WO2013092011A1 - 2-oxo-1,3-dioxolane-4-carboxamides, their preparation and use - Google Patents

2-oxo-1,3-dioxolane-4-carboxamides, their preparation and use Download PDF

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Publication number
WO2013092011A1
WO2013092011A1 PCT/EP2012/072589 EP2012072589W WO2013092011A1 WO 2013092011 A1 WO2013092011 A1 WO 2013092011A1 EP 2012072589 W EP2012072589 W EP 2012072589W WO 2013092011 A1 WO2013092011 A1 WO 2013092011A1
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oxo
dioxolane
formula
groups
preparation
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French (fr)
Inventor
Heimo WOELFLE
Burkhard Walther
Maximilian KÖHLER
Sophie PUTZIEN
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Construction Research and Technology GmbH
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Construction Research and Technology GmbH
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Priority to CN201280064040.1A priority Critical patent/CN104011040B/en
Priority to AU2012358695A priority patent/AU2012358695B2/en
Priority to MX2014007549A priority patent/MX351799B/en
Priority to ES12784024.7T priority patent/ES2592631T3/en
Priority to RU2014129920A priority patent/RU2632903C2/en
Priority to BR112014012358-6A priority patent/BR112014012358B1/en
Priority to JP2014547794A priority patent/JP6072067B2/en
Priority to EP12784024.7A priority patent/EP2794585B1/en
Priority to US14/364,413 priority patent/US9309218B2/en
Priority to CA2859450A priority patent/CA2859450C/en
Publication of WO2013092011A1 publication Critical patent/WO2013092011A1/en
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D317/34—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C269/04—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from amines with formation of carbamate groups
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C329/00—Thiocarbonic acids; Halides, esters or anhydrides thereof
    • C07C329/02—Monothiocarbonic acids; Derivatives thereof
    • C07C329/04—Esters of monothiocarbonic acids
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D317/34—Oxygen atoms
    • C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
    • C07D317/38—Ethylene carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/281—Monocarboxylic acid compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/71—Monoisocyanates or monoisothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/02—Aliphatic polycarbonates
    • C08G64/0208—Aliphatic polycarbonates saturated
    • C08G64/0225—Aliphatic polycarbonates saturated containing atoms other than carbon, hydrogen or oxygen
    • C08G64/0241—Aliphatic polycarbonates saturated containing atoms other than carbon, hydrogen or oxygen containing nitrogen
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/38—General preparatory processes using other monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides

Definitions

  • the present invention relates to 2-oxo-1 ,3-dioxolane-4-carboxamides of formula (I),
  • R2 can be, inter alia, an n-valent radical (n > 1 ), which is substituted with n-1 further 2-Oxo-l ,3-dioxolane-4-carboxamide groups of general formula (II),
  • R 4 may be hydrogen, straight-chain or branched Ci-s-alkyl, Cs-i2-cycloalkyl or C6-i5-aryl.
  • R3 may be straight-chain or branched Ci-s-alkyl or C6-i5-aryl.
  • WO 2004/003001 A1 describes the enzymatic race- mate separation of the enantiomers of type (VI) but without indicating a synthesis for these compounds.
  • EP 1941946 A1 describes the use of a carbonitride catalyst inter alia for the preparation of certain disubstituted organic carbonates. These may also be compounds of the general formula (VII),
  • R 10 and R 1 1 are selected optional substituents.
  • Possible meanings of the substituents are alkyl, aryl, herteroaryl and ester groups CO2A, where A may in turn be alkyl or aryl, e.g. straight-chain or branched Ci-6-alkyl, preferably Ci-3-alkyl and particularly preferably methyl or ethyl.
  • A may in turn be alkyl or aryl, e.g. straight-chain or branched Ci-6-alkyl, preferably Ci-3-alkyl and particularly preferably methyl or ethyl.
  • JP 2006-003433 A discloses a sealing composition for liquid crystal display elements which comprises a compound of the general formula (VIII),
  • R is H, a hydroxyl group, a cyano group, a carboxylic acid group, an optionally substituted aromatic ring, a straight-chain, branched or cyclic alkyl group, an acyl group or an ester group.
  • EP 0001088 A1 describes inter alia 2-oxo-1 ,3-dioxolanes of the general formula (IX), where R can be H or CH3.
  • EP 2397474 A1 describes 2-oxo-1 ,3-dioxolane-4-carboxylic acid esters of formula (X)
  • Ri may preferably be Me or Et or an n-valent radical which may be substituted with a maximum of n-1 further 2-oxo-1 ,3-dioxolane-4-carboxyl groups, a process for their preparation by means of carboxylation of the corresponding epoxides, a process for their transesterification, and also their use for the preparation of hydroxyurethanes and as end groups for the blocking of amines.
  • At least one of the radicals W1 or W1 a comprises a protected glycoside, and each of the radicals W1 and W1 a, independently of one another, may inter alia also be an amide group.
  • each of the radicals W1 and W1 a independently of one another, may inter alia also be an amide group.
  • no protected glycoside groups are provided.
  • Polyurethanes based on polyisocyanates belong to the prior art. These are used for example as adhesives, sealants, casting compositions, as corrosion protection and for coatings. The high resistance to acids, alkalis and chemicals of the cured compositions obtained in this way are advantageous. However, monomeric low molecular weight (poly)isocyanate compounds are toxicologically unacceptable, especially if they are readily volatile or migrate.
  • Polyurethane systems can also be obtained starting from cyclic carbonate compounds, which are toxicologically acceptable.
  • glycerol carbonate (4-(hydro- xymethyl)-2-oxo-1 ,3-dioxolane) is regularly used in cosmetics.
  • the aim was to provide an alternative 2-oxo-1 ,3-dioxolane system with an electron-withdrawing group.
  • the aim was to provide a 2-oxo-1 ,3-dioxolane system which is toxicologically acceptable, readily accessible and highly reactive with amine hardeners and is moreover suitable as a crosslinkable binder (with a bonding to the polymer chain which is less prone to attack by amines).
  • the present invention provides a 2-oxo-1 ,3-dioxolane-4-carboxamide of formula (I),
  • Ri and R2 in each case independently of one another, are selected from H, straight-chain, branched or cyclic Ci-12-alkyl groups, C6-io-aryl groups, C6-i2-aralkyl groups and C6-i2-alkaryl groups or, together with the N atom to which they are bonded, form a 5- to 8-membered ring, and R3 is selected from H and straight-chain, branched or cyclic Ci-12-alkyl groups, or
  • Ri and R3 are each H, and R2 is an n-valent radical, wherein n is an integer greater than 1 , which is substituted with n-1 further 2-oxo-1 ,3-dioxolane-4-carboxamide groups of general formula (II)
  • the carbon atom to which R3 is bonded can additionally also carry a further Ci-12-alkyl group.
  • the carbon atom in the 4 position can also additionally carry a Ci-12-alkyl group. Both may be the case at the same time.
  • the groups Ri and R3 are preferably each H, and R2 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, 2-ethyl-n-hexyl, n-lauryl, cyclohexyl, phenyl and benzyl.
  • the 2-0X0-1 ,3-dioxolane-4-carboxamides of the invention can be used as curable binders. In this case, a functionality with regard to the 2-oxo-1 ,3-dioxolane group of greater than 1 is required (as defined hereinabove).
  • n can be 2 to 5, in particular 2 to 3.
  • R2 is the polymeric backbone of the curable binder and is selected from straight-chain or branched C2-22-alkylene groups, polyether groups of the general formula -(AiO)m-, wherein Ai is C2-5-alkylene and m is 1 -100, polycarbonate groups, polyester groups, poly(meth)acrylate groups, and combinations thereof.
