WO2001060780A1 - Procede de production d'ester fumarique - Google Patents
Procede de production d'ester fumarique Download PDFInfo
- Publication number
- WO2001060780A1 WO2001060780A1 PCT/JP2001/001028 JP0101028W WO0160780A1 WO 2001060780 A1 WO2001060780 A1 WO 2001060780A1 JP 0101028 W JP0101028 W JP 0101028W WO 0160780 A1 WO0160780 A1 WO 0160780A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- mass
- producing
- fumaric
- ruthenium
- Prior art date
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- 150000002148 esters Chemical class 0.000 title claims abstract description 95
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 158
- -1 1-propenyloxy group Chemical group 0.000 claims abstract description 145
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 109
- 150000001875 compounds Chemical class 0.000 claims abstract description 44
- 229910021472 group 8 element Inorganic materials 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims description 99
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 86
- 229910052751 metal Inorganic materials 0.000 claims description 69
- 239000002184 metal Substances 0.000 claims description 69
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 67
- 238000004519 manufacturing process Methods 0.000 claims description 60
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 41
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 36
- 239000001530 fumaric acid Substances 0.000 claims description 35
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 32
- 229910052707 ruthenium Inorganic materials 0.000 claims description 28
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 25
- 229910052703 rhodium Inorganic materials 0.000 claims description 23
- 239000010948 rhodium Substances 0.000 claims description 23
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 23
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 22
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 19
- 239000011976 maleic acid Substances 0.000 claims description 19
- 229910052763 palladium Inorganic materials 0.000 claims description 18
- 229910052741 iridium Inorganic materials 0.000 claims description 17
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 17
- 150000004696 coordination complex Chemical class 0.000 claims description 16
- 229910052697 platinum Inorganic materials 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 12
- 150000002739 metals Chemical class 0.000 claims description 11
- 239000012327 Ruthenium complex Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 150000003283 rhodium Chemical class 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 claims 5
- 229920005989 resin Polymers 0.000 abstract description 4
- 239000011347 resin Substances 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 3
- 239000004014 plasticizer Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 57
- 239000002904 solvent Substances 0.000 description 43
- 239000000243 solution Substances 0.000 description 36
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid group Chemical group C(\C=C/C(=O)O)(=O)O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 34
- 239000000203 mixture Substances 0.000 description 29
- 239000000178 monomer Substances 0.000 description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 20
- 239000003446 ligand Substances 0.000 description 20
- 238000005160 1H NMR spectroscopy Methods 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- RURYLEBCDPDWJS-WAYWQWQTSA-N bis(2-prop-2-enoxyethyl) (z)-but-2-enedioate Chemical compound C=CCOCCOC(=O)\C=C/C(=O)OCCOCC=C RURYLEBCDPDWJS-WAYWQWQTSA-N 0.000 description 18
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 18
- 239000000654 additive Substances 0.000 description 17
- 239000011521 glass Substances 0.000 description 16
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 16
- 230000000694 effects Effects 0.000 description 13
- 239000002994 raw material Substances 0.000 description 13
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 12
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 12
- 238000005481 NMR spectroscopy Methods 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- 230000000996 additive effect Effects 0.000 description 11
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 11
- 238000001914 filtration Methods 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- WIWBLJMBLGWSIN-UHFFFAOYSA-L dichlorotris(triphenylphosphine)ruthenium(ii) Chemical compound [Cl-].[Cl-].[Ru+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 WIWBLJMBLGWSIN-UHFFFAOYSA-L 0.000 description 10
- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 description 10
- 229960004419 dimethyl fumarate Drugs 0.000 description 10
- 150000002688 maleic acid derivatives Chemical class 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 239000003112 inhibitor Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000011068 loading method Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 229940049920 malate Drugs 0.000 description 7
- BJEPYKJPYRNKOW-UHFFFAOYSA-L malate(2-) Chemical compound [O-]C(=O)C(O)CC([O-])=O BJEPYKJPYRNKOW-UHFFFAOYSA-L 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- 229920006305 unsaturated polyester Polymers 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 125000006017 1-propenyl group Chemical group 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 150000004678 hydrides Chemical class 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000036632 reaction speed Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- VIHDTGHDWPVSMM-UHFFFAOYSA-N ruthenium;triphenylphosphane Chemical compound [Ru].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 VIHDTGHDWPVSMM-UHFFFAOYSA-N 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 125000005595 acetylacetonate group Chemical group 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- ANJRHVRISPYJBM-KTKRTIGZSA-N bis(4-prop-2-enoxybutyl) (z)-but-2-enedioate Chemical compound C=CCOCCCCOC(=O)\C=C/C(=O)OCCCCOCC=C ANJRHVRISPYJBM-KTKRTIGZSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 2
- 239000004914 cyclooctane Substances 0.000 description 2
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 2
