CN114341114B - 1, 3-dipolar compounds comprising aromatic heterocyclic and imidazole rings - Google Patents
1, 3-dipolar compounds comprising aromatic heterocyclic and imidazole rings Download PDFInfo
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- CN114341114B CN114341114B CN202080042210.0A CN202080042210A CN114341114B CN 114341114 B CN114341114 B CN 114341114B CN 202080042210 A CN202080042210 A CN 202080042210A CN 114341114 B CN114341114 B CN 114341114B
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 142
- 125000002883 imidazolyl group Chemical group 0.000 title claims abstract description 32
- 125000006615 aromatic heterocyclic group Chemical group 0.000 title description 2
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 68
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 57
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 51
- 125000003118 aryl group Chemical group 0.000 claims abstract description 46
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 39
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 18
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 16
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 16
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 28
- 238000003786 synthesis reaction Methods 0.000 claims description 18
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 7
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 125000004434 sulfur atom Chemical group 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Chemical group 0.000 claims description 4
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 abstract description 20
- 125000001072 heteroaryl group Chemical group 0.000 abstract description 18
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 2
- 229920006395 saturated elastomer Polymers 0.000 description 53
- -1 thiophene-diyl Chemical group 0.000 description 48
- 239000000203 mixture Substances 0.000 description 21
- 238000005481 NMR spectroscopy Methods 0.000 description 16
- 229920001971 elastomer Polymers 0.000 description 16
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 125000004429 atom Chemical group 0.000 description 11
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 description 11
- 239000012429 reaction media Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 229920003048 styrene butadiene rubber Polymers 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000000806 elastomer Substances 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000005060 rubber Substances 0.000 description 8
- 229930091371 Fructose Natural products 0.000 description 7
- 239000005715 Fructose Substances 0.000 description 7
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- CKRZKMFTZCFYGB-UHFFFAOYSA-N N-phenylhydroxylamine Chemical compound ONC1=CC=CC=C1 CKRZKMFTZCFYGB-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 229920003244 diene elastomer Polymers 0.000 description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 6
- 125000001634 furandiyl group Chemical group O1C(=C(C=C1)*)* 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 5
- 239000002174 Styrene-butadiene Substances 0.000 description 5
- 239000012190 activator Substances 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 239000008103 glucose Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000006467 substitution reaction Methods 0.000 description 5
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 230000014509 gene expression Effects 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 238000001542 size-exclusion chromatography Methods 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 3
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- QNRMTGGDHLBXQZ-UHFFFAOYSA-N buta-1,2-diene Chemical group CC=C=C QNRMTGGDHLBXQZ-UHFFFAOYSA-N 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- SATDLKYRVXFXRE-UHFFFAOYSA-N methyl 4-(chloromethyl)benzoate Chemical compound COC(=O)C1=CC=C(CCl)C=C1 SATDLKYRVXFXRE-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- XOJVVFBFDXDTEG-UHFFFAOYSA-N pristane Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 description 3
- 239000012763 reinforcing filler Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- 125000003161 (C1-C6) alkylene group Chemical group 0.000 description 2
- UDVZQBOKCFSBEU-UHFFFAOYSA-N 1-[4-[(2-methylimidazol-1-yl)methyl]phenyl]-N-phenylmethanimine oxide Chemical compound CC1=NC=CN1CC1=CC=C(C=[N+](C2=CC=CC=C2)[O-])C=C1 UDVZQBOKCFSBEU-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- KAZRCBVXUOCTIO-UHFFFAOYSA-N 5-(chloromethyl)furan-2-carbaldehyde Chemical compound ClCC1=CC=C(C=O)O1 KAZRCBVXUOCTIO-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 101000801643 Homo sapiens Retinal-specific phospholipid-transporting ATPase ABCA4 Proteins 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 102100033617 Retinal-specific phospholipid-transporting ATPase ABCA4 Human genes 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 230000000035 biogenic effect Effects 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000006352 cycloaddition reaction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 229940043279 diisopropylamine Drugs 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- SQDFHQJTAWCFIB-UHFFFAOYSA-N n-methylidenehydroxylamine Chemical compound ON=C SQDFHQJTAWCFIB-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 150000007855 nitrilimines Chemical class 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 238000001208 nuclear magnetic resonance pulse sequence Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011002 quantification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000002827 triflate group Chemical group FC(S(=O)(=O)O*)(F)F 0.000 description 2
- 238000012584 2D NMR experiment Methods 0.000 description 1
- UYVCCHAKRASOGU-UHFFFAOYSA-N 5-[(2-methylimidazol-1-yl)methyl]furan-2-carbaldehyde Chemical compound Cc1nccn1Cc1ccc(C=O)o1 UYVCCHAKRASOGU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- 229910010082 LiAlH Inorganic materials 0.000 description 1
- 239000012359 Methanesulfonyl chloride Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000011000 absolute method Methods 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 125000005997 bromomethyl group Chemical group 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011208 chromatographic data Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000011903 deuterated solvents Substances 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012039 electrophile Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 1
- 238000003919 heteronuclear multiple bond coherence Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 1
- 125000006574 non-aromatic ring group Chemical group 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/61—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with hydrocarbon radicals, substituted by nitrogen atoms not forming part of a nitro radical, attached to ring nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/22—Incorporating nitrogen atoms into the molecule
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The present invention relates to 1, 3-dipolar compounds comprising a heterocyclic ring. The present invention relates to compounds of formula (I) for functionalizing a polymer by grafting, and to a process for preparing the compounds of formula (I), wherein: -Q represents a dipole comprising at least one nitrogen atom; -a represents a divalent heteroaromatic ring optionally substituted with one or more hydrocarbon chains, which may be the same or different, may be aliphatic, linear or branched, optionally substituted or interrupted with one or more heteroatoms; -E represents a divalent hydrocarbon linking group, which may optionally contain one or more heteroatoms; -R 1 Represents a hydrogen atom or C 1 ‑C 20 An alkyl group; y and Z, which may be the same or different, each represent a hydrogen atom or a hydrocarbon chain, Y and Z being also able to form, together with the carbon atom of the imidazole ring to which they are attached, a ring, in particular an aromatic ring.
Description
Technical Field
The present invention relates to 1, 3-dipole compounds comprising heteroaromatic rings, said 1, 3-dipole compounds being capable of grafting onto polymers. The invention also relates to a method for producing these compounds.
Background
When it is desired to combine the polymer with the filler in the composition, it is particularly sought to modify the structure of the polymer, for example to functionalize the polymer by grafting. Such changes may enable, for example, improved dispersion of the filler in the polymer matrix, resulting in a more uniform material and ultimately improved properties of the composition.
In the case of certain fillers, such as reinforcing fillers (e.g., carbon black or silica), better dispersion of the filler is generally reflected by a reduction in the hysteresis of the composition. This property is sought in particular in rubber compositions intended for use in, for example, tire applications. Specifically, reducing the hysteresis of the rubber composition is advantageous in reducing the rolling resistance of the tire, thereby reducing the fuel consumption of a vehicle traveling with such a tire.
Now, it is known that the decrease in hysteresis is generally accompanied by a decrease in rigidity of the rubber composition in the cured state, which may make the composition unsuitable for the intended use in some cases.
Accordingly, it is desirable to have a compound that, after reaction with the polymer, can promote the dispersion of the reinforcing filler without causing excessive reduction in the rigidity of the rubber composition in the cured state.
Compounds of formula Q-a-B are known from WO 2015/059269 A1, wherein group Q comprises a dipole containing at least one nitrogen atom, a is a divalent group (which may or may not be aromatic) and B is an imidazole ring. When an elastomer grafted with such a compound is mixed with a reinforcing filler in a rubber composition, the rubber composition has an improved compromise between stiffness and hysteresis in the cured state relative to a rubber composition that does not contain the grafted elastomer. These compounds are therefore particularly advantageous.
The applicant continues his research and seeks to improve 1, 3-dipole compounds with imidazole rings.
After multiple tests, the applicant has found that a series of specific 1, 3-dipole compounds have improved grafting compared to prior art 1, 3-dipole compounds comprising an aromatic or non-aromatic ring and an imidazole ring.
Disclosure of Invention
Accordingly, one subject of the present invention is a compound of formula (I)
Wherein:
-Q represents a dipole comprising at least one nitrogen atom;
-a represents a divalent heteroaromatic ring optionally substituted by one or more identical or different aliphatic hydrocarbon chains, preferably saturated, linear or branched, optionally substituted or interrupted by one or more heteroatoms;
-E represents a divalent hydrocarbon-based binding group, which may optionally contain one or more heteroatoms;
r1 represents a hydrogen atom or C 1 -C 20 An alkyl group; and
y and Z, which may be identical or different, each represent a hydrogen atom or a hydrocarbon chain, Y and Z possibly also forming a ring, in particular an aromatic ring, together with the carbon atoms of the imidazole ring to which they are attached.
