atom in the iodinated diaryl carbonate of formula (I) is also independently located at the meta position relative to the carbonate group replacing the same aromatic ring. In other words, if each iodine atom in the iodinated diaryl carbonate of formula (I) is independently located in the meta position relative to the carbonate group that replaces the same aromatic ring, then the linking group of formula (IVa) and / or (IVb) in each repeating unit of formula (IIIa) and / or formula (IIIb) of the resulting polycarbonate is also independently located in the meta position relative to the carbonate group that replaces the same aromatic ring, i.e. meta-linking is observed in the resulting polycarbonate. This is because, as described above, in the metal-catalyzed cross-coupling reaction of the iodinated diaryl carbonate of formula (I) with the terminal alkyne of formula (IIa) or the terminal olefin of formula (IIb), the iodine atoms in the iodinated diaryl carbonate of formula (I) are each independently formally substituted by the linking group of formula (IVa) or (IVb) in the repeating unit of formula (IIIa) or (IIIb) of the corresponding polycarbonate obtained as a product of the process according to the present invention (i.e. coupled at the same position). For example, the iodinated diaryl carbonate of structure (I) can be an iodinated bio-based carbonate, such as iodinated guaiacol carbonate or iodinated bis(2-methoxy-4-propylphenyl) carbonate. For example, the iodinated bio-based carbonate of structure (I) can be an iodinated bio-based diaryl carbonate at the meta position relative to the carbonate group replacing the same aromatic ring, such as bis(5-iodo-2-methoxyphenyl) carbonate or bis(5-iodo-2-methoxy-4-propylphenyl) carbonate. In this context, the iodinated diaryl carbonate of formula (I) (wherein each iodine atom is independently located at the meta position relative to the carbonate group replacing the same aromatic ring) can be obtained by the electrophilic iodination reaction of the corresponding (non-iodinated) diaryl carbonate with an electrophilic iodination agent, wherein the (non-iodinated) diaryl carbonate comprises at least one substituent R on each aromatic ring. 1 and / or R 2 , which can activate the aromatic ring it replaces through the mediating effect and / or the inductive effect. Therefore, by selecting R on the (one or more) aromatic rings of the diaryl carbonate 1 and / or R 2Substituents, those skilled in the art can influence the structure of the resulting diaryl iodide carbonate of formula (I), as well as the structure of the polycarbonate produced by the metal-catalyzed cross-coupling reaction of the diaryl iodide carbonate of formula (I) (ie, the linkages in the polycarbonate).

[0081] In a preferred embodiment of the present invention, each of the two aromatic rings in each repeating unit of formula (IIIb) is independently connected to a linking group (including substituents R 4 and R 5 ) is substituted so that each repeating unit represents an (E,E)-isomer. In this context, in the structure of the repeating unit of formula (IIIb) of the polycarbonate produced by the process according to the present invention, the CC single bond directly attached to the aromatic ring and the terminal C=C double bond of the linking group each independently appears as an undefined stereo bond This is not to be understood as a restriction, but because, depending on the choice of the substituents R4 and R5, which themselves can represent optionally substituted groups, the repeating units of formula (IIIb) in the polycarbonate produced by the process according to the invention can represent different isomers. In general, in compounds containing a C=C double bond, free rotation about the bond axis is hindered. Therefore, in compounds with a C=C double bond (olefins), (E / Z)-isomers can exist, which differ in the position of the substituents on the double bond atoms. The (E / Z) nomenclature, also known as the Cahn-Ingold-Prelog (CIP) nomenclature, is a nomenclature known to the person skilled in the art for naming isomers and is described in various textbooks on organic chemistry. According to the CIP nomenclature, the substituents on the C=C double bond are sorted according to the CIP priority rules. In this context, if the substituents with higher priority are located on the same side of the double bond, the isomers are referred to as (Z)-isomers (Z: "zusammen" = together). If, on the other hand, the substituent with the higher priority is located on the opposite side of the double bond, the isomer is called an (E) isomer (E: "entgegen" = separate). (E / Z)-isomers are diastereoisomers because they are stereoisomers of the same structure, i.e. the connections between each atom are identical and the molecules do not have a mirror-image relationship. Therefore, they have different physical and chemical properties. Therefore, by choosing R representing the optional substituent groups on the terminal olefin of formula (IIb), 4 and R 5Substituents and reaction conditions of the polymerization reaction, such as the choice of a certain metal catalyst, can influence the structure of the repeating unit of formula (IIIb) in the polycarbonate obtained by the process according to the invention, which means that the skilled person can influence the structure and properties of the resulting polycarbonate comprising repeating units of formula (IIIb). According to the invention, as described above, it is preferred to make such a choice that each repeating unit of formula (IIIb) represents an (E,E)-isomer, in which each of the two aromatic rings is independently connected by a linking group (including the substituent R 4 and R 5 )replace.

[0082] According to the invention, the method comprises reacting a compound having a structure of formula (I) with a compound having a structure of formula (IIa) or (IIb) in the presence of a metal catalyst and a base. The compound of formula (I) is a diaryl iodide carbonate, the compound of formula (IIa) is a terminal alkyne, and the compound of formula (IIb) is a terminal olefin. In the context of the present invention, however, it should be noted that it is not limited to the use of terminal olefins of formula (IIb). On the contrary, it should be understood that in principle terminal olefins other than the acrylate derivatives of formula (IIb) shown - that is, other than being interrupted by two ester groups -C(=O)O- having an electron-withdrawing effect as defined below, and thus being able to activate the olefin in a metal-catalyzed cross-coupling reaction with the compound of formula (I) - can also be used in the reaction. The skilled person is fully aware of the effect of electron-withdrawing groups directly attached to the terminal double bond of the terminal olefin, thereby being able to activate the olefin in a metal-catalyzed cross-coupling reaction. For example, an electron withdrawing group other than an ester group can be directly attached to the terminal double bond of a terminal olefin to activate the olefin in a cross-coupling reaction with a compound of formula (I), preferably resulting in a selective conversion to the (E,E)-isomer relative to the repeating unit of the resulting polycarbonate.

[0083] In a preferred embodiment of the present invention, the compound of formula (IIa) or the compound of formula (IIb) is added in an amount of 0.1 to 10.0 equivalents relative to the compound of formula (I). Preferably, the compound of formula (IIa) or the compound of formula (IIb) is added in an amount of 0.1 to 5.0 equivalents relative to the compound of formula (I). More preferably, the compound of formula (IIa) or the compound of formula (IIb) is added in an amount of 0.5 to 1.5 equivalents relative to the compound of formula (I). It has been found that the compound of formula (IIa) or the compound of formula (IIb) with the above equivalents is beneficial to obtain a good yield.

[0084] In a preferred embodiment of the present invention, the metal catalyst is a transition metal catalyst. Transition metals are particularly suitable metals used as metal catalysts because they can exist in various oxidation states, change between oxidation states, form complexes with organic ligands, and act as good electron sources. Transition metal catalysts can be used as homogeneous or heterogeneous metal catalysts as described above. For example, the transition metal catalyst can include palladium (Pd), copper (Cu), nickel (Ni) or gold (Au). Preferably, the transition metal catalyst includes palladium and / or copper. This means that in an alternative, the transition metal catalyst includes palladium but does not include copper. For example, the transition metal catalyst can be bis(triphenylphosphine) palladium dichloride (II) [Pd(PPh3)2Cl2]. In a second alternative, the transition metal catalyst can include palladium and copper. In this context, in the reaction mechanism of the reaction using a beneficial combination of copper and palladium as a transition metal catalyst, it is meant that a palladium compound and a copper compound are added to the reaction mixture independently, and copper can act as a copper co-catalyst to promote the transfer metallization of nucleophilic carbon to the catalytically active palladium species produced by the palladium compound. For example, the transition metal catalyst can be a combination of Pd(PPh3)2Cl2 and cuprous iodide (I) (CuI), or a combination of palladium on carbon (Pd / C) and CuI. In the third alternative, the transition metal catalyst can include copper but does not include palladium. For example, the transition metal catalyst can be a combination of CuI and triphenylphosphine (PPh3) without palladium. More preferably, the transition metal catalyst is selected from the combination of Pd(PPh3)2Cl2, Pd(PPh3)2Cl2 and CuI, the combination of Pd / C and CuI, or the combination of CuI and PPh3. Most preferably, the metal catalyst is selected from the combination of Pd(PPh3)2Cl2 or Pd(PPh3)2Cl2 and CuI.

[0085] The metal catalyst and the amount thereof when added to the reaction mixture can be selected according to whether the compound of formula (IIa) or the compound of formula (IIb) is used when reacting with the iodinated diaryl carbonate of formula (I). In a preferred embodiment of the present invention, in the reaction using the compound of formula (IIa), the metal catalyst is respectively a Pd(PPh3)2Cl2 and CuI combination with a molar ratio of 1:2. Pd(PPh3)2Cl2 and CuI are each independently added to the reaction mixture. In this context, Pd(PPh3)2Cl2 and CuI can be added in an amount of 0.1 to 10 mol% and 0.2 to 20 mol% relative to the compound of formula (I). Preferably, Pd(PPh3)2Cl2 and CuI are added in an amount of 2 to 6 mol% and 4 to 12 mol% relative to the compound of formula (I). More preferably, Pd(PPh3)2Cl2 and CuI are added in an amount of 4 mol% and 8 mol% relative to the compound of formula (I). In a further preferred embodiment of the present invention, in the reaction using the compound of formula (IIb), the metal catalyst is Pd(PPh3)2Cl2, wherein Pd(PPh3)2Cl2 is added in an amount of 0.1 to 5 mol %, preferably 2 to 4 mol %, and more preferably 3 to 4 mol % relative to the compound of formula (I).

[0086] In another preferred embodiment of the present invention, the base is an amine. Preferably, the amine is a tertiary amine. More preferably, the base is triethylamine (NEt3) or N, N-dicyclohexylmethylamine (Cy2NMe). Most preferably, the base is triethylamine (NEt3). In a preferred embodiment of the present invention, the base is added in an amount of 2.0 to 10.0 equivalents relative to the compound of formula (I). Preferably, the base is added in an amount of 2.0 to 5.0 equivalents relative to the compound of formula (I). More preferably, the base is added in an amount of 2.0 to 4.0 equivalents relative to the compound of formula (I).

[0087] Depending on the substitution pattern on the starting materials of formula (I) and (IIa) or (IIb), the reaction can be carried out at different temperatures to obtain a good yield of the desired polycarbonate. Preferably, the reaction is carried out at room temperature, or at a reaction temperature of 30°C to 190°C. In this context, the reaction can be carried out under reflux conditions, wherein the reaction temperature corresponds to the boiling point of the solvent used. Most preferably, the reaction temperature is 70°C to 80°C. It has been found that these reaction conditions are beneficial to the yield of the desired polycarbonate. In particular, it has been found that a reaction temperature of 70°C to 80°C is beneficial to the yield. However, a person skilled in the art is able to adjust the reaction temperature and reaction time to optimize the yield.

[0088] Furthermore, it is preferred that the reaction is carried out under an inert atmosphere so that no oxygen can interfere with the desired reaction and the yield of the desired polycarbonate. However, this is not to be understood as limiting the invention to reactions carried out under an inert atmosphere. In this context, the skilled person is aware of the existing possibilities of carrying out metal-catalyzed cross-coupling reactions under non-inert reaction conditions.

[0089] In a further preferred embodiment of the present invention, a solvent is used. More preferably, the solvent is selected from acetonitrile (MeCN), dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), toluene, 1,2-dichloroethane (DCE) or tetrahydrofuran (THF). Most preferably, acetonitrile is used as a solvent to achieve a high yield.

[0090] Another aspect of the present invention provides polycarbonates obtainable by the process of the present invention. These polycarbonates exhibit improved properties, in particular with regard to mechanical and / or optical properties, heat resistance and / or weathering resistance.