  • the present invention further provides a process for the preparation of a 2-oxo-1 ,3-di- oxolane-4-carboxamide of formula (I) which, according to one embodiment, is characterized in that a 2-oxo-1 ,3-dioxolane-4-carboxylic acid of formula (III) is reacted with an amine of the formula R1-NH-R2 to give the 2-oxo-1 ,3-dioxolane-4-carboxamide (I) ac- cording to the invention, where Ri , R2 and R3 have the meanings given. It is possible, by virtue of this reaction, to obtain 2-oxo-1 ,3-dioxolane-4-carboxamides of formula (I) wherein Ri and R2 are both different from H.
  • the 2-oxo-1 ,3-dioxolane-4-carboxylic acid of formula (III) can be reacted either with a monoisocyanate or with a polyisocyanate having n NCO groups, where n has the meaning given above.
  • the reaction is preferably carried out in the presence of a catalyst selected from tertiary amines, organometallic compounds, and mixtures thereof.
  • a catalyst selected from tertiary amines, organometallic compounds, and mixtures thereof.
  • the tertiary amine can be selected e.g. from dimethylcyclohexylamine, 4-dimethylaminopyridine (DMAP), diazabi- cyclooctane (DABCO), and diazabicycloundecene (DBU);
  • the organometallic compound can be selected e.g.
  • DBTL dibutyltin dilaurate
  • a bismuth carboxylate such as bismuth octanoate or bismuth neodecanoate
  • titanium or zirconium alkoxy- late or carboxylate and the like catalysts known in the prior art.
  • R2 is preferably selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, 2-ethyl-n-hexyl, n-lauryl, cyclohexyl, phenyl and benzyl.
  • Suitable polyisocyanates include tetramethylene 1 ,4-diisocyanate, 2-methylpenta- methylene 1 ,5-diisocyanate, hexamethylene 1 ,6-diisocyanate (HDI), 2,2,4- and 2,4,4- trimethylhexamethylene 1 ,6-diisocyanate (TMDI), dodecamethylene 1 ,12-diisocyanate, lysine diisocyanate and lysine ester diisocyanate, 1 -isocyanato-3,3,5-trimethyl- 5-isocyanatomethylcyclohexane (isophorone diisocyanate - IPDI), 1 ,4-diisocyanato- 2,2,6-trimethylcyclohexane (TMCDI), 2,2'-, 2,4'- and 4,4'-dicyclohexylmethane diisocyanate (H12MDI), cyclohexane 1
  • the polyisocyanates according to the invention are also intended to include dimers (uretdiones) and trimers (isocyanurates). Particular importance is attributed here to the HDI trimer.
  • prepolymers of polyisocyanates with polyols can also be used if a stoichiometric excess of NCO groups is present.
  • Suitable polyols include polyoxyalkylene polyols (also called “polyether polyols”), which can contain inter alia ethylene oxide units, propylene oxide units and butylene oxide units, aliphatic diols and polyols, and also polyester polyols and polycarbonate polyols, castor oil, hydroxylated epoxidized soya oil, and also mixtures of the aforementioned polyols.
  • the present invention furthermore provides a process for the preparation of a 2-oxo- 1 ,3-dioxolane-4-carboxylic acid of formula (III) hereinabove, which is a key intermediate in the preparation of the 2-oxo-1 ,3-dioxolane-4-carboxamide of the invention.
  • the 2-oxo-1 ,3-dioxolane-4-carboxylic acid of formula (III) can be prepared by hydrolysing a 2-oxo-1 ,3-dioxolane-4-carboxylic acid ester of formula (IV)
  • R2 and R3 have the meanings given, in an acidic medium, preferably in aqueous acetic acid. It is also possible to arrive from the 2-oxo-1 ,3-dioxolane-4-carboxylic acid ester of formula (IV) directly at the 2-oxo-1 ,3-dioxolane-4-carboxamide according to the invention of formula (I) by reacting the ester (IV) with a formamide of the formula R1R2N-CHO, where Ri and R2 have the meanings given.
  • the 2-oxo-1 ,3-dioxolane-4-carboxylic acid of formula (III) can be prepared by oxidizing a glycerol carbonate of formula (V)
  • R3 has the meaning given, and more specifically for example by means of N- oxide-mediated oxidation, or by means of aerobic oxidation.
  • the N-oxide-mediated oxidation may be carried out with 1 ,3,5-trichloroisocyanuric acid and 2,2,6,6-tetramethylpiperidin-1 -oxyl (TEMPO). It may also be carried out with hydro- gen peroxide as an oxidant, e.g. in the presence of a manganese salt.
  • TEMPO 2,2,6,6-tetramethylpiperidin-1 -oxyl
  • the aerobic oxidation uses oxygen from air or oxygen in pure form as the oxidant. It is suitably carried out in the presence of at least one transition metal salt selected from Co, Mn, Cu, Fe, and mixtures thereof, preferably Mn. It is preferably carried out in a suitable solvent or in (e.g. aqueous) acetic acid.
  • the oxygen pressure should be in the range of 0.1 to 100 bar.
  • the presence of an N-oxide such as TEMPO is preferred.
  • the aerobic oxidation reaction is particularly preferred to oxidize glycerol carbonate (4-(hy- droxymethyl)-2-oxo-1 ,3-dioxolane) to form 2-oxo-1 ,3-dioxolane-4-carboxylic acid.
  • a source of oxygen may also be the decomposition reaction of hydrogen peroxide with e.g. manganese ions.
  • the aerobic oxidation reaction hereinabove elegantly solves the problem of providing a source of 2-oxo-1 ,3-dioxolane-4-carboxylic acid from glycerol carbonate.
  • the invention further provides the use of the 2-oxo-1 ,3-dioxolane-4-carboxamides according to the invention for the preparation of hydroxyurethanes.
  • the amides according to the invention react, as has been shown in the formula scheme listed at the outset, with R'-Nhb to give hydroxyurethanes.
  • hydroxyurethanes with secondary hydroxyl groups are predominantly formed here since during the attack of the nucleophilic nitrogen atom, the negative charge on the oxygen atom, which is closer to the CONR1R2 group, is better stabilized.
  • Suitable amines here are primary and secondary amines with alkyl groups, aryl groups, aralkyl groups and also alkaryl groups as radicals. Primary amines react more quickly than secondary amines; aliphatic amines react more quickly than aromatic amines.
  • relatively high molecular weight (poly)amines such as e.g. Jeffamine® from Huntsman Corp. and polyetheramines from BASF SE are of suitability here.
  • the invention further provides the use of the 2-oxo-1 ,3-dioxolane-4-carboxamides according to the invention for the preparation of hydroxycarbonates.
  • the formula scheme below shows only the preferred reaction to give the hydroxycarbonate with a secondary hydroxyl group.
  • Suitable alcohols of the formula R'-OH are in particular the aforementioned polyols.
  • the invention further provides the use of the 2-oxo-1 ,3-dioxolane-4-carboxamides according to the invention for the preparation of hydroxysulphanylformates according to an analogous formula scheme:
  • polyvalent 2-oxo-1 ,3-dioxolane- 4-carboxamide binders (where n > 1 ) can be readily cured with polyamines, polyols and/or polythiols.
  • the present invention further consists in the use of the 2-oxo-1 ,3- dioxolane-4-carboxamides according to the invention for the preparation of polymeric hydroxyurethanes, hydroxycarbonates and/or hydroxysulphanylformat.es.
  • polyhydroxyurethane systems lies in the relatively high hydrophilicity of these systems, which can be attributed to the OH groups present. These OH groups are in principle also available for the crosslinking with polyisocyanates, although the isocyanate-free systems possible according to the invention are preferred on account of their lower toxicity.
  • thermal stability of such polyhydroxyurethane systems is also higher than the stability of classic polyurethane systems.
  • the low molecular weight 2-oxo-1 ,3-dioxolane-4-carboxamides can be used to block amines as end groups (so-called "end caps"), which constitutes a further subject matter of the present invention.