- 239000004913 cyclooctene Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- 150000003058 platinum compounds Chemical class 0.000 description 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229920006337 unsaturated polyester resin Polymers 0.000 description 2
- FWUIHQFQLSWYED-ARJAWSKDSA-N (z)-4-oxo-4-propan-2-yloxybut-2-enoic acid Chemical compound CC(C)OC(=O)\C=C/C(O)=O FWUIHQFQLSWYED-ARJAWSKDSA-N 0.000 description 1
- AYAUWVRAUCDBFR-ARJAWSKDSA-N (z)-4-oxo-4-propoxybut-2-enoic acid Chemical compound CCCOC(=O)\C=C/C(O)=O AYAUWVRAUCDBFR-ARJAWSKDSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- UJUIJZWQFDQKHO-UHFFFAOYSA-N 1-chlorocyclopentene Chemical compound ClC1=CCCC1 UJUIJZWQFDQKHO-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- LAXBNTIAOJWAOP-UHFFFAOYSA-N 2-chlorobiphenyl Chemical group ClC1=CC=CC=C1C1=CC=CC=C1 LAXBNTIAOJWAOP-UHFFFAOYSA-N 0.000 description 1
- RVGLUKRYMXEQAH-UHFFFAOYSA-N 3,3-dimethyloxetane Chemical compound CC1(C)COC1 RVGLUKRYMXEQAH-UHFFFAOYSA-N 0.000 description 1
- GQZXRLWUYONVCP-UHFFFAOYSA-N 3-[1-(dimethylamino)ethyl]phenol Chemical compound CN(C)C(C)C1=CC=CC(O)=C1 GQZXRLWUYONVCP-UHFFFAOYSA-N 0.000 description 1
- VUTBELPREDJDDH-UHFFFAOYSA-N 4-amino-5-hydroxymethyl-2-methylpyrimidine Chemical compound CC1=NC=C(CO)C(N)=N1 VUTBELPREDJDDH-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- XLYMOEINVGRTEX-ARJAWSKDSA-N Ethyl hydrogen fumarate Chemical compound CCOC(=O)\C=C/C(O)=O XLYMOEINVGRTEX-ARJAWSKDSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 101150000419 GPC gene Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- ZQRLHBAMCGVPRF-UHFFFAOYSA-N [Rh+].ClP(C(=O)P(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1)(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound [Rh+].ClP(C(=O)P(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1)(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 ZQRLHBAMCGVPRF-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000005452 alkenyloxyalkyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZDBDHFJDNJGRDF-FPLPWBNLSA-N bis(3-prop-2-enoxypropyl) (z)-but-2-enedioate Chemical compound C=CCOCCCOC(=O)\C=C/C(=O)OCCCOCC=C ZDBDHFJDNJGRDF-FPLPWBNLSA-N 0.000 description 1
- UTOVMEACOLCUCK-PLNGDYQASA-N butyl maleate Chemical compound CCCCOC(=O)\C=C/C(O)=O UTOVMEACOLCUCK-PLNGDYQASA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- AIXAANGOTKPUOY-UHFFFAOYSA-N carbachol Chemical group [Cl-].C[N+](C)(C)CCOC(N)=O AIXAANGOTKPUOY-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- FNMTVMWFISHPEV-WAYWQWQTSA-N dipropan-2-yl (z)-but-2-enedioate Chemical compound CC(C)OC(=O)\C=C/C(=O)OC(C)C FNMTVMWFISHPEV-WAYWQWQTSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 description 1
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- WJIBZZVTNMAURL-UHFFFAOYSA-N phosphane;rhodium Chemical compound P.[Rh] WJIBZZVTNMAURL-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 1
- GSNYHCYKJZVAMV-UHFFFAOYSA-N ruthenium(2+);triphenylphosphane Chemical compound [Ru+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 GSNYHCYKJZVAMV-UHFFFAOYSA-N 0.000 description 1
- OIWNHEPSSHYXTG-UHFFFAOYSA-L ruthenium(2+);triphenylphosphane;dichloride Chemical compound Cl[Ru]Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 OIWNHEPSSHYXTG-UHFFFAOYSA-L 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001542 size-exclusion chromatography Methods 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
-
- 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
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
- B01J27/13—Platinum group metals
-
- 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
- B01J31/20—Carbonyls
-
- 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
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
-
- 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
- B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
- B01J2231/52—Isomerisation reactions
-
- 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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0202—Polynuclearity
- B01J2531/0211—Metal clusters, i.e. complexes comprising 3 to about 1000 metal atoms with metal-metal bonds to provide one or more all-metal (M)n rings, e.g. Rh4(CO)12
-
- 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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
-
- 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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
-
- 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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/822—Rhodium
Definitions
- the present invention relates to a method for producing fumaric acid esters by converting maleic acid esters into heterogeneous compounds, and a method for isomerizing maleic esters containing a 2-propenyloxy group in a molecule, the method comprising the steps of:
- the present invention relates to a method for producing fumaric esters containing a 1-propenyloxy group by isomerizing a penoxy group into a 1-propenyloxy group and isomerizing maleic esters into fumaric esters.
- the resulting fumaric acid ester is excellent in polymerizability and gives a polymer having excellent physical properties, and thus is extremely useful in the resin field such as paints and adhesives. Background art
- the double bond of fumaric acid residue is superior to the corresponding double bond of maleic acid residue in its polymerizability and its copolymerizability with a reactive diluent such as styrene.
- a reactive diluent such as styrene.
- maleic anhydride is widely used as a raw material for polybasic acid anhydride. It is known that when a resin is produced using this, isomerization of a maleic acid ester to a fumaric acid ester is performed depending on the type of the saturated polybasic acid or polyhydric alcohol used in combination or the production temperature. However, depending on the conditions, it was not always possible to obtain a fully isomerized unsaturated polyester.
- the present invention has been made in view of such circumstances, and one of the objects of the present invention is to convert maleic acid esters into isomers under mild reaction conditions using a highly active and low corrosive catalyst.
- An object of the present invention is to provide an economically excellent method for producing fumaric acid esters by converting the compound into an ester.
