WO2022128791A1 - Bismuth-containing catalyst comprising at least one aromatic substituent - Google Patents
Bismuth-containing catalyst comprising at least one aromatic substituent Download PDFInfo
- Publication number
- WO2022128791A1 WO2022128791A1 PCT/EP2021/085199 EP2021085199W WO2022128791A1 WO 2022128791 A1 WO2022128791 A1 WO 2022128791A1 EP 2021085199 W EP2021085199 W EP 2021085199W WO 2022128791 A1 WO2022128791 A1 WO 2022128791A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- alkyl
- hydroxyl
- bismuth
- substituents
- monosubstituted
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 87
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 150000001875 compounds Chemical class 0.000 claims abstract description 49
- 125000003118 aryl group Chemical group 0.000 claims abstract description 38
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 33
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 31
- 239000012634 fragment Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 12
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000001424 substituent group Chemical group 0.000 claims description 92
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 70
- 229910052739 hydrogen Inorganic materials 0.000 claims description 64
- 239000001257 hydrogen Substances 0.000 claims description 63
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 63
- 239000000460 chlorine Substances 0.000 claims description 45
- 229910052801 chlorine Inorganic materials 0.000 claims description 45
- -1 monosubstituted phenyl Chemical group 0.000 claims description 45
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 44
- 125000000217 alkyl group Chemical group 0.000 claims description 38
- 125000005915 C6-C14 aryl group Chemical group 0.000 claims description 33
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 32
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 31
- 229910052736 halogen Inorganic materials 0.000 claims description 28
- 150000002367 halogens Chemical class 0.000 claims description 28
- 150000003839 salts Chemical class 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims description 14
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 13
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 12
- 150000002431 hydrogen Chemical class 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 11
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 claims description 11
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 8
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 150000001350 alkyl halides Chemical class 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 229940036348 bismuth carbonate Drugs 0.000 claims description 2
- XAEZALCLBRUCLR-UHFFFAOYSA-K bismuth;hydrogen carbonate Chemical compound [Bi+3].OC([O-])=O.OC([O-])=O.OC([O-])=O XAEZALCLBRUCLR-UHFFFAOYSA-K 0.000 claims description 2
- GMZOPRQQINFLPQ-UHFFFAOYSA-H dibismuth;tricarbonate Chemical compound [Bi+3].[Bi+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GMZOPRQQINFLPQ-UHFFFAOYSA-H 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 abstract description 23
- 150000003254 radicals Chemical class 0.000 description 45
- 230000000052 comparative effect Effects 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 13
- 239000003446 ligand Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 125000004429 atom Chemical group 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- PYHXGXCGESYPCW-UHFFFAOYSA-N alpha-phenylbenzeneacetic acid Natural products C=1C=CC=CC=1C(C(=O)O)C1=CC=CC=C1 PYHXGXCGESYPCW-UHFFFAOYSA-N 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229910052718 tin Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- LSSYDKBADXXERA-UHFFFAOYSA-N 2,2-diphenyldecanoic acid Chemical compound C=1C=CC=CC=1C(C(O)=O)(CCCCCCCC)C1=CC=CC=C1 LSSYDKBADXXERA-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- ZHXAZZQXWJJBHA-UHFFFAOYSA-N triphenylbismuthane Chemical compound C1=CC=CC=C1[Bi](C=1C=CC=CC=1)C1=CC=CC=C1 ZHXAZZQXWJJBHA-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000001733 carboxylic acid esters Chemical class 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000008199 coating composition Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- NCXCFZUKRMOFHW-UHFFFAOYSA-N 2,6-dibenzhydryl-4-methylaniline Chemical compound NC=1C(C(C=2C=CC=CC=2)C=2C=CC=CC=2)=CC(C)=CC=1C(C=1C=CC=CC=1)C1=CC=CC=C1 NCXCFZUKRMOFHW-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000002619 bicyclic group Chemical group 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000004896 high resolution mass spectrometry Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- XMARTJPCJQWCKN-UHFFFAOYSA-M lithium 2,6-dibenzhydryl-4-methylbenzoate Chemical compound CC1=CC(C(C2=CC=CC=C2)C2=CC=CC=C2)=C(C([O-])=O)C(C(C2=CC=CC=C2)C2=CC=CC=C2)=C1.[Li+] XMARTJPCJQWCKN-UHFFFAOYSA-M 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229960003390 magnesium sulfate Drugs 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 239000003039 volatile agent Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- QMGZERSATUYJLL-UHFFFAOYSA-N 1,3-dibenzhydryl-2-iodo-5-methylbenzene Chemical compound IC1=C(C=C(C=C1C(C1=CC=CC=C1)C1=CC=CC=C1)C)C(C1=CC=CC=C1)C1=CC=CC=C1 QMGZERSATUYJLL-UHFFFAOYSA-N 0.000 description 1
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 1
- ODELFXJUOVNEFZ-UHFFFAOYSA-N 2,2-diphenylpropanoic acid Chemical compound C=1C=CC=CC=1C(C(O)=O)(C)C1=CC=CC=C1 ODELFXJUOVNEFZ-UHFFFAOYSA-N 0.000 description 1
- QXLJXLKJFKSTML-UHFFFAOYSA-N 2,6-dibenzhydryl-4-methylbenzoic acid Chemical compound CC1=CC(C(C2=CC=CC=C2)C2=CC=CC=C2)=C(C(O)=O)C(C(C2=CC=CC=C2)C2=CC=CC=C2)=C1 QXLJXLKJFKSTML-UHFFFAOYSA-N 0.000 description 1
- BKSYWSWWJYBIRP-UHFFFAOYSA-N 2-ethylhexyl n-(6-isocyanatohexyl)carbamate Chemical compound CCCCC(CC)COC(=O)NCCCCCCN=C=O BKSYWSWWJYBIRP-UHFFFAOYSA-N 0.000 description 1
- WBJWXIQDBDZMAW-UHFFFAOYSA-N 2-hydroxynaphthalene-1-carbonyl chloride Chemical compound C1=CC=CC2=C(C(Cl)=O)C(O)=CC=C21 WBJWXIQDBDZMAW-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- USXAANGLQRWHJS-UHFFFAOYSA-N CC(C=C1)=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C(C(C2=CC=CC=C2)C2=CC=CC=C2)=C1C(O)=O Chemical compound CC(C=C1)=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C(C(C2=CC=CC=C2)C2=CC=CC=C2)=C1C(O)=O USXAANGLQRWHJS-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 101100443807 Pyrobaculum islandicum (strain DSM 4184 / JCM 9189 / GEO3) dpdh gene Proteins 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001210 attenuated total reflectance infrared spectroscopy Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001621 bismuth Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 1
- QILSFLSDHQAZET-UHFFFAOYSA-N diphenylmethanol Chemical compound C=1C=CC=CC=1C(O)C1=CC=CC=C1 QILSFLSDHQAZET-UHFFFAOYSA-N 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 125000003106 haloaryl group Chemical group 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229940091250 magnesium supplement Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910000064 phosphane Inorganic materials 0.000 description 1
- 150000003002 phosphanes Chemical class 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000005599 propionic acid derivatives Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- WRTMQOHKMFDUKX-UHFFFAOYSA-N triiodide Chemical compound I[I-]I WRTMQOHKMFDUKX-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- 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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/227—Catalysts containing metal compounds of antimony, bismuth or arsenic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
-
- 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
- C08G18/2815—Monohydroxy compounds
- C08G18/282—Alkanols, cycloalkanols or arylalkanols including terpenealcohols
-
- 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
- C08G18/714—Monoisocyanates or monoisothiocyanates containing nitrogen in addition to isocyanate or isothiocyanate nitrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
- B01J2531/54—Bismuth
Definitions
- Bismuth-containing catalyst comprising at least one aromatic substituent
- the invention relates to a bismuth-containing catalyst as such, which is defined by the general formula (I) detailed in the subsequent text.
- the bismuth-containing catalyst comprises at least one residue R 1 , which comprises a carboxyl fragment according to the general formula (II), wherein the first carbon atom (a-carbon), which is bonded directly to the carbon atom of the carboxyl group, is part of an aromatic fragment.
- the present invention further relates to a method for preparing a bismuth-containing catalyst of this kind and also to the use of such a bismuth-containing catalyst for preparing compounds comprising a urethane group.
- WO 2018/069018 relates to a coating composition system comprising the components (A) to (C) and optionally further components.
- the component (A) is at least one polyhydroxyl group-containing compound and the component (B) is at least one polyisocyanate-containing compound.
- the component (C) is a catalyst comprising at least two salts of an aliphatic monocarboxylic acid having at least 4 carbon atoms.
- the metal component of the first salt is bismuth (Bi)
- the second salt comprises magnesium (Mg), sodium (Na), potassium (K) or calcium (Ca) as metal component.
- the coating composition system according to WO 2018/069018 may be configured according to a first option such that all components are present separately from one another, i.e. the individual components are not mixed with one another, whereas according to a second option of the corresponding coating composition system, the respective components can also be present completely or at least partially mixed with one another.
- US-A 4,895,827 discloses a catalyst in the form of a metal salt, in which the catalyst is a constituent of a heat-sensitive color-forming composition, which, in addition to the catalyst, comprises a chromogenic material comprising an acidic developer and a suitable binder.
- the metal salt may comprise different metals as central metal atom/metal ion comprising, for example, zinc, tin, aluminum or nickel.
- the corresponding metal salt comprises organic compounds as ligands which, in addition to a carboxyl group, also comprise aromatic fragments and vinyl groups.
- bismuth-containing catalysts are not disclosed in US-A 4,895,827.
- JP-A 58 87 087 discloses the use of a multivalent metal salt of diphenylacetic acid, especially diphenylzinc acetate, as colorants, wherein a water-proof colored picture can be produced.
- bismuth-containing metal salts or the use of metal salts for preparing a compound comprising a urethane bond are not disclosed in JP-A 58 87 087.
- WO 2020/160939 relates to a bismuth-containing catalyst as such, which is defined by the general formula (I).
- the bismuth-containing catalyst comprises at least one residue R 1 , which comprises a carboxyl fragment according to the general formula (II), wherein a first carbon atom (a-carbon) is bonded to the carbon atom of the carboxyl group, which in turn is directly substituted with at least one aromatic system according to the invention.
- the residue R 1 of the bismuth-containing catalyst of WO 2020/160939 does not comprise any aromatic fragments bonded directly to the carbon atom of the carboxyl group.
- a compound having a urethane group is generally obtained if a compound comprising an isocyanate group is reacted with a compound comprising an hydroxyl group.
- the reaction generally takes place in the presence of a catalyst.
- tin-containing catalysts exhibit very high activity in such reactions, the use of such tin- containing catalysts, especially alkyltin compounds, should be avoided owing to their (very high) toxicity.
- the object of the present invention was to provide a novel catalyst that can be used for preparing compounds comprising a urethane group.
