JP7472438B2 - Imidazole Compounds - Google Patents
Imidazole Compounds Download PDFInfo
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- JP7472438B2 JP7472438B2 JP2019114713A JP2019114713A JP7472438B2 JP 7472438 B2 JP7472438 B2 JP 7472438B2 JP 2019114713 A JP2019114713 A JP 2019114713A JP 2019114713 A JP2019114713 A JP 2019114713A JP 7472438 B2 JP7472438 B2 JP 7472438B2
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- 150000002460 imidazoles Chemical class 0.000 title claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 47
- -1 imidazole compound Chemical class 0.000 claims description 45
- 125000001424 substituent group Chemical group 0.000 claims description 28
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 27
- 239000000539 dimer Substances 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 102
- 230000015572 biosynthetic process Effects 0.000 description 82
- 238000003786 synthesis reaction Methods 0.000 description 82
- 238000000034 method Methods 0.000 description 48
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 26
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 21
- 239000002904 solvent Substances 0.000 description 21
- 125000001931 aliphatic group Chemical group 0.000 description 20
- 150000002430 hydrocarbons Chemical group 0.000 description 18
- 229940126062 Compound A Drugs 0.000 description 17
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 17
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 17
- 239000000047 product Substances 0.000 description 17
- 125000002723 alicyclic group Chemical group 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- 229920005989 resin Polymers 0.000 description 15
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 14
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 14
- 239000000203 mixture Substances 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 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- 229910052801 chlorine Inorganic materials 0.000 description 11
- 125000005843 halogen group Chemical group 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 125000001309 chloro group Chemical group Cl* 0.000 description 10
- 229910052731 fluorine Inorganic materials 0.000 description 10
- 229910052740 iodine Inorganic materials 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 125000001153 fluoro group Chemical group F* 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 238000003776 cleavage reaction Methods 0.000 description 7
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 7
- 235000019341 magnesium sulphate Nutrition 0.000 description 7
- 238000001906 matrix-assisted laser desorption--ionisation mass spectrometry Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000007810 chemical reaction solvent Substances 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 5
- UNMJLQGKEDTEKJ-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methanol Chemical compound CCC1(CO)COC1 UNMJLQGKEDTEKJ-UHFFFAOYSA-N 0.000 description 4
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical compound OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 description 4
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 4
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
- 150000004292 cyclic ethers Chemical class 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 4
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 4
- 125000003367 polycyclic group Chemical group 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- BQXUPNKLZNSUMC-YUQWMIPFSA-N CCN(CCCCCOCC(=O)N[C@H](C(=O)N1C[C@H](O)C[C@H]1C(=O)N[C@@H](C)c1ccc(cc1)-c1scnc1C)C(C)(C)C)CCOc1ccc(cc1)C(=O)c1c(sc2cc(O)ccc12)-c1ccc(O)cc1 Chemical compound CCN(CCCCCOCC(=O)N[C@H](C(=O)N1C[C@H](O)C[C@H]1C(=O)N[C@@H](C)c1ccc(cc1)-c1scnc1C)C(C)(C)C)CCOc1ccc(cc1)C(=O)c1c(sc2cc(O)ccc12)-c1ccc(O)cc1 BQXUPNKLZNSUMC-YUQWMIPFSA-N 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 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 3
- 238000000605 extraction Methods 0.000 description 3
- FVIZARNDLVOMSU-UHFFFAOYSA-N ginsenoside K Natural products C1CC(C2(CCC3C(C)(C)C(O)CCC3(C)C2CC2O)C)(C)C2C1C(C)(CCC=C(C)C)OC1OC(CO)C(O)C(O)C1O FVIZARNDLVOMSU-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000002883 imidazolyl group Chemical group 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 125000002950 monocyclic group Chemical group 0.000 description 3
- 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 3
- 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 3
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 3
