JP4618412B2 - Alicyclic tetracarboxylic acid compound and process for producing the same - Google Patents
Alicyclic tetracarboxylic acid compound and process for producing the same Download PDFInfo
- Publication number
- JP4618412B2 JP4618412B2 JP2004216940A JP2004216940A JP4618412B2 JP 4618412 B2 JP4618412 B2 JP 4618412B2 JP 2004216940 A JP2004216940 A JP 2004216940A JP 2004216940 A JP2004216940 A JP 2004216940A JP 4618412 B2 JP4618412 B2 JP 4618412B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- tetracarboxylic acid
- carbon atoms
- alkyl group
- alicyclic tetracarboxylic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- -1 Alicyclic tetracarboxylic acid compound Chemical class 0.000 title claims description 75
- 238000000034 method Methods 0.000 title description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 32
- 125000000217 alkyl group Chemical group 0.000 claims description 30
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 26
- 239000004593 Epoxy Substances 0.000 claims description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 15
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 12
- 239000007800 oxidant agent Substances 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 10
- 150000002736 metal compounds Chemical class 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 47
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 36
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 35
- 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 32
- 239000013078 crystal Substances 0.000 description 32
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 21
- 229910052751 metal Inorganic materials 0.000 description 20
- 239000002184 metal Substances 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 19
- 239000002904 solvent Substances 0.000 description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 229910052763 palladium Inorganic materials 0.000 description 14
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 238000004817 gas chromatography Methods 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 9
- VHILMKFSCRWWIJ-UHFFFAOYSA-N dimethyl acetylenedicarboxylate Chemical compound COC(=O)C#CC(=O)OC VHILMKFSCRWWIJ-UHFFFAOYSA-N 0.000 description 9
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 0 CCC1(C2)C3C(C(O*)=O)=C(*)C(*)=C(*)C3*2C2C3C(C)(C4)CC(C)(*)C=CC4(C)C3C1C2 Chemical compound CCC1(C2)C3C(C(O*)=O)=C(*)C(*)=C(*)C3*2C2C3C(C)(C4)CC(C)(*)C=CC4(C)C3C1C2 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 6
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- STRNXFOUBFLVIN-UHFFFAOYSA-N diethyl but-2-ynedioate Chemical compound CCOC(=O)C#CC(=O)OCC STRNXFOUBFLVIN-UHFFFAOYSA-N 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 229910052707 ruthenium Inorganic materials 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000004811 liquid chromatography Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- VIHDTGHDWPVSMM-UHFFFAOYSA-N ruthenium;triphenylphosphane Chemical compound [Ru].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 VIHDTGHDWPVSMM-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- 125000005595 acetylacetonate group Chemical group 0.000 description 3
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- HOXINJBQVZWYGZ-UHFFFAOYSA-N fenbutatin oxide Chemical compound C=1C=CC=CC=1C(C)(C)C[Sn](O[Sn](CC(C)(C)C=1C=CC=CC=1)(CC(C)(C)C=1C=CC=CC=1)CC(C)(C)C=1C=CC=CC=1)(CC(C)(C)C=1C=CC=CC=1)CC(C)(C)C1=CC=CC=C1 HOXINJBQVZWYGZ-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 239000009719 polyimide resin Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 239000013638 trimer Substances 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- JSZOAYXJRCEYSX-UHFFFAOYSA-N 1-nitropropane Chemical compound CCC[N+]([O-])=O JSZOAYXJRCEYSX-UHFFFAOYSA-N 0.000 description 2
- XQQZRZQVBFHBHL-UHFFFAOYSA-N 12-crown-4 Chemical compound C1COCCOCCOCCO1 XQQZRZQVBFHBHL-UHFFFAOYSA-N 0.000 description 2
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 description 2
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 2
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 2
- 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 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- FOXVAJWLRIUEQB-UHFFFAOYSA-N [Co].C1(C=CC=C1)C1=CC=CCC1 Chemical compound [Co].C1(C=CC=C1)C1=CC=CCC1 FOXVAJWLRIUEQB-UHFFFAOYSA-N 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical group C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 2
- 239000005078 molybdenum compound Substances 0.000 description 2
- 150000002752 molybdenum compounds Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000003658 tungsten compounds Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WCBPJVKVIMMEQC-UHFFFAOYSA-N 1,1-diphenyl-2-(2,4,6-trinitrophenyl)hydrazine Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1NN(C=1C=CC=CC=1)C1=CC=CC=C1 WCBPJVKVIMMEQC-UHFFFAOYSA-N 0.000 description 1
- JKMPXGJJRMOELF-UHFFFAOYSA-N 1,3-thiazole-2,4,5-tricarboxylic acid Chemical compound OC(=O)C1=NC(C(O)=O)=C(C(O)=O)S1 JKMPXGJJRMOELF-UHFFFAOYSA-N 0.000 description 1
- XPUJOEOXHUYRPJ-UHFFFAOYSA-N 2,4-ditert-butyl-4-methylcyclohexa-1,5-dien-1-ol Chemical compound CC(C)(C)C1=C(O)C=CC(C)(C(C)(C)C)C1 XPUJOEOXHUYRPJ-UHFFFAOYSA-N 0.000 description 1
- KIAPWMKFHIKQOZ-UHFFFAOYSA-N 2-[[(4-fluorophenyl)-oxomethyl]amino]benzoic acid methyl ester Chemical compound COC(=O)C1=CC=CC=C1NC(=O)C1=CC=C(F)C=C1 KIAPWMKFHIKQOZ-UHFFFAOYSA-N 0.000 description 1
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 description 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- QAUHLCPHAPCCLR-UHFFFAOYSA-N C=1C=CC=CC=1P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C(=O)P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C(=O)P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 QAUHLCPHAPCCLR-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- STMCHJFZHAFLPF-UHFFFAOYSA-N [Ni].C=1C=CC=CC=1P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C(=O)P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 Chemical compound [Ni].C=1C=CC=CC=1P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C(=O)P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 STMCHJFZHAFLPF-UHFFFAOYSA-N 0.000 description 1
- GPWHDDKQSYOYBF-UHFFFAOYSA-N ac1l2u0q Chemical compound Br[Br-]Br GPWHDDKQSYOYBF-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001334 alicyclic compounds Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- LWGLGSPYKZTZBM-UHFFFAOYSA-N benzenecarbonothioylsulfanyl benzenecarbodithioate Chemical compound C=1C=CC=CC=1C(=S)SSC(=S)C1=CC=CC=C1 LWGLGSPYKZTZBM-UHFFFAOYSA-N 0.000 description 1
- WXNOJTUTEXAZLD-UHFFFAOYSA-L benzonitrile;dichloropalladium Chemical compound Cl[Pd]Cl.N#CC1=CC=CC=C1.N#CC1=CC=CC=C1 WXNOJTUTEXAZLD-UHFFFAOYSA-L 0.000 description 1
- YOUGRGFIHBUKRS-UHFFFAOYSA-N benzyl(trimethyl)azanium Chemical class C[N+](C)(C)CC1=CC=CC=C1 YOUGRGFIHBUKRS-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- MLIYPCQSOXNTLJ-UHFFFAOYSA-N carbon monoxide;ruthenium dihydride;triphenylphosphane Chemical compound [RuH2].[O+]#[C-].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 MLIYPCQSOXNTLJ-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- NEUSVAOJNUQRTM-UHFFFAOYSA-N cetylpyridinium Chemical class CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 NEUSVAOJNUQRTM-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- ZCUJUGHEDABDFN-UHFFFAOYSA-N cyclohex-3-ene-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCC=CC1(C(O)=O)C(O)=O ZCUJUGHEDABDFN-UHFFFAOYSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- JHYLUAZDEONDSF-UHFFFAOYSA-N dibutyl but-2-ynedioate Chemical compound CCCCOC(=O)C#CC(=O)OCCCC JHYLUAZDEONDSF-UHFFFAOYSA-N 0.000 description 1
- WIWBLJMBLGWSIN-UHFFFAOYSA-L dichlorotris(triphenylphosphine)ruthenium(ii) Chemical compound [Cl-].[Cl-].[Ru+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 WIWBLJMBLGWSIN-UHFFFAOYSA-L 0.000 description 1
- IWGSFZZFRMNYNV-UHFFFAOYSA-N dicyclohexyl but-2-ynedioate Chemical compound C1CCCCC1OC(=O)C#CC(=O)OC1CCCCC1 IWGSFZZFRMNYNV-UHFFFAOYSA-N 0.000 description 1
- ZRYFVBSDXVBOAS-UHFFFAOYSA-N dicyclopentyl but-2-ynedioate Chemical compound C1CCCC1OC(=O)C#CC(=O)OC1CCCC1 ZRYFVBSDXVBOAS-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- RWZIFQNJJLZYSI-UHFFFAOYSA-N dihexyl but-2-ynedioate Chemical compound CCCCCCOC(=O)C#CC(=O)OCCCCCC RWZIFQNJJLZYSI-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- OTBAGALLPLIXRZ-UHFFFAOYSA-N dipentyl but-2-ynedioate Chemical compound CCCCCOC(=O)C#CC(=O)OCCCCC OTBAGALLPLIXRZ-UHFFFAOYSA-N 0.000 description 1
- OPTPSVGIMYCMQJ-UHFFFAOYSA-N dipropyl but-2-ynedioate Chemical compound CCCOC(=O)C#CC(=O)OCCC OPTPSVGIMYCMQJ-UHFFFAOYSA-N 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- VMDTXBZDEOAFQF-UHFFFAOYSA-N formaldehyde;ruthenium Chemical compound [Ru].O=C VMDTXBZDEOAFQF-UHFFFAOYSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- ZUZLIXGTXQBUDC-UHFFFAOYSA-N methyltrioctylammonium Chemical compound CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC ZUZLIXGTXQBUDC-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 125000005574 norbornylene group Chemical group 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- ZVSLRJWQDNRUDU-UHFFFAOYSA-L palladium(2+);propanoate Chemical compound [Pd+2].CCC([O-])=O.CCC([O-])=O ZVSLRJWQDNRUDU-UHFFFAOYSA-L 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- LEIZJJNFNQIIKH-UHFFFAOYSA-K propanoate;ruthenium(3+) Chemical compound [Ru+3].CCC([O-])=O.CCC([O-])=O.CCC([O-])=O LEIZJJNFNQIIKH-UHFFFAOYSA-K 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- DKNJHLHLMWHWOI-UHFFFAOYSA-L ruthenium(2+);sulfate Chemical compound [Ru+2].[O-]S([O-])(=O)=O DKNJHLHLMWHWOI-UHFFFAOYSA-L 0.000 description 1
- BNBKCTCLPAQLAH-UHFFFAOYSA-K ruthenium(3+) triformate Chemical compound [Ru+3].[O-]C=O.[O-]C=O.[O-]C=O BNBKCTCLPAQLAH-UHFFFAOYSA-K 0.000 description 1
- AOXSEDODBLDTLD-UHFFFAOYSA-K ruthenium(3+);phosphate Chemical compound [Ru+3].[O-]P([O-])([O-])=O AOXSEDODBLDTLD-UHFFFAOYSA-K 0.000 description 1
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 description 1
- WYRXRHOISWEUST-UHFFFAOYSA-K ruthenium(3+);tribromide Chemical compound [Br-].[Br-].[Br-].[Ru+3] WYRXRHOISWEUST-UHFFFAOYSA-K 0.000 description 1
- LJZVDOUZSMHXJH-UHFFFAOYSA-K ruthenium(3+);triiodide Chemical compound [Ru+3].[I-].[I-].[I-] LJZVDOUZSMHXJH-UHFFFAOYSA-K 0.000 description 1
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- BFPFOLJFUVTHEP-UHFFFAOYSA-N ruthenium;triphenylphosphane Chemical compound [Ru].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 BFPFOLJFUVTHEP-UHFFFAOYSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical class CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical class CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical class C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical class CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- WRTMQOHKMFDUKX-UHFFFAOYSA-N triiodide Chemical compound I[I-]I WRTMQOHKMFDUKX-UHFFFAOYSA-N 0.000 description 1
- 238000002424 x-ray crystallography Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Epoxy Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は、高分子材料用のモノマーに関する。 The present invention relates to monomers for polymeric materials.