  • end caps amines as end groups
  • This is also of interest with regard to conventional, amine-crosslinked polyurethane systems since an amine excess can lead to discolorations, while an isocyanate excess is toxicologically unacceptable.
  • the present invention is now illustrated in more detail by reference to the examples hereinbelow.
  • Example 1 Preparation of 4-methoxycarbonyl-2-oxo-1 ,3-dioxolane (Reference)
  • IR (v [cm- 1 ]): 2977 bs (OH acid), 2751 bw, 2658 bw, 2621 bw, 2538 bw, 2407 bw, 1785 bm (CO cyclocarbonate), 1793 bs (CO acid), 1546 w, 1481 w, 1431 w, 1399 s, 1345 w, 1325 w, 128 m, 1 196 s, 1087 s, 1074 s, 1039 m, 928 w, 832 s, 769 s, 724 m, 699 s, 650 m, 633 s, 525 s.
  • Example 8 Aerobic oxidation of glycerol carbonate
  • IR (v [cm- 1 ]): 3284 bm (NH); 2933 m; 2909 m; 2852 m; 1807 s, 1790 s (CO cyclocarbonate); 1649 s (CO amide); 1544 s (CN); 1485 w; 1448 w; 1380 m; 1321 w; 1 150 s; 1084 s; 1058 s; 1013 s; 934 w; 893 m; 869 w; 815 w; 767 s; 732 m; 689 m; 637w; 529 m.
  • Example 1 Reaction of 2-oxo-1 ,3-dioxolane-4-carboxylic acid with HDI
  • HDI trimer (Desmodur® N3600, Bayer AG, or Basonat® LR 9046, BASF SE), 64 g (0.48 mol) of 2-oxo-1 ,3-dioxolane-4-carboxylic acid and 0.585 g (4.8 mmol) of DMAP were dissolved in one litre of THF and stirred overnight at room temperature. Then, 10 g of activated carbon and 5 mmol of acetic acid were added, and the mixture was stirred for a further hour. It was then filtered off and the solvent was distilled off.
  • HDI trimer Desmodur® N3600, Bayer AG, or Basonat® LR 9046, BASF SE
  • Example 13 Curing experiments with the binder from Example 12
  • the binder resin from Example 12 was cured with customary amines, i.e. isophorone diamine (I PDA) and trimethyl hexamethylenediamine isomeric mixture (TMD).
  • customary amines i.e. isophorone diamine (I PDA) and trimethyl hexamethylenediamine isomeric mixture (TMD).
  • I PDA isophorone diamine
  • TMD trimethyl hexamethylenediamine isomeric mixture
  • Table 2 gives the dynamic viscosities [mPas] of the reaction products obtained from the reaction products of two molecules of 2-oxo-1 ,3-dioxolane-4-carb- oxylic acid methyl ester with one molecule of 1 ,6-hexanediol ("hexanediol diester", "HDDE”) and, respectively, of two molecules of 2-oxo-1 ,3-dioxolane-4-carboxylic acid with one molecule of HDI (“hexamethylene diamide", "HMDA”) with equimolar amounts of said customary amines, i.e. I PDA and TMD after seven days of curing at room temperature.
  • HDI hexamethylene diamide

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Abstract

The present invention relates to 2-oxo-1,3-dioxolane-4-carboxamides of formula (I), in which F½ can be, inter alia, an n-valent radical (n > 1), which is substituted with n-1 further 2-oxo-1,3-dioxolane-4-carboxamide groups of general formula (II), to processes for the preparation of these 2-oxo-1,3-dioxolane-4-carboxamides, to processes for the preparation of the 2-oxo-l,3-diox-olane-4-carboxylic acids of formula (III), which are suitable starting materials for the above processes, and to the use of said 2-oxo-1,3-dioxolane-4-carboxamides for the preparation of (poly)hydroxyurethanes, -hydroxycarbonates and -hydroxysulfanylformates, and also as end groups for the blocking of amines.

Description

2-Oxo-l ,3-dioxolane-4-carboxamides, their preparation and use
The present invention relates to 2-oxo-1 ,3-dioxolane-4-carboxamides of formula (I),
Figure imgf000003_0001
in which R2 can be, inter alia, an n-valent radical (n > 1 ), which is substituted with n-1 further 2-Oxo-l ,3-dioxolane-4-carboxamide groups of general formula (II),
Figure imgf000003_0002
to processes for the preparation of these 2-oxo-1 ,3-dioxolane-4-carboxamides, to processes for the preparation of the 2-oxo-1 ,3-dioxolane-4-carboxylic acids of formula (Hi),
Figure imgf000003_0003
which are suitable starting materials for the above processes, and to the use of said 2- oxo-1 ,3-dioxolane-4-carboxamides for the preparation of (poly)hydroxyurethanes, -hy- droxycarbonates and -hydroxysulfanylformates, and also as end groups for the blocking of amines. Structurally similar compounds are already known in the prior art. For example, WO 2004/003001 A1 describes compounds of the general formula (VI)
Figure imgf000004_0001
where Ri and R2 may be radicals independent of one another, R1 +R2 = O or CR1 +R2 may be a 3-6-membered cycloalkyl group. R4 may be hydrogen, straight-chain or branched Ci-s-alkyl, Cs-i2-cycloalkyl or C6-i5-aryl. R3 may be straight-chain or branched Ci-s-alkyl or C6-i5-aryl. In general, WO 2004/003001 A1 describes the enzymatic race- mate separation of the enantiomers of type (VI) but without indicating a synthesis for these compounds.
EP 1941946 A1 describes the use of a carbonitride catalyst inter alia for the preparation of certain disubstituted organic carbonates. These may also be compounds of the general formula (VII),
Figure imgf000004_0002
where R10 and R1 1 , independently of one another, are selected optional substituents. Possible meanings of the substituents are alkyl, aryl, herteroaryl and ester groups CO2A, where A may in turn be alkyl or aryl, e.g. straight-chain or branched Ci-6-alkyl, preferably Ci-3-alkyl and particularly preferably methyl or ethyl. However, no syntheses for 2-OXO-1 ,3-dioxolane systems are stated. JP 2006-003433 A discloses a sealing composition for liquid crystal display elements which comprises a compound of the general formula (VIII),
Figure imgf000004_0003
where R is H, a hydroxyl group, a cyano group, a carboxylic acid group, an optionally substituted aromatic ring, a straight-chain, branched or cyclic alkyl group, an acyl group or an ester group. The 2-oxo-1 ,3-dioxolane-4-carboxylic acid (R = COOH) is also mentioned.
EP 0001088 A1 describes inter alia 2-oxo-1 ,3-dioxolanes of the general formula (IX), where R can be H or CH3.
Figure imgf000005_0001
EP 2397474 A1 describes 2-oxo-1 ,3-dioxolane-4-carboxylic acid esters of formula (X)
Figure imgf000005_0002
in which Ri may preferably be Me or Et or an n-valent radical which may be substituted with a maximum of n-1 further 2-oxo-1 ,3-dioxolane-4-carboxyl groups, a process for their preparation by means of carboxylation of the corresponding epoxides, a process for their transesterification, and also their use for the preparation of hydroxyurethanes and as end groups for the blocking of amines.
US 2010/0317838 A1 describes compounds of formula (XI)
Figure imgf000005_0003
in which Z = O and n = 0, at least one of the radicals W1 or W1 a comprises a protected glycoside, and each of the radicals W1 and W1 a, independently of one another, may inter alia also be an amide group. The difference with respect to the present invention is that, in accordance with the invention no protected glycoside groups are provided. Polyurethanes based on polyisocyanates belong to the prior art. These are used for example as adhesives, sealants, casting compositions, as corrosion protection and for coatings. The high resistance to acids, alkalis and chemicals of the cured compositions obtained in this way are advantageous. However, monomeric low molecular weight (poly)isocyanate compounds are toxicologically unacceptable, especially if they are readily volatile or migrate.