[0091] The definitions / explanations given above in the context of the described method can be directly transferred to the polycarbonates described before and after this paragraph. All mandatory or preferred / advantageous features described with respect to the method according to the invention can also form mandatory or preferred / advantageous features of the polycarbonate according to the invention.

[0092] As stated above, the objects of the present invention are (at least partly) solved by polycarbonates.

[0093] In particular, the present invention relates to a polycarbonate comprising repeating units having the structure of formula (IIIa)

[0094]

[0095] The repeating unit having the structure of formula (IIIa) comprises two aromatic rings, a carbonate group -OC(=O)O- and a linking group having the structure of formula (IVa)

[0096]

[0097] wherein one of the two aromatic rings is substituted by a carbonate group, the two aromatic rings are connected via a linking group, and the linking group in each repeating unit is independently located at the ortho position, meta position or para position relative to the carbonate group,

[0098] Or a repeating unit having the structure of formula (IIIb)

[0099]

[0100] The repeating unit having the structure of formula (IIIb) comprises two aromatic rings, a carbonate group -OC(=O)O- and a linking group having the structure of formula (IVb)

[0101]

[0102] wherein one of the two aromatic rings is substituted by a carbonate group, the two aromatic rings are connected via a linking group, and the linking group in each repeating unit is independently located at the ortho position, meta position or para position relative to the carbonate group,

[0103] And among them

[0104] - each m is independently 0 to 4, preferably 1 to 3,

[0105] - Each R 1 and R 2 R 1 Substituents and R 2 a substituent which is capable of activating the aromatic ring it replaces by mesenchymal and / or inductive effects,

[0106] -R 3 express

[0107] o optionally substituted alkyl, alkenyl or alkynyl, wherein the optionally substituted alkyl, alkenyl or alkynyl is optionally interrupted by at least one heteroatom,

[0108] o optionally substituted cycloalkyl or cycloalkenyl, or

[0109] o optionally substituted phenyl,

[0110] -R 4 express

[0111] o optionally substituted alkyl or alkenyl,

[0112] o optionally substituted cycloalkyl or cycloalkenyl, or

[0113] o optionally substituted aryl,

[0114] - Each R 5 Independently express

[0115] o Hydrogen atoms, or

[0116] o optionally substituted alkyl or alkenyl, wherein the optionally substituted alkyl or alkenyl is optionally interrupted by an ester group, and

[0117] -n is the number of repeating units.

[0118] With respect to polycarbonate, preferably, at least one R 1 Substituents and / or at least one R 2The substituent is located at the ortho position relative to the carbonate group substituting the same aromatic ring. Further, relative to the polycarbonate, preferably, each R 1 and each R 2 The alkyl group or alkoxy group independently represents an alkyl group or an alkoxy group, preferably an alkyl group or an alkoxy group having 1 to 6 carbon atoms, and more preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a neopentyl group, a 1-ethylpropyl group, a cyclohexyl group, a cyclopentyl group, an n-hexyl group, a 1,1-dimethylpropyl group, a 1,2-dimethylpropyl group, a 1,2-dimethylpropyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, a -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, 1-ethyl-2-methylpropyl, 1-ethyl-2-methylpropyl, methoxy, ethoxy , n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, neopentoxy, 1-ethylpropoxy, cyclohexyloxy, cyclopentyloxy, n-hexyloxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 1,2-dimethylpropoxy, 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, 1-ethyl-2-methylpropoxy or 1-ethyl-2-methylpropoxy, most preferably n-propyl or methoxy.

[0119] With respect to polycarbonate, preferably, R 3 represents an alkyl group having 1 to 20 carbon atoms, wherein the alkyl group is optionally interrupted by at least one heteroatom, and wherein the at least one heteroatom is preferably selected from an oxygen atom or a nitrogen atom. Alternatively, with respect to polycarbonate, preferably, R 3 represents a phenyl group, or a substituted phenyl group having 6 to 12 carbon atoms in total. Further, with respect to the polycarbonate, preferably, R 4 represents an alkyl group having 1 to 20 carbon atoms. In addition, with respect to the polycarbonate, preferably, R 5 represents a hydrogen atom, or an alkyl group having 1 to 20 carbon atoms, wherein the alkyl group is optionally interrupted by an ester group.

[0120] With respect to polycarbonate, preferably, the linking group in each repeating unit is independently located at the meta position relative to the carbonate group substituted on the same aromatic ring.

[0121] Furthermore, with respect to polycarbonates, preferably, each of the two aromatic rings in each repeating unit of formula (IIIb) is independently substituted with a linking group, such that each repeating unit represents an (E,E)-isomer. BRIEF DESCRIPTION OF THE DRAWINGS

[0123] Figure 1 .Nano-electrospray mass spectrometry in DMSO of Example 38 of the present invention.

[0124] Figure 2 .Nano-electrospray mass spectrometry in DMSO of Example 53 of the present invention. Example

[0125] The following examples are used to describe the present invention. It should be noted that sometimes the studied reaction does not represent polymerization, but studies the coupling of an aromatic moiety with another aromatic moiety, wherein at least one of those moieties comprises a carbonate group. However, based on those examples (expressed as "reference examples"), those skilled in the art can easily draw how such polymerization can be carried out.

[0126] General considerations and approach

[0127] At 300K (unless otherwise stated) on a Bruker Avance III 400 (for 13 C101MHz) Fourier transform NMR spectrometer using non-deuterated or partially deuterated solvents as internal standards (for CDCl3, 1 H: δ = 7.26 ppm, 13 C: δ = 77.16 ppm) nuclear magnetic resonance (NMR) spectra were recorded. Chemical shifts (δ) are given in ppm and coupling constants (J) are reported in Hertz (Hz). Multiplicities are described as s (singlet), d (doublet), t (triplet), q (quartet), br s (broad multiplet) and m (multiplet) or combinations thereof.

[0128] High-resolution mass spectrometry (HRMS) samples were prepared by dissolving 0.1-5 mg of compound in DMSO or CH3CN / H2O and further diluting to 10 -5 -10 -6M concentration was prepared. Formic acid (0.1%) was added before injection. 10 μL of each sample was injected using a CapLC system (Waters, Manchester, UK) and electrosprayed using a standard electrospray source. The sample injection interval was 3 minutes. Accurate mass spectra in positive ion mode were obtained using a Q-TOF II instrument (Waters, Manchester, UK). MS was calibrated with a 0.1% H3PO4 solution before use. The spectra were locked mass corrected using the known mass of the nearest H3PO4 cluster or known background ions. Analytes were detected as protonated or sodium adducts. Unless otherwise stated, all measured masses were within a 5 ppm difference compared to the calculated masses.

[0129] Nano-electrospray mass spectrometry analysis sample is prepared by dissolving 4mg of the solid obtained in 1mL DMSO.By taking 10 μ L mixture and dissolving it in 990 μ L DMSO and from this solution, taking 100 μ L and adding in 900 μ L DMSO to dilute the mixture.By putting the sample obtained by 3 μ L into gold-plated borosilicate needle (homemade) to measure.Then use nano-electrospray source (Waters) to spray sample from this needle.Use Q-TOFII instrument (Waters, Manchester, UK) to obtain positive ion mode accurate mass spectrum.

[0130] The specified eluent was used to wash the samples in SiO2 (particle size 40-63 μm, pore size ) and visualized by UV detection (254 nm) or on an automated chromatography system ( One IsoleraAutomaticFlash) and use Silica flash cartridges are tested online with UV light.

[0131] Thin layer chromatography (TLC) was performed using TLC plates from Merck (SiO2, Kieselgel 60F254 neutral on aluminum with fluorescent indicator) and compounds were visualized by UV detection (254 nm) unless otherwise mentioned.

[0132] Melting points were recorded on a Büchi M-565 melting point apparatus and are uncorrected.

[0133] Size exclusion chromatography was performed using a PSS SECcurity system; polycarbonate calibration (according to the method 2301-0257502-09D of Currenta GmbH & Co. OHG, Leverkusen), dichloromethane as eluent, column 1 (PL-PC5), concentration of 2 g / L, flow rate of 1.0 ml / min, and detection using UV and / or RI at a temperature of 30°C.

[0134] Materials used in the examples

[0135] All solvents and commercial reagents were used as received.

[0136] A) Commercially available chemicals

[0137]

[0138]

[0139]

[0140] Non-commercial chemicals

[0141] B) Carbonates, alkynes and alkenes

[0142] General procedure 1:

[0143] Substituted phenol (1.0 equivalent), triethylamine (1.2 equivalent) and dichloromethane (25mL) are loaded in a round-bottom flask equipped with a stirring rod. The mixture is cooled to 0 ° C in an ice-water bath. Subsequently, methyl chloroformate (1.2 equivalent) is added dropwise in the time period of 10 minutes. The mixture is stirred at room temperature for a specified time. The precipitate is filtered out on a paper filter. Filtrate is extracted with HCl (1M, 1x30mL), NaOH (0.5M, 30mL) and saturated NaCl aqueous solution (1x 30mL). The organic layer is passed through anhydrous MgSO4 drying, filtering and concentrated in a vacuum. The product is purified according to instructions.

[0144] 2-Methoxyphenyl Methyl Carbonate

[0145] The general procedure was applied using 2-methoxyphenol (1.241 g, 10.0 mmol), NEt3 (1.7 mL, 12.0 mmol) and methyl chloroformate (980 μL, 9.6 mmol) for 12 hours. The product was obtained in 80% (1.455 g) yield.

[0146] White solid, melting point: 31-32℃, 1H NMR (400MHz, CDCl3): δ7.28-7.24(m,1H),7.19(dd,J=7.9,1.6Hz,1H),7.15(dd ,J=8.3,1.3Hz,1H),6.97(td,J=7.7,1.5Hz,1H),3.81(s,3H),3.79(s,3H)ppm. 13 C NMR (101MHz, CDCl3): δ153.3(C), 150.9(C), 139.5(C), 127.3(CH), 122.4(CH), 120.6(CH), 113.0(CH), 55.8(CH3), 55.5(CH3)ppm. C9H 11 O4[M+H] + The HRMS calculated value is 183.0652 and the measured value is 183.0653.

[0147] Bis(2-methoxy-4-propylphenyl) carbonate

[0148] 2-methoxy-4-propylphenol (83.1 g, 0.5 mol), pyridine (79.1 g, 1.0 mol) and dichloromethane (606 mL) were loaded into the reactor. The temperature was maintained at 25 ° C via a thermostatic bath, and then phosgene (27.2 g, 0.28 mol) was added over a period of 15 minutes. The mixture was flushed with nitrogen for 45 minutes, then washed twice with HCl aqueous solution (10%, 400 mL) and washed three times with H2O (400 mL). The solvent was removed and the product was dried overnight under vacuum at room temperature. The product was obtained in a yield of 99% (88.95 g).

[0149] White solid, melting point: 66-67℃, 1 H NMR (400MHz, CDCl3): δ7.13(d,J=8.1Hz,2H), 6.81(d,J=1.7Hz,2H), 6.77(dd,J=8.1,1. 8Hz,2H),3.89(s,6H),2.75-2.21(m,4H),1.75-1.60(m,4H),0.96(t,J=7.3Hz,6H)ppm. 13 C NMR (101MHz, CDCl3): δ151.8(C), 150.9(C), 142.1(C), 138.4(C), 122.0(CH), 120.6(CH), 113.1(CH), 56.2(CH3), 38.1(CH2), 24.6(CH2), 13.9(CH3)ppm. C 21 H 26 O5Na[M+Na] +The HRMS calculated value is 381.1672 and the measured value is 381.1674.

[0150] 1,2-Bis(prop-2-yn-1-yloxy)ethane

[0151] This compound has been prepared according to literature procedure (Org. Biomol. Chem. 2009, 7, 1680-1688.).