Preferably, the compound of formula (I) is selected from the group consisting of compounds of formula (IIa)
Wherein:
-a represents a divalent heteroaromatic ring optionally substituted by one or more identical or different aliphatic hydrocarbon chains, preferably saturated, linear or branched, optionally substituted or interrupted by one or more heteroatoms;
-E represents a divalent hydrocarbon-based binding group, which may optionally contain one or more heteroatoms;
-R 1 represents a hydrogen atom or C 1 -C 20 An alkyl group;
y and Z, which may be the same or different, each represent a hydrogen atom or a hydrocarbon chain, Y and Z possibly also forming a ring, in particular an aromatic ring, together with the carbon atoms of the imidazole ring to which they are attached;
-R 2 selected from hydrogen atoms, linear or branched C 1 -C 20 Alkyl, optionally covered byOne or more preferably saturated, linear or branched aliphatic hydrocarbon chain-substituted C 3 -C 20 Cycloalkyl, and C optionally substituted with one or more preferably saturated, linear or branched aliphatic hydrocarbon chains 6 -C 20 An aryl group; and
-R 3 selected from linear or branched C 1 -C 20 Alkyl, C optionally substituted by one or more, preferably saturated, linear or branched, aliphatic hydrocarbon chains 3 -C 20 Cycloalkyl, and C optionally substituted with one or more preferably saturated, linear or branched aliphatic hydrocarbon chains 6 -C 20 Aryl groups.
Another subject of the invention is a process for the synthesis of a compound of formula (IIa) as defined above, comprising at least one reaction of a compound of formula (III) with a compound of formula (IV) according to the following reaction scheme
Wherein in formulae (IIa), (III) and (IV):
-a represents a divalent heteroaromatic ring optionally substituted by one or more identical or different aliphatic hydrocarbon chains, preferably saturated, linear or branched, optionally substituted or interrupted by one or more heteroatoms;
-E represents a divalent hydrocarbon-based binding group, which may optionally contain one or more heteroatoms;
-R 1 represents a hydrogen atom or C 1 -C 20 An alkyl group;
y and Z, which may be the same or different, each represent a hydrogen atom or a hydrocarbon chain, Y and Z possibly also forming a ring, in particular an aromatic ring, together with the carbon atoms of the imidazole ring to which they are attached;
-R 2 selected from hydrogen atoms, linear or branched C 1 -C 20 Alkyl, C optionally substituted by one or more, preferably saturated, linear or branched, aliphatic hydrocarbon chains 3 -C 20 Cycloalkyl, and optionally one orA plurality of C, preferably saturated, linear or branched, aliphatic hydrocarbon chain-substituted 6 -C 20 An aryl group; and
-R 3 selected from linear or branched C 1 -C 20 Alkyl, C optionally substituted by one or more, preferably saturated, linear or branched, aliphatic hydrocarbon chains 3 -C 20 Cycloalkyl, and C optionally substituted with one or more preferably saturated, linear or branched aliphatic hydrocarbon chains 6 -C 20 Aryl groups.
In this document, all percentages (%) shown are mass percentages (%), unless otherwise indicated.
Furthermore, any numerical interval expressed by the expression "between a and b" means a numerical range from greater than a to less than b (i.e., limits a and b are not included), while any numerical interval expressed by the expression "a to b" means a numerical range from a up to b (i.e., strict limits a and b are included). In this context, when a numerical interval is represented by the expressions "a to b", it is also preferable to represent an interval represented by the expression "between a and b".
The term "heteroatom" means an atom selected from the group consisting of a sulfur atom, an oxygen atom and a nitrogen atom, unless otherwise specified.
The carbon-containing compounds mentioned in the description may be of fossil origin or bio-based compounds. In the case of biobased compounds, they may be derived partially or fully from biomass, or from renewable raw materials derived from biomass. Of particular interest are polymers, plasticizers, fillers, and the like.
The invention and its advantages will be readily understood from the following description and examples.
Detailed Description
As previously mentioned, one subject of the invention is therefore a compound of formula (I)
Wherein:
-Q represents a dipole comprising at least one nitrogen atom;
-a represents a divalent heteroaromatic ring optionally substituted by one or more identical or different aliphatic hydrocarbon chains, preferably saturated, linear or branched, optionally substituted or interrupted by one or more heteroatoms;
-E represents a divalent hydrocarbon-based binding group, which may optionally contain one or more heteroatoms;
-R 1 represents a hydrogen atom or C 1 -C 20 An alkyl group; and
y and Z, which may be identical or different, each represent a hydrogen atom or a hydrocarbon chain, Y and Z possibly also forming a ring, in particular an aromatic ring, together with the carbon atoms of the imidazole ring to which they are attached.
According to formula (I), the compounds according to the invention comprise a group Q representing a dipole comprising at least one nitrogen atom.
For the purposes of the present invention, the term "dipole" means a function capable of forming a 1, 3-dipole addition on an unsaturated carbon-carbon bond.
Preferably, the dipoles comprising at least one nitrogen atom are selected from the group consisting of nitrile oxides, nitrones and nitrilimines.
For the purposes of the present invention, the term "nitrile oxide" means a dipole corresponding to the formula c≡n→o, including its meso form.
For the purposes of the present invention, the term "nitrilimine" means a dipole corresponding to the formula c≡n→n, including its meso form.
For the purposes of the present invention, the term "nitrone" means a dipole corresponding to the formula c=n (→o), including its meso form.
More preferably, Q is a group of formula (II), (III) or (IV)
Wherein:
-symbol x represents the attachment of Q to a;
-R 2 and R is 4 Independently of one another, from hydrogen atoms, linear or branchedC 1 -C 20 Alkyl, C optionally substituted by one or more, preferably saturated, linear or branched, aliphatic hydrocarbon chains 3 -C 20 Cycloalkyl, and C optionally substituted with one or more preferably saturated, linear or branched aliphatic hydrocarbon chains 6 -C 20 An aryl group;
-R 3 Selected from linear or branched C 1 -C 20 Alkyl, C optionally substituted by one or more, preferably saturated, linear or branched, aliphatic hydrocarbon chains 3 -C 20 Cycloalkyl, and C optionally substituted with one or more preferably saturated, linear or branched aliphatic hydrocarbon chains 6 -C 20 Aryl groups.
Preferably, R 2 And R is 4 Independently of one another, from hydrogen atoms, linear or branched C 1 -C 20 Alkyl, optionally with one or more linear or branched C 1 -C 6 C of alkyl groups 3 -C 30 Cycloalkyl, optionally C-substituted by one or more linear or branched groups 1 -C 6 Alkyl substituted C 6 -C 20 Aryl and R 3 Selected from linear or branched C 1 -C 20 Alkyl, optionally C-substituted by one or more linear or branched groups 1 -C 6 Alkyl substituted C 3 -C 20 Cycloalkyl, and optionally C, which is linear or branched, one or more 1 -C 6 Alkyl substituted C 6 -C 20 Aryl groups.
Preferably, the compound of formula (I) is selected from the group consisting of compounds of formula (IIa)
Wherein:
-a represents a divalent heteroaromatic ring optionally substituted by one or more identical or different aliphatic hydrocarbon chains, preferably saturated, linear or branched, optionally substituted or interrupted by one or more heteroatoms;
-E represents a divalent hydrocarbon-based binding group, which may optionally contain one or more heteroatoms;
-R 1 represents a hydrogen atom or C 1 -C 20 An alkyl group;
Y and Z, which may be the same or different, each represent a hydrogen atom or a hydrocarbon chain, Y and Z possibly also forming a ring, in particular an aromatic ring, together with the carbon atoms of the imidazole ring to which they are attached;
-R 2 selected from hydrogen atoms, linear or branched C 1 -C 20 Alkyl, C optionally substituted by one or more, preferably saturated, linear or branched, aliphatic hydrocarbon chains 3 -C 20 Cycloalkyl, and C optionally substituted with one or more preferably saturated, linear or branched aliphatic hydrocarbon chains 6 -C 20 An aryl group; and
-R 3 selected from linear or branched C 1 -C 20 Alkyl, C optionally substituted by one or more, preferably saturated, linear or branched, aliphatic hydrocarbon chains 3 -C 20 Cycloalkyl, and C optionally substituted with one or more preferably saturated, linear or branched aliphatic hydrocarbon chains 6 -C 20 Aryl groups.