Polyurethane systems can also be obtained starting from cyclic carbonate compounds, which are toxicologically acceptable. Thus, for instance, glycerol carbonate (4-(hydro- xymethyl)-2-oxo-1 ,3-dioxolane) is regularly used in cosmetics.
Cyclic carbonate compounds react with amines with ring opening inter alia to give hy- droxyurethanes (cf. formula scheme below):
Figure imgf000006_0001
Disadvantages of the systems based on glycerol carbonate are the low regioselectivity, which leads to reaction pathways A, B and C, the comparatively low reactivity of the systems at room temperature, and the fact that catalysts which increase the rate of the ring opening obviously also promote the back-reaction, which can lead to a partial decomposition of the products already formed.
In the aforementioned EP 2397474 A1 , these problems have been partially solved by using an ester group instead of an ether group in R. This electron-withdrawing group led to a considerable increase in the rate of the reaction and to a preference for reac- tion pathway A. In the case of the secondary hydroxyurethanes [I] formed, no back- reaction was observed. However, the production of binders which comprise two or more 2-oxo-1 ,3-dioxolane-4-carboxyl groups in the molecule is difficult since this takes place via a transesterification, during which the cyclocarbonate ring can also be attacked.
The aforementioned US 2010/0317838 A1 gives the impression that this ring opening reaction is independent of the nature of R (cf. claim 17 of US 2010/0317838 A1 which is directed to the ring opening of compounds of claim 1 which may contain ester groups or amide groups alike). However, this impression is quite misleading.
Firstly, studies have been carried out (cf. H. Tomita, F. Sanda, T. Endo, Journal of Po- lymer Science: Part A: Polymer Chemistry, Vol. 39, 3678-3685 (2001 )) according to which the reactivity of the 2-oxo-1 ,3-dioxolanes, which are substituted in 4-position with the group R, with amines increases in the order: R = Me < R = H < R = Ph < R = CH2OPh « R = CF3. Secondly, in the case of the products of the aforementioned EP 2397474 A1 where the polymeric main chain is attached through ester bonds, i.e. R in the formula scheme below means the polymeric main chain, the ring opening (hardening) reaction is accompanied by a certain amount of aminolysis of the ester bond leading to the detachment of the main chain in the form of an unreactive alcohol.
Figure imgf000007_0001
unreacti\«
10-20%
alcohol
It was the object of the present invention to essentially avoid at least some of the disadvantages of the prior art described above. In general terms, the aim was to provide an alternative 2-oxo-1 ,3-dioxolane system with an electron-withdrawing group. In particular, the aim was to provide a 2-oxo-1 ,3-dioxolane system which is toxicologically acceptable, readily accessible and highly reactive with amine hardeners and is moreover suitable as a crosslinkable binder (with a bonding to the polymer chain which is less prone to attack by amines).
This object has been achieved with the features of the independent claims. The dependent claims relate to preferred embodiments.
In the case of the amides of the present invention aminolysis is per se not possible. If any transamination occurred, the formed amine would be capable of acting as a reactive hardener to attack further cyclic carbonate groups. Crosslinking and hardening of the products are thus much higher. This follows from the formula scheme below and will be demonstrated in the experimental section hereinbelow.
Figure imgf000008_0001
The present invention provides a 2-oxo-1 ,3-dioxolane-4-carboxamide of formula (I),
Figure imgf000008_0002
which is characterized in that Ri and R2, in each case independently of one another, are selected from H, straight-chain, branched or cyclic Ci-12-alkyl groups, C6-io-aryl groups, C6-i2-aralkyl groups and C6-i2-alkaryl groups or, together with the N atom to which they are bonded, form a 5- to 8-membered ring, and R3 is selected from H and straight-chain, branched or cyclic Ci-12-alkyl groups, or
Ri and R3 are each H, and R2 is an n-valent radical, wherein n is an integer greater than 1 , which is substituted with n-1 further 2-oxo-1 ,3-dioxolane-4-carboxamide groups of general formula (II)
Figure imgf000008_0003
The carbon atom to which R3 is bonded can additionally also carry a further Ci-12-alkyl group. The carbon atom in the 4 position can also additionally carry a Ci-12-alkyl group. Both may be the case at the same time.
In the 2-OXO-1 ,3-dioxolane-4-carboxamide of the invention the groups Ri and R3 are preferably each H, and R2 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, 2-ethyl-n-hexyl, n-lauryl, cyclohexyl, phenyl and benzyl. The 2-0X0-1 ,3-dioxolane-4-carboxamides of the invention can be used as curable binders. In this case, a functionality with regard to the 2-oxo-1 ,3-dioxolane group of greater than 1 is required (as defined hereinabove). Preferably, n can be 2 to 5, in particular 2 to 3.
In this case R2 is the polymeric backbone of the curable binder and is selected from straight-chain or branched C2-22-alkylene groups, polyether groups of the general formula -(AiO)m-, wherein Ai is C2-5-alkylene and m is 1 -100, polycarbonate groups, polyester groups, poly(meth)acrylate groups, and combinations thereof.
Key intermediates in the preparation of the 2-oxo-1 ,3-dioxolane-4-carboxamides (I) according to the invention are 2-oxo-1 ,3-dioxolane-4-carboxylic acids of formula (III).
Figure imgf000009_0001
The present invention further provides a process for the preparation of a 2-oxo-1 ,3-di- oxolane-4-carboxamide of formula (I) which, according to one embodiment, is characterized in that a 2-oxo-1 ,3-dioxolane-4-carboxylic acid of formula (III) is reacted with an amine of the formula R1-NH-R2 to give the 2-oxo-1 ,3-dioxolane-4-carboxamide (I) ac- cording to the invention, where Ri , R2 and R3 have the meanings given. It is possible, by virtue of this reaction, to obtain 2-oxo-1 ,3-dioxolane-4-carboxamides of formula (I) wherein Ri and R2 are both different from H.
Since water is formed during this reaction, it is particularly advantageous to carry out the reaction in the presence of a water-withdrawing agent, in particular a carbodiimide.
According to another embodiment, the 2-oxo-1 ,3-dioxolane-4-carboxylic acid of formula (III) can also be reacted with an isocyanate of the formula R2-NCO to give the 2-oxo- 1 ,3-dioxolane-4-carboxamide (I) according to the invention, where Ri = H and R2 and R3 have the meanings given.
According to this embodiment, the 2-oxo-1 ,3-dioxolane-4-carboxylic acid of formula (III) can be reacted either with a monoisocyanate or with a polyisocyanate having n NCO groups, where n has the meaning given above.
The reaction is preferably carried out in the presence of a catalyst selected from tertiary amines, organometallic compounds, and mixtures thereof. The tertiary amine can be selected e.g. from dimethylcyclohexylamine, 4-dimethylaminopyridine (DMAP), diazabi- cyclooctane (DABCO), and diazabicycloundecene (DBU); the organometallic compound can be selected e.g. from dibutyltin dilaurate (DBTL), a bismuth carboxylate such as bismuth octanoate or bismuth neodecanoate, a titanium or zirconium alkoxy- late or carboxylate, and the like catalysts known in the prior art.
In the case of the monoisocyanate of the formula R2-NCO according to the invention, R2 is preferably selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, 2-ethyl-n-hexyl, n-lauryl, cyclohexyl, phenyl and benzyl.
The polyisocyanate according to the invention is preferably an aliphatic isocyanate, an aromatic isocyanate or a combined aliphatic/aromatic isocyanate with a NCO functionality (number of NCO groups in the molecule) of n = 2 to 5, preferably n = 2 to 3.