[0152] Under argon atmosphere, ethylene glycol (drying, 560 μ L, 10.0mmol) and sodium hydride (1.2g, 50.0mmol) in DMF (drying, 10mL) are loaded into the drying round-bottom flask equipped with a stirring rod and are cooled to 0 ℃. Subsequently, 3-bromopropyne (3.1mL, 28.0mmol) is added. The mixture is stirred at 0 ℃ for 1 hour, then at room temperature for 24 hours. The reaction mixture is concentrated under reduced pressure, diluted with water, and extracted with MTBE (3x 40mL). The organic layer is extracted with a saturated NaCl aqueous solution (3x 20mL), and then with anhydrous MgSO4 drying, filtered and evaporated under reduced pressure. Use heptane / EtOAc gradient (from 100% heptane to 50% EtOAc in 40 minutes, 25mL / min) by automatic flash chromatography system purification of product. The product is obtained with a yield of 63% (874mg).

[0153] Colorless oil, 1 HNMR (400MHz, CDCl3): δ4.20 (d, J = 2.4Hz, 4H), 3.72 (s, 4H), 2.42 (t, J = 2.4Hz, 2H) ppm. 13 C NMR (101MHz, CDCl3): δ79.6(C), 74.7(C), 69.0(CH2), 58.5(CH2)ppm. C8H 10 O2Na[M+Na] + The HRMS calculated value is 161.0573 and the measured value is 161.0576.

[0154] Ethane-1,2-diyl diacrylate

[0155] This compound has been prepared according to literature procedure (RSCAdv., 2019, 9, 40455-40461).

[0156] Under argon atmosphere, ethylene glycol (drying, 560 μ L, 10.0 mmol) in DCM (drying, 20 mL) was loaded into a drying round-bottom flask equipped with a stirring rod and cooled to 0 ° C. Subsequently, acryloyl chloride (2.4 mL, 30.0 mmol) was added. The mixture was stirred at 0 ° C for 1 hour, then at room temperature for 24 hours. The reaction mixture was filtered, and the filtrate was washed with saturated NaHCO3 aqueous solution (3x 30 mL). The organic layer was concentrated and dried in vacuo. The product was obtained in a yield of 70% (1.18 g).

[0157] Yellow oily substance, 1 H NMR (400MHz, CDCl3): δ6.44(dd,J=17.4,1.4Hz,2H), 6.14(dd,J=17.3,10.4Hz,2H), 5.86(dd,J=10.4,1.4Hz,2H), 4.41(s,4H)ppm. 13 C NMR (101MHz, CDCl3): δ166.1(C), 131.5(CH2), 128.1(CH), 62.4(CH2)ppm. C8H 10 O4Na[M+Na] + The HRMS calculated value is 193.0471 and the measured value is 193.0464.

[0158] C) Halogenated Carbonates

[0159] Comparative Example 1: N-iodosuccinimide (NIS) as electrophilic reactant Under inert atmosphere, FeCl3 (81mg, 0.5mmol) and N-iodosuccinimide (NIS, 1.687g, 7.5mmol) were loaded into a 25mL drying vial equipped with a stirring rod. Subsequently, 2-methoxyphenyl carbonate (911mg, 5.0mmol) dissolved in acetonitrile (5mL) was added. The resulting mixture was then stirred at room temperature for 1 hour, after which the resulting mixture was quenched by adding water (10mL). After extraction with EtOAc (3x 10mL), the organic phase was washed with a saturated NaCl solution (20mL), and dried with anhydrous MgSO4, filtered and evaporated in vacuo to dryness. Crude NMR showed that the required 5-iodo-2-methoxyphenyl carbonate was not formed.

[0160] Comparative Example 2: N-chlorosuccinimide (NCS) as an electrophilic reactant

[0161] The conditions described for similar substrates in Nature Catal. 2020, 3, 107 were applied.

[0162] Under air atmosphere, 2-methoxyphenyl methyl carbonate (182 mg, 1.0 mmol), N-chlorosuccinimide (160 mg, 1.2 mmol) and chloroform (2 mL) were loaded into a vial equipped with a stirring bar. Then, dimethyl sulfoxide (14 μL) was added to the solution, and the mixture was stirred at 30 ° C overnight. The next morning, the mixture was filtered on a paper filter and evaporated to dryness in vacuo. The desired 5-chloro-2-methoxyphenyl methyl carbonate was not formed.

[0163] Comparative Example 3: N-bromosuccinimide (NBS) as an electrophilic reactant

[0164] The conditions described in J. Braz. Chem. Soc. 2016, 27, 1217 for similar substrates without carbonate moiety were applied.

[0165] Under air atmosphere, 2-methoxyphenyl methyl carbonate (182mg, 1.0mmol), N-bromosuccinimide (196mg, 1.2mmol), SiO2 (100mg) and DCM (2mL) were loaded into a vial equipped with a stirring rod. The mixture was stirred overnight at 30 ℃. The next morning, the mixture was filtered on a paper filter, washed with DCM (3x 15mL) and evaporated in vacuo to dryness. No required 5-bromo-2-methoxyphenyl methyl carbonate was formed.

[0166] Comparative Example 4: Tetrabutylammonium iodide as electrophilic reactant

[0167] The conditions described in Tetrahedron Lett. 2004, 8015 for similar substrates without carbonate moieties were applied.

[0168] In the 25mL round-bottomed flask equipped with stirring rod, tetrabutylammonium iodide (813mg, 2.2mmol) and 2-methoxyphenyl methyl carbonate (364mg, 2.0mmol) and methyl alcohol (5mL) are loaded.Then, potassium persulfate (1.352g, 2.2mmol) is added, and the mixture is stirred at room temperature overnight.In the morning of the second day, the mixture is filtered on a paper filter and vacuum evaporated to dryness.Do not form required 5-iodo-2-methoxyphenyl methyl carbonate.

[0169] Reference Example 5: Iodine as an electrophilic reactant

[0170] The conditions described for phenolic substrates in J. Am. Chem. Soc. 2013, 135, 14012 were applied.

[0171] Under inert atmosphere, [bis(trifluoroacetyloxy)iodo]benzene (5.16g, 12.0mmol), iodine (3.05g, 12.0mmol) and DCM (drying, 20mL) were loaded into the 100mL drying vial equipped with a stirring rod. 2-methoxyphenyl methyl carbonate (1.822g, 10.0mmol) was added to the vigorously stirred solution at 0°C. Then the resulting mixture was stirred at room temperature for 90 minutes, and then the resulting mixture was quenched by adding saturated sodium thiosulfate aqueous solution (30mL). The mixture was separated and the aqueous layer was extracted with DCM (25ml). The organic layer was dried with anhydrous MgSO4, filtered and evaporated in vacuo to dryness. The residue was purified by an automatic flash chromatography system using a heptane / EtOAc gradient (from 100% heptane to 10% EtOAc in 60 minutes, 25mL / min).

[0172] Methyl 5-iodo-2-methoxyphenyl carbonate was obtained in a yield of 29% (909 mg).

[0173] White solid, melting point: 82-83℃, 1 HNMR (400MHz, CDCl3): δ7.51(dd,J=8.6,2.1Hz,1H),7.43(d,J=2.1Hz,1H),6.73(d,J=8.6Hz,1H),3.90(s,3H),3.83(s,3H)ppm. 13 C NMR (101MHz, CDCl3): δ153.7(C), 151.6(C), 140.7(C), 136.2(CH), 131.4(CH), 114.6(CH), 81.3(C), 56.2(CH3), 55.8(CH3)ppm. C9H 10 IO4[M+H] + The HRMS (ESI) calculated value was 308.9618 and the found value was 308.9622.

[0174] Methyl 3,5-diiodo-2-methoxyphenyl carbonate was obtained as a side compound in a yield of 38% (1.0 g).

[0175] Off-white solid, melting point: 126-127℃, 1 HNMR (400MHz, CDCl3): δ7.98(d,J=2.0Hz,1H),7.47(d,J=2.0Hz,1H),3.92(s,3H),3.82(s,3H)ppm. 13C NMR (101MHz, CDCl3): δ153.3(C), 152.3(C), 144.7(C), 144.2(CH), 132.6(CH), 93.4(C), 87.1(C), 61.5(CH3), 56.2(CH3)ppm. C9H8I2O4Na[M+Na] + The HRMS (ESI) calculated value was 456.8404 and the found value was 456.8412.

[0176] Reference Example 6: Iodine monochloride as an electrophilic reactant

[0177] The conditions described in OPRD 2003, 7, 98 for similar substrates without carbonate moieties were applied.

[0178] In the 50mL bottle equipped with stirring bar, iodine monochloride (357g, 2.2mmol) and methanol (10mL) are loaded. Subsequently, the mixture is cooled to 0 ℃, then 2-methoxyphenyl methyl carbonate (364mg, 2.0mmol) is added. The bottle is equipped with reflux condenser, and the mixture is stirred overnight under reflux. Then the mixture is poured into cold sodium thiosulfate aqueous solution (1M), and stir until the red disappears. After extraction with DCM (2x 30mL), the organic phase anhydrous MgSO4 of merging is dried, filtered and evaporated in vacuo to dryness. Obtain complicated crude NMR, wherein required 5-iodo-2-methoxyphenyl methyl carbonate is only a trace compound.

[0179] General Procedure 2:

[0180] Under inert atmosphere, carbonate and dichloromethane (5mL, dry) are loaded into a drying round-bottom flask equipped with a stirring rod, and the solution is cooled to 0°C. Iodone monochloride (1M in DCM) is added dropwise to the solution. The resulting mixture is then stirred at room temperature for a specified time. Cold Na2S2O3 aqueous solution (1M) is used to quench the mixture and stir until the red color disappears. The aqueous phase is extracted with dichloromethane (2x 20mL), and the organic phase merged is dried with anhydrous MgSO4, filtered and evaporated in vacuo to dryness. Purify as described.

[0181] Reference Example 7-Synthesis of 5-iodo-2-methoxyphenyl methyl carbonate

[0182] Use 2-methoxyphenyl methyl carbonate (3.64g, 20mmol) and iodine monochloride (1M, 30mL, 30mmol) to apply general procedure 2.The mixture was stirred for 3 hours.Use heptane / EtOAc gradient (from 100% heptane to 30%EtOAc, 25mL / min) purified product by automatic flash chromatography system.Obtain 5-iodo-2-methoxyphenyl methyl carbonate in a productive rate of 88% (5.44g).

[0183] White solid, melting point: 82-83℃, 1 HNMR (400MHz, CDCl3): δ7.51(dd,J=8.6,2.1Hz,1H),7.43(d,J=2.1Hz,1H),6.73(d,J=8.6Hz,1H),3.90(s,3H),3.83(s,3H)ppm. 13 C NMR (101MHz, CDCl3): δ153.7(C), 151.6(C), 140.7(C), 136.2(CH), 131.4(CH), 114.6(CH), 81.3(C), 56.2(CH3), 55.8(CH3)ppm. C9H 10 IO4[M+H] + The HRMS (ESI) calculated value was 308.9618 and the found value was 308.9622.

[0184] Comparative Example 8 - Iodination of phenylmethyl carbonate

[0185] General Procedure 2 was applied using phenylmethyl carbonate (300 μL, 3.0 mmol) and iodine monochloride (1 M, 3.6 mL, 3.6 mmol). The mixture was stirred for 4 h. The desired 4-iodophenylmethyl carbonate was not obtained.

[0186] Comparative Example 9 - Iodination of diphenyl carbonate

[0187] General Procedure 2 was applied using diphenyl carbonate (857 mg, 4.0 mmol) and iodine monochloride (1 M, 8.8 mL, 8.8 mmol). The mixture was stirred for 4 h. The desired bis(4-iodophenyl) carbonate was not obtained.

