(19)
(11)EP 3 668 849 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
22.12.2021 Bulletin 2021/51

(21)Application number: 18750464.2

(22)Date of filing:  14.08.2018
(51)International Patent Classification (IPC): 
C07D 317/40(2006.01)
(52)Cooperative Patent Classification (CPC):
C07D 317/40; Y02E 60/10
(86)International application number:
PCT/EP2018/072014
(87)International publication number:
WO 2019/034648 (21.02.2019 Gazette  2019/08)

(54)

PROCESS FOR PREPARING CYCLIC CARBONATES

VERFAHREN ZUR HERSTELLUNG VON CYCLISCHEN CARBONATEN

PROCÉDÉ DE PRÉPARATION DE CARBONATES CYCLIQUES


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 14.08.2017 EP 17186136

(43)Date of publication of application:
24.06.2020 Bulletin 2020/26

(73)Proprietor: BASF SE
67056 Ludwigshafen am Rhein (DE)

(72)Inventors:
  • BAYARMAGNAI, Bilguun
    69120 Heidelberg (DE)
  • SCHAUB, Thomas
    67056 Ludwigshafen (DE)
  • MORMUL, Verena
    67056 Ludwigshafen (DE)
  • RUDOLF, Peter
    67056 Ludwigshafen (DE)

(74)Representative: BASF IP Association 
BASF SE G-FLP-C006
67056 Ludwigshafen
67056 Ludwigshafen (DE)


(56)References cited: : 
  
  • ANDREA K. BUZAS ET AL: "Gold-catalyzed rearrangement of propargylic tert-butyl carbonates", TETRAHEDRON, vol. 65, no. 9, 1 February 2009 (2009-02-01), pages 1889-1901, XP055135539, ISSN: 0040-4020, DOI: 10.1016/j.tet.2008.11.108
  • CHAORONG Q. ET AL.: "Efficient synthesis of beta-oxoalkyl carbamates from carbon dioxide, internal propargylic alcohols, and secondary amines catalysed by silver salts and DBU", SYNTHESIS, vol. 9, 11 February 2010 (2010-02-11), pages 1433-1440, XP002775643,
  
Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


Description


[0001] The present invention relates to a process for preparing cyclic carbonates of formula Ia or Ib or mixtures thereof

comprising the process step:
  1. a) reacting a propargylic alcohol of formula II

    with carbon dioxide in the presence of at least one transition metal catalyst TMC1, which comprises a transition metal selected from metals of groups 10, 11 and 12 of the periodic table of the elements according to IUPAC and at least one bulky ligand.


[0002] Exo-vinylene carbonates are valuable compounds, especially for the use in electrolytes for batteries as described in US 2013/0059178 A1 or as monomers in polymer applications as described in WO 2011/157671 A1. Exo-Vinylene carbonates with substituents in the 4,4-position are available via the reaction of secondary or tertiary propargylic alcohols with CO2 using different catalysts like metals or bases.



[0003] None of the protocols, which are described in the literature, like the Silver-, Copper-, Cobalt- or guanidine catalyzed cyclisations could until now be applied to the conversion of simple primary propargylic alcohols with CO2 towards the simple Exo-vinylene carbonates with two hydrogens in the 4,4-positions.

[0004] In Eur. J Org. Chem. 2007, 2604-2607 the silver-catalyzed incorporation of carbon dioxide into propargylic alcohol is reported, where AgOAc in combination with DBU is the catalyst system. This catalyst system worked well for the cyclisation of tertiary propargylic alcohols, but the method was not applicable to primary or secondary propargylic alcohols for their conversion into the corresponding cyclic products.

[0005] in Journal of Organometallic Chemistry, 1997, 545-546, 337-344, a Cu-catalyzed cyclisation of propargylic alcohols with CO2 is reported. The copper catalyst, which comprised a tetradentate imine ligand was used in combination with different amine bases. These catalysts worked well for the cyclisation of tertiary propargylic alcohols, but no cyclisation product was formed from primary propargylic alcohol.

[0006] In the attempts for the guanidine-catalyzed cyclisation of propargylic alcohols with CO2 reported in Advanced Synthesis and Catalysis, 2011, 353, 133-146, no metal catalyst was added. These catalysts worked well for the cyclisation of tertiary- and secondary propargylic alcohols, but no Exo-vinylenecarbonate from primary propargylic alcohol was formed under these conditions.

[0007] In the attempts for the Cobalt-catalyzed cyclisation of propargylic alcohols with CO2 reported in Bulletin of the Chemical Society of Japan, 1987, 60, 1204-1206, PPh3 was added as the donor ligand in combination with NEt3 as the base. This catalyst worked well for the cyclisation of tertiary propargylic alcohols, but no Exo-vinylene carbonate from primary propargylic alcohol was formed under these conditions.

[0008] In the prior art, the only reasonable synthetic approach to the 4-methylene-1,3-dioxolan-2-one, the simplest Exo-vinylene carbonate, is the Gold- or Mercury catalyzed cyclisation of propargylic tert-butylcarbonates which is described in Synlett, 2006, 17, 2727-2730 and in Tetrahedron Letters, 2006, 47, 8369-8373.



[0009] One disadvantage of this route is, that the propargylic tert-butylcarbonate must be prepared first from propargylic alcohol and the relatively expensive BOC-anhydride.

[0010] Another disadvantage of the cyclisation of the propargylic tert-butlycarboante is, that the other tBu group is released as Isobutene and therefore a byproduct is formed, which must be disposed or recycled.

[0011] Another route towards 4-methylene-1,3-dioxolan-2-one is described in J. Org. Chem. 1983, 48(19), 3346-3347. This method starts from a chlorinated glycerol derivative and uses PhSeNa as reagent. This route does not allow commercial production of the product.

[0012] The synthesis of exo-vinylene cyclic carbonates is also disclosed inTETRAHEDRON 2009, vol. 65, no. 9, pages 1889-1901 and SYNTHESIS 2010, vol. 9, pages 1433-1440.

[0013] Accordingly, it is an object of the invention to provide a more economic process for preparing cyclic carbonates from primary propargylic alcohols and CO2, preferably directly from primary propargylic alcohols and CO2.

[0014] This object is achieved by a process for preparing cyclic carbonates of formula Ia or Ib or mixtures thereof

wherein
R1 is hydrogen or an organic radical having from 1 to 40 carbon atoms, comprising the process step:
  1. a) reacting a propargylic alcohol of formula II

    wherein R1 has the same meaning as in formula la or Ib, with carbon dioxide in the presence of at least one transition metal catalyst TMC1, which comprises a transition metal selected from metals of groups 10, 11 and 12 of the periodic table of the elements according to IUPAC, preferably selected from Cu, Ag and Au, more preferably Ag, and at least one bulky ligand selected from the group of ligands consisting of compounds of formula III and compounds of formula IV, preferably compounds of formula III,


wherein
D
is P, As or Sb, preferably P or As, in particular P,
R2
is an organic radical having from 1 to 40 carbon atoms, preferably from 2 to 40 carbon atoms, preferably comprising at least one cyclic ring, more preferably, in formula III R2 is a C3 to C40 cycloalkyl radical, a C2 to C40 heterocycloalkyl radical, a C6 to C40 aryl radical, a C2 to C40 heteroaromatic radical, a C3 to C40 cycloalkoxy radical, a C2 to C40 heterocycloalkoxy radical, a C6 to C40 aryloxy radical or a C2 to C40 hetaryloxy radical, in particular a C6 to C40 aryl radical or a C2 to C40 heteroaromatic radical,
R3, R4
are identical or different, and are each an organic radical having from 1 to 40 carbon atoms, and,
R5
is an organic radical having from 1 to 40 carbon atoms or is identical to R2,
and Z
is a divalent bridging group selected from -CR7=CR8-, -CR7=N-,-CR7R9-CR8R10- and -CR7R9-CR8R10-CR11R12-, wherein R7, R8, R9, R10, R11 and R12 are independently from each other hydrogen or as defined as R5 or two adjacent radicals R7 and R8 and/or R10 and R11 together with the atoms connecting them form a monocyclic or polycyclic, substituted or unsubstituted, aliphatic or aromatic ring system which has from 4 to 40 carbon atoms and can also comprise at least one heteroatom selected from the group consisting of the elements Si, Ge, N, P, O and S.


[0015] In one embodiment of the present invention, the inventive process is characterized in that
D
is P,
R2
is a C3 to C40 cycloalkyl radical, a C2 to C40 heterocycloalkyl radical, a C6 to C40 aryl radical or a C2 to C40 heteroaromatic radical, preferably a C6 to C40 aryl radical or a C2 to C40 heteroaromatic radical, wherein R2 is substituted in at least one of the two ortho positions relative to P or N with a radical R6, which is an organic radical having from 1 to 40 carbon atoms, a halogen, in particular Cl or Br, hydroxy, SO3H or nitro or wherein R6 together with an adjacent radical substituting R2 in the meta position forms together with the atoms connecting them a monocyclic or polycyclic, substituted or unsubstituted, aliphatic or aromatic ring system, which has from 4 to 40 carbon atoms and can also comprise at least one heteroatom selected from the group consisting of the elements Si, Ge, N, P, O and S, preferably N and O,
R3, R4 R5 and Z
are defined as described above.