近年、エポキシ樹脂、ポリアミド樹脂、ポリエステル樹脂、ポリイミド樹脂等の樹脂は、液晶表示素子や半導体における保護材料若しくは絶縁材料、並びに光通信分野の光導波路用材料として実用化されてきている。
この分野の発展は目覚ましく、それに対応して、用いられる材料に対しても益々高度な特性が要求される様になっている。即ち、光透過性、耐熱性、有機溶媒溶解性及び絶縁性等の用途に応じた性能を多数合わせ持つことが期待されている。
In recent years, resins such as epoxy resins, polyamide resins, polyester resins, and polyimide resins have been put into practical use as liquid crystal display elements, protective materials or insulating materials in semiconductors, and optical waveguide materials in the field of optical communication.
The development of this field is remarkable, and correspondingly, more and more advanced properties are required for the materials used. That is, it is expected to have many performances according to applications such as light transmittance, heat resistance, organic solvent solubility and insulation.
一方、脂環式化合物としてテトラフェニルシクロヘキサジエン化合物（４）が知られている。該化合物は、ジシクロペンタジエン（DCPD）、ジフェニルアセチレン（DPA）及びCpCo(CO)2から、（シクロペンタジエニル）（シクロヘキサジエン）コバルト錯体（exo１, endo２）を合成した後、CuCl2・２H2Oで酸化することにより得られる（非特許文献１参照）。 On the other hand, a tetraphenylcyclohexadiene compound ( 4 ) is known as an alicyclic compound. The compound was synthesized from (cyclopentadienyl) (cyclohexadiene) cobalt complex (exo 1 , endo 2 ) from dicyclopentadiene (DCPD), diphenylacetylene (DPA) and CpCo (CO) 2 and then CuCl 2. * Obtained by oxidation with 2H 2 O (see Non-Patent Document 1).
本発明は、上記事情に鑑みてなされたものであり、光透過性、耐熱性、有機溶媒溶解性及び絶縁性等が改善された各種の電子材料や光通信用材料として有用なエポキシ樹脂、ポリアミド樹脂、ポリエステル樹脂、ポリイミド樹脂等の原料（モノマー）である脂環式テトラカルボン酸化合物及びエポキシ脂環式テトラカルボン酸化合物を提供することを課題とする。
更に、工業的に簡便で有利なそれらの製造法の提供を課題とする。
The present invention has been made in view of the above circumstances, and epoxy resins and polyamides useful as various electronic materials and optical communication materials with improved light transmission, heat resistance, organic solvent solubility, insulation properties, and the like. It is an object to provide an alicyclic tetracarboxylic acid compound and an epoxy alicyclic tetracarboxylic acid compound which are raw materials (monomers) such as a resin, a polyester resin, and a polyimide resin.
Furthermore, it is an object to provide an industrially simple and advantageous production method thereof.
本発明者は、上記課題を解決するため鋭意研究を行い本発明を完成させた。
すなわち、本発明は、以下の（１）から（９）の発明に関する。
（１） 式［１］
で表されるエポキシ脂環式テトラカルボン酸化合物。
（２） 式［３］
で表されるエポキシ脂環式テトラカルボン酸化合物。
（３） 式［４］
で表される（１）記載のエポキシ脂環式テトラカルボン酸化合物。
（４） 式［６］
で表される（２）記載のエポキシ脂環式テトラカルボン酸化合物。
（５） 式［７］
で表される脂環式テトラカルボン酸化合物を酸化剤により酸化することを特徴とする式［１］
で表されるエポキシ脂環式テトラカルボン酸化合物の製造法。
（６） 式［９］
で表される脂環式テトラカルボン酸化合物を酸化剤により酸化することを特徴とする式［３］
で表されるエポキシ脂環式テトラカルボン酸化合物の製造法。
（７） 式［１１］
で表されるジオレフィン化合物と、式［１２］
で表されるアセチレン化合物とを、周期律表第８族金属化合物触媒下で反応させることにより、式［１３］
で表される脂環式テトラカルボン酸化合物を得、次いで該化合物を酸化剤により酸化することを特徴とする式［２０］
で表されるエポキシ脂環式テトラカルボン酸化合物の製造法。
（８） 式［１１］
で表されるジオレフィン化合物と、式［１２］
で表されるアセチレン化合物とを、周期律表第８族金属化合物触媒下で反応させることにより、式［１４］
で表される脂環式テトラカルボン酸化合物を得、次いで該化合物を酸化剤により酸化することを特徴とする式［２１］
で表されるエポキシ脂環式テトラカルボン酸化合物の製造法。
（９） 酸化剤が、過酸化水素であることを特徴とする（５）乃至（８）記載のエポキシ脂環式テトラカルボン酸化合物の製造法。
The present inventor has intensively studied to solve the above problems and completed the present invention.
That is, the present invention relates to the following inventions (1) to ( 9 ).
(1) Formula [1]
An epoxy alicyclic tetracarboxylic acid compound represented by:
( 2 ) Formula [3]
An epoxy alicyclic tetracarboxylic acid compound represented by:
( 3 ) Formula [4]
The epoxy alicyclic tetracarboxylic acid compound as described in (1) represented by these.
( 4 ) Formula [6]
The epoxy alicyclic tetracarboxylic acid compound of ( 2 ) description represented by these.
( 5 ) Formula [7]
Formula [ 1 ], wherein the alicyclic tetracarboxylic acid compound represented by the formula is oxidized with an oxidizing agent
The manufacturing method of the epoxy alicyclic tetracarboxylic acid compound represented by these.
( 6 ) Formula [9]
Expression in alicyclic tetracarboxylic acid compound represented by you, characterized in that the oxidized with an oxidizing agent [3]
The manufacturing method of the epoxy alicyclic tetracarboxylic acid compound represented by these.
(7) Formula [11]
A diolefin compound represented by formula [12]
And an acetylene compound represented by the formula [13]
Formula [20], wherein an alicyclic tetracarboxylic acid compound represented by the formula: is obtained, and then the compound is oxidized with an oxidizing agent.
The manufacturing method of the epoxy alicyclic tetracarboxylic acid compound represented by these.
(8) Formula [11]
A diolefin compound represented by formula [12]
Is reacted with an acetylene compound represented by the formula [14] in the periodic table group 8 metal compound catalyst.
Wherein the alicyclic tetracarboxylic acid compound represented by the formula is obtained, and then the compound is oxidized with an oxidizing agent [21]
The manufacturing method of the epoxy alicyclic tetracarboxylic acid compound represented by these.
(9) an oxidizing agent, characterized in that hydrogen peroxide (5) to (8) the preparation of the epoxy alicyclic tetracarboxylic acid compounds described.
本発明の脂環式テトラカルボン酸化合物及びエポキシ脂環式テトラカルボン酸化合物は、光透過性、耐熱性、有機溶媒溶解性及び絶縁性等の改善された各種の電子材料や光通信用材料として有用なエポキシ樹脂、ポリアミド樹脂、ポリエステル樹脂、ポリイミド樹脂等の原料として使用することができる。
また、本発明の製造法では、ジオレフィン化合物とアセチレン化合物から触媒量の金属化合物を用いて、一工程で直接対応する脂環式テトラカルボン酸化合物を製造することができる。
The alicyclic tetracarboxylic acid compound and epoxy alicyclic tetracarboxylic acid compound of the present invention are used as various electronic materials and optical communication materials with improved light transmission, heat resistance, organic solvent solubility, insulation, and the like. It can be used as a raw material for useful epoxy resins, polyamide resins, polyester resins, polyimide resins and the like.
In the production method of the present invention, a corresponding alicyclic tetracarboxylic acid compound can be produced directly in one step using a catalytic amount of a metal compound from a diolefin compound and an acetylene compound.
以下、本発明についてさらに詳しく説明する。
本発明に係るエポキシ脂環式テトラカルボン酸化合物は、上記式［１］、［３］、［４］、［６］、［２０］及び［２１］で表されることを特徴とする。
式［１］、［３］、［４］、［６］、［２０］及び［２１］のＲ１、Ｒ ２ 、Ｚ１及びＺ２において、炭素数１〜１０のアルキル基としては、直鎖、分岐、環状のいずれでもよく
、例えば、メチル、エチル、ｎ−プロピル、ｉ−プロピル、ｎ−ブチル、ｉ−ブチル、ｓ−ブチル、ｔ−ブチル、ｎ−ペンチル、ｉ−アミル、ｔ−アミル、ｎｅｏ−ペンチル、ｎ−ヘキシル、ヘプチル、オクチル、ノニル、デシル基等が挙げられる。
なお、以上において、ｎはノルマルを、ｉはイソを、ｓはセカンダリーを、ｔはターシャリーをそれぞれ表す。
Hereinafter, the present invention will be described in more detail.
The epoxy alicyclic tetracarboxylic acid compound according to the present invention is represented by the above formulas [1], [3], [4], [6], [20] and [21] .
In R 1 , R 2 , Z 1 and Z 2 of the formulas [1], [3], [4], [6], [20] and [21] , the alkyl group having 1 to 10 carbon atoms is Any of chain, branched, and cyclic may be used. For example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, i-amyl, t- Examples include amyl, neo-pentyl, n-hexyl, heptyl, octyl, nonyl, decyl group and the like.
In the above, n represents normal, i represents iso, s represents secondary, and t represents tertiary.
本発明の脂環式テトラカルボン酸化合物及びエポキシ脂環式テトラカルボン酸化合物の製造法は、下記の反応スキームで表される。 The production method of the alicyclic tetracarboxylic acid compound and the epoxy alicyclic tetracarboxylic acid compound of the present invention is represented by the following reaction scheme.
（式中、Ｒ2、Ｚ１、Ｚ2、ｎ、ｘ及びｙは前記と同じ意味を表す。）
(Wherein R 2 , Z 1 , Z 2 , n, x and y have the same meaning as described above).
（式中、Ｒ2、Ｚ１、Ｚ2、ｎ、ｘ及びｙは前記と同じ意味を表す。）
(Wherein R 2 , Z 1 , Z 2 , n, x and y have the same meaning as described above).
（式中、Ｒ2、Ｚ１、Ｚ2、ｎ、ｘ及びｙは前記と同じ意味を表す。）
(Wherein R 2 , Z 1 , Z 2 , n, x and y have the same meaning as described above).
まず（１）の触媒付加反応から説明する。原料のジオレフィン化合物［１１］は、下記に示すシクロペンタジエン二量体（ＣＤ二量体）、シクロペンタジエン三量体（ＣＤ三量体）及びシクロペンタジエン四量体（ＣＤ四量体）が挙げられる。 First, the catalyst addition reaction (1) will be described. Examples of the raw diolefin compound [11] include cyclopentadiene dimer (CD dimer), cyclopentadiene trimer (CD trimer) and cyclopentadiene tetramer (CD tetramer) shown below. It is done.
実用的には、シクロペンタジエン二量体（ジシクロペンタジエン：ＤＣＰＤと略す。）が、経済的に入手できるため好ましい。以下、ｎが１の場合について説明するが、２及び３の場合も同様に製造できる。ＤＣＰＤは、市販品をそのまま使用することができる。
アセチレン化合物［１２］としては、種々の化合物が使用できる。例えば、具体的には、ジメチルアセチレンジカルボキシレート、ジエチルアセチレンジカルボキシレート、ジプロピルアセチレンジカルボキシレート、ジブチルアセチレンジカルボキシレート、ジペンチルアセチレンジカルボキシレート、ジヘキシルアセチレンジカルボキシレート、ジシクロペンチルアセチレンジカルボキシレート及びジシクロヘキシルアセチレンジカルボキシレート等が挙げられる。
アセチレン化合物［１２］の仕込み量は、シクロヘキサジエンテトラエステル化合物［１３］を目的とする場合は、ＤＣＰＤに対して、１．０〜２．８モル当量が好ましく、３．０モル当量以上になるとその３量体であるヘキサキス（アルコキシカルボニル）ベンゼンの副生量が増加する。更には１．５〜２．５モル当量が好ましい。
又、シクロヘキセンテトラエステル化合物［１４］を目的とする場合は、ＤＣＰＤに対して、０．５〜２．０モル当量が好ましく、特には０．８〜１．５モル当量が好ましい。アセチレン化合物［１２］の仕込み法は、５０〜９０℃でＤＣＰＤと触媒中に０．５〜１０時間かけて分割滴下することによりヘキサキス（アルコキシカルボニル）ベンゼンの副生を抑制しつつ反応を進行させることができる。アセチレン化合物の滴下終了後、昇温させて反応を更に進行させることができる。
Practically, a cyclopentadiene dimer (dicyclopentadiene: abbreviated as DCPD) is preferable because it is economically available. Hereinafter, the case where n is 1 will be described. As the DCPD, a commercially available product can be used as it is.