Suitable polyisocyanates include tetramethylene 1 ,4-diisocyanate, 2-methylpenta- methylene 1 ,5-diisocyanate, hexamethylene 1 ,6-diisocyanate (HDI), 2,2,4- and 2,4,4- trimethylhexamethylene 1 ,6-diisocyanate (TMDI), dodecamethylene 1 ,12-diisocyanate, lysine diisocyanate and lysine ester diisocyanate, 1 -isocyanato-3,3,5-trimethyl- 5-isocyanatomethylcyclohexane (isophorone diisocyanate - IPDI), 1 ,4-diisocyanato- 2,2,6-trimethylcyclohexane (TMCDI), 2,2'-, 2,4'- and 4,4'-dicyclohexylmethane diisocyanate (H12MDI), cyclohexane 1 ,3-diisocyanate and cyclohexane 1 ,4-diisocyanate (CHDI), 1 ,3- and 1 ,4-bis(isocyanatomethyl)cyclohexane, 4,4'-diisocyanatodicyclohexyl- 2,2-propane, m- and p-phenylene diisocyanate, 2,3,5,6-tetramethyl-1 ,4-diisocyanato- benzene, 3,3'-dimethyl-4,4'-diisocyanatodiphenyl (TODI), 2,4- and 2,6-tolylene diisocyanate (TDI), 2,2'-, 2,4'- and 4,4'-diphenylmethane diisocyanate (MDI), naphthalene 1 ,2-diisocyanate and naphthalene 1 ,5-diisocyanate (NDI), m- and p-xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), and also any desired mixtures of the aforementioned isocyanates.
For the purposes of the present invention, the polyisocyanates according to the invention are also intended to include dimers (uretdiones) and trimers (isocyanurates). Particular importance is attributed here to the HDI trimer. Furthermore, oligomers are also to be included, such as e.g. "polymeric MDI" where n = 1 to 8:
Figure imgf000010_0001
Moreover, prepolymers of polyisocyanates with polyols can also be used if a stoichiometric excess of NCO groups is present. Suitable polyols include polyoxyalkylene polyols (also called "polyether polyols"), which can contain inter alia ethylene oxide units, propylene oxide units and butylene oxide units, aliphatic diols and polyols, and also polyester polyols and polycarbonate polyols, castor oil, hydroxylated epoxidized soya oil, and also mixtures of the aforementioned polyols.
An exemplary, non-exhaustive overview of reaction products of 2-oxo-1 ,3-dioxolane- 4-carboxylic acid with mono- and polyisocyanates is given in the formula scheme below:
Figure imgf000011_0001
The present invention furthermore provides a process for the preparation of a 2-oxo- 1 ,3-dioxolane-4-carboxylic acid of formula (III) hereinabove, which is a key intermediate in the preparation of the 2-oxo-1 ,3-dioxolane-4-carboxamide of the invention.
According to one embodiment, the 2-oxo-1 ,3-dioxolane-4-carboxylic acid of formula (III) can be prepared by hydrolysing a 2-oxo-1 ,3-dioxolane-4-carboxylic acid ester of formula (IV)
Figure imgf000011_0002
where R2 and R3 have the meanings given, in an acidic medium, preferably in aqueous acetic acid. It is also possible to arrive from the 2-oxo-1 ,3-dioxolane-4-carboxylic acid ester of formula (IV) directly at the 2-oxo-1 ,3-dioxolane-4-carboxamide according to the invention of formula (I) by reacting the ester (IV) with a formamide of the formula R1R2N-CHO, where Ri and R2 have the meanings given.
Moreover, according to another embodiment, the 2-oxo-1 ,3-dioxolane-4-carboxylic acid of formula (III) can be prepared by oxidizing a glycerol carbonate of formula (V)
Figure imgf000012_0001
where R3 has the meaning given, and more specifically for example by means of N- oxide-mediated oxidation, or by means of aerobic oxidation.
The N-oxide-mediated oxidation may be carried out with 1 ,3,5-trichloroisocyanuric acid and 2,2,6,6-tetramethylpiperidin-1 -oxyl (TEMPO). It may also be carried out with hydro- gen peroxide as an oxidant, e.g. in the presence of a manganese salt.
The aerobic oxidation uses oxygen from air or oxygen in pure form as the oxidant. It is suitably carried out in the presence of at least one transition metal salt selected from Co, Mn, Cu, Fe, and mixtures thereof, preferably Mn. It is preferably carried out in a suitable solvent or in (e.g. aqueous) acetic acid. The oxygen pressure should be in the range of 0.1 to 100 bar. The presence of an N-oxide such as TEMPO is preferred. The aerobic oxidation reaction is particularly preferred to oxidize glycerol carbonate (4-(hy- droxymethyl)-2-oxo-1 ,3-dioxolane) to form 2-oxo-1 ,3-dioxolane-4-carboxylic acid. A source of oxygen may also be the decomposition reaction of hydrogen peroxide with e.g. manganese ions. Generally speaking, the aerobic oxidation reaction hereinabove elegantly solves the problem of providing a source of 2-oxo-1 ,3-dioxolane-4-carboxylic acid from glycerol carbonate.
The invention further provides the use of the 2-oxo-1 ,3-dioxolane-4-carboxamides according to the invention for the preparation of hydroxyurethanes. The amides according to the invention react, as has been shown in the formula scheme listed at the outset, with R'-Nhb to give hydroxyurethanes. As in the case of the 2-oxo-1 ,3- dioxolane-4-carboxylic acid esters (PCT/ EP201 1/058945), hydroxyurethanes with secondary hydroxyl groups are predominantly formed here since during the attack of the nucleophilic nitrogen atom, the negative charge on the oxygen atom, which is closer to the CONR1R2 group, is better stabilized. Hydroxyurethanes with secondary hydroxyl groups have the advantage that no back-reaction takes place. Theoretically, an amine attack on the amide group would also be conceivable. However, it has been shown that the amine only attacks the 2-oxo-1 ,3-dioxolane group. Suitable amines here are primary and secondary amines with alkyl groups, aryl groups, aralkyl groups and also alkaryl groups as radicals. Primary amines react more quickly than secondary amines; aliphatic amines react more quickly than aromatic amines. In particular, relatively high molecular weight (poly)amines such as e.g. Jeffamine® from Huntsman Corp. and polyetheramines from BASF SE are of suitability here.
In the case of primary amines with the formula R'-NH2, the reaction can be shown as follows, with only the preferred reaction to give the hydroxyurethane with a secondary hydroxyl group being shown here:
Figure imgf000013_0001
The invention further provides the use of the 2-oxo-1 ,3-dioxolane-4-carboxamides according to the invention for the preparation of hydroxycarbonates. The formula scheme below shows only the preferred reaction to give the hydroxycarbonate with a secondary hydroxyl group. Suitable alcohols of the formula R'-OH are in particular the aforementioned polyols.
Figure imgf000013_0002
The invention further provides the use of the 2-oxo-1 ,3-dioxolane-4-carboxamides according to the invention for the preparation of hydroxysulphanylformates according to an analogous formula scheme:
Figure imgf000014_0001
If both the amines, alcohols and/or thiols used and also the 2-oxo-1 ,3-dioxolane- 4-carboxamides according to the invention are polyvalent (R2 = n-valent radical with n-1 further 2-OXO-1 ,3-dioxolane-4-carboxamide groups), the reaction of the same leads to polymeric products, namely to polylmeric hydroxyurethanes, hydroxycarbonates and/or hydroxysulphanylformat.es. In other words, polyvalent 2-oxo-1 ,3-dioxolane- 4-carboxamide binders (where n > 1 ) can be readily cured with polyamines, polyols and/or polythiols.
Accordingly, the present invention further consists in the use of the 2-oxo-1 ,3- dioxolane-4-carboxamides according to the invention for the preparation of polymeric hydroxyurethanes, hydroxycarbonates and/or hydroxysulphanylformat.es.