[0016] The substituents according to the present invention are, unless restricted further, defined as follows:
The term "organic radical having from 1 to 40 carbon atoms" as used in the present text refers to, for example, C1-C40-alkyl radicals, C1-C10-fluoroalkyl radicals, C1-C12-alkoxy radicals, saturated C3-C20-heterocyclic radicals, C6-C40-aryl radicals, C2-C40-heteroaromatic radicals, C6-C10-fluoroaryl radicals, C6-C10-aryloxy radicals, silyl radicals having from 3 to 24 carbon atoms, C2-C20-alkenyl radicals, C2-C20-alkynyl radicals, C7-C40-arylalkyl radicals or C8-C40-arylalkenyl radicals. An organic radical is in each case derived from an organic compound. Thus, the organic compound methanol can in principle give rise to three different organic radicals having one carbon atom, namely methyl (H3C-), methoxy (H3C-O-) and hydroxymethyl (HOC(H2)-). Therefore, the term "organic radical having from 1 to 40 carbon atoms" comprises beside alkoxy radicals for example also dialkylamino radicals, monoalkylamino radicals or alkylthio radicals.

[0017] In the present description, the term radical is used interchangeably with the term group, when defining the variables Rx in the presented formulas.

[0018] The term "alkyl" as used in the present text encompasses linear or singly or multiply branched saturated hydrocarbons which can also be cyclic. Preference is given to a C1-C18-alkyl radical such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, cyclopentyl, cyclohexyl, isopropyl, isobutyl, isopentyl, isohexyl, sec-butyl or tert-butyl

[0019] The term "alkenyl" as used in the present text encompasses linear or singly or multiply branched hydrocarbons having one or more C-C double bonds which can be cumulated or alternating.

[0020] The term "saturated heterocyclic radical" as used in the present text refers to, for example, monocyclic or polycyclic, substituted or unsubstituted aliphatic or partially unsaturated hydrocarbon radicals in which one or more carbon atoms, CH groups and/or CH2 groups have been replaced by heteroatoms which are preferably selected from the group consisting of the elements O, S, N and P. Preferred examples of substituted or unsubstituted saturated heterocyclic radicals are pyrrolidinyl, imidazolidinyl, pyrazolidinyl, piperidyl, piperazinyl, morpholinyl, tetrahydrofuranyl, tetrahydropyranyl, tetrahydrothiophenyl and the like, and also methyl-, ethyl-, propyl-, isopropyl- and tert- butyl-substituted derivatives thereof.

[0021] The term "aryl" as used in the present text refers to, for example, aromatic and optionally fused polyaromatic hydrocarbon radicals which may be monosubstituted or polysubstituted by linear or branched C1-C18-alkyl, C1-C18-alkoxy, C2-C10-alkenyl or halogen, in particular fluorine. Preferred examples of substituted and unsubstituted aryl radicals are, in particular, phenyl, pentafluorophenyl, 4-methylphenyl, 4-ethylphenyl, 4-n-propylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4- methoxyphenyl, 1-naphthyl, 9-anthryl, 9-phenanthryl, 3,5-dimethylphenyl, 3,5-di-tert-butylphenyl or 4-trifluoromethylphenyl.

[0022] The term "heteroaromatic radical" as used in the present text refers to, for example, aromatic hydrocarbon radicals in which one or more carbon atoms or CH groups have been replaced by nitrogen, phosphorus, oxygen or sulfur atoms or combinations thereof. These may, like the aryl radicals, optionally be monosubstituted or polysubstituted by linear or branched C1-C18-alkyl, C2-C10-alkenyl or halogen, in particular fluorine. Preferred examples are furyl, thienyl, pyrrolyl, pyridyl, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, pyrimidinyl, pyrazinyl and the like, and also methyl-, ethyl-, propyl-, isopropyl- and tert-butyl-substituted derivatives thereof.

[0023] The term "arylalkyl" as used in the present text refers to, for example, aryl-comprising substitu- ents whose aryl radical is linked via an alkyl chain to the remainder of the molecule. Preferred examples are benzyl, substituted benzyl, phenethyl, substituted phenethyl and the like.

[0024] The terms fluoroalkyl and fluoroaryl mean that at least one hydrogen atom, preferably more than one and at most all hydrogen atoms, of the corresponding radical have been replaced by fluorine atoms. Examples of preferred fluorine-comprising radicals are trifluoromethyl, 2,2,2-trifluoroethyl, pentafluorophenyl, 4-trifluoromethylphenyl, 4-perfluoro-tert-butylphenyl and the like.

[0025] R1 in formulas Ia, Ib and II is hydrogen or an organic radical having from 1 to 40 carbon atoms, preferably hydrogen, acyclic or cyclic, substituted or unsubstituted C1-C10-alkyl, substituted or unsubstituted C6-C10-aryl or substituted or unsubstituted C7-C12-arylalkyl, in particular hydrogen or hydroxymethyl or a corresponding ester or carbonate thereof, in particular acetoxy-methylene (-CH2OC(O)CH3), formyloxy-methylene -CH2OC(O)H or -CH2OC(O)OCH3. In one embodiment of the present invention, the inventive process is characterized in that R1 is hydrogen, hydroxymethyl (-CH2OH), acetoxy-methylene (-CH2OC(O)CH3), formyloxy-methylene (-CH2OC(O)H) or -CH2OC(O)OCH3.

[0026] For the avoidance of doubt, the term "propargylic alcohol of formula II" as used in the present description is not restricted to 2-Propyn-1-ol alone but it describes all compounds, which comprise the prop-2-yn-1-ol group.



[0027] In the process of the invention, the propargylic alcohol of formula II is reacted with carbon dioxide in the presence of at least one transition metal catalyst TMC1. Transition metal catalyst TMC1 comprises a transition metal selected from metals of groups 10, 11 and 12 of the periodic table of the elements according to IUPAC, such as Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd and Hg, preferably selected from Cu, Ag and Au, more preferably selected from Cu or Ag, in particular Ag.

[0028] In one embodiment of the present invention, the inventive process is characterized in that the transition metal of transition metal catalyst TMC1 is Ag

[0029] The transition metal catalyst TMC1 of the process of the invention can be employed in the form of a preformed metal complex which comprises a transition metal and at least one bulky ligand selected from the group of ligands consisting of compounds of formula III and compounds of formula IV, preferably compounds of formula III, as shown above. Alternatively, the transition metal catalyst TMC1 is formed in situ in the reaction medium by combining a metal compound, herein also termed pre-catalyst, which does not comprise any bulky ligand, with one or more suitable bulky ligand to form a catalytically active metal complex, the transition metal catalyst TMC1, in the reaction medium. In case the bulky ligand is a N-heterocyclic carbene ligand (NHC-ligand) of formula IV, it is also possible that the transition metal catalyst TMC1 is formed in situ in the reaction medium by combining a pre-catalyst with one or more NHC-precursor, in particular the protonated form of a NHC-ligand, which is in situ converted to the corresponding NHC-ligand of formula IV, to form a catalytically active metal complex in the reaction medium.

[0030] In one embodiment of the present invention, the inventive process is characterized in that the transition metal catalyst TMC1 is prepared in situ by using a transition metal compound, which does not comprise any bulky ligand, the compound of formula III or formula IV as bulky ligand or the protonated form of the compound of formula IV represented by formula V,

wherein R2, R5 and Z are defined as described above and X- is an anion equivalent, together with a base.

[0031] Suitable bases for deprotonating the protonated form of different NHC ligands according to formula V are described by de Fremont et al., Coordination Chemistry Reviews 253 (2009) 876 to 881. The deprotonation of the protonated forms of NHC ligands can be carried out in ammonia or in non-protic solvents such as THF or ethers. The deprotonation requires anhydrous conditions and the use of strong bases, with pKa values above 14. Usually, potassium or sodium hydride with a catalytic amount of tert-butoxide is employed, but tert-butoxide itself, lithium aluminum hydride, n-butyllithium, MeLi, t-BuLi, potassium hexamethyldisilazide (KHMDS) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) are also efficient alternatives.

[0032] Suitable pre-catalysts are selected from neutral metal complexes, oxides and salts of metals of groups 10, 11 and 12 of the periodic table of the elements. Preferred pre-catalysts are selected from metal complexes, oxides and salts of copper, silver and gold, in particular silver.

[0033] Silver compounds that are useful as pre-catalyst are, for example Ag(OAc), AgF, AgNO3, silver trifluoroacetate, Ag2O, Ag2CO3.

[0034] In one embodiment of the present invention, the inventive process is characterized in that the transition metal compound, also called pre-catalyst, is selected from AgOAc, AgF, Ag2O and Ag2CO3.

[0035] In addition to the transition metal, the transition metal catalyst TMC1 comprises at least one bulky ligand selected from the group of ligands consisting of compounds of formula III and compounds of formula IV, preferably compounds of formula III.