Various compounds can be used as the acetylene compound [12]. For example, dimethyl acetylenedicarboxylate, diethyl acetylenedicarboxylate, dipropyl acetylenedicarboxylate, dibutyl acetylenedicarboxylate, dipentyl acetylenedicarboxylate, dihexyl acetylenedicarboxylate, dicyclopentyl acetylenedicarboxylate And dicyclohexyl acetylenedicarboxylate and the like.
The charge amount of the acetylene compound [12] is preferably 1.0 to 2.8 molar equivalents and more than 3.0 molar equivalents with respect to DCPD when the cyclohexadiene tetraester compound [13] is intended. The by-product amount of the trimer hexakis (alkoxycarbonyl) benzene is increased. Furthermore, 1.5-2.5 molar equivalent is preferable.
Moreover, when aiming at cyclohexene tetraester compound [14], 0.5-2.0 molar equivalent is preferable with respect to DCPD, and 0.8-1.5 molar equivalent is especially preferable. The acetylene compound [12] is charged by splitting dropwise into DCPD and the catalyst at 50 to 90 ° C. over 0.5 to 10 hours, thereby allowing the reaction to proceed while suppressing the by-production of hexakis (alkoxycarbonyl) benzene. be able to. After completion of the dropwise addition of the acetylene compound, the reaction can be further advanced by raising the temperature.
触媒として用いる周期律表第８族金属としては、ルテニウム、ロジウム、パラジウム、白金、鉄、ニッケル及びコバルト等である。特に好ましいのはパラジウム及びルテニウムであり、更には、パラジウムが高収率を与え優れている。触媒の形態としては、金属錯体、金属塩、金属単身、担持金属及び金属酸化物等が使用できる。
金属錯体としては、ヒドリドカルボニルトリス（トリフェニルホスフィン）金属、ジヒドリドテトラキス（トリフェニルホスフィン）金属、ジヒドリドカルボニルトリス（トリフェニルホスフィン）金属、ハロゲノヒドリドカルボニルトリス（トリフェニルホスフィン）金属、ジハロゲノトリス（トリフェニルホスフィン）金属、ジハロゲノテトラキス（トリフェニルホスフィン）金属、ジアロゲノビスベンゾニトリル金属、トリス（アセチルアセトナト）金属、ジハロゲノシクロジエン金属、ホルマトジカルボニル金属、ドデカカルボニル三金属、カルボニルビス（トリフェニルホスフィン）金属及びテトラキストリフェニルホスフィン金属等が使用できる。
金属塩としては、塩酸、硫酸、硝酸及び燐酸等の鉱酸塩、蟻酸、酢酸及びプロピオン酸等の有機酸塩が挙げられる。担持金属としては、炭素、アルミナ及び珪藻土等の担体に担持させた金属が使用できる。
更に、具体的にはテトラキストリフェニルホスフィンパラジウム、ジクロロビス（ベンゾニトリル）パラジウム、トリス（アセチルアセトナト）パラジウム、ジヒドリドテトラキス（トリフェニルホスフィン）ルテニウム、ジヒドリドカルボニルトリス（トリフェニルホスフィン）ルテニウム、クロロヒドリドカルボニルトリス（トリフェニルホスフィン）ルテニウム、ジクロロトリス（トリフェニルホスフィン）ルテニウム、ジブロモトリス（トリフェニルホスフィン）ルテニウム、ジヨウドトリス（トリフェニルホスフィン）ルテニウム、ジクロロテトラキス（トリフェニルホスフィン）ルテニウム、トリス（アセチルアセトナト）ルテニウム、ドデカカルボニル三ルテニウム、ヒドリドカルボニルトリス（トリフェニルホスフィン）ロジウム、カルボニルビス（トリフェニルホスフィン）ニッケル、三塩化パラジウム、三臭化パラジウム、三沃化パラジウム、硫酸パラジウム、硝酸パラジウム、リン酸パラジウム、蟻酸パラジウム、酢酸パラジウム、プロピオン酸パラジウム、三塩化ルテニウム、三臭化ルテニウム、三沃化ルテニウム、硫酸ルテニウム、硝酸ルテニウム、リン酸ルテニウム、蟻酸テニウム、酢酸ルテニウム、プロピオン酸ルテニウム、パラジウム／活性炭、パラジウム／シリカ、パラジウム／アルミナ、パラジウム／シリカ・アルミナ、パラジウム／ゼオライト、ルテニウム／活性炭、ルテニウム／アルミナ、パラジウム黒、酸化パラジウム、ルテニウム黒及び酸化ルテニウム等が挙げられる。
これらの中で、特に好ましい触媒は、パラジウム／活性炭、三塩化パラジウム及び酢酸パラジウム等が挙げられる。
その使用量は、原料のＤＣＰＤに対し、０．１〜３０モル％、特には、０．５〜１０モル％が好ましい。
Examples of the Group 8 metal in the periodic table used as a catalyst include ruthenium, rhodium, palladium, platinum, iron, nickel, and cobalt. Particular preference is given to palladium and ruthenium. Furthermore, palladium is excellent because of its high yield. As a catalyst form, a metal complex, a metal salt, a single metal, a supported metal, a metal oxide, or the like can be used.
Metal complexes include hydridocarbonyltris (triphenylphosphine) metal, dihydridotetrakis (triphenylphosphine) metal, dihydridocarbonyltris (triphenylphosphine) metal, halogenohydridocarbonyltris (triphenylphosphine) metal, dihalogenotris. (Triphenylphosphine) metal, dihalogenotetrakis (triphenylphosphine) metal, diallogenobisbenzonitrile metal, tris (acetylacetonato) metal, dihalogenocyclodiene metal, formatodicarbonyl metal, dodecacarbonyl trimetal, carbonylbis (Triphenylphosphine) metal and tetrakistriphenylphosphine metal can be used.
Examples of the metal salt include mineral acid salts such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, and organic acid salts such as formic acid, acetic acid and propionic acid. As the supported metal, a metal supported on a carrier such as carbon, alumina and diatomaceous earth can be used.
More specifically, tetrakistriphenylphosphine palladium, dichlorobis (benzonitrile) palladium, tris (acetylacetonato) palladium, dihydridotetrakis (triphenylphosphine) ruthenium, dihydridocarbonyltris (triphenylphosphine) ruthenium, chlorohydride Carbonyltris (triphenylphosphine) ruthenium, dichlorotris (triphenylphosphine) ruthenium, dibromotris (triphenylphosphine) ruthenium, diiodotris (triphenylphosphine) ruthenium, dichlorotetrakis (triphenylphosphine) ruthenium, tris (acetylacetonato) Ruthenium, dodecacarbonyl triruthenium, hydridocarbonyl tris (triphenylphosphine) , Carbonylbis (triphenylphosphine) nickel, palladium trichloride, palladium tribromide, palladium triiodide, palladium sulfate, palladium nitrate, palladium phosphate, palladium formate, palladium acetate, palladium propionate, ruthenium trichloride, three Ruthenium bromide, ruthenium triiodide, ruthenium sulfate, ruthenium nitrate, ruthenium phosphate, ruthenium formate, ruthenium acetate, ruthenium propionate, palladium / activated carbon, palladium / silica, palladium / alumina, palladium / silica alumina, palladium / zeolite , Ruthenium / activated carbon, ruthenium / alumina, palladium black, palladium oxide, ruthenium black and ruthenium oxide.
Among these, particularly preferable catalysts include palladium / activated carbon, palladium trichloride, palladium acetate, and the like.
The amount of use is preferably 0.1 to 30 mol%, particularly 0.5 to 10 mol%, based on the raw material DCPD.
溶媒としては例えば、芳香族炭化水素、脂肪族エーテル化合物及び脂肪族ニトロ化合物等が挙げられる。更に具体的には、芳香族炭化水素としては、ベンゼン、トルエン、キシレン、エチルベンゼン等、脂肪族エーテル化合物としては、１，２−ジメトキシエタン、ジエチレングリコールジメチルエーテル（ジグライム）等の鎖状エーテル類、１，４−ジオキサン、１２−クラウン−４−エーテル、１５−クラウン−５−エーテル、１８−クラウン−６−エーテル、ジベンゾ−１８−クラウン−６−エーテル等の環状エーテル類等、脂肪族ニトロ化合物としては、ニトロメタン、ニトロエタン及びニトロプロパン等が一例として挙げられる。特には、芳香族炭化水素としては、トルエン、キシレン、脂肪族エーテル化合物としては、１，２−ジメトキシエタン、ジエチレングリコールジメチルエーテル（ジグライム）、１，４−ジオキサン等が好ましい。又これらの溶媒を組み合わせて使用することもできる。
その使用量は、ＤＣＰＤに対し１〜２０質量倍、特には１〜１０質量倍が経済的にも好ましい。
Examples of the solvent include aromatic hydrocarbons, aliphatic ether compounds, and aliphatic nitro compounds. More specifically, aromatic hydrocarbons include benzene, toluene, xylene, and ethylbenzene, and aliphatic ether compounds include chain ethers such as 1,2-dimethoxyethane and diethylene glycol dimethyl ether (diglyme), As aliphatic nitro compounds such as cyclic ethers such as 4-dioxane, 12-crown-4-ether, 15-crown-5-ether, 18-crown-6-ether, dibenzo-18-crown-6-ether, etc. Examples thereof include nitromethane, nitroethane, and nitropropane. In particular, the aromatic hydrocarbon is preferably toluene, xylene, and the aliphatic ether compound is preferably 1,2-dimethoxyethane, diethylene glycol dimethyl ether (diglyme), 1,4-dioxane, or the like. These solvents can also be used in combination.
The amount used is preferably 1 to 20 times by mass, more preferably 1 to 10 times by mass, more economically than DCPD.
本発明で重要なのが溶媒の選択に加えて反応温度の設定である。高温ほど反応が速いが重合等の副反応を伴うので、通常５０〜１８０℃の範囲が好ましく、特には６０〜１５０℃の範囲で行うのが好ましい。本触媒存在下では、アセチレン化合物が特に重合し易く、滴下温度を低温側の５０〜８０℃間で０．５〜１０時間かけて、分割仕込みすることによりヘキサキス（アルコキシカルボニル）ベンゼンの副生を抑制させながら本反応を進行させることができる。アセチレン化合物の滴下後は、昇温し未反応ＤＣＰＤの反応を完結させることができる。 What is important in the present invention is the setting of the reaction temperature in addition to the selection of the solvent. The higher the temperature, the faster the reaction, but it is accompanied by side reactions such as polymerization. Therefore, it is usually preferably in the range of 50 to 180 ° C, particularly preferably in the range of 60 to 150 ° C. In the presence of this catalyst, the acetylene compound is particularly easy to polymerize, and the by-product of hexakis (alkoxycarbonyl) benzene is produced by split charging at a dropping temperature of 50 to 80 ° C. for 0.5 to 10 hours. This reaction can be allowed to proceed while being suppressed. After dropwise addition of the acetylene compound, the temperature can be raised to complete the reaction of unreacted DCPD.
また、本反応の原料であるＤＣＰＤやアセチレン化合物の重合を抑制するために重合禁止剤を添加することもできる。
重合禁止剤としては例えば、ジフェニルピクリルヒドラジン、トリ−ｐ−ニトロフェニルメチル、Ｎ−（３−Ｎ−オキシアニリノ−１，３−ジメチルブチリデン）アニリンオキシド、ｐ−ベンゾキノン、ｐ−ｔｅｒｔ−ブチルカテコール、ニトロベンゼン、ピクリン酸、ジチオベンゾイルジスルフィド、ヒドロキノン、ｐ−メトキシフェノール、２，４−ジ−ｔ−ブチル−４−メチルフェノール及び塩化銅（II）等が挙げられる。
重合禁止剤の添加量は、ＤＣＰＤやアセチレン化合物に対して０．０１〜１モル％が好ましい。
反応時間は、ガスクロマトグラフィー（ＧＣ）や液体クロマトグラフィー（ＬＣ）で反応追跡して決定することができるが、通常４〜３０時間で終了させることができる。
In addition, a polymerization inhibitor can be added to suppress the polymerization of DCPD and acetylene compounds which are raw materials for this reaction.
Examples of the polymerization inhibitor include diphenylpicrylhydrazine, tri-p-nitrophenylmethyl, N- (3-N-oxyanilino-1,3-dimethylbutylidene) aniline oxide, p-benzoquinone, and p-tert-butylcatechol. , Nitrobenzene, picric acid, dithiobenzoyl disulfide, hydroquinone, p-methoxyphenol, 2,4-di-t-butyl-4-methylphenol, and copper (II) chloride.