- Another purpose is to use a heterogeneous catalyst that is easy to separate after the reaction and does not corrode, so that high-purity fumarate esters with no remaining catalyst from maleate esters are easier to use than before. It also provides a manufacturing method. Still another object is to react a maleic ester containing a 2-propenyloxy group in the molecule with isomerization of a 2-propenyloxy group into a 1-propenyloxy group and maleic ester. An object of the present invention is to provide a method for isomerizing an acid ester into a fumaric ester to produce a fumaric ester containing a 1-propenyloxy group in one step. Disclosure of the invention
- the present inventors have made intensive studies to solve the above problems, and as a result, obtained maleic esters by isomerization using a catalyst containing a Group VIII element to obtain fumaric esters with high selectivity and high yield A manufacturing method was found.
- maleic esters are isomerized in the presence of a Group VIII metal-supported catalyst, and the catalyst is removed by filtration or the like, so that esters of fumaric acid having no remaining catalyst can be selected with high yield. They have also found that they can be obtained industrially advantageously, and have completed the present invention. That is, the present invention relates to the following matters.
- a method for producing a fumaric acid ester which comprises using an isomerization catalyst containing a VIII group element in a reaction for obtaining a fumaric acid ester by isomerizing a maleic acid ester.
- a phosphine compound represented by a chemical formula PR 3 (wherein R independently represents an alkyl group, a cycloalkyl group or a phenyl group), and / or a base
- R independently represents an alkyl group, a cycloalkyl group or a phenyl group
- the addition amount of the phosphine compound is from 01 to 55.00 parts by mass with respect to 100 parts by mass of the maleic acid ester, and the addition amount of Z or the base is 100 parts by mass of the maleic acid ester.
- the isomerization catalyst is a metal salt or a metal complex containing at least one element selected from the group consisting of ruthenium, rhodium, palladium, iridium and platinum, or (13), 1 A method for producing a fumaric acid ester containing one propenyloxy group.
- the isomerization catalyst is RuC 1 2 (PPh 3 ) 3 , RhC 1 (CO) (PPh 3 ) 2 or RuC 1 H (CO) (PPh 3 ) 3
- a phosphine compound represented by a chemical formula PR 3 (wherein R independently represents an alkyl group, a cycloalkyl group or a phenyl group), and Z or a base (13).
- the addition amount of the phosphine compound is 0.01 to 55.00 parts by mass with respect to 100 parts by mass of maleic esters, and the addition amount of Z or a base is 100 parts by mass of maleic esters.
- the group VIII metal is at least one metal selected from the group consisting of ruthenium, rhodium, palladium, iridium and platinum, and the fumaric acid ester containing a 1-propenyloxy group according to (19), Manufacturing method.
- the maleic esters used in the present invention include compounds having a structural unit represented by the following general formula (I) having a maleic acid residue double bond.
- ⁇ and ⁇ each independently represent ⁇ or an organic group, and ⁇ and ⁇ are not simultaneously ⁇ .
- the maleic esters include compounds having two or more double bonds from a maleic acid residue in the same molecule.
- Compounds included in such maleate esters include, for example, dimethyl maleate, getyl maleate, dipropyl maleate, diisopropyl maleate, dialkyl maleate such as dibutyl maleate, and diaryl maleate.
- Dialkenyl maleate bis (2 Bis (alkenyl) such as 1- (2-propenyloxy) ethyl) malate, bis (3- (2-propenyloxy) propyl) malate, bis (4- (2-propenyloxy) butyl) maleate
- Monoalkyl maleate such as maleate, monomethyl maleate, monoethyl maleate, monopropyl maleate, monoisopropyl maleate, monobutyl maleate, monoalkenyl maleate such as monoaryl maleate, maleate Esters such as monopropoxyshethyl acid, dipropoxyshethyl maleate, monoallyloxyshethyl maleate, diaryloxyshethyl maleate, and 2- (2-provenyloxy) ethyl maleate , 3- (2-propenyloxy) propyl maleate, 4- (2-pro Niruokishi) such alkenyl O alkoxyalkyl maleate such as butyl maleate and the like
- the corresponding maleic esters are isomerized in the presence of a catalyst to produce the corresponding fumaric esters, and further, bis (2- (2-propenyloxy) ethyl) is prepared.
- Bis (alkenyloxyalkyl) malate such as maleate, bis (3- (2-propenyloxy) propyl) maleate, bis (4- (2-propenyloxy) butyl) maleate, or Alkenyloxyalkyl malates, such as 2- (2-Propenyloxy) ethyl maleate, 3- (2-Propenyloxy) propyl maleate, 4- (2-Propenyloxy) butyl maleate, or 2-Propyl
- an unsaturated polyester containing a maleic ester unit having a niloxy group, a high-molecular-weight polymer or an oligomer is represented by As described above, isomerization of 2-propenyloxy group to 1-propenyloxy group
- maleates includes not only the above-mentioned maleic acid esters and derivatives thereof, but also high-molecular-weight substances and oligomers such as unsaturated polyesters containing maleic ester units and urethane oligomers. included.
- female esters includes not only fumaric esters and derivatives thereof, but also high molecular weight substances and oligomers such as unsaturated polyesters containing uranic ester units and urethane oligomers.
- the present invention (1) is a process for producing fumaric esters, which comprises isomerizing maleic esters using an isomerization catalyst containing a Group VIII element to obtain fumaric esters. is there.
