WO2017209199A1 - Procédé de production de dianhydride d'acide tétracarboxylique alicyclique - Google Patents
Procédé de production de dianhydride d'acide tétracarboxylique alicyclique Download PDFInfo
- Publication number
- WO2017209199A1 WO2017209199A1 PCT/JP2017/020320 JP2017020320W WO2017209199A1 WO 2017209199 A1 WO2017209199 A1 WO 2017209199A1 JP 2017020320 W JP2017020320 W JP 2017020320W WO 2017209199 A1 WO2017209199 A1 WO 2017209199A1
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- WO
- WIPO (PCT)
- Prior art keywords
- compound
- group
- carbon atoms
- alkyl group
- represented
- Prior art date
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- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 36
- 150000000000 tetracarboxylic acids Chemical class 0.000 title claims description 25
- 125000002723 alicyclic group Chemical group 0.000 title claims description 22
- -1 olefin compound Chemical class 0.000 claims abstract description 208
- 238000006243 chemical reaction Methods 0.000 claims abstract description 139
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 121
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 121
- 239000000203 mixture Substances 0.000 claims abstract description 83
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000005749 Copper compound Substances 0.000 claims abstract description 37
- 150000001880 copper compounds Chemical class 0.000 claims abstract description 37
- 150000002941 palladium compounds Chemical class 0.000 claims abstract description 36
- 239000002253 acid Substances 0.000 claims abstract description 27
- 238000007789 sealing Methods 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000006467 substitution reaction Methods 0.000 claims abstract description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 118
- 125000000217 alkyl group Chemical group 0.000 claims description 99
- 239000002904 solvent Substances 0.000 claims description 68
- 238000003756 stirring Methods 0.000 claims description 56
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 41
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 40
- 150000001875 compounds Chemical class 0.000 claims description 38
- 229910052799 carbon Inorganic materials 0.000 claims description 33
- 239000007789 gas Substances 0.000 claims description 30
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 30
- 125000003118 aryl group Chemical group 0.000 claims description 28
- 150000001721 carbon Chemical group 0.000 claims description 28
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 26
- 239000003960 organic solvent Substances 0.000 claims description 24
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 23
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 125000004185 ester group Chemical group 0.000 claims description 17
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 125000003342 alkenyl group Chemical group 0.000 claims description 11
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 claims description 5
- VIJUZNJJLALGNJ-UHFFFAOYSA-N n,n-dimethylbutanamide Chemical compound CCCC(=O)N(C)C VIJUZNJJLALGNJ-UHFFFAOYSA-N 0.000 claims description 5
- 150000002148 esters Chemical group 0.000 claims description 4
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 150000002632 lipids Chemical class 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- 229940125898 compound 5 Drugs 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 238000013019 agitation Methods 0.000 abstract description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 156
- VAALVBPLSFRYMJ-XXMNONFOSA-N O=C1OC(=O)[C@@H]([C@@H](C23)C4)[C@H]1[C@@H]4C3[C@@H]1C[C@H]2[C@H]2C(=O)OC(=O)[C@@H]12 Chemical compound O=C1OC(=O)[C@@H]([C@@H](C23)C4)[C@H]1[C@@H]4C3[C@@H]1C[C@H]2[C@H]2C(=O)OC(=O)[C@@H]12 VAALVBPLSFRYMJ-XXMNONFOSA-N 0.000 description 91
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 90
- 239000000243 solution Substances 0.000 description 88
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 63
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 58
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 58
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 54
- 239000007787 solid Substances 0.000 description 52
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 43
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 39
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 38
- 239000000706 filtrate Substances 0.000 description 36
- 230000015572 biosynthetic process Effects 0.000 description 33
- 238000003786 synthesis reaction Methods 0.000 description 33
- 238000001914 filtration Methods 0.000 description 31
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 29
- 229910052786 argon Inorganic materials 0.000 description 29
- 235000019253 formic acid Nutrition 0.000 description 29
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 23
- 239000004642 Polyimide Substances 0.000 description 22
- 239000007788 liquid Substances 0.000 description 22
- 229920001721 polyimide Polymers 0.000 description 22
- 229910052763 palladium Inorganic materials 0.000 description 19
- 239000000725 suspension Substances 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 238000004128 high performance liquid chromatography Methods 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 15
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 15
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 14
- 238000002425 crystallisation Methods 0.000 description 14
- 238000004817 gas chromatography Methods 0.000 description 14
- 239000011521 glass Substances 0.000 description 14
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 13
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 238000000746 purification Methods 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 230000005587 bubbling Effects 0.000 description 11
- 230000008025 crystallization Effects 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 239000012044 organic layer Substances 0.000 description 11
- 238000002203 pretreatment Methods 0.000 description 11
- 235000017557 sodium bicarbonate Nutrition 0.000 description 11
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 9
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- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 9
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- 0 *[C@](C(C([C@](C1)[C@@]2O)[C@](*)C3[C@@](C4)[C@@]5N)[C@]1[C@]2*=C)C3[C@@]4[C@]5O Chemical compound *[C@](C(C([C@](C1)[C@@]2O)[C@](*)C3[C@@](C4)[C@@]5N)[C@]1[C@]2*=C)C3[C@@]4[C@]5O 0.000 description 8
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 8
- 101150003085 Pdcl gene Proteins 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
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- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 8
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- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 2
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- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 2
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- DNXUGBMARDFRGG-UHFFFAOYSA-N 3,6-dioxocyclohexa-1,4-diene-1,2-dicarbonitrile Chemical compound O=C1C=CC(=O)C(C#N)=C1C#N DNXUGBMARDFRGG-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- BMTAFVWTTFSTOG-UHFFFAOYSA-N Butylate Chemical compound CCSC(=O)N(CC(C)C)CC(C)C BMTAFVWTTFSTOG-UHFFFAOYSA-N 0.000 description 1
- GXGBARTYHJDIID-UHFFFAOYSA-N C(CO)O.C(C)OC(C)O Chemical compound C(CO)O.C(C)OC(C)O GXGBARTYHJDIID-UHFFFAOYSA-N 0.000 description 1
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000012359 Methanesulfonyl chloride Substances 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZCJHLBHJGLCVRU-UHFFFAOYSA-N O=C(C1C2C3C=CC1C3)C(C1C=CC3C1)C3C2=O Chemical compound O=C(C1C2C3C=CC1C3)C(C1C=CC3C1)C3C2=O ZCJHLBHJGLCVRU-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical class [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
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- 229910021536 Zeolite Inorganic materials 0.000 description 1
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
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- 239000004927 clay Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
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- SBTSVTLGWRLWOD-UHFFFAOYSA-L copper(ii) triflate Chemical compound [Cu+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F SBTSVTLGWRLWOD-UHFFFAOYSA-L 0.000 description 1
- JIDMEYQIXXJQCC-UHFFFAOYSA-L copper;2,2,2-trifluoroacetate Chemical compound [Cu+2].[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F JIDMEYQIXXJQCC-UHFFFAOYSA-L 0.000 description 1
- ITFUHOHJQIDNQW-UHFFFAOYSA-L copper;2,2-dimethylpropanoate Chemical compound [Cu+2].CC(C)(C)C([O-])=O.CC(C)(C)C([O-])=O ITFUHOHJQIDNQW-UHFFFAOYSA-L 0.000 description 1
- DYROSKSLMAPFBZ-UHFFFAOYSA-L copper;2-hydroxypropanoate Chemical compound [Cu+2].CC(O)C([O-])=O.CC(O)C([O-])=O DYROSKSLMAPFBZ-UHFFFAOYSA-L 0.000 description 1
- KOKFUFYHQQCNNJ-UHFFFAOYSA-L copper;2-methylpropanoate Chemical compound [Cu+2].CC(C)C([O-])=O.CC(C)C([O-])=O KOKFUFYHQQCNNJ-UHFFFAOYSA-L 0.000 description 1
- MRYMYQPDGZIGDM-UHFFFAOYSA-L copper;4-methylbenzenesulfonate Chemical compound [Cu+2].CC1=CC=C(S([O-])(=O)=O)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 MRYMYQPDGZIGDM-UHFFFAOYSA-L 0.000 description 1
- PUHAKHQMSBQAKT-UHFFFAOYSA-L copper;butanoate Chemical compound [Cu+2].CCCC([O-])=O.CCCC([O-])=O PUHAKHQMSBQAKT-UHFFFAOYSA-L 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- XNEQAVYOCNWYNZ-UHFFFAOYSA-L copper;dinitrite Chemical compound [Cu+2].[O-]N=O.[O-]N=O XNEQAVYOCNWYNZ-UHFFFAOYSA-L 0.000 description 1