- R 1 is mutually independently a residue of the general formula (II)
- x 1, 2 or 3;
- R 2 is mutually independently a residue of the general formula (III) and y is 0, 1 or 2 ;
- X is mutually independently hydroxyl, halogen, carbonate, hydrogencarbonate or R 12 and z is 0, 1 or
- R 3 is unsubstituted or at least monosubstituted C 1
- R 4 and R 5 are mutually independently residues of the general formula (IV)
- R 6 , R 7 and R 8 are mutually independently hydrogen or unsubstituted or at least monosubstituted C 1 -C 30 - alkyl, C 6 -C 14 -aryl or C 7 -C 30 -aralkyl, wherein the substituents are selected from hydroxyl, halogen, carboxyl, -CF 3 , -NH 2 , C 1 -C 6 - alkoxy, C 1 -C 30 -alkyl or C 6 -C 14 -aryl and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by hydroxyl, halogen, -CF 3 , -NH 2 or C 1 -C 6 -alkoxy,
- R 9 , R 10 and R 11 are mutually independently hydrogen or unsubstituted or at least monosubstituted C 1 -C 30 - alkyl, C 6 -C 14 -aryl or C 7 -C 30 -aralkyl, wherein the substituents are selected from hydroxyl, halogen, carboxyl, -CF 3 , -NH 2 , C 1 -C 6 - alkoxy, C 1 -C 30 -alkyl or C 6 -C 14 -aryl and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by hydroxyl, halogen, -CF 3 , -NH 2 or C 1 -C 6 -alkoxy, and wherein at least one of the residues R 9 , R 10 or R 11 is unsubstituted or at least monosubstituted C 6 -C 14 -aryl,
- R 12 is unsubstituted or at least monosubstituted C 1 - C 30 -alkyl, C 6 -C 14 -aryl or C 7 -C 30 -aralkyl, wherein the substituents are selected from hydroxyl, halogen, carboxyl, -CF 3 , -NH 2 , C 1 -C 6 - alkoxy, C 1 -C 30 -alkyl or C 6 -C 14 -aryl and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by hydroxyl, halogen, -CF 3 , -NH 2 or C 1 -C 6 -alkoxy.
- the bismuth-containing catalysts according to the invention are characterized in that, inter alia, the use of toxic tin-containing catalysts in the production of compounds comprising a urethane group can be avoided.
- the bismuth-containing catalysts according to the invention have a comparable catalytic activity as known representatives of the effective, on the one hand catalytically active, but on the other hand toxic, tin- containing catalysts.
- the catalytic activity of the bismuth-containing catalysts according to the invention is better than the corresponding catalytic activity of the bismuth- or zinc- containing catalysts already known.
- the catalytic activity of the bismuth-containing catalysts according to general formula (I) of the present invention is better than the respective catalytic activity of bismuth-containing catalysts as described in WO 2020/16093 having an aliphatic first carbon atom (cx- carbon) bonded to the carbon atom of the carboxyl group.
- the bismuth-containing catalysts according to the invention exhibit improved hydrolytic stability compared to bismuth-containing catalysts already known.
- the bismuth-containing catalysts according to the invention are much more stable. Owing to the increased stability to hydrolysis - and thus also storage stability - the bismuth-containing catalysts according to the invention exhibit their improved catalytic properties over a much longer time period.
- the catalyst in the case of the bismuth-containing catalysts according to the invention, it is also not required that the catalyst must be present as a salt of the corresponding acid.
- the bismuth-containing catalysts according to the invention can thus be used without the presence of the corresponding acid at high catalytic activity in order to form compounds having urethane groups.
- Advantageous properties are then already obtained in the catalysts according to the invention if in at least one of the substituents/ligands of the bismuth central atom, an aromatic fragment is directly bonded to the carbon atom of the carboxyl group of the corresponding ligands as shown in formula (II).
- the aromatic fragment (directly bonded to the carbon atom of the carboxyl group) in turn is again substituted in both p-positions (residues R 4 and R 5 ) with at least one further residue containing an aromatic fragment such as R 9 , R 10 and/or R 11 as shown in formulas (II) and (IV).
- this first carbon atom of the aromatic part of the residue according to formula (II), which is directly bonded to the carbon atom of the carboxyl group is referred to as the a-carbon (atom).
- the two carbon atoms of the aromatic part of the residue according to formula (II), which are directly bonded to the a-carbon atom are both referred to as p-carbons
- the said carboxyl group of this substituent is located (spatially speaking) in proximity to the bismuth central atom of the bismuth-containing catalyst.
- the bismuth- containing catalysts according to the invention are represented as salts, wherein the bismuth central atom of the bismuth-containing catalyst according to the invention is represented as a (triple positively charged) cation of the corresponding salt (see for example the general formula (I))•
- the corresponding substituents/ligands of the bismuth-containing catalyst which are represented by the substituents/radicals R 1 , R 2 and X in the general formula (I) detailed above, form the corresponding anion components of the bismuth-containing catalyst in this salt representation.
- each of these so-called substituents/ligands is singly negatively charged.
- the two substituents R 1 and R 2 each comprise a carboxyl group.
- the negative charge in the corresponding substituents/ligands of said carboxyl group is localized and/or the corresponding carboxyl group is located in spatial proximity to the (positively charged) bismuth central atom.
- definitions such as C 1 -C 30 -alkyl such as defined, for example, for the radical R 8 in formula (II) above, signifies that this substituent (radical) is an alkyl radical having a carbon atom number of 1 to 30, wherein substituents optionally present are not taken into consideration in the carbon atom number.
- the alkyl radical may be either linear or branched as well as optionally cyclic. Alkyl radicals having both a cyclic and a linear component also fall under this definition. The same applies to other alkyl radicals such as a C 1 -C 6 -alkyl radical or a C 1 -C 12 -alkyl radical for example.
- alkyl radicals are methyl, ethyl, n-propyl, sec-propyl, n-butyl, sec-butyl, isobutyl, 2-ethylhexyl, tertiary-butyl (tert-Bu/t-Bu), pentyl, hexyl, heptyl, cyclohexyl, octyl, nonyl or decyl.
- aryl or the term "C 6 -C 14 ⁇ aryl, as defined, for example, for the radical R 9 in formula (IV) above, signifies that the substituent (radical) is an aromatic system.
- the corresponding aromatic system has a carbon atom number of 6 to 14, wherein substituents optionally present are not taken into consideration in the carbon atom number.
- the aromatic system may be a monocyclic, bicyclic or optionally polycyclic aromatic system. In the case of bicyclic or polycyclic aromatic systems, individual rings may optionally be fully or partially saturated. Preferably, all rings of the corresponding aromatic systems are fully unsaturated.
- Preferred examples of aryl are phenyl, naphthyl or anthracyl, especially phenyl.
- C 7 -C 30 ⁇ aralkyl as defined for example for the radical R 9 in formula (IV) above, signifies that the substituent (radical) comprises an alkyl radical (such as C 1 -C 6 -alkyl according to the definitions above), wherein this alkyl radical is in turn substituted by an aryl radical (according to the definitions above).
- the corresponding aralkyl substituent has a carbon atom number of 7 to 30, wherein substituents optionally present are not taken into consideration in the carbon atom number.
- the alkyl radical itself present therein may be either linear or branched as well as optionally cyclic.
- C 1 - C 6 -alkoxy as defined for example as (additional) substituent of the radical R 9 in formula (IV) above, signifies that it is a substituent (radical) in this case which is derived from an alcohol.
- the corresponding substituent thus comprises an oxygen fragment (-O-), which is in turn linked to an alkyl radical, such as C 1 - C 6 -alkyl (according to the definitions above).
- the alkyl radical itself may be either linear or branched as well as optionally cyclic.
- halogen such as defined for example for the radical X in formula (I) above, signifies that the substituent (radical) is fluorine, chlorine, bromine or iodine, X preferably being fluorine or chlorine, particularly preferably chlorine.
- the term "unsubstituted or at least monosubstituted C 1 -C 30 -alkyl, C 6 -C 14 -aryl or C 7 -C 30 -aralkyl" signifies that each of the in total three substituents (radicals) detailed corresponding to their definitions already specified above may be present either in unsubstituted form or have at least one further substituent (monosubstituted) . If one or more substituents are present (for example disubstituted, trisubstituted or even higher substituted), the appropriate substituents are selected independently of one another from the substituent groups specified in each case.
- the corresponding aryl unit such as phenyl for example, may be substituted for example by an hydroxyl and a C 1 - C 30 -alkyl substituent, such as methyl or ethyl.
- Alkyl or aryl fragments may themselves in turn comprise at least one additional substituent according to the definitions stated. The substitution may be at any desired position of the corresponding fragment.
- an appropriate radical such as R 8 for example, owing to the definition of, for example, formula (I), may occur two or more times in connection with formula (II), the individual radicals R 8 may be selected completely independently of one another according to the respective definitions.
- the radical R 1 which in turn comprises the radical R 8 , can therefore be present three times independently of one another in this scenario.
- the individual radicals R 1 can therefore be configured differently according to their basic definition.
- a first radical R 1 with regard to the constituent of the radical R 8 necessarily present therein, has a definition other than the corresponding second and/or third radical R 1 . Unless otherwise stated in the following text, this logically applies also for all other radicals, such as R 2 to R 7 , R 9 , R 10 and/or R 11 .
- the present invention firstly relates to a bismuth- containing catalyst of the general formula (I) in which the variables are defined as follows:
- R 1 is mutually independently a residue of the general formula (II)
- x 1, 2 or 3;
- R 2 is mutually independently a residue of the general formula (III) and y is 0, 1 or 2;
- X is mutually independently hydroxyl, halogen, carbonate, hydrogencarbonate or R 12 and z is 0, 1 or 2; wherein the sum total of x, y and z is equal to 3;
- R 3 is unsubstituted or at least monosubstituted C 1 -
- R 4 and R 5 are mutually independently residues of the general formula (IV)
- R 6 , R 7 and R 8 are mutually independently hydrogen or unsubstituted or at least monosubstituted C 1 -C 30 - alkyl, C 6 -C 14 -aryl or C 7 -C 30 -aralkyl, wherein the substituents are selected from hydroxyl, halogen, carboxyl, -CF 3 , -NH 2 , C 1 -C 6 - alkoxy, C 1 -C 30 -alkyl or C 6 -C 14 -aryl and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by hydroxyl, halogen, -CF 3 , -NH 2 or C 1 -C 6 -alkoxy,
- R 9 , R 10 and R 11 are mutually independently hydrogen or unsubstituted or at least monosubstituted C 1 -C 30 - alkyl, C 6 -C 14 -aryl or Cv-Cso-aralkyl, wherein the substituents are selected from hydroxyl, halogen, carboxyl, -CF 3 , -NH 2 , C 1 -C 6 - alkoxy, C 1 -C 30 -alkyl or C 6 -C 14 -aryl and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by hydroxyl, halogen, -CF 3 , -NH 2 or C 1 -C 6 -alkoxy, and wherein at least one of the residues R 9 , R 10 or R 11 is unsubstituted or at least monosubstituted C 6 -C 14 -aryl,
- R 12 is unsubstituted or at least monosubstituted Ci- Cso-alkyl, C 6 -C 14 -aryl or Cv-Cso-aralkyl, wherein the substituents are selected from hydroxyl, halogen, carboxyl, -CF 3 , -NH 2 , C 1 -C 6 - alkoxy, C 1 -C 30 -alkyl or C 6 -C 14 -aryl and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by hydroxyl, halogen, -CF 3 , -NH 2 or C 1 -C 6 -alkoxy.