- the term “isomerization catalyst” refers to a reaction for isomerizing maleic acid to fumaric acid, and a reaction for isomerizing maleic esters having a 2-propenyloxy group in the molecule.
- the present invention (2) is a method for obtaining a fumaric ester by isomerizing a maleic ester using a compound containing a VIII group element as a catalyst.
- the form of the compound containing a Group VIII element used in the isomerization reaction includes metals or inorganic salts such as sulfates, nitrates, and chlorides, organic acid salts such as acetates and oxalates, and various ligands. Metal complexes are indicated.
- the form of these compounds is particularly preferably a metal complex having a suitable ligand.
- ligands of these metal complexes include triphenylphosphine, carbonyl, hydride, halogen, water, cyclopentadiene, cyclooctane, acetylacetonate, and aryl ligand. It is not limited to.
- These metal complexes include, for example, dichlorotris triphenylphosphine ruthenium (11), dichlorotetrakistriphenylphosphine ruthenium (I I), triruthenium dodeca-potassium ruponyl, carbonyl chlorohydrido tris triphenylphosphine ruthenium (11), chlorocyclopentene genyl bistriphenylphosphine ruthenium (11), biscyclopentene genyl ruthenium, potassium chlorodiphenyl Tris triphenyl phosphine ruthenium (11), dicarponyl diclo pistrif phenyl phosphine ruthenium (II) chloro mouth carbyl bistriphenyl phosphine rhodium (I), tetrakis triphenyl phosphine palladium (0), bis acetate Examples thereof include enylphosphine palla
- these metal complexes When these metal complexes are used as catalysts, these metal complexes may be used as they are, or the components of these metal complexes, that is, metals, ligands, etc. may be separately added to the raw materials, As a result, a method of generating a metal complex during the reaction may be used. Further, a method in which a compound resulting from decomposition of a metal complex during the reaction is used as a catalyst may be used.
- the amount of the isomerization catalyst used in the invention (2) is preferably from 0.01 to 50.00 parts by mass, more preferably from 0.10 to 30.00 parts by mass, per 100 parts by mass of the maleic acid ester. . If the amount of the catalyst is 0.01 parts by mass or less, the isomerization reaction rate becomes slow, and it takes a long time to obtain a high isomerization rate, which is not industrially useful. When the amount of the catalyst exceeds 50.00 parts by mass, the reaction rate increases, but the cost of the catalyst increases, which is economically disadvantageous.
- the catalyst used in the present invention may be used alone or in combination of two or more.
- the invention (3) to the invention (5) are directed to a catalyst used in the invention (2), among the compounds containing a Group VIII element, particularly a group consisting of ruthenium, rhodium, palladium, iridium, and platinum.
- This method is performed using a metal salt or a metal complex containing at least one element selected from the group consisting of:
- the present inventors have found that when the isomerization reaction of maleic esters shown in Invention (2) is performed using a compound containing a Group VIII element as a catalyst, the reason is not clear. However, it has been found that when compounds containing elements such as iron, cobalt, and nickel are used, the activity of group VIII elements tends to be relatively low. Elements such as iron, cobalt, and nickel are relatively inexpensive and readily available industrially, but if their catalytic activity is low, their use must be increased.
- a metal salt or a metal complex containing at least one element selected from the group consisting of ruthenium, rhodium, palladium, iridium, and platinum of the same group VIII when used, high activity can be achieved by selecting an appropriate ligand. , And by-products are also found to be reduced. Further, among compounds containing ruthenium, rhodium, palladium, iridium and platinum used as an isomerization catalyst, compounds containing ruthenium and rhodium are particularly preferred. That is, it is a ruthenium salt, a ruthenium complex, a rhodium salt or a rhodium complex. Further, RuC 1 2 (PPh 3 ) 3 , RhC 1 (CO) (PPh 3 ) 2 and RuC 1 H (CO) (PPh 3 ) 3 are most suitable.
- invention (6) when maleic acid ester le such isomerization reaction, producing side of fumaric acid esters, characterized in that the addition of phosphine compounds and Z or base shown in addition to the isomerization catalyst in the chemical formula PR 3 Is the law.
- R represents an alkyl group, a cycloalkyl group, or a phenyl group. Further, these Rs may be the same substituent or different substituents.
- a compound containing a VIII group element can be used similarly to the catalyst of the invention (2).
- Examples of the form of the compound containing a Group VIII element used in the invention (6) include metals or inorganic salts, organic acid salts, and metal complexes which coordinate various ligands, as in the catalyst of the invention (2). It is.
- the form of these compounds is particularly preferably a metal complex which coordinates a suitable ligand.
- the ligands of these metal complexes include triphenylphosphine, phenol, hydride, halogen, water, cyclopentene, cyclooctene, acetylacetonate, and aryl ligand. It is not limited to. Further, when these metal complexes are used as catalysts, their usage is as described in the case of the invention (2).
- the amount of the isomerization catalyst used in the invention (6) is preferably 0.01 to 50.0 parts by mass with respect to 100 parts by mass of the maleic acid ester. 30.0 parts by mass is more preferred.
- the amount of the catalyst is less than 0.01 part by mass, the rate of the isomerization reaction becomes slow, and it takes a long time to obtain a high isomerization rate, which is not industrially advantageous.
- the amount of the catalyst is 50.0 parts by mass or more, the reaction speed is increased, but the cost of the catalyst is increased, which is economically disadvantageous.