One advantage of polyhydroxyurethane systems lies in the relatively high hydrophilicity of these systems, which can be attributed to the OH groups present. These OH groups are in principle also available for the crosslinking with polyisocyanates, although the isocyanate-free systems possible according to the invention are preferred on account of their lower toxicity.
Moreover, when producing polyhydroxyurethane systems which are based on 2-oxo- 1 ,3-dioxolanes, bubble formation as a result of CO2 that is formed may not arise, even in the presence of moisture. Consequently, largely pore- and bubble-free coatings are possible, which is sometimes problematic for classic polyurethane systems.
Furthermore, the thermal stability of such polyhydroxyurethane systems is also higher than the stability of classic polyurethane systems.
Moreover, the low molecular weight 2-oxo-1 ,3-dioxolane-4-carboxamides can be used to block amines as end groups (so-called "end caps"), which constitutes a further subject matter of the present invention. This is also of interest with regard to conventional, amine-crosslinked polyurethane systems since an amine excess can lead to discolorations, while an isocyanate excess is toxicologically unacceptable. The present invention is now illustrated in more detail by reference to the examples hereinbelow. Example 1 : Preparation of 4-methoxycarbonyl-2-oxo-1 ,3-dioxolane (Reference)
Figure imgf000015_0001
80 g of sodium carbonate were dissolved in 200 ml of distilled water in a 1000 ml three- neck flask. The solution was cooled to 10°C. 58.5 g of methyl acrylate were then added and, after ca. 10 minutes, likewise at 10°C, 400 ml of a 7% strength aqueous sodium hypochlorite solution were stirred in. Then, the system was immediately flushed intensively with CO2. The temperature was allowed to increase to room temperature. The flask was flushed intensively with CO2 for a further 1 h at ca. 25 to 30°C, during which the temperature was held in the stated range by means of occasional cooling with an ice bath. The resulting white solid was filtered off via a suction filter. The filtrate was extracted with 4 x 90 ml of dichloromethane. The combined organic phase was dried with sodium sulphate and filtered off. The filtrate was removed on a rotary evaporator. Methyl epoxypropionate was obtained in 50 to 60% yield and a purity of 97%.
20 g of the methyl epoxypropionate were mixed with 20 g of tert-butyl methyl ether and 1 g of tetrabutylammonium bromide. The homogeneous mixture was transferred to a 100 ml pressurized reactor and carboxylated for 4 days at 40°C and a CO2 pressure of 20 bar. After the carboxylation, a two-phase system was obtained; the upper phase consisted of tert-butyl methyl ether, and the lower phase consisted of
4-methoxycarbonyl-2-oxo-1 ,3-dioxolane (purity 94% (GC), yield 94%). The product was characterized as follows: 1H NMR (500 MHz, CDCI3): 3.82 (3H, s,
CH3), 4.50 (1 H, dd, J = 5.5, 9.0, CH2), 4.66 (1 H, dd, J = 9.0, 9.0, CH2), 5.09 (1 H, dd, J = 9.0, 5.5, CH); 3C NMR (125 MHz, CDC ): 53.81 (CH3), 67.00 (CH2), 72.34 (CH), 153.97 (-O-CO-O-), 167.42 (-CO-O-); IR (neat): 1812 cm-1, (-O-CO-O- ), 1742 cm-1 (-CO-O-).
Example 2: Preparation of 4-methoxycarbonyl-2-oxo-1 ,3-dioxolane (Reference)
Figure imgf000015_0002
940 ml of a 7% strength aqueous sodium hypochlorite solution were introduced as initial charge in a 2000 ml three-neck flask. The solution was cooled to 0°C with the help of an ice/salt water bath. 58.5 g of methyl acrylate were then added and the mixture was held at 0°C for 30 minutes. The low-temperature mixture was then removed and further stirred for ca. 1.5 h such that the mixture heated up by itself (65-70°C). A colourless, cloudy solution was formed. Then, the solution was cooled to room temperature and extracted with 4 x 150 ml of dichloromethane. The combined organic phase was dried with magnesium sulphate and filtered off. The filtrate was removed on a rotary evaporator. Methyl epoxypropionate was obtained in 70 to 80% yield and a purity of 97%. The further reaction to give 4-methoxycarbonyl-2-oxo-1 ,3- dioxolane proceeded as described in Example 1. Example 3: Preparation of 4-methoxycarbonyl-2-oxo-1 ,3-dioxolane (Reference)
Figure imgf000016_0001
20 g of methyl epoxypropionate were mixed with 20 g of acetonitrile, 1 .5 g of benzyltrimethylammonium chloride and 1.5 g of ZnBr2. The homogeneous mixture was transferred to a 100 ml pressurized reactor and carboxylated for 6 days at 25°C and a CO2 pressure of 30 bar. After the carboxylation, the mixture was diluted with 100 g of acetonitrile. The mixture was purified with aluminium oxide and activated carbon. Then, the acetonitrile was distilled off. This gave 4-methoxycarbonyl-2-oxo-1 ,3-dioxolane (purity 72% (GC), yield 65%).
Example 4: Preparation of 4-methoxycarbonyl-2-oxo-1 ,3-dioxolane (Reference)
Figure imgf000016_0002
20 g of methyl epoxypropionate were mixed with 20 g of tert-butyl methyl ether, 1.5 g of tetrabutylammonium bromide and 1 .5 g of potassium iodide. The homogeneous mixture was transferred to a 100 ml pressurized reactor and carboxylated for 6 days at 50°C and a CO2 pressure of 30 bar. After the carboxylation, a two-phase system was obtained; the upper phase consisted of tert-butyl methyl ether, and the lower phase consisted of 4-methoxycarbonyl-2-oxo-1 ,3-dioxolane (purity 83% (GC), yield 79%).
Example 5: Acidic hydrolysis of 4-methoxycarbonyl-2-oxo-1 ,3-dioxolane
Figure imgf000017_0001
73 g (0.5 mol) of 4-methoxycarbonyl-2-oxo-1 ,3-dioxolane were heated under reflux for 3 hours with 1 1 g (0.55 mol) of water and 48 g (0.8 mol) of acetic acid. The mixture was then added to cyclohexane, the separated-off oil was carefully freed from all volatile constituents and the residue was ground with methylene chloride until a colourless crystalline precipitate had formed. The precipitate was washed with diethyl ether and dried in vacuo. This gave 2-oxo-1 ,3-dioxolane-4-carboxylic acid. m.p.: 1 19-121 °C. 1H-NMR (CDCI3/DMSO-d6 (1/0.1 [mol/mol])): 9.486 (broad, s; 1 H); 5.012 (dd; 1 H); 4.637 (t; 1 H); 4.506 (dd; 1 H). 3C-NMR (CDCI3/DMSO-d6 (1/0.1 [mol/ mol])): 168.425 (CO acid); 153.348 (CO cyclocarbonate); 72.247 (CH-COOH); 66.988 (CH2CH-COOH). IR (v [cm-1]): 2977 bs (OH acid), 2751 bw, 2658 bw, 2621 bw, 2538 bw, 2407 bw, 1785 bm (CO cyclocarbonate), 1793 bs (CO acid), 1546 w, 1481 w, 1431 w, 1399 s, 1345 w, 1325 w, 128 m, 1 196 s, 1087 s, 1074 s, 1039 m, 928 w, 832 s, 769 s, 724 m, 699 s, 650 m, 633 s, 525 s.