[0036] In case the bulky ligand is a compound of formula III,

the variables are preferably defined as follows:
D
is P, As or Sb, preferably P or As, in particular P,
R2
is an organic radical having from 1 to 40 carbon atoms, preferably from 2 to 40 carbon atoms, preferably comprising at least one cyclic ring, more preferably R2 is a C3 to C40 cycloalkyl radical, a C2 to C40 heterocycloalkyl radical, a C6 to C40 aryl radical, a C2 to C40 heteroaromatic radical, a C3 to C40 cycloalkoxy radical, a C2 to C40 heterocycloalkoxy radical, a C6 to C40 aryloxy radical, a C2 to C40 hetaryloxy radical, even more preferably R2 is a C3 to C40 cycloalkyl radical, a C2 to C40 heterocycloalkyl radical, a C6 to C40 aryl radical or a C2 to C40 heteroaromatic radical, preferably a C6 to C40 aryl radical or a C2 to C40 heteroaromatic radical, wherein R2 is substituted in at least one of the two ortho positions relative to D with a radical R6, which is an organic radical having from 1 to 40 carbon atoms, preferably a C6 to C40 aryl radical, a C1 to C10 alkoxy radical or a C2 to C12 dialkyl amino radical or wherein R6 together with an adjacent radical substituting R2 in the meta position forms together with the atoms connecting them a monocyclic or polycyclic, substituted or unsubstituted, aliphatic or aromatic ring system, which has from 4 to 40 carbon atoms and can also comprise at least one heteroatom selected from the group consisting of the elements Si, Ge, N, P, O and S, preferably N, O and S, and
R3, R4
are identical or different, preferably identical, and are each an organic radical having from 1 to 40 carbon atoms, preferably C3 to C21 cyclic or acyclic alkyl, in particular tert.-butyl or cyclohexyl, or C6 to C14 aryl, in particular phenyl.


[0037] In case the bulky ligand is a compound of formula IV,

the variables are preferably defined as follows:
R2
is an organic radical having from 1 to 40 carbon atoms, preferably from 2 to 40 carbon atoms, preferably comprising at least one cyclic ring, more preferably R2 is a C6 to C40 aryl radical or a C2 to C40 heteroaromatic radical, preferably wherein R2 is substituted in at least one of the two ortho positions relative to N with a radical R6, which is an organic radical having from 1 to 40 carbon atoms, preferably a C1 to C10 alkyl radical, in particular isopropyl,
R5
is an organic radical having from 1 to 40 carbon atoms or is identical to R2, preferably R5 is identical to R2,
and
Z
is a divalent bridging group selected from -CR7=CR8-, -CR7=N-, -CR7R9-CR8R10- and -CR7R9-CR8R10-CR11R12-, preferably -CR7=CR8- and -CR7R9-CR8R10-, wherein R7, R8, R9, R10, R11 and R12 are independently from each other hydrogen or as defined as R5, preferably H, or two adjacent radicals R7 and R8 and/or R10 and R11 together with the atoms connecting them form a monocyclic or polycyclic, substituted or unsubstituted, aliphatic or aromatic ring system which has from 4 to 40 carbon atoms and can also comprise at least one heteroatom selected from the group consisting of the elements Si, Ge, N, P, O and S.


[0038] In one embodiment of the present invention, the inventive process is characterized in that the bulky ligand is a compound of formula III.

[0039] In one embodiment of the present invention, the inventive process is characterized in that the bulky ligand is a compound of formula III

wherein the variables are defined as follows:
D
is P,
R2
is a C6 to C40 aryl radical or a C2 to C40 heteroaromatic radical, wherein R2 is substituted in at least one of the two ortho positions relative to D with a radical R6, which is a C6 to C40 aryl radical, a C1 to C10 alkoxy radical, in particular methoxy, ethoxy, isopropoxy or cyclohexyloxy, or a C2 to C12 dialkyl amino radical, in particular dimethyl amino, diethyl amino, di-isopropyl amino, N-morpholinyl or N-piperidyl, or wherein R6 together with an adjacent radical substituting R2 in the meta position forms together with the atoms connecting them a monocyclic or polycyclic, substituted or unsubstituted, aliphatic or aromatic ring system, which has from 4 to 40 carbon atoms and can also comprise at least one heteroatom selected from the group consisting of the elements Si, Ge, N, P, O and S, preferably N, O and S,
and
R3, R4
are identical or different, preferably identical, and are each an organic radical having from 1 to 40 carbon atoms, preferably C3 to C20 cyclic or acyclic alkyl, in particular tert.-butyl, adamantyl or cyclohexyl, or C6 to C14 aryl, in particular phenyl.


[0040] In one embodiment of the present invention, the inventive process is characterized in that the bulky ligand is selected from a compound of formulas A to P and mixtures thereof, preferably a compound of formulas A to D and mixtures thereof.









[0041] In one embodiment of the present invention, the inventive process is characterized in that the transition metal catalyst TMC1 is selected from a compound of the following formulas.



[0042] The molar ratio of the bulky ligand to the transition metal of transition metal catalyst TMC1 can be varied in wide range. Preferably the molar ratio of the bulky ligand to the transition metal is below 2. More preferably the ratio of the bulky ligand to the transition metal is in the range from 0.2 to 1.8, even more preferably in the range from 0.3 to 1.5, in particular in the range from 0.4 to 1.2.

[0043] In one embodiment of the present invention, the inventive process is characterized in that the molar ratio of the bulky ligand to the transition metal of transition metal catalyst TMC1 is in the range from 0.4 to 1.2.

[0044] In the inventive process the amount of transition metal catalyst TMC1 used in process step a) based on the amount of propargylic alcohol of formula II can be varied in a wide range. Usually the transition metal catalyst TMC1 is used in a sub-stoichiometric amount relative to the propargylic alcohol of formula II. Typically, the amount of transition metal catalyst TMC1 is not more than 50 mol%, frequently not more than 20 mol% and in particular not more than 10 mol% or not more than 5 mol%, based on the amount of propargylic alcohol of formula II. An amount of transition metal catalyst TMC1 of from 0.001 to 50 mol%, frequently from 0.001 mol% to 20 mol% and in particular from 0.005 to 5 mol%, based on the amount the propargylic alcohol of formula II is preferably used in the process of the invention. Preference is given to using an amount of transition metal catalyst TMC1 of from 0.01 to 5 mol%. All amounts of transition metal complex catalyst indicated are calculated as transition metal and based on the amount of propargylic alcohol.

[0045] In one embodiment of the present invention, the inventive process is characterized in that the amount of transition metal catalyst TMC1 used in process step a) based on the amount of propargylic alcohol of formula II is in the range from 0.005 to 5 mol%.

[0046] The reaction can principally be performed according to all processes known to a person skilled in the art which are suitable for the reaction of primary propargylic alcohols with CO2,
The CO2 used for the carboxylation-cyclisation reaction can be used in pure form or, if desired, also in the form of mixtures with other, preferably inert gases, such as nitrogen or argon. Preference is given to using CO2 in undiluted form.

[0047] The reaction is typically carried at a CO2 pressure in the range from 0.1 to 200 bar, preferably in the range from 1 to 50 bar, more preferably in the range from 1 to 40 bar.

[0048] In one embodiment of the present invention, the inventive process is characterized in that the process step a) is performed at a pressure in the range from 1 to 50 bar, more preferably in the range from 1 to 40 bar.

[0049] The reaction can principally be performed continuously, semi-continuously or discontinuously. Preference is given to a continuous process.

[0050] The reaction can principally be performed in all reactors known by a person in the art for this type of reaction and therefore, will select the reactors accordingly. Suitable reactors are described and reviewed in the relevant prior art, e.g. appropriate monographs and reference works such as mentioned in US 6639114 B2, column 16, line 45-49. Preferably, for the reaction an autoclave is employed which may have an internal stirrer and an internal lining.

[0051] The composition obtained in the carboxylation-cyclisation reaction of the present invention comprises an unsubstituted Exo-Vinylene carbonate, that is a cyclic carbonate of formula Ia or Ib.

[0052] Process step a) of the inventive process can be performed in a wide temperature range. Preferably process step a) is performed at a temperature in the range preferably in the range from 0° C to 150 ° C and particularly preferably in the range from 10° C to 80 ° C. Temperatures below 100 ° C have surprisingly been found to be particularly advantageous.

[0053] In one embodiment of the present invention, the inventive process is characterized in that the process step a) is performed at a temperature in the range from 0 ° C to 100 ° C, preferably in the range from 10° C to 80 ° C.