- LZJJVTQGPPWQFS-UHFFFAOYSA-L copper;propanoate Chemical compound [Cu+2].CCC([O-])=O.CCC([O-])=O LZJJVTQGPPWQFS-UHFFFAOYSA-L 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- RYPWQHONZWFXBN-UHFFFAOYSA-N dichloromethyl(methylidene)-$l^{3}-chlorane Chemical compound ClC(Cl)Cl=C RYPWQHONZWFXBN-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- FVRDWQRPXYJEJK-UHFFFAOYSA-N dimethyl tricyclo[6.2.1.02,7]undeca-2(7),4,9-triene-4,5-dicarboxylate Chemical compound COC(=O)C1=C(CC2=C(C1)C1CC2C=C1)C(=O)OC FVRDWQRPXYJEJK-UHFFFAOYSA-N 0.000 description 1
- CMROXXQZKZJCMK-UHFFFAOYSA-N dimethyl tricyclo[6.2.1.02,7]undeca-2,4,6,9-tetraene-4,5-dicarboxylate Chemical compound COC(=O)c1cc2C3CC(C=C3)c2cc1C(=O)OC CMROXXQZKZJCMK-UHFFFAOYSA-N 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
- 238000006073 displacement reaction Methods 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
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- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
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- 150000002500 ions Chemical group 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 1
- RMAZRAQKPTXZNL-UHFFFAOYSA-N methyl bicyclo[2.2.1]hept-2-ene-5-carboxylate Chemical compound C1C2C(C(=O)OC)CC1C=C2 RMAZRAQKPTXZNL-UHFFFAOYSA-N 0.000 description 1
- GXMIHVHJTLPVKL-UHFFFAOYSA-N n,n,2-trimethylpropanamide Chemical compound CC(C)C(=O)N(C)C GXMIHVHJTLPVKL-UHFFFAOYSA-N 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- PZKNFJIOIKQCPA-UHFFFAOYSA-N oxalic acid palladium Chemical compound [Pd].OC(=O)C(O)=O PZKNFJIOIKQCPA-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 1
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 description 1
- 229940090668 parachlorophenol Drugs 0.000 description 1
- BMWSHTRJDNMWIV-UHFFFAOYSA-N pentacyclo[8.6.0.03,8.011,13.014,16]hexadeca-1(16),3,5,7,10,13-hexaene-2,9-dione Chemical compound C12=C(C3=C(C=4C(C5=CC=CC=C5C(C1=4)=O)=O)C3)C2 BMWSHTRJDNMWIV-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- REIBSTGDUUEVSB-HGSJOUDDSA-N tetramethyl (1S,8R,9S,10R)-tricyclo[6.2.1.02,7]undeca-2,4,6-triene-4,5,9,10-tetracarboxylate Chemical compound COC(=O)[C@H]1[C@H]2C[C@@H]([C@H]1C(=O)OC)C3=CC(=C(C=C23)C(=O)OC)C(=O)OC REIBSTGDUUEVSB-HGSJOUDDSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- KKCRFSXXFNWENY-UHFFFAOYSA-N trimethyl bicyclo[2.2.1]heptane-2,3,5-tricarboxylate Chemical compound C1C2C(C(=O)OC)CC1C(C(=O)OC)C2C(=O)OC KKCRFSXXFNWENY-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
- C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C69/753—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of polycyclic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/08—Bridged systems
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Definitions
- the present invention relates to a method for producing alicyclic tetracarboxylic acid dianhydride, and a method for producing an ester compound which is an intermediate thereof.
- alicyclic tetracarboxylic acid dianhydride is a compound useful as a monomer for producing a polyimide.
- alicyclic carbonyl compounds are utilized in various fields, and alicyclic tetracarboxylic acid dianhydride is a compound useful as a monomer for polyimide production.
- 3aR, 4R, 5R, 5aR, 8aS, 9S, 10S, 10aS) -decahydro-1H, 3H-4, 10: 5, 9-dimethanonaphtho [2,3-c: 6, 7-c '] difuran -1,3,6,8-tetraone (hereinafter sometimes referred to as DNDA) is one of useful compounds.
- DNDA 1,3R, 4, 4a, 5, 8, 8a-hexahydro-1,4: 5,8- produced from norbornadiene and cyclopentadiene Dimethanonaphthalene (hereinafter sometimes referred to as BNDE) is reacted with carbon monoxide in the presence of a palladium catalyst to give tetramethyl (1R, 2R, 3S, 4S, 5S, 6S, 7R, 8R) -decahydro-1, After conversion to 4: 5,8-dimethanonaphthalene-2,3,6,7-tetracarboxylate (hereinafter sometimes referred to as DNME), this is subjected to an anhydride reaction in the presence of an acid to obtain DNDA.
- Methods of manufacturing are known (see, for example, Patent Documents 1 and 2 and Non-Patent Document 1).
- Patent Document 1 reports on a method for producing DNDA and a polyimide using DNDA. Specifically, BNDE, methanol, palladium carbon, and copper chloride are placed in a reaction vessel and then reacted with carbon monoxide to obtain DNME, which is an ester compound, which is a tetracarboxylic acid using hydrochloric acid. The compound is converted to a cyclization reaction with acetic anhydride.
- Patent Document 2 describes a method for producing a carboxylic acid anhydride from a carboxylic acid ester compound.
- DNDA is produced by reacting the ester compound DNME in acetic acid in the presence of an acid such as an ion exchange resin or p-toluenesulfonic acid.
- an acid such as an ion exchange resin or p-toluenesulfonic acid.
- acetic acid is distilled off under reduced pressure to obtain DNDA as a solid, and the precipitate is filtered.
- Non-Patent Document 1 DNDA is reacted with a diamine to synthesize a polyimide having solubility and transparency.
- cyclopentadiene and norbornadiene are reacted under heating to obtain BNDE, followed by BNDE, methanol, palladium carbon, copper chloride and reacting with carbon monoxide to obtain ester compound DNME, Transesterification is carried out in formic acid in the presence of an acid (p-toluenesulfonic acid), and dehydration (cyclization reaction) is carried out in acetic anhydride.
- the obtained DNDA is crystallized with acetic anhydride, but the purity is not described.
- JP-A-2-235842 Japanese Patent Application Laid-Open No. 5-140141
- Patent Document 1 When the inventor of the present application re-tested Patent Document 1, since BNDE was not dissolved in methanol, the reproducibility of the reaction was poor, and the result was a very low yield. Further, when the production method of Patent Document 2 was additionally tested, acetic anhydride remained in DNDA, and it was found that it was unsuitable as a production method of acid dianhydride used when synthesizing a polyimide. Furthermore, when the same crystallization method as in Non-Patent Document 1 was performed, several weight percent of acetic anhydride and acetic acid remained in DNDA. Since acetic anhydride reacts with diamine, this crystallization method was found to be unsuitable as a method for producing acid dianhydride for polyimide synthesis.
- the object of the present invention is industrially suitable which can produce alicyclic tetracarboxylic acid dianhydride such as DNDA or an ester compound in high yield and high purity by a simple method under a mild condition. It is an object of the present invention to provide a process for producing an alicyclic tetracarboxylic acid dianhydride or an ester compound. Another object of the present invention is to provide an alicyclic tetracarboxylic acid dianhydride and an ester compound suitable as a monomer for polymer production such as polyimide.
- the present invention relates to the following matters.
- Process 1 wherein an norbornadiene represented by the following formula (1) and a cyclopentadiene represented by the following formula (2) are reacted to obtain an olefin compound represented by the following formula (3) Then, an olefin compound represented by the formula (3), an alcohol compound and carbon monoxide are reacted in the presence of a palladium compound and a copper compound to obtain an ester compound represented by the following formula (4): Then, the ester compound represented by the formula (4) is reacted in the presence of an acid in an organic solvent to obtain an alicyclic tetracarboxylic acid dianhydride represented by the following formula (5): Including In the step 2, at least one of the following two operations (A) and (B) is performed, and a method for producing an alicyclic tetracarboxylic acid dianhydride.
- R represents an alkyl group having 1 to 10 carbon atoms
- a method for producing an ester compound comprising performing at least one of the following two operations (A) and (B) in the step: (A) After mixing a palladium compound, a copper compound, and an alcohol compound in a reaction vessel, the following substitution operation of (C-2) and stirring operation of following (C-1) are sequentially performed to be mixed with the olefin compound .
- R 1 is an alkyl group having 1 to 15 carbon atoms or an alkenyl group having 1 to 15 carbon atoms.
- Three R 1 s may be the same as or different from each other, and two or more R 1 s may be R 1 may be bonded to each other to form one or more rings together with the carbon atom to which they are attached
- the hydrogen atom on the alkyl group is an alkenyl group having 1 to 5 carbon atoms, -COOR a A carbon atom in the alkyl group which may be substituted by the ester group, aryl group having 6 to 15 carbon atoms, alkoxy group represented by -OR b , cyano group, or group represented by -OSO 2 R c
- the hydrogen atom on the aryl group may be substituted by a phenyl group, an alkyl group having 1 to 10 carbon atoms, or an alkenyl group having 1 to 10 carbon atoms.
- R a , R b and R c are
- R 1 is as defined above, and R represents an alkyl group having 1 to 10 carbon atoms).
- the olefin compound and the ester compound are represented by the following formulas (8) and (8-1), the following formulas (9) and (9-1), the following formulas (10) and (10-1), and the following formula (11) And (11-1), the following formulas (11-2) and (11-3), the following formulas (12) and (12-1), the following formulas (13) and (13-1), the following formula (14) And (14-1), the following formulas (15) and (15-1), the following formulas (16) and (16-1), or the following formulas (17) and (17-1).
- R 2 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an ester group represented by —COOR d , or a cyano group.