The addition amount of the polymerization inhibitor is preferably 0.01 to 1 mol% with respect to DCPD or the acetylene compound.
The reaction time can be determined by tracking the reaction with gas chromatography (GC) or liquid chromatography (LC), but it can usually be completed in 4 to 30 hours.
次に、スキーム（２）のジオレフィン化合物［１１］とシクロヘキサジエンテトラエステル化合物［１３］のDiels-Alder反応によるシクロヘキセンテトラエステル化合物［１４］の製造法について述べる。
本反応は、熱によって進行し、反応温度は５０〜２５０℃で可能であり、特には、６０〜１８０℃が好ましい。
溶媒は無しでも可能であるが、使用する方が好ましい。その種類としては、例えば、芳香族炭化水素、脂肪族エーテル化合物及び脂肪族ニトロ化合物等が挙げられる。更に具体的には、芳香族炭化水素としては、ベンゼン、トルエン、キシレン、エチルベンゼン等、脂肪族エーテル化合物としては、１，２−ジメトキシエタン、ジエチレングリコールジメチルエーテル（ジグライム）等の鎖状エーテル類、１，４−ジオキサン、１２−クラウン−４−エーテル、１５−クラウン−５−エーテル、１８−クラウン−６−エーテル、ジベンゾ−１８−クラウン−６−エーテル等の環状エーテル類等、脂肪族ニトロ化合物としては、ニトロメタン、ニトロエタン及びニトロプロパン等が一例として挙げられる。特には、芳香族炭化水素としては、トルエン、キシレン、脂肪族エーテル化合物としては、１，２−ジメトキシエタン、ジエチレングリコールジメチルエーテル（ジグライム）、１，４−ジオキサン等が好ましい。又これらの溶媒を組み合わせて使用することもできる。
その使用量は、ＤＣＰＤに対し１〜２０質量倍、特には１〜１０質量倍が経済的にも好ましい。
Next, a production method of the cyclohexene tetraester compound [14] by the Diels-Alder reaction of the diolefin compound [11] of the scheme (2) and the cyclohexadiene tetraester compound [13] will be described.
This reaction proceeds by heat, and the reaction temperature can be 50 to 250 ° C. In particular, 60 to 180 ° C is preferable.
Although it is possible without a solvent, it is preferable to use it. Examples of the type include aromatic hydrocarbons, aliphatic ether compounds, and aliphatic nitro compounds. More specifically, aromatic hydrocarbons include benzene, toluene, xylene, and ethylbenzene, and aliphatic ether compounds include chain ethers such as 1,2-dimethoxyethane and diethylene glycol dimethyl ether (diglyme), As aliphatic nitro compounds such as cyclic ethers such as 4-dioxane, 12-crown-4-ether, 15-crown-5-ether, 18-crown-6-ether, dibenzo-18-crown-6-ether, etc. Examples thereof include nitromethane, nitroethane, and nitropropane. In particular, the aromatic hydrocarbon is preferably toluene, xylene, and the aliphatic ether compound is preferably 1,2-dimethoxyethane, diethylene glycol dimethyl ether (diglyme), 1,4-dioxane, or the like. These solvents can also be used in combination.
The amount used is preferably 1 to 20 times by mass, more preferably 1 to 10 times by mass, more economically than DCPD.
次に、スキーム（３）のシクロヘキサジエンテトラエステル化合物［１３］の加水分解によるシクロヘキサジエンテトラカルボン酸化合物［１８］及びスキーム（４）のシクロヘキセンテトラエステル化合物［１４］の加水分解によるシクロヘキセンテトラカルボン酸化合物［１９］の製造法について述べる。
これらの加水分解は、酸性下で行うこともできるが、塩基性下の方が簡便で高収率を与える。塩基の種類としては、アルカリ金属及びアルカリ土類金属の水酸化物を用いるのが経済的に好ましい。具体的には、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム及び水酸化バリウム等であり、特には、水酸化ナトリウムが最も好ましい。その使用量は、基質に対し２〜３当量が、特には２〜２．４当量が好ましい。溶媒としては、アルコールと水の混合系が一般的である。他に、１，４−ジオキサン、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）、Ｎ−メチルピロリドン（ＮＭＰ）等を用いることができる。アルコールの種類としては、メタノール、エタノール及びプロパノール等の低級アルコールが好ましい。その使用量は、基質に対し、１〜２０質量倍が、特には、２〜１０質量倍が好ましい。水の添加量は、基質に対し０．１〜２０質量倍が、特には１〜１０質量倍が好ましい。アルコールと水の混合比は、質量比で１対２０から２０対１の間で選択でき、特には１対５から５対１間で選択するのが好ましい。 反応温度は、溶媒の沸点から加圧下での沸点以上で行うことができる。
反応後は、アルコールを留去した後、その残渣からメチルイソブチルケトンで抽出した後、濃縮して得られた粗結晶を再結晶法で精製するか、反応中に生成した目的物を濾取・溶媒洗浄することにより目的物が得られる。
もう一法として、酸による方法であるが、酸の種類としては、塩酸、硫酸及び燐酸等の無機酸類、蟻酸、酢酸及びプロピオン酸等の脂肪酸類、メタンスルホン酸、エタンスルホン酸及びトリフルオロメタンスルホン酸等のスルホン酸類が挙げられる。しかし、本化合物群では塩基性下での加水分解が好ましい。
Next, cyclohexadiene tetracarboxylic acid compound [18] by hydrolysis of cyclohexadiene tetraester compound [13] in scheme (3) and cyclohexene tetracarboxylic acid by hydrolysis of cyclohexene tetraester compound [14] in scheme (4) A method for producing compound [19] will be described.
These hydrolysis can be carried out under acidic conditions, but the basic one is simpler and gives a higher yield. It is economically preferable to use alkali metal and alkaline earth metal hydroxides as the type of base. Specifically, they are sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, etc. Especially sodium hydroxide is the most preferable. The amount used is preferably 2 to 3 equivalents, more preferably 2 to 2.4 equivalents, relative to the substrate. As the solvent, a mixed system of alcohol and water is generally used. In addition, 1,4-dioxane, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP) and the like can be used. As the type of alcohol, lower alcohols such as methanol, ethanol and propanol are preferable. The amount used is preferably 1 to 20 times by mass, and particularly preferably 2 to 10 times by mass with respect to the substrate. The amount of water added is preferably 0.1 to 20 times by mass, particularly 1 to 10 times by mass, with respect to the substrate. The mixing ratio of alcohol and water can be selected in a mass ratio of 1 to 20 to 20 to 1, and particularly preferably 1 to 5 to 5 to 1. The reaction temperature can be from the boiling point of the solvent to the boiling point under pressure.
After the reaction, the alcohol is distilled off, and then the residue is extracted with methyl isobutyl ketone and then concentrated, and then the crude crystals obtained by concentration are purified by a recrystallization method, or the target product produced during the reaction is collected by filtration. The target product is obtained by washing with a solvent.
Another method is an acid method. The types of acids include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, fatty acids such as formic acid, acetic acid and propionic acid, methanesulfonic acid, ethanesulfonic acid and trifluoromethanesulfone. Examples thereof include sulfonic acids such as acids. However, basic hydrolysis is preferred in this compound group.
さて、スキーム（５）及び（６）の不飽和化合物のエポキシ化反応について述べる。
酸化剤としては、分子態酸素、過酸化水素、過酢酸、過安息香酸及び過酸化ヘテロポリ酸等を挙げることが出来る。触媒として、モリブデン化合物やタングステン化合物を共存させることもできる。経済的には、分子態酸素や過酸化水素とモリブデン化合物やタングステン化合物との組み合わせが好ましい。又過酢酸も簡便な酸化剤として好ましい。酸化剤の使用量は、基質に対し１〜２モル倍、より好ましくは１〜１．５モル倍である
本反応は溶媒を使用するのが好ましい。第１の方法は、過酸化水素水と均一になる溶媒系の方法である。この方法には、例えば、アセトニトリルやプロピオニトリル等の低級ニトリル類、アセトンやメチルエチルケトン等の低級ケトン類、メタノールやエタノール等の低級アルコール類及び１，４−ジオキサン等が挙げられ、特にはアセトニトリルなどの低級ニトリル類が好ましい溶媒である。
Now, the epoxidation reaction of the unsaturated compound in the schemes (5) and (6) will be described.
Examples of the oxidizing agent include molecular oxygen, hydrogen peroxide, peracetic acid, perbenzoic acid and peroxyheteropolyacid. As a catalyst, a molybdenum compound or a tungsten compound can also coexist. Economically, a combination of molecular oxygen or hydrogen peroxide with a molybdenum compound or a tungsten compound is preferable. Peracetic acid is also preferred as a simple oxidizing agent. The amount of the oxidizing agent used is 1 to 2 mol times, more preferably 1 to 1.5 mol times with respect to the substrate. This reaction preferably uses a solvent. The first method is a solvent-based method that is uniform with hydrogen peroxide water. Examples of this method include lower nitriles such as acetonitrile and propionitrile, lower ketones such as acetone and methyl ethyl ketone, lower alcohols such as methanol and ethanol, 1,4-dioxane, etc. These lower nitriles are preferred solvents.
第２の方法は、過酸化水素水と不均一になる溶媒系の方法である。この方法には、例えば、クロロホルムや１，２−ジクロロエタン（ＥＤＣ）等のハロゲン化炭化水素類、トルエンやキシレン等の芳香族炭化水素類、ｎ−ヘキサンやｎ−ヘプタン等の脂肪族炭化水素類等が挙げられ、特にはＥＤＣやトルエン等が好ましい溶媒である。
また、反応基質の溶解性が低い場合は、１，４−ジオキサンやＮ，Ｎ−ジメチルホルムアミド（ＤＭＦ）等を溶媒として、一部溶解させたスラリー状態で行うことが好ましい場合もある。
また、過酢酸が酸化剤の場合は前述のいずれも用いることができるが、特には均一になる溶媒系が好ましい。これらの使用量は、反応基質に対し好ましくは１〜５０質量倍であり、より好ましくは２〜１０質量倍である。
不均一になる溶媒系の方法では、反応促進させるために、相間移動触媒の添加が有効である。中でも、四級アンモニウム塩、ピリジニウム塩、ホスホニウム塩等が好ましく、具体的には、テトラメチルアンモニウム塩、テトラプロピルアンモニウム塩、テトラブチルアンモニウム塩、トリメチルベンジルアンモニウム塩、トリオクチルメチルアンモニウム、セチルピリジニウム塩、テトラブチルホスホニウム塩、硫酸水素テトラブチルアンモニウム塩等を挙げることができる。
これらの使用量は、反応基質に対し好ましくは０．００１〜５モル％であり、より好ましくは０．００５〜１モル％である。
反応温度は、０〜１５０℃で行うことができ、好ましくは２０〜１００℃が高収率を与える。反応時間は、１〜５０時間で行うことができ、通常２〜２４時間で行うのが実用的ある。この様にして目的物が得られる。これらの目的物は、再結晶法又は、カラムクロマトグラフィー法等で精製することができる。
以上述べた本発明の反応及び精製は、回分式でも連続式でも可能である。
また、反応は常圧でも加圧でも行うことができる
The second method is a solvent-based method that becomes heterogeneous with the hydrogen peroxide solution. This method includes, for example, halogenated hydrocarbons such as chloroform and 1,2-dichloroethane (EDC), aromatic hydrocarbons such as toluene and xylene, and aliphatic hydrocarbons such as n-hexane and n-heptane. In particular, EDC, toluene and the like are preferable solvents.
In addition, when the solubility of the reaction substrate is low, it may be preferable to carry out in a partially dissolved slurry state using 1,4-dioxane, N, N-dimethylformamide (DMF) or the like as a solvent.
In addition, when peracetic acid is an oxidizing agent, any of the above can be used, but a uniform solvent system is particularly preferable. The amount of these used is preferably 1 to 50 times by mass, more preferably 2 to 10 times by mass with respect to the reaction substrate.
In the solvent-based method in which the reaction becomes heterogeneous, it is effective to add a phase transfer catalyst in order to promote the reaction. Among them, quaternary ammonium salts, pyridinium salts, phosphonium salts and the like are preferable, specifically, tetramethylammonium salt, tetrapropylammonium salt, tetrabutylammonium salt, trimethylbenzylammonium salt, trioctylmethylammonium, cetylpyridinium salt, Examples thereof include tetrabutylphosphonium salt and tetrabutylammonium hydrogen sulfate salt.
The amount of these used is preferably 0.001 to 5 mol%, more preferably 0.005 to 1 mol%, based on the reaction substrate.