The compounds of formulae (I) and (IIa) according to the invention comprise a group a which represents a divalent heteroaromatic ring which is optionally substituted by one or more identical or different aliphatic hydrocarbon chains, preferably saturated, linear or branched, optionally substituted or interrupted by one or more heteroatoms.
The term "divalent heteroaromatic ring" means an aromatic ring system comprising one or more heteroatoms selected from nitrogen atoms, sulfur atoms, and oxygen atoms. The system may be monocyclic or bicyclic and may be formed from 5 to 10 atoms. Preferably, the system is monocyclic and is formed from 5 to 6 atoms. The system may optionally be substituted with one or more identical or different aliphatic hydrocarbon chains, preferably saturated, linear or branched, optionally substituted or interrupted with one or more heteroatoms (e.g. O, N and S);
Preferably, when the divalent heteroaromatic ring is substituted or interrupted by one or more identical or different linear or branched aliphatic hydrocarbon chains (optionally substituted or interrupted by one or more heteroatomsBreak) substitution, the chain or chains are preferably substituted with respect to R bearing substituents 1 The imidazole rings of X and Y are inert with respect to the group Q.
For the purposes of the present invention, the term "relative to R bearing a substituent 1 The imidazole rings of X and Y, and the hydrocarbon chain inert with respect to the group Q "means a hydrocarbon chain that does not react with the imidazole heterocycle or the group Q. Thus, the hydrocarbon chain which is inert with respect to the heterocycle and with respect to the group is, for example, a hydrocarbon chain which does not carry any alkenyl or alkynyl function capable of reacting with the ring or the group. Preferably, these linear or branched aliphatic hydrocarbon chains comprise from 1 to 24 carbon atoms and are saturated.
Preferably, A is a divalent heteroaromatic ring formed from 5 to 10 atoms, preferably 5 to 6 atoms, optionally interrupted by one or more identical or different linear or branched aliphatic C 1 -C 24 Hydrocarbon chain substitution, the aliphatic C 1 -C 24 The hydrocarbon chain is optionally substituted or interrupted with one or more heteroatoms.
Even more preferably, in the compounds of formulae (I) and (IIa), a is a divalent heteroaromatic ring formed from 5 to 10 atoms, preferably from 5 to 6 atoms, optionally substituted with one or more substituents selected from: linear or branched C 1 -C 12 (more preferably C 1 -C 6 Even more preferably C 1 -C 4 ) Alkyl, group-OR ', group-NHR', group-SR ', wherein R' is C 1 -C 12 Preferably C 1 -C 6 Even more preferably C 1 -C 4 An alkyl group.
More preferably, in the compounds of formulae (I) and (IIa), A is selected from furan-diyl, thiophene-diyl, pyrrole-diyl, thiazole-diyl, imidazole-diyl, pyridine-diyl, pyrazine-diyl, pyrimidine-diyl, indole-diyl, benzofuran-diyl, isoindole-diyl, isobenzofuran-diyl and benzothiophene-diyl; these rings are optionally substituted with one or more identical or different aliphatic hydrocarbon chains, preferably saturated, optionally substituted or interrupted with one or more heteroatoms (e.g. O, N and S); more preferably, the rings may beOne or more C 1 -C 6 Alkyl substitution. Even more preferably, these rings are unsubstituted.
More preferably, in the compounds of formulae (I) and (IIa), A is selected from furan-diyl, thiophene-diyl and pyrrole-diyl, even more preferably furan-diyl.
Among the compounds of formula (IIa), particular preference is given to those of formula (IIb):
wherein:
-X represents a heteroatom selected from sulfur, oxygen and nitrogen atoms; preferably, X is an oxygen atom;
-E represents a divalent hydrocarbon-based binding group, which may optionally contain one or more heteroatoms;
-R 1 represents a hydrogen atom or C 1 -C 20 An alkyl group;
y and Z, which may be the same or different, each represent a hydrogen atom or a hydrocarbon group, Y and Z possibly forming a ring, in particular an aromatic ring, together with the carbon atoms of the imidazole ring to which they are attached;
-R 2 selected from hydrogen atoms, linear or branched C 1 -C 20 Alkyl, C optionally substituted by one or more, preferably saturated, linear or branched, aliphatic hydrocarbon chains 3 -C 20 Cycloalkyl, and C optionally substituted with one or more preferably saturated, linear or branched aliphatic hydrocarbon chains 6 -C 20 An aryl group; and
-R 3 selected from linear or branched C 1 -C 20 Alkyl, C optionally substituted by one or more, preferably saturated, linear or branched, aliphatic hydrocarbon chains 3 -C 20 Cycloalkyl, and C optionally substituted with one or more preferably saturated, linear or branched aliphatic hydrocarbon chains 6 -C 20 Aryl groups.
The compounds of the formulae (I), (IIa) and (IIb) according to the invention comprise a radical E which denotes that it may optionally comprise oneDivalent hydrocarbon-based binding groups of one or more heteroatoms. For the purposes of the present invention, the term "divalent hydrocarbon-based binding group" means that the group A and the substituent R are present 1 A bridging spacer group between the imidazole rings of X and Y, which spacer group is linear or branched, preferably saturated, preferably C which may optionally contain one or more heteroatoms (e.g. N, O and S) 1 -C 24 Aliphatic hydrocarbon chains. The hydrocarbon chain may optionally be substituted, provided that the substituents are not identical to the groups Q and R are present 1 Imidazole ring reactions of X and Y.
Preferably, in the compounds of formulae (I), (IIa) and (IIb) according to the invention, E is selected from linear or branched, saturated C 1 -C 24 More preferably C 1 -C 10 And even more preferably C 1 -C 6 Aliphatic hydrocarbon chains, optionally interrupted by one or more heteroatoms (e.g., N, S and O).
Preferably, in the compounds of formulae (I), (IIa) and (IIb) according to the invention, E is selected from the group consisting of-R-, -NH-R-; -O-R-and-S-R-, R is linear or branched C 1 -C 24 Preferably C 1 -C 10 More preferably C 1 -C 6 An alkylene group.
Even preferably, in the compounds of formulae (I), (IIa) and (IIb) according to the invention, E is selected from the group consisting of-R-and-O-R-, R is a linear or branched C 1 -C 24 Preferably C 1 -C 10 More preferably C 1 -C 6 An alkylene group.
Even preferably, in the compounds of formulae (I), (IIa) and (IIb) according to the invention, E is selected from the group consisting of-CH 2 -、-CH 2 -CH 2 -、-CH 2 -CH 2 -CH 2 -、-CH 2 -CH 2 -CH 2 -CH 2 -、-O-CH 2 -、-O-CH 2 -CH 2 -、-O-CH 2 -CH 2 -CH 2 -and-O-CH 2 -CH 2 -CH 2 -CH 2 -。
Even preferably, in the compounds of formulae (I), (IIa) and (IIb) according to the invention, E is selected from linear or branched C 1 -C 24 Preferably C 1 -C 10 More preferably C 1 -C 6 Alkylene groups, even more preferably selected from-CH 2 -、-CH 2 -CH 2 -、-CH 2 -CH 2 -CH 2 -and-CH 2 -CH 2 -CH 2 -CH 2 -。
Even preferably, in the compounds of formulae (I) and (IIa) according to the invention, E is selected from the group consisting of-CH 2 -、-CH 2 -CH 2 -、-CH 2 -CH 2 -CH 2 -and-CH 2 -CH 2 -CH 2 -CH 2 -。
The compounds of the formulae (I), (IIa) and (IIb) according to the invention comprise a radical R 1 The radicals R 1 Represents a hydrogen atom or C 1 -C 20 An alkyl group. Preferably, in the compounds of formulae (I), (IIa) and (IIb) according to the invention, R 1 Represents a hydrogen atom or C 1 -C 6 Alkyl groups, preferably methyl. These alkyl groups may be linear or branched.
The compounds of formulae (I), (IIa) and (IIb) according to the invention comprise the radicals Y and Z, which may be identical or different, each represent a hydrogen atom or a hydrocarbon chain, Y and Z possibly also forming a ring, in particular an aromatic ring, together with the carbon atoms of the imidazole ring to which they are attached.
Preferably, in the compounds of formulae (I), (IIa) and (IIb) according to the invention, Y and Z, which may be identical or different, each represent a hydrogen atom or a linear or branched C 1 -C 24 Preferably C 1 -C 10 More preferably C 1 -C 6 Alkyl groups, Y and Z may also form a ring, particularly an aromatic ring, together with the carbon atoms of the imidazole ring to which they are attached.