- 125000003566 oxetanyl group Chemical group 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 3
- UAOUIVVJBYDFKD-XKCDOFEDSA-N (1R,9R,10S,11R,12R,15S,18S,21R)-10,11,21-trihydroxy-8,8-dimethyl-14-methylidene-4-(prop-2-enylamino)-20-oxa-5-thia-3-azahexacyclo[9.7.2.112,15.01,9.02,6.012,18]henicosa-2(6),3-dien-13-one Chemical compound C([C@@H]1[C@@H](O)[C@@]23C(C1=C)=O)C[C@H]2[C@]12C(N=C(NCC=C)S4)=C4CC(C)(C)[C@H]1[C@H](O)[C@]3(O)OC2 UAOUIVVJBYDFKD-XKCDOFEDSA-N 0.000 description 2
- AOSZTAHDEDLTLQ-AZKQZHLXSA-N (1S,2S,4R,8S,9S,11S,12R,13S,19S)-6-[(3-chlorophenyl)methyl]-12,19-difluoro-11-hydroxy-8-(2-hydroxyacetyl)-9,13-dimethyl-6-azapentacyclo[10.8.0.02,9.04,8.013,18]icosa-14,17-dien-16-one Chemical compound C([C@@H]1C[C@H]2[C@H]3[C@]([C@]4(C=CC(=O)C=C4[C@@H](F)C3)C)(F)[C@@H](O)C[C@@]2([C@@]1(C1)C(=O)CO)C)N1CC1=CC=CC(Cl)=C1 AOSZTAHDEDLTLQ-AZKQZHLXSA-N 0.000 description 2
- ABJSOROVZZKJGI-OCYUSGCXSA-N (1r,2r,4r)-2-(4-bromophenyl)-n-[(4-chlorophenyl)-(2-fluoropyridin-4-yl)methyl]-4-morpholin-4-ylcyclohexane-1-carboxamide Chemical compound C1=NC(F)=CC(C(NC(=O)[C@H]2[C@@H](C[C@@H](CC2)N2CCOCC2)C=2C=CC(Br)=CC=2)C=2C=CC(Cl)=CC=2)=C1 ABJSOROVZZKJGI-OCYUSGCXSA-N 0.000 description 2
- GLGNXYJARSMNGJ-VKTIVEEGSA-N (1s,2s,3r,4r)-3-[[5-chloro-2-[(1-ethyl-6-methoxy-2-oxo-4,5-dihydro-3h-1-benzazepin-7-yl)amino]pyrimidin-4-yl]amino]bicyclo[2.2.1]hept-5-ene-2-carboxamide Chemical compound CCN1C(=O)CCCC2=C(OC)C(NC=3N=C(C(=CN=3)Cl)N[C@H]3[C@H]([C@@]4([H])C[C@@]3(C=C4)[H])C(N)=O)=CC=C21 GLGNXYJARSMNGJ-VKTIVEEGSA-N 0.000 description 2
- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 2
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 2
- WWTBZEKOSBFBEM-SPWPXUSOSA-N (2s)-2-[[2-benzyl-3-[hydroxy-[(1r)-2-phenyl-1-(phenylmethoxycarbonylamino)ethyl]phosphoryl]propanoyl]amino]-3-(1h-indol-3-yl)propanoic acid Chemical compound N([C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)O)C(=O)C(CP(O)(=O)[C@H](CC=1C=CC=CC=1)NC(=O)OCC=1C=CC=CC=1)CC1=CC=CC=C1 WWTBZEKOSBFBEM-SPWPXUSOSA-N 0.000 description 2
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 2
- IWZSHWBGHQBIML-ZGGLMWTQSA-N (3S,8S,10R,13S,14S,17S)-17-isoquinolin-7-yl-N,N,10,13-tetramethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-amine Chemical compound CN(C)[C@H]1CC[C@]2(C)C3CC[C@@]4(C)[C@@H](CC[C@@H]4c4ccc5ccncc5c4)[C@@H]3CC=C2C1 IWZSHWBGHQBIML-ZGGLMWTQSA-N 0.000 description 2
- KQZLRWGGWXJPOS-NLFPWZOASA-N 1-[(1R)-1-(2,4-dichlorophenyl)ethyl]-6-[(4S,5R)-4-[(2S)-2-(hydroxymethyl)pyrrolidin-1-yl]-5-methylcyclohexen-1-yl]pyrazolo[3,4-b]pyrazine-3-carbonitrile Chemical compound ClC1=C(C=CC(=C1)Cl)[C@@H](C)N1N=C(C=2C1=NC(=CN=2)C1=CC[C@@H]([C@@H](C1)C)N1[C@@H](CCC1)CO)C#N KQZLRWGGWXJPOS-NLFPWZOASA-N 0.000 description 2
- WZZBNLYBHUDSHF-DHLKQENFSA-N 1-[(3s,4s)-4-[8-(2-chloro-4-pyrimidin-2-yloxyphenyl)-7-fluoro-2-methylimidazo[4,5-c]quinolin-1-yl]-3-fluoropiperidin-1-yl]-2-hydroxyethanone Chemical compound CC1=NC2=CN=C3C=C(F)C(C=4C(=CC(OC=5N=CC=CN=5)=CC=4)Cl)=CC3=C2N1[C@H]1CCN(C(=O)CO)C[C@@H]1F WZZBNLYBHUDSHF-DHLKQENFSA-N 0.000 description 2
- ONBQEOIKXPHGMB-VBSBHUPXSA-N 1-[2-[(2s,3r,4s,5r)-3,4-dihydroxy-5-(hydroxymethyl)oxolan-2-yl]oxy-4,6-dihydroxyphenyl]-3-(4-hydroxyphenyl)propan-1-one Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1OC1=CC(O)=CC(O)=C1C(=O)CCC1=CC=C(O)C=C1 ONBQEOIKXPHGMB-VBSBHUPXSA-N 0.000 description 2
- UNILWMWFPHPYOR-KXEYIPSPSA-M 1-[6-[2-[3-[3-[3-[2-[2-[3-[[2-[2-[[(2r)-1-[[2-[[(2r)-1-[3-[2-[2-[3-[[2-(2-amino-2-oxoethoxy)acetyl]amino]propoxy]ethoxy]ethoxy]propylamino]-3-hydroxy-1-oxopropan-2-yl]amino]-2-oxoethyl]amino]-3-[(2r)-2,3-di(hexadecanoyloxy)propyl]sulfanyl-1-oxopropan-2-yl Chemical compound O=C1C(SCCC(=O)NCCCOCCOCCOCCCNC(=O)COCC(=O)N[C@@H](CSC[C@@H](COC(=O)CCCCCCCCCCCCCCC)OC(=O)CCCCCCCCCCCCCCC)C(=O)NCC(=O)N[C@H](CO)C(=O)NCCCOCCOCCOCCCNC(=O)COCC(N)=O)CC(=O)N1CCNC(=O)CCCCCN\1C2=CC=C(S([O-])(=O)=O)C=C2CC/1=C/C=C/C=C/C1=[N+](CC)C2=CC=C(S([O-])(=O)=O)C=C2C1 UNILWMWFPHPYOR-KXEYIPSPSA-M 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- YSUIQYOGTINQIN-UZFYAQMZSA-N 2-amino-9-[(1S,6R,8R,9S,10R,15R,17R,18R)-8-(6-aminopurin-9-yl)-9,18-difluoro-3,12-dihydroxy-3,12-bis(sulfanylidene)-2,4,7,11,13,16-hexaoxa-3lambda5,12lambda5-diphosphatricyclo[13.2.1.06,10]octadecan-17-yl]-1H-purin-6-one Chemical compound NC1=NC2=C(N=CN2[C@@H]2O[C@@H]3COP(S)(=O)O[C@@H]4[C@@H](COP(S)(=O)O[C@@H]2[C@@H]3F)O[C@H]([C@H]4F)N2C=NC3=C2N=CN=C3N)C(=O)N1 YSUIQYOGTINQIN-UZFYAQMZSA-N 0.000 description 2
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Description
本発明は、イミダゾール化合物に関する。 The present invention relates to an imidazole compound.