- R 1 in accordance with general formulas (II) and optionally (IV) is preferably defined that i) R 9 , R 10 and R 11 are mutually independently hydrogen or unsubstituted or at least monosubstituted C 1 -C 12 -alkyl or C 6 -C 14 -aryl, wherein the substituents are selected from hydroxyl, chlorine, -CF 3 and C 1 -C 6 -alkyl, and wherein at least one of the residues R 9 , R 10 or R 11 is unsubstituted or at least monosubstituted C 6 -C 14 -aryl, and/or ii) R 6 , R 7 and R 8 are mutually independently hydrogen or unsubstituted or at least monosubstituted C 1 -C 12 -alkyl or C 6 -C 14 -aryl, wherein the substituents are selected from hydroxyl, chlorine, -CF 3 and C 1 -C 6 -alkyl.
- the radical R 1 in accordance with general formula (II) is more preferably defined according to the invention such that R 4 and R 5 have the same definitions according to formula (IV) in connection with the residue R 9 to R 11 . It should be noted that the staggered line crossing the bond on the left side of formula (IV) indicates that this bond is the connection of the respective residue R 4 or R 5 to the aromatic fragment of formula (II).
- R 1 in accordance with general formulas (II) and (IV) is more preferably defined in connection with the residue R 9 to R 11 as follows: i) R 9 is unsubstituted or at least monosubstituted phenyl, wherein the substituents are selected from hydroxyl, chlorine, -CF 3 and C 1 -C 6 -alkyl, and/or ii) R 10 is hydrogen or unsubstituted or at least monosubstituted phenyl or C 1 -C 12 -alkyl, wherein the substituents are selected from hydroxyl, chlorine, -CF 3 and C 1 -C 6 -alkyl, and/or iii) R 11 is hydrogen or unsubstituted or at least monosubstituted phenyl or C 1 -C 12 ⁇ alkyl, wherein the substituents are selected from hydroxyl, chlorine, -CF 3 and C 1 -C 6 -alkyl.
- radical R 3 present therein is unsubstituted or at least monosubstituted C 1 -C 12 ⁇ alkyl, wherein the substituents are selected from hydroxyl, chlorine or -CF 3 .
- radical X it is preferred in accordance with the invention that this is hydroxyl, chlorine or R 12 and R 12 is unsubstituted or at least monosubstituted C 1 -C 12 -alkyl or C 6 -C 14 -aryl, wherein the substituents are selected from hydroxyl, chlorine, -CF 3 and C 1 -C 6 -alkyl.
- the radicals R 1 , R 2 and X present in each case can be present in each case in any combination.
- a precondition in this case however is that x is at least 1, i.e. at least one radical R 1 is present in the bismuth-containing catalyst according to the invention according to general formula (I).
- the sum total of x, y and z is 3, the total number of ligands or negative charges is 3, so that in total charge neutrality is present with respect to the 3-fold positively charged bismuth central atom. If individual ligands/radicals such as R 1 , R 2 or X occur repeatedly, these can have the same or different definitions according to the respective basic definition.
- the bismuth-containing catalyst according to the general formula (I), (II) and optionally (IV) is defined as follows: i) the residues R 4 and R 5 have the same definition, ii) R 9 is unsubstituted or at least monosubstituted phenyl, wherein the substituents are selected from hydroxyl, chlorine, -CF 3 and C 1 -C 6 -alkyl, iii) R 10 is hydrogen or unsubstituted or at least monosubstituted phenyl or C 1 -C 12 ⁇ alkyl, wherein the substituents are selected from hydroxyl, chlorine, -CF 3 and C 1 -C 6 -alkyl, iv) R 11 is hydrogen or unsubstituted or at least monosubstituted phenyl or C 1 -C 12 -alkyl, wherein the substituents are selected from hydroxyl, chlorine, -CF 3 and C 1 -C 6 -alkyl, i
- the bismuth-containing catalyst is defined as follows: i) the residues R 4 and R 5 have the same definition, ii) R 9 is unsubstituted or at least monosubstituted phenyl, wherein the substituents are selected from hydroxyl, chlorine, -CF 3 and C 1 -C 6 -alkyl, iii) R 10 is hydrogen or unsubstituted or at least monosubstituted phenyl, wherein the substituents are selected from hydroxyl, chlorine, -CF 3 and C 1 -C 6 -alkyl, iv) R 11 is hydrogen or unsubstituted or at least monosubstituted C 1 -C 12 ⁇ alkyl, wherein the substituents are selected from hydroxyl, chlorine and -CF 3 , v) R 6 and R 7 are hydrogen, vi) R 8 is hydrogen or unsubstituted or at least monosubstituted phenyl or
- the bismuth-containing catalyst is defined as follows: i) the residues R 4 and R 5 have the same definition, ii) R 9 and R 10 are each phenyl, iii) R 11 is hydrogen or C 1 -C 12 ⁇ alkyl, preferably hydrogen or C 1 -C 5 -alkyl, especially hydrogen, iv) R 6 and R 7 are hydrogen, v) R 8 is hydrogen or C 1 -C 12 ⁇ alkyl, preferably hydrogen or C 1 -C 5 -alkyl, especially methyl, and vi) x is equal to 3 and y and z are each equal to 0.
- the bismuth-containing catalyst is defined by the general formula (la):
- the catalyst according to the invention in this embodiment has in total three residues R 1 according to general formula (I).
- Each of these in total three residues R 1 in each case comprises one residue R 6 , one residue R 7 , one residue R 8 , one residue R 9 , one residue R 10 and one residue R 11 .
- the corresponding definitions of the residues R 4 to R 11 can be the same or different from one another.
- each of the total of three residues R 6 are the same, each of the total of three residues R 7 are the same, each of the total of three residues R 8 are the same, each of the total of three residues R 9 are the same, each of the total of three residues R 10 are the same and each of the total of three residues R 11 are the same.
- R 9 is unsubstituted or at least monosubstituted phenyl, wherein the substituents are selected from hydroxyl, chlorine, -CF 3 and C 1 -C 6 -alkyl
- R 10 is hydrogen or unsubstituted or at least monosubstituted phenyl, wherein the substituents are selected from hydroxyl, chlorine, -CF 3 and C 1 -C 6 -alkyl
- iii) R 11 is hydrogen or unsubstituted or at least monosubstituted C 1 -C 12 ⁇ alkyl, wherein the substituents are selected from hydroxyl, chlorine and -CF 3
- R 6 and R 7 are hydrogen
- R 8 is hydrogen or unsubstituted or at least monosubstituted phenyl or C 1 -C 12 ⁇ alkyl, wherein the substituents are selected
- R 9 and R 10 are each phenyl
- R 11 is hydrogen or C 1 -C 12 ⁇ alkyl, preferably hydrogen or C 1 -C 5 -alkyl, especially hydrogen
- iii) R 6 and R 7 are hydrogen
- iv) R 8 is hydrogen or C 1 -C 12 ⁇ alkyl, preferably hydrogen or C 1 -C 5 -alkyl, especially methyl.
- the present invention therefore further relates also to a method for preparing a bismuth-containing catalyst of the general formula (I) or of the general formula (la) according to the definitions above.
- the method according to the invention for preparing such bismuth-containing catalysts can be carried out for example, in which i) at least one compound of the general formula (Ila)
- radicals R 6 to R 11 are defined according to the embodiments/definitions above ii) optionally at least one compound of the general formula (Illa) or a corresponding salt thereof, wherein the radical R 3 is defined according to the embodiments/definitions above, iii) is reacted with at least one bismuth-containing compound selected from Bi 2 O 3 , bismuth carbonate, bismuth hydrogencarbonate, bismuth halide, Bi (C 6 -C 14 -aryl)3, Bi (C 1 -C 12 -alkyl) 3 or metallic bismuth.
- bismuth-containing compound selected from Bi 2 O 3 , bismuth carbonate, bismuth hydrogencarbonate, bismuth halide, Bi (C 6 -C 14 -aryl)3, Bi (C 1 -C 12 -alkyl) 3 or metallic bismuth.
- the reactants listed above i.e. the acids according to the general formulae (Ila) or (Illa) or the appropriate corresponding salts as such, are known to those skilled in the art.
- the corresponding salts used can be, for example, sodium, potassium or calcium salts.
- corresponding carboxylic esters instead of the aforementioned acids according to the general formulae (Ila) or (Illa) or corresponding salts thereof as reactants, it is also possible to use corresponding carboxylic esters, for example a methyl or ethyl ester.
- Such carboxylic esters can be prepared by reacting the aforementioned acids or a corresponding salt thereof with a suitable alcohol, for example methanol or ethanol, optionally in the presence of a catalyst.
- the appropriate preparation methods of such carboxylic esters are known to a person skilled in the art.
- any bismuth-containing compound can be used in the method according to the invention, which is suitable for the purpose of forming the bismuth central atom in the bismuth-containing catalyst of the general formula (I) according to the invention, by reaction with the appropriate compound according to the general formula (Ila) or optionally (Illa).
- Bismuth-containing compounds as such are known to those skilled in the art.
- a bismuth halide is used as bismuth-containing compound, it is preferably a chlorine-containing compound, especially BiCI 3 .
- Any specific substituents/substitution patterns, such as the radicals R 6 to R 11 for example, may already be present in the corresponding reactant.
- substituents/substitution patterns can also be attached or completed even after the preparation process of a bismuth-containing catalyst according to the general formula (I) described above.
- the bismuth-containing compound is selected from Bi2O3, BiCis, Bi(C6Hs)3 or metallic bismuth.
- the bismuth-containing catalysts according to the general formula (I) according to the invention are preferably prepared by reacting at least one compound of the general formula (Ila) and optionally at least one compound of the general formula (Illa) with at least one bismuth- containing compound, wherein i) the reaction is carried out under a protective atmosphere and/or in the presence of at least one solvent, especially toluene or tetrahydrofuran, and/or ii) the reaction is conducted for at least 10 hours and/or at a temperature of at least 100°C, and/or iii) following the reaction, volatile constituents are removed, the bismuth-containing catalyst is dried under reduced pressure and/or a recrystallization is carried out.
- the at least one compound of the general formula (Ila) used as reactant in the method according to the invention is prepared from a corresponding compound according to the general formula (lib), wherein the compounds according to the general formula (Ila) only differ from the corresponding compounds of the general formula (lib) in that one or at most two radicals selected from R 9 , R 10 and R 11 is defined as H (hydrogen) in place of the definitions listed for the compounds according to general formula (Ila).
- This is preferably effected by reacting a corresponding compound (lib), but in which R 9 , R 10 and/or R 11 is H, with a lithium-containing compound, especially with n-butyllithium, and the intermediate obtained in this case is subsequently reacted with a haloalkane to introduce the radicals R 9 , R 10 and R 11 to obtain a compound according to the general formula (Ila).
- Haloalkanes used can be, for example, 1-bromooctane or 1-bromopropane .