The reaction temperature can be 0 to 150 ° C., and preferably 20 to 100 ° C. gives a high yield. The reaction time can be 1 to 50 hours, usually 2 to 24 hours is practical. In this way, the target product is obtained. These objects can be purified by a recrystallization method or a column chromatography method.
The reaction and purification of the present invention described above can be performed batchwise or continuously.
The reaction can be carried out at normal pressure or under pressure.
以下に実施例を挙げ、本発明を具体的に説明するが、本発明はこれらに限定されるものではない。
尚、実施例で用いた分析法は以下の通りである。
[1] [ガスクロマトグラフィー (GC)]
機種: Shimadzu GC-17A, Column : キャピラリカラム CBP1-W25-100 ( 25 m x 0.53 mm φx 1μm ), カラム温度: 100℃( 保持 2 min.)- 8℃/min. ( 昇温速度 )-290℃( 保持15 min. ), 注入口温度 : 290 ℃, 検出器温度 : 290 ℃, キャリアガス ： ヘリウム, 検出法 : FID 法.
[2] [質量分析 (MASS)]
機種: LX-1000 (JEOL Ltd.), 検出法: FAB 法.
[3] [1H NMR]
機種: INOVA500 (VARIAN Corp.), 測定溶媒: DMSO-d6
[4] [13C NMR]
機種: INOVA500 (VARIAN Corp.), 測定溶媒: DMSO-d6
[5][融点(mp)]
測定機器: 自動融点測定装置、FP62 (METTLER TOLEDO)
[6] [液体クロマトグラフィー (LC)]
機種: Shimadzu LC-10A, Column : YMC-Pack ODS-AM（S-5μm, 120A, AM-303, AM12S05-2546WT ） ( 250 mm x 4.6 mm φ ), カラム温度: 40℃, 検出器波長 : UV 230 nm, 溶離液： H2O/CH3CN＝1/2, 流速：0.5ml/min.
[7] [Ｘ線結晶解析 ]
装置: DIP2030K（マックサイエンス製）
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
The analytical methods used in the examples are as follows.
[1] [Gas chromatography (GC)]
Model: Shimadzu GC-17A, Column: Capillary column CBP1-W25-100 (25 mx 0.53 mm φx 1μm), Column temperature: 100 ℃ (holding 2 min.)-8 ℃ / min. (Raising rate) -290 ℃ (Holding 15 min.), Inlet temperature: 290 ° C, detector temperature: 290 ° C, carrier gas: helium, detection method: FID method.
[2] [Mass Spectrometry (MASS)]
Model: LX-1000 (JEOL Ltd.), Detection method: FAB method.
[3] [ 1 H NMR]
Model: INOVA500 (VARIAN Corp.), Measuring solvent: DMSO-d 6
[4] [ 13 C NMR]
Model: INOVA500 (VARIAN Corp.), Measuring solvent: DMSO-d 6
[5] [Melting point (mp)]
Measuring instrument: Automatic melting point measuring device, FP62 (METTLER TOLEDO)
[6] [Liquid chromatography (LC)]
Model: Shimadzu LC-10A, Column: YMC-Pack ODS-AM (S-5μm, 120A, AM-303, AM12S05-2546WT) (250 mm x 4.6 mm φ), Column temperature: 40 ℃, Detector wavelength: UV 230 nm, eluent: H 2 O / CH 3 CN = 1/2, flow rate: 0.5 ml / min.
[7] [X-ray crystallography]
Device: DIP2030K (manufactured by Mac Science)
［実施例１］（スキーム１）
１００ml 四つ口反応フラスコにジシクロペンタジエン（DCPD）６．６ｇ（５０mmol）、ジグライム３３ｇ及び酢酸パラジウム（Pd(OAc)2）０．４４９ｇ（2mmol）(4mol%)を仕込み７５℃で攪拌中に、ジメチルアセチレンジカルボキシレート（DMA）１０．７ｇ（７５ｍｍｏｌ）を４５分かけて滴下した。更に１００℃の油浴（内温９２℃）で８時間攪拌した。反応液をガスクロマトグラフィーで分析の結果、DMAは消失し、DCPDが１２．２面積％残余し、新たなピークが７６．７面積％で出現した。反応を停止してから濃縮し得られた油状物をシリカゲル１４０ｇを用いてカラムクロマトグラフィー（溶離液／酢酸エチル：ｎ−ヘプタン＝１：９〜１：５）で精製すると純度９４．９％の結晶１２．１ｇ（単離収率７３．６％（DMA基準））が得られた。この結晶を酢酸エチル：ｎ−ヘプタン＝１：１から再結晶化することにより、純度１００％の白色結晶８．１ｇが得られた。
この結晶は、下記の分析結果からテトラメチルテトラシクロ［６．５．１．０２，７．０９，１３］テトラデセ−３，５，１０−トリエン−３，４，５，６−テトラカルボキシレート（TMTEと略記する）であることを確認した。
A 100 ml four-necked reaction flask was charged with 6.6 g (50 mmol) of dicyclopentadiene (DCPD), 33 g of diglyme and 0.449 g (2 mmol) (4 mol%) of palladium acetate (Pd (OAc) 2 ) while stirring at 75 ° C. Then, 10.7 g (75 mmol) of dimethylacetylene dicarboxylate (DMA) was added dropwise over 45 minutes. The mixture was further stirred for 8 hours in a 100 ° C. oil bath (internal temperature 92 ° C.). As a result of analyzing the reaction solution by gas chromatography, DMA disappeared, DCPD remained at 12.2 area%, and a new peak appeared at 76.7 area%. The oil obtained by concentrating the reaction after stopping the reaction was purified by column chromatography (eluent / ethyl acetate: n-heptane = 1: 9 to 1: 5) using 140 g of silica gel to obtain a purity of 94.9%. 12.1 g of crystals (isolated yield 73.6% (DMA basis)) was obtained. The crystals were recrystallized from ethyl acetate: n-heptane = 1: 1 to obtain 8.1 g of white crystals having a purity of 100%.
This crystal was found to be tetramethyltetracyclo [6.5.1.0 2,7 . 0 9,13] was confirmed that a Tetoradese -3,5,10- triene-3,4,5,6-carboxylate (abbreviated as TMTE).
MASS(FAB+, m/e(%)) : 417([M+H]+, 3), 385(100), 279(58), 105(68).
1H NMR(DMSO-d6,δppm) : 1.46(d, J=10.39Hz, 1H), 1.74(d, J=10.39Hz, 1H), 2.18(d, J=3.97Hz, 1H), 2.27〜2.29(m, 2H), 2.40(d, J=4.89Hz, 1H), 2.54〜2.60(m, 1H), 2.83(d, J=2.53Hz, 1H), 2.93(d, J=12.53Hz, 1H), 3.13〜3.16(m, 1H)，3.67(s, 3H), 3.68(s, 3H), 3.69(s, 6H), 5.57(dd, J1=2.44Hz, J2=5.49Hz, 1H), 5.70(dd, J1=1.83Hz, J2=5.50Hz, 1H).
13C NMR(DMSO-d6,δppm) : 32.3786, 36.1097, 37.0482, 40.0087, 43.9230, 48.2340, 51.0190, 52.3314(2), 52,4458(2), 53.9871, 130,9675, 131.8678，131.9289, 131.9823, 133.6151, 136.4078, 166.5010，166.5544, 166.8978, 167.0199.
mp.( ℃) : 90〜91
MASS (FAB + , m / e (%)): 417 ([M + H] + , 3), 385 (100), 279 (58), 105 (68).
1 H NMR (DMSO-d 6 , δppm): 1.46 (d, J = 10.39Hz, 1H), 1.74 (d, J = 10.39Hz, 1H), 2.18 (d, J = 3.97Hz, 1H), 2.27〜 2.29 (m, 2H), 2.40 (d, J = 4.89Hz, 1H), 2.54 ~ 2.60 (m, 1H), 2.83 (d, J = 2.53Hz, 1H), 2.93 (d, J = 12.53Hz, 1H ), 3.13-3.16 (m, 1H), 3.67 (s, 3H), 3.68 (s, 3H), 3.69 (s, 6H), 5.57 (dd, J 1 = 2.44Hz, J 2 = 5.49Hz, 1H) , 5.70 (dd, J 1 = 1.83Hz, J 2 = 5.50Hz, 1H).
13 C NMR (DMSO-d 6 , δppm): 32.3786, 36.1097, 37.0482, 40.0087, 43.9230, 48.2340, 51.0190, 52.3314 (2), 52,4458 (2), 53.9871, 130,9675, 131.8678, 131.9289, 131.9823, 133.6151, 136.4078, 166.5010, 166.5544, 166.8978, 167.0199.
mp. (° C): 90 ~ 91
TMTE単結晶Ｘ線測定結果
Formula C22H24O8
Fw 416.426
Crystal color, habit colorless, plate
Crystal dimensions 0.9 x 0.50 x 0.20 mm3
Crystal system Monoclinic
Lattic type Cube
Lattic parameters a=11.275(1) Å, b=19.402(1) Å, c=17.700(1) Å
α=90.00 °, β=147.881(6) °, γ=90.00 °
V=2058.7(3) Å3
Z value = 4
Dcalc ＝ 1.344 Mg/m3
Mo K<α> radiation
λ（MoKa）＝ 0.71073 Å, μ（MoKa）＝ 0.10 mm-1
No. of measured reflections = 4666
No. of observed reflections = 2279
R(gt) = 0.049
WR(gt) = 0.109
Temp. = 297 K
TMTE single crystal X-ray measurement results
Formula C 22 H 24 O 8
Fw 416.426
Crystal color, habit colorless, plate
Crystal dimensions 0.9 x 0.50 x 0.20 mm 3
Crystal system monoclinic
Lattic type Cube
Lattic parameters a = 11.275 (1) b, b = 19.402 (1) Å, c = 17.700 (1) Å
α = 90.00 °, β = 147.881 (6) °, γ = 90.00 °
V = 2058.7 (3) Å 3
Z value = 4
Dcalc = 1.344 Mg / m 3
Mo K <α> radiation
λ (MoKa) = 0.71073 Å, μ (MoKa) = 0.10 mm -1
No. of measured reflections = 4666
No. of observed reflections = 2279
R (gt) = 0.049
WR (gt) = 0.109
Temp. = 297 K
［実施例２］（スキーム１）
５０ml 四つ口反応フラスコにジシクロペンタジエン（DCPD）１．３２ｇ（１０mmol）、トルエン１０．６ｇ及び酢酸パラジウム（Pd(OAc)2）８９．８ｍｇ（０．４mmol）(4mol%)を仕込み８５℃で攪拌中に、ジメチルアセチレンジカルボキシレート（DMA）２．１３ｇ（１５ｍｍｏｌ）を１０分かけて滴下した。更に１１０℃の油浴（内温１０３℃）で１時間攪拌した後、１３０℃の油浴（内温１０８℃）で２０時間攪拌した後、反応液をガスクロマトグラフィーで分析の結果、DMAは消失し、DCPDが２．６面積％残余し、TMTEが５２．５面積％生成し、更に新たなピークが２９．１面積％で出現した。反応を停止してから濃縮し得られた油状物をシリカゲル１３０ｇを用いてカラムクロマトグラフィー（溶離液／酢酸エチル：ｎ−ヘプタン＝１：９〜１：０）で精製すると留分１に１．０１ｇ（新たなピークが７７．６面積％）の結晶が得られた。この結晶を酢酸エチル：ｎ−ヘプタン＝１：１から再結晶化することにより、純度１００％の白色結晶０．５２１ｇが得られた。
この結晶は、下記の分析結果からテトラメチルオクタシクロ[9.9.2.02,10.13,9.04,8.012,20.113,19.014,18]テトラコセ−５，１５，２１−トリエン−１，１１，２１，２２−テトラカルボキシレート（TMOEと略記する）であることを確認した。
A 50 ml four-necked reaction flask was charged with 1.32 g (10 mmol) of dicyclopentadiene (DCPD), 10.6 g of toluene and 89.8 mg (0.4 mmol) (4 mol%) of palladium acetate (Pd (OAc) 2 ) at 85 ° C. While stirring, 2.13 g (15 mmol) of dimethylacetylene dicarboxylate (DMA) was added dropwise over 10 minutes. Further, after stirring for 1 hour in a 110 ° C. oil bath (internal temperature 103 ° C.), the mixture was stirred for 20 hours in a 130 ° C. oil bath (internal temperature 108 ° C.). It disappeared, DCPD remained at 2.6 area%, TMTE was generated at 52.5 area%, and a new peak appeared at 29.1 area%. The oily substance obtained by concentrating the reaction after stopping the reaction was purified by column chromatography (eluent / ethyl acetate: n-heptane = 1: 9 to 1: 0) using 130 g of silica gel. 01 g of crystals (77.6 area% new peak) were obtained. The crystals were recrystallized from ethyl acetate: n-heptane = 1: 1 to obtain 0.521 g of 100% pure white crystals.