[0188] Reference Example 10 - Iodination of guaiacol carbonate

[0189] General Procedure 2 was applied using guaiacol carbonate (1.371 mg, 5.0 mmol) and iodine monochloride (1 M, 12.5 mL, 12.5 mmol). The mixture was stirred overnight. The product was purified by an automatic flash chromatography system using a heptane / EtOAc gradient (100% heptane to 20% EtOAc in 30 minutes, 25 mL / min). Bis-(5-iodo-2-methoxyphenyl) carbonate was obtained in a yield of 87% (2.3 g).

[0190] White solid, melting point: 162-163℃, 1 H NMR (400MHz, CDCl3): δ7.54-7.51 (m, 4H), 6.75 (d, J = 8.3Hz, 2H), 3.87 (s, 6H) ppm. 13 C NMR (101MHz, CDCl3): δ151.5(C), 150.6(C), 140.8(C), 136.4(C), 131.3(CH), 114.8(CH), 81.2(C), 56.4(CH3)ppm. C 15 H 12 I2O5Na[M+Na] + The HRMS (ESI) calculated value was 548.8666 and the found value was 548.8688.

[0191] Reference Example 11 - Iodination of bis(2-methoxy-4-propylphenyl) carbonate

[0192] General Procedure 2 was applied using bis(2-methoxy-4-propylphenyl)carbonate (5.4 g, 15 mmol) and iodine monochloride (1 M, 34.5 mL, 34.5 mmol). The mixture was stirred overnight. The product was purified by an automatic flash chromatography system using a heptane / EtOAc gradient (100% heptane to 20% EtOAc in 30 minutes, 25 mL / min). Bis-(5-iodo-2-methoxy-4-propylphenyl)carbonate was obtained in a yield of 90% (8.2 g).

[0193] White solid, melting point: 133-134℃, 1 HNMR (400MHz, CDCl3): δ7.60(s,2H),6.84(s,2H),3.87(s,6H),2.72-2.58(m,4H),1.65-1.59(m,4H),1.01(t,J=7.3Hz,6H)ppm. 13C NMR (101MHz, CDCl3): δ151.4(C), 151.0(C), 144.6(C), 138.6(C), 132.3(CH), 113.5(CH), 87.1(C), 56.3(CH3), 42.9(CH2), 23.7(CH2), 14.0(CH3)ppm. C 21 H 24 I2O5Na[M+Na] + The HRMS (ESI) calculated value was 632.9605 and the found value was 632.9625.

[0194] General Procedure 3:

[0195] Halogenated phenol, 4-dimethylaminopyridine and triethylamine in dichloromethane (20mL) are loaded into a round-bottom flask equipped with a stirring rod. The reaction mixture is cooled to 0 ℃, and methyl chloroformate is then added. The mixture is then stirred at room temperature for a specified time. The solution is extracted with HCl (1M, 1x 30mL), NaOH (0.5M, 30mL) and saturated NaCl aqueous solution (1x 30mL). The organic layer combined is dried with anhydrous MgSO4, filtered and concentrated in vacuo. Purified product is indicated.

[0196] Reference Example 12-Synthesis of 4-iodo-2-methoxyphenyl methyl carbonate

[0197] General Procedure 3 was applied using 4-iodo-2-methoxyphenol (625 mg, 2.5 mmol), 4-dimethylaminopyridine (15 mg, 5 mol%), triethylamine (418 μL, 3.0 mmol) and methyl chloroformate (290 μL, 3.0 mmol). Methyl 4-iodo-2-methoxyphenyl carbonate was obtained in quantitative (799 mg) yield without further purification.

[0198] White solid, melting point: 94-95℃, 1 HNMR (400MHz, CDCl3): δ7.28-7.25(m,2H),6.85(d,J=8.1Hz,1H),3.89(s,3H),3.83(s,3H)ppm. 13 C NMR (101MHz, CDCl3): δ153.6(C), 152.0(C), 140.3(C), 130.0(CH), 124.2(CH), 122.1(CH), 90.6(C), 56.3(CH3), 55.8(CH3)ppm. C9H 10 IO4[M+H] + The HRMS (ESI) calculated value was 308.9618 and the found value was 308.9622.

[0199] Reference Example 13-Synthesis of 2-iodophenyl methyl carbonate

[0200] General Procedure 3 was applied using 2-iodophenol (880 mg, 4.0 mmol), 4-dimethylaminopyridine (24 mg, 5 mol%), triethylamine (669 μL, 4.8 mmol) and methyl chloroformate (464 μL, 4.8 mmol). The reaction mixture was stirred for 3 h. Methyl 2-iodophenyl carbonate was obtained in 89% (988 mg) yield without further purification.

[0201] Orange oil, 1 H NMR (400MHz, CDCl3): δ7.83(dd,J=7.9,1.3Hz,1H),7.39-7.35(m,1H),7.20(dd,J=8.1,1.4Hz,1H),7.01-6.97(m,1H),3.94(s,3H)ppm. 13 C NMR (101MHz, CDCl3): δ153.5(C), 151.4(C), 139.7(CH), 129.7(CH), 128.0(CH), 122.7(CH), 90.0(C), 56.0(CH3)ppm. C8H7IO3Na[M+Na] + The HRMS (ESI) calculated value was 300.9332 and the found value was 300.9329.

[0202] Reference Example 14-Synthesis of 2-bromophenyl methyl carbonate

[0203] General Procedure 3 was applied using 2-bromophenol (464 μL, 4.0 mmol), 4-dimethylaminopyridine (24 mg, 5 mol%), triethylamine (669 μL, 4.8 mmol) and methyl chloroformate (464 μL, 4.8 mmol). The reaction mixture was stirred for 4 h. Methyl 2-bromophenyl carbonate was obtained in quantitative (950 mg) yield without further purification.

[0204] Colorless oil, 1 H NMR (400MHz, CDCl3): δ7.61 (dd, J=8.0, 1.5Hz, 1H), 7.34 (td, J=8.1, 1.5Hz, 1H), 7.23 (dd, J=8.1, 1.5Hz, 1H), 7.14 (td, J=7.9, 1.5Hz, 1H), 3.94 (s, 3H) ppm. 13C NMR (101MHz, CDCl3): δ153.4(C), 148.5(C), 133.6(CH), 128.7(CH), 127.8(CH), 123.4(CH), 116.1(C), 56.0(CH3)ppm. C8H8BrO3[M+H] + The HRMS (ESI) calculated value was 230.9651 and the found value was 230.9649.

[0205] Reference Example 15 - Synthesis of 4-chlorophenyl methyl carbonate

[0206] General Procedure 3 was applied using 4-chlorophenol (643 mg, 5.0 mmol), 4-dimethylaminopyridine (31 mg, 5 mol%), triethylamine (836 μL, 6.0 mmol) and methyl chloroformate (580 μL, 6.0 mmol). The reaction mixture was stirred overnight. Methyl 4-chlorophenyl carbonate was obtained in quantitative (950 mg) yield without further purification.

[0207] Colorless oil, 1 HNMR (400MHz, CDCl3): δ7.48-7.26(m,2H),7.17-7.04(m,2H),3.90(s,3H)ppm. 13 C NMR (101MHz, CDCl3): δ154.1(C), 149.8(C), 131.6(C), 129.7(CH), 122.5(CH), 55.6(CH3)ppm.

[0208] in conclusion :The synthesis of halogenated aromatic carbonates via electrophilic halogenation of aromatic carbonates, i.e., the aromatic ring already contains a carbonate moiety, was studied. The electrophilic halogenation of 2-methoxyphenyl methyl carbonate with conventional halogenating agents such as N-iodosuccinimide (Example 1), N-chlorosuccinimide (Example 2), N-bromosuccinimide (Example 3), and tetrabutylammonium iodide (Example 4) all proved to be unsuccessful. Fortunately, iodine monochloride (as a solution in DCM) was able to deliver 5-iodo-2-methoxyphenyl methyl carbonate (Example 7). Subsequently, symmetrical aromatic carbonates such as guaiacol carbonate (Example 10) and bis(2-methoxy-4-propylphenyl) carbonate (Example 11) were also successfully iodinated via this method. The +M effect via the methoxy moiety was shown to be crucial to the nucleophilicity of aromatic carbonates, because phenyl methyl carbonate and diphenyl carbonate did not couple (Examples 8 and 9). In order to investigate the metal-catalyzed coupling of other halogenated carbonates (bromo and chloro derivatives) with alkynes and alkenes, an alternative synthetic method for these latter was determined based on halogenated phenols and subsequent carbonate formation (Examples 12-15).

[0209] Metal-based cross-coupling with alkynes

[0210] A) Solvent Evaluation

[0211] Synthesis procedure 4:

[0212] Under inert atmosphere, 5-iodo-2-methoxyphenyl methyl carbonate (154mg, 0.5mmol), cuprous iodide (I) (4mg, 4 mol%), bis(triphenylphosphine) palladium dichloride (7mg, 2 mol%) and the solvent (5mL, dry) shown in Table 1 were loaded into a drying round-bottom flask equipped with a stirring rod. While stirring at room temperature, triethylamine (140 μL, 1.0mmol) was added. The vial was sealed with a septum, and the mixture was degassed by a stable argon stream for 10 minutes. Subsequently, phenylacetylene (60 μL, 0.55mmol) was added, and the reaction mixture was stirred at 30 ° C for 17h under an argon atmosphere. Afterwards, the mixture was diluted with saturated NH4Cl aqueous solution and separated. EtOAc (3x 10mL) was used for water layer extraction. The organic phase merged was dried with anhydrous MgSO4, filtered and evaporated in vacuo to dryness.

[0213] analyze : Add a known amount of ethylene carbonate as an internal standard and dissolve all materials in CDCl3. Record 1 H NMR spectrum and the signal was integrated relative to the internal standard to determine the yield of the desired product, 2-methoxy-5-(phenylethynyl)phenyl methyl carbonate.

[0214] Table 1.

[0215] Example type Solvents Yield (%) 16 refer to <![CDATA[CH3CN]]> 97 17 refer to DMSO 95 18 refer to DMF 94 19 refer to Toluene 98

[0216] in conclusion Four different solvents were evaluated for the coupling between 5-iodo-2-methoxyphenyl methyl carbonate and phenylacetylene, and gratifyingly, the desired product, 2-methoxy-5-(phenylethynyl)phenyl methyl carbonate, was obtained in high yields in all evaluated solvents.

[0217] B) Other catalytic systems for coupling of halogenated carbonates with alkynes

[0218] Synthesis procedure 5:

[0219] Under inert atmosphere, 5-iodo-2-methoxyphenyl methyl carbonate (154mg, 0.5mmol) and acetonitrile (5mL) are loaded into the drying round-bottom flask equipped with stirring rod. Subsequently, catalyst, cocatalyst and part are added as shown in Table 2. When stirring at room temperature, triethylamine (140 μL, 1.0mmol) is added. With septum sealed bottle, and the mixture is degassed by stable argon gas flow for 10 minutes. Subsequently, phenylacetylene (60 μL, 0.55mmol) is added, and the reaction mixture is stirred at a specified temperature for 17h under argon atmosphere. Afterwards, with saturated NH4Cl aqueous solution dilution mixture and separation phase. Water layer is extracted with EtOAc (3x 10mL). By the organic phase anhydrous MgSO4 that merges, dry, filter and vacuum evaporate to dryness.

[0220] Analysis was performed as described in Synthetic Procedure 4 to determine the yield of the desired product, methyl 2-methoxy-5-(phenylethynyl)phenyl carbonate.

[0221] Table 2.

[0222]

[0223]

[0224] in conclusion :Other catalytic systems have been evaluated for the coupling of 5-iodo-2-methoxyphenyl methyl carbonate and phenylacetylene.The reaction conditions in the table 2 are selected based on the literature conditions of phenolic substrates, but they have not yet been applied to iodinated aromatic carbonates.Except standard Sonogashira cross-coupling conditions (embodiment 20), palladium on carbon has also been shown to successfully obtain 2-methoxyl-5-(phenylethynyl) phenyl methyl carbonate, although the productive rate is lower (embodiment 21).The combination of copper catalyst and triphenylphosphine, but in the absence of noble metals, has also successfully produced required product (embodiment 25).