ヘキサアリールビイミダゾール（ＨＡＢＩ）は、光照射により発色し、熱消色を示すフォトクロミック化合物として知られており、調色材料や光記録材料、ホログラム等の表示材料など、様々な分野への応用が検討されている。 Hexaarylbiimidazole (HABI) is known as a photochromic compound that changes color when exposed to light and fades when heated. Its applications in various fields, such as color-matching materials, optical recording materials, and display materials for holograms, are being considered.
ＨＡＢＩは、また、光照射によりトリアリールイミダゾリルラジカルを生成することでも知られており、光重合開始剤としても広く利用されている（例えば、特許文献１～３参照）。また、 HABI is also known to generate triaryl imidazolyl radicals upon irradiation with light, and is widely used as a photopolymerization initiator (see, for example, Patent Documents 1 to 3).
近年では、ＨＡＢＩのフォトクロミズムをトナーに適用する試みがなされており、トナーバインダーとして、トリアリールイミダゾールのイミダゾール環間の結合により架橋された共重合体を用いると、圧力の付与によりガラス転移点を低下させることができるため、低温定着性が発現することなどが提案されている（例えば、特許文献４参照）。 In recent years, attempts have been made to apply the photochromism of HABI to toner, and it has been proposed that if a copolymer crosslinked by bonds between the imidazole rings of triaryl imidazole is used as a toner binder, the glass transition point can be lowered by applying pressure, resulting in low-temperature fixability (see, for example, Patent Document 4).
本発明者らは、樹脂成形体にＨＡＢＩの可逆的な二量化－開裂反応を適用することが可能か検討する中、従来から知られるイミダゾール化合物では、樹脂合成時の原料への溶解性が十分ではなく、また、樹脂中での二量化－開裂反応の反応性が十分に満足できるものではないことを見出した。本発明は、前記事情に鑑みてなされたものであり、樹脂合成時の原料への溶解性と、樹脂中における二量化－開裂反応の反応性が良好なイミダゾール化合物を提供することを課題とする。 While investigating whether the reversible dimerization-cleavage reaction of HABI can be applied to resin molded bodies, the inventors discovered that conventionally known imidazole compounds do not have sufficient solubility in the raw materials used in resin synthesis, and that the reactivity of the dimerization-cleavage reaction in the resin is not fully satisfactory. The present invention was made in view of the above circumstances, and aims to provide an imidazole compound that has good solubility in the raw materials used in resin synthesis and good reactivity of the dimerization-cleavage reaction in the resin.
本発明のイミダゾール化合物は、式（１）で表される。 The imidazole compound of the present invention is represented by formula (1).
Ａｒ1は、炭素原子数６～２０の芳香族炭化水素基を表す。
Ａｒ2は、炭素原子数６～２０の芳香族炭化水素基を表す。
Ａｒ3は、炭素原子数６～２０の２価の芳香族炭化水素基を表す。
Ｌ1は、－Ｏ－、－ＣＯＯ－又は－ＯＣＯ－を表す。
Ｌ2は、単結合又は－Ｏ－を表す。
Ｒ1は、ポリオキシアルキレン基又は置換基を有していてもよい炭素原子数１～５０の２価の炭化水素基を表し、該炭化水素基に含まれる－ＣＨ2－は、－Ｏ－及び／又は－ＣＯ－に置き換わっていてもよい。
Ｒa1は、反応性基を表す。］。
Ar 1 represents an aromatic hydrocarbon group having 6 to 20 carbon atoms.
Ar2 represents an aromatic hydrocarbon group having 6 to 20 carbon atoms.
Ar3 represents a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms.
L1 represents -O-, -COO- or -OCO-.
L2 represents a single bond or --O--.
R 1 represents a polyoxyalkylene group or a divalent hydrocarbon group having 1 to 50 carbon atoms which may have a substituent, and --CH 2 -- contained in the hydrocarbon group may be replaced by --O-- and/or --CO--.
R a1 represents a reactive group.
本発明のイミダゾール化合物は、樹脂合成時の原料への溶解性が良好であるとともに、樹脂中における二量化－開裂反応の反応性が良好である。 The imidazole compound of the present invention has good solubility in the raw materials used in resin synthesis and good reactivity in the dimerization-cleavage reaction in the resin.
以下、「式（ｘ）で表される化合物」を単に「化合物（ｘ）」などという場合がある。また、本発明の化合物には、その互変異性体やそれらの塩も含まれ、以下に例示する各成分、置換基及び官能基は、それぞれ単独で、或いは組み合わせて使用できる。 Hereinafter, the "compound represented by formula (x)" may simply be referred to as "compound (x)". The compounds of the present invention also include their tautomers and salts, and each of the components, substituents, and functional groups exemplified below can be used alone or in combination.