- a hydrogen atom on the alkyl group is an ester represented by —COOR a
- R 2 may be substituted to an aryl group having a carbon number of 6 to 10.
- the two R 2 s may be the same as or different from each other, and are bonded to each other together with the carbon atom to which they are bonded
- R d and R a in the ester group represent an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, wherein R represents Indicates an alkyl group having 1 to 10 carbon atoms.
- R 3 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cyano group, or an ester group represented by —COOR d .
- a hydrogen atom on an alkyl group is an ester represented by —COOR a
- R 6 may be substituted to an aryl group having a carbon number of 6 to 10.
- the two R 3 s may be the same as or different from each other, and are bonded to each other together with one carbon atom to which they are bonded
- R d and R a in the ester group represent an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, wherein R represents Indicates an alkyl group having 1 to 10 carbon atoms.
- R 4 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
- Two R 4 may be the same as or different from each other, and they are bonded to each other to bind to each other) And may form one or more rings together with the atom, wherein R represents an alkyl group having 1 to 10 carbon atoms.
- R 5 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group represented by —OR b , or a group represented by —OSO 2 R c.
- R b has 1 to carbon atoms 10 alkyl group, or an aryl group having 6 to 10 carbon atoms
- R c is an alkyl group having 1 to 10 carbon atoms, or .2 one R 5 which represents an aryl group having 6 to 10 carbon atoms are the same to each other They may also be different and may be combined with each other to form one or more rings with the carbon atom to which they are attached, wherein R represents an alkyl group having 1 to 10 carbon atoms.
- R represents an alkyl group having 1 to 10 carbon atoms
- R 6 represents a hydrogen atom, a phenyl group, or an alkyl group having 1 to 10 carbon atoms.
- Six R 6 may be the same as or different from each other, and two or more R 6 may be They may be bonded to each other to form one or more rings together with the carbon atom to which they are bonded, wherein R represents an alkyl group having 1 to 10 carbon atoms.
- R 7 represents a hydrogen atom, a phenyl group, or an alkyl group having 1 to 10 carbon atoms.
- Three R 7 s may be the same as or different from each other, and two or more R 7 s may be They may be bonded to each other to form one or more rings together with the carbon atom to which they are bonded, wherein R represents an alkyl group having 1 to 10 carbon atoms.
- R 8 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
- R 8 s may be the same or different, and two or more R 8 s may be bonded to each other And may form one or more rings together with the carbon atom to which they are attached, wherein R represents an alkyl group having 1 to 10 carbon atoms.
- R 9 represents a hydrogen atom, a phenyl group, or an alkyl group having 1 to 10 carbon atoms.
- Three R 9 s may be the same as or different from each other, and two or more R 9 s may be They may be bonded to each other to form one or more rings together with the carbon atom to which they are bonded, wherein R represents an alkyl group having 1 to 10 carbon atoms.
- R represents an alkyl group having 1 to 10 carbon atoms
- R represents an alkyl group having 1 to 10 carbon atoms
- R 10 may be the same or different, and represents any of a methyl group, an ethyl group, an n-propyl group, or an isopropyl group).
- Ms represents a mesyl group represented by —SO 2 CH 3 ).
- Ms represents a mesyl group represented by —SO 2 CH 3.
- R 11 may be the same or different and is a methyl group, an ethyl group, an n-propyl group, or an isopropyl group Show one)
- Industrially suitable alicyclic tetracarboxylic acid dianhydride capable of producing an alicyclic tetracarboxylic acid dianhydride such as DNDA or an ester compound in high yield by a simple method under mild conditions according to the present invention It is possible to provide a method for producing an organic compound or an ester compound.
- an alicyclic tetracarboxylic acid dianhydride and an ester compound suitable as a monomer for polymer production such as polyimide can be provided.
- DNDA alicyclic tetracarboxylic acid dianhydride
- R is as defined above, and represents an alkyl group having 1 to 10 carbon atoms).
- Step 1 of the present invention is a step of reacting norbornadiene with cyclopentadiene to obtain an olefin compound represented by the above formula (3).
- Step 1 of reacting norbornadiene of the present invention with cyclopentadiene as shown in the figure below, (1R, 4S, 5S, 8R) -1, 4, 4a, 5, 8 having the same steric structure as the target product DNDA.
- 1R, 4S, 5S, 8R 1, 4, 4a, 5, 8 having the same steric structure as the target product DNDA.
- 8a-hexahydro-1,4 5,8-dimethanonaphthalene (BNDE), (1R, 4S, 4as, 5R, 8S, 8as) -1,4,4a, 5,8, which are stereoisomers.
- 8a-Hexahydro-1,4 5,8-dimethanonaphthalene (BNDE-1) and (1R, 4S, 4ar, 5R, 8S, 8ar) -1, 4, 4a, 5, 8, 8a-hexahydro-1 , 4: 5,8-Dimethanonaphthalene (BNDE-2) is obtained. Thereafter, the desired product BNDE can be obtained by distilling the obtained reaction mixture.
- the target products BNDE, BNDE-1 and BNDE-2 have similar boiling points, and if rectification, only high-purity target product BNDE can be obtained, but in simple distillation, a mixture consisting mainly of these three compounds can be obtained. .
- high-purity BNDE may be used in the next step 2, but a mixture containing BNDE and BNDE-1 may be used.
- highly pure DNME can be produced even by using a mixture of BNDE and BNDE-1.
- the mass ratio of BNDE / BNDE-1 is preferably 50/50 to 99/1 as the mixture (ie, the olefin compound represented by the formula (3)), and the content of BNDE in the mixture is Preferably, it is 50 to 99% by weight.
- the mass fraction after reaction is very small and is not a problem throughout the present invention.
- BNDE is a compound shown by said Formula (6).
- the cyclopentadiene used in step 1 of the present invention is represented by the above formula (2).
- Cyclopentadiene is a monomer of dicyclopentadiene, and by heating dicyclopentadiene at 160 to 200 ° C., cyclopentadiene can be quantitatively obtained.
- the cyclopentadiene used in step 1 of the present invention can also be generated in situ by the thermal decomposition of dicyclopentadiene.
- Dicyclopentadiene is a compound represented by the following formula (21).
- the amount of the norbornadiene to be used is preferably 1 mol or more, more preferably 2 to 10 mol, per 1 mol of cyclopentadiene.
- the amount of norbornadiene used is preferably 2 mol or more, more preferably 4 to 20 mol, per 1 mol of dicyclopentadiene. is there.
- an organic solvent may or may not be used.
- the solvent used is not particularly limited as long as it does not inhibit the reaction, and for example, formic acid, aliphatic carboxylic acids (eg, acetic acid, propionic acid, trifluoroacetic acid etc.), organic sulfonic acids (eg, methanesulfonic acid) Trifluoromethanesulfonic acid etc.), alcohols (eg methanol, ethanol, isopropyl alcohol, t-butyl alcohol, ethylene glycol, triethylene glycol etc.), ketones (eg acetone, butanone, cyclohexanone etc.), aliphatic carbonization Hydrogens (eg, n-pentane, n-hexane, n-heptane, cyclohexane etc.), amides (eg, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone etc.), amides
- the amount of the organic solvent used is appropriately adjusted depending on the uniformity and the stirring property of the reaction solution, but usually 1 to 50 g, more preferably 2 to 20 g per 1 g of norbornadiene. .
- Step 1 of the present invention is carried out, for example, by a method such as mixing norbornadiene and cyclopentadiene, or norbornadiene, cyclopentadiene and an organic solvent and stirring.
- the reaction temperature at that time is preferably 140 to 250 ° C., more preferably 150 to 220 ° C.
- the reaction pressure of the reaction in step 1 of the present invention is not particularly limited.
- the reaction environment is also not particularly limited, but the reaction in Step 1 of the present invention is preferably performed in an inert gas (for example, nitrogen, argon, helium) stream or under an inert gas atmosphere.
- an inert gas for example, nitrogen, argon, helium
- the reaction is usually carried out using an equimolar amount or an excess of norbornadiene to cyclopentadiene.
- the olefin compound represented by the formula (3) containing the target product BNDE is filtered, distilled, column chromatography, etc. Once isolated and purified by a general method such as, the next step is carried out.
- distilling BNDE it is preferable to carry out distillation at a temperature at which BNDE does not undergo thermal decomposition.
- the distillation of BNDE is preferably carried out at 50 to 180 ° C., more preferably 50 to 160 ° C.
- the norbornadiene used in excess in the reaction can be recovered and purified after purification by a general method such as distillation, column chromatography and the like.
- step 2 of the present invention an olefin compound represented by the formula (3), an alcohol compound and carbon monoxide are reacted in the presence of a palladium compound and a copper compound to obtain an ester compound represented by the following formula (4) It is a process.
- R represents an alkyl group having 1 to 10 carbon atoms, preferably a methyl group, an ethyl group, an n-propyl group or an isopropyl group, more preferably a methyl group, an ethyl group or an isopropyl group.
- the olefin compound represented by the formula (3) which can be used in this step is not limited to only BNDE as described above, but may be a mixture containing BNDE and BNDE-1.
- the content of BNDE in the mixture is preferably 50 to 99% by weight.