- Additives used in the invention (6) is a phosphine compound and Z or bases represented by the chemical formula PR 3. Hereinafter, each additive will be described in detail.
- the substituent R of the phosphine compound PR 3 substituents customary, for example, an alkyl group, a cycloalkyl group, a Hue sulfonyl group and the like can be used. Specific examples thereof include, but are not limited to, tri-n-butyl phosphine, triphenyl phosphine, tricyclohexyl phosphine, and the like. These Rs may be the same substituent, or may be different substituents.
- the base used as an additive a usual inorganic base or organic base is used.
- the inorganic base include sodium hydroxide, potassium hydroxide, calcium hydroxide, and ammonia.
- the organic base include triethylamine and tripropropyl. Examples include, but are not limited to, pyramine, pyridine, morpholine, and the like.
- the invention (7) shows the optimum range of the phosphine compound to be added and the addition amount of Z or a base in the invention (6).
- the present inventors the invention as shown in (6), in addition to the isomerization catalyst, in the et, dramatically isomerization reaction rate and a phosphine compound represented by the chemical formula PR 3 and adding a Z or base We found that the selectivity was high.
- the amount of phosphine to be added is as large as 50.0 parts by mass or more with respect to 100 parts by mass of maleic ester, and / or the amount of base added is 100% by mass of maleic ester.
- a large amount such as 50.0 parts by mass or more with respect to parts by mass, even if the amount is further increased, the effect of addition is saturated and the reaction rate does not increase, so that it is considered to be ineffective.
- the present invention (8) to invention (11) show that in the above isomerization, it is possible to use one or more kinds of VIII group metal-supported catalysts in which a VHI group metal is supported on a carrier. It is preferable that the supported amount of the VIII group metal is 0.05 to 10% by mass based on the total mass of the metal-supported catalyst (the carrier and the VIII group metal).
- the present invention shows that among group VIII metals, ruthenium, rhodium, palladium, iridium, and platinum are preferable from the viewpoint of activity.
- the present invention shows that in the isomerization catalyst, it is particularly preferable that at least one of the group VIII metals is ruthenium.
- the present invention (11) shows that it is preferable to use one or more types of supported catalysts in which the ruthenium metal is supported on the support so that the content of the ruthenium metal is 0.05 to 10% by mass in the total catalyst.
- silica, alumina, silica-alumina, zeolite, activated carbon, titania, magnesia, or other inorganic compounds can be used, but not limited thereto.
- the amount of the metal supported on the carrier is preferably 0.05 to 20% by mass, more preferably 0.05 to 10% by mass, and particularly preferably 2 to 10% by mass based on the total amount of the catalyst. If the supported amount is less than 0.05% by mass, the reaction time will be delayed, and if it exceeds 20% by mass, the amount of metal not involved in the isomerization reaction increases, which is not preferable.
- the amount of the metal-supported catalyst to be used is as follows.
- It is preferably from 01 to 50 parts by mass, more preferably from 1 to 30 parts by mass.
- catalyst amount is 0.0
- the amount is less than 1 part by mass, the reaction time is delayed. If the amount is more than 50 parts by mass, the amount of metal that does not participate in the isomerization reaction increases, which is not preferable.
- the catalyst used in the present invention a single catalyst or a plurality of catalysts can be used.
- the reaction temperature is 30 to 200 ° C, preferably 80 to 180 ° C, more preferably 120 to 160 ° C.
- Reaction temperature 3 When the temperature is lower than 0 ° C., the reaction is slow. When the temperature exceeds 200 ° C., a side reaction relating to other functional groups such as esters and urethane proceeds, which is not preferable.
- the isomerization reaction using a catalyst supported on a carrier as in inventions (8) to (11) can be performed in a solvent.
- the solvent that can be used is not particularly limited, but some of the specific solvents are exemplified below. When these solvents are used, two or more solvents may be mixed. In particular, the presence of alcohols can improve the catalytic activity.
- the metal-supported catalyst can be easily separated by filtration or the like, so that they are particularly useful in the method for producing fumaric esters according to the present invention.
- a known polymerization inhibitor may be added. I do not care.
- the reaction pressure is not particularly limited, and the reaction can be performed under reduced pressure, normal pressure, or pressurized pressure.
- the reaction is performed in an atmosphere of an inert gas such as nitrogen, helium, argon, or the like, but preferably in an inexpensive nitrogen stream.
- an inert gas such as nitrogen, helium, argon, or the like, but preferably in an inexpensive nitrogen stream.
- the invention (12) is a process for isomerizing a maleic ester having a 2-propenyloxy group in a molecule by using an isomerization catalyst containing a Group VIII element.
- Fumaric esters containing one propenyloxy group are one of radically polymerizable monomers having excellent properties as described above.
- the production method is as follows. After synthesizing a monomer containing a 2-propenyloxy group and a maleic acid group, under mild conditions, the 2-propenyloxy group is converted into a 1-propenyloxy group, A preferred method is one in which the group is isomerized into a fumaric acid group at the same time in one step. We have:
- the catalyst used in the invention (12) is an isomerization catalyst containing a group VIII element similar to the catalyst of the invention (1).
- the present invention (13) is characterized in that the above-mentioned isomerization reaction is carried out using a compound containing a Group VIII element as an isomerization catalyst, and the production of fumaric esters containing 1-propenyloxy group Is the way.
- the form of the compound containing a Group VIII element used in the present invention (13) may be a metal or an inorganic salt such as a sulfate, a nitrate or a chloride, an acetate, or an oxalate as in the catalyst of the invention (2).