本発明のイミダゾール化合物は、式（１）で表される。本発明のイミダゾール化合物では、イミダゾールの２位に結合した芳香族環に直接反応性基が結合するのではなく、炭化水素基や結合性基を介して結合しているため、樹脂合成時の原料への溶解性が良好であるとともに、樹脂中における二量化－開裂反応の反応性が良好である。 The imidazole compound of the present invention is represented by formula (1). In the imidazole compound of the present invention, the reactive group is not directly bonded to the aromatic ring bonded to the 2-position of the imidazole, but is bonded via a hydrocarbon group or a bonding group, so that the imidazole compound has good solubility in the raw materials during resin synthesis and good reactivity in the dimerization-cleavage reaction in the resin.
［式（１）中、
Ａｒ1は、炭素原子数６～２０の芳香族炭化水素基を表す。
Ａｒ2は、炭素原子数６～２０の芳香族炭化水素基を表す。
Ａｒ3は、炭素原子数６～２０の２価の芳香族炭化水素基を表す。
Ｌ1は、－Ｏ－、－ＣＯＯ－又は－ＯＣＯ－を表す。
Ｌ2は、単結合又は－Ｏ－を表す。
Ｒ1は、ポリオキシアルキレン基又は置換基を有していてもよい炭素原子数１～５０の２価の炭化水素基を表し、該炭化水素基に含まれる－ＣＨ2－は、－Ｏ－及び／又は－ＣＯ－に置き換わっていてもよい。
Ｒa1は、反応性基を表す。］
[In formula (1),
Ar 1 represents an aromatic hydrocarbon group having 6 to 20 carbon atoms.
Ar2 represents an aromatic hydrocarbon group having 6 to 20 carbon atoms.
Ar3 represents a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms.
L1 represents -O-, -COO- or -OCO-.
L2 represents a single bond or --O--.
R 1 represents a polyoxyalkylene group or a divalent hydrocarbon group having 1 to 50 carbon atoms which may have a substituent, and --CH 2 -- contained in the hydrocarbon group may be replaced by --O-- and/or --CO--.
R a1 represents a reactive group.
本発明の化合物には、その互変異性体やそれらの塩も含まれ、以下に例示する各成分及び官能基は、それぞれ、単独で、或いは組み合わせて使用することができる。 The compounds of the present invention include their tautomers and salts, and each of the components and functional groups exemplified below can be used alone or in combination.
Ａｒ1、Ａｒ2で表される芳香族炭化水素基としては、それぞれ独立に、フェニル基、ナフチル基、アントラセニル基等が挙げられる。 The aromatic hydrocarbon groups represented by Ar 1 and Ar 2 each independently include a phenyl group, a naphthyl group, an anthracenyl group, and the like.
Ａｒ1、Ａｒ2で表される芳香族炭化水素基は、置換基を有していてもよい。前記置換基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基等の炭素原子数１～１０（好ましくは炭素原子数１～５）のアルキル基；フェニル基、ナフチル基等の炭素原子数６～１０の芳香族炭化水素基：フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；ヒドロキシ基等が挙げられる。 The aromatic hydrocarbon groups represented by Ar 1 and Ar 2 may have a substituent. Examples of the substituent include alkyl groups having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms), such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl; aromatic hydrocarbon groups having 6 to 10 carbon atoms, such as phenyl and naphthyl; halogen atoms, such as fluorine, chlorine, bromine, and iodine; and hydroxyl groups.
Ａｒ1、Ａｒ2で表される芳香族の炭素原子数（置換基を有する場合、置換基も含めた炭素原子数）は、６～２０であり、好ましくは６～１０である。 The aromatic groups represented by Ar 1 and Ar 2 each have 6-20 carbon atoms (including the number of carbon atoms of the substituent, if any) and preferably 6-10 carbon atoms.
Ａｒ3で表される芳香族炭化水素基としては、フェニレン基、ナフチレン基、アントラセンジイル基等が挙げられる。 Examples of the aromatic hydrocarbon group represented by Ar3 include a phenylene group, a naphthylene group, and an anthracenediyl group.
Ａｒ3で表される芳香族炭化水素基は、置換基を有していてもよい。前記置換基としては、Ａｒ1、Ａｒ2が有していてもよい置換基として挙げた基と同様の基が挙げられる。 The aromatic hydrocarbon group represented by Ar3 may have a substituent. Examples of the substituent include the same groups as those exemplified as the substituents that Ar1 and Ar2 may have.
Ａｒ3で表される芳香族炭化水素基の炭素原子数（置換基を有する場合、置換基も含めた炭素原子数）は、６～２０であり、好ましくは６～１０である。 The aromatic hydrocarbon group represented by Ar3 has 6 to 20 carbon atoms (including the carbon atoms of the substituent if it has a substituent) and preferably has 6 to 10 carbon atoms.
Ｌ1としては、－Ｏ－、－ＣＯＯ－又は－ＯＣＯ－が挙げられ、－Ｏ－又は－ＣＯＯ－が好ましい。なお－Ｏ－、－ＣＯＯ－、－ＯＣＯ－は、左側の結合手でＡｒ3に結合しているものとする。 L1 includes -O-, -COO-, and -OCO-, and is preferably -O- or -COO-. In addition, -O-, -COO-, and -OCO- are bonded to Ar3 via the left bond.
Ｌ2は、単結合又は－Ｏ－を表す。 L2 represents a single bond or --O--.