The crystals tetramethyl octamethylene cyclo from the following analysis results [9.9.2.0 2,10 .1 3,9 .0 4,8 .0 12,20 .1 13,19 .0 14,18] Tetorakose -5, It was confirmed to be 15,21-triene-1,11,1,22-tetracarboxylate (abbreviated as TMOE).
MASS(FAB+, m/e(%)) : 549([M+H]+, 9), 517(44), 385(20), 154(100).
1H NMR(DMSO-d6,δppm) : 0.90(dd, J1=5.65Hz, J2=10.84Hz, 2H), 1.92(t, J=10.08Hz, 2H), 2.01〜2.07(m, 4H), 2.11〜2.18(m, 4H), 2.22〜2.37(m, 6H), 2.92〜2.94(m, 2H), 3.68(t, J=4.58Hz, 12H), 5.42〜5.46(m, 2H)，5.68(t, J=2.75Hz, 2H).
13C NMR(DMSO-d6,δppm) : 31.3790, 31.4171, 37.4984, 37.6128, 42.5800, 42.6334, 43.6025, 43.7093, 44.1671, 44.3731, 45.4489, 49.3327, 50.5459, 52.0185(4), 52,1787, 53.6819(2), 54.7424, 54.9485, 131.4253，131.6542, 132.0814, 132.2112, 135.5303(2), 166.7528(2)，172.2159(2).
mp.( ℃) : 222〜224(Z89) 240〜241(A8)
MASS (FAB + , m / e (%)): 549 ([M + H] + , 9), 517 (44), 385 (20), 154 (100).
1 H NMR (DMSO-d 6 , δppm): 0.90 (dd, J 1 = 5.65Hz, J 2 = 10.84Hz, 2H), 1.92 (t, J = 10.08Hz, 2H), 2.01 to 2.07 (m, 4H ), 2.11 to 2.18 (m, 4H), 2.22 to 2.37 (m, 6H), 2.92 to 2.94 (m, 2H), 3.68 (t, J = 4.58Hz, 12H), 5.42 to 5.46 (m, 2H), 5.68 (t, J = 2.75Hz, 2H).
13 C NMR (DMSO-d 6 , δppm): 31.3790, 31.4171, 37.4984, 37.6128, 42.5800, 42.6334, 43.6025, 43.7093, 44.1671, 44.3731, 45.4489, 49.3327, 50.5459, 52.0185 (4), 52,1787, 53.6819 (2 ), 54.7424, 54.9485, 131.4253, 131.6542, 132.0814, 132.2112, 135.5303 (2), 166.7528 (2), 172.2159 (2).
mp. (° C): 222 ~ 224 (Z89) 240 ~ 241 (A8)
TMOE単結晶Ｘ線測定結果
Formula C32H36O8
Fw 548.62
Crystal color, habit colorless, plate
Crystal dimensions 0.9 x 0.50 x 0.20 mm3
Crystal system Monoclinic
Lattic type Cube
Lattic parameters a=16.091(1) Å, b=11.271(1) Å, c=16.206(1) Å
α=90.00 °, β=109.072(6) °, γ=90.00 °
V=2777.8(5) Å3
Z value = 4
Dcalc ＝ 1.312 Mg/m3
Mo K<α> radiation
λ（MoKa）＝ 0.71073 Å, μ（MoKa）＝ 0.10 mm-1
No. of measured reflections = 2849
No. of observed reflections = 2649
R(gt) = 0.057
WR(gt) = 0.210
Temp. = 297 K
TMOE single crystal X-ray measurement results
Formula C 32 H 36 O 8
Fw 548.62
Crystal color, habit colorless, plate
Crystal dimensions 0.9 x 0.50 x 0.20 mm 3
Crystal system monoclinic
Lattic type Cube
Lattic parameters a = 16.091 (1) Å, b = 11.271 (1) Å, c = 16.206 (1) Å
α = 90.00 °, β = 109.072 (6) °, γ = 90.00 °
V = 2777.8 (5) Å 3
Z value = 4
Dcalc = 1.312 Mg / m 3
Mo K <α> radiation
λ (MoKa) = 0.71073 Å, μ (MoKa) = 0.10 mm -1
No. of measured reflections = 2849
No. of observed reflections = 2649
R (gt) = 0.057
WR (gt) = 0.210
Temp. = 297 K
［実施例３〜２２］
前記実施例１及び２の触媒、溶媒、反応条件等を変更してTMTE及びTMOEを合成した結果を表１に示す。
Table 1 shows the results of synthesizing TMTE and TMOE by changing the catalysts, solvents, reaction conditions, etc. of Examples 1 and 2.
［実施例２３］（スキーム２）
５０ml 四つ口反応フラスコにTMTE ０．８３２ｇ（２mmol）、ジシクロペンタジエン（DCPD）０．７９２ｇ（６mmol）及び１，４−ジオキサン９ｇを仕込み１００℃で２４時間攪拌しながら還流させた。反応液をガスクロマトグラフィーで分析の結果、DCPD ：TMTE ：TMOE ＝５１．８：２３．３：２２．３（面積％）であった。よって、TMTE転化率４８．９％、TMOE収率４８．９％であった。 A 50 ml four-necked reaction flask was charged with 0.832 g (2 mmol) of TMTE, 0.792 g (6 mmol) of dicyclopentadiene (DCPD) and 9 g of 1,4-dioxane and refluxed at 100 ° C. for 24 hours with stirring. As a result of analyzing the reaction solution by gas chromatography, it was DCPD: TMTE: TMOE = 51.8: 23.3: 22.3 (area%). Therefore, the TMTE conversion was 48.9% and the TMOE yield was 48.9%.
［実施例２４］（スキーム２）
５０ml 四つ口反応フラスコにTMTE ０．８３２ｇ（２mmol）、ジシクロペンタジエン（DCPD）０．７９２ｇ（６mmol）及びジグライム９ｇを仕込み１５０℃で７時間攪拌しながら還流させた。反応液をガスクロマトグラフィーで分析の結果、DCPD ：TMTE ：TMOE：未知物質１＝２３．１：１０．４：３１．１：２２．４（面積％）であった。よって、TMTE転化率８４．６％、TMOE収率４６．６％であった。 A 50 ml four-necked reaction flask was charged with 0.832 g (2 mmol) of TMTE, 0.792 g (6 mmol) of dicyclopentadiene (DCPD) and 9 g of diglyme and refluxed at 150 ° C. with stirring for 7 hours. The reaction liquid was analyzed by gas chromatography. As a result, it was found that DCPD: TMTE: TMOE: unknown substance 1 = 23.1: 10.4: 31.1: 22.4 (area%). Therefore, the TMTE conversion was 84.6% and the TMOE yield was 46.6%.
［実施例２５］（スキーム２）
５０ml 四つ口反応フラスコにTMTE０．８３２ｇ（２mmol）、ジシクロペンタジエン（DCPD）０．７９２ｇ（６mmol）、１，４−ジオキサン９ｇ、酢酸パラジウム（Pd(OAc)2）０．０４５ｇ（０．４mmol）(１０mol%)を仕込み１００℃で２４時間攪拌しながら還流させた。反応液をガスクロマトグラフィーで分析の結果、DCPD ：TMTE ：TMOE未知物質２：未知物質３＝３４．４：３０．４：３１．４：２．１：０．５（面積％）であった。よって、TMTE転化率５２．８％、TMOE収率４８．８％であった。更に、１００℃で２４時間攪拌しながら還流させて、反応液をガスクロマトグラフィーで分析の結果、DCPD ：TMTE ：TMOE未知物質２：未知物質３＝３．９：６．３：８１．０：７．１：１．２（面積％）であった。よって、TMTE転化率９３．４％、TMOE収率８４．７％であった。 In a 50 ml four-necked reaction flask, 0.832 g (2 mmol) of TMTE, 0.792 g (6 mmol) of dicyclopentadiene (DCPD), 9 g of 1,4-dioxane, 0.045 g (0.4 mmol) of palladium acetate (Pd (OAc) 2 ) ) (10 mol%) was added and refluxed at 100 ° C. with stirring for 24 hours. The reaction liquid was analyzed by gas chromatography. As a result, DCPD: TMTE: TMOE unknown substance 2: unknown substance 3 = 34.4: 30.4: 31.4: 2.1: 0.5 (area%) . Therefore, TMTE conversion rate was 52.8% and TMOE yield was 48.8%. Further, the mixture was refluxed with stirring at 100 ° C. for 24 hours, and the reaction solution was analyzed by gas chromatography. As a result, DCPD: TMTE: TMOE unknown substance 2: unknown substance 3 = 3.9: 6.3: 81.0: 7.1: 1.2 (area%). Therefore, the TMTE conversion was 93.4% and the TMOE yield was 84.7%.
［実施例２６］（スキーム１）
１００ml 四つ口反応フラスコにジシクロペンタジエン（DCPD）６．６ｇ（５０mmol）、１，４−ジオキサン３３ｇ及び塩化パラジウム（PdCl2）０．３５４ｇ（０．２mmol）(４mol%)を仕込み８０℃で攪拌中に、ジエチルアセチレンジカルボキシレート（DEA）１２．８ｇ（７５ｍｍｏｌ）を２時間かけて滴下した。更に１２０℃の油浴（内温１０２℃）で２２時間攪拌した。反応液をガスクロマトグラフィーで分析の結果、DEAは消失し、新たなピークが７４．９面積％で出現した。反応を停止してから濃縮し得られた油状物をシリカゲル１４０ｇを用いてカラムクロマトグラフィー（溶離液／酢酸エチル：ｎ−ヘプタン＝１：９〜１：５）で精製すると油状物１５．６ｇ（単離収率８７．６％（DEA基準））が得られた。（この結晶を酢酸エチル：ｎ−ヘプタン＝１：１から再結晶化することにより、純度１００％の白色結晶８．１ｇが得られた。）
この油状物は、下記の分析結果からテトラエチルテトラシクロ［６．５．１．０２，７．０９，１３］テトラデセ−３，５，１０−トリエン−３，４，５，６−テトラカルボキシレート（TETE）であることを確認した。
A 100 ml four-necked reaction flask was charged with 6.6 g (50 mmol) of dicyclopentadiene (DCPD), 33 g of 1,4-dioxane and 0.354 g (0.2 mmol) (4 mol%) of palladium chloride (PdCl 2 ) at 80 ° C. While stirring, 12.8 g (75 mmol) of diethyl acetylenedicarboxylate (DEA) was added dropwise over 2 hours. Further, the mixture was stirred for 22 hours in an oil bath at 120 ° C. (internal temperature: 102 ° C.). As a result of analyzing the reaction solution by gas chromatography, DEA disappeared and a new peak appeared at 74.9 area%. The oily substance obtained by concentrating the reaction after stopping the reaction was purified by column chromatography (eluent / ethyl acetate: n-heptane = 1: 9 to 1: 5) using 140 g of silica gel to obtain 15.6 g of an oily substance ( An isolated yield of 87.6% (DEA basis) was obtained. (The crystals were recrystallized from ethyl acetate: n-heptane = 1: 1 to obtain 8.1 g of 100% pure white crystals.)
This oily substance was found to be tetraethyltetracyclo [6.5.1.0 2,7 . 0 9,13] was confirmed to be Tetoradese -3,5,10- triene-3,4,5,6-carboxylate (TETE).
MASS(FAB−, m/e(%)) : 472(M−, 100), 443(18), 399(25).
1H NMR(DMSO-d6,δppm) : 1.21〜1.25(ｍ, 12H), 1.46(d, J=10.4Hz, 1H), 1.79 (d, J=10.4Hz, 1H), 2.21(d, J=4.0Hz, 1H), 2.24〜2.35(m, 2H), 2.43(d, J=4.89Hz, 1H), 2.56〜2.61(m, 1H), 2.83(d, J=12.8Hz, 1H), 2.95(d, J=12.5Hz, 1H), 3.14〜3.16(m, 1H)，4.10〜4.17(m, 8H), 5.58(dd, J1=2.14Hz, J2=5.50Hz, 1H), 5.71(dd, J1=1.83Hz, J2=5.50Hz, 1H).