[0225] C) Scope Evaluation

[0226] General Procedure 6:

[0227] Under inert atmosphere, halogenated carbonate, cuprous iodide (I), bis(triphenylphosphine) palladium dichloride and acetonitrile (5mL) are loaded into the drying round-bottom flask equipped with stirring rod. When stirring at room temperature, triethylamine is added. With septum sealed bottle, the mixture is degassed by stable argon gas flow for 10 minutes. Subsequently, alkynes are added, and the reaction mixture is stirred for a specified time at a specified temperature under argon atmosphere. Afterwards, saturated NH is used The Cl aqueous solution dilutes the mixture and separates phases. EtOAc (3x 10mL) is used for water layer extraction. By anhydrous MgSO4 drying of the organic layer merged, filter and vacuum concentrate. Purify the crude product as indicated.

[0228] Reference Example 26-Coupling of 5-iodo-2-methoxyphenyl methyl carbonate with phenylacetylene

[0229] Use 5-iodo-2-methoxyphenyl methyl carbonate (154mg, 0.5mmol), CuI (4mg, 4 mol %), Pd(PPh ) Cl (7mg, 2 mol %), NEt (140 μ L, 1.0mmol) and phenylacetylene (62 μ L, 0.6mmol) to apply general procedure 6.At room temperature stir the mixture for 4h.Use heptane / EtOAc gradient (from 100% heptane to 25%EtOAc in 40 minutes, 25mL / min) purified product by automatic flash chromatography system.Obtain 2-methoxy-5-(phenylethynyl)phenyl methyl carbonate in a yield of 97% (138mg).

[0230] Light yellow solid, melting point: 105-106℃, 1 HNMR (400MHz, CDCl3): δ7.51-7.49(m,2H),7.43-7.39(m,1H),7.37-7.31(m,4H),6.94(d,J=8.5Hz,1H),3.92(s,3H),3.88(s,3H)ppm. 13 CNMR(101MHz, CDCl3): δ153.8(C),151.7(C),139.9(C),131.7(CH),130.9(CH),128.5(CH),128.3 (CH),125.8(CH),123.4(C),116.0(C),112.6(CH),88.9(C),88.4(C),56.2(CH3),55.8(CH3)ppm. C 17 H 15 O4[M+H] + The HRMS (ESI) calculated value was 283.0965 and the found value was 283.0967.

[0231] Reference Example 27-Coupling of 4-iodo-2-methoxyphenyl methyl carbonate with phenylacetylene

[0232] Use 4-iodo-2-methoxyphenyl methyl carbonate (154mg, 0.5mmol), CuI (4mg, 4 mol %), Pd(PPh ) Cl (7mg, 2 mol %), NEt (140 μ L, 1.0mmol) and phenylacetylene (62 μ L, 0.6mmol) general procedure 6 is applied.The mixture is stirred at room temperature for 17h.Use heptane / EtOAc gradient (from 100% heptane to 25%EtOAc in 40 minutes, 25mL / min) purified product by automatic flash chromatography system.Obtain 2-methoxy-4-(phenylethynyl)phenyl methyl carbonate in a yield of 92% (130mg).

[0233] Yellow solid, melting point: 82-83℃, 1 HNMR (400MHz, CDCl3): δ7.55-7.52(m,2H),7.37-7.37(m,3H),7.15-7.10(m,3H),3.91(s,3H),3.88(s,3H)ppm. 13 C NMR (101MHz, CDCl3): δ153.8(C),151.1(C),140.4(C),131.8(CH),128.6(CH),128.5(CH),124.5 (CH),123.1(C),122.6(CH),122.4(C),115.8(CH),89.6(C),88.8(C),56.2(CH3),55.7(CH3)ppm. C 17 H 15 O4[M+H] + The HRMS (ESI) calculated value was 283.0965 and the found value was 283.0963.

[0234] Reference Example 28-Coupling of 2-iodophenyl methyl carbonate and phenylacetylene

[0235] General Procedure 6 was applied using 2-iodophenyl methyl carbonate (139 mg, 0.5 mmol), CuI (4 mg, 4 mole %), Pd(PPh ) Cl (7 mg, 2 mole %), NEt (140 μL, 1.0 mmol) and phenylacetylene (62 μL, 0.6 mmol). The mixture was stirred at 80° C. for 17 hours. The product was purified by an automatic flash chromatography system using a heptane / EtOAc gradient (from 100% heptane to 25% EtOAc in 40 minutes, 25 mL / min). 2-(phenylethynyl)phenyl methyl carbonate was obtained in a yield of 99% (126 mg).

[0236] Yellow oily substance, 1H NMR (400MHz, CDCl3): δ7.58(dd,J=7.7,1.6Hz,1H),7.54-7.47(m,2H),7.39-7.33(m,4H),7.29-7.18(m,2H),3.92(s,3H)ppm. 13 C NMR (101MHz, CDCl3): δ153.8(C), 151.8(C), 133.1(CH), 131.8(CH), 129.7(CH), 128.8(CH), 128.5(CH),126.3(CH),123.1(C),121.9(CH),117.5(C),95.1(C),83.7(C),55.8(CH3)ppm. C 16 H 13 O3[M+H] + The HRMS (ESI) calculated value was 253.0859 and the found value was 253.0849.

[0237] Comparative Example 29-Coupling of 2-bromophenyl methyl carbonate and phenylacetylene

[0238] General Procedure 6 was applied using methyl 2-bromophenyl carbonate (116 mg, 0.5 mmol), CuI (4 mg, 4 mol%), Pd(PPh3)2Cl2 (7 mg, 2 mol%), NEt3 (140 μL, 1.0 mmol) and phenylacetylene (62 μL, 0.6 mmol). The mixture was stirred at room temperature or 80°C overnight, but the desired methyl 2-(phenylethynyl)phenyl carbonate was not obtained.

[0239] Comparative Example 30-Coupling of 4-chlorophenyl methyl carbonate with phenylacetylene

[0240] General Procedure 6 was applied using methyl 4-chlorophenyl carbonate (93 mg, 0.5 mmol), CuI (4 mg, 4 mol%), Pd(PPh3)2Cl2 (7 mg, 2 mol%), NEt3 (140 μL, 1.0 mmol) and phenylacetylene (62 μL, 0.6 mmol). The mixture was stirred at 80°C overnight, but the desired methyl 4-(phenylethynyl)phenyl carbonate was not obtained.

[0241] Reference Example 31-Coupling of 3,5-diiodo-2-methoxyphenyl methyl carbonate with phenylacetylene

[0242] General Procedure 6 was applied using 3,5-diiodo-2-methoxyphenyl methyl carbonate (434 mg, 1.0 mmol), CuI (15 mg, 8 mol%), Pd(PPh3)2Cl2 (28 mg, 4 mol%), NEt3 (488 μL, 3.5 mmol) and phenylacetylene (242 μL, 2.2 mmol). The mixture was stirred at room temperature for 17 hours. The product was purified by an automated flash chromatography system using a heptane / EtOAc gradient (100% heptane to 20% EtOAc in 40 minutes, 25 mL / min). 2-methoxy-3,5-bis(phenylethynyl)phenyl methyl carbonate was obtained in a yield of 93% (355 mg).

[0243] Light orange oil, 1 H NMR (400MHz, CDCl3): δ7.56 (d, J = 2.1Hz, 1H), 7.52-7.49 (m, 4H), 7.33-7.24 (m, 7H), 4.07 (s, 3H), 3.90 (s, 3H) ppm. 13 C NMR (101MHz, CDCl3): δ153.8(C),153.1(C),143.9(C),134.8(CH),131.8(CH),131.7(CH),128.9(CH),128.7(CH),128.6(CH),12 8.5(CH),126.0(CH),123.0(C),123.0(C),119.1(C),118.5(C),95.4(C),90.1(C),87.5(C),84.3(C),61.6(CH3),56.0(CH3)ppm. C 25 H 19 O4[M+H] + The HRMS (ESI) calculated value was 383.1278 and the found value was 383.1281.

[0244] Reference Example 3-Coupling of bis(5-iodo-2-methoxyphenyl)carbonate with phenylacetylene

[0245] General Procedure 6 was applied using bis(5-iodo-2-methoxyphenyl)carbonate (263 mg, 0.5 mmol), CuI (8 mg, 8 mol%), Pd(PPh ) Cl (14 mg, 4 mol%), NEt (280 μL, 2.0 mmol) and phenylacetylene (121 μL, 2.2 mmol). The mixture was stirred at room temperature for 17 hours. The product was purified by an automated flash chromatography system using a heptane / EtOAc gradient (100% heptane to 50% EtOAc in 40 minutes, 25 mL / min). Bis(2-methoxy-5-(phenylethynyl)phenyl)carbonate was obtained in a yield of 68% (161 mg).

[0246] Off-white solid, melting point: 173-174℃, 1 HNMR (400MHz, CDCl3): δ7.52-7.50(m,4H),7.43-7.41(m,4H),7.35-7.32(m,6H),6.98-6.95(m,2H),3.93(s,6H)ppm. 13 C NMR (101MHz, CDCl3): δ151.7(C), 151.0(C), 140.0(C), 131.7(CH), 131.2(CH), 128.5(CH), 128.4(CH),125.7(CH),123.4(C),116.0(C),112.8(CH),89.0(C),88.4(C),56.4(CH3)ppm. C 31 H 22 O5Na[M+Na] + The HRMS (ESI) calculated value was 497.1359 and the found value was 497.1376.

[0247] Reference Example 33 - Coupling of bis(5-iodo-2-methoxy-4-propylphenyl)carbonate with phenylacetylene

[0248] General Procedure 6 was applied using bis(5-iodo-2-methoxy-4-propylphenyl)carbonate (305 mg, 0.5 mmol), CuI (8 mg, 8 mol%), Pd(PPh3)2Cl2 (14 mg, 4 mol%), NEt3 (280 μL, 2.0 mmol) and phenylacetylene (121 μL, 2.2 mmol). The mixture was stirred at room temperature for 17 hours. The product was purified by an automated flash chromatography system using a heptane / EtOAc gradient (100% heptane to 50% EtOAc in 40 minutes, 25 mL / min). Bis(2-methoxy-5-(phenylethynyl)-4-propylphenyl)carbonate was obtained in a yield of 66% (185 mg).

[0249] Yellow solid, melting point: 145-147℃, 1 H NMR (400MHz, CDCl3): δ7.50 (dd, J=7.7, 1.7Hz, 4H), 7.37-7.31 (m, 8H), 6.83 (s, 2 H),3.92(s,6H),2.85-2.81(m,4H),1.99-1.65(m,4H),1.02(t,J=7.3Hz,6H)ppm. 13 C NMR (101MHz, CDCl3): δ151.3(C),144.9(C),138.1(C),131.5(CH),128.5(CH),128.2(CH),125.8(CH),123 .8(C),115.0(C),113.3(CH),100.1(C),92.2(C),87.6(C),56.3(CH3),37.1(CH2),24.1(CH2),14.2(CH3). C 37 H 34 O5Na[M+Na] + The HRMS (ESI) calculated value was 581.2298 and the found value was 581.2313.

[0250] Reference Example 34-Coupling of bis(5-iodo-2-methoxy-4-propylphenyl)carbonate with oct-1-yne

[0251] General Procedure 6 was applied using bis(5-iodo-2-methoxy-4-propylphenyl)carbonate (305 mg, 0.5 mmol), CuI (8 mg, 8 mol%), Pd(PPh3)2Cl2 (14 mg, 4 mol%), NEt3 (280 μL, 2.0 mmol), acetonitrile (2 mL) and oct-1-yne (176 μL, 1.2 mmol). The mixture was stirred at 70°C for 20 hours. The product was purified by an automated flash chromatography system using a heptane / EtOAc gradient (100% heptane to 50% EtOAc in 30 minutes, 25 mL / min). Bis(2-methoxy-5-(oct-1-yne-1-yl)-4-propylphenyl)carbonate was obtained in a yield of 59% (170 mg).