- a catalyst according to the invention in accordance with general formula (I) is intended to be prepared in which at least one of the radicals R 9 to R 11 , preferably precisely one of these radicals, is a C 1 -C 30 - alkyl.
- an appropriate haloaryl or haloaralkyl compound is used if, in the context of this method step, a fully or partially aromatic substituent is intended to be introduced into the corresponding compound (lIb).
- the compound according to the general formula (lib) used is 2-arylacetic acid, 2,2- diarylacetic acid, particularly 2-phenylacetic acid or 2,2-diphenylacetic acid, particularly preferably 2,2- diphenylacetic acid.
- the present invention further relates to the use of at least one bismuth-containing catalyst according to the definitions above for preparing compounds comprising a urethane group.
- Diphenylmethanol (114.79 g, 623.1 mmol), 4-methylaniline (33.25 g, 310.3 mmol) and zinc chloride (21.66 g, 158.9 mmol) are placed together in a 1 L round-bottom flask with a large stir bar. After adding concentrated hydrochloric acid (37.0 %, 35 mL), the flask is equipped with a condenser and the mixture is heated to 150 °C for 2 hours in an oil bath. After cooling to ambient temperature, the product is extracted with dichloromethane (600 mL). Residual acid is neutralized via slow addition of an aqueous potassium carbonate solution (55 g in 400 mL).
- 2,2-Diphenylacetic acid (10.6 g; 48 mmol) are dissolved in 75 ml of dry tetrahydrofuran (THF) under a protective gas atmosphere (argon or nitrogen) in a 200 ml Schlenk flask and cooled to -15°C.
- a 1.6M solution of n- butyllithium in hexane 60 ml; 96 mmol is then added with stirring and over a period of 30 minutes.
- the reaction solution is stirred at -15°C for one hour and cooled to -78°C for the addition of 1-bromooctane (8.3 ml; 48 mmol). Subsequently, the reaction solution is slowly warmed to room temperature and stirred for a further 24 hours.
- a saturated ammonium chloride solution (60 mL) is added to the reaction solution and stirred for 30 minutes.
- the aqueous phase is separated by means of a separating funnel and extracted with 3 x 25 mL of diethyl ether.
- the combined organic phases were dried over magnesium sulfate (MgSO 4 )• All volatile solvents are then removed under reduced pressure (1 • 10" 3 mbar) and the resulting solid dried at 140°C under reduced pressure (1 • 10 3 mbar) for 24 hours.
- Triphenylbismuth (1.1 g; 2.5 mmol) and 2,2- diphenyldecanoic acid (2.43 g; 7.5 mmol) are initially charged under a protective gas atmosphere in a 25 mL three-necked flask equipped with stirrer bar, reflux condenser, thermometer and protective gas atmosphere inlet (argon or nitrogen).
- 12.5 mL of dry tetrahydrofuran or dry toluene (5 mL of solvent per 1 mmol of triphenylbismuth) are added to the reactants and the mixture is heated at 110°C under a protective gas atmosphere for at least 16 hours.
- the reaction course is monitored by ⁇ -H-NMR (nuclear magnetic resonance spectroscopy) .
- the catalyst Bi (dpp)3 according to comparative example 4 is prepared analogously to the comparative catalyst Bi(dpd)s described above, in which no synthesis of the precursor is required since the corresponding propionic acid derivative is commercially available (from Sigma- Aldrich), which is reacted with triphenylbismuth to give the comparative catalyst Bi (dpp)3.
- the respective catalytic activity of the individual working and comparative examples can be found in Table 1 below.
- the catalytic activity is tested by means of a reaction in which a compound is formed comprising a urethane group.
- a compound is formed comprising a urethane group.
- 11 mmol of 2-ethylhexyl (6-isocyanatohexyl)carbamate (commercially available as Desmodur LD (3.3 mL)) are reacted with 11 mmol of n- butanol (1 mL) as reactants.
- the reaction was carried out in the presence of a solvent (2 mL of xylene) and the catalysts listed in Table 1 (with a content of 0.05 mol% catalyst based on the amount of bismuth) at a temperature of 21°C.
- the isocyanate decrease and thus the formation of a urethane group are investigated by horizontal ATR-IR spectroscopy.
- 0.05 mL of the reaction solution are withdrawn at defined time intervals and investigated directly by spectroscopy.
- the conversion is determined by the relative decrease in intensity of the asymmetrical isocyanate stretching vibration at 2250 - 2285 cm 1 .
- the starting content of free isocyanate of the reaction solution at room temperature in the absence of catalyst was determined. All IR spectra were normalized to the bands of the symmetrical and asymmetrical stretching vibrations of the CH2 groups (3000 - 2870 cm 1 ).
- Example 1 Bi(dbhmb)3, wherein dbhmb is 2,6-
- Comparative example 2 DBTL (Dibutyltin dilaurate), commercially available catalyst
- the catalyst according to the invention shows a better catalytic activity to the known tin-containing catalysts according to comparative example 2. Tin-containing catalysts should be avoided however, owing to their considerable toxicity.
- the catalytic activity of working example 1 is however distinctly improved in comparison to bismuth-containing catalysts according to the prior art (comparative examples 3 and 4) or conducting the experiment wholly without catalyst (comparative example 5).
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Abstract
The invention relates to a bismuth-containing catalyst as such, which is defined by the general formula (I) detailed in the subsequent text. The bismuth-containing catalyst comprises at least one residue R1, which comprises a carboxyl fragment according to the general formula (II), wherein the first carbon atom (α-carbon), which is bonded directly to the carbon atom of the carboxyl group, is part of an aromatic fragment. The present invention further relates to a method for preparing a bismuth-containing catalyst of this kind and also to the use of such a bismuth-containing catalyst for preparing compounds comprising a urethane group.
Description
Bismuth-containing catalyst comprising at least one aromatic substituent
Description
The invention relates to a bismuth-containing catalyst as such, which is defined by the general formula (I) detailed in the subsequent text. The bismuth-containing catalyst comprises at least one residue R1, which comprises a carboxyl fragment according to the general formula (II), wherein the first carbon atom (a-carbon), which is bonded directly to the carbon atom of the carboxyl group, is part of an aromatic fragment. The present invention further relates to a method for preparing a bismuth-containing catalyst of this kind and also to the use of such a bismuth-containing catalyst for preparing compounds comprising a urethane group.
WO 2018/069018 relates to a coating composition system comprising the components (A) to (C) and optionally further components. The component (A) is at least one polyhydroxyl group-containing compound and the component (B) is at least one polyisocyanate-containing compound. In contrast, the component (C) is a catalyst comprising at least two salts of an aliphatic monocarboxylic acid having at least 4 carbon atoms. In this case, the metal component of the first salt is bismuth (Bi), while the
second salt comprises magnesium (Mg), sodium (Na), potassium (K) or calcium (Ca) as metal component. The coating composition system according to WO 2018/069018 may be configured according to a first option such that all components are present separately from one another, i.e. the individual components are not mixed with one another, whereas according to a second option of the corresponding coating composition system, the respective components can also be present completely or at least partially mixed with one another.
US-A 4,895,827 discloses a catalyst in the form of a metal salt, in which the catalyst is a constituent of a heat-sensitive color-forming composition, which, in addition to the catalyst, comprises a chromogenic material comprising an acidic developer and a suitable binder. The metal salt may comprise different metals as central metal atom/metal ion comprising, for example, zinc, tin, aluminum or nickel. The corresponding metal salt comprises organic compounds as ligands which, in addition to a carboxyl group, also comprise aromatic fragments and vinyl groups. However, bismuth-containing catalysts are not disclosed in US-A 4,895,827.
JP-A 58 87 087 discloses the use of a multivalent metal salt of diphenylacetic acid, especially diphenylzinc acetate, as colorants, wherein a water-proof colored
picture can be produced. However, bismuth-containing metal salts or the use of metal salts for preparing a compound comprising a urethane bond are not disclosed in JP-A 58 87 087.
WO 2020/160939 relates to a bismuth-containing catalyst as such, which is defined by the general formula (I). The bismuth-containing catalyst comprises at least one residue R1, which comprises a carboxyl fragment according to the general formula (II), wherein a first carbon atom (a-carbon) is bonded to the carbon atom of the carboxyl group, which in turn is directly substituted with at least one aromatic system according to the invention. By consequence, the residue R1 of the bismuth-containing catalyst of WO 2020/160939 does not comprise any aromatic fragments bonded directly to the carbon atom of the carboxyl group.
J. Bresien et al., Dalton Trans. 2019, 48, 3786, relates to the synthesis of sterically demanding primary phosphanes of the type RBhp-PH2 (Bhp = 2,6- bis (benzylhydryl)-4-R-phenyl, R = Me, tBu) as well as the isolation and characterization of several halogenated precursors, a diazonium intermediate and a dihalostibane. Bresien et al. does not disclose any bismuth-containing catalysts.
The preparation of compounds comprising a urethane group (urethane bond) has likewise been known for a long time.
A compound having a urethane group is generally obtained if a compound comprising an isocyanate group is reacted with a compound comprising an hydroxyl group. The reaction generally takes place in the presence of a catalyst. Although tin-containing catalysts exhibit very high activity in such reactions, the use of such tin- containing catalysts, especially alkyltin compounds, should be avoided owing to their (very high) toxicity.
The object of the present invention, therefore, was to provide a novel catalyst that can be used for preparing compounds comprising a urethane group.
The object is achieved by a bismuth-containing catalyst of the general formula (I)
in which the variables are defined as follows:
R1 is mutually independently a residue of the general formula (II)
X is mutually independently hydroxyl, halogen, carbonate, hydrogencarbonate or R12 and z is 0, 1 or
2; wherein the sum total of x, y and z is equal to 3;
R3 is unsubstituted or at least monosubstituted C1
C30-alkyl, C6-C14-aryl or C7-C30-aralkyl,
wherein the substituents are selected from hydroxyl, halogen, carboxyl, -CF3, -NH2, C1-C6- alkoxy, C1-C30-alkyl or C6-C14-aryl and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by hydroxyl, halogen, -CF3, -NH2 or C1-C6-alkoxy, under the proviso that in case R3 is unsubstituted or at least monosubstituted C1- C30-alkyl or C7-C30-aralkyl, the carbon atom of the residue R3 bonded directly to carbon atom of the carboxyl group of the general formula (III) does not comprise any unsubstituted or at least monosubstituted C6-C14-aryl as substituent,
R6, R7 and R8 are mutually independently hydrogen or unsubstituted or at least monosubstituted C1-C30- alkyl, C6-C14-aryl or C7-C30-aralkyl,
wherein the substituents are selected from hydroxyl, halogen, carboxyl, -CF3, -NH2, C1-C6- alkoxy, C1-C30-alkyl or C6-C14-aryl and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by hydroxyl, halogen, -CF3, -NH2 or C1-C6-alkoxy,
R9, R10 and R11 are mutually independently hydrogen or unsubstituted or at least monosubstituted C1-C30- alkyl, C6-C14-aryl or C7-C30-aralkyl, wherein the substituents are selected from hydroxyl, halogen, carboxyl, -CF3, -NH2, C1-C6- alkoxy, C1-C30-alkyl or C6-C14-aryl and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by hydroxyl, halogen, -CF3, -NH2 or C1-C6-alkoxy, and wherein at least one of the residues R9, R10 or R11 is unsubstituted or at least monosubstituted C6-C14-aryl,
R12 is unsubstituted or at least monosubstituted C1- C30-alkyl, C6-C14-aryl or C7-C30-aralkyl,
wherein the substituents are selected from hydroxyl, halogen, carboxyl, -CF3, -NH2, C1-C6- alkoxy, C1-C30-alkyl or C6-C14-aryl and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by hydroxyl, halogen, -CF3, -NH2 or C1-C6-alkoxy.