- Examples of the alcohol compound used in step 2 of the present invention include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, pentyl alcohol, methoxyethanol and ethoxyethanol
- Ethylene glycol, triethylene glycol and the like can be mentioned, preferably methanol, ethanol, n-propyl alcohol, isopropyl alcohol, more preferably methanol, ethanol, isopropyl alcohol.
- the amount of the alcohol compound used is preferably 0.1 to 200 g, more preferably 1 to 100 g, based on 1 g of the olefin compound of the formula (3).
- an organic solvent other than the alcohol may or may not be used.
- the organic solvent other than the alcohol used is not particularly limited as long as it does not inhibit the reaction, and for example, formic acid, aliphatic carboxylic acids (for example, acetic acid, propionic acid, trifluoroacetic acid etc.), organic sulfonic acids (for example Methanesulfonic acid, trifluoromethanesulfonic acid, etc.), aliphatic hydrocarbons (eg, n-pentane, n-hexane, n-heptane, cyclohexane, etc.), amides (eg, N, N-dimethylformamide, N , N-dimethylacetamide, N-methylpyrrolidone etc.), ureas (N, N'-dimethylimidazolidinone etc.), ethers (eg diethylether, diisopropylether, tetrahydrofuran, dioxane, 1,2-methylenedioxy Benzene, etc.), aromatic
- the amount of the organic solvent other than the alcohol used is preferably 0.1 to 200 g, and more preferably 1 to 100 g, per 1 g of the olefin compound of the formula (3).
- the palladium compound used in this reaction is not particularly limited as long as it contains palladium, for example, palladium halides such as palladium chloride and palladium bromide; palladium organic acid salts such as palladium acetate and palladium oxalate; Palladium inorganic acid salts such as palladium and palladium sulfate; palladium complexes such as bis (acetylacetonato) palladium, bis (1,1,1-5,5,5-hexafluoroacetylacetonato) palladium; palladium on carbon And palladium carbon and palladium alumina supported on a carrier such as alumina and the like, and preferably palladium chloride and palladium carbon are used.
- palladium halides such as palladium chloride and palladium bromide
- palladium organic acid salts such as palladium acetate and palladium oxalate
- Palladium inorganic acid salts such
- palladium compound is used in a meaning including a so-called compound, palladium metal alone, or carrier-supported palladium on which a palladium metal alone is supported on a carrier.
- the palladium compounds may be used singly or in combination of two or more.
- the amount of the palladium compound used is preferably 0.0001 to 0.2 mol, more preferably 0.001 to 0.1 mol, per 1 mol of the olefin compound of the formula (3).
- Pd (0) can be oxidized to Pd (II) if Pd (II) in the palladium compound is reduced to Pd (0).
- Pd (0) It is not particularly limited, and examples thereof include copper compounds, iron compounds and the like, with preference given to copper compounds.
- copper compound specifically, copper, copper acetate, copper propionate, copper normal butylate, copper 2-methylpropionate, copper pivalate, copper lactate, copper butyrate, copper benzoate, copper trifluoroacetate, bis (Acetylacetonato) copper, bis (1,1,1-5,5,5-hexafluoroacetylacetonato) copper, copper chloride, copper bromide, copper iodide, copper nitrate, copper nitrite, copper sulfate, Examples thereof include copper phosphate, copper oxide, copper hydroxide, copper trifluoromethanesulfonate, copper p-toluenesulfonate, and copper cyanide.
- iron compound ferric chloride, ferric nitrate, ferric sulfate, ferric acetate and the like can be mentioned.
- a divalent copper compound is used, more preferably copper (II) chloride is used.
- a "copper compound” shall be used in the meaning also containing a copper simple substance.
- metal compounds such as “iron compound” shall also be used in the meaning also containing a metal simple substance. In addition, you may use these metallic compounds individually or in mixture of 2 or more types.
- the amount of the copper compound used is preferably 4 to 50 mol, more preferably 5 to 20 mol, per 1 mol of the olefin compound of the above formula (3).
- the temperature (the temperature at the time of operation before the reaction, and the reaction temperature) is usually -10 to 100 ° C, preferably -10 to 70 ° C, and more preferably 0 to 50 ° C.
- step 2 at least one of the following operations (A) and (B) needs to be performed.
- substitution operation (C-2) and stirring operation (C-1) are sequentially performed to mix with the olefin compound.
- C-2 After mixing a palladium compound, a copper compound, an alcohol compound, and an ortho ester compound in a reaction vessel, the following substitution operation (C-2) is carried out to mix with the olefin compound.
- C-1) Stir under an atmosphere of carbon monoxide.
- C-2) After depressurizing the reaction vessel, the operation of sealing carbon monoxide gas is performed once or more.
- the operations (C-2) and (C-1) may be alternately repeated twice or more, and after performing the operation (C-1), the operation (C-2) is further performed.
- the olefin compound may be mixed after performing the operation of
- the operation (B) after performing the operation (C-2), the operation (C-1) may be performed.
- the carbonylation reaction that is, the reaction for producing the ester compound represented by the formula (4)
- the carbonylation reaction proceeds rapidly, and the ester compound is obtained in a high yield. If the pretreatment is not carried out or is insufficient, the yield of ester compound is reduced.
- the operation of reducing the pressure in the reaction vessel and the operation of sealing carbon monoxide are repeated once or twice or more (the operation of (C-2)), and stirring is performed for a fixed time ( It is carried out by the operation (C-1).
- the operation (C-2) is carried out in order to replace the gas in the reaction vessel with carbon monoxide, and is appropriately controlled depending on the degree of reduced pressure and the amount of carbon monoxide enclosed, but after reducing the pressure in the reaction vessel
- the operation of sealing the carbon monoxide gas is performed once or more, preferably 2 to 5 times.
- the solution containing palladium compound, copper compound, alcohol compound and, if necessary, other organic solvent may be stirred. It is not necessary to stir.
- the degree of pressure reduction is appropriately adjusted and is not particularly limited. For example, by setting the pressure to 50 to 200 torr, preferably 70 to 150 torr, the gas in the reaction vessel can be efficiently replaced with carbon monoxide.
- the operation (C-1) may be carried out while circulating carbon monoxide, or it may be carried out by temporarily putting carbon monoxide in a bag or container having confidentiality, such as natural rubber.
- the reaction vessel may be pressurized with carbon monoxide.
- the volume of the carbon monoxide bag or container is, for example, 0.1 L or more, preferably 0.2 to 10 L, per 1 L of the reaction container.
- Operation (C-1) One required time, ie, a stirring time of the solution is, for example, 1 hour or more, preferably 1 to 5 hours.
- the number of pre-treatments may be appropriately adjusted according to the reaction vessel and the volume of carbon monoxide used, but preferably once or more. Two to five times.
- the operation of (C-1) and the operation of (C-2) do not necessarily have to be repeated the same number of times.
- the operation of (C-1) is not performed,
- the solution obtained and the olefin compound may be mixed.
- the temperature at the time of operation is usually ⁇ 10 to 100 ° C., preferably ⁇ 10 to 70 ° C., and more preferably 0 to 50 ° C.
- Operation (B) In operation (B), after mixing a palladium compound, a copper compound, an alcohol compound, an ortho ester compound and, if necessary, another organic solvent in a reaction vessel, an operation of reducing the pressure in the reaction vessel, and carbon monoxide gas Are enclosed (operation (C-2) above), and mixed with the olefin compound.
- operation (B) is the same as the operation (A) except that the operation is mixed with the ortho ester compound and the operation of the (C-1) does not have to be performed.
- the operation (B) after the operation (C-2) and before the addition of the olefin compound, in the same manner as the operation (A), the operation (C-1) of the above (under an atmosphere of carbon monoxide)
- the solution may be stirred, but in the case of the operation (B) using an ortho ester compound, the carbonylation reaction (that is, in the formula (4)) may be performed without performing the operation of the above (C-1)
- the reaction to form the ester compound shown) proceeds rapidly, and the ester compound is obtained in high yield.
- this operation (B) by using the ortho ester compound, it is possible to reduce the number of times of repeating the pressure reducing operation and the carbon monoxide gas charging operation in the operation (C-2).
- the operation (C-2) is also performed in operation (B) to replace the gas in the reaction vessel with carbon monoxide, and is appropriately adjusted depending on the degree of pressure reduction and the amount of carbon monoxide enclosed.
- the operation of sealing carbon monoxide gas is performed once or more, preferably 2 to 5 times.
- a solution containing a palladium compound, a copper compound, an alcohol compound, an ortho ester compound, and, if necessary, another organic solvent, while reducing pressure or sealing carbon monoxide The stirring may or may not be stirring.
- the degree of pressure reduction is appropriately adjusted and is not particularly limited. For example, by setting the pressure to 50 to 200 torr, preferably 70 to 150 torr, the gas in the reaction vessel can be efficiently replaced with carbon monoxide.
- the temperature at the time of operation is usually ⁇ 10 to 100 ° C., preferably ⁇ 10 to 70 ° C., and more preferably 0 to 50 ° C.
- Examples of the ortho ester compound used in this operation (B) include compounds represented by the following formula (22), such as methyl orthoformate and ethyl orthoformate, and preferably methyl orthoformate is used.