According to a preferred embodiment, in the compounds of formulae (I), (IIa) and (IIb) according to the invention, Y and Z are hydrogen atoms.
According to another preferred embodiment, in the compounds of formulae (I), (IIa) and (IIb) according to the invention, Y and Z form together with the carbon atom of the imidazole ring to which they are attached an aromatic ring; preferably, Y and Z form a benzene ring with the carbon atoms of the imidazole ring to which they are attached.
Preferably, in the compounds of the formulae (IIa) and (IIb),R 2 represents a hydrogen atom or a group selected from the group consisting of: linear or branched C 1 -C 20 Alkyl, optionally C 1 -C 6 Alkyl substituted C 3 -C 20 Cycloalkyl, or optionally C 1 -C 6 Alkyl substituted C 6 -C 20 Aryl groups.
Preferably, in the compounds of formulae (IIa) and (IIb), R 3 Selected from linear or branched C 1 -C 20 Alkyl, optionally C 1 -C 6 Alkyl substituted C 3 -C 20 Cycloalkyl, or optionally C 1 -C 6 Alkyl substituted C 6 -C 20 Aryl groups.
Even more preferably, in the compounds of formulae (IIa) and (IIb), R 2 Is a hydrogen atom and R 3 Selected from C 1 -C 20 Alkyl and C 6 -C 20 Aryl groups.
Even more preferably, in the compounds of formulae (IIa) and (IIb), R 2 Is a hydrogen atom and R 3 Is phenyl.
Of the compounds of the formulae (I), (IIa) and (IIb), particular preference is given to compounds of the formula (VIII)
The subject of the invention is also a process for preparing a compound (IIa) as defined above, comprising at least one reaction (c) of a compound of formula (III) with a compound of formula (IV) according to the following reaction scheme
Wherein in formulae (IIa), (III) and (IV):
-a represents a divalent heteroaromatic ring optionally substituted by one or more identical or different aliphatic hydrocarbon chains, preferably saturated, linear or branched, optionally substituted or interrupted by one or more heteroatoms;
-E represents a divalent hydrocarbon-based binding group, which may optionally contain one or more heteroatoms;
-R 1 represents a hydrogen atom or C 1 -C 20 An alkyl group;
y and Z, which may be the same or different, each represent a hydrogen atom or a hydrocarbon group, Y and Z possibly forming a ring, in particular an aromatic ring, together with the carbon atoms of the imidazole ring to which they are attached;
-R 2 selected from hydrogen atoms, linear or branched C 1 -C 20 Alkyl, C optionally substituted by one or more, preferably saturated, linear or branched, aliphatic hydrocarbon chains 3 -C 20 Cycloalkyl, and C optionally substituted with one or more preferably saturated, linear or branched aliphatic hydrocarbon chains 6 -C 20 An aryl group; and
-R 3 selected from linear or branched C 1 -C 20 Alkyl, C optionally substituted by one or more, preferably saturated, linear or branched, aliphatic hydrocarbon chains 3 -C 20 Cycloalkyl, and C optionally substituted with one or more preferably saturated, linear or branched aliphatic hydrocarbon chains 6 -C 20 Aryl groups.
A、E、R 1 、R 2 、R 3 Preferred forms of Y and Z are also suitable for the preparation of the compounds of the formula (IIa) from the compounds of the formulae (III) and (IV).
Those skilled in the art know how to adjust the above reaction to obtain the compound of formula (I) according to the invention from the compound of formula (III).
The compounds of formula (IV) are commercially available from suppliers such as Sigma-Aldrich, fischer and the like.
The process for preparing the compound of formula (IIa) as defined above further comprises at least one reaction (b) of the compound of formula (V) with at least one compound of formula (IV) to form the compound of formula (III)
Wherein:
-group E, A, R 1 、R 2 、R 3 Y and Z are as previously defined, including preferred forms thereof; and
-the group T is selected from chlorine, bromine, iodine, fluorine, mesylate, tosylate, acetate and triflate groups.
The compounds of formula (IV) are commercially available from chemical suppliers such as Aldrich, ABCR, and the like.
The process for preparing the compound of formula (IIa) as defined above further comprises at least one electrophilic activation reaction (a) of a compound of formula (VII) in the presence of an electrophilic activator according to the following reaction scheme to form a compound of formula (V)
Wherein:
-group E, A and R 2 As defined above, including preferred forms thereof, T is a leaving group provided by the electrophilic activator; and
-the group T is selected from chlorine, bromine, iodine, fluorine, mesylate, tosylate, acetate and triflate groups.
The term "electrophilic activator" means an agent that reacts with hydroxyl-OH to impart electrophilic properties thereto. Such electrophilic activation reactions on these electrophilic activators and hydroxyl groups are well known to those skilled in the art. Examples of electrophilic activators that may be mentioned include thionyl chloride, methanesulfonyl chloride, 4-toluenesulfonyl chloride, p-toluenesulfonyl chloride and the like.
Preferably, the electrophile provides a leaving group T selected from the group consisting of chlorine, bromine, iodine, mesylate and tosylate.
The compounds of formulas (VII) and (VI) are commercially available from chemical suppliers such as Aldrich, ABCR, and the like.
According to a preferred embodiment, the process for preparing the compound of formula (IIa) comprises at least the following successive reactions: reaction (b) and then reaction (c) as defined previously.
According to another preferred embodiment, the process for preparing the compound of formula (IIa) comprises at least the following successive reactions: reaction (a) then reaction (b) then reaction (c) as defined previously. Preferably, in this embodiment, the compound of formula (VII) is obtained by dehydration of fructose or glucose; even more preferably, the compound of formula (VII) is obtained by dehydration of fructose of biological origin or glucose of biological origin. For the purposes of the present invention, the terms "biogenic fructose" and "biogenic glucose" mean fructose and glucose obtained from biomass, which can be distinguished from fructose and glucose, respectively, synthesized from fossil raw materials by the method described in standard ASTM D6866-12.
As previously explained, compounds of the formula (I), in particular those of the formula (IIa) or (IIb), are used as grafting reagents. They may be grafted onto one or more polymers containing at least one unsaturated carbon-carbon bond. In particular, the polymer may be an elastomer and more particularly a diene elastomer. The compounds of formula (I), in particular those of formulae (IIa) and (IIb), advantageously have an improved yield of grafting to the polymer bearing at least one unsaturated group compared to the compounds of the prior art.
The term "diene elastomer" (or an indiscriminate rubber), whether natural or synthetic, is understood to mean an elastomer composed at least in part (i.e. a homopolymer or a copolymer) of diene monomer units (monomers bearing two conjugated or non-conjugated carbon-carbon double bonds) in a known manner.
Grafting of the polymer comprising at least one unsaturated carbon-carbon bond occurs by reaction of the polymer with a compound of formula (I), in particular a compound of formula (IIa) or (IIb). Grafting of these compounds is carried out by cycloaddition of the group Q of the compound of formula (I) (or of the nitrone of the compound of formula (IIa) or (IIb), respectively) [3+2] to an unsaturated carbon-carbon bond of the polymer chain. The mechanism of this cycloaddition is particularly described in WO 2012/007441. During this reaction, the compound of formula (I), in particular the compound of formula (IIa) or (IIb), forms a covalent bond with the polymer chain.
The grafting of the compounds of the formula (I), in particular of the formula (IIa) or (IIb), can be carried out in bulk (for example in an extruder, an internal mixer or an open mixer (for example a roll mill)) or in solution. The grafting process may be carried out continuously or batchwise in solution. The polymer thus obtained by grafting can be separated from its solution by any type of process known to the person skilled in the art, in particular by a stripping operation.
In addition to the previously described subject matter, the present invention also relates to at least one subject matter described in the following embodiments:
1. a compound of formula (I)
Wherein:
-Q represents a dipole comprising at least one nitrogen atom;
-a represents a divalent heteroaromatic ring optionally substituted with one or more identical or different linear or branched aliphatic hydrocarbon chains optionally substituted or interrupted with one or more heteroatoms;
-E represents a divalent hydrocarbon-based binding group, which may optionally contain one or more heteroatoms;
-R 1 represents a hydrogen atom or C 1 -C 20 An alkyl group; and
y and Z, which may be identical or different, each represent a hydrogen atom or a hydrocarbon chain, Y and Z possibly also forming a ring, in particular an aromatic ring, together with the carbon atoms of the imidazole ring to which they are attached.