[0252] Light yellow oil, 1H NMR (400MHz, CDCl3): δ7.20(s,2H),6.75(s,2H),3.87(s,6H),2.73-2.69(m,4H),2.41(t,J=6.9Hz,4H),1 .68-1.58(m,8H),1.50-1.43(m,4H),1.35-1.31(m,8H),0.97(t,J=7.3Hz,6H),0.91(t,J=6.9Hz,6H)ppm. 13 C NMR (101MHz, CDCl3): δ151.3(C),150.6(C),144.3(C),137.9(C),125.8(CH),116.0(C),113.1(CH),93.1(C),78.5(C),5 6.2(CH3),37.0(CH2),31.6(CH2),29.0(CH2),28.8(CH2),24.0(CH2),22.8(CH2),19.7(CH2),14.2(CH3),14.1(CH3)ppm. C 37 H 51 O5[M+H] + The HRMS (ESI) calculated value was 575.3731 and the found value was 575.3724.

[0253] Reference Example 35 - Formation of Biscarbonate from 5-iodo-2-methoxyphenyl Methyl Carbonate and 1,7-Octadiyne

[0254] General Procedure 6 was applied using 5-iodo-2-methoxyphenyl methyl carbonate (308 or 154 mg, 1.0 or 0.5 mmol), CuI (8 or 4 mg, 8 mol%), Pd(PPh3)2Cl2 (14 or 7 mg, 4 mol%), NEt3 (280 or 140 μL, 2.0 or 1.0 mmol) and 1,7-octadiene (73 or 33 μL, 0.55 or 0.25 mmol). The mixture was stirred at room temperature for 17 hours. The product was purified by an automated flash chromatography system using a heptane / EtOAc gradient (100% heptane to 100% EtOAc in 45 minutes, 25 mL / min). Dimethyl (octa-1,7-diyne-1,8-diyl) bis(6-methoxy-3,1-phenylene) biscarbonate was obtained in a yield of 77% (89 mg). When the reaction was carried out in toluene instead of acetonitrile, the desired compound was obtained in 75% (174 mg).

[0255] White solid, melting point: 138-139℃, 1H NMR (400MHz, CDCl3): δ7.25 (dd, J=8.5, 2.0Hz, 2H), 7.17 (d, J=2.0Hz, 2H), 6.87 (d, J=8.5Hz,2H),3.89(s,6H),3.84(s,6H),2.46-2.40(m,4H),1.76-1.73(m,4H)ppm. 13 CNMR(101MHz, CDCl3): δ153.9(C),151.1(C),139.8(C),130.8(CH),125.8(CH),116.8 (C),112.5(CH),89.2(C),79.9(C),56.2(CH3),55.7(CH3),28.0(CH2),19.1(CH2)ppm. C 26 H 27 O8[M+H] + The HRMS (ESI) calculated value was 467.1700 and the found value was 467.1705.

[0256] Reference Example 36 - Formation of Biscarbonate from 5-iodo-2-methoxyphenyl methyl carbonate and 1,2-bis(prop-2-yn-1-yloxy)ethane

[0257] General Procedure 6 was applied using 5-iodo-2-methoxyphenyl methyl carbonate (308 mg, 1.0 mmol), CuI (8 mg, 8 mol%), Pd(PPh3)2Cl2 (14 mg, 4 mol%), NEt3 (280 μL, 2.0 mmol) and 1,2-bis(prop-2-yn-1-yloxy)ethane (69 mg, 0.5 mmol). The mixture was stirred at 50 °C for 17 hours. The product was purified by an automated flash chromatography system using a heptane / EtOAc gradient (100% heptane to 100% EtOAc in 40 minutes, 25 mL / min). ([(ethane-1,2-diyl)bis(oxy)prop-1-yn-3,1-diyl]-6-methoxy-3,1-phenylene)dimethylbiscarbonate was obtained in a yield of 94% (235 mg). When the reaction was carried out in dichloroethane (DCE) or tetrahydrofuran (THF), yields of 50% and 16%, respectively, were obtained.

[0258] Beige solid, melting point: 78-79℃, 1 H NMR (400MHz, CDCl3): δ7.31(dd,J=8.5,2.1Hz,2H),7.22(d,J=2.0Hz,2H),6.89(d,J=8.5Hz,2H),4.42(s,4H),3.89(s,6H),3.85(s,6H)3.79(s,4H)ppm.13 C NMR (101MHz, CDCl3): δ135.8(C),151.8(C),139.8(C),131.2(CH),126.0(CH),115.3( C),112.5(CH),85.5(C),84.5(C),69.1(CH2),59.3(CH2),56.2(CH3),55.7(CH3)ppm. C 26 H 26 O 10 Na[M+Na] + The HRMS calculated value is 521.1418 and the measured value is 521.1437.

[0259] Reference Example 37 - Formation of tricarbonate from 5-iodo-2-methoxyphenyl methyl carbonate and 1,2-bis(prop-2-yn-1-yloxy)ethane

[0260] General Procedure 6 was applied using 5-iodo-2-methoxyphenyl methyl carbonate (462 mg, 1.5 mmol), CuI (11 mg, 12 mol%), Pd(PPh3)2Cl2 (21 mg, 6 mol%), NEt3 (418 μL, 3.0 mmol) and tripropargylamine (71 μL, 0.5 mmol). The mixture was stirred at room temperature for 17 hours. The product was purified by an automated flash chromatography system using a heptane / EtOAc gradient (100% heptane to 100% EtOAc in 40 minutes, 25 mL / min). Trimethyl (nitrilotri[(prop-1-yne-3,1-diyl)]-6-methoxy-3,1-phenylene) tricarbonate was obtained in a yield of 77% (258 mg).

[0261] Yellow oily substance, 1 H NMR (400MHz, CDCl3): δ7.31(dd,J=8.5,2.0Hz,3H),7.22(d,J=2.0Hz,3H),6.88(d,J=8.6Hz,3H),3.90(s,9H),3.85(s,9H),3.77(br s,6H)ppm. 13 C NMR (101MHz, CDCl3): δ153.8(C),151.6(C),139.8(C),131.2(CH),126.0(CH),1 15.6(C),112.5(CH),84.4(C),83.8(C),56.2(CH3),55.7(CH3),43.1(CH2)ppm. C 36 H 34 NO 12 [M+H +The HRMS calculated value of ] is 672.2076 and the measured value is 672.2067.

[0262] Example 38 of the present invention - oligomerization of bis(5-iodo-2-methoxy-4-propylphenyl) carbonate and 1,7-octanediyne

[0263] General Procedure 6 was applied using bis(5-iodo-2-methoxy-4-propylphenyl) carbonate (305 mg, 0.5 mmol), CuI (8 mg, 8 mol%), Pd(PPh3)2Cl2 (14 mg, 4 mol%), NEt3 (280 μL, 2.0 mmol), 1.7-octanediyne (80 μL) and acetonitrile (2 mL). The mixture was stirred at 70°C for 3 hours. After the general work-up, a viscous compound was obtained, in which the formation of oligomers was confirmed via nanomass electrospray analysis (see Figure 1 ). Toluene was used as the reaction solvent and the mixture was stirred at room temperature for 17 hours. After extraction, the organic phase was washed with saturated aqueous NaCl solution. The combined organic layers were dried over anhydrous MgSO4, filtered and concentrated in vacuo. Methanol was added and an orange solid was obtained after evaporation of the solvent. The formation of oligomers was confirmed by nanomass electrospray analysis (see Figure 1 ). The m / z value of the repeating unit (n) was 460.2, and from 841.4 (n=1) to 3142.5 (n=6), an analyte with a carbonate end group was detected as a sodium adduct. From 945.4 (n=1) to 3246.5 (n=6), an analyte with one alkyne end group was also detected as a sodium adduct. From 1049.5 (n=1) to 3246.6 (n=6), an analyte with two alkyne end groups was also detected as a sodium adduct.

[0264] in conclusion:The coupling of iodinated methyl carbonate with phenylacetylene was studied as a model reaction. It is gratifying that even at room temperature, when the iodine atom is located at the ortho, meta and para positions relative to the carbonate moiety, the coupling is also successful (Examples 26-28). Additional substituents (such as methoxy) with +M effect on the aromatic moiety are beneficial to the reactivity of aromatic carbonates, because in the absence of this substituent, a reaction temperature of 80°C is required to achieve complete conversion (Example 28). Unfortunately, even at elevated reaction temperatures, the corresponding less reactive bromo and chloro derivatives are not observed to couple (Comparative Examples 29 and 30). When two iodine atoms are present on the aromatic carbonate, double coupling with phenylacetylene is successfully achieved (Example 31). Symmetrical iodinated aromatic carbonates, such as bis(5-iodo-2-methoxyphenyl) carbonate and bis(5-iodo-2-methoxy-4-propylphenyl) carbonate are also successfully coupled with phenylacetylene, although the yield is slightly lower (Examples 32 and 33). Interestingly, unactivated aliphatic alkynes such as octan-1-yne also gave the desired products when coupled with bis(5-iodo-2-methoxy-4-propylphenyl) carbonate, although higher temperatures (70 °C) were required, as bis(5-iodo-2-methoxy-4-propylphenyl) carbonate was only poorly soluble in acetonitrile at room temperature (Example 34). Subsequent coupling of methyl 5-iodo-2-methoxyphenyl carbonate with 1,7-octanediyne (Example 35), 1,2-bis(prop-2-yn-1-yloxy)ethane (Example 36), or propargylamine (Example 37) afforded two biscarbonates and one tricarbonate in good to excellent yields. Finally, oligomerization between bis(5-iodo-2-methoxy-4-propylphenyl) carbonate and 1,7-octanediyne was successfully demonstrated in Example 38.

[0265] Metal-based cross-coupling with activated olefins

[0266] A) Alkali and Temperature Evaluation

[0267] Synthesis procedure 7:

[0268] Under an inert atmosphere, a dried round-bottom flask equipped with a stirring bar was charged with 5-iodo-2-methoxyphenyl methyl carbonate (154 mg, 0.5 mmol), Pd(PPh3)2Cl2 (7.0 mg, 2 mol%), a base shown in Table 3 (1.0 mmol) and acetonitrile (5 mL). The vial was sealed with a septum and the mixture was degassed for 10 minutes by a steady stream of argon. Subsequently, ethyl acrylate (65 μL, 0.6 mmol) was added, the vial was sealed and stirred at 70°C for 17 hours. Afterwards, the crude mixture was filtered over diatomaceous earth using EtOAc (25 mL), diluted with saturated aqueous NH4Cl solution (15 mL) and the phases were separated. The aqueous layer was extracted with EtOAc (3 x 10 mL). The combined organic layers were dried over anhydrous MgSO4, filtered and concentrated in vacuo. A known amount of ethylene carbonate was added as an internal standard, and all substances were dissolved in CDCl3. Record 1 H NMR spectrum and the signal was integrated relative to the internal standard to determine the yield of the desired product, ethyl (2E)-3-[4-methoxy-3-[(methoxycarbonyl)oxy]phenyl)prop-2-enoate.

[0269] Table 3.

[0270] Example type Alkali Temperature(℃) Yield (%) 39 contrast <![CDATA[NEt3]]> 30 0 40 refer to <![CDATA[NEt3]]> 70 85 41 contrast <![CDATA[Cs2CO3]]> 70 0 42 contrast <![CDATA[K3PO4]]> 70 0 43 refer to <![CDATA[Cy2NMe]]> 70 88 44 contrast Pyridine 70 0

[0271] in conclusion : From the five bases evaluated, triethylamine (Example 40) and dicyclohexylmethylamine (Example 43) proved successful for the coupling of 5-iodo-2-methoxyphenyl methyl carbonate with ethyl acrylate. Reaction temperatures above 30°C were required to achieve the conversion (Examples 39 and 40).