The bismuth-containing catalysts according to the invention are characterized in that, inter alia, the use of toxic tin-containing catalysts in the production of compounds comprising a urethane group can be avoided. The bismuth-containing catalysts according to the invention have a comparable catalytic activity as known representatives of the effective, on the one hand catalytically active, but on the other hand toxic, tin- containing catalysts.
However, the catalytic activity of the bismuth-containing catalysts according to the invention is better than the corresponding catalytic activity of the bismuth- or zinc- containing catalysts already known. In particular, the catalytic activity of the bismuth-containing catalysts according to general formula (I) of the present invention is better than the respective catalytic activity of bismuth-containing catalysts as described in WO 2020/16093 having an aliphatic first carbon atom (cx- carbon) bonded to the carbon atom of the carboxyl group.
Moreover, the bismuth-containing catalysts according to the invention exhibit improved hydrolytic stability compared to bismuth-containing catalysts already known. For example, low amounts of water can already be sufficient in order to significantly or fully reduce the catalytic activity of bismuth-containing catalysts based on pure alkyl ligands, such as laurate-containing bismuth catalysts. Whereas such catalysts known from the prior art start to precipitate on contact with water, the bismuth-containing catalysts according to the invention are much more stable. Owing to the increased stability to hydrolysis - and thus also storage stability - the bismuth-containing catalysts according to the invention exhibit their improved catalytic properties over a much longer time period.
Furthermore, in the case of the bismuth-containing catalysts according to the invention, it is also not required that the catalyst must be present as a salt of the corresponding acid. The bismuth-containing catalysts according to the invention can thus be used without the presence of the corresponding acid at high catalytic activity in order to form compounds having urethane groups.
Advantageous properties are then already obtained in the catalysts according to the invention if in at least one of the substituents/ligands of the bismuth central atom, an aromatic fragment is directly bonded to the carbon atom of the carboxyl group of the corresponding ligands as shown in formula (II). The aromatic fragment (directly bonded to the carbon atom of the carboxyl group) in turn is again substituted in both p-positions (residues R4 and R5) with at least one further residue containing an aromatic fragment such as R9, R10 and/or R11 as shown in formulas (II) and (IV).
In accordance with the invention, this first carbon atom of the aromatic part of the residue according to formula (II), which is directly bonded to the carbon atom of the carboxyl group, is referred to as the a-carbon (atom). Within the context of the present invention, the two carbon atoms of the aromatic part of the residue according to formula (II), which are directly bonded to the a-carbon atom, are both referred to as p-carbons
(atoms).
The said carboxyl group of this substituent is located (spatially speaking) in proximity to the bismuth central atom of the bismuth-containing catalyst. The bismuth- containing catalysts according to the invention are represented as salts, wherein the bismuth central atom
of the bismuth-containing catalyst according to the invention is represented as a (triple positively charged) cation of the corresponding salt (see for example the general formula (I))• The corresponding substituents/ligands of the bismuth-containing catalyst, which are represented by the substituents/radicals R1, R2 and X in the general formula (I) detailed above, form the corresponding anion components of the bismuth-containing catalyst in this salt representation. Each of these so- called substituents/ligands is singly negatively charged. As detailed below, the two substituents R1 and R2 each comprise a carboxyl group. In general, the negative charge in the corresponding substituents/ligands of said carboxyl group is localized and/or the corresponding carboxyl group is located in spatial proximity to the (positively charged) bismuth central atom.
From a scientific standpoint however, it is also tenable, in place of the salt notation used in the context of the present application for the bismuth-containing catalysts according to the invention, to select a notation/representation in which a chemical bond between the bismuth central atom and the three ligands R1, R2 and X according to general formula (I) is completely or at least partially formed in each case. Expressed in other words, this means that the bismuth central atom is not
present as a positively charged cation and the corresponding ligands are also not present as negatively charged anions, but rather the corresponding charge form a chemical bond between the corresponding ligands on the one hand and the bismuth central atom on the other hand. In the context of the present invention, the bismuth- containing catalysts disclosed according to the invention therefore also describe such a definition that is not based on a salt.
In the context of the present invention, definitions such as C1-C30-alkyl, such as defined, for example, for the radical R8 in formula (II) above, signifies that this substituent (radical) is an alkyl radical having a carbon atom number of 1 to 30, wherein substituents optionally present are not taken into consideration in the carbon atom number. The alkyl radical may be either linear or branched as well as optionally cyclic. Alkyl radicals having both a cyclic and a linear component also fall under this definition. The same applies to other alkyl radicals such as a C1-C6-alkyl radical or a C1-C12-alkyl radical for example. Examples of alkyl radicals are methyl, ethyl, n-propyl, sec-propyl, n-butyl, sec-butyl, isobutyl, 2-ethylhexyl, tertiary-butyl (tert-Bu/t-Bu), pentyl, hexyl, heptyl, cyclohexyl, octyl, nonyl or decyl.
In the context of the present invention, the term "aryl" or the term "C6-C14~aryl", as defined, for example, for the radical R9 in formula (IV) above, signifies that the substituent (radical) is an aromatic system. The corresponding aromatic system has a carbon atom number of 6 to 14, wherein substituents optionally present are not taken into consideration in the carbon atom number. The aromatic system may be a monocyclic, bicyclic or optionally polycyclic aromatic system. In the case of bicyclic or polycyclic aromatic systems, individual rings may optionally be fully or partially saturated. Preferably, all rings of the corresponding aromatic systems are fully unsaturated. Preferred examples of aryl are phenyl, naphthyl or anthracyl, especially phenyl.
In the context of the present invention, the definition "C7-C30~aralkyl ", as defined for example for the radical R9 in formula (IV) above, signifies that the substituent (radical) comprises an alkyl radical (such as C1-C6-alkyl according to the definitions above), wherein this alkyl radical is in turn substituted by an aryl radical (according to the definitions above). The corresponding aralkyl substituent has a carbon atom number of 7 to 30, wherein substituents optionally present are not taken into consideration in the carbon atom number. The alkyl radical itself present therein may be either linear or branched as well as optionally cyclic.
In the context of the present invention, the term "C1- C6-alkoxy", as defined for example as (additional) substituent of the radical R9 in formula (IV) above, signifies that it is a substituent (radical) in this case which is derived from an alcohol. The corresponding substituent thus comprises an oxygen fragment (-O-), which is in turn linked to an alkyl radical, such as C1- C6-alkyl (according to the definitions above). The alkyl radical itself may be either linear or branched as well as optionally cyclic.
In the context of the present invention, the term "halogen", such as defined for example for the radical X in formula (I) above, signifies that the substituent (radical) is fluorine, chlorine, bromine or iodine, X preferably being fluorine or chlorine, particularly preferably chlorine.
In the context of the present invention, the term "unsubstituted or at least monosubstituted C1-C30-alkyl, C6-C14-aryl or C7-C30-aralkyl ", such as defined for example for the radical R9 in formula (IV) above, signifies that each of the in total three substituents (radicals) detailed corresponding to their definitions already specified above may be present either in unsubstituted form or have at least one further substituent
(monosubstituted) . If one or more substituents are present (for example disubstituted, trisubstituted or even higher substituted), the appropriate substituents are selected independently of one another from the substituent groups specified in each case.
In the case of a disubstituted C6-C14-aryl for example, the corresponding aryl unit, such as phenyl for example, may be substituted for example by an hydroxyl and a C1- C30-alkyl substituent, such as methyl or ethyl. Alkyl or aryl fragments may themselves in turn comprise at least one additional substituent according to the definitions stated. The substitution may be at any desired position of the corresponding fragment.
Provided that an appropriate radical, such as R8 for example, owing to the definition of, for example, formula (I), may occur two or more times in connection with formula (II), the individual radicals R8 may be selected completely independently of one another according to the respective definitions. For example, if in the general formula (I) the variable x=3, the radical R1 occurs in total three times in the general formula (I). The radical R1, which in turn comprises the radical R8, can therefore be present three times independently of one another in this scenario. The individual radicals R1 can therefore be configured differently according to their basic
definition. Thus, it is feasible that a first radical R1, with regard to the constituent of the radical R8 necessarily present therein, has a definition other than the corresponding second and/or third radical R1 . Unless otherwise stated in the following text, this logically applies also for all other radicals, such as R2 to R7, R9, R10 and/or R11.
Unless otherwise specified in the following description, the respective definitions of the radicals R1 to R12 are in each case the preferred unsubstituted definitions.
The present invention is further specified hereinbelow.
The present invention firstly relates to a bismuth- containing catalyst of the general formula (I)
in which the variables are defined as follows:
R1 is mutually independently a residue of the general formula (II)
X is mutually independently hydroxyl, halogen, carbonate, hydrogencarbonate or R12 and z is 0, 1 or 2; wherein the sum total of x, y and z is equal to 3;
R3 is unsubstituted or at least monosubstituted C1-
C30-alkyl, C6-C14-aryl or C7-C30-aralkyl,
wherein the substituents are selected from hydroxyl, halogen, carboxyl, -CF3, -NH2, C1-C6- alkoxy, C1-C30-alkyl or C6-C14-aryl and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by hydroxyl, halogen, -CF3, -NH2 or C1-C6-alkoxy, under the proviso that in case R3 is unsubstituted or at least monosubstituted C1- C30-alkyl or C7-C30-aralkyl, the carbon atom of the residue R3 bonded directly to carbon atom of the carboxyl group of the general formula (III) does not comprise any unsubstituted or at least monosubstituted C6-C14-aryl as substituent,
R6, R7 and R8 are mutually independently hydrogen or unsubstituted or at least monosubstituted C1-C30- alkyl, C6-C14-aryl or C7-C30-aralkyl,
wherein the substituents are selected from hydroxyl, halogen, carboxyl, -CF3, -NH2, C1-C6- alkoxy, C1-C30-alkyl or C6-C14-aryl and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by hydroxyl, halogen, -CF3, -NH2 or C1-C6-alkoxy,
R9, R10 and R11 are mutually independently hydrogen or unsubstituted or at least monosubstituted C1-C30- alkyl, C6-C14-aryl or Cv-Cso-aralkyl, wherein the substituents are selected from hydroxyl, halogen, carboxyl, -CF3, -NH2, C1-C6- alkoxy, C1-C30-alkyl or C6-C14-aryl and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by hydroxyl, halogen, -CF3, -NH2 or C1-C6-alkoxy, and wherein at least one of the residues R9, R10 or R11 is unsubstituted or at least monosubstituted C6-C14-aryl,
R12 is unsubstituted or at least monosubstituted Ci- Cso-alkyl, C6-C14-aryl or Cv-Cso-aralkyl,
wherein the substituents are selected from hydroxyl, halogen, carboxyl, -CF3, -NH2, C1-C6- alkoxy, C1-C30-alkyl or C6-C14-aryl and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by hydroxyl, halogen, -CF3, -NH2 or C1-C6-alkoxy.