2. The compound of embodiment 1 wherein Q is a group of formula (II), (III) or (IV)
Wherein:
-symbol x represents the attachment of Q to a;
-R 2 and R is 4 Independently of one another, from hydrogen atoms, linear or branched C 1 -C 20 Alkyl, C optionally substituted by one or more, preferably saturated, linear or branched, aliphatic hydrocarbon chains 3 -C 20 Cycloalkyl, and C optionally substituted with one or more preferably saturated, linear or branched aliphatic hydrocarbon chains 6 -C 20 An aryl group; and
-R 3 selected from linear or branched C 1 -C 20 Alkyl, C optionally substituted by one or more, preferably saturated, linear or branched, aliphatic hydrocarbon chains 3 -C 20 Cycloalkyl, and C optionally substituted with one or more preferably saturated, linear or branched aliphatic hydrocarbon chains 6 -C 20 Aryl groups.
3. The compound according to embodiment 2, wherein the compound of formula (I) is selected from the group consisting of compounds of formula (IIa)
Wherein:
-a represents a divalent heteroaromatic ring optionally substituted with one or more identical or different linear or branched aliphatic hydrocarbon chains optionally substituted or interrupted with one or more heteroatoms;
-E represents a divalent hydrocarbon-based binding group, which may optionally contain one or more heteroatoms;
-R 1 represents a hydrogen atom or C 1 -C 20 An alkyl group;
y and Z, which may be the same or different, each represent a hydrogen atom or a hydrocarbon chain, Y and Z possibly also forming a ring, in particular an aromatic ring, together with the carbon atoms of the imidazole ring to which they are attached;
-R 2 selected from hydrogen atoms, linear or branched C 1 -C 20 Alkyl, C optionally substituted by one or more, preferably saturated, linear or branched, aliphatic hydrocarbon chains 3 -C 20 Cycloalkyl groups, and optionally one or morePreferably saturated, linear or branched aliphatic hydrocarbon chain-substituted C 6 -C 20 An aryl group; and
-R 3 selected from linear or branched C 1 -C 20 Alkyl, C optionally substituted by one or more, preferably saturated, linear or branched, aliphatic hydrocarbon chains 3 -C 20 Cycloalkyl, and C optionally substituted with one or more preferably saturated, linear or branched aliphatic hydrocarbon chains 6 -C 20 Aryl groups.
4. A compound according to any one of embodiments 1 to 3 wherein a is a divalent heteroaromatic ring formed from 5 to 10 atoms, preferably 5 to 6 atoms, optionally interrupted by one or more identical or different linear or branched aliphatic C 1 -C 24 Hydrocarbon chain substitution, the aliphatic C 1 -C 24 The hydrocarbon chain is optionally substituted or interrupted with one or more heteroatoms.
5. A compound according to any one of embodiments 1 to 4, wherein a is a divalent heteroaryl ring formed from 5 to 10 atoms, preferably 5 to 6 atoms, optionally substituted with one or more substituents selected from the group consisting of: linear or branched C 1 -C 12 (more preferably C 1 -C 6 Even more preferably C 1 -C 4 ) Alkyl, group-OR ', group-NHR', group-SR ', wherein R' is C 1 -C 12 Preferably C 1 -C 6 Even more preferably C 1 -C 4 An alkyl group.
6. A compound according to any one of embodiments 1 to 5 wherein a is selected from furan-diyl, thiophene-diyl, pyrrole-diyl, thiazole-diyl, imidazole-diyl, pyridine-diyl, pyrazine-diyl, pyrimidine-diyl, indole-diyl, benzofuran-diyl, isoindole-diyl, isobenzofuran-diyl and benzothiophene-diyl; these rings are optionally substituted with one or more identical or different aliphatic hydrocarbon chains, preferably saturated, optionally substituted or interrupted with one or more heteroatoms (e.g. O, N and S); more preferably, the rings may be substituted with one or more C' s 1 -C 6 Alkyl substitution.
7. A compound according to embodiment 6 wherein a is selected from furan-diyl, thiophene-diyl and pyrrole-diyl, even more preferably furan-diyl.
8. A compound according to any one of embodiments 1 to 7, wherein a as defined in embodiments 1 to 6 is unsubstituted.
9. The compound according to any of embodiments 3 to 8, wherein the compound of formula (IIa) is selected from the group consisting of compounds of formula (IIb)
Wherein:
-X represents a heteroatom group selected from sulfur, oxygen and nitrogen atoms; preferably, X is an oxygen atom;
-E represents a divalent hydrocarbon-based binding group, which may optionally contain one or more heteroatoms;
-R 1 represents a hydrogen atom or C 1 -C 20 An alkyl group;
y and Z, which may be the same or different, each represent a hydrogen atom or a hydrocarbon chain, Y and Z possibly also forming a ring, in particular an aromatic ring, together with the carbon atoms of the imidazole ring to which they are attached;
-R 2 selected from hydrogen atoms, linear or branched C 1 -C 20 Alkyl, C optionally substituted by one or more, preferably saturated, linear or branched, aliphatic hydrocarbon chains 3 -C 20 Cycloalkyl, and C optionally substituted with one or more preferably saturated, linear or branched aliphatic hydrocarbon chains 6 -C 20 An aryl group; and
-R 3 selected from linear or branched C 1 -C 20 Alkyl, C optionally substituted by one or more, preferably saturated, linear or branched, aliphatic hydrocarbon chains 3 -C 20 Cycloalkyl, and C optionally substituted with one or more preferably saturated, linear or branched aliphatic hydrocarbon chains 6 -C 20 Aryl groups.
10. According to any one of embodiments 2 to 9The compound, wherein R 2 Is a hydrogen atom and R 3 Selected from C 1 -C 20 Alkyl and C 6 -C 20 Aryl groups.
11. The compound according to any one of the preceding embodiments, wherein E is selected from linear or branched, saturated aliphatic C 1 -C 24 Preferably C 1 -C 10 More preferably C 1 -C 6 A hydrocarbon chain, optionally interrupted by one or more nitrogen, sulfur or oxygen atoms.
12. The compound according to any one of the preceding embodiments, wherein E is selected from the group-R-, -NHR-, -OR-, and-SR-, wherein R is linear OR branched C 1 -C 24 Preferably C 1 -C 10 More preferably C 1 -C 6 An alkylene group.
13. The compound of embodiment 12 wherein E is selected from the group consisting of-R-and-O-R-, R is linear or branched C 1 -C 24 Preferably C 1 -C 10 More preferably C 1 -C 6 An alkylene group.
14. The compound of embodiment 13 wherein E is selected from the group consisting of-CH 2 -、-CH 2 -CH 2 -、-CH 2 -CH 2 -CH 2 -、-CH 2 -CH 2 -CH 2 -CH 2 -、-O-CH 2 -、-O-CH 2 -CH 2 -、-O-CH 2 -CH 2 -CH 2 -and-O-CH 2 -CH 2 -CH 2 -CH 2 -。
15. The compound of embodiment 12 wherein E is linear or branched C 1 -C 24 Preferably C 1 -C 10 More preferably C 1 -C 6 Alkylene groups, even more preferably selected from-CH 2 -、-CH 2 -CH 2 -、-CH 2 -CH 2 -CH 2 -and-CH 2 -CH 2 -CH 2 -CH 2 -。
16. A compound according to any one of the preceding embodiments, wherein Y and Z, which may be the same or different, each represent a hydrogen atom or a linear or branched chainC of (2) 1 -C 24 Preferably C 1 -C 10 More preferably C 1 -C 6 Alkyl groups, Y and Z may also form a ring, particularly an aromatic ring, together with the carbon atoms of the imidazole ring to which they are attached.
17. A compound according to any one of the preceding embodiments wherein Y and Z are hydrogen atoms.
18. A compound according to any one of embodiments 1 to 16 wherein Y and Z together with the carbon atom of the imidazole ring to which they are attached form an aromatic ring; preferably, Y and Z form a benzene ring with the carbon atoms of the imidazole ring to which they are attached.
19. The compound according to any one of the preceding embodiments, wherein R 1 Is a hydrogen atom or C 1 -C 6 Alkyl is preferably methyl.