Example 6: N-oxide-mediated oxidation of glycerol carbonate
(Procedure analogous to JOC 2003; 68; pages 4999 ff.) 1 18.1 g (1 mol) of glycerol carbonate, 168 g (2 mol) of sodium hydrogencarbonate, 232 g (1 mol) of trichloroisocya- nuric acid, 18 g (1 mol) of water, 1 .5 g (0.01 mol) of TEMPO (2,2,6,6-tetramethylpiper- idin-1 -oxyl) and 5 g (0.05 mol) of NaBr were introduced as initial charge in 1.5 I of acetone at 0°C with stirring. The mixture was left to warm to room temperature and stirred for a further 12 hours, after which it was filtered off. The filtrate was concentrated by evaporation. The resulting oil was heated at reflux with chloroform. This gave 2-oxo- 1 ,3-dioxolane-4-carboxylic acid in 97% yield. Example 7: Aerobic oxidation of glycerol carbonate
Figure imgf000018_0001
1 18 g (1 mol) of glycerol carbonate (4-(hydroxymethyl)-2-oxo-1 ,3-dioxolane), 16.3 g (0.1 mol) of N-hydroxyphthalimide, 7.8 g (0.045 mol) of m-chlorobenzoic acid and 1 .3 g (0.05 mol) of cobalt(ll) acetylacetonate were dissolved in 300ml of glacial acetic acid and 1 I of ethyl acetate. The solution was saturated with oxygen and heated at reflux for 6 hours under an oxygen atmosphere. All volatile constituents were distilled off and the residue was ground with diethyl ether. Insoluble constituents were removed by means of washing with dichloromethane and toluene. This gave 2-oxo-1 ,3-dioxolane- 4-carboxylic acid. The yield was about 15%.
Example 8: Aerobic oxidation of glycerol carbonate
Figure imgf000018_0002
1 1.81 g (0.1 mol) of glycerol carbonate (4-(hydroxymethyl)-2-oxo-1 ,3-dioxolane), 0.50 g (0.002 mol) of manganese(ll) nitrate tetrahydrate (Mn(N03)2 · 4 H20), 0.58 g (0.002 mol) of cobalt(ll) nitrate hexahydrate (Co(N03)2 · 6 H20) and 1.88 g (0.012 mol) of TEMPO (2,2,6,6-tetramethylpiperidin-1 -oxyl) were dissolved in 100 ml of acetic acid. The reddish solution was stirred for 72 hours at room temperature under an oxygen atmosphere, evaporated to dryness, and the crude product was purified by recrystal- lization. This gave 2-oxo-1 ,3-dioxolane-4-carboxylic acid in the form of white to yellowish crystal needles. The yield was about 75 %, and the analytical data were in agreement with the known data (Example 5).
Example 9: Reaction of 2-oxo-1 ,3-dioxolane-4-carboxylic acid with n-butyl isocyanate
Figure imgf000019_0001
(The procedure was carried out analogously to Synthesis 2001 ; 2, pp. 243-246.) Equi- molar amounts of 2-oxo-1 ,3-dioxolane-4-carboxylic acid (4.089 g; 37 mmol) and n-butyl isocyanate (3.67g; 37 mmol) were dissolved in 100 ml of anhydrous THF. 1 mol% of DMAP (4-dimethylaminopyridine) was added and the mixture was stirred at room temperature until the IR spectrum indicated the disappearance of the isocyanate signal at 2050 cm-1 and the appearance of an amine signal at 1690 cm-1. After adding silicon dioxide, the mixture was filtered off and the solvent was removed. The residue was recrystallized from cyclohexane. m.p.: 69-71 °C. H-NMR (DMSO-d6): 8.454 (broad, s; 1 H;); 5.134 (dd; 1 H); 4.676 (t; 1 H); 4.412 (dd; 1 H); 3.126 (dd; 2H); 1 .438 (quint.; 2H); 1.302 (hex.; 2H); 0.895 (t; 3H). 3C-NMR (DMSO-d6): 165.836 (CO amide); 153.510 (CO cyclocarbonate); 73.103 (CH-CONHBu); 67.305 (CH2CH-CONHBu); 38.267 (N-CH2CH2CH2CH3); 30.821
(N-CH2CH2CH2CH3); 19.534 (N-CH2CH2CH2CH3); 13.704 (N-CH2CH2CH2CH3). IR (v [cm-1]): 3307 m (NH); 2959 m, 2933 m, 2873 m, 1780 s (CO cyclocarbonate), 1657 s (CO amide), 1561 s (CN amide) 1473 w, 1385 m, 1298 w, 1248 w, 1 161 s, 1093 m, 1075 m, 1052 s, 999 w, 878 w, 820 w, 766 s, 740 w, 708 m, 672 s, 617 s.
Example 10: Reaction of 2-oxo-1 ,3-dioxolane-4-carboxylic acid with cyclohexyl isocyanate
Figure imgf000019_0002
(The procedure was carried out analogously to Synthesis 2001 ; 2, pp. 243-246.) 2.56 g (19 mmol) of 2-oxo-1 ,3-dioxolane-4-carboxylic acid and 2.42 g (19 mmol) of cyclohexyl isocyanate were dissolved in 50 ml of anhydrous THF. 0.05 g (1 mol%) of DMAP were added and the mixture was stirred overnight at room temperature, during which a colourless precipitate was formed. The solvent was removed and the residue was extracted with diethyl ether, from which the product crystallized out upon evaporation. This gave N-cyclohexyl-2-oxo-1 ,3-dioxolane-4-carboxamide. m.p.: 123-125°C. H-NMR (CDCI3/DMSO-d6 (1/0.1 [mol/mol])): 6.284 (broad, s; 1 H); 5.007 (dd; 1 H); 4.735 (t; 1 H); 4.506 (dd; 1 H); 3.803 (m; 1 H); 1 .935 - 1 .232 (m; 10H). 3C-NMR (CDCI3/DMSO-d6 (1/0.1 [mol/mol])): 165.273 (CO amide); 153.002 (CO cy- clocarbonate); 73.088 (CH-CONHCyHex); 67.077 (CH2CH-CONHCyHex); 48.843 (NH- CH(CyHex)); 33.021 (CyHex); 32.952 (CyHex); 25.560 (CyHex); 25.1 10 (CyHex). IR (v [cm-1]): 3284 bm (NH); 2933 m; 2909 m; 2852 m; 1807 s, 1790 s (CO cyclocarbonate); 1649 s (CO amide); 1544 s (CN); 1485 w; 1448 w; 1380 m; 1321 w; 1 150 s; 1084 s; 1058 s; 1013 s; 934 w; 893 m; 869 w; 815 w; 767 s; 732 m; 689 m; 637w; 529 m.
Example 1 1 : Reaction of 2-oxo-1 ,3-dioxolane-4-carboxylic acid with HDI
Figure imgf000020_0001
(The procedure was carried out analogously to Synthesis 2001 ; 2, pp. 243-246.) 9.55 g (57 mmol) of HDI and 0.14 g (14 mmol) of DMAP were dissolved in 20 ml of anhydrous THF. A solution of 15 g (140 mmol) of 2-oxo-1 ,3-dioxolane-4-carboxylic acid in 50 ml of anhydrous THF was added dropwise and the resulting mixture was stirred overnight at room temperature. The resulting precipitate was collected, washed with THF and ether and recrystallized from water. This gave the difunctional amide. m.p.: 181 -182°C (decomposition). 1H-NMR (CDCI3/DMSO-d6 (1/0.1 [mol/mol])): 9.486 (broad, s; 1 H;); 5.012 (dd; 1 H); 4.637 (t; 1 H); 4.506 (dd; 1 H). 13C-NMR (CDC /DMSO- d6 (1/0.1 [mol/mol])): 168.425 (CO acid); 153.348 (CO cyclocarbonate); 72.247 (CH- CONH-Bu-); 66.988 (CH2 CH-CONH-Bu-).
Example 12: Reaction of 2-oxo-1 ,3-dioxolane-4-carboxylic acid with trimeric HDI
80 g (0.16 mol) of HDI trimer (Desmodur® N3600, Bayer AG, or Basonat® LR 9046, BASF SE), 64 g (0.48 mol) of 2-oxo-1 ,3-dioxolane-4-carboxylic acid and 0.585 g (4.8 mmol) of DMAP were dissolved in one litre of THF and stirred overnight at room temperature. Then, 10 g of activated carbon and 5 mmol of acetic acid were added, and the mixture was stirred for a further hour. It was then filtered off and the solvent was distilled off.