Ｒ1で表されるポリオキシアルキレン基としては、ポリオキシエチレン基、ポリオキシプロピレン基、ポリオキシブチレン基等の炭素原子数が２～５のアルキレン基と－Ｏ－との組合せを繰り返し単位とする基などが挙げられる。前記繰り返し単位は、好ましくは２～５０、より好ましくは２～２０、さらに好ましくは２～１０である。 Examples of the polyoxyalkylene group represented by R1 include groups having a repeating unit consisting of a combination of an alkylene group having 2 to 5 carbon atoms, such as a polyoxyethylene group, a polyoxypropylene group, or a polyoxybutylene group, and -O-. The number of repeating units is preferably 2 to 50, more preferably 2 to 20, and even more preferably 2 to 10.
Ｒ1で表される２価の炭化水素基としては、炭素原子数１～５０の２価の脂肪族炭化水素基、炭素原子数３～２０の２価の脂環式炭化水素基、炭素原子数６～２０の２価の芳香族炭化水素基、前記２価の脂肪族炭化水素基、２価の脂環式炭化水素基及び２価の芳香族炭化水素基の２種以上を組み合わせた炭素原子数４～５０の基が挙げられる。 Examples of the divalent hydrocarbon group represented by R1 include divalent aliphatic hydrocarbon groups having 1 to 50 carbon atoms, divalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms, divalent aromatic hydrocarbon groups having 6 to 20 carbon atoms, and groups having 4 to 50 carbon atoms which are a combination of two or more of the above divalent aliphatic hydrocarbon groups, divalent alicyclic hydrocarbon groups, and divalent aromatic hydrocarbon groups.
前記脂肪族炭化水素基としては、飽和又は不飽和の脂肪族炭化水素基が挙げられ、メチレン基、エチレン基、プロパンジイル基、ブタンジイル基、ペンタンジイル基、ヘキサンジイル基、ヘプタンジイル基、オクタンジイル基、ノナンジイル基、デカンジイル基、ウンデカンジイル基、ドデカンジイル基、トリデカンジイル基、テトラデカンジイル基、ペンタデカンジイル基、ヘキサデカンジイル基、ヘプタデカンジイル基、オクタデカンジイル基、ノナデカンジイル基、エイコサンジイル基等のアルカンジイル基などが好ましい。前記脂肪族炭化水素基は、直鎖状であっても分岐鎖状であってもよい。 The aliphatic hydrocarbon group may be a saturated or unsaturated aliphatic hydrocarbon group, and is preferably an alkanediyl group such as a methylene group, an ethylene group, a propanediyl group, a butanediyl group, a pentanediyl group, a hexanediyl group, a heptanediyl group, an octanediyl group, a nonanediyl group, a decanediyl group, an undecanediyl group, a dodecanediyl group, a tridecanediyl group, a tetradecanediyl group, a pentadecanediyl group, a hexadecanediyl group, a heptadecanediyl group, an octadecanediyl group, a nonadecanediyl group, or an eicosanediyl group. The aliphatic hydrocarbon group may be linear or branched.
Ｒ1は、前記脂肪族炭化水素基に含まれる１個以上の－ＣＨ2－が－Ｏ－及び／又は－ＣＯ－に置き換わった基であってもよい。また、２個以上の－ＣＨ2－が、－Ｏ－及び／又は－ＣＯ－に置き換わり、エステル結合（－ＯＣＯ－、－ＣＯＯ－）、カーボネート結合（－ＯＣＯＯ－）を形成していてもよい。－ＣＨ2－が－Ｏ－及び／又は－ＣＯ－に置き換わる個数は、脂肪族炭化水素基中、例えば１個以上、２個以上であってもよく、１０個以下、５個以下であってもよい。ただし、隣接する－ＣＨ2－が、同時に－Ｏ－に置き換わらない基であることが好ましい。 R 1 may be a group in which one or more -CH 2 - contained in the aliphatic hydrocarbon group are replaced with -O- and/or -CO-. Furthermore, two or more -CH 2 - may be replaced with -O- and/or -CO- to form an ester bond (-OCO-, -COO-) or a carbonate bond (-OCOO-). The number of -CH 2 - replaced with -O- and/or -CO- in the aliphatic hydrocarbon group may be, for example, 1 or more, 2 or more, or 10 or less, 5 or less. However, it is preferable that adjacent -CH 2 - are not simultaneously replaced with -O-.
前記脂肪族炭化水素基には、置換基として、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；ヒドロキシ基；－Ｒ2－Ｌ3－Ｒa2で表される基などが結合していてもよい。 The aliphatic hydrocarbon group may have bonded thereto, as a substituent, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a hydroxy group; a group represented by --R.sup.2 - L.sup.3 - R.sup.a2 ; or the like.
前記脂肪族炭化水素基の炭素原子数は、好ましくは１～５０、より好ましくは１～２０、さらに好ましくは１～１０である。 The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 50, more preferably 1 to 20, and even more preferably 1 to 10.
前記脂環式炭化水素基としては、飽和又は不飽和の脂環式炭化水素基が挙げられ、シクロプロパンジイル基、シクロブタンジイル基、シクロペンタンジイル基、シクロヘキサンジイル基、シクロオクタンジイル基、シクロノナンジイル基、シクロデカンジイル基等の単環の脂環式炭化水素基；ビシクロ［１．１．０］ブタンジイル基、トリシクロ［２．２．１．０］ヘプタンジイル基、ビシクロ［３．２．１］オクタンジイル基、ビシクロ［２．２．２．］オクタンジイル基、アダマンタンジイル基、ビシクロ［４．３．２］ウンデカンジイル基、トリシクロ［５．３．１．１］ドデカンジイル基等の多環の脂環式炭化水素基などが好ましい。 Examples of the alicyclic hydrocarbon group include saturated or unsaturated alicyclic hydrocarbon groups, and preferred are monocyclic alicyclic hydrocarbon groups such as cyclopropanediyl group, cyclobutanediyl group, cyclopentanediyl group, cyclohexanediyl group, cyclooctanediyl group, cyclononanediyl group, and cyclodecanediyl group; and polycyclic alicyclic hydrocarbon groups such as bicyclo[1.1.0]butanediyl group, tricyclo[2.2.1.0]heptanediyl group, bicyclo[3.2.1]octanediyl group, bicyclo[2.2.2.]octanediyl group, adamantanediyl group, bicyclo[4.3.2]undecanediyl group, and tricyclo[5.3.1.1]dodecanediyl group.