20. A compound according to any one of the preceding embodiments, characterized in that the compound is of formula (VIII)
21. A process for the synthesis of a compound of formula (IIa) as defined in any one of embodiments 3 to 14, comprising at least one reaction of a compound of formula (III) with a compound of formula (IV) according to the following reaction scheme
Wherein in formulae (IIa), (III) and (IV):
-a represents a divalent heteroaromatic ring optionally substituted with one or more identical or different linear or branched aliphatic hydrocarbon chains optionally substituted or interrupted with one or more heteroatoms;
-E represents a divalent hydrocarbon-based binding group, which may optionally contain one or more heteroatoms;
-R 1 represents a hydrogen atom or C 1 -C 20 An alkyl group;
y and Z, which may be the same or different, each represent a hydrogen atom or a hydrocarbon chain, Y and Z possibly also forming a ring, in particular an aromatic ring, together with the carbon atoms of the imidazole ring to which they are attached; and
-R 2 selected from hydrogen atoms, linear or branched C 1 -C 20 Alkyl, C optionally substituted by one or more, preferably saturated, linear or branched, aliphatic hydrocarbon chains 3 -C 20 Cycloalkyl, and C optionally substituted with one or more preferably saturated, linear or branched aliphatic hydrocarbon chains 6 -C 20 An aryl group; and
-R 3 selected from linear or branched C 1 -C 20 Alkyl, C optionally substituted by one or more, preferably saturated, linear or branched, aliphatic hydrocarbon chains 3 -C 20 Cycloalkyl, and C optionally substituted with one or more preferably saturated, linear or branched aliphatic hydrocarbon chains 6 -C 20 Aryl groups.
Examples
1.Characterization of molecules
The structural analysis and determination of the molar purity of the synthesized molecules were carried out by NMR analysis. Spectra were collected on a Bruker Avance 3 400MHz spectrometer equipped with a "5mm BBFO Z-stage broadband" probe. 1 The H NMR quantification experiment uses a simple 30 ° pulse sequence and a 3 second repetition delay between each of the 64 acquisitions. Unless otherwise indicated, the samples were dissolved in a deuterated solvent (deuterated dimethyl sulfoxide (DMSO)). Deuterated solvents are also used to "lock" the signal. For example, proton signals of deuterated DMSO at 2.44ppm were calibrated against a TMS reference of 0 ppm. And 2D 1 H/ 13 CHSQC 1 H/ 13 Coupled by C HMBC experiment 1 H NMR spectroscopy, the structure of the molecule can be determined (see distribution table). Molar basis of basis 1D 1 H NMR spectroscopy was performed.
2.Characterization of molecules grafted onto diene elastomer
Determination of the molar content of the graft compounds tested on the diene elastomer by NMR analysisIs carried out. Spectra were collected on a Bruker 500MHz spectrometer equipped with a "5mm BBFO Z-grade CryoProbe" probe. 1 The H NMR quantification experiment uses a simple 30 ° pulse sequence and a repetition delay of 5 seconds between each acquisition. Unless otherwise indicated, the samples were dissolved in deuterated solvents (deuterated chloroform (CDCl) 3 ) To obtain a "lock" signal. 2D NMR experiments can confirm the nature of the grafted units by chemical shift of carbon atoms and protons.
3.Measurement of the number average molar mass (Mn) and weight average molar mass (Mw) of diene elastomers and polydispersity index.
Unless explicitly stated otherwise, the number average molar mass and the weight average molar mass of the diene elastomer used are measured by Size Exclusion Chromatography (SEC) techniques. SEC makes it possible to separate macromolecules in solution by a column packed with a porous gel, depending on the size of the macromolecules. Macromolecules are separated according to their hydrodynamic volume, the largest volume being eluted first.
Although not an absolute method, SEC makes it possible to determine the molar mass distribution of the elastomer. The individual number average molar masses (Mn) and weight average molar masses (Mw) can be determined from commercially available standards, and the polydispersity index (pi=mw/Mn) can be calculated by "Moore" calibration.
There was no particular treatment of the elastomer samples prior to analysis. The sample was simply dissolved in chloroform or a mixture of the following to a concentration of about 1 g/l: tetrahydrofuran+1 vol% diisopropylamine+1 vol% triethylamine+1 vol% distilled water (vol% = vol%). The solution was then filtered through a filter with a porosity of 0.45 μm prior to injection.
The device used was a Waters Alliance chromatograph. The eluting solvent is chloroform or a mixture of the following: tetrahydrofuran+1 vol% diisopropylamine+1 vol% triethylamine, depending on the solvent used to dissolve the elastomer. The flow rate was 0.7ml/min, the system temperature was 35℃and the analysis time was 90min. A series of four Waters columns were used, with trade names Styragel HMW7, styragel HMW6E and two Styragel HT6E.
The volume of the injected elastomer sample solution was 100. Mu.l. The detector is a Waters2410 differential refractometer with a wavelength of 810 nm. The software used to process the chromatographic data is the Waters Empower system.
The calculated average molar mass is relative to a calibration curve generated from polystyrene standards commercially available from PSS Ready Cal-Kit.
4.1- (5- ((2-methyl-1H-imidazol-1-yl) methylfuran-2-yl) -N-phenylazomethine oxide (Compound E) Is synthesized by (a)
1- (5- ((2-methyl-1H-imidazol-1-yl) methylfuran-2-yl) -N-phenylazomethine oxide can be synthesized according to the following reaction scheme
1- (5- ((2-methyl-1H-imidazol-1-yl) methylfuran-2-yl) -N-phenylazomethine oxide was synthesized according to the two steps described below.
5- (hydroxymethyl) furan-2-carbaldehyde (Compound A, CAS 67-47-0) is commercially available or can be synthesized from fructose by biochemical or chemical methods.
The product N-phenylhydroxylamine (Compound D, CAS 100-65-2) is commercially available or can be obtained from nitrobenzene according to Organic Syntheses, coll. Volume 1, page 445 (1941); volume 4, page 57 (1925).
5- (chloromethyl) furan-2-carbaldehyde (compound B) can be prepared from fructose or 5- (hydroxymethyl) furan-2-carbaldehyde according to Sanda, komla et al Synthesis of5- (bromomethyl) -and of5- (chloromethyl) -2-furancarboxaldehyde, carbohydrate Research,187 (1), 15-23; the synthesis is described in 1989.
4.1 step 1: synthesis of5- ((2-methyl-1H-imidazol-1-yl) methyl) furan-2-carbaldehyde (product C)
A mixture of 2-methylimidazole (4.83 g;58.80mmol;2.5 eq.) and 5- (chloromethyl) furan-2-carbaldehyde (3.40 g;23.52 mmol) in DMF (4 ml) was heated to a bath temperature of 70 ℃. After stirring at this temperature for 2-3 hours and then at a bath temperature of 80℃for 2 hours, the reaction medium was diluted with water (50 mL) and the organic phase was separated off. The aqueous phase was extracted four times with dichloromethane (four times 20 ml). The organic phase portions were combined and then washed with water (four times 5 ml) and then concentrated under reduced pressure (2-3 mbar; 32 ℃) to give a black oil (2.44 g;12.8 mmol) in 55% yield. The product was used in the following step without further purification.
4.2 step 2: synthesis of 1- (5- ((2-methyl-1H-imidazol-1-yl) methyl) furan-2-yl) -N-phenylazomethine oxide (product E)
N-phenylhydroxylamine (2.87 g;26.3mmol;1 eq.) was added in portions over 5 minutes to a solution of 5- ((2-methyl-1H-imidazol-1-yl) methyl) furan-2-carbaldehyde (compound C) (5.00 g;26.3 mmol) in ethanol (5 ml) at a bath temperature of 35-40 ℃. The reaction medium was heated to a bath temperature of 60 ℃. After stirring at this temperature for 1.5 hours, the temperature was returned to 30-35℃and tert-butyl methyl ether (15 ml) was added dropwise. After stirring for one hour at room temperature (23 ℃), the precipitate obtained is filtered off and washed on the filter with a mixture of ethanol and tert-butyl methyl ether (1 ml and 5 ml) and then with tert-butyl methyl ether (8 ml). A light brown solid with a melting point of 147-150℃is obtained in a yield of 68.4% (5.06 g;17.99 mmol) and a molar purity of more than 98% ("A") 1 H NMR)。
TABLE 1
5. Grafting polymers with Compound E
5.1 use of 1- (5- ((2-methyl-1H-imidazol-1-yl) methyl) furan-2-yl) -N-benzeneAzomethine oxide (chemical)
Preparation of the styrene-butadiene copolymer grafted with Compound E)
1- (5- ((2-methyl-1H-imidazol-1-yl) methyl) furan-2-yl) -N-phenyl-azomethine oxide (0.31; 1.14 mmol) was added to 15g of styrene-butadiene copolymer SBR (containing 26.5% by weight of styrene (relative to the total weight of the copolymer) and 24% by weight of 1, 2-butadiene units (relative to the weight of the butadiene portion), 28% by weight of 1, 4-cis-butadiene units (relative to the weight of the butadiene portion) and 48% by weight of 1, 4-trans-butadiene units (relative to the weight of the butadiene portion) on a rolling mill at 23℃Mn=120 g/mol and PI=1.84 measured according to the method described in paragraph 3. The mixture was homogenized by 15 passes of the combination (passes portefeuille). This mixing stage is followed by a heat treatment at 160℃for 60 minutes in a press with a pressure of 10 bar.