[0054] The process of the invention can be carried out in the presence of a solvent. Suitable solvents are selected from aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, amides, ureas, nitriles, sulfoxides, sulfones, esters, carbonates, ethers, alcohols and mixtures thereof. Preferred solvents are
  • aliphatic hydrocarbons such as pentane, hexane, heptane, octane or cyclohexane;
  • aromatic hydrocarbons such as benzene, toluene, xylenes, ethylbenzene, mesitylene or benzotrifluoride;
  • halogenated hydrocarbons such as dichloromethane,
  • amides such as dimethylformamide, diethylformamide, N-methylpyrrolidone, N-ethylpyrrolidone or dimethylacetamide;
  • ureas such as tetramethylurea, N,N-dimethylimidazolinone (DMI) and N,N-dimethylpropyleneurea (DMPU);
  • nitriles such as acetonitrile or propionitrile;
  • sulfoxides such as dimethyl sulfoxide;
  • sulfones such as sulfolane;
  • esters such as methyl acetate, ethyl acetate, t-butyl acetate;
  • carbonates such as diethyl carbonate, ethylene carbonate and propylene carbonate; and
  • ethers such as dioxane, tetrahydrofuran, diethyl ether, dibutyl ether, methyl t-butyl ether, diisopropyl ether or diethylene glycol dimethyl ether;


[0055] If desired, mixtures of two or more of the afore-mentioned solvents can also be used.

[0056] Preference is given to using dichloromethane, acetone, dimethylformamide or acetonitrile as solvents.

[0057] In one embodiment of the present invention, the inventive process is characterized in that the reaction is carried out in the presence of a solvent selected from aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, amides, ureas, nitriles, sulfoxides, sulfones, esters, carbonates, ethers, alcohols and mixtures thereof, preferably selected from dichloromethane, acetone, dimethylformamide or acetonitrile.

[0058] Alternatively, the process of the invention can be carried out in the absence of any of the above-mentioned organic solvent, so-called neat conditions, preferably in the presence of liquid or supercritical carbon dioxide, in particular in the presence of supercritical carbon dioxide.

[0059] Alternatively, the process of the invention can be carried out in the presence of liquid or supercritical carbon dioxide, in particular in the presence of supercritical carbon dioxide, which is mixed with one of the above-mentioned organic solvent, so-called CO2-expanded solvents.

[0060] The composition obtained in the carboxylation-cyclisation of the invention comprises an unsubstituted Exo-Vinylene carbonate, the cyclic carbonate of formula Ia or Ib.

[0061] The work-up of the reaction mixture of the inventive process and the isolation of the cyclic carbonate of formula Ia or Ib are effected in a customary manner, for example by filtration, an aqueous extractive work-up or by a distillation, for example under reduced pressure. The cyclic carbonate of formula Ia or Ib may be obtained in sufficient purity by applying such measures or a combination thereof, obviating additional purification steps. Alternatively, further purification can be accomplished by methods commonly used in the art, such as chromatography.

[0062] In one embodiment of the present invention, the inventive process is characterized in that the cyclic carbonates of formula Ia or Ib or mixtures thereof are separated from the transition metal catalyst TMC1 after process step a) via distillation.

[0063] The distillation residue usually still comprises the transition metal catalyst TMC1 in an active form, that can be reused in a new carboxylation-cyclisation reaction step, that is a new process step a. As long as the distillation conditions, in particular the temperature treatment, are not too harsh, the transition metal catalyst TMC1 remains active.

[0064] In one embodiment of the present invention, the inventive process is characterized in that the transition metal catalyst TMC1 is recycled to the reaction step a) after the cyclic carbonate of formula Ia or Ib or mixture thereof were removed via distillation.

[0065] The cyclic carbonates of formula Ia or Ib or mixtures thereof, which are prepared according to the inventive process show a high purity and are advantageously used in applications such as reactive diluent in the manufacture of epoxy resins, as electrolyte additive in electrochemical storage systems or as monomer in polymerization reactions

[0066] A further aspect of the invention is the use of the cyclic carbonates of formula Ia or Ib or mixtures thereof prepared according to the above described inventive process as reactive diluent in the manufacture of epoxy resins, as electrolyte additive in electrochemical storage systems or as monomer in polymerization reactions.

[0067] The inventive process for preparing cyclic carbonates of formula Ia or Ib or mixtures thereof as described above allows not only the preparation of known compounds (e.g. R1 = H) but also the preparation of new compounds, which can be used as reactive diluent in the manufacture of epoxy resins, as electrolyte additive in electrochemical storage systems, as monomer in polymerization reactions or as building blocks in the synthesis of active compounds for pharmaceutical or agricultural applications.

[0068] A further aspect of the invention is a cyclic carbonate of formula Ia' or Ib',

wherein
R1
is -CH2OR13, wherein R13 is hydrogen, SiR14aR14bR14c, C(O)R15 or C(O)OR16, more preferably hydrogen, C(O)R15 or C(O)OR16
wherein
R14aR14bR14c
are identical or different, and are each independently from each other hydrogen or an organic radical with 1 to 40 carbon atoms, preferably C1-C6 alkyl or C6 to C14 aryl, more preferably methyl, ethyl, i-propyl, tert.-butyl or phenyl,
R15
is hydrogen or an organic radical with 1 to 40 carbon atoms, preferably hydrogen, C1-C6 alkyl or C6 to C14 aryl, more preferably hydrogen, methyl, ethyl,-propyl or phenyl and
R16
is methyl, ethyl,-propyl or phenyl.


[0069] The inventive cyclic carbonates of formula Ia' or Ib' are derivatives of (E or Z)-4-(2-hydroxyethylidene)-1,3-dioxolan-2-one, wherein the hydroxy group is preferably protected as corresponding ester or carbonate, or (E or Z)-4-(2-hydroxyethylidene)-1,3-dioxolan-2-one itself.

[0070] Preferred examples of the inventive cyclic carbonates of formula Ia' or Ib' are:



[0071] Preferred examples of cyclic carbonate of formula Ia' or Ib' are those, wherein R1 is hydrogen, C(O)R15 or C(O)OR16, and wherein R15 is hydrogen or methyl and R16 is methyl.

[0072] The invention is illustrated by the examples which follow, but these do not restrict the invention.

[0073] Figures in percent are each based on % by weight, unless explicitly stated otherwise.

General



[0074] All chemicals and solvents were purchased from Sigma-Aldrich or ABCR and used without further purification.

[0075] 1H and 13C NMR spectra were recorded on Bruker Avance 200 MHz spectrometer and were referenced to the residual proton (1H) or carbon (13C) resonance peaks of the solvent. Chemical shifts (δ) are reported in ppm.

[0076] Used abbreviations: Davephos-Ligand A = 2-Dicyclohexylphosphino-2' -(N,N-dimethylamino)biphenyl = L1; DCM = Dichloromethane; DIPEA = N,N-Diisopropylethylamine; DMAP = 4-Dimethylaminopyridine; DMF = Dimethylformamide;PE = Petroleum ether; THF = Tetrahydrofuran; TMEDA = Tetramethylethylenediamine;

Ligands



[0077] 










Protocols for carboxylation reactions


Standard procedure A



[0078] Screening reactions were performed in a ChemSpeed Accelerator SLT 106 high-throughput robot system. Alcohol 1 (1 mmol), [M]-catalyst (0.05 mmol) and ligand (0.05 mmol) in organic solvent (2 mL) were pressurized with CO2 (20 bar) and stirred at room temperature for 12 h. After releasing the CO2 overpressure, anisole (1 mmol) and CDCl3 (1 mL) were added to the reaction mixture and stirred for 5 min. The resulting mixture was analyzed by 1H NMR to determine the yield.

Standard procedure B



[0079] A Fisher-Porter tube with Teflon-coated stirrer-bar was charged with the alcohol (5 mmol), [M]-catalyst (0.25 mmol), and ligand (0.25 mmol) and solvent (5 mL). The reaction mixture was pressurized with CO2 (8 bar) and stirred at room temperature for 16 h. Then CO2 overpressure was carefully released and solvent evaporated. The resulting crude mixture was distilled by a Kugelrohr (0.5 mbar, 100 ° C). The corresponding cyclic carbonate product was obtained pure.