- Organic salts such as salts, and metal complexes that coordinate various ligands are shown.
- the form of these compounds is particularly preferably a metal complex which coordinates a suitable ligand.
- ligands of these metal complexes include triphenylphosphine, carbonyl, hydride, halogen, water, cyclopentadiene, cyclooctane, acetylacetonato, and aryl ligand. It is not limited.
- these metal complexes When these metal complexes are used as catalysts, these metal complexes may be used as they are, or the components of these metal complexes, that is, metals, ligands, etc. may be separately added to the raw materials, As a result, a method of generating a metal complex during the reaction may be used. Further, a method in which a compound resulting from decomposition of a metal complex during the reaction is used as a catalyst may be used.
- the amount of the isomerization catalyst used in the invention (13) is preferably from 0.01 to 55.00 parts by mass, preferably from 0.1 to 30.00 parts by mass, per 100 parts by mass of the maleic acid esters. Parts by weight are more preferred. If the amount of the catalyst is 0.01 parts by mass or less, the rate of the isomerization reaction becomes slow, and it takes a long time to obtain a high isomerization rate, which is not industrially advantageous. When the amount of the catalyst is more than 50000 parts by mass, the reaction speed increases, but the cost of the catalyst increases, which is economically disadvantageous.
- invention (16) is a compound containing a group VIII element as a catalyst used in the invention (13).
- the method is performed using a metal salt or a metal complex containing at least one element selected from the group consisting of ruthenium, rhodium, palladium, iridium, and platinum.
- the compounds containing ruthenium, rhodium, palladium, iridium and platinum used as the catalyst for isomerism particularly preferred are compounds containing ruthenium and rhodium. That is, it is a ruthenium salt, a ruthenium complex, a rhodium salt, or an oral dime complex. Also in particular: RuCl 2 (PPh 3 ) 3 , RhCl (CO) (PP h 3 ) 2 and RuCl H (CO) (PPh 3 ) 3 are optimal.
- Invention (17) includes a group VIII element as described in inventions (13) to (16) as an isomerization catalyst when producing fumaric esters containing 1-propenyloxy group. in addition to using compounds, further comprising a dramatically isomerization reaction rate and selectivity is high effective and phosphine compound represented by the chemical formula PR 3 and adding a Z or a base.
- Additives used in the present invention (17) is a contact and / or basic phosphine compound represented by the chemical formula PR 3.
- the catalyst used in the invention (17) can be embodied using the same compound as the catalyst of the invention (6) and containing a VIII element.
- the form of the compound containing a group VIII element used in the invention (17) is the same as that of the catalyst of the invention (6), and includes an inorganic salt, an organic acid salt, and a metal complex which coordinates various ligands. Is shown.
- the form of these compounds is particularly preferably a metal complex which coordinates a suitable ligand.
- the ligands of these metal complexes also include, but are not limited to, triphenylphosphine, carbonyl, hydride, halogen, water, cyclopentene, cyclooctene, acetylacetonato, and aryl ligands. Not something. Further, when these metal complexes are used as catalysts, their usage is as described in the case of the invention (2).
- the amount of the isomerization catalyst used in the invention (17) is preferably from 0.01 to 50.00 parts by mass, preferably from 0.1 to 30.00 parts by mass, per 100 parts by mass of the maleic acid ester. Parts by weight are more preferred. If the amount of the catalyst is 0.01 parts by mass or less, the rate of the isomerization reaction becomes slow, and it takes a long time to obtain a high isomerization rate, which is not industrially advantageous. When the amount of the catalyst is 50000 parts by mass or more, the reaction speed increases, but the cost of the catalyst increases, which is economically disadvantageous.
- the present invention (18) characterized by adding 2- propenyl Niruokishi based on maleic acid esters containing in addition to the reaction of the catalyst for isomerization, a phosphine compound Contact and / or base represented by the chemical formula PR 3
- a phosphine compound Contact and / or base represented by the chemical formula PR 3
- the optimum range of the added amount of the phosphine compound and Z or the base is shown.
- the description of the inventions (8) to (11) is based on the reaction for isomerizing maleic esters containing a 2-propenyloxy group in the molecule.
- 2-propenyloxy group isomerized to 1-proenyloxy group
- maleic esters are converted to fumaric esters This also applies to the reaction of making a kind of isomerism.
- the present invention provides an isomerization catalyst using one or more types of supported catalysts in which a Group VIII metal is supported on a carrier in a concentration of 0.05 to 10% by mass in the supported catalyst.
- one propenyl Niruokishi c present invention is a method for producing fumaric acid esters containing a group (20), VIII group metals, ruthenium, rhodium, palladium, at least one selected from the group consisting of I Rijiumu and platinum This is a method for producing a fumaric acid ester containing a 1-hydroxyl-hydroxy group as a metal.
- the present invention (21) is a process for producing a fumaric acid ester containing a 1-propenyloxy group in which at least one kind of Group VI metal is ruthenium in the isomerization catalyst.
- the present invention (22) provides a method for producing fumaric esters containing 1-propenyloxy group, wherein one or more types of supported catalysts in which ruthenium metal is supported on a carrier in an amount of 0.05 to 10% by mass. Indicates that it is preferable to use
- the reaction temperature is from 0 to 200 ° C, preferably from 50 to 180, more preferably from 80 ° C to 160. If the reaction temperature is lower than 0 ° C, the reaction is slow. If it exceeds 200 ° C, the monomer may be polymerized, which may lower the reaction yield.