In connection with the residues (radicals/substituents/ligands ) present in the general formula (I), particularly the necessary residue R1 and the optional residue R2, it should be noted that the further/exact chemical definition of these radicals R1 or R2 is a result of the residues R4 to R11 of the general formulas (II) and (IV) with respect to the residue R1 and is a result of the residue R3 of the general formula (III) with respect to the residue R2 . In accordance with the invention, the residue R2 is chemically always defined differently than the residue R1 . Expressed in other words, this signifies that a specific radical R2 or R3 in accordance with general formula (III) cannot fall under the corresponding definition of a radical R1 or the radicals R4 to R11 according to general formulas (II) and (IV).
The radical R1 in accordance with general formulas (II) and optionally (IV) is preferably defined that
i) R9, R10 and R11 are mutually independently hydrogen or unsubstituted or at least monosubstituted C1-C12-alkyl or C6-C14-aryl, wherein the substituents are selected from hydroxyl, chlorine, -CF3 and C1-C6-alkyl, and wherein at least one of the residues R9, R10 or R11 is unsubstituted or at least monosubstituted C6-C14-aryl, and/or ii) R6, R7 and R8 are mutually independently hydrogen or unsubstituted or at least monosubstituted C1-C12-alkyl or C6-C14-aryl, wherein the substituents are selected from hydroxyl, chlorine, -CF3 and C1-C6-alkyl.
The radical R1 in accordance with general formula (II) is more preferably defined according to the invention such that R4 and R5 have the same definitions according to formula (IV) in connection with the residue R9 to R11. It should be noted that the staggered line crossing the bond on the left side of formula (IV) indicates that this bond is the connection of the respective residue R4 or R5 to the aromatic fragment of formula (II).
The radical R1 in accordance with general formulas (II) and (IV) is more preferably defined in connection with the residue R9 to R11 as follows: i) R9 is unsubstituted or at least monosubstituted phenyl, wherein the substituents are selected from hydroxyl, chlorine, -CF3 and C1-C6-alkyl, and/or ii) R10 is hydrogen or unsubstituted or at least monosubstituted phenyl or C1-C12-alkyl, wherein the substituents are selected from hydroxyl, chlorine, -CF3 and C1-C6-alkyl, and/or iii) R11 is hydrogen or unsubstituted or at least monosubstituted phenyl or C1-C12~alkyl, wherein the substituents are selected from hydroxyl, chlorine, -CF3 and C1-C6-alkyl.
With respect to the radical R2 according to general formula (III), it is preferable that the radical R3 present therein is unsubstituted or at least monosubstituted C1-C12~alkyl, wherein the substituents are selected from hydroxyl, chlorine or -CF3.
With regard to the radical X, it is preferred in accordance with the invention that this is hydroxyl,
chlorine or R12 and R12 is unsubstituted or at least monosubstituted C1-C12-alkyl or C6-C14-aryl, wherein the substituents are selected from hydroxyl, chlorine, -CF3 and C1-C6-alkyl.
In the bismuth-containing catalyst according to general formula (I) according to the invention, the radicals R1, R2 and X present in each case can be present in each case in any combination. A precondition in this case however is that x is at least 1, i.e. at least one radical R1 is present in the bismuth-containing catalyst according to the invention according to general formula (I). Furthermore, the sum total of x, y and z is 3, the total number of ligands or negative charges is 3, so that in total charge neutrality is present with respect to the 3-fold positively charged bismuth central atom. If individual ligands/radicals such as R1, R2 or X occur repeatedly, these can have the same or different definitions according to the respective basic definition.
In the context of general formula (I), the following scenarios are preferred in accordance with the invention, wherein i) x is equal to 2 or 3, y is equal to 0 or 1 and z is equal to 0 or 1, or
ii) x is equal to 3 and y and z are each equal to 0, or iii) x is equal to 2, y is equal to 0 and z is equal to 1, or iv) x is equal to 2, y is equal to 1 and z is equal to 0, wherein preferably x is equal to 3 and y and z are each equal to 0.
In a preferred embodiment of the present invention, the bismuth-containing catalyst according to the general formula (I), (II) and optionally (IV) is defined as follows: i) the residues R4 and R5 have the same definition, ii) R9 is unsubstituted or at least monosubstituted phenyl, wherein the substituents are selected from hydroxyl, chlorine, -CF3 and C1-C6-alkyl, iii) R10 is hydrogen or unsubstituted or at least monosubstituted phenyl or C1-C12~alkyl, wherein the substituents are selected from hydroxyl, chlorine, -CF3 and C1-C6-alkyl,
iv) R11 is hydrogen or unsubstituted or at least monosubstituted phenyl or C1-C12-alkyl, wherein the substituents are selected from hydroxyl, chlorine, -CF3 and C1-C6-alkyl, v) R6 is hydrogen or unsubstituted or at least monosubstituted C1-C12~alkyl, wherein the substituents are selected from hydroxyl, chlorine and -CF3, vi) R7 is hydrogen or unsubstituted or at least monosubstituted C1-C12~alkyl, wherein the substituents are selected from hydroxyl, chlorine, -CF3 and C1-C6-alkyl, and vii) R8 is hydrogen or unsubstituted or at least monosubstituted phenyl or C1-C12~alkyl, wherein the substituents are selected from hydroxyl, chlorine, -CF3 and C1-C6-alkyl.
In a more preferred embodiment of the present invention, the bismuth-containing catalyst is defined as follows: i) the residues R4 and R5 have the same definition,
ii) R9 is unsubstituted or at least monosubstituted phenyl, wherein the substituents are selected from hydroxyl, chlorine, -CF3 and C1-C6-alkyl, iii) R10 is hydrogen or unsubstituted or at least monosubstituted phenyl, wherein the substituents are selected from hydroxyl, chlorine, -CF3 and C1-C6-alkyl, iv) R11 is hydrogen or unsubstituted or at least monosubstituted C1-C12~alkyl, wherein the substituents are selected from hydroxyl, chlorine and -CF3, v) R6 and R7 are hydrogen, vi) R8 is hydrogen or unsubstituted or at least monosubstituted phenyl or C1-C12~alkyl, wherein the substituents are selected from hydroxyl, chlorine, -CF3 and C1-C6-alkyl, and vii) x is equal to 3 and y and z are each equal to 0.
In an even more preferred embodiment of the present invention, the bismuth-containing catalyst is defined as follows:
i) the residues R4 and R5 have the same definition, ii) R9 and R10 are each phenyl, iii) R11 is hydrogen or C1-C12~alkyl, preferably hydrogen or C1-C5-alkyl, especially hydrogen, iv) R6 and R7 are hydrogen, v) R8 is hydrogen or C1-C12~alkyl, preferably hydrogen or C1-C5-alkyl, especially methyl, and vi) x is equal to 3 and y and z are each equal to 0.
In a particularly preferred embodiment of the present invention, the bismuth-containing catalyst is defined by the general formula (la):
wherein the residues R6 to R11 mutually independently correspond to the definitions described above. As evident from formula (la) compared to the general formula (I), the catalyst according to the invention in this embodiment has in total three residues R1 according to general formula (I). Each of these in total three residues R1 in each case comprises one residue R6, one residue R7, one residue R8, one residue R9, one residue R10 and one residue R11. In each of these three residues R1, the corresponding definitions of the residues R4 to R11 can be the same or different from one another. However, it is preferred in accordance with the invention that each of the total of three residues R6 are the same, each of the total of three residues R7 are the same, each of the total of three residues R8 are the same, each of the total of three residues R9 are the same, each of the total of three residues R10 are the same and each of the total of three residues R11 are the same.
Furthermore, in the context of the general formula (la), it is preferable that i) R9 is unsubstituted or at least monosubstituted phenyl, wherein the substituents are selected from hydroxyl, chlorine, -CF3 and C1-C6-alkyl, ii) R10 is hydrogen or unsubstituted or at least monosubstituted phenyl, wherein the substituents are selected from hydroxyl, chlorine, -CF3 and C1-C6-alkyl, iii) R11 is hydrogen or unsubstituted or at least monosubstituted C1-C12~alkyl, wherein the substituents are selected from hydroxyl, chlorine and -CF3, iv) R6 and R7 are hydrogen, and v) R8 is hydrogen or unsubstituted or at least monosubstituted phenyl or C1-C12~alkyl, wherein the substituents are selected from hydroxyl, chlorine, -CF3 and C1-C6-alkyl.
In the context of the general formula (la), it is even more preferable that
i) R9 and R10 are each phenyl, ii) R11 is hydrogen or C1-C12~alkyl, preferably hydrogen or C1-C5-alkyl, especially hydrogen, iii) R6 and R7 are hydrogen, and iv) R8 is hydrogen or C1-C12~alkyl, preferably hydrogen or C1-C5-alkyl, especially methyl.
The present invention therefore further relates also to a method for preparing a bismuth-containing catalyst of the general formula (I) or of the general formula (la) according to the definitions above. The method according to the invention for preparing such bismuth-containing catalysts can be carried out for example, in which i) at least one compound of the general formula (Ila)
or a corresponding salt thereof, wherein the radicals R6 to R11 are defined according to the embodiments/definitions above ii) optionally at least one compound of the general formula (Illa)
or a corresponding salt thereof, wherein the radical R3 is defined according to the embodiments/definitions above,
iii) is reacted with at least one bismuth-containing compound selected from Bi2O3, bismuth carbonate, bismuth hydrogencarbonate, bismuth halide, Bi (C6-C14-aryl)3, Bi (C1-C12-alkyl)3 or metallic bismuth.
The reactants listed above, i.e. the acids according to the general formulae (Ila) or (Illa) or the appropriate corresponding salts as such, are known to those skilled in the art. The corresponding salts used can be, for example, sodium, potassium or calcium salts. Optionally, instead of the aforementioned acids according to the general formulae (Ila) or (Illa) or corresponding salts thereof as reactants, it is also possible to use corresponding carboxylic esters, for example a methyl or ethyl ester. Such carboxylic esters can be prepared by reacting the aforementioned acids or a corresponding salt thereof with a suitable alcohol, for example methanol or ethanol, optionally in the presence of a catalyst. The appropriate preparation methods of such carboxylic esters are known to a person skilled in the art.
In principle, any bismuth-containing compound can be used in the method according to the invention, which is suitable for the purpose of forming the bismuth central atom in the bismuth-containing catalyst of the general formula (I) according to the invention, by reaction with
the appropriate compound according to the general formula (Ila) or optionally (Illa). Bismuth-containing compounds as such are known to those skilled in the art. If, in accordance with the invention, a bismuth halide is used as bismuth-containing compound, it is preferably a chlorine-containing compound, especially BiCI3. Any specific substituents/substitution patterns, such as the radicals R6 to R11 for example, may already be present in the corresponding reactant. Optionally, such substituents/substitution patterns can also be attached or completed even after the preparation process of a bismuth-containing catalyst according to the general formula (I) described above.