前記脂環式炭化水素基には、置換基として、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基等の炭素原子数１～１０（好ましくは炭素原子数１～５）のアルキル基；フェニル基、ナフチル基等の炭素原子数６～１０の芳香族炭化水素基：フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；ヒドロキシ基；－Ｒ2－Ｒaで表される基などが結合していてもよい。 The alicyclic hydrocarbon group may have bonded thereto, as a substituent, an alkyl group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms), such as a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, or decyl group; an aromatic hydrocarbon group having 6 to 10 carbon atoms, such as a phenyl group or naphthyl group; a halogen atom, such as a fluorine atom, chlorine atom, bromine atom, or iodine atom; a hydroxy group; or a group represented by -R 2 -R a .
前記脂環式炭化水素基には、置換基として、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；ヒドロキシ基；－Ｒ2－Ｌ3－Ｒa2で表される基などが結合していてもよい。 The alicyclic hydrocarbon group may have bonded thereto, as a substituent, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a hydroxy group; a group represented by --R.sup.2 - L.sup.3 - R.sup.a2 ; or the like.
前記脂環式炭化水素基の炭素原子数（置換基を有する場合、置換基も含めた炭素原子数）は、好ましくは３～５０、より好ましくは５～２０、さらに好ましくは３～１０である。 The number of carbon atoms in the alicyclic hydrocarbon group (including the number of carbon atoms of the substituent if the group has a substituent) is preferably 3 to 50, more preferably 5 to 20, and even more preferably 3 to 10.
前記芳香族炭化水素基は、単環であっても多環であってもよく、フェニレン基、ナフチレン基、アントラセンジイル基、フルオレンジイル基等が挙げられる。 The aromatic hydrocarbon group may be monocyclic or polycyclic, and examples thereof include a phenylene group, a naphthylene group, an anthracenediyl group, and a fluorenediyl group.
前記芳香族炭化水素基には、置換基として、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基等の炭素原子数１～１０（好ましくは炭素原子数１～５）のアルキル基；フェニル基、ナフチル基等の炭素原子数６～１０の芳香族炭化水素基：フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；ヒドロキシ基等；－Ｒ2－Ｒaで表される基などが結合していてもよい。 The aromatic hydrocarbon group may have bonded thereto, as a substituent, an alkyl group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms), such as a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, or decyl group; an aromatic hydrocarbon group having 6 to 10 carbon atoms, such as a phenyl group or naphthyl group; a halogen atom, such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; a hydroxy group; or a group represented by -R 2 -R a .
前記芳香族炭化水素基には、置換基として、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；ヒドロキシ基；－Ｒ2－Ｌ3－Ｒaで表される基などが結合していてもよい。 The aromatic hydrocarbon group may have bonded thereto, as a substituent, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a hydroxy group; or a group represented by --R.sup.2 - L.sup.3 - R.sup.a .
芳香族炭化水素基の炭素原子数（置換基を有する場合、置換委も含めた炭素原子数）は、好ましくは６～５０、より好ましくは６～２０、さらに好ましくは６～１０である。 The number of carbon atoms in the aromatic hydrocarbon group (including the number of carbon atoms of the substituent if it has a substituent) is preferably 6 to 50, more preferably 6 to 20, and even more preferably 6 to 10.
前記２価の脂肪族炭化水素基、２価の脂環式炭化水素基、２価の芳香族炭化水素基の２種以上を組み合わせた基としては、脂肪族炭化水素基と脂環式炭化水素基とを組み合わせた２価の基、又は、脂肪族炭化水素基と芳香族炭化水素基とを組み合わせた２価の基が好ましい。 As the group that combines two or more of the divalent aliphatic hydrocarbon group, the divalent alicyclic hydrocarbon group, and the divalent aromatic hydrocarbon group, a divalent group that combines an aliphatic hydrocarbon group and an alicyclic hydrocarbon group, or a divalent group that combines an aliphatic hydrocarbon group and an aromatic hydrocarbon group, is preferred.
前記脂肪族炭化水素基、脂環式炭化水素基、芳香族炭化水素基の２種以上を組み合わせた基の炭素原子数は、好ましくは４～５０、より好ましくは４～２０、さらに好ましくは４～１０である。 The number of carbon atoms in the group that combines two or more of the aliphatic hydrocarbon group, alicyclic hydrocarbon group, and aromatic hydrocarbon group is preferably 4 to 50, more preferably 4 to 20, and even more preferably 4 to 10.
Ｒ1で表される炭化水素基が置換基として有していてもよい－Ｒ2－Ｌ3－Ｒa2で表される基において、Ｒ2は、ポリオキシアルキレン基又は炭素原子数１～５０の２価の炭化水素基を表し、該炭化水素基に含まれる－ＣＨ2－は、－Ｏ－及び／又は－ＣＯ－に置き換わっていてもよく、該炭化水素基に含まれる水素原子は、ヒドロキシ基に置換されていてもよい。Ｌ3は、単結合又は－Ｏ－を表す。Ｒa2は、反応性基を表す。 In the group represented by -R 2 -L 3 -R a2 which the hydrocarbon group represented by R 1 may have as a substituent, R 2 represents a polyoxyalkylene group or a divalent hydrocarbon group having 1 to 50 carbon atoms, -CH 2 - contained in the hydrocarbon group may be replaced by -O- and/or -CO-, and a hydrogen atom contained in the hydrocarbon group may be substituted by a hydroxy group. L 3 represents a single bond or -O-. R a2 represents a reactive group.