- R f represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom, a methyl group, more preferably a hydrogen atom.
- R e represents an alkyl group having 1 to 5 carbon atoms, preferably a methyl group or an ethyl group, more preferably a methyl group.
- the three R e may be the same or different, but are preferably the same.
- the amount of the ortho ester compound used is preferably 0.5 to 5 mol, more preferably 0.8 to 3 mol, per 1 mol of the olefin compound of the above formula (3). By setting the amount used in this range, the carbonylation reaction can proceed efficiently, and the ester compound represented by the above formula (4) can be obtained in an industrially suitable yield.
- the olefin compound is mixed with the obtained solution.
- an olefin compound dropwise to the obtained solution may be dropped as it is in the case of a liquid, but is preferably dropped as a mixture with an organic solvent, preferably an organic solvent other than alcohols.
- the time taken for the dropping is not particularly limited, for example, the total amount to be dropped is dropped into the solution for 1 hour or more, preferably 2 hours or more, more preferably 2 hours or more and 16 hours or less.
- the solvent in which the olefin compound is dissolved can be changed as appropriate, it is preferable that the solvent mentioned as the organic solvent other than the alcohol used in the above-mentioned step 2 is included.
- reaction The reaction in the step 2 of the present invention may be carried out, for example, after the operation of the above (C-1) or (C-2) and then the obtained solution (a solution containing a palladium compound, a copper compound and an alcohol compound, or palladium
- the olefin compound (BNDE) is mixed with a solution containing a compound, a copper compound, an alcohol compound, and an ortho ester compound and stirred.
- the reaction temperature at that time is generally ⁇ 10 to 100 ° C., preferably ⁇ 10 to 70 ° C., and more preferably 0 to 50 ° C.
- Carbon monoxide is also used after the operation of (C-1) or (C-2) is finished.
- BNDE olefin compound
- carbon monoxide absorption continues with the progress of the reaction, so carbon monoxide needs to be continuously supplied to the reactor. Therefore, even after the operation of (C-1) or (C-2) is finished, it is preferable to mix with the olefin compound while stirring under an atmosphere of carbon monoxide.
- the reaction pressure of the reaction in step 2 of the present invention may be atmospheric pressure (normal pressure) or may be increased.
- the reaction in step 2 of the present invention is performed under an atmosphere of carbon monoxide, but diluted with an inert gas (for example, nitrogen, argon, helium) to an atmosphere containing carbon monoxide and an inert gas. You may go.
- the number of operations (C-1) and (C-2) and the reaction time are also appropriately adjusted according to the pressure and concentration of carbon monoxide.
- step 2 of the present invention the ester compound represented by the above formula (4) is obtained, but in the present invention, for example, after completion of the reaction, filtration, concentration, crystallization, recrystallization, distillation, column chromatography etc.
- the ester compound may be isolated and purified once by a general method, the next step may be carried out, but the reaction solution obtained is used as it is or in the next step without isolation and purification. After switching to the solvent, it may be used in the next step.
- the olefin compound shown by a following formula may be contained depending on the reaction conditions of process 1, and refinement
- this ester compound include the following compounds.
- the solvent to be used is not particularly limited as long as it can separate these compounds, but alcohols (eg, methanol, ethanol, isopropyl alcohol, t-butyl alcohol, ethylene glycol, triethylene glycol etc.), ketones (Eg, acetone, butanone, cyclohexanone etc.), aliphatic hydrocarbons (eg, n-pentane, n-hexane, n-heptane, cyclohexane etc.), amides (eg, N, N-dimethylformamide, N , N-dimethylacetamide, N-methylpyrrolidone, N, N-dimethylbutyroamide etc., ureas (N, N'-dimethylimidazolidinone etc.), ethers (eg diethyl ether, diisopropyl ether, tetrahydro
- halogenated hydrocarbons aliphatic hydrocarbons and aromatic hydrocarbons are used.
- an activated carbon in order to remove the impurity produced
- the activated carbon treatment is carried out by adding activated carbon to the solution containing the ester compound after reaction, stirring and filtering.
- the stirring temperature is usually 10 to 100 ° C., preferably 15 to 70 ° C.
- the amount of activated carbon to be used is usually 30% by weight or less, preferably 0.01 to 20% by weight, based on BNDE.
- step 3 of the present invention the ester compound represented by the above formula (4) is reacted in the presence of an acid in an organic solvent to obtain the alicyclic tetracarboxylic acid dianhydride (DNDA represented by the above formula (5) ) Is obtained.
- DNDA alicyclic tetracarboxylic acid dianhydride
- the acid is not particularly limited, and examples thereof include mineral acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, chlorosulfuric acid and nitric acid; organic substances such as methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid Sulfonic acids; Halogenated carboxylic acids such as chloroacetic acid and trifluoroacetic acid, ion exchange resins, sulfuric acid silica gel, zeolite, acidic alumina and the like are mentioned, preferably mineral acids, organic sulfonic acids, more preferably organic sulfonic acids Be done. In addition, you may use these acids individually or in mixture of 2 or more types.
- the amount of the acid used is preferably 0.0001 to 0.1 mol, more preferably 0.001 to 0.05 mol, per 1 mol of the ester compound represented by the formula (4).
- the reaction of step 3 of the present invention is preferably carried out in an organic solvent.
- organic solvents particularly organic acid solvents such as formic acid, acetic acid, propionic acid and the like are preferable. These solvents may be used alone or in combination of two or more.
- the amount of the solvent used is appropriately adjusted depending on the homogeneity and the stirring property of the reaction solution, preferably 0.1 to 100 ml, more preferably 1 to 10 ml per 1 g of the ester compound represented by the formula (4). It is.
- the reaction in step 3 of the present invention is carried out, for example, by mixing the ester compound represented by the above formula (4), an acid, and an organic solvent (preferably an organic acid solvent) and stirring the mixture.
- the reaction temperature at that time is preferably 50 to 180 ° C., more preferably 70 to 150 ° C.
- the reaction pressure of the reaction in step 3 of the present invention is not particularly limited.
- the reaction environment is also not particularly limited, but the reaction in step 3 of the present invention is preferably performed in an inert gas (for example, nitrogen, argon, helium) stream or under an inert gas atmosphere.
- an inert gas for example, nitrogen, argon, helium
- DNDA obtained here can be isolated and purified by a general method such as filtration, concentration, recrystallization, sublimation and the like.
- DNDA in order to obtain DNDA, it is desirable to obtain by filtration.
- an organic acid in particular formic acid
- the formic acid dissolves DNDA, so if filtering in the formic acid solvent, the amount of DNDA obtained decreases. Therefore, it is desirable to replace formic acid with another solvent and then filter to obtain DNDA.
- the solvent used for the solvent substitution is not particularly limited as long as it does not react with DNDA, but hydrocarbon solvents such as toluene and heptane are preferable in view of low solubility in DNDA and solubility in formic acid.
- the DNDA obtained by filtration is preferably further purified by crystallization or the like.
- Non-Patent Document 1 DNME is treated with formic acid, p-toluenesulfonic acid and acetic anhydride, and then crystallization operation is carried out with acetic anhydride to obtain DNDA.
- acetic anhydride and acetic acid remain in DNDA obtained by the same crystallization method as in Non-Patent Document 1.
- Polyimides are produced by the reaction of acid dianhydrides with diamines. Since acetic anhydride and acetic acid react with diamine, DNDA in which acetic anhydride and acetic acid remain is not suitable as a raw material for synthesizing a polyimide.
- treatment with acetic anhydride may be performed. Similar to Non-Patent Document 1, acetic anhydride and acetic acid remain as DNDA obtained at this time.
- the crystallization operation is performed in another solvent system.
- This crystallization operation is performed by a general method.
- the solid is dissolved in a solvent having high solubility (hereinafter also referred to as a good solvent) while heating, a solvent having low solubility (hereinafter also referred to as a poor solvent) is added, and cooling is performed to precipitate crystals.
- a solvent having high solubility hereinafter also referred to as a good solvent
- a solvent having low solubility hereinafter also referred to as a poor solvent
- the good solvent used for crystallization is not particularly limited as long as it is a solvent having high solubility in DNDA, but dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, and the like used in polyimide production N-methyl pyrrolidone, N, N-dimethyl butyroamide, ⁇ -caprolactone, N, N-dimethyl isobutyramide, 1,3-dimethyl-2-imidazolidinone and the like are preferable.
- One poor solvent is not particularly limited as long as it is a solvent having a low solubility in DNDA, but a solvent having a low boiling point in view of remaining in solid crystals is preferable.
- hexane, cyclohexane, heptane, toluene, chlorobenzene, tetrahydrofuran, diethyl ether, diisopropyl ether, ethyl acetate, acetonitrile, acetone, cyclohexanone and the like can be mentioned.
- the good solvent is contained, for example, in an amount of about 0.05 to 5% by weight in the DNDA.
- the good solvent is used at the time of polyimide production, the remaining of the good solvent has no problem.
- DNDA has low solubility in many organic solvents.