According to 1 The grafting results of the H NMR analysis are shown in Table 2.
5.2 grafting 1- (5- ((2-methyl-1H-imidazol-1-yl) methyl) furan-2-yl) -N-phenylazomethine Oxidation
Preparation of polybutadiene Polymer of Compound (Compound E)
0.5g of polybutadiene (75.4 mol% of 1, 2-butadiene units and 24.6mol% of 1, 4-butadiene units; mn=7800 g/mol and PI=1.02 measured according to the method described in paragraph 3) was purged with nitrogen for 15 minutes. Next, 2ml of methylene chloride, which had been previously bubbled with nitrogen for 5 minutes, was added to dissolve the polymer.
Once the polymer was dissolved, 0.265g of 1- (5- ((2-methyl-1H-imidazol-1-yl) methyl) furan-2-yl) -N-phenyl azomethide oxide (compound E) (0.94 mmol) pre-dissolved in 2ml of dichloromethane was added to the reaction medium with stirring. After stirring for 15 minutes, the reaction medium was left under a nitrogen sweep for 15 minutes to evaporate the dichloromethane. Once all solvent was evaporated, the reaction medium was heated to 150 ℃ (bath temperature) under a constant nitrogen flow. After 10 hours and 30 minutes of reaction, the reaction medium was brought to room temperature (23 ℃).
According to 1 Grafting for H NMR analysisThe results are shown in Table 2.
5.3 grafting 1- (5- ((2-methyl-1H-imidazol-1-yl) methyl) furan-2-yl) -N-phenylazomethine Oxidation
Preparation of ethylene-butadiene copolymer of Compound (Compound E)
1- (5- ((2-methyl-1H-imidazol-1-yl) methyl) furan-2-yl) -N-phenyl-azomethine oxide (0.57; 2 mmol) was added to 15g of ethylene-butadiene copolymer EBR (containing 16.8mol% butadiene, 7.7mol% butadiene/ethylene rings and 75.5mol% ethylene) on a rolling mill at 23 ℃. The mixture was homogenized by 15 passes of the combination. This mixing stage is followed by a heat treatment at 160℃for 60 minutes in a press with a pressure of 10 bar.
According to 1 The grafting results of the H NMR analysis are shown in Table 2.
TABLE 2
6.1,3-dipole N- (4- ((2-methyl-1H-imidazol-1-yl) methyl) benzylidene) aniline oxide (chemical)
Synthesis of Compound E1)
The compound can be prepared in five steps according to the following reaction scheme:
6.1 step 1: synthesis of methyl 4- (chloromethyl) benzoate (Compound A1)
Thionyl chloride SOCl was added at-8deg.C (bath temperature) over 10 minutes 2 (2.4 ml;32.2 mmol) was added dropwise to 150ml of methanol cooled to a temperature of-8℃C (bath temperature). After stirring at-8deg.C (bath temperature) for 5 min, the mixture was separated at-8deg.C (bath temperature) for 10 min4- (chloromethyl) benzoic acid (5.0 g;29.3 mmol) was added in portions. After stirring at-8 ℃ (bath temperature) for 20 minutes, the reaction medium was heated at 14 ℃ (bath temperature) for 20 minutes. The reaction medium was then heated to 50℃over 1 hour (bath temperature) and stirred at that temperature for 2 hours. The product solution was concentrated under reduced pressure (28 mbar, 40 ℃, bath temperature) to give an oil which crystallized at room temperature. A white solid (5.16 g;27.9mmol, molar yield 95%) was obtained with a melting point of 38-40 ℃.
The molar purity is more than 95mol percent 1 H NMR)。
TABLE 3
| Sequence number | δ 1 H(ppm) | δ 13 C(ppm) |
| 1 | 3.92 | 45.4 |
| 2 | / | 166.5 |
| 3 | / | 128.5 |
| 4 | 8.04 | 130.0 |
| 5 | 7.47 | 129.2 |
| 6 | / | 142.2 |
| 7 | 4.62 | 52.2 |
Solvent: CDCl 3
6.2 step 2: synthesis of methyl 4- ((2-methyl-1H-imidazol-1-yl)) benzoate:
methyl 4- (chloromethyl) benzoate (5.15 g;28 mmol) and 2-methyl-1H-imidazole (2.52 g;31 mmol) and K 2 CO 3 (2.89 g;21 mmol) in DMF (4 ml) was heated at 60℃for 1 to 1.5 hours and then at 80℃for 5 hours. After cooling, the reaction medium was diluted with water (50 ml) and ethyl acetate (25 ml) at 0 ℃. The aqueous phase was separated and extracted with ethyl acetate (3 times 10 ml). The combined organic phases were washed with water (3 times 5 ml). The product solution was concentrated under reduced pressure (7 mbar, 40 ℃ C., bath temperature) to give a yellow oil (4.266 g;18.5mmol, 66% molar yield).
TABLE 4
| Sequence number | δ 1 H(ppm) |
| 1 | 5.09 |
| 2 | / |
| 3 | 7.08 |
| 4 | 7.99 |
| 5 | / |
| 6 | / |
| 7 | 3.46 |
| 8 | 7.99 |
| 9 | 7.08 |
| 10 | 6.96 |
| 11 | 6.84 |
| 12 | / |
| 13 | 2.30 |
Solvent: CDCl 3
6.3 step 3: synthesis of 4- ((2-methyl-1H-imidazol-1-yl)) methyl) benzyl alcohol:
LiAlH is prepared 4 A solution of (1.50 g,0.039 mol) in anhydrous THF (230 ml) was cooled to-60 ℃. A solution of ethyl 4- ((2-methyl-1H-imidazol-1-yl) methyl) benzoate (7.80 g,0.028mol,81 mol%) in anhydrous THF (100 ml) was added under argon over 15 minutes. The reaction medium is stirred at-60℃for 1 hour and then at room temperature for 10-12 hours. Water (20 ml) was added dropwise (exothermic reaction). The precipitate formed is filtered off and the filtrate is then concentrated under reduced pressure. Dissolving the obtained crude product in CH 2 Cl 2 (100 ml) to precipitate insoluble material. After filtration and concentration under reduced pressure, a yellow oil (4.96 g, 93% molar yield) was obtained. Molar purity of more than 85 percent 1 H NMR)。
TABLE 5
| Sequence number | δ 1 H(ppm) |
| 1 | 4.99 |
| 2 | / |
| 3 | 7.30 |
| 4 | 6.97 |
| 5 | / |
| 6 | 4.66 |
| 7 | 7.63 |
| 8 | 6.97 |
| 9 | 7.30 |
| 10 | 6.82 |
| 11 | 6.79 |
| 12 | / |
| 13 | 2.23 |
Solvent: CDCl 3
6.4 step 4: synthesis of 4- ((2-methyl-1H-imidazol-1-yl)) methyl) benzaldehyde:
MnO 2 (6.88 g;0.079 mol) and 4- ((2-methyl-1H-imidazol-1-yl)) methyl) benzyl alcohol (4.57 g;0.021mol,85 mol% by 1 H NMR measurement) in CHCl 3 The mixture in (180 ml) was stirred at reflux temperature for 4 hours. The reaction medium is cooled to room temperature and kept stirring at that temperature for 10-12 hours. Insoluble product was filtered off, and then the filtrate was concentrated under reduced pressure. After concentration under reduced pressure, a yellow oil (3.78 g, 98% molar yield) was obtained. The molar purity is more than 81 percent 1 H NMR)。
TABLE 6
| Sequence number | δ 1 H(ppm) |
| 1 | 5.16 |
| 2 | / |
| 3 | 7.20 |
| 4 | 7.89 |
| 5 | / |
| 6 | 10.01 |
| 7 | 7.89 |
| 8 | 7.20 |
| 9 | 7.02 |
| 10 | 6.88 |
| 11 | / |
| 12 | 2.34 |
Solvent: CDCl 3
6.5 Synthesis of phenylhydroxylamine:
phenylhydroxylamine was prepared according to org.syntheses col. 1, page 445, 1941; the synthesis was carried out as described in org.syntheses Coll.3, page 668, 1955.