Ｒ2で表されるポリオキシアルキレン基としては、Ｒ1で表されるポリオキシアルキレン基として例示した基と同様の基が挙げられる。 Examples of the polyoxyalkylene group represented by R2 include the same groups as those exemplified as the polyoxyalkylene group represented by R1 .
Ｒ2で表される炭化水素基（該炭化水素基に含まれる－ＣＨ2－が、－Ｏ－及び／又は―ＣＯ－に置き換わっている基も含む）としては、Ｒ1で表される炭化水素基として例示した基と同様の基が挙げられる。 Examples of the hydrocarbon group represented by R2 (including groups in which the --CH2-- contained in the hydrocarbon group is replaced by --O-- and/or --CO--) include the same groups as those exemplified as the hydrocarbon group represented by R1 .
Ｒ2で表される炭化水素基が有していてもよい置換基としては、ヒドロキシ基が挙げられる。 The substituent that the hydrocarbon group represented by R2 may have includes a hydroxy group.
Ｌ3は、単結合又は－Ｏ－を表す。 L3 represents a single bond or --O--.
Ｒa1、Ｒa2で表される反応性基としては、重縮合反応により、ポリマー主鎖を形成しうる基が挙げられ、具体的には、ビニル基、（メタ）アクリロイル基、（メタ）アリル基等のエチレン性二重結合を含む基；オキセタニル基等の環状エーテルを含む基などが挙げられる。前記環状エーテルを含む基は、置換基として、メチル基、エチル基、プロピル基等の炭素原子数１～５の脂肪族炭化水素基を有していてもよい。なかでも、Ｒa1、Ｒa2で表される反応性基としては、ビニル基、（メタ）アクリロイル基、置換基を有していてもよいオキセタニル基が好ましい。 Examples of the reactive groups represented by R a1 and R a2 include groups capable of forming a polymer main chain by a polycondensation reaction, and specific examples thereof include groups containing an ethylenic double bond such as a vinyl group, a (meth)acryloyl group, or a (meth)allyl group; and groups containing a cyclic ether such as an oxetanyl group. The group containing a cyclic ether may have an aliphatic hydrocarbon group having 1 to 5 carbon atoms as a substituent, such as a methyl group, an ethyl group, or a propyl group. Of these, examples of the reactive groups represented by R a1 and R a2 are preferably a vinyl group, a (meth)acryloyl group, or an oxetanyl group which may have a substituent.
前記化合物（１）としては、例えば、以下の式（１－１）～（１－６８）で表される化合物等が挙げられる。式中、ｎは、２～１０の整数を表す。 Examples of the compound (1) include compounds represented by the following formulas (1-1) to (1-68), where n is an integer from 2 to 10.
前記化合物（１）の製造方法の概要は、例えば、以下のスキームで表される。すなわち、本発明の化合物（１）は、
ルート１：化合物（ａ－１）と化合物（ｂ）とを反応させて化合物（ｃ）を得て（工程１）、化合物（ｄ）及び化合物（ｅ）を反応させることによって製造することができ（工程２）、
ルート２：化合物（ａ－２）と化合物（ｄ）及び化合物（ｅ）を反応させて（工程３）、化合物（ｇ－１）又は化合物（ｇ－２）を反応させることによって製造することもでき（工程４）、
ルート３：化合物（ａ－１）と化合物（ｈ）とを反応させて化合物（ｉ）を得て（工程５）、化合物（ｉ）のエステル結合を加水分解して化合物（ｊ）を得て（工程６）、化合物（ｄ）及び化合物（ｅ）を反応させて化合物（ｋ）を得た後（工程７）、さらに化合物（ｌ）を反応させることによって製造することもできる。
The outline of the method for producing the compound (1) is, for example, represented by the following scheme.
Route 1: Compound (a-1) is reacted with compound (b) to obtain compound (c) (step 1), and compound (d) and compound (e) are reacted to produce compound (c) (step 2).
Route 2: It can also be produced by reacting compound (a-2) with compound (d) and compound (e) (step 3), and then reacting compound (g-1) or compound (g-2) (step 4),
Route 3: Compound (a-1) can also be produced by reacting compound (h) with compound (a-1) to obtain compound (i) (step 5), hydrolyzing the ester bond of compound (i) to obtain compound (j) (step 6), reacting compound (d) with compound (e) to obtain compound (k) (step 7), and then further reacting with compound (l).
［上記スキーム中、
Ａｒ1、Ａｒ2、Ａｒ3、Ｌ1、Ｌ2、Ｒ1、Ｒa1は、上記と同義である。
Ａ1は、酸素原子を含む複素環基を表す。
Ｒ3は、ポリオキシアルキレン基又は炭素原子数１～４７の炭化水素基を表し、該炭化水素基に含まれる－ＣＨ2－は、－Ｏ－及び／又は－ＣＯ－に置き換わっていてもよい。
Ｒ4は、炭素原子数１～５の脂肪族炭化水素基を表す。
Ｘ1、Ｘ2は、それぞれ独立に、ハロゲン原子を表す。］
[In the above scheme,
Ar1 , Ar2 , Ar3 , L1 , L2 , R1 and R a1 are as defined above.