This gave 130 g of a reddish oil, which was used for the subsequent curing experiments without further purification. Viscosity: 35 500 mPas. IR (v [cm-1]): 3345, 2935, 2860, 1803, 1670, 1544, 1461 , 1400, 1 179, 1080, 747, 665. 1H-NMR (CDCI3); 7.21 (t; 1 H); 4.952 (dd; 1 H); 4.601 (t; 1 H); 4.414 (dd; 1 H); 3.698 (bs; 1 H); 3.147 (decapl., 2H); 1.484 (wt, 2H); 1 .416 (wt, 2H); 1 .217 (bs, 4H). 13C-NMR (CDCI3); 166.109 (CONH); 153.089 (0-CO-O); 148.095 (N- CO-N), 77.194 (CH2-CH-CONH-), 73.057 (CH2-CH-CONH-); 42.504; 39.156; 28.855; 27.474; 26.133 (the last 5 signals: -n-hex-).
Example 13: Curing experiments with the binder from Example 12
The binder resin from Example 12 was cured with customary amines, i.e. isophorone diamine (I PDA) and trimethyl hexamethylenediamine isomeric mixture (TMD). The results (given miscibility, potlife and Shore A hardness after 3 days of curing at room temperature) are shown in Table 1 below.
Table 1
Figure imgf000021_0001
It is clear from the results given in Table 1 that the binder resin has a very high reactivity towards these amines, and the mechanical properties are also very good.
Example 14:
In order to demonstrate the superiority of the carboxamides of the invention over the esters according to EP 2397474 A1 , N-butyl-2-oxo-1 ,3-dioxolane-4-carboxamide and 2-OXO-1 ,3-dioxolane-4-carboxylic acid methyl ester were titrated with n-butylamine. In the case of the carboxamide 92 ± 5 mole-% of amine was used up while in the case of the ester 1 14 ± 5 mole-% of amine was used up. This demonstrates that noticable ami- nolysis was going on with respect to the ester bond. Moreover, Table 2 below gives the dynamic viscosities [mPas] of the reaction products obtained from the reaction products of two molecules of 2-oxo-1 ,3-dioxolane-4-carb- oxylic acid methyl ester with one molecule of 1 ,6-hexanediol ("hexanediol diester", "HDDE") and, respectively, of two molecules of 2-oxo-1 ,3-dioxolane-4-carboxylic acid with one molecule of HDI ("hexamethylene diamide", "HMDA") with equimolar amounts of said customary amines, i.e. I PDA and TMD after seven days of curing at room temperature. The superiority of the carboxamide products is thus clearly demonstrated.
Table 2
HDDE HMDA
I PDA 206.000 2.900.000
TMD 1 .600.000 9.400.000

Claims

Patent claims
2-Oxo-1 ,3-dioxolane-4-carboxamide of formula (I),
Figure imgf000023_0001
characterized in that
Ri and R2, in each case independently of one another, are selected from H, straight-chain, branched or cyclic Ci-12-alkyl groups, C6-io-aryl groups, C6-i2-ar- alkyl groups and C6-i2-alkaryl groups or, together with the N atom to which they are bonded, form a 5- to 8-membered ring, and R3 is selected from H and straight-chain, branched or cyclic Ci-12-alkyl groups, or
Ri and R3 are each H, and R2 is an n-valent radical, wherein n is an integer greater than 1 , which is substituted with n-1 further 2-oxo-1 , 3-dioxolane-4-carbox- amide groups of general formula (I I)
Figure imgf000023_0002
2-Oxo-1 ,3-dioxolane-4-carboxamide according to Claim 1 , characterized in that Ri and R3 are each H, and R2 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, 2-ethyl-n-hexyl, n-lauryl, cyclohexyl, phenyl and benzyl.
2-Oxo-l ,3-dioxolane-4-carboxamide according to Claim 1 , characterized in that n is 2 to 5.
2-Oxo-l ,3-dioxolane-4-carboxamide according to Claim 1 , characterized in that n is 2 to 3.
2-Oxo-l ,3-dioxolane-4-carboxamide according to Claim 3 or 4, characterized in that R2 is selected from straight-chain or branched C2-22-alkylene groups, poly- ether groups of the general formula -(AiO)m-, wherein Ai is C2-5-alkylene and m is 1 -100, polycarbonate groups, polyester groups, poly(meth)acrylate groups, and combinations thereof.
Process for the preparation of a 2-oxo-1 ,3-dioxolane-4-carboxamide as defined in
Figure imgf000024_0001
one of Claims 1 to 5, characterized in that a 2-oxo-1 ,3-dioxolane-4-carboxylic acid of formula (I I I)
Figure imgf000024_0002
is reacted with an amine of the formula R1-NH-R2, where Ri , R2 and R3 have the meanings given.
Process according to Claim 6, characterized in that it is carried out in the presence of a water-withdrawing agent.
Process for the preparation of a 2-oxo-1 ,3-dioxolane-4-carboxamide as defined in one of Claims 1 to 5, wherein Ri is H, characterized in that a 2-oxo-1 ,3-dioxo- lane-4-carboxylic acid of formula (II I) is reacted with an isocyanate of the formula R2-NCO, where R2 and R3 have the meanings given.
Process according to Claim 8, characterized in that the isocyanate is a mono- isocyanate or a polyisocyanate with n NCO groups, where n has the meaning given.
Process according to claim 8 or 9, characterized in that the reaction is carried out in the presence of a catalyst selected from tertiary amines, organometallic compounds, and mixtures thereof.
Process for the preparation of a 2-oxo-1 ,3-dioxolane-4-carboxylic acid of formula (I I I) as defined in Claim 6, characterized in that a 2-oxo-1 ,3-dioxolane-4-carb- oxylic acid ester of formula (IV)
(IV)
Figure imgf000024_0003
where R2 and R3 have the meanings given, is hydrolysed in an acidic medium.
12. Process for the preparation of a 2-oxo-1 ,3-dioxolane-4-carboxylic acid of formula (III) as defined in Claim 6, characterized in that a glycerol carbonate of formula (V)
Figure imgf000025_0001
where R3 has the meaning given, is oxidized.
13. Process according to Claim 12, characterized in that the oxidation is effected with a combination of 1 ,3,5-trichloroisocyanuric acid and an n-oxide such as 2,2,6,6- tetramethylpiperidin-1 -oxyl. 14. Process according to Claim 12 or 13, characterized in that the oxidation is effected as an aerobic oxidation.
15. Use of the 2-oxo-1 ,3-dioxolane-4-carboxamides as defined in one of Claims 1 to 5 for the preparation of hydroxyurethanes.
16. Use of the 2-oxo-1 ,3-dioxolane-4-carboxamides as defined in one of Claims 1 to 5 for the preparation of hydroxycarbonates.
17. Use of the 2-oxo-1 ,3-dioxolane-4-carboxamides as defined in one of Claims 1 to 5 for the preparation of hydroxysulfanylformates.
18. Use according to one of Claims 15 to 17 for the preparation of polymeric hydroxyurethanes, hydroxycarbonates and/or hydroxysulfanylformates. 19. Use of the 2-oxo-1 ,3-dioxolane-4-carboxamides as defined in Claim 1 or 2 as end groups for the blocking of amines.
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EP2794585B1 (en) 2016-06-15
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CN104011040B (en) 2017-03-15
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AU2012358695A1 (en) 2014-07-10
CA2859450A1 (en) 2013-06-27
CA2859450C (en) 2020-01-07
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JP2015502374A (en) 2015-01-22
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