- the product obtained as a result of the isomerization reaction can be increased in purity by a known purification method.
- the purification method include, but are not limited to, ordinary distillation, extraction, recrystallization, gas chromatography, dialysis, and the like.
- the reaction pressure is not particularly limited, and the reaction can be performed under reduced pressure, normal pressure, or pressurized pressure.
- the atmosphere of the reaction system There is no particular limitation on the atmosphere of the reaction system, and the reaction can be performed in a reducing or oxidizing atmosphere. Atmosphere such as air or inert gas such as nitrogen, helium, argon Although it can be carried out under air, it is preferably carried out under a practically inexpensive nitrogen atmosphere.
- an isomerization reaction is carried out by adding a polymerization inhibitor, the effect of inhibiting the polymerization by adding a small amount of oxygen may increase depending on the type of polymerization inhibitor such as a phenolic polymerization inhibitor.
- the isomerization reaction in the present invention can naturally be performed without a solvent when the raw material maleate is liquid. However, when the raw material maleic ester is solid, or when the raw material maleic ester is liquid, it does not dissolve the catalyst etc. or does not mix evenly In some cases, the reaction rate may not be sufficient, or the reaction product may gel during the reaction.
- the solvent is preferably selected so as to dissolve the raw materials such as maleic acid ester, catalyst, polymerization inhibitor and the like well. Further, it is desirable that the solvent be modified during the reaction or the solvent itself does not react with the raw material.
- aromatic hydrocarbons such as benzene, toluene, and xylene
- ethers such as dimethyl ether, dimethyloxetane, methoxyethyl ether, tetrahydrofuran, and 1,4-dioxane
- Esters such as ethyl and butyl acetate, ketones such as acetone and methyl ethyl ketone, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, isobutanol, etc.
- Alcohols and water aromatic hydrocarbons such as benzene, toluene, and xylene
- ethers such as dimethyl ether, dimethyloxetane, methoxyethyl ether, tetrahydrofuran, and 1,4-dioxane
- Esters such as ethyl and butyl acetate
- solvents when used, they may be used alone, or two or more solvents may be mixed.
- the amount of the solvent used is preferably from 1 part by mass to 1,000 parts by mass, more preferably from 100 parts by mass to 200 parts by mass, based on 100 parts by mass of the maleic acid ester as the reaction raw material. preferable.
- the amount of the solvent is 1 part by mass or less, the effect of the solvent does not appear because the amount is too small for the raw material.
- the amount of the solvent is more than 1,000 parts by mass, a problem arises when the amount of the solvent is too large, the raw material concentration becomes low, and the reaction rate becomes slow.
- the reaction vessel used for the isomerization reaction of the present invention is not particularly limited. Lath lining, stainless steel, Teflon containers, etc. can be used. Example
- the compound was dissolved in deuterated methylform and the chemical shift was calculated using tetramethylsilane as the internal standard.
- a 100 ml glass reaction tube was charged with 2.0 g of dimethyl maleate and 2.0 g of toluene, and 0.020 g of dichlorotris (triphenylphosphine) ruthenium (II) as a catalyst at 140 ° C. The temperature rose. Then, the mixture was heated and stirred at the same temperature for 3 hours. After removing the solvent from the reaction mixture under reduced pressure, the reaction mixture was analyzed by 1 H-NMR and GPC. I got it. Dimethyl maleate was 97% converted to dimethyl fumarate, and the selectivity of the monomer on GPC was 98%.
- the maleic group in bis (2_ (2-probenyloxy) ethyl) maleate is converted to 95% to fumaric group, and the 2-propenyl group is converted to 91% to 1-propenyl group.
- the selectivity of the monomer on GPC was 92%.
- the maleic group in bis (2- (2-p-butenyloxy) ethyl) malate is converted to 99% of fumaral group, and the 2-propenyl group is converted to 85% of 11-propenyl group.
- the selectivity of the monomer on GPC was 89%.
- the male group in bis (2- (2-propenyloxy) ethyl) malate is 89% converted to a fumaric group, and the 2-propenyl group is converted to 76% in a 1-propyl group.
- I was The selectivity of the monomer on GPC is 96%.
- the maleic group in bis (2- (2-propenyloxy) ethyl) maleate is 35% converted to a fumaric group, and the 2-butanol group is 28% converted to a 1-propenyl group.
- the selectivity of the monomer on GPC was 92%.
- a 10 ml glass reaction tube was charged with dimethyl maleate 2.00 g and toluene 2.00 g, and dichlorotris (triphenylphosphine) ruthenium (II) 0.002 g as a catalyst, and heated to 140 ° C. Then, the mixture was heated and stirred at the same temperature for 3 hours. After the solvent was removed from the reaction solution under reduced pressure, the reaction solution was analyzed by 1 H-NMR and GPC. Dimethyl maleate was 36% converted to dimethyl fumarate, and the selectivity of monomer on GPC was 98%.
- Table 1 shows a list of Examples 1 to 15 and Comparative Examples 1 to 3.
- a 20 ml autoclave was charged with 2.07 g of dimethyl maleate and 437 mg of RuZ activated carbon having a metal loading of 5% by mass, 4 ml of 1-propanol, and the temperature was raised to 150. Then, the mixture was heated and stirred at the same temperature for 2 hours to precipitate a white solid. After dissolving the contents with methanol, the catalyst was removed by filtration, and the solvent was distilled off from the obtained filtrate under reduced pressure to obtain 1.95 g of a white solid. NMR analysis confirmed that the product was 100% isomerized to dimethyl fumarate.