13C NMR(DMSO-d6,δppm) : 13.7076, 13.9060, 13.9365, 32.3023, 36.1402, 37.1321, 39.9019, 43.9077, 48.2340, 50.8664, 54.0329, 60,2514, 61.1976, 61.2662, 61.4723, 131,3108, 131.7763，131.9213, 132.1807, 133.3328, 135.6982, 166.1119，166.1805, 166.3713, 166.5849.
MASS (FAB − , m / e (%)): 472 (M − , 100), 443 (18), 399 (25).
1 H NMR (DMSO-d 6 , δppm): 1.21 ~ 1.25 (m, 12H), 1.46 (d, J = 10.4Hz, 1H), 1.79 (d, J = 10.4Hz, 1H), 2.21 (d, J = 4.0Hz, 1H), 2.24 to 2.35 (m, 2H), 2.43 (d, J = 4.89Hz, 1H), 2.56 to 2.61 (m, 1H), 2.83 (d, J = 12.8Hz, 1H), 2.95 (d, J = 12.5Hz, 1H), 3.14-3.16 (m, 1H), 4.10-4.17 (m, 8H), 5.58 (dd, J 1 = 2.14Hz, J 2 = 5.50Hz, 1H), 5.71 ( dd, J 1 = 1.83Hz, J 2 = 5.50Hz, 1H).
13 C NMR (DMSO-d 6 , δppm): 13.7076, 13.9060, 13.9365, 32.3023, 36.1402, 37.1321, 39.9019, 43.9077, 48.2340, 50.8664, 54.0329, 60,2514, 61.1976, 61.2662, 61.4723, 131,3108, 131.7763, 131.9213, 132.1807, 133.3328, 135.6982, 166.1119, 166.1805, 166.3713, 166.5849.
［実施例２７］（スキーム３）
５０ｍLガラス製反応器にＴＭＴＥ２．５０ｇ（６．０ｍｍｏｌ）、エタノール１３．３ｇ、８５％水酸化カリウム２．３８ｇと水６ｇの水溶液を仕込み、９０℃油浴で３時間還流した。終了後、濃縮してから残渣に水２０ｍＬを加えてから氷冷下３５％塩酸３．６ｇを滴下しｐＨ＜１にした。続いてメチルイソブチルケトンを加えて抽出した後、濃縮・乾燥すると１．７８ｇの結晶が得られた。更に、これに酢酸エチルを加えて加温した後氷冷してから濾過、酢酸エチルで洗浄してから乾燥すると結晶１．３０ｇ（収率６０％）が得られた。
５０ｍLガラス製反応器にＴＭＴＥ２．０８ｇ（５．０ｍｍｏｌ）、エタノール１０．４ｇ、８５％水酸化カリウム１．９８ｇと水６ｇの水溶液を仕込み、１００℃油浴で８時間還流した。終了後、濃縮してから残渣に水２０ｍＬを加えてから氷冷下３５％塩酸３．０ｇを滴下しｐＨ＜１にした。続いてメチルイソブチルケトンを加えて抽出した後、濃縮すると２．１１ｇの粗結晶が得られた。更に、これに酢酸エチルを加えて加温した後氷冷してから濾過、酢酸エチルで洗浄してから乾燥すると結晶１．５２ｇ（収率８４．４％）が得られた。
この結晶の構造は、下記の分析結果からテトラシクロ［６．５．１．０２，７．０９，１３］テトラデセ−３，５，１０−トリエン−３，４，５，６−テトラカルボン酸 （ＴＴＣＡ）であることを確認した。
A 50 mL glass reactor was charged with an aqueous solution of 2.50 g (6.0 mmol) TMTE, 13.3 g ethanol, 2.38 g 85% potassium hydroxide and 6 g water, and refluxed in an oil bath at 90 ° C. for 3 hours. After completion, the mixture was concentrated, 20 mL of water was added to the residue, and 3.6 g of 35% hydrochloric acid was added dropwise under ice cooling to pH <1. Subsequently, methyl isobutyl ketone was added for extraction, followed by concentration and drying to obtain 1.78 g of crystals. Further, ethyl acetate was added to the mixture, and the mixture was heated and then cooled with ice, filtered, washed with ethyl acetate and dried to obtain 1.30 g (yield 60%) of crystals.
A 50 mL glass reactor was charged with 2.08 g (5.0 mmol) of TMTE, 10.4 g of ethanol, 1.98 g of 85% potassium hydroxide and 6 g of water and refluxed in a 100 ° C. oil bath for 8 hours. After completion, the mixture was concentrated, 20 mL of water was added to the residue, and 3.0 g of 35% hydrochloric acid was added dropwise under ice cooling to pH <1. Subsequently, methyl isobutyl ketone was added for extraction, followed by concentration to obtain 2.11 g of crude crystals. Further, ethyl acetate was added to the mixture, and the mixture was warmed and cooled with ice, filtered, washed with ethyl acetate and dried to obtain 1.52 g of crystals (yield 84.4%).
The structure of this crystal is tetracyclo [6.5.1.0 2,7 . 0 9,13] was confirmed to be Tetoradese -3,5,10- triene-3,4,5,6-tetracarboxylic acid (TTCA).
MASS(FAB-, m/e(%)) : 359([M-H]-, 100), 341 (48), 297 (65).
1H NMR(DMSO-d6,δppm) : 1.46(d, J=9.78Hz, 1H), 1.61(d, J=10.1Hz, 1H), 2.18(d, J=3.67Hz, 1H), 2.24〜2.28(m, 2H), 2.40(d, J=4.89Hz, 1H), 2.55~2.61(m, 1H)，2.68(d, J=12.53Hz, 1H)，2.78(d, J=12.53Hz, 1H), 3.13~3.16(m, 1H)，5.58(dd, J1=2.14Hz, J2=5.50Hz, 1H), 5.56(dd, J1=1.99Hz, J2=5.65Hz, 1H), 12.97(brs, 4H).
13C NMR(DMSO-d6,δppm) : 32.1378, 35.6400, 36.4793, 38.9973, 43.2472, 47.5583, 50.4196, 53.4487, 130.9327, 131.6957, 131.7796, 131.9856, 132.2222, 134.5036, 167.5192，167.8320，167.9312，168.1906.
mp.( ℃) : 190.5〜191.5
MASS (FAB -, m / e (%)): 359 ([MH] -, 100), 341 (48), 297 (65).
1 H NMR (DMSO-d 6 , δppm): 1.46 (d, J = 9.78Hz, 1H), 1.61 (d, J = 10.1Hz, 1H), 2.18 (d, J = 3.67Hz, 1H), 2.24〜 2.28 (m, 2H), 2.40 (d, J = 4.89Hz, 1H), 2.55 ~ 2.61 (m, 1H), 2.68 (d, J = 12.53Hz, 1H), 2.78 (d, J = 12.53Hz, 1H ), 3.13-3.16 (m, 1H), 5.58 (dd, J 1 = 2.14Hz, J 2 = 5.50Hz, 1H), 5.56 (dd, J 1 = 1.99Hz, J 2 = 5.65Hz, 1H), 12.97 (brs, 4H).
13 C NMR (DMSO-d 6 , δppm): 32.1378, 35.6400, 36.4793, 38.9973, 43.2472, 47.5583, 50.4196, 53.4487, 130.9327, 131.6957, 131.7796, 131.9856, 132.2222, 134.5036, 167.5192, 167.8320, 167.9931, 168.1906.
mp. (° C): 190.5〜191.5
［実施例２８］（スキーム５）
５０ｍLガラス製反応器にＴＭＴＥ４．１６ｇ（１０．０ｍｍｏｌ）、H2WO4 ０．１２５ｇ(0.5mmol)、トルエン１２．５ｇ、８５％リン酸０．０１５ｇ（０．１３mmol）と９０％トリオクチルメチルクロライド（ＴＯＭＡＣ）０．１５７ｇ（０．３５mmol）を仕込み、攪拌下に４５℃で３５％過酸化水素１．９４ｇ（２０．０mmol）を２０分かけて滴下した。その後５０℃に昇温し５時間反応させた。終了後、トルエンと水を加えてから有機相を分液し、３回水洗後濃縮すると油状物５．２ｇが得られた。更にこれをシリカゲルカラムクロマトグラフィーで精製することにより４．２ｇ（ＧＣ純度９７．８％）（収率97.6％）が得られた。これを酢酸エチル１７ｇに溶解後室温で一夜静置すると結晶が析出し、これを濾取・乾燥すると透明な結晶１．７１ｇが得られた。
この結晶の構造は、下記の分析結果からテトラメチル １０，１１−エポキシテトラシクロ［６．５．１．０２，７．０９，１３］テトラデセ−３，５−ジエン−３，４，５，６−テトラカルボキシレート （ＴＭＥＥ）であることを確認した。
In a 50 mL glass reactor TMTE 4.16 g (10.0 mmol), H 2 WO 4 0.125 g (0.5 mmol), toluene 12.5 g, 85% phosphoric acid 0.015 g (0.13 mmol) and 90% trioctylmethyl 0.157 g (0.35 mmol) of chloride (TOMAC) was charged, and 1.94 g (20.0 mmol) of 35% hydrogen peroxide was added dropwise at 45 ° C. over 20 minutes with stirring. Thereafter, the temperature was raised to 50 ° C. and reacted for 5 hours. After completion, toluene and water were added, the organic phase was separated, washed with water three times, and concentrated to obtain 5.2 g of an oily substance. This was further purified by silica gel column chromatography to obtain 4.2 g (GC purity 97.8%) (yield 97.6%). When this was dissolved in 17 g of ethyl acetate and allowed to stand at room temperature overnight, crystals were precipitated, and this was collected by filtration and dried to obtain 1.71 g of transparent crystals.
The structure of this crystal is shown in the following analytical results from tetramethyl 10,11-epoxytetracyclo [6.5.1.0 2,7 . 0 9,13] was confirmed to be Tetoradese 3,5-diene-3,4,5,6-carboxylate (TMEE).
MASS(FAB-, m/e(%)) : 432 ([M]-・, 100), 417 (15), 386 (15), 305(21).
1H NMR(DMSO-d6,δppm) : 1.59(dd, J1=10.8Hz, J2=38.3Hz, 2H), 1.81~1.82(m, 2H), 2.17(d, J=3.97Hz, 1H), 2.45~2.48(m, 2H), 2.49~2.52(m, 1H), 3.19(d, J=12.2Hz, 1H), 3.31(d, J=12.2Hz, 1H), 3.38(d, J=2.14Hz, 1H), 3.60(s, 1H)，3.65(s, 3H)，3.66(s, 3H)，3.72(s, 3H), 3.75(s, 3H).
13C NMR(DMSO-d6,δppm) : 27.8367, 36.7410, 37.1988, 37.8856, 45.8819, 47.5148, 48.5143, 49.4986, 52.4438, 52.4591, 52.6041, 52.6346, 59.0668, 60.4631, 130.9579, 131.1715, 133.4453, 134.6051, 165.9420，166.0336，166.1175，166.1480.
mp.( ℃) : 123〜124
MASS (FAB -, m / e (%)): 432 ([M] - ·, 100), 417 (15), 386 (15), 305 (21).
1 H NMR (DMSO-d 6 , δppm): 1.59 (dd, J 1 = 10.8Hz, J 2 = 38.3Hz, 2H), 1.81 ~ 1.82 (m, 2H), 2.17 (d, J = 3.97Hz, 1H ), 2.45 ~ 2.48 (m, 2H), 2.49 ~ 2.52 (m, 1H), 3.19 (d, J = 12.2Hz, 1H), 3.31 (d, J = 12.2Hz, 1H), 3.38 (d, J = 2.14Hz, 1H), 3.60 (s, 1H), 3.65 (s, 3H), 3.66 (s, 3H), 3.72 (s, 3H), 3.75 (s, 3H).