- DNDA having no residual good solvent eg, one obtained by completely removing the solvent by sublimation purification
- Polyimides are usually produced by the reaction of an acid dianhydride with a diamine in a solvent. If the solubility of the acid dianhydride is poor, the reaction with the diamine is slow, which is very disadvantageous as an industrial process for producing a polyimide.
- DNDA in which a good solvent is solvated is a suitable compound for producing a polymer such as polyimide. That is, the preferred compound (DNDA) obtained according to the present invention can be prepared from a good solvent, specifically N, N-dimethylformamide, N, N-acetamide, N-methylpyrrolidone and N, N-dimethylbutyroamide. And cycloaliphatic tetracarboxylic acid dianhydride represented by the following formula (5) containing at least one solvent molecule selected from the group consisting of It is preferred that the content of the solvated solvent is 0.05 to 5% by weight with respect to the total amount of the acid dianhydride described by the solvated formula (5).
- Step 2 Application of Step 2 (Production Method of Ester Compound)
- the reaction of the olefin compound, the alcohol compound and the carbon monoxide in the step 2 is not limited to the olefin compound of the formula (3) as a substrate but can be applied to the olefin compound represented by the following general formula (7).
- the reaction conditions and the operation method may be appropriately changed depending on the solubility, the reactivity and the like of the compound, but are the same as the olefin compound of the formula (3).
- R 1 is an alkyl group having 1 to 15 carbon atoms or an alkenyl group having 1 to 15 carbon atoms.
- Three R 1 s may be the same as or different from each other, and two or more R 1 s may be bonded to each other to form one or more rings (for example, 6 to 15 carbon atoms) together with the carbon atom to which they are bonded.
- An aryl group, preferably a phenyl group) may be formed.
- the hydrogen atom on the alkyl group is an alkenyl group of 1 to 5 carbon atoms, an ester group of -COOR a , an aryl group of 6 to 15 carbon atoms, an alkoxy group of -OR b , a cyano group, or -OSO
- the group represented by 2 R c may be substituted, and a carbon atom in the alkyl group may form a carbonyl group.
- the hydrogen atom on the aryl group is a phenyl group, an alkyl group having 1 to 10 carbon atoms, or an alkenyl group having 1 to 10 carbon atoms, preferably a phenyl group or an alkenyl group having 1 to 10 carbon atoms, more preferably carbon It may be substituted by several 1 to 10 alkenyl groups.
- R a , R b and R c each represent an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, preferably a methyl group, an ethyl group, an n-propyl group or an isopropyl group It is.
- the olefin compound represented by the general formula (7) more preferably contains a group derived from bicyclo [2.2.1] hept-2-ene, in other words, contains a norbornene ring structure.
- bonds and forms may contain the structure shown by the said General formula (7).
- the olefin compound may contain two or more of the structures represented by the general formula (7).
- An ester compound obtained by reacting the olefin compound represented by the general formula (7) with carbon monoxide is a compound represented by the following general formula (7-1).
- R represents an alkyl group having 1 to 10 carbon atoms, preferably a methyl group, an ethyl group, an n-propyl group or an isopropyl group.
- R 1 is as defined above.
- the olefin compound represented by the general formula (7) and the ester compound represented by the general formula (7-1) preferably, the following formulas (8) and (8-1), and the following formulas (9) and (9) -1), the following formulas (10) and (10-1), the following formulas (11) and (11-1), the following formulas (11-2) and (11-3), the following formulas (12) and (12) -1), the following formulas (13) and (13-1), the following formulas (14) and (14-1), the following formulas (15) and (15-1), the following formulas (16) and (16-1) And compounds represented by any one of the following formulas (17) and (17-1).
- R 2 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an ester group represented by —COOR d , or a cyano group.
- the hydrogen atom on the alkyl group may be substituted by an ester group represented by -COOR a or an aryl group having 6 to 10 carbon atoms.
- the two R 2 s may be the same as or different from each other, and may be bonded to each other to form one or more rings together with the carbon atom to which they are bonded.
- R d and R a in the ester group each represent an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, preferably a methyl group, an ethyl group, an n-propyl group or an isopropyl group.
- R represents an alkyl group having 1 to 10 carbon atoms, preferably a methyl group, an ethyl group, an n-propyl group or an isopropyl group.
- R 3 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cyano group, or an ester group represented by —COOR d .
- the hydrogen atom on the alkyl group may be substituted by an ester group represented by -COOR a or an aryl group having 6 to 10 carbon atoms.
- Two R 3 s may be the same as or different from each other, and may be bonded to each other to form one or more rings together with the carbon atom to which they are bonded.
- R d and R a in the ester group each represent an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, preferably a methyl group, an ethyl group, an n-propyl group or an isopropyl group.
- R represents an alkyl group having 1 to 10 carbon atoms, preferably a methyl group, an ethyl group, an n-propyl group or an isopropyl group.
- R 4 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
- the two R 4 s may be the same as or different from each other, and may be bonded to each other to form one or more rings together with the carbon atom to which they are bonded.
- R represents an alkyl group having 1 to 10 carbon atoms, preferably a methyl group, an ethyl group, an n-propyl group or an isopropyl group.
- R 5 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group represented by —OR b or a group represented by —OSO 2 R c .
- R b is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, preferably a methyl group.
- R c represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, preferably a methyl group.
- Two R 5 s may be the same as or different from each other, and may be bonded to each other to form one or more rings together with the carbon atom to which they are bonded.
- R represents an alkyl group having 1 to 10 carbon atoms, preferably a methyl group, an ethyl group, an n-propyl group or an isopropyl group.
- R represents an alkyl group having 1 to 10 carbon atoms, preferably a methyl group, an ethyl group, an n-propyl group or an isopropyl group.
- R 6 represents a hydrogen atom, a phenyl group, or an alkyl group having 1 to 10 carbon atoms.
- Six R 6 s may be the same as or different from each other, and two or more R 6 s may be bonded to each other to form one or more rings together with the carbon atom to which they are bonded.
- R represents an alkyl group having 1 to 10 carbon atoms, preferably a methyl group, an ethyl group, an n-propyl group or an isopropyl group.
- R 7 represents a hydrogen atom, a phenyl group, or an alkyl group having 1 to 10 carbon atoms. Three R 7 s may be the same as or different from each other, and two or more R 7 s may be bonded to each other to form one or more rings together with the carbon atom to which they are bonded.
- R represents an alkyl group having 1 to 10 carbon atoms, preferably a methyl group, an ethyl group, an n-propyl group or an isopropyl group.
- R 8 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
- R 8 s may be the same as or different from each other, and two or more R 8 s may be bonded to each other to form one or more rings together with the carbon atom to which they are bonded.
- R represents an alkyl group having 1 to 10 carbon atoms, preferably a methyl group, an ethyl group, an n-propyl group or an isopropyl group.
- R 9 represents a hydrogen atom, a phenyl group, or an alkyl group having 1 to 10 carbon atoms. Three R 9 s may be the same as or different from each other, and two or more R 9 s may be bonded to each other to form one or more rings together with the carbon atom to which they are bonded.
- R represents an alkyl group having 1 to 10 carbon atoms, preferably a methyl group, an ethyl group, an n-propyl group or an isopropyl group.
- R represents an alkyl group having 1 to 10 carbon atoms, preferably a methyl group, an ethyl group, an n-propyl group or an isopropyl group.
- R represents an alkyl group having 1 to 10 carbon atoms, preferably a methyl group, an ethyl group, an n-propyl group or an isopropyl group.
- R 2 and R are as defined above.
- R and Ms are as defined above.
- the same ester compound can be obtained.
- the compounds represented by the formula (8b) and the compound represented by the formula (17a) are different, the compound represented by the formula (8B) formed therefrom and the compound represented by the formula (17A)
- the structures of the compounds are the same.
- stereochemistry may differ depending on the raw material to be used and reaction conditions.
- an ester compound represented by the following formula (18) is preferable.
- R 10 which may be the same or different, represents any one of a methyl group, an ethyl group, an n-propyl group and an isopropyl group, preferably a methyl group and an ethyl group.
- the olefin compound represented by following formula (19) is preferable.
- Ms represents a mesyl group represented by -SO 2 CH 3 .
- ester compound represented by the formula (11-1) an ester compound represented by the following formula (20) is preferable.
- R 11 which may be the same or different, is a methyl group, an ethyl group, an n-propyl group or an isopropyl group, and is preferably a methyl group or an ethyl group.
- BNDE and BNDE-1 correspond to the olefin compound represented by the formula (3)
- DNME corresponds to the ester compound represented by the formula (4)
- DNDA represents the alicyclic tetracarboxylic acid represented by the formula (5) It corresponds to acid dianhydride.
- BNDE-1 (1R, 4S, 4as, 5R, 8S, 8as) -1, 4, 4a, 5, 8, 8a-hexahydro-1,4: 5,8-dimethanonaphthalene
- DNME tetramethyl (1R, 2R, 3S, 4S, 5S, 6S, 7R, 8R) -decahydro-1,4: 5,8-dimethanonaphthalene-2,3,6,7-tetracarboxylate
- the physical property values of the BNDE mixture were as follows.
- the reaction vessel was depressurized in a reaction vessel and charged with carbon monoxide (gas displacement with carbon monoxide) three times to make the inside of the system carbon monoxide atmosphere and stirred at 23 to 26 ° C. for 6 hours. In this operation, the degree of pressure reduction was 100 torr. The same applies to the following embodiments.