Preferably, the bismuth-containing compound is selected from Bi2O3, BiCis, Bi(C6Hs)3 or metallic bismuth.
The bismuth-containing catalysts according to the general formula (I) according to the invention are preferably prepared by reacting at least one compound of the general formula (Ila) and optionally at least one compound of the general formula (Illa) with at least one bismuth- containing compound, wherein i) the reaction is carried out under a protective atmosphere and/or in the presence of at least one
solvent, especially toluene or tetrahydrofuran, and/or ii) the reaction is conducted for at least 10 hours and/or at a temperature of at least 100°C, and/or iii) following the reaction, volatile constituents are removed, the bismuth-containing catalyst is dried under reduced pressure and/or a recrystallization is carried out.
Furthermore, it is preferred in accordance with the invention that the at least one compound of the general formula (Ila) used as reactant in the method according to the invention is prepared from a corresponding compound according to the general formula (lib), wherein the compounds according to the general formula (Ila) only differ from the corresponding compounds of the general formula (lib) in that one or at most two radicals selected from R9, R10 and R11 is defined as H (hydrogen) in place of the definitions listed for the compounds according to general formula (Ila). This is preferably effected by reacting a corresponding compound (lib), but in which R9, R10 and/or R11 is H, with a lithium-containing compound, especially with n-butyllithium, and the intermediate obtained in this case is subsequently reacted with a haloalkane to introduce the radicals R9, R10 and R11 to
obtain a compound according to the general formula (Ila). Haloalkanes used can be, for example, 1-bromooctane or 1-bromopropane . This method variant is thus used in particular if a catalyst according to the invention in accordance with general formula (I) is intended to be prepared in which at least one of the radicals R9 to R11, preferably precisely one of these radicals, is a C1-C30- alkyl. Alternatively, it is also conceivable that, instead of a haloalkane, an appropriate haloaryl or haloaralkyl compound is used if, in the context of this method step, a fully or partially aromatic substituent is intended to be introduced into the corresponding compound (lIb). Preferably, the compound according to the general formula (lib) used is 2-arylacetic acid, 2,2- diarylacetic acid, particularly 2-phenylacetic acid or 2,2-diphenylacetic acid, particularly preferably 2,2- diphenylacetic acid.
The present invention further relates to the use of at least one bismuth-containing catalyst according to the definitions above for preparing compounds comprising a urethane group.
The invention is illustrated hereinafter by examples.
I) Preparation of catalysts according to the invention
1.1 Synthesis of 2,6-Bis(benzhydryl)-4-methylaniline
Diphenylmethanol (114.79 g, 623.1 mmol), 4-methylaniline (33.25 g, 310.3 mmol) and zinc chloride (21.66 g, 158.9 mmol) are placed together in a 1 L round-bottom flask with a large stir bar. After adding concentrated hydrochloric acid (37.0 %, 35 mL), the flask is equipped with a condenser and the mixture is heated to 150 °C for 2 hours in an oil bath. After cooling to ambient temperature, the product is extracted with dichloromethane (600 mL). Residual acid is neutralized via slow addition of an aqueous potassium carbonate solution (55 g in 400 mL). Layers are separated and the organic layer is washed twice with water. After drying over sodium sulfate, the solution is decanted and volatiles are removed at the rotary evaporator. The crude product is crushed into a fine powder and washed with cold ethyl acetate, leaving a white solid.
1.2 Synthesis of 2,6-bis(benzhydryl)-4-methyl-jodide
In a 2 L two-neck round-bottom flask, equipped with a big stir bar, a dropping funnel and a condenser, 2,6- bis (benzhydryl)-4-methyl-aniline (66.50 g, 151.3 mmol) is dissolved in dichloromethane (500 mL). After cooling to 0 °C, concentrated hydrochloric acid (37.0 %, 90 mL) and glacial acetic acid (99.5 %, 90 mL) are added. Afterwards, an aqueous solution (40 mL) of sodium nitrite (12.00 g, 173.9 mmol) is added dropwise, resulting in a bright red mixture, which is stirred for 30 min. An aqueous solution (400 mL) of potassium iodide (253.00 g,
1524.1 mmol) is subsequently added dropwise, resulting in visible gas formation. The mixture is then warmed to ambient temperature and stirred for another 30 min. Remaining iodine/triiodide is reduced by adding an aqueous solution (500 mL) of sodium sulfite (120.00 g,
952.1 mmol), resulting in a colorless aqueous and orange organic layer. Phases are separated, the aqueous layer is washed twice with dichloromethane and the organic layer is washed with water to pH neutrality. Organic
phases are combined, dried over magnesiumsulfate and decanted. Volatiles are removed at the rotary evaporator and the product is crystallized from a mixture of toluene and n-pentane (3:2).
1.3 Synthesis of Lithium-2,6-dibenzhydryl-4-methyl- benzoate (precursor)
2,6-bis (benzhydryl)-4-methyl-phenyliodide (1.76 g, 3.20 mmol, 1.00 eq.) was dissolved in 50 mL Tetrahydrofurane in a Schlenk tube and cooled to -78 °C. Then a 1.6 M solution of n-butyllithium in hexane (2 mL, 3.20 mmol, 1.0 eq.) was slowly added and the resulting red solution was stirred for 1 h at this temperature. Subsequently, carbon dioxide was passed through the reaction solution with a Teflon tube for 15 min and then stirred for 1 h at room temperature. The product was precipitated with 100 mL n-pentane, then filtered and washed with n- pentane. The resulting material was air dried and obtained as a white solid.
1.4 Synthesis of 2,6-Bis (benzhydryl)-4-methyl- benzoate ("dbhmb"/precursor)
To a suspension of Lithium-2,6-dibenzhydryl-4- methylbenzoate (0.76 g, 1.60 mmol, 1.00 eq.) in 60 mL Et2O, a 1 M aqueous solution of hydrochloric acid (1.60
mL, 1.60 mmol, 1.00 eq.) was added at room temperature and stirred for 30 min. The reaction solution was transferred to a separating funnel and washed with water (3 x 10 mL). The organic phase was then separated, then dried and filtered with MgSO4. The solvent was removed under vacuum and the product 2b was obtained as white solid.
1.5 Synthesis of the respective Bi-Salt
In a Schlenk tube 0.75 mmol, 3.00 eq.of the precursor (of step 1.4) and BiPhs (110 mg, 0.25 mmol, 1.00 eq.) was heated in 5 ml acetonitrile to 110 °C for 16 h. In each case a crystalline solid was obtained after slowly cooling the solution. The crystalline compound was washed with diethyl ether (3x5 mL) and dried in vacuum at 80°C to give bismuth salts as white solid.
II) Preparation of comparative examples
Ila) Precursor of comparative example 3:
2,2-Diphenylacetic acid (10.6 g; 48 mmol) are dissolved in 75 ml of dry tetrahydrofuran (THF) under a protective gas atmosphere (argon or nitrogen) in a 200 ml Schlenk flask and cooled to -15°C. A 1.6M solution of n- butyllithium in hexane (60 ml; 96 mmol) is then added with stirring and over a period of 30 minutes. The reaction solution is stirred at -15°C for one hour and cooled to -78°C for the addition of 1-bromooctane (8.3 ml; 48 mmol). Subsequently, the reaction solution is slowly warmed to room temperature and stirred for a further 24 hours.
For the work-up and purification of the 2,2- diphenyldecanoic acid, a saturated ammonium chloride solution (60 mL) is added to the reaction solution and stirred for 30 minutes. The aqueous phase is separated by means of a separating funnel and extracted with 3 x 25 mL of diethyl ether. The combined organic phases were
dried over magnesium sulfate (MgSO4)• All volatile solvents are then removed under reduced pressure (1 • 10" 3 mbar) and the resulting solid dried at 140°C under reduced pressure (1 • 103 mbar) for 24 hours.
Characterization by ^-H-NMR, 13C-NMR, HRMS (high- resolution mass spectrometry), infra-red spectroscopy. lib) Catalyst according to comparative example 3: Bi(2,2- diphenyldecanoate)3 (Bi(dpd)3)
Triphenylbismuth (1.1 g; 2.5 mmol) and 2,2- diphenyldecanoic acid (2.43 g; 7.5 mmol) are initially charged under a protective gas atmosphere in a 25 mL three-necked flask equipped with stirrer bar, reflux condenser, thermometer and protective gas atmosphere inlet (argon or nitrogen). 12.5 mL of dry tetrahydrofuran or dry toluene (5 mL of solvent per 1 mmol of triphenylbismuth) are added to the reactants and the mixture is heated at 110°C under a protective gas atmosphere for at least 16 hours. The reaction course is monitored by ^-H-NMR (nuclear magnetic resonance spectroscopy) . After complete conversion of triphenylbismuth with formation of benzene, the reaction is terminated and cooled. All volatile solvents are then removed under reduced pressure (1 • 103 mbar) and the resulting solid dried at 60°C under reduced pressure (1
103 mbar) for 24 hours. As required, the resulting compound is purified from toluene and hexane at -40 °C or by recrystallization from hot toluene.
Characterization by ^-H-NMR, 13C-NMR, C/H/N elemental analysis, infra-red spectroscopy. lie) Catalyst according to comparative example 4: Bi(2,2- diphenylpropionate)3 (Bi(dpp)3)
The catalyst Bi (dpp)3 according to comparative example 4 is prepared analogously to the comparative catalyst Bi(dpd)s described above, in which no synthesis of the precursor is required since the corresponding propionic acid derivative is commercially available (from Sigma- Aldrich), which is reacted with triphenylbismuth to give the comparative catalyst Bi (dpp)3.
The respective catalytic activity of the individual working and comparative examples can be found in Table 1 below. The catalytic activity is tested by means of a
reaction in which a compound is formed comprising a urethane group. For this purpose, 11 mmol of 2-ethylhexyl (6-isocyanatohexyl)carbamate (commercially available as Desmodur LD (3.3 mL)) are reacted with 11 mmol of n- butanol (1 mL) as reactants. The reaction was carried out in the presence of a solvent (2 mL of xylene) and the catalysts listed in Table 1 (with a content of 0.05 mol% catalyst based on the amount of bismuth) at a temperature of 21°C.
The isocyanate decrease and thus the formation of a urethane group are investigated by horizontal ATR-IR spectroscopy. For this purpose, 0.05 mL of the reaction solution are withdrawn at defined time intervals and investigated directly by spectroscopy. The conversion is determined by the relative decrease in intensity of the asymmetrical isocyanate stretching vibration at 2250 - 2285 cm 1 . The starting content of free isocyanate of the reaction solution at room temperature in the absence of catalyst was determined. All IR spectra were normalized to the bands of the symmetrical and asymmetrical stretching vibrations of the CH2 groups (3000 - 2870 cm 1).
The catalysts used are detailed in Table 1.