1. Ligand variation



[0080] 

Table 1 summarizes the results of experiments, which were run in analogy to standard procedure A using a metal - ligand ratio of 2 to 1.
Table 1
EntryLigand L [5 mol%]Yield of 1 [%]2 [%]3 [%]
1 L1 0 99 0
2 C-L2 83 0 0
3 L3 0 21 35
4 L4 0 41 15
5 L5 0 60 20
6 L6 0 51 27
7 L7 0 74 7
 
EntryLigand L [5 mol%]Yield of 1 [%]2 [%]3 [%]
8 L8 0 43 35
9 L9 0 54 15
10 L10 0 47 20
11 L11 0 62 18
12 L12 0 82 5
13 L13 0 32 4
14 L14 0 94 7
15 L15 80 10 10
16 L16 0 41 55
17 L17 0 57 0
18 L18 80 2 0
19 L19 0 90 0

2. Ligand variation and variation of catalyst composition



[0081] 



[0082] Table 2 summarizes the results of inventive and comparative experiments, which were run in analogy to standard procedure B using different amounts of metal and ligand. Propargyl alcohol 1 (5 mmol), AgOAc (0.5 mmol) and ligand L (0.5 mmol) in anhydrous DCM (2 mL) were pressurized with CO2 (8 bar) and stirred for 16 h. Yields were determined by 1H NMR spectroscopy using anisole as an internal standard. Isolated yields are given in parentheses.
Table 2
EntryAgOAc [mol%]Ligand L [10 mol%]Yield of 2 [%]
1 10 (n-C7H15)4NBr -
2 10 Et N 3 -
3 10 DBU -
4 10 TMEDA -
5 10 Cs2 CO3 -
6 10 L4 60
7 10 L1 75
8 10 L1 (5 mol%) 85
9 10 L1 83
10 5 L1 (5 mol%) 91 (86)

3. Variation of the transition metal compound (pre-catalyst) and Ligand



[0083] 



[0084] Table 3 summarizes the results of inventive and comparative experiments, which were run in analogy to standard procedure A. Propargyl alcohol 1 (1 mmol), transition metal compound [M] (0.05 mmol) and ligand L (0.05 mmol) in anhydrous DCM (2 mL) were pressurized with CO2 (20 bar) and stirred for 12 h. Yields were determined by 1H NMR spectroscopy using anisole as an internal standard.
Table 3
Entry[M] [5 mol%]Ligand L [5 mol%]Yield of 2 [%]
1 AgOAc L1 98
2 AgF L1 98
3 AgNO3 L1 20
4 AgTFA L1 18
5 Ag2CO3 L1 72
6 NaOAc L1 0
7 CuOAc L1 traces
8 CuOAc DMAP 0
9 CuOAc 1,10-phenanthroline 0
10 CuOAc 2,2'-bipyridine 0
11 CuOAc DBU 0
12 CuOAc NEt3 0
13a IPrAgOAc - 99
  1. a) 0.035 mmol propargylic alcohol, 1 mol % IPrAgOAc, 0.7 mL CD3CN, 20 bar CO2; IPrAgOAc was prepared according to a literature procedure : D. V. Partyka, T. J. Robilotto, J. B. Updegraff III, M. Zeller, A. D. Hunter, T. G. Gray, Organometallics 2009, 28, 795-801.


4. Variation of the solvent



[0085] 

Table 4 summarizes the results of inventive experiments, which were run in analogy to standard procedure B. Propargyl alcohol 1 (5 mmol), AgOAc (0.25 mmol) and L1 (0.25 mmol) in solvent (5 mL) were pressurized with CO2 (8 bar) and stirred for 16 h. Yields were determined by 1H NMR spectroscopy using anisole as an internal standard.
Table 4
EntrysolventYield of 2 [%]
1 DCM 98
2 acetone 96
3 DMF 84
4 MeCN 85

5. Recycling of the catalytic system



[0086] 



[0087] Table 5 summarizes the results of inventive experiments, wherein the catalyst system was recycled and which were run in analogy to standard procedure B. Propargyl alcohol 1 (5 mmol), AgOAc (0.25 mmol) and L1 (0.25 mmol) in solvent (5 mL) were pressurized with CO2 (8 bar) and stirred for 16 h. Yields were determined by 1H NMR spectroscopy using anisole as an internal standard. After a Kugelrohrdestillation (100° C, 0.5 mbar) product was isolated and the residual crude used for further reaction.
Table 5
Cycle (Recycling the catalyst system)Yield 2 [%]
1 98
2 84
3 70
4 70

6. Variation of the propargylic alcohol of formula II


6.1 Use of 1,4-Butynediol as propargylic alcohol of formula II



[0088] 



[0089] In a ChemSpeed Accelerator SLT 106 high-throughput robot system, 1,4-Butynediol (1 mmol), AgOAc (0.05 mmol) and L1 (0.05 mmol) in MeCN (2 mL) were pressurized with CO2 (20 bar) and stirred at room temperature for 12 h. After releasing the CO2 overpressure, anisole (1 mmol) and CDCl3 (1 mL) were added to the reaction mixture and stirred for 5 min. The resulting mixture was analyzed by 1H NMR to determine the yield. Isolation was done by column chromatography (silica, EtOAc/hexane gradient).

(E)-4-(2-hydroxyethylidene)-1,3-dioxolan-2-one 2a

1H NMR (400 MHz, CDCl3) δ 5.01-4.98 (m, 3H), 4.24-4.21 (m, 2H), 2.9 (s, 1H).

13C NMR (50 MHz, CDCl3) δ 152.6, 143.1, 102.4, 67.4, 55.8.


(2)-4-(2-hydroxyethylidene)-1,3-dioxolan-2-one



[0090] 



[0091] Colorless oil, 423 mg (65%). Rf (EtOAc/PE 1:1) = 0.62.1H NMR (200 MHz, CDCl3): δ = 4.97 - 4.88 (m, 3 H), 4.18 - 4.15 (m, 2 H), 3.33 (s, 1 H). 13C NMR (50 MHz, CDCl3): δ = 152.9, 143.2, 102.4, 67.6, 55.7. IR (KBr): v = 3649, 3565, 3134, 3026, 2974, 2416, 2261, 1856 (C=O), 1812, 1694. 1465, 1395. 1359, 1287, 1129, 1062, 974, 853, 767, 727, 548 cm-1. HRMS (El): m/z calcd. for C5H6O4: 130.0260 [M+]; found: 130.0259.

6.2 Use of 4-hydroxybut-2-yn-1-yl acetate as propargylic alcohol of formula II


6.2.1 Synthesis of 4-hydroxybut-2-yn-1-yl acetate



[0092] 



[0093] Distilled Et3N (10.2 mL, 81.2 mmol, 1.4 eq.) was added to a solution of but-2-yne-1,4-diol (5.0 g, 58.0 mmol, 1.0 eq.) in dry DCM/THF (24 mL/8 mL), and the resulting suspension was stirred at room temperature until dissolution was complete. Acetic anhydride (6.0 mL, 63.5 mmol, 1.1 eq.) was then added to the reaction mixture at 0 ° C dropwise over 30 min. The reaction mixture was then warmed to room temperature and stirred overnight. Water was added and the reaction mixture was extracted with DCM (3044x4 mL). The collected organic layers were dried and the solvents were evaporated in vacuo. Flash chromatography of the crude products (silica gel, EtOAc/PE 2:3) gave the pure product as a colourless oil (3.34 g, 45%).

[0094] 1H NMR (400 MHz, CDCl3): δ = 4.64 - 4.63 (m, 2 H), 4.22 - 4.21 (m, 2 H), 3.17 (br.s, 1 H), 2.03 (s, 3 H). 13C NMR (101 MHz, CDCl3): δ = 170.7, 85.2, 79.2, 52.4, 50.5, 20.7. HRMS (ESI, 70 eV): m/z calcd. for C6H8O3: 128.0468 [M+]; found: 128.0461.

6.2.2 Synthesis of (E)-2-(2-oxo-1,3-dioxolan-4-ylidene)ethyl acetate 2b



[0095] 



[0096] In a ChemSpeed Accelerator SLT 106 high-throughput robot system. 4-hydroxybut-2-yn-1-yl acetate (1b, 1 mmol), AgOAc (0.05 mmol) and L1 (0.05 mmol) in MeCN (2 mL) were pressurized with CO2 (20 bar) and stirred at room temperature for 12 h. After releasing the CO2 overpressure, anisole (1 mmol) and CDCl3 (1 mL) were added to the reaction mixture and stirred for 5 min. The resulting mixture was analyzed by 1H NMR to determine the yield. Isolation was done by column chromatography (silica, EtOAc/hexane gradient).

(E)-2-(2-oxo-1,3-dioxolan-4-ylidene)ethyl acetate 2b

1H NMR (400 MHz, CDCl3) δ 4.97-4.96 (m, 2H), 4.92-4.88 (m, 1H), 4.64-4.59 (m, 2H), 2.9 (s, 3H).

13C NMR (50 MHz, CDCl3) δ 170.5, 151.9, 145.2, 97.4, 67.3, 57.4, 20.5.


6.2.3 (Z)-2-(2-oxo-1,3-dioxolan-4-ylidene)ethyl acetate



[0097] 

Colorless oil, 688 mg (80%). Rf (EtOAc/PE 3:7) = 0.35.1H NMR (400 MHz, CDCl3): δ = 5.01 - 4.92 (m, 3 H), 4.71 - 4.67 (m, 2 H), 2.05 (m, 3 H). 13C NMR (101 MHz, CDCl3): δ = 170.8, 152.0, 145.4, 97.9, 67.4, 57.7, 20.9. IR (KBr): v = 2971, 2257, 1830 (C=O), 1727 (C=O), 1462, 1374, 1435, 1132, 1231, 1096, 1028, 965, 765. 733 cm-1. HRMS (EI): m/ z calcd. for C7H8O5: 172.0366 [M+]; found: 172.0391. Anal. Calcd. for C7H8O4: C 48.84%, H 4.68%, Found: C 49.23%, H 5.00%.