[0272] B) Scope Evaluation

[0273] General Procedure 8:

[0274] Under inert atmosphere, halogenated carbonate, Pd(PPh3)2Cl2 and acetonitrile (5mL) are loaded into the drying round-bottom flask equipped with stirring rod. When stirring at room temperature, triethylamine is added. With septum sealed bottle, the mixture is degassed by stable argon stream for 10 minutes. Subsequently, olefin is added, the bottle is equipped with reflux condenser and inert atmosphere balloon, and the reaction mixture is stirred at specified temperature and time. Afterwards, with saturated NH4Cl aqueous solution (15mL) dilute the mixture and separate phase. EtOAc (3x 10mL) is used for water layer extraction. By anhydrous MgSO4 drying of the organic layer merged, filter and vacuum concentrate. Purify crude product as indicated.

[0275] Reference Example 45-Coupling of 5-iodo-2-methoxyphenyl methyl carbonate with ethyl acrylate

[0276] General Procedure 8 was applied using 5-iodo-2-methoxyphenyl methyl carbonate (154 mg, 0.5 mmol), Pd(PPh ) Cl (7 mg, 2 mole %), NEt (140 μL, 1.0 mmol) and ethyl acrylate (65 μL, 0.60 mmol). The mixture was stirred at 70° C. for 17 hours. The product was purified by an automated flash chromatography system using a heptane / EtOAc gradient (100% heptane to 50% EtOAc in 30 minutes, 25 mL / min). (2E)-3-[4-methoxy-3-[(methoxycarbonyl)oxy]phenyl]prop-2-enoic acid ethyl ester was obtained in a yield of 84% (118 mg).

[0277] White solid, melting point: 72-73℃, 1 H NMR (400MHz, CDCl3): δ7.59(d,J=16.0Hz,1H),7.38(dd,J=8.5,2.1Hz,1H),7.33(d,J=2.1Hz,1H),6.97(d,J=8 .5Hz,1H),6.29(d,J=15.9Hz,1H),4.25(q,J=7.1Hz,2H),3.92(s,3H),3.89(s,3H),1.33(t,J=7.1Hz,3H)ppm. 13 C NMR (101MHz, CDCl3): δ167.1(C),153.8(C),153.0(C),143.3(CH),140.5(C),127.9(CH),127 .8(C),121.7(CH),117.3(CH),112.7(CH),60.6(CH2),56.3(CH3),55.8(CH3),14.5(CH3)ppm. C 14 H 16 O6Na[M+Na] + The HRMS (ESI) calculated value is 303.0839 and the found value is 303.0840.

[0278] Reference Example 46-Coupling of 2-iodophenyl methyl carbonate and ethyl acrylate

[0279] General Procedure 8 was applied using methyl 2-iodophenyl carbonate (139 mg, 0.5 mmol), Pd(PPh3)2Cl2 (7 mg, 2 mol%), NEt3 (140 μL, 1.0 mmol) and ethyl acrylate (65 μL, 0.60 mmol). The desired product, ethyl (2E)-3-[2-[(methoxycarbonyl)oxy]phenyl)prop-2-enoate, was formed only in trace amounts.

[0280] Comparative Example 47-Coupling of 2-bromophenyl methyl carbonate and ethyl acrylate

[0281] General Procedure 8 was applied using methyl 2-bromophenyl carbonate (116 mg, 0.5 mmol), Pd(PPh3)2Cl2 (7 mg, 2 mol%), NEt3 (140 μL, 1.0 mmol) and ethyl acrylate (65 μL, 0.60 mmol). The desired product, ethyl (2E)-3-[4-methoxy-3-[(methoxycarbonyl)oxy]phenyl)prop-2-enoate, was not obtained.

[0282] Reference Example 48 - Coupling of bis-(5-iodo-2-methoxyphenyl) carbonate with ethyl acrylate

[0283] General Procedure 8 was applied using bis-(5-iodo-2-methoxyphenyl) carbonate (526 mg, 1.0 mmol), Pd(PPh3)2Cl2 (28 mg, 4 mole %), NEt3 (558 μL, 4.0 mmol) and ethyl acrylate (240 μL, 2.2 mmol). The mixture was stirred at 80 ° C for 17 hours. The product was purified by an automatic flash chromatography system using a heptane / EtOAc gradient (from 100% heptane to 50% EtOAc in 40 minutes, 25 mL / min). (2E, 2'E) 3,3'-[carbonylbis(oxy[4-methoxy-3,1-phenylene])]di(prop-2-enoic acid diethyl ester) was obtained in a yield of 48% (227 mg).

[0284] White solid, melting point: 121-122℃, 1 HNMR (400MHz, CDCl3): δ7.61(d,J=16.0Hz,2H),7.43(d,J=2.1Hz,2H),7.40(dd,J=8.5,2.1Hz,2H),7.00 (d,J=8.5Hz,2H),6.32(d,J=15.9Hz,2H),4.26(q,J=7.1Hz,4H),3.94(s,6H),1.33(t,J=7.1Hz,6H)ppm. 13 C NMR (101MHz, CDCl3): δ167.1(C),152.9(C),151.0(C),143.3(CH),140.5(C),128.1(CH ),127.9(C),121.6(CH),117.4(CH),112.9(CH),60.6(CH2),56.4(CH3),14.5(CH3)ppm. C 25 H 26 O9Na[M+Na] +The HRMS (ESI) calculated value was 493.1469 and the found value was 493.1469.

[0285] Comparative Example 49 - Coupling of bis-(5-iodo-2-methoxyphenyl) carbonate with styrene

[0286] General Procedure 8 was applied using bis-(5-iodo-2-methoxyphenyl) carbonate (263 mg, 0.5 mmol), Pd(PPh3)2Cl2 (14 mg, 4 mol%), NEt3 (279 μL, 2.0 mmol) and styrene (120 μL, 2.1 mmol). The desired product was not obtained.

[0287] Reference Example 50 Coupling of bis-(5-iodo-2-methoxy-4-propylphenyl) carbonate with ethyl acrylate

[0288] General Procedure 8 was applied using bis-(5-iodo-2-methoxy-4-propylphenyl) carbonate (305 mg, 0.5 mmol), Pd(PPh3)2Cl2 (14 mg, 4 mole %), NEt3 (280 μL, 2.0 mmol) and ethyl acrylate (120 μL, 1.1 mmol). The mixture was stirred at 90 ° C for 17 hours. The product was purified by an automatic flash chromatography system using a heptane / EtOAc gradient (from 100% heptane to 50% EtOAc in 40 minutes, 25 mL / min). (2E, 2'E) 3,3'-[carbonylbis(oxy[4-methoxy-6-propyl-3,1-phenylene])]di(prop-2-enoic acid diethyl ester) was obtained in a yield of 71% (196 mg). When ethyl acrylate (164 μL, 1.5 mmol) was used, the desired product was obtained in a yield of 68% (189 mg). Note: This compound is unstable in CDCl3, so NMR should be measured immediately after the solution is prepared.

[0289] White solid, melting point: 119-120℃, 1 HNMR (400MHz, CDCl3): δ7.90(d,J=15.8Hz,2H),7.46(s,2H),6.79(s,2H),6.26(d,J=15.7Hz,2H),4.26(q,J=7 .1Hz,4H),3.92(s,6H),2.77-2.64m,4H),1.66-1.57(m,4H),1.33(t,J=7.1Hz,6H),0.98(t,J=7.3Hz,6H)ppm. 13C NMR (101MHz, CDCl3): δ167.3(C),152.4(C),151.4(C),142.5(C),140.9(CH),138.7(C),125.7(C),120.3 (CH),118.2(CH),114.0(CH),60.6(CH2),56.3(CH3),35.5(CH2),25.0(CH2),14.5(CH3),14.1(CH3)ppm. C 31 H 39 O9[M+H] + The HRMS (ESI) calculated value was 555.2589 and the found value was 555.2574.

[0290] Reference Example 5 Coupling of 1-bis-(5-iodo-2-methoxyphenyl) carbonate with dimethyl itaconate

[0291] General Procedure 8 was applied using bis-(5-iodo-2-methoxyphenyl) carbonate (236 mg, 0.5 mmol), Pd(PPh3)2Cl2 (14 mg, 4 mol%), NEt3 (280 μL, 2.0 mmol) and dimethyl itaconate (155 μL, 1.1 mmol). The mixture was stirred at 90 °C for 17 hours. The product was purified by an automated flash chromatography system using a heptane / EtOAc gradient (100% heptane to 50% EtOAc in 40 minutes, 25 mL / min). (2E, 2'E) 2,2'-[carbonylbis(oxy[4-methoxy-3,1-phenylene]methylene)] disuccinic acid tetramethyl ester was obtained in a yield of 35% (102 mg).

[0292] Off-white oily substance, 1 H NMR (400MHz, CDCl3): δ7.81 (br s, 2H), 7.28-7.26 (m, 4H), 7.02 (d, J = 9.1Hz, 2H), 3.92 (s, 6H), 3.82 (s, 6H), 3.73 (s, 6H), 3.56 (s, 4H) ppm. 13 C NMR (101MHz, CDCl3): δ171.7(C),167.9(C),151.9(C),151.0(C),140.9(CH),140.2(C),128.8(CH ),127.9(C),125.3(C),123.4(CH),112.9(CH),56.3(CH3),52.4(CH3),52.3(CH3),33.6(CH2)ppm. C 29 H 30 O 13 Na[M+Na]+ The HRMS (ESI) calculated value was 609.1579 and the found value was 609.1574.

[0293] Reference Example 52 - Formation of dicarbonate from 5-iodo-2-methoxyphenyl methyl carbonate and ethane-1,2-diyl diacrylate

[0294] General Procedure 8 was applied using 5-iodo-2-methoxyphenyl methyl carbonate (308 mg, 1.0 mmol), Pd(PPh3)2Cl2 (7 mg, 2 mol%), NEt3 (280 μL, 2.0 mmol) and ethane-1,2-diyl diacrylate (85 mg, 0.5 mmol). The mixture was stirred at 70 °C for 17 hours. The product was purified by an automated flash chromatography system using a heptane / EtOAc gradient (100% heptane to 50% EtOAc in 30 minutes, 25 mL / min). Bis(3-[4-methoxy-3-((methoxycarbonyl)oxy)phenyl]prop-2-enoic acid ethane-1,2-diyl ester was obtained in a yield of 62% (165 mg).

[0295] Yellow solid, melting point: 113-115℃, 1 HNMR (400MHz, CDCl3): δ7.63 (d, J=15.9Hz, 2H), 7.39 (dd, J=8.5, 2.2Hz, 2H), 7.34 (d, J=2.1Hz, 2H),6.97(d,J=8.5Hz,2H),6.33(d,J=16.0Hz,2H),4.46(s,4H),3.91(s,6H),3.89(s,6H)ppm. 13 C NMR (101MHz, CDCl3): δ166.8(C),153.8(C),153.2(C),144.2(CH),140.5(C),128.1(CH ),127.6(C),121.8(CH),116.5(CH),112.7(CH),62.5(CH2),56.3(CH3),55.8(CH3)ppm. C 26 H 27 O 12 [M+H] + The HRMS (ESI) calculated value was 531.1497 and the found value was 531.1510.