13 C NMR (DMSO-d 6 , δppm): 27.8367, 36.7410, 37.1988, 37.8856, 45.8819, 47.5148, 48.5143, 49.4986, 52.4438, 52.4591, 52.6041, 52.6346, 59.0668, 60.4631, 130.9579, 131.1715, 133.4453, 134.6051, 165.9420, 166.0336, 166.1175, 166.1480.
mp. (° C): 123 ~ 124
［実施例２９］（スキーム６）
５０ｍLガラス製反応器にＴＭOＥ２．７４ｇ（５．０ｍｍｏｌ）、H2WO4０．１２５ｇ(0.5mmol)、１，４−ジオキサン１３．７ｇ、８５％リン酸０．０１５ｇ（０．１３mmol）と９０％トリオクチルメチルクロライド（ＴＯＭＡＣ）０．１５７ｇ（０．３５mmol）を仕込み、攪拌下に５０℃で３５％過酸化水素２．９２ｇ（１５．０mmol）を２０分かけて滴下した。その後５４℃に昇温し１６時間反応させた。TMOEが残余したので更に、３５％過酸化水素１．４６ｇ（１５．０mmol）を滴下し、５４℃で６時間反応させて終了させた。濃縮後、酢酸エチルと水を加えてから有機相を分液し、水洗後濃縮すると結晶２．２ｇ（ＧＣ純度８２．１％）（収率６２.１％）が得られた。更にこれをシリカゲルカラムクロマトグラフィーで精製することにより結晶１．２１ｇが得られた。
この結晶の構造は、下記の分析結果からテトラメチル ５，６：１５，１６−ジエポキシオクタシクロ[9.9.2.02,10.13,9.04,8.012,20.113,19.014,18]テトラコセ−２１−エン−１，１１，２１，２２−テトラカルボキシレート（DEOEと略記する）であることを確認した。
In a 50 mL glass reactor, TMOE 2.74 g (5.0 mmol), H 2 WO 4 0.125 g (0.5 mmol), 1,4-dioxane 13.7 g, 85% phosphoric acid 0.015 g (0.13 mmol) and 90 % Trioctylmethyl chloride (TOMAC) 0.157 g (0.35 mmol) was charged, and 2.92 g (15.0 mmol) of 35% hydrogen peroxide was added dropwise at 50 ° C. over 20 minutes with stirring. Thereafter, the temperature was raised to 54 ° C. and reacted for 16 hours. Since TMOE remained, 1.46 g (15.0 mmol) of 35% hydrogen peroxide was further added dropwise, and the reaction was terminated at 54 ° C. for 6 hours. After concentration, ethyl acetate and water were added, the organic phase was separated, washed with water and concentrated to obtain 2.2 g of crystals (GC purity 82.1%) (yield 62.1%). This was further purified by silica gel column chromatography to obtain 1.21 g of crystals.
The structure of this crystal, tetramethyl from the following analyzes 5,6: 15,16-diepoxy octa cyclo [9.9.2.0 2,10 .1 3,9 .0 4,8 .0 12,20 .1 13 , it was confirmed that a 19.0 14,18] Tetorakose 21- ene -1,11,21,22- tetracarboxylate (abbreviated as DEOE).
MASS(FAB+, m/e(%)) : 581 ([M+H]+, 27), 565 (18), 549(90), 396 (62), 154(100).
1H NMR(DMSO-d6,δppm) : 0.823(d, J=10.7Hz, 2H), 1.65(dd, J1=8.71Hz, J2=15.1Hz, 2H), 1.80(d, J=10.9Hz, 2H), 1.93(d, J=10.7Hz, 2H), 1.97(s, 2H), 2.19~2.26(m, 6H), 2.34(dd, J1=8.44Hz, J2=16.35Hz, 2H), 2.49(s, 2H)，3.32(s, 2H), 3.60~3.74(m, 2H), 3.64(s, 6H), 3.71(s, 6H).
13C NMR(DMSO-d6,δppm) : 26.6679(2), 37.9452(2), 41.8824(2), 43.7823, 43.8433, 44.7132(2), 46.2621, 46.3307, 46.7122(2), 48.8563(2), 52.2517(2), 52.3357(2), 52.9766(2), 58.6076(2), 61.1027(2), 135.2599(2), 165.8567(2),171.1291(2). （(2)は炭素原子２個分を表す。）
mp.( ℃) : 263〜264
MASS (FAB + , m / e (%)): 581 ([M + H] + , 27), 565 (18), 549 (90), 396 (62), 154 (100).
1 H NMR (DMSO-d 6 , δppm): 0.823 (d, J = 10.7Hz, 2H), 1.65 (dd, J 1 = 8.71Hz, J 2 = 15.1Hz, 2H), 1.80 (d, J = 10.9 Hz, 2H), 1.93 (d, J = 10.7Hz, 2H), 1.97 (s, 2H), 2.19-2.26 (m, 6H), 2.34 (dd, J 1 = 8.44Hz, J 2 = 16.35Hz, 2H ), 2.49 (s, 2H), 3.32 (s, 2H), 3.60 to 3.74 (m, 2H), 3.64 (s, 6H), 3.71 (s, 6H).
13 C NMR (DMSO-d 6 , δppm): 26.6679 (2), 37.9452 (2), 41.8824 (2), 43.7823, 43.8433, 44.7132 (2), 46.2621, 46.3307, 46.7122 (2), 48.8563 (2), 52.2517 (2), 52.3357 (2), 52.9766 (2), 58.6076 (2), 61.1027 (2), 135.2599 (2), 165.8567 (2), 171.1291 (2). ((2) is equivalent to 2 carbon atoms. Represents.)
mp. (° C): 263 ~ 264
［実施例３０］（第４工程）
５０ｍLガラス製反応器にＴＭOＥ２．７４ｇ（５．０ｍｍｏｌ）、エタノール２１．９ｇ、８５％水酸化カリウム１．９８ｇと水８ｇの水溶液を仕込み、１００℃油浴で２４時間還流した。反応は、スラリー状態で終了した。これを濃縮してから残渣に水２０ｍＬを加えてから氷冷下３５％塩酸３．０ｇを滴下しｐＨ＜１にした。続いて濾過、水で洗浄してから乾燥すると結晶２．４１ｇ（収率９７．８％）が得られた。
この結晶の構造は、下記の分析結果からオクタシクロ[9.9.2.02,10.13,9.04,8.012,20.113,19.014,18]テトラコセ−５，１５，２１−トリエン−１，１１，２１，２２−テトラカルボン酸−２１，２２−ジメチルエステル（OTCMと略記する）であることを確認した。
A 50 mL glass reactor was charged with 2.74 g (5.0 mmol) of TMOE, 21.9 g of ethanol, 1.98 g of 85% potassium hydroxide and 8 g of water and refluxed in an oil bath at 100 ° C. for 24 hours. The reaction was completed in a slurry state. After concentration, 20 mL of water was added to the residue, and then 3.0 g of 35% hydrochloric acid was added dropwise under ice cooling to pH <1. Subsequent filtration, washing with water and drying yielded 2.41 g of crystals (yield 97.8%).
The structure of this crystal, octacyclo from the following analysis results [9.9.2.0 2,10 .1 3,9 .0 4,8 .0 12,20 .1 13,19 .0 14,18] Tetorakose -5,15 , 21-triene-1,11,21,2-tetracarboxylic acid-21,22-dimethyl ester (abbreviated as OTCM).
MASS(FAB-, m/e(%)) : 519 ([M-H]-, 100), 475 (27).
1H NMR(DMSO-d6,δppm) : 0.81(dd, J1=5.19Hz, J2=9.77Hz, 2H), 1.75(d, J=8.55Hz, 1H), 1.90(s, 1H), 1.94(d, J=8.25Hz, 1H), 2.00(brs, 3H), 2.11~2.14(m, 4H), 2.20~2.25(m, 4H), 2.30~2.35(m, 4H), 2.92(brs, 2H)，3.64(d, J=2.14Hz, 6H), 5.48(dd, J1=1.83Hz, J2=5.50Hz, 2H), 12.72(brs, 2H).
13C NMR(DMSO-d6,δppm) : 31.0504(2), 37.0706, 37.1774, 42.1370, 42.2133, 42.9534, 43.0450, 43.4799, 43.7470, 43.9454, 44.7694, 48.7981, 49.9961, 51.7434(2), 52.5827(2), 54.3223, 54.4902, 131.6321, 131.7694, 131.8610, 131.9907, 134.4171(2), 167.3869(2),171.7513(2). （(2)は炭素原子２個分を表す。）
mp.( ℃) : 244.5〜245.5
MASS (FAB -, m / e (%)): 519 ([MH] -, 100), 475 (27).
1 H NMR (DMSO-d 6 , δppm): 0.81 (dd, J 1 = 5.19Hz, J 2 = 9.77Hz, 2H), 1.75 (d, J = 8.55Hz, 1H), 1.90 (s, 1H), 1.94 (d, J = 8.25Hz, 1H), 2.00 (brs, 3H), 2.11 ~ 2.14 (m, 4H), 2.20 ~ 2.25 (m, 4H), 2.30 ~ 2.35 (m, 4H), 2.92 (brs, 2H), 3.64 (d, J = 2.14Hz, 6H), 5.48 (dd, J 1 = 1.83Hz, J 2 = 5.50Hz, 2H), 12.72 (brs, 2H).
13 C NMR (DMSO-d 6 , δppm): 31.0504 (2), 37.0706, 37.1774, 42.1370, 42.2133, 42.9534, 43.0450, 43.4799, 43.7470, 43.9454, 44.7694, 48.7981, 49.9961, 51.7434 (2), 52.5827 (2) , 54.3223, 54.4902, 131.6321, 131.7694, 131.8610, 131.9907, 134.4171 (2), 167.3869 (2), 171.7513 (2). ((2) represents two carbon atoms.)
mp. (° C): 244.5-245.5
Claims (9)
独立して水素原子又は炭素数１〜１０のアルキル基を表し、ｎは１〜３の整数を表し、ｘ及びｙは１〜６の整数を表す。）
で表されるエポキシ脂環式テトラカルボン酸化合物。 Formula [1]
An epoxy alicyclic tetracarboxylic acid compound represented by:
独立して水素原子又は炭素数１〜１０のアルキル基を表し、ｎは１〜３の整数を表し、ｘ及びｙは１〜６の整数を表す。）
で表されるエポキシ脂環式テトラカルボン酸化合物。 Formula [3]
An epoxy alicyclic tetracarboxylic acid compound represented by:
で表される請求項１記載のエポキシ脂環式テトラカルボン酸化合物。 Formula [4]
The epoxy alicyclic tetracarboxylic acid compound of Claim 1 represented by these.
で表される請求項２記載のエポキシ脂環式テトラカルボン酸化合物。 Formula [6]
The epoxy alicyclic tetracarboxylic acid compound of Claim 2 represented by these.
独立して水素原子又は炭素数１〜１０のアルキル基を表し、ｎは１〜３の整数を表し、ｘ及びｙは１〜６の整数を表す。）
で表される脂環式テトラカルボン酸化合物を酸化剤により酸化することを特徴とする式［１］
で表されるエポキシ脂環式テトラカルボン酸化合物の製造法。 Formula [7]
Wherein the alicyclic tetracarboxylic acid compound represented by the formula is oxidized with an oxidizing agent [1]
The manufacturing method of the epoxy alicyclic tetracarboxylic acid compound represented by these.
独立して水素原子又は炭素数１〜１０のアルキル基を表し、ｎは１〜３の整数を表し、ｘ及びｙは１〜６の整数を表す。）
で表される脂環式テトラカルボン酸化合物を酸化剤により酸化することを特徴とする式［３］
で表されるエポキシ脂環式テトラカルボン酸化合物の製造法。 Formula [9]
Independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms and, n represents Represents an integer of 1 to 3, x and y is an integer of 1-6. )
Formula [3], wherein the alicyclic tetracarboxylic acid compound represented by the formula is oxidized with an oxidizing agent
The manufacturing method of the epoxy alicyclic tetracarboxylic acid compound represented by these.
で表されるジオレフィン化合物と、式［１２］A diolefin compound represented by formula [12]
で表されるアセチレン化合物とを、周期律表第８族金属化合物触媒下で反応させることにより、式［１３］And an acetylene compound represented by the formula [13]
で表される脂環式テトラカルボン酸化合物を得、次いで該化合物を酸化剤により酸化することを特徴とする式［２０］Formula [20], wherein an alicyclic tetracarboxylic acid compound represented by the formula:
で表されるエポキシ脂環式テトラカルボン酸化合物の製造法。The manufacturing method of the epoxy alicyclic tetracarboxylic acid compound represented by these.
で表されるジオレフィン化合物と、式［１２］A diolefin compound represented by formula [12]
で表されるアセチレン化合物とを、周期律表第８族金属化合物触媒下で反応させることにより、式［１４］Is reacted with an acetylene compound represented by the formula [14] in the periodic table group 8 metal compound catalyst.
で表される脂環式テトラカルボン酸化合物を得、次いで該化合物を酸化剤により酸化することを特徴とする式［２１］A alicyclic tetracarboxylic acid compound represented by the formula:
で表されるエポキシ脂環式テトラカルボン酸化合物の製造法。The manufacturing method of the epoxy alicyclic tetracarboxylic acid compound represented by these.
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