6.3 Synthesis of different alcohols of formula II


6.3.1 Synthesis of 4-(benzyloxy)but-2-yn-1-ol



[0098] 



[0099] But-2-yne-1,4-diol (3.9 g, 45.2 mmol, 2.0 eq.) was added into a solution of KOH (2.5 g, 44.5 mmol, 2.0 eq.) in water (40 mL). The mixture was stirred for 10 min at room temperature. Benzyl bromide (3.9 g, 22.8 mmol, 1.0 eq.) was then added into the above solution dropwise and the mixture was stirred for 2 days at room temperature. The reaction mixture was extracted with DCM, the combined organic phases were washed with brine and dried over MgSO4. The organic layer was concentrated in vacuo. Flash chromatography on silica gel (EtOAc/PE 2:3) yielded the desired mono-benzylated alcohol as colourless oil (3.0 g, 75%).

[0100] 1H NMR (400 MHz, CDCl3): δ = 7.25 - 7.15 (m, 5 H), 4.48 (s, 2 H), 4.16 - 4.17 (m, 2 H), 4.10 - 4.09 (m, 2 H), 2.81 (s, 1 H). 13C NMR (101 MHz, CDCl3): δ = 137.2, 128.4 (2 C), 128.1, 127.9 (2 C), 85.1, 81.3, 71.7, 57.4, 50.7. HRMS (ESI, 70 eV): m/z calcd. for C11H12O2: 176.0832 [M+]; found: 176.0827.

6.3.2 Synthesis of 4-hydroxybut-2-yn-1-yl methyl carbonate



[0101] 



[0102] But-2-yne-1,4-diol (15g, 174 mmol, 3 eq.) dissolved in anhydrous DCM (350 mL) was cooled to 0 ° C. DIPEA (33.5 mL, 181.7 mmol, 3.3 eq.) and DMAP (708 mg, 5.8 mmol, 0.1 eq.) were then added to the above solution followed by the dropwise addition of methyl chloroformate (4.49 mL, 58.1 mmol, 1.0 eq.) via a syringe. The reaction mixture was stirred at 0 ° C for 2 h followed by stirring it overnight at room temperature. The reaction mixture was concentrated to half of its original volume followed by the addition of Et2O and NaHCO3. The phases were separated and the organic phase was washed three times with sat. NaHCO3 before drying it over MgSO4. The solvent was removed under reduced pressure and the crude was purified by column chromatography (silica gel, EtOAc/PE 3:7) yielding the product as a colourless oil (7.3g, 87%).

[0103] 1H NMR (400 MHz, CDCl3): δ = 4.77-4.76 (m, 2 H), 4.30-4.29 (m, 2 H), 3.81 (s, 3 H). 13C NMR (101 MHz, CDCl3): δ = 155.3, 85.9, 79.1, 55.6, 55.2, 50.9.

6.4 Synthesis of different 1,3-dioxolan-2-ones


General procedure for the carboxylative cyclization of but-2-ynol derivatives



[0104] A steel autoclave was charged with Alkynol (5.0 mmol), AgOAc (1 or 2 mol%), Davephos-Ligand (1 or 2 mol%) and solvent (10 mL) under atmospheric conditions. The reaction mixture was pressurized with CO2 (20 bar) and stirred at room temperature for 18 h. Then CO2 overpressure was carefully released and solvent evaporated. The resulting crude mixture was purified by flash column chromatograph


6.4.1 Characterization of the isolated exo-vinylene carbonate products


6.4.1.1 4-methylene-1,3-dioxolan-2-one



[0105] 



[0106] White solid, 450 mg (90%), mp: 28.3 -29.0 ° C. Rf (EtOAc/PE 3:7) = 0.38.1H NMR (200 MHz, CDCl3): δ = 4.98 - 4.96 (m, 2 H), 4.84 - 4.80 (m, 1 H), 4.42 - 4.37 (m, 1 H). 13C NMR (50 MHz, CDCl3): δ = 152.8, 148.8, 87.1, 67.6. IR (KBr): v = 2974, 1836 (C=O), 1695, 1394, 1464, 1359, 1287, 1128, 1062, 974, 853, 767, 727 cm-1. HRMS (EI): m/ z calcd. for C4H4O3: 100.0155 [M+]; found: 100.1054.

6.4.1.2 (Z)-5-(2-hydroxy-2-methylpropylidene)-4,4-dimethyl-1,3-dioxolan-2-one (comparison)



[0107] 



[0108] Colorless oil, 837 mg (90%). Rf (EtOAc/PE 3:7) = 0.26.1H NMR (200 MHz, CDCl3): δ = 4.70 (s, 1 H), 2.91 (s, 1 H), 1.42 (s, 6 H), 1.27 (s, 6 H). 13C NMR (50 MHz, CDCl3): δ = 151.1, 149.0, 109.6, 84.9, 69.4, 29.8 (2 C), 27.4 (2 C). IR (KBr): v = 3461, 2982, 2937, 1818 (C=O), 1712, 1548, 1563, 1373, 1286, 1250, 1168, 1055, 1023, 980, 924, 770 cm-1. HRMS (ESI): m/z calcd. for C9H14O4: 187.0965 [M+H+]; found: 187.0968.

6.4.1.3 4-methyl-5-methylene-1,3-dioxolan-2-one (comparison)



[0109] 



[0110] Light yellow oil, 524 mg (92%). Rf (EtOAc/PE 3:7) = 0.57.1H NMR (200 MHz, CDCl3): δ = 5.31 - 5.20 (m, 1 H), 4.82 (dd, J = 4.0 Hz, 2.5 Hz, 1 H), 4.35 (dd, J = 4.0 Hz, 2.0 Hz m, 1 H), 1.56 (d, J = 6.5 Hz, 3 H). 13C NMR (50 MHz, CDCl3): δ = 154.7, 152.0, 86.7, 76.3, 20.5. IR (KBr): ν = 2991, 1837 (C=O), 1752, 1686, 1458, 1379, 1351, 1324, 1156, 1112, 1080, 1044, 1007, 856, 769, 710, 640, 587, 556 cm-1. HRMS (EI): m/ z calcd. for C5H6O3: 114.0311 [M+]; found: 114.0326.

6.4.1.4 4,4-dimethyl-5-methylene-1,3-dioxolan-2-one (comparison)



[0111] 



[0112] Viscous oil, 557 mg (87%). Rf (EtOAc/PE 3:7) = 0.65.1H NMR (200 MHz, CDCl3): δ = 4.74 (d, J = 3.9 Hz, 1 H), 4.31 (d, J = 3.9 Hz, 1 H) 1.58 (s, 6 H). 13C NMR (50 MHz, CDCl3): δ = 158.8, 151.3, 85.4, 84.7, 27.6 (2 C). HRMS (EI): m/ z calcd. for C6H8O3: 128.0468 [M+]; found: 128.0469.

6.4.1.5 (Z)-methyl (2-(2-oxo-l,3-dioxolan-4-ylidene)ethyl) carbonate



[0113] 



[0114] Colorless oil, 611 mg (65%). Rf (EtOAc/PE 3:7) = 0.24.1H NMR (400 MHz, CDCl3): δ = 5.02 - 4.97 (m, 3 H), 4.81 - 4.77 (m, 2 H), 3.80 (s, 3 H). 13C NMR (101 MHz, CDCl3): δ = 155.8, 152.0, 146.1, 97.5, 67.5, 61.1, 55.3. IR (KBr): v = 3017, 2967, 2351, 2214, 1834 (C=O), 1749 (C=O), 1681, 1448, 1371, 1262, 1130, 1050, 943, 766, 567 cm-1. HRMS (EI): m/ z calcd. for C7H8O6: 188.0315 [M+]; found: 188.0303. Anal. Calcd. for C7H8O6: C 44.69, H 4.29%, Found: C 44.41%, H 5.13%.

6.4.1.6 ((Z)-4-(2-(benzyloxy)ethylidene)-1,3-dioxolan-2-one



[0115] 

Colorless oil, 770 mg (70%). Rf (EtOAc/PE 3:7) = 0.44. 1H NMR (400 MHz, CDCl3): δ = 7.37 - 7.29 (m, 5 H), 4.99 - 4.92 (m, 3 H), 4.53 (s, 2 H) 4.23 - 4.18 (m, 2 H). 13C NMR (101 MHz, CDCl3): δ = 152.4, 144.0, 137.9, 128.5 (2 C), 127.9 (3 C), 100.3, 72.8, 67.4, 63.4. IR (KBr): v = 3065, 3038, 3032, 2867, 1839 (C=O), 1723, 1455, 1381, 1274, 1210, 1108, 1045, 912, 734, 700 cm-1. HRMS (EI): m/ z calcd. for C12H12O4: 220.0730 [M+]; found: 220.0735. Anal. Calcd. for C12H12O4: C 65.45%, H 5.49%, Found: C 65.40%, H 5.53%.