[0296] Example 53 of the present invention - Oligomerization of bis(5-iodo-2-methoxy-4-propylphenyl)carbonate and ethane-1,2-diyl diacrylate

[0297] General Procedure 8 was applied using bis(5-iodo-2-methoxy-4-propylphenyl)carbonate (305 mg, 0.5 mmol), Pd(PPh3)2Cl2 (14 mg, 0.02 mmol), NEt3 (280 μL, 2.0 mmol), ethane-1.2-diyl diacrylate (85 μL, 0.5 mmol / L) and acetonitrile (2 mL). The mixture was stirred at 80°C for 17 hours. A yellow oil was obtained which gave a solid foam after the addition of acetone and evaporation of the solvent. The formation of small oligomers was confirmed via nanomass electrospray analysis (see Figure 2 ). The m / z value of the repeating unit (n) was 524.2, with analytes detected as sodium adducts from 905.4 (n=1) to 2477.9 (n=4). Analytes with phenolic end groups were also detected as sodium adducts from 713.2 (n=1) to 2285.9 (n=4). Some closed-ring oligomers were also detected as sodium adducts from 1071.4 (n=1) to 2119.8 (n=3).

[0298] in conclusion : Substituents with a +M effect on the aromatic moiety (such as methoxy in Example 45) are beneficial to the reactivity of aromatic carbonates, since in the absence of this substituent, only traces of the expected product were obtained (Example 46). No coupling was observed for the less reactive 2-bromophenyl methyl carbonate (Example 47). Iodinated symmetrical aromatic carbonates were also successfully coupled with ethyl acrylate, as shown for bis-(5-iodo-2-methoxyphenyl) carbonate (Example 48) and bis-(5-iodo-2-methoxy-4-propylphenyl) carbonate (Example 50). Styrene was incompatible (Comparative Example 49), but on the other hand dimethyl itaconate was successfully coupled (Example 51). Biscarbonates were also successfully prepared from bis-(5-iodo-2-methoxyphenyl) carbonate and ethane-1,2-diyl diacrylate (Example 52). Finally, the formation of small oligomers was demonstrated via the coupling of bis(5-iodo-2-methoxy-4-propylphenyl) carbonate with ethane-1,2-diyl diacrylate (Example 53).

Claims

1. A method for preparing polycarbonate using metal-catalyzed cross-coupling, the method comprising a compound having a structure of formula (I) and a compound having the structure of formula (IIa) or (IIb) A reaction in the presence of a metal catalyst and a base, wherein a) using compound (IIa) to produce a polycarbonate comprising repeating units having the structure of formula (IIIa) The repeating unit having the structure of formula (IIIa) comprises two aromatic rings, a carbonate group -OC(=O)O- and a linking group having the structure of formula (IVa) wherein one of the two aromatic rings is substituted by the carbonate group, the two aromatic rings are connected via the connecting group, and the connecting group in each repeating unit is independently located at the ortho position, meta position or para position relative to the carbonate group, b) using the reaction of compound (IIb) to produce a polycarbonate comprising repeating units having the structure of formula (IIIb) The repeating unit having the structure of formula (IIIb) comprises two aromatic rings, a carbonate group -OC(=O)O- and a linking group having the structure of formula (IVb) wherein one of the two aromatic rings is substituted by a carbonate group, the two aromatic rings are connected via a linking group, and the linking group in each repeating unit is independently located at the ortho position, meta position or para position relative to the carbonate group, And among them - each m is independently 0 to 4, preferably 1 to 3, - Each R 1 and R 2 R 1 Substituents and R 2 a substituent which is capable of activating the aromatic ring it replaces by mesenchymal and / or inductive effects, -R 3 express o optionally substituted alkyl, alkenyl or alkynyl, wherein the optionally substituted alkyl, alkenyl or alkynyl is optionally interrupted by at least one heteroatom, o optionally substituted cycloalkyl or cycloalkenyl, or o optionally substituted phenyl, -R 4 express o optionally substituted alkyl or alkenyl, o optionally substituted cycloalkyl or cycloalkenyl, or o optionally substituted aryl, - Each R 5 Independently express o Hydrogen atoms, or o optionally substituted alkyl or alkenyl, wherein the optionally substituted alkyl or alkenyl is optionally interrupted by an ester group, and -n is the number of repeating units.

2. The method according to claim 1, wherein at least one R 1 Substituents and / or at least one R 2 The substituent is located in the ortho position relative to the carbonate group substituting the same aromatic ring.

3. The method according to any one of claims 1 to 2, wherein each R 1 and each R 2 The alkyl group or alkoxy group independently represents an alkyl group or an alkoxy group, preferably an alkyl group or an alkoxy group having 1 to 6 carbon atoms, and more preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a neopentyl group, a 1-ethylpropyl group, a cyclohexyl group, a cyclopentyl group, an n-hexyl group, a 1,1-dimethylpropyl group, a 1,2-dimethylpropyl group, a 1,2-dimethylpropyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, a -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, 1-ethyl-2-methylpropyl, 1-ethyl-2-methylpropyl, methoxy, ethoxy The invention also includes but is not limited to propyl, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, neopentoxy, 1-ethylpropoxy, cyclohexyloxy, cyclopentyloxy, n-hexyloxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 1,2-dimethylpropoxy, 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, 1-ethyl-2-methylpropoxy or 1-ethyl-2-methylpropoxy, and most preferably n-propyl or methoxy.

4. The method according to any one of claims 1 to 3, wherein -R 3 express o an alkyl group having 1 to 20 carbon atoms, wherein the alkyl group is optionally interrupted by at least one heteroatom, wherein the at least one heteroatom is preferably selected from an oxygen atom or a nitrogen atom, or o phenyl, or a substituted phenyl having a total of 6 to 12 carbon atoms, -R 4 represents an alkyl group having 1 to 20 carbon atoms, and / or -R 5 represents a hydrogen atom, or an alkyl group having 1 to 20 carbon atoms, wherein the alkyl group is optionally interrupted by an ester group.

5. The method according to any one of claims 1 to 4, wherein - the linking group in each repeating unit of formula (IIIa) and / or each repeating unit of formula (IIIb) is independently located in the meta position relative to the carbonate group substituting the same aromatic ring, and / or - Each of the two aromatic rings in each repeating unit of formula (IIIb) is independently substituted by a linking group, such that each repeating unit represents an (E,E)-isomer.

6. The method according to any one of claims 1 to 5, wherein the metal catalyst is a transition metal catalyst, wherein preferably the transition metal catalyst comprises palladium and / or copper, and more preferably the transition metal catalyst is selected from -bis(triphenylphosphine)palladium(II) dichloride [Pd(PPh3)2Cl2], - Combination of Pd(PPh3)2Cl2 and copper(I) iodide (CuI), - a combination of palladium on carbon (Pd / C) and CuI, or -Combination of CuI and triphenylphosphine (PPh3).

7. The process according to any one of claims 1 to 6, wherein the base is an amine, preferably a tertiary amine, more preferably triethylamine (NEt3) or N,N-dicyclohexylmethylamine (Cy2NMe).

8. The method according to any one of claims 1 to 7, wherein - the compound of formula (IIa) or the compound of formula (IIb) is added in an amount of 0.1 to 10.0 equivalents, preferably 0.1 to 5.0 equivalents, more preferably 0.5 to 1.5 equivalents relative to the compound of formula (I), and / or - The base is added in an amount of 2.0 to 10.0 equivalents, preferably 2.0 to 5.0 equivalents, more preferably 2.0 to 4.0 equivalents, relative to the compound of formula (I).

9. The method according to any one of claims 1 to 8, wherein - In the reaction using the compound of formula (IIa), the metal catalyst is a combination of Pd(PPh3)2Cl2 and CuI in a molar ratio of 1:2, wherein oPd(PPh3)2Cl2 is added in an amount of 0.1 to 10 mol %, preferably 2 to 6 mol %, more preferably 4 mol % relative to the compound of formula (I), and oCuI is added in an amount of 0.2 to 20 mol %, preferably 4 to 12 mol %, more preferably 8 mol % relative to the compound of formula (I), or - In the reaction using the compound of formula (IIb), the metal catalyst is Pd(PPh3)2Cl2, wherein Pd(PPh3)2Cl2 is added in an amount of 0.1 to 5 mol %, preferably 2 to 4 mol %, more preferably 3 to 4 mol % relative to the compound of formula (I).

10. The process according to any one of claims 1 to 9, wherein a solvent is used, preferably wherein the solvent is selected from acetonitrile (MeCN), dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), toluene, 1,2-dichloroethane (DCE) or tetrahydrofuran (THF).

11. A polycarbonate comprising a repeating unit having a structure of formula (IIIa) The repeating unit having the structure of formula (IIIa) comprises two aromatic rings, a carbonate group -OC(=O)O- and a linking group having the structure of formula (IVa) wherein one of the two aromatic rings is substituted by a carbonate group, the two aromatic rings are connected via a linking group, and the linking group in each repeating unit is independently located at the ortho position, meta position or para position relative to the carbonate group, Or a repeating unit having the structure of formula (IIIb) The repeating unit having the structure of formula (IIIb) comprises two aromatic rings, a carbonate group -OC(=O)O- and a linking group having the structure of formula (IVb) wherein one of the two aromatic rings is substituted by a carbonate group, the two aromatic rings are connected via a linking group, and the linking group in each repeating unit is independently located at the ortho position, meta position or para position relative to the carbonate group, And among them - each m is independently 0 to 4, preferably 1 to 3, - Each R 1 and R 2 R 1 Substituents and R 2 a substituent which is capable of activating the aromatic ring it replaces by mesenchymal and / or inductive effects, -R 3 express o optionally substituted alkyl, alkenyl or alkynyl, wherein the optionally substituted alkyl, alkenyl or alkynyl is optionally interrupted by at least one heteroatom, o optionally substituted cycloalkyl or cycloalkenyl, or o optionally substituted phenyl, -R 4 express o optionally substituted alkyl or alkenyl, o optionally substituted cycloalkyl or cycloalkenyl, or o optionally substituted aryl, - Each R 5 Independently express o Hydrogen atoms, or o optionally substituted alkyl or alkenyl, wherein the optionally substituted alkyl or alkenyl is optionally interrupted by an ester group, and -n is the number of repeating units.

12. The polycarbonate according to claim 11, wherein at least one R 1 Substituents and / or at least one R 2 The substituent is located in the ortho position relative to the carbonate group substituting the same aromatic ring.

13. The polycarbonate according to any one of claims 11 to 12, wherein each R 1 and each R 2 The alkyl group or alkoxy group independently represents an alkyl group or an alkoxy group, preferably an alkyl group or an alkoxy group having 1 to 6 carbon atoms, and more preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a neopentyl group, a 1-ethylpropyl group, a cyclohexyl group, a cyclopentyl group, an n-hexyl group, a 1,1-dimethylpropyl group, a 1,2-dimethylpropyl group, a 1,2-dimethylpropyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, a -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, 1-ethyl-2-methylpropyl, 1-ethyl-2-methylpropyl, methoxy, ethoxy The invention also includes but is not limited to propyl, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, neopentoxy, 1-ethylpropoxy, cyclohexyloxy, cyclopentyloxy, n-hexyloxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 1,2-dimethylpropoxy, 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, 1-ethyl-2-methylpropoxy or 1-ethyl-2-methylpropoxy, and most preferably n-propyl or methoxy.

14. The polycarbonate according to any one of claims 11 to 13, wherein -R 3 express o an alkyl group having 1 to 20 carbon atoms, wherein the alkyl group is optionally interrupted by at least one heteroatom, wherein the at least one heteroatom is preferably selected from an oxygen atom or a nitrogen atom, or o phenyl, or a substituted phenyl having a total of 6 to 12 carbon atoms, -R 4 represents an alkyl group having 1 to 20 carbon atoms, and -R 5 represents a hydrogen atom, or an alkyl group having 1 to 20 carbon atoms, wherein the alkyl group is optionally interrupted by an ester group.

15. The polycarbonate according to any one of claims 11 to 14, wherein - the linking group in each repeating unit of formula (IIIa) and / or each repeating unit of formula (IIIb) is independently located in the meta position relative to the carbonate group substituting the same aromatic ring, and / or - Each of the two aromatic rings in each repeating unit of formula (IIIb) is independently substituted by a linking group, such that each repeating unit represents an (E,E)-isomer.

Images