- Example 7 Synthesis of DNME 13.9 L of methanol was charged in a 20 L flask, and 4.50 kg (33.5 mol) of CuCl 2 and 65 g of 10% by weight Pd / C (30.5 mmol in terms of Pd; made by NE Chemcat; 50% by weight water-containing product) was added.
- Example 8 Synthesis of DNME 4.2 L of methanol is charged into a 10 L flask, and 1.37 kg (10.2 mol) of CuCl 2, 19.8 g of 10 wt% Pd / C (9.3 mmol in terms of Pd; NE Chemcat); 50 wt% water content Product and 706 g of toluene were added.
- Example 9 Synthesis of DNME In a 0.3 L four-necked flask, 10 wt% Pd / C 0.69 g (0.32 mmol in terms of Pd; made by NE Chemcat; 50 wt% hydrous product) and 44.2 g (329 mmol) CuCl 2 were added . To this, 135 mL of MeOH and 31 mL of toluene were added, and bubbling was performed with N 2 for 0.5 hour. Next, the pressure was reduced by a diaphragm pump until the liquid level was slightly bubbled, carbon monoxide was enclosed, and the inside of the system was gas-replaced with carbon monoxide.
- a syringe pump is used to obtain 20 ° C. to 30 ° C. Dropwise in 2 hours at. The mixture was stirred at the same temperature for 6 hours. HPLC analysis of the reaction solution was performed. The yield of DNME was 78.9%.
- Example 10 Synthesis of DNME In a 0.3 L four-necked flask, 10 wt% Pd / C 0.70 g (0.33 mmol of Pd conversion; made by NE Chemcat; 50 wt% hydrous product) and 44.4 g (330 mmol) of CuCl 2 were added . 70 mL of MeOH and 18.5 mL of CHCl 3 were added thereto, and bubbling was performed for 0.5 hour with N 2 . Next, the pressure was reduced by a diaphragm pump until the liquid level was slightly bubbled, carbon monoxide was enclosed, and the inside of the system was gas-replaced with carbon monoxide.
- Example 11 Synthesis of DNME In a 1.0 L four-necked flask, 10 wt% Pd / C 2.87 g (1.35 mmol in Pd conversion; made by NE Chemcat; 50 wt% water-containing product), 182.5 g (1.36 mol) CuCl 2 Added. Here, 434 mL of MeOH and 76 mL of CHCl 3 were added and bubbling was performed for 0.5 hour with N 2 . Next, the pressure was reduced by a diaphragm pump until the liquid level was slightly bubbled, carbon monoxide was enclosed, and the inside of the system was gas-replaced with carbon monoxide.
- Example 12 Synthesis of DNME In a 1.0 L separable flask, 10 wt% Pd / C 2.86 g (Pd conversion 1.34 mmol; made by NE Chemcat; 50 wt% water-containing product), 183.2 g CuCl 2 (1.36 mol) Added. Here, 443 mL of MeOH and 77 mL of CHCl 3 were added, and Ar was bubbled for 0.5 hours. Next, the pressure was reduced by a diaphragm pump until the liquid level was slightly bubbled, carbon monoxide was enclosed, and the inside of the system was gas-replaced with carbon monoxide. It stirred at room temperature (25 degreeC) for 2 hours (pretreatment).
- Example 13 Synthesis of DNME 0.126 g (0.71 mmol) of PdCl 2 and 182.9 g (1.36 mol) of CuCl 2 were added to a 1.0 L separable flask. 452 mL of MeOH and 77 mL of CHCl 3 were added thereto, and bubbling was performed for 0.5 hour with N 2 . Next, the pressure was reduced by a diaphragm pump until the liquid level was slightly bubbled, carbon monoxide was enclosed, and the inside of the system was gas-replaced with carbon monoxide. Stir at room temperature for 2 hours (pretreatment). The pressure in the flask was reduced, and carbon monoxide was again sealed.
- Example 14 Synthesis of DNME 0.023 g (0.13 mmol) of PdCl 2 and 187.0 g (1.39 mol) of CuCl 2 were added to a 1.0 L separable flask. To this, 451.3 mL of MeOH and 77.2 mL of CHCl 3 were added, and bubbling was performed for 0.5 hour with N 2 . Next, the pressure was reduced by a diaphragm pump until the liquid level was slightly bubbled, carbon monoxide was enclosed, and the inside of the system was gas-replaced with carbon monoxide. Stir at room temperature for 2 hours (pretreatment).
- Example 15 Synthesis of DNME
- 0.062 g (0.35 mmol) of PdCl 2 and 233.8 g (1.74 mol) of CuCl 2 were added.
- 454 mL of MeOH and 81.4 mL of CHCl 3 were added, and bubbling was performed for 0.5 hour with N 2 .
- the pressure was reduced by a diaphragm pump until the liquid level was slightly bubbled, carbon monoxide was enclosed, and the inside of the system was gas-replaced with carbon monoxide.
- Example 16 Synthesis of DNME
- 0.067 g (0.38 mmol) of PdCl 2 and 139.6 g (1.04 mol) of CuCl 2 were added.
- 465 mL of MeOH and 102 mL of CHCl 3 were added, and bubbling was performed for 0.5 hour with N 2 .
- the pressure was reduced by a diaphragm pump until the liquid level was slightly bubbled, carbon monoxide was enclosed, and the inside of the system was gas-replaced with carbon monoxide.
- Example 17 Synthesis of DNME
- 0.067 g (0.38 mmol) of PdCl 2 and 139.6 g (1.04 mol) of CuCl 2 were added.
- 465 mL of MeOH, 102 mL of CHCl 3, and 18 g (171 mmol) of trimethyl orthoformate were added, and bubbling was performed with N 2 for 0.5 hour.
- the pressure was reduced by a diaphragm pump until the liquid level was lightly bubbled, carbon monoxide was enclosed, and the inside of the system was gas-replaced with carbon monoxide.
- Example 18 Synthesis of DNME
- 0.061 g (0.35 mmol) of PdCl 2 and 233.5 g (1.74 mol) of CuCl 2 were added.
- 440 mL of MeOH and 77 mL of CHCl 3 were added thereto, and bubbling was performed for 0.5 hour with N 2 .
- the pressure was reduced by a diaphragm pump until the liquid level was slightly bubbled, carbon monoxide was enclosed, and the inside of the system was gas-replaced with carbon monoxide.
- Example 19 Synthesis of DNME
- 0.064 g (0.36 mmol) of PdCl 2 and 233.4 g (1.74 mol) of CuCl 2 were added.
- 441 mL of MeOH and 77 mL of CHCl 3 were added thereto, and bubbling was performed for 0.5 hour with N 2 .
- the pressure was reduced by a diaphragm pump until the liquid level was slightly bubbled, carbon monoxide was enclosed, and the inside of the system was gas-replaced with carbon monoxide.
- Example 20 Synthesis of DNEE
- PdCl 2 In a 2 L glass flask, 51.7 mg (0.29 mmol) of PdCl 2 and 195.1 g (1451 mmol) of CuCl 2 were added. To this was added 455 mL of EtOH (ethanol) and 21.5 g (145.1 mmol) of triethyl orthoformate. Next, the pressure was reduced by a diaphragm pump until the liquid level was lightly bubbled, carbon monoxide was enclosed, and the inside of the system was gas-replaced with carbon monoxide.
- the 5 L GL reaction vessel was replaced with argon gas, 3.0 kg of acetic anhydride and 199 g of DNDA crude product (I) were added, and the mixture was heated and stirred at an internal temperature of 121 ° C. to dissolve DNDA crude product (I) completely. Then, it cooled to 20 degreeC and stirred at 20 degreeC for 19 hours. The filtration was performed, the solid was washed with 0.8 kg of toluene, and the obtained solid was dried under reduced pressure. As a pale gray white solid, 59 g of DNDA crude product (II) (purity 89.6% by weight by NMR, yield 27.3% based on DNME) was obtained.
- the crude DNDA (II) contained 3.5% by weight of acetic anhydride and 1.0% by weight of acetic acid.
- Example 22 Synthesis of DNDA A 500 mL glass flask was replaced with Ar, and 29.93 g of DNME (purity 97.5%; 74.0 mmol) obtained in Example 18, 150 g of formic acid, para-toluenesulfonic acid monohydrate 0 28 g was added, and the mixture was heated and stirred at an internal temperature of 95 ° C to 99 ° C for 10 hours. After completion of the reaction, the reaction solution was concentrated under reduced pressure to remove formic acid, and an azeotropic operation with 90.0 g of toluene was performed twice to completely remove the formic acid. The toluene suspension was filtered and the solid was washed with toluene and dried in vacuo. 22.6 g of DNDA crude (I) was obtained as a light gray solid.
- the glass flask was replaced with argon gas, 300 g of N, N-dimethylacetamide was added, 17.1 g of DNDA crude product (II) obtained above was added, and the mixture was heated and stirred at an internal temperature of 50-60 ° C. It was completely dissolved. After that, 0.8 g of activated carbon (white coral A) was added and stirred at the same temperature. After filtration, the filtrate was washed with 17.1 g of N, N-dimethylacetamide, and the filtrate and the washing solution were combined and concentrated under reduced pressure to distill off 222 g of the solvent.