6.4.1.7 4-methyl-5-methylene-4-(4-methylpent-3-en-1-yl)-1,3-dioxolan-2-one (comparison)



[0116] 

Colorless oil, 922 mg (94%). Rf (EtOAc/PE 3:7) = 0.81. 1H NMR (300 MHz, CDCl3): δ = 5.07 - 5.01 (m, 1 H), 4.80 (d, J = 3.9 Hz, 1 H), 4.27 (d, J = 3.9 Hz, 1 H), 2.15 - 1.97 (m, 2 H) 1.94 - 1.84 (m, 1 H), 1.76 - 1.68 (m, 1 H), 1.66 (s, 3H), 1.57 (s, 6 H). 13C NMR (75 MHz, CDCl3): δ = 157.7, 151.5, 133.3, 122.0, 87.2, 85.6, 40.3, 26.6, 25.7, 22.0, 17.7. IR (KBr): v = 2981, 1829 (C=O), 1685, 1451, 1379, 1303, 1260, 1221, 1183, 1154, 1121, 1102, 1069, 1033, 852, 767 cm-1. HRMS (EI): m/ z calcd. for C11H16O3: 196.1094 [M+]; found: 196.1113. Anal. Calcd. for C11H16O3: C 67.32%, H 8.22%, Found: C 66.94%, H 8.34%.


Claims

1. A process for preparing cyclic carbonates of formula la or Ib or mixtures thereof

wherein

R1 is hydrogen or an organic radical having from 1 to 40 carbon atoms,

comprising the process step:

a) reacting a propargylic alcohol of formula II

wherein R1 has the same meaning as in formula Ia or Ib,
with carbon dioxide in the presence of at least one transition metal catalyst TMC1, which comprises a transition metal selected from metals of groups 10, 11 and 12 of the periodic table of the elements according to IUPAC and at least one bulky ligand selected from the group of ligands consisting of compounds of formula III and compounds of formula IV

wherein

D is P, As or Sb,

R2 is an organic radical having from 1 to 40 carbon atoms,

R3, R4 are identical or different, and are each an organic radical having from 1 to 40 carbon atoms, and,

R5 is an organic radical having from 1 to 40 carbon atoms or is identical to R2,

and Z is a divalent bridging group selected from -CR7=CR8-, -CR7=N-, -CR7R9-CR8R10- and -CR7R9-CR8R10-CR11R12-, wherein R7, R8, R9, R10, R11 and R12 are independently from each other hydrogen or as defined as R5 or two adjacent radicals R7 and R8 and/or R10 and R11 together with the atoms connecting them form a monocyclic or polycyclic, substituted or unsubstituted, aliphatic or aromatic ring system which has from 4 to 40 carbon atoms and can also comprise at least one heteroatom selected from the group consisting of the elements Si, Ge, N, P, O and S.


 
2. The process according to claim 1, wherein R1 is hydrogen, hydroxymethyl (-CH2OH), acetoxy-methylene (-CH2OC(O)CH3), formyloxy-methylene (-CH2OC(O)H) or -CH2OC(O)OCH3.
 
3. The process according to claim 1 or 2, wherein the transition metal of transition metal catalyst TMC1 is Ag.
 
4. The process according to any of claims 1 to 3, wherein the transition metal catalyst TMC1 is prepared in situ by using a transition metal compound, which does not comprise any bulky ligand, the compound of formula III or formula IV as bulky ligand or the protonated form of the compound of formula IV represented by formula V,

wherein R2, R5 and Z are defined as in claim 1 and X- is an anion equivalent, together with a base.
 
5. The process according to claim 4, wherein the transition metal compound is selected from AgOAc, AgF, Ag2O and Ag2CO3.
 
6. The process according to any of claims 1 to 5, wherein the bulky ligand is a compound of formula III.
 
7. The process according to any of claims 1 to 6, wherein the bulky ligand is selected from a compound of formulas A to P and mixtures thereof.








 
8. The process according to any of claims 1 to 7, wherein the molar ratio of the bulky ligand to the transition metal of transition metal catalyst TMC1 is in the range from 0.4 to 1.2.
 
9. The process according to any of claims 1 to 8, wherein the amount of transition metal catalyst TMC1 used in process step a) based on the amount of propargylic alcohol of formula II is in the range from 0.005 to 5 mol%.
 
10. The process according to any of claims 1 to 9, wherein process step a) is performed at a pressure in the range from 1 to 50 bar.
 
11. The process according to any of claims 1 to 10, wherein process step a) is performed at a temperature in the range from 0 °C to 100 °C.
 
12. The process according to any of claims 1 to 11, wherein process step a) is carried out in the presence of a solvent selected from aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, amides, ureas, nitriles, sulfoxides, sulfones, esters, carbonates, ethers, alcohols and mixtures thereof.
 
13. The process according to any of claims 1 to 12 wherein the cyclic carbonates of formula la or Ib or mixtures thereof are separated from the transition metal catalyst TMC1 after process step a) via distillation.
 
14. The process according to any of claims 1 to 13 wherein the transition metal catalyst TMC1 is recycled to the reaction step a) after the cyclic carbonate of formula Ia or Ib or mixture thereof were removed via distillation.
 
15. A cyclic carbonate of formula Ia' or Ib',

wherein

R1 is -CH2OR13, wherein R13 is hydrogen, SiR14aR14bR14c, C(O)R15 or C(O)OR16

wherein

R14aR14bR14c are identical or different, and are each independently from each other hydrogen or an organic radical with 1 to 40 carbon atoms,

R15 is hydrogen or an organic radical with 1 to 40 carbon atoms and

R16 is methyl, ethyl,-propyl or phenyl.


 
16. Use of the cyclic carbonates of formula Ia' or Ib' or mixtures thereof according to claim 15 prepared according to any of claims 1 to 14 as reactive diluent in the manufacture of epoxy resins, as electrolyte additive in electrochemical storage systems or as monomer in polymerization reactions.
 


Ansprüche

1. Verfahren zur Herstellung von cyclischen Carbonaten der Formel Ia oder Ib oder Gemischen davon

wobei

R1 für Wasserstoff oder einen organischen Rest mit 1 bis 40 Kohlenstoffatomen steht,

das folgenden Verfahrensschritt umfasst:

a) Umsetzen eines Propargylalkohols der Formel II

wobei R1 die gleiche Bedeutung wie in Formel Ia oder Ib hat,
mit Kohlendioxid in Gegenwart mindestens eines Übergangsmetallkatalysators TMC1, der ein aus Metallen der Gruppen 10, 11 und 12 des Periodensystems der Elemente gemäß IUPAC ausgewähltes Übergangsmetall und mindestens einen sperrigen Liganden, der aus der Gruppe von Liganden bestehend aus Verbindungen der Formel III und Verbindungen der Formel IV

wobei

D für P, As oder Sb steht,

R2 für einen organischen Rest mit 1 bis 40 Kohlenstoffatomen steht,

R3, R4 gleich oder verschieden sind und jeweils für einen organischen Rest mit 1 bis 40 Kohlenstoffatomen stehen und

R5 für einen organischen Rest mit 1 bis 40 Kohlenstoffatomen steht oder mit R2 identisch ist,

und Z für eine zweiwertige Brückengruppe steht, die aus -CR7=CR8-, -CR7=N-, -CR7R9-CR8R10- und -CR7R9-CR8R10-CR11R12- ausgewählt ist, wobei R7, R8, R9, R10, R11 und R12 unabhängig voneinander für Wasserstoff stehen oder wie R5 definiert sind oder 2 benachbarte Reste R7 und R8 und/oder R10 und R11 zusammen mit den sie verbindenden Atomen ein monocyclisches oder polycyclisches, substituiertes oder unsubstituiertes, aliphatisches oder aromatisches Ringsystem bilden, das 4 bis 40 Kohlenstoffatome aufweist und außerdem mindestens ein Heteroatom aus der Gruppe bestehend aus den Elementen Si, Ge, N, P, O und S umfassen kann,

ausgewählt ist, umfasst.
 
2. Verfahren nach Anspruch 1, wobei R1 für Wasserstoff, Hydroxymethyl (-CH2OH), Acetoxymethylen (-CH2OC(O)CH3), Formyloxymethylen (-CH2OC(O)H) oder -CH2OC(O)OCH3 steht.
 
3. Katalysator nach Anspruch 1 oder 2, wobei es sich bei dem Übergangsmetall des Übergangsmetallkatalysators TMC1 um Ag handelt.
 
4. Verfahren nach einem der Ansprüche 1 bis 3, wobei der Übergangsmetallkatalysator TMC1 durch Verwendung einer Übergangsmetallverbindung, die keinen sperrigen Liganden, die Verbindung der Formel III oder Formel IV als sperrigen Liganden oder die durch Formel V wiedergegebene protonierte Form der Verbindung der Formel IV

wobei R2, R5 und Z wie in Anspruch 1 definiert sind und X- für ein Anionäquivalent steht,
zusammen mit einer Base umfasst, in situ hergestellt wird.
 
5. Verfahren nach Anspruch 4, wobei die Übergangsmetallverbindung aus AgOAc, AgF, Ag2O und Ag2CO3 ausgewählt wird.
 
6. Verfahren nach einem der Ansprüche 1 bis 5, wobei es sich bei dem sperrigen Liganden um eine Verbindung der Formel III handelt.
 