Example 1: Bi(dbhmb)3, wherein dbhmb is 2,6-
Bis(benzhydryl)-4-methyl-benzoate
Comparative example 2: DBTL (Dibutyltin dilaurate), commercially available catalyst
Comparative example 3: Bi(dpd)3, wherein dpd is 2,2'- diphenyl decanoate Comparative example 4: Bi(dpp)s, wherein dpp is 2,2'- diphenyl propionate
Comparative example 5: without catalyst
H PJ cr
CD
■u
As can be deduced from Table 1, the catalyst according to the invention (working example 1) shows a better catalytic activity to the known tin-containing catalysts according to comparative example 2. Tin-containing catalysts should be avoided however, owing to their considerable toxicity. The catalytic activity of working example 1 is however distinctly improved in comparison to bismuth-containing catalysts according to the prior art (comparative examples 3 and 4) or conducting the experiment wholly without catalyst (comparative example 5).
Claims
1. A bismuth-containing catalyst of the general formula (I)
in which the variables are defined as follows:
R2 is mutually independently a residue of the general formula (III)
and y is 0, 1 or 2;
X is mutually independently hydroxyl, halogen, carbonate, hydrogencarbonate or R12 and z is 0, 1 or 2; wherein the sum total of x, y and z is equal to 3;
R3 is unsubstituted or at least monosubstituted C1-C30-alkyl, C6-C14-aryl or C7-C30-aralkyl, wherein the substituents are selected from hydroxyl, halogen, carboxyl, -CF3, -NH2, C1-C6-alkoxy, C1-C30- alkyl or C6-C14~aryl and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by hydroxyl, halogen, -CF3, -NH2 or C1- C6-alkoxy, under the proviso that in case R3 is unsubstituted or at least monosubstituted C1-C30-alkyl or C7-C30-aralkyl, the carbon atom of the residue R3 bonded directly to carbon atom of the carboxyl group of the general formula (III) does not comprise any unsubstituted or at least monosubstituted C6-C14-aryl as substituent,
(IV)
R6, R7 and R8 are mutually independently hydrogen or unsubstituted or at least monosubstituted C1-C30-alkyl, C6- C14~aryl or C7-C30-aralkyl, wherein the substituents are selected from hydroxyl, halogen, carboxyl, -CF3, -NH2, C1-C6-alkoxy, C1-C30- alkyl or C6-C14~aryl and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by hydroxyl, halogen, -CF3, -NH2 or C1- Cg-alkoxy,
R9, R10 and R11 are mutually independently hydrogen or unsubstituted or at least monosubstituted C1-C30-alkyl, C6- C14~aryl or C7-C30-aralkyl, wherein the substituents are selected from hydroxyl, halogen, carboxyl, -CF3, -NH2, C1-C6-alkoxy, C1-C30- alkyl or C6-C14~aryl and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by hydroxyl, halogen, -CF3, -NH2 or Ci- Cg-alkoxy,
and wherein at least one of the residues R9, R10 or R11 is unsubstituted or at least monosubstituted C6-C14- aryl,
R12 is unsubstituted or at least monosubstituted C1-C30- alkyl, C6-C14-aryl or C7-C30-aralkyl, wherein the substituents are selected from hydroxyl, halogen, carboxyl, -CF3, -NH2, C1-C6-alkoxy, C1-C30- alkyl or C6-C14~aryl and the alkyl and aryl fragments of these substituents may in turn be at least monosubstituted by hydroxyl, halogen, -CF3, -NH2 or C1- C6-alkoxy. The bismuth-containing catalyst as claimed in claim 1, wherein i) R9, R10 and R11 are mutually independently hydrogen or unsubstituted or at least monosubstituted C1-C12-alkyl or C6-C14-aryl, wherein the substituents are selected from hydroxyl, chlorine, -CF3 and C1-C6-alkyl, and wherein at least one of the residues R9, R10 or R11 is unsubstituted or at least monosubstituted C6-C14- aryl, and/or ii) R6, R7 and R8 are mutually independently hydrogen or unsubstituted or at least monosubstituted C1-C12-alkyl
or C6-C14-aryl, wherein the substituents are selected from hydroxyl, chlorine, -CF3 and C1-C6-alkyl, and/or iii) R3 is unsubstituted or at least monosubstituted C1-C12- alkyl, wherein the substituents are selected from hydroxyl, chlorine or -CF3, and/or iv) X is hydroxyl, chlorine or R12 and R12 is unsubstituted or at least monosubstituted C1-C12-alkyl or C6-C14-aryl, wherein the substituents are selected from hydroxyl, chlorine, -CF3 and C1-C6-alkyl. The bismuth-containing catalyst as claimed in claim 1 or 2, wherein i) x is equal to 2 or 3, y is equal to 0 or 1 and z is equal to 0 or 1, or ii) x is equal to 3 and y and z are each equal to 0, or iii) x is equal to 2, y is equal to 0 and z is equal to 1, or iv) x is equal to 2, y is equal to 1 and z is equal to 0, wherein preferably x is equal to 3 and y and z are each equal to 0.
The bismuth-containing catalyst as claimed in any of claims 1 to 3, wherein i) the residues R4 and R5 have the same definition, ii) R9 is unsubstituted or at least monosubstituted phenyl, wherein the substituents are selected from hydroxyl, chlorine, -CF3 and C1-C6-alkyl, iii) R10 is hydrogen or unsubstituted or at least monosubstituted phenyl or C1-C12~alkyl, wherein the substituents are selected from hydroxyl, chlorine, -CF3 and C1-C6-alkyl, iv) R11 is hydrogen or unsubstituted or at least monosubstituted phenyl or C1-C12~alkyl, wherein the substituents are selected from hydroxyl, chlorine, -CF3 and C1-C6-alkyl, v) R6 is hydrogen or unsubstituted or at least monosubstituted C1-C12~alkyl, wherein the substituents are selected from hydroxyl, chlorine and -CF3, vi) R7 is hydrogen or unsubstituted or at least monosubstituted C1-C12~alkyl, wherein the substituents are selected from hydroxyl, chlorine, -CF3 and C1-C6- alkyl, and
vii) R8 is hydrogen or unsubstituted or at least monosubstituted phenyl or C1-C12-alkyl, wherein the substituents are selected from hydroxyl, chlorine, -CF3 and C1-C6-alkyl. The bismuth-containing catalyst as claimed in any of claims 1 to 4, wherein i) the residues R4 and R5 have the same definition, ii) R9 is unsubstituted or at least monosubstituted phenyl, wherein the substituents are selected from hydroxyl, chlorine, -CF3 and C1-C6-alkyl, iii) R10 is hydrogen or unsubstituted or at least monosubstituted phenyl, wherein the substituents are selected from hydroxyl, chlorine, -CF3 and C1-C6-alkyl, iv) R11 is hydrogen or unsubstituted or at least monosubstituted C1-C12~alkyl, wherein the substituents are selected from hydroxyl, chlorine and -CF3, v) R6 and R7 are hydrogen, vi) R8 is hydrogen or unsubstituted or at least monosubstituted phenyl or C1-C12-alkyl, wherein the substituents are selected from hydroxyl, chlorine, -CF3 and C1-C6-alkyl, and
vii) x is equal to 3 and y and z are each equal to 0. The bismuth-containing catalyst as claimed in any of claims 1 to 5, wherein i) the residues R4 and R5 have the same definition, ii) R9 and R10 are each phenyl, iii) R11 is hydrogen or C1-C12~alkyl, preferably hydrogen or C1-C5-alkyl, especially hydrogen, iv) R6 and R7 are hydrogen, v) R8 is hydrogen or C1-C12~alkyl, preferably hydrogen or C1-C5-alkyl, especially methyl, and vi) x is equal to 3 and y and z are each equal to 0. The bismuth-containing catalyst as claimed in any of claims
1 to 6, wherein the bismuth-containing catalyst is defined according to the general formula (la)
wherein the residues R6 to R11 are mutually independently defined as claimed in any of claims 1 to 6. The bismuth-containing catalyst as claimed in claim 7, wherein each of the total of three residues R6 are the same, each of the total of three residues R7 are the same, each of the total of three residues R8 are the same, each of the total of three residues R9 is the same, each of the total of three residues R10 is the same and each of the total of three residues R11 is the same. The bismuth-containing catalyst as claimed in claim 7 or 8, wherein i) R9 is unsubstituted or at least monosubstituted phenyl, wherein the substituents are selected from hydroxyl, chlorine, -CF3 and C1-C6-alkyl,
ii) R10 is hydrogen or unsubstituted or at least monosubstituted phenyl, wherein the substituents are selected from hydroxyl, chlorine, -CF3 and C1-C6-alkyl, iii) R11 is hydrogen or unsubstituted or at least monosubstituted C1-C12-alkyl, wherein the substituents are selected from hydroxyl, chlorine and -CF3, iv) R6 and R7 are hydrogen, and v) R8 is hydrogen or unsubstituted or at least monosubstituted phenyl or C1-C12~alkyl, wherein the substituents are selected from hydroxyl, chlorine, -CF3 and C1-C6-alkyl. The bismuth-containing catalyst as claimed in any of claims 7 to 9, wherein i) R9 and R10 are each phenyl, ii) R11 is hydrogen or C1-C12~alkyl, preferably hydrogen or C1-C5-alkyl, especially hydrogen, iii) R6 and R7 are hydrogen, and iv) R8 is hydrogen or C1-C12~alkyl, preferably hydrogen or C1-C5-alkyl, especially methyl.
A method for preparing a bismuth-containing catalyst of the general formula (I) as claimed in any of claims 1 to 10, wherein i) at least one compound of the general formula (Ila)
or a corresponding salt thereof, wherein the residues R6 to R11 are defined as claimed in any of claims 1 to 10, ii) optionally at least one compound of the general formula
(Illa)
or a corresponding salt thereof
wherein the residue R3 is defined as claimed in any of claims 1 to 10, iii) is reacted with at least one bismuth-containing compound selected from Bi2O3, bismuth carbonate, bismuth hydrogencarbonate, bismuth halide, Bi (C6-C14- aryl)3, Bi (C1-C12-alkyl)3 or metallic bismuth. The method as claimed in claim 10, wherein the bismuth- containing compound is selected from BI2O3, BiCI3, Bi(C6H5)3 or metallic bismuth. The method as claimed in claim 11 or 12, wherein i) the reaction is carried out under a protective atmosphere and/or in the presence of at least one solvent, especially toluene or tetrahydrofuran, and/or ii) the reaction is conducted for at least 10 hours and/or at a temperature of at least 100°C, and/or iii) following the reaction, volatile constituents are removed, the bismuth-containing catalyst is dried under reduced pressure and/or a recrystallization is carried out.
The method as claimed in any of claims 11 to 13, wherein a compound of the general formula (Ila) is prepared by reacting a corresponding compound (lib), but in which at least one of the two fragments consisting of the carbon atom and the residues R9, R10 and R11 are replaced by H, with a lithium-containing compound, especially with n- butyllithium, and the intermediate obtained in this case is subsequently reacted with a haloalkane to introduce the corresponding fragment consisting of the carbon atom and the residues R9, R10 and R11 to obtain a compound according to the general formula (Ila). The use of at least one bismuth-containing catalyst as claimed in any of claims 1 to 10 for preparing compounds comprising a urethane group.
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