- activated carbon white coral A
- Example 23 Synthesis of DNDA A 500 mL glass flask is replaced with argon gas, and 24.8 g of DNME (purity 99.1% by weight; 62.3 mmol), 74 g of formic acid, and 0.23 g of paratoluenesulfonic acid monohydrate are added. The mixture was heated and stirred at an internal temperature of 95 ° C. to 99 ° C. for 10 hours. After completion of the reaction, the reaction solution was concentrated under reduced pressure to remove formic acid, and an azeotropic operation with 74.4 g of toluene was performed twice to completely remove the formic acid. The toluene suspension was filtered and the solid was washed with toluene and dried in vacuo. 18.8 g of DNDA crude (I) was obtained as a light gray solid.
- the glass flask was replaced with argon gas, 240 g of N, N-dimethylacetamide was added, 16.0 g of DNDA crude product (II) obtained above was added, and the mixture was heated and stirred at an internal temperature of 50 to 60 ° C. It was completely dissolved. Thereafter, 0.8 g of activated carbon was added and stirred at the same temperature. After filtration, the filtrate was washed with 17.1 g of N, N-dimethylacetamide, and the filtrate and the washing solution were combined and concentrated under reduced pressure to evaporate 216.4 g of the solvent.
- Example 24 Synthesis of DNDA A 500 mL glass flask was replaced with argon gas, and 72 g (purity 99.1%; 180.9 mmol) of DNME, 360 g of formic acid, 0.69 g (3.6 mmol) of paratoluenesulfonic acid monohydrate were dissolved in The mixture was heated and stirred at an internal temperature of 95 ° C. to 100 ° C. for 8 hours. After completion of the reaction, the reaction solution was concentrated under reduced pressure to remove formic acid, and an azeotropic operation with 144 g of toluene was performed twice to completely remove the formic acid. The toluene suspension was filtered and the solid was washed with 72 g of toluene and dried in vacuo. 53.4 g of DNDA crude (I) was obtained as a light gray solid.
- the glass flask is replaced with argon gas, 375 g of N, N-dimethylacetamide is added, 25 g of the crude DNDA (I) obtained above is added, and the mixture is heated and stirred at an internal temperature of 50 to 60 ° C. It was dissolved. Thereafter, 1.3 g of activated carbon was added and stirred at the same temperature. After filtration, the filtrate was washed with 17.1 g of N, N-dimethylacetamide, and the filtrate and the washing solution were combined and concentrated under reduced pressure to evaporate 216.4 g of the solvent.
- Example 25 Synthesis of DNDA A 500 mL glass flask was replaced with argon gas and 39.7 g (purity 98.5%; 99.2 mmol) of DNME, 200 g of formic acid, 0.39 g (2.05 mmol) of paratoluenesulfonic acid monohydrate. ) was added, and the mixture was heated and stirred at an internal temperature of 95 ° C. to 99 ° C. for 11 hours. After completion of the reaction, the formic acid was removed by concentration under reduced pressure to distill off the formic acid, and an azeotropic operation with 84 g of toluene was performed twice to completely remove the formic acid. The toluene suspension was filtered and the solid was washed with toluene and dried in vacuo. 29.3 g of DNDA crude (I) was obtained as a light gray solid.
- the glass flask is replaced with argon gas, 150 g of N-methylpyrrolidone is added, 10.0 g of the DNDA crude product (II) obtained above is added, and the mixture is heated and stirred at an internal temperature of 50 to 60 ° C. It was dissolved. Thereafter, 0.5 g of activated carbon was added and stirred at the same temperature. After filtration, the filtrate was washed with 10 g of N-methylpyrrolidone, and the filtrate and the washing solution were combined and concentrated under reduced pressure to distill off 131 g of the solvent.
- Example 26 Synthesis of DNDA A 200 mL glass flask is replaced with argon gas, 19.0 g of DNEE (purity 99.4% by volume; 41.9 mmol), 95 g of formic acid and 82.5 mg of methanesulfonic acid are added, and the internal temperature is 95 ° C. It heat-stirred at 99 degreeC for 16 hours. After completion of the reaction, the formic acid was removed by concentration under reduced pressure to distill off the formic acid, and an azeotropic operation with 38 g of toluene was carried out three times to completely remove the formic acid. The toluene suspension was filtered and the solid was washed with toluene and dried in vacuo. Obtained 12.3 g of DNDA crude (I) as a light gray solid.
- a 200 mL glass flask is replaced with argon gas, 165 g of N-methylpyrrolidone is added, 11.0 g of the DNDA crude product (I) obtained above is added, and the mixture is heated and stirred at an internal temperature of 50 ° C. to 60 ° C. It was completely dissolved. Thereafter, 0.5 g of activated carbon was added and stirred at the same temperature. After filtration, the filtrate was washed with N-methylpyrrolidone, and the filtrate and the washing solution were combined and concentrated under reduced pressure to distill off 132.5 g of the solvent.
- the obtained white solid was washed five times with 200 mL of 10 wt% hydrochloric acid, 200 mL of 10 wt% aqueous sodium hydrogen carbonate solution, and 200 mL of ion exchanged water, and vacuum dried. 128.9 g of the obtained white solid was dissolved in 2800 g of ethyl acetate and dried (dehydrated) with 35 g of anhydrous magnesium sulfate. Subsequently, this ethyl acetate solution is passed through a silica gel column, and the solvent is distilled off with an evaporator to obtain (1R, 4S, 5S, 8R, 9R, 10R) -1, 4, 4a, 5, 8, as a white solid.
- the obtained solution is washed 3 times with 324 g of saturated aqueous sodium hydrogen carbonate solution and further 3 times with 324 g of purified water, then 2.7 g of anhydrous magnesium sulfate is added to the organic layer and stirred, and then 2.7 g of activated carbon is added Stir and filter. Then, the obtained solution was concentrated under reduced pressure to obtain 51 g of a white solid.
- the obtained solution is washed 3 times with 269 g of saturated aqueous sodium hydrogen carbonate solution and further 3 times with 269 g of purified water, 2.2 g of anhydrous magnesium sulfate is added to the organic layer and stirred, and 2.2 g of activated carbon is added Stir and filter. Then, the solution was filtered and concentrated under reduced pressure to obtain 46.63 g of a brown solid.
- the resulting solution is washed three times with 648 g of saturated aqueous sodium hydrogen carbonate solution and three times with 240 g of purified water, and then 11 g of anhydrous magnesium sulfate is added to the organic layer and stirred, and then 5.4 g of activated carbon is added and stirred And filtered. Then, the solution was filtered and concentrated under reduced pressure to obtain 98 g of a yellow liquid.
- the present invention relates to a process for producing alicyclic tetracarboxylic acid dianhydride and an ester compound.
- alicyclic tetracarboxylic acid dianhydride is a compound useful as a monomer for producing a polyimide.
- industrially suitable alicyclic tetracarboxylic acid dianhydride capable of producing an alicyclic tetracarboxylic acid dianhydride such as DNDA or an ester compound in high yield by a simple method under mild conditions. It is possible to provide a method for producing an organic compound or an ester compound.
- an alicyclic tetracarboxylic acid dianhydride and an ester compound suitable as a monomer for polymer production such as polyimide can be provided. Further, completely separating stereoisomers in Step 1 of obtaining an olefin compound from norbornadiene and cyclopentadiene, and Step 2 of reacting an olefin compound, an alcohol compound, and carbon monoxide to obtain an ester compound. Instead, by crystallization, alicyclic tetracarboxylic acid dianhydride can be obtained with industrially suitable operation and purity.
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Abstract
La présente invention concerne un procédé de production d'un dianhydride d'acide, caractérisé en ce que l'action (A) et/ou l'action (B) ci-dessous sont effectuées lorsqu'un composé d'oléfine est mis à réagir avec du monoxyde de carbone. (A) Suite au mélange d'un composé de palladium, d'un composé de cuivre et d'un composé d'alcool dans un récipient de réaction, le mélange résultant est mélangé avec le composé d'oléfine en réalisant séquentiellement la mise en œuvre d'une substitution (C-2) décrite ci-dessous et la mise en œuvre d'une agitation (C-1) décrite ci-dessous. (B) Suite au mélange d'un composé de palladium, d'un composé de cuivre, d'un composé d'alcool et d'un composé d'orthoester dans un récipient de réaction, le mélange résultant est mélangé avec le composé d'oléfine en effectuant l'étape de substitution (C-2) décrite ci-dessous. (C-1) Il convient de procédé à l'agitation dans une atmosphère de monoxyde de carbone. (C-2) Suite à la réduction de la pression du récipient de réaction, la mise en œuvre d'un enfermement étanche d'un gaz de monoxyde de carbone dans ledit récipient de réaction est réalisée une ou plusieurs fois.
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PCT/JP2017/020315 WO2017209197A1 (fr) | 2016-05-31 | 2017-05-31 | Précurseur de polyimide, polyimide, film de polyimide, substrat, et dianhydride d'acide tétracarboxylique utilisé en vue de produire le polyimide |
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