7. Verfahren nach einem der Ansprüche 1 bis 6, wobei der sperrige Ligand aus einer Verbindung der Formel A bis P und Mischungen davon ausgewählt wird.








 
8. Verfahren nach einem der Ansprüche 1 bis 7, wobei das Molverhältnis von sperrigem Liganden zu Übergangsmetall des Übergangsmetallkatalysators TMC1 im Bereich von 0,4 bis 1,2 liegt.
 
9. Verfahren nach einem der Ansprüche 1 bis 8, wobei die in Verfahrensschritt a) verwendete Menge von Übergangsmetallkatalysator TMC1, bezogen auf die Menge von Propargylalkohol der Formel II, im Bereich von 0,005 bis 5 Mol-% liegt.
 
10. Verfahren nach einem der Ansprüche 1 bis 9, wobei Verfahrensschritt a) bei einem Druck im Bereich von 1 bis 50 bar durchgeführt wird.
 
11. Verfahren nach einem der Ansprüche 1 bis 10, wobei Verfahrensschritt a) bei einer Temperatur im Bereich von 0 °C bis 100 °C durchgeführt wird.
 
12. Verfahren nach einem der Ansprüche 1 bis 11, wobei Verfahrensschritt a) in Gegenwart eines aus aliphatischen Kohlenwasserstoffen, aromatischen Kohlenwasserstoffen, halogenierten Kohlenwasserstoffen, Amiden, Harnstoffen, Nitrilen, Sulfoxiden, Sulfonen, Estern, Carbonaten, Ethern, Alkoholen und Mischungen davon ausgewählten Lösungsmittels durchgeführt wird.
 
13. Verfahren nach einem der Ansprüche 1 bis 12, wobei man das cyclische Carbonat der Formel Ia oder Ib oder Mischungen davon nach Verfahrensschritt a) durch Destillation von dem Übergangsmetallkatalysator TMC1 abtrennt.
 
14. Verfahren nach einem der Ansprüche 1 bis 13, wobei der Übergangsmetallkatalysator TMC1 nach Entfernung des cyclischen Carbonats der Formel Ia oder Ib oder dem Gemisch davon durch Destillation in Reaktionsschritt a) zurückgeführt wird.
 
15. Cyclisches Carbonat der Formel Ia'oder Ib',

wobei

R1 für -CH2OR13 steht, wobei R13 für Wasserstoff, SiR14aR14bR14c, C(O)R15 oder C (O) OR16 steht,

wobei R14a, R14b, R14c gleich oder verschieden sind und jeweils unabhängig voneinander für Wasserstoff oder einen organischen Rest mit 1 bis 40 Kohlenstoffatomen stehen,

R15 für Wasserstoff oder einen organischen Rest mit 1 bis 40 Kohlenstoffatomen steht und

R16 für Methyl, Ethyl, -Propyl oder Phenyl steht.


 
16. Verwendung der cyclischen Carbonate der Formel Ia' oder Ib' oder Gemischen davon nach Anspruch 15, hergestellt nach einem der Ansprüche 1 bis 14, als reaktives Verdünnungsmittel bei der Herstellung von Epoxidharzen, als Elektrolytadditiv in elektrochemischen Speichersystemen oder als Monomer in Polymerisationsreaktionen.
 


Revendications

1. Procédé pour la préparation de carbonates cycliques de formule Ia ou Ib ou de mélanges correspondants

R1 étant hydrogène ou un radical organique possédant de 1 à 40 atomes de carbone,

comprenant l'étape de procédé :

a) mise en réaction d'un alcool propargylique de formule II

R1 possédant la même signification que dans la formule Ia ou Ib

avec du dioxyde de carbone en la présence d'au moins un catalyseur de métal de transition TMC1, qui comprend un métal de transition choisi parmi des métaux des groupes 10, 11 et 12 du tableau périodique des éléments selon l'UICPA et au moins un ligand encombré choisi dans le groupe de ligands constitué de composés de formule III et de composés de formule IV

D étant P, As ou Sb,

R2 étant un radical organique possédant de 1 à 40 atomes de carbone,

R3, R4 étant identiques ou différents, et étant chacun un radical organique possédant de 1 à 40 atomes de carbone,

R5 étant un radical organique possédant de 1 à 40 atomes de carbone ou étant identique à R2,

et Z étant un groupe pontant divalent choisi parmi -CR7=CR8-, -CR7=N-, -CR7R9-CR8R10- et -CR7R9-CR8R10-CR11R12-, dans lesquels R7, R8, R9, R10, R11 et R12 sont indépendamment les uns des autres hydrogène ou définis comme R5 ou deux radicaux R7 et R8 et/ou R10 et R12 adjacents, conjointement avec les atomes qui les relient, formant un système cyclique monocyclique ou polycyclique, substitué ou non substitué, aliphatique ou aromatique qui possède de 4 à 40 atomes de carbone et peut également comprendre au moins un hétéroatome choisi dans le groupe constitué par les éléments Si, Ge, N, P, O et S.


 
2. Procédé selon la revendication 1, R1 étant hydrogène, hydroxyméthyle (-CH2OH), acétoxy-méthylène (-CH2OC(O)CH3), formyloxy-méthylène (-CH2OC (O) H) ou -CH2OC (O) OCH3.
 
3. Procédé selon la revendication 1 ou 2, le métal de transition du catalyseur de métal de transition TMC1 étant Ag.
 
4. Procédé selon l'une quelconque des revendications 1 à 3, le catalyseur de métal de transition TMC1 étant préparé in situ en utilisant un composé de métal de transition, qui ne comprend aucun ligand encombré, le composé de formule III ou de formule IV en tant que ligand encombré ou la forme protonée du composé de formule IV représentée par la formule V,

R2, R5 et Z étant définis comme dans la revendication 1 et X- étant un équivalent d'anion, conjointement avec une base.
 
5. Procédé selon la revendication 4, le composé de métal de transition étant choisi parmi AgOAc, AgF, Ag2O et Ag2CO3.
 
6. Procédé selon l'une quelconque des revendications 1 à 5, le ligand encombré étant un composé de formule III.
 
7. Procédé selon l'une quelconque des revendications 1 à 6, le ligand encombré étant choisi parmi un composé parmi les formules A à P et des mélanges correspondants,








 
8. Procédé selon l'une quelconque des revendications 1 à 7, le rapport molaire du ligand encombré sur le métal de transition du catalyseur de métal de transition TMC1 étant dans la plage de 0,4 à 1,2.
 
9. Procédé selon l'une quelconque des revendications 1 à 8, la quantité de catalyseur de métal de transition TMC1 utilisée dans l'étape de procédé a), sur la base de la quantité d'alcool propargylique de formule II, étant dans la plage de 0,005 à 5 % en moles.
 
10. Procédé selon l'une quelconque des revendications 1 à 9, l'étape de procédé a) étant réalisée à une pression dans la plage de 1 à 50 bars.
 
11. Procédé selon l'une quelconque des revendications 1 à 10, l'étape de procédé a) étant réalisée à une température dans la plage de 0 °C à 100 °C.
 
12. Procédé selon l'une quelconque des revendications 1 à 11, l'étape de procédé a) étant mise en œuvre en la présence d'un solvant choisi parmi des hydrocarbures aliphatiques, des hydrocarbures aromatiques, des hydrocarbures halogénés, des amides, des urées, des nitriles, des sulfoxydes, des sulfones, des esters, des carbonates, des éthers, des alcools et des mélanges correspondants.
 
13. Procédé selon l'une quelconque des revendications 1 à 12, les carbonates cycliques de formule Ia ou Ib ou des mélanges correspondants étant séparés du catalyseur de métal de transition TMC1 après l'étape de procédé a) via distillation.
 
14. Procédé selon l'une quelconque des revendications 1 à 13, le catalyseur de métal de transition TMC1 étant recyclé dans l'étape de réaction a) après que le carbonate cyclique de formule Ia ou Ib ou un mélange correspondant a été éliminé via distillation.
 
15. Carbonate cyclique de formule Ia' ou Ib',

R1 étant -CH2OR13, R13 étant hydrogène, SiR14aR14bR14c, C(O)R15 ou C(O)OR16,

R14a, R14b, R14c étant identiques ou différents et étant chacun indépendamment les uns des autres hydrogène ou un radical organique comportant 1 à 40 atomes de carbone,

R15 étant hydrogène ou un radical organique comportant 1 à 40 atomes de carbone et

R16 étant méthyle, éthyle, -propyle ou phényle.


 
16. Utilisation des carbonates cycliques de formule Ia' ou Ib' ou de mélanges correspondants selon la revendication 15 préparés selon l'une quelconque des revendications 1 à 14 en tant que diluant réactif dans la fabrication de résines époxy, en tant qu'additif d'électrolyte dans des systèmes de stockage électrochimique ou en tant que monomère dans des réactions de polymérisation.
 






Cited references

REFERENCES CITED IN THE DESCRIPTION



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Patent documents cited in the description




Non-patent literature cited in the description