6.5 step 5: synthesis of N-4- ((2-methyl-1H-imidazol-1-yl)) methyl) benzylidene) aniline oxide:
4- ((2-methyl-1H-imidazol-1-yl)) methyl) benzaldehyde (3.48 g;0.015mol,81 mol%, by 1 H NMR measurement) and phenylhydroxylamine (2.86 g;0.026 mol) in absolute ethanol (20 ml) was stirred at 60℃for 2 hours, then at room temperature for 12 hours. The yellow precipitate (0.249 g, containing the expected product) was filtered off. Water (30 ml) was added to the filtrate with vigorous stirring. After stirring for 20 minutes, the yellow precipitate which then formed was filtered off, washed with a mixture of EtOH (10 ml) and water (20 ml) and then with water (50 ml). The two solid portions were combined and then dried at normal pressure and room temperature for 10-12 hours. Obtaining the catalyst with the molar purity of more than 82 percent 1 H NMR) yellow solid (3.71 g, molar yield 89%). Additional purification was performed by stirring at room temperature for 1.5 hours, filtration, washing on the filter with 50ml of diethyl ether and drying at room temperature for 2 days.
A yellow solid (3.04 g, 78% molar yield) was obtained with a melting point of 115-116 ℃. Molar purity is more than 88 percent 1 H NMR)。
TABLE 7
Solvent: CDCl 3
7. Investigation of the grafting Rate of Compound E over time
In this test, the grafting of the 1, 3-dipole compound according to the invention (compound E) onto the styrene/butadiene copolymer SBR over time is compared with that of the 1, 3-dipole compound of the prior art (compound E1).
The styrene/butadiene copolymer used was an SBR containing 26.5 wt.% styrene (relative to the total weight of the copolymer), 24 wt.% 1, 2-butadiene units (in the butadiene part of the SBR, relative to the weight of the butadiene part), 28 wt.% 1, 4-cis-butadiene units and 48 wt.% 1, 4-trans-butadiene units (relative to the weight of the butadiene part). Mn equal to 120 g/mol, PI equal to 1.84; they were measured according to the method described in paragraph 3.
The process is carried out in the following manner:
1- (5- ((2-methyl-1H-imidazol-1-yl) methyl) furan-2-yl) -N-phenyl-azomethine oxide (0.27 g,0.97 mmol) (compound E according to the invention) or N- (4- ((2-methyl-1H-imidazol-1-yl) methyl) benzylidene) aniline oxide (non-conforming compound E1) (0.28 g,0.97 mmol) was added to 15g SBR as described above on a rolling mill at 23 ℃. The mixture was homogenized by 15 passes of the combination. This mixing stage is followed by a heat treatment at 160℃for 15 minutes in a press with a pressure of 10 bar.
The same experiment was performed for grafting times of 30 minutes and 60 minutes.
At the end of each experiment, according to the method described in paragraph 2, by 1 The H NMR analysis determines the grafting mole of the compounds E according to the invention or of the compounds E1 not according to the invention. The results are collated in Table 8.
TABLE 8
Surprisingly, it can be seen from table 8 that the grafting of the compound E according to the invention is always significantly increased relative to the compound E1 not according to the invention. Furthermore, the grafting of compound E according to the invention continued to increase after 30 minutes of reaction, whereas compound E1 not according to the invention reached plateau within 15 minutes.
Claims (11)
1. Compounds of formula (IIb)
Wherein:
-X represents a heteroatom selected from sulfur, oxygen and nitrogen atoms;
-E represents a divalent hydrocarbon-based binding group, which may optionally contain one or more heteroatoms;
-R 1 represents a hydrogen atom or C 1 -C 20 An alkyl group;
-Y and Z, which may be the same or different, each represent a hydrogen atom or a hydrocarbon chain, Y and Z optionally forming a ring together with the carbon atom of the imidazole ring to which they are attached;
-R 2 selected from hydrogen atoms, linear or branched C 1 -C 20 Alkyl, C optionally substituted by one or more aliphatic hydrocarbon chains 3 -C 20 Cycloalkyl groups, and C optionally substituted with one or more aliphatic hydrocarbon chains 6 -C 20 An aryl group; and
-R 3 selected from linear or branched C 1 -C 20 Alkyl, C optionally substituted by one or more aliphatic hydrocarbon chains 3 -C 20 Cycloalkyl groups, and C optionally substituted with one or more aliphatic hydrocarbon chains 6 -C 20 Aryl groups.
2. The compound of claim 1, wherein R 2 Is a hydrogen atom and R 3 Selected from C 1 -C 20 Alkyl and C 6 -C 20 Aryl groups.
3. The compound of claim 1, wherein E is selected from linear or branched, saturated aliphatic C 1 -C 24 A hydrocarbon chain, optionally interrupted by one or more nitrogen, sulfur or oxygen atoms.
4. According to claimThe compound according to claim 1, wherein, E is selected from the group consisting of-R-, -NHR-; -OR-and-SR-, wherein R is linear OR branched C 1 -C 24 An alkylene group.
5. The compound of claim 1, wherein E is linear or branched C 1 -C 24 An alkylene group.
6. The compound according to claim 1, wherein Y and Z, which may be the same or different, each represent a hydrogen atom or a linear or branched C 1 -C 24 The alkyl groups, Y and Z optionally form a ring together with the carbon atoms of the imidazole ring to which they are attached.
7. The compound of claim 1, wherein Y and Z are hydrogen atoms.
8. A compound according to claim 1 wherein the groups Y and Z together with the carbon atom of the imidazole ring to which they are attached form an aromatic ring.
9. The compound of claim 1, wherein R 1 Is a hydrogen atom or C 1 -C 6 An alkyl group.
10. The compound of claim 1, wherein the compound is of formula (VIII)
11. A process for the synthesis of a compound of formula (IIb) as defined in any one of claims 1 to 10, comprising at least one reaction of a compound of formula (III) with a compound of formula (IV) according to the following reaction scheme
Wherein in formulae (IIb), (III) and (IV):
-X represents a heteroatom selected from sulfur, oxygen and nitrogen atoms;
-E represents a divalent hydrocarbon-based binding group, which may optionally contain one or more heteroatoms;
-R 1 represents a hydrogen atom or C 1 -C 20 An alkyl group;
-Y and Z, which may be the same or different, each represent a hydrogen atom or a hydrocarbon chain, Y and Z optionally forming a ring together with the carbon atom of the imidazole ring to which they are attached; and
-R 2 selected from hydrogen atoms, linear or branched C 1 -C 20 Alkyl, C optionally substituted by one or more aliphatic hydrocarbon chains 3 -C 20 Cycloalkyl groups, and C optionally substituted with one or more aliphatic hydrocarbon chains 6 -C 20 An aryl group; and
-R 3 selected from linear or branched C 1 -C 20 Alkyl, C optionally substituted by one or more aliphatic hydrocarbon chains 3 -C 20 Cycloalkyl groups, and C optionally substituted with one or more aliphatic hydrocarbon chains 6 -C 20 Aryl groups.
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| CN105683165A (en) * | 2013-10-25 | 2016-06-15 | 米其林集团总公司 | 1,3-dipolar compound bearing an imidazole function |
| WO2017064296A1 (en) * | 2015-10-14 | 2017-04-20 | Arkema France | Method for synthesising aromatic nitrones |
| WO2019002756A1 (en) * | 2017-06-28 | 2019-01-03 | Compagnie Generale Des Etablissements Michelin | Diene rubber bearing imidazole groups |
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2019
- 2019-06-11 FR FR1906181A patent/FR3097222B1/en active Active
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2020
- 2020-06-10 EP EP20732824.6A patent/EP3983390A1/en active Pending
- 2020-06-10 CN CN202080042210.0A patent/CN114341114B/en active Active
- 2020-06-10 WO PCT/EP2020/066112 patent/WO2020249623A1/en unknown
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| CN102985445A (en) * | 2010-07-13 | 2013-03-20 | 米其林集团总公司 | Graft polymer to which combined nitrogen molecules are grafted |
| CN105683165A (en) * | 2013-10-25 | 2016-06-15 | 米其林集团总公司 | 1,3-dipolar compound bearing an imidazole function |
| WO2017064296A1 (en) * | 2015-10-14 | 2017-04-20 | Arkema France | Method for synthesising aromatic nitrones |
| WO2019002756A1 (en) * | 2017-06-28 | 2019-01-03 | Compagnie Generale Des Etablissements Michelin | Diene rubber bearing imidazole groups |
Also Published As
| Publication number | Publication date |
|---|---|
| EP3983390A1 (en) | 2022-04-20 |
| CN114341114A (en) | 2022-04-12 |
| WO2020249623A1 (en) | 2020-12-17 |
| FR3097222A1 (en) | 2020-12-18 |
| FR3097222B1 (en) | 2021-05-28 |
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