- Example 21 In a 1L autoclave, 30.0 g of bis (2- (2-propenyloxy) ethyl) malate and 6.4 g of 1 ⁇ 11 activated carbon with a metal loading of 5% by mass, and tetrakis [methylene-1-3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] 30 mg of methane (trade name: I RGANO XI 010, manufactured by Nippon Ciba Geigy Co., Ltd.) and 300 ml of 2-propanol were charged. The temperature rose. Then, the mixture was heated and stirred at the same temperature for 2 hours.
- methane trade name: I RGANO XI 010, manufactured by Nippon Ciba Geigy Co., Ltd.
- isomerization of maleic esters in the presence of a catalyst enables high-yield and highly selective fumaric esters to be obtained, and particularly in the fields of resin raw materials and plasticizers. It is extremely useful.
- a maleic ester having a 2-propenyloxy group in a molecule is isomerized from a 2-propenyloxy group to a 1-propenyloxy group, The reaction for isomerizing the compounds into fumaric esters can be efficiently performed in one step.
- a heterogeneous catalyst that is easy to separate and does not corrode, high-purity fumaric acid esters with no catalyst remaining can be obtained.
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Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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EP01904427A EP1176136A4 (en) | 2000-02-15 | 2001-02-14 | PROCESS FOR THE PREPARATION OF FUMIC ACID ESTERS |
AU32283/01A AU3228301A (en) | 2000-02-15 | 2001-02-14 | Process for producing fumaric ester |
KR1020017013167A KR20010112941A (ko) | 2000-02-15 | 2001-02-14 | 푸마르산에스테르류의 제조방법 |
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JP2000-41343 | 2000-02-15 | ||
JP2000041343 | 2000-02-15 |
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WO2001060780A1 true WO2001060780A1 (fr) | 2001-08-23 |
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PCT/JP2001/001028 WO2001060780A1 (fr) | 2000-02-15 | 2001-02-14 | Procede de production d'ester fumarique |
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US (1) | US20020002306A1 (ja) |
EP (1) | EP1176136A4 (ja) |
KR (1) | KR20010112941A (ja) |
CN (1) | CN1362944A (ja) |
AU (1) | AU3228301A (ja) |
WO (1) | WO2001060780A1 (ja) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2006525402A (ja) * | 2003-05-08 | 2006-11-09 | ザ ユニバーシティ オブ サザン ミシシッピ リサーチ ファンデーション | 塗料配合物中の反応性希釈剤 |
US8101701B2 (en) | 2006-12-01 | 2012-01-24 | Menicon Nect Co., Ltd. | Fumaric acid derivatives and ophthalmic lenses using the same |
JP2012506397A (ja) * | 2008-10-21 | 2012-03-15 | ロディア オペレーションズ | ニトリル官能基を有する化合物を製造するための方法 |
CN112624919A (zh) * | 2020-10-13 | 2021-04-09 | 南京紫鸿生物科技有限公司 | 一种药用辅料硬脂富马酸钠的低成本制备方法 |
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DE10163586A1 (de) * | 2001-12-21 | 2003-07-03 | Clariant Gmbh | Verwendung von weichmacherfreien, wässrigen copolymeren Poly(vinylester)- Dispersionen in Lebensmittelbeschichtungsmassen |
US20140099364A2 (en) | 2004-10-08 | 2014-04-10 | Forward Pharma A/S | Controlled release pharmaceutical compositions comprising a fumaric acid ester |
CN100376540C (zh) * | 2006-04-25 | 2008-03-26 | 华中科技大学 | 一种合成富马酸二(1,2-丙二醇)酯的工艺方法 |
CN103649041A (zh) * | 2011-06-08 | 2014-03-19 | 比奥根艾迪克Ma公司 | 制备高纯度和结晶的富马酸二甲酯的方法 |
CN106187775B (zh) * | 2015-05-05 | 2020-10-27 | 国药集团化学试剂有限公司 | 一种马来酸二甲酯提纯方法 |
WO2017013672A1 (en) | 2015-07-23 | 2017-01-26 | Natco Pharma Ltd | Process for the preparation of pharmaceutical grade dimethyl fumarate |
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JP2006525402A (ja) * | 2003-05-08 | 2006-11-09 | ザ ユニバーシティ オブ サザン ミシシッピ リサーチ ファンデーション | 塗料配合物中の反応性希釈剤 |
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JP2012506397A (ja) * | 2008-10-21 | 2012-03-15 | ロディア オペレーションズ | ニトリル官能基を有する化合物を製造するための方法 |
CN112624919A (zh) * | 2020-10-13 | 2021-04-09 | 南京紫鸿生物科技有限公司 | 一种药用辅料硬脂富马酸钠的低成本制备方法 |
CN112624919B (zh) * | 2020-10-13 | 2023-02-03 | 南京紫鸿生物科技有限公司 | 一种药用辅料硬脂富马酸钠的低成本制备方法 |
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AU3228301A (en) | 2001-08-27 |
US20020002306A1 (en) | 2002-01-03 |
KR20010112941A (ko) | 2001-12-22 |
CN1362944A (zh) | 2002-08-07 |
EP1176136A1 (en) | 2002-01-30 |
EP1176136A4 (en) | 2005-12-07 |
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