A 1 represents a heterocyclic group containing an oxygen atom.
R 3 represents a polyoxyalkylene group or a hydrocarbon group having 1 to 47 carbon atoms, and --CH 2 -- contained in the hydrocarbon group may be replaced by --O-- and/or --CO--.
R 4 represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
X 1 and X 2 each independently represent a halogen atom.
Ａ1で表される酸素原子を含む複素環基は、単環であっても多環であってもよく、多環の場合、複数の単環の複素環基が共有結合により結合されたものであってもよく、橋かけ環であってもよい。前記Ａ1で表される酸素原子を含む複素環基としては、オキシラニル基、オキセタニル基等の環状エーテル基；エポキシシクロヘキシル基、エポキシシクロペンチル基等のエポキシシクロアルキル基などが挙げられる。 The heterocyclic group containing an oxygen atom represented by A 1 may be a monocyclic or polycyclic group, and in the case of a polycyclic group, a plurality of monocyclic heterocyclic groups may be bonded by a covalent bond, or may be a bridged ring. Examples of the heterocyclic group containing an oxygen atom represented by A 1 include cyclic ether groups such as oxiranyl group and oxetanyl group; epoxycycloalkyl groups such as epoxycyclohexyl group and epoxycyclopentyl group, etc.
Ｒ3で表されるオキシアルキレン基としては、Ｒ1で表されるポリオキシアルキレン基と同様の基が挙げられ、オキシアルキレンの繰り返し単位は、好ましくは２～４９、より好ましくは２～１９、さらに好ましくは２～９である。 The oxyalkylene group represented by R 3 may be the same as the polyoxyalkylene group represented by R 1 , and the number of repeating units of the oxyalkylene is preferably 2 to 49, more preferably 2 to 19, and even more preferably 2 to 9.
Ｒ3で表される炭化水素基としては、Ｒ1で表される炭化水素基として説明した基のうち、炭素原子数が１～４７である基が挙げられる。Ｒ3で表される脂肪族炭化水素基は、置換基として、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；ヒドロキシ基；－Ｒ2－Ｌ3－Ｒa2で表される基などが結合していてもよい。Ｒ3で表される脂肪族炭化水素基の炭素原子数は、好ましくは１～４７、より好ましくは１～１７、さらに好ましくは１～７である。 Examples of the hydrocarbon group represented by R3 include groups having 1 to 47 carbon atoms among the groups explained as the hydrocarbon group represented by R1 . The aliphatic hydrocarbon group represented by R3 may have bonded thereto, as a substituent, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; a hydroxy group; or a group represented by -R2 - L3 - Ra2 . The number of carbon atoms in the aliphatic hydrocarbon group represented by R3 is preferably 1 to 47, more preferably 1 to 17, and even more preferably 1 to 7.
Ｒ3で表される前記脂環式炭化水素基には、置換基として、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；ヒドロキシ基；－Ｒ2－Ｌ3－Ｒa2で表される基などが結合していてもよい。Ｒ3で表される脂環式炭化水素基の炭素原子数は、好ましくは３～４７、より好ましくは３～１７、さらに好ましくは３～７である。 The alicyclic hydrocarbon group represented by R3 may have bonded thereto, as a substituent, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a hydroxy group; a group represented by -R2 - L3 - Ra2 , etc. The number of carbon atoms in the alicyclic hydrocarbon group represented by R3 is preferably 3 to 47, more preferably 3 to 17, and even more preferably 3 to 7.
Ｒ3で表される芳香族炭化水素基には、置換基として、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；ヒドロキシ基；－Ｒ2－Ｌ3－Ｒa2で表される基などが結合していてもよい。Ｒ3で表される芳香族炭化水素基の炭素原子数は、好ましくは６～４７、より好ましくは６～２０、さらに好ましくは６～１０である。 The aromatic hydrocarbon group represented by R3 may have bonded thereto, as a substituent, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, a group represented by -R2 - L3 - Ra2 , etc. The aromatic hydrocarbon group represented by R3 preferably has 6 to 47 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 10 carbon atoms.
Ｒ3で表される脂肪族炭化水素基、脂環式炭化水素基、芳香族炭化水素基の２種以上を組み合わせた基の炭素原子数は、好ましくは４～４７、より好ましくは４～１７、さらに好ましくは４～７である。 The number of carbon atoms in the group consisting of two or more of aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups represented by R3 is preferably 4 to 47, more preferably 4 to 17, and even more preferably 4 to 7.
Ｒ4で表される脂肪族炭化水素基としては、メチル基、エチル基、ブチル基、ペンチル基が挙げられる。Ｒ4で表される脂肪族炭化水素基の炭素原子数は、好ましくは１～５、より好ましくは１～３である。 Examples of the aliphatic hydrocarbon group represented by R4 include a methyl group, an ethyl group, a butyl group, and a pentyl group. The number of carbon atoms in the aliphatic hydrocarbon group represented by R4 is preferably 1 to 5, and more preferably 1 to 3.
Ｘ1、Ｘ2で表されるハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられ、塩素原子が好ましい。 Examples of the halogen atom represented by X 1 or X 2 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, with a chlorine atom being preferred.
以下、各工程について説明する。 Each step is explained below.
工程１、５について
工程１、５では、化合物（ａ－２）と、化合物（ｂ）又は化合物（ｈ）とを反応させることにより、化合物（ｃ）又は化合物（ｉ）を得ることができる。
Regarding steps 1 and 5: In steps 1 and 5, compound (a-2) is reacted with compound (b) or compound (h) to obtain compound (c) or compound (i).
前記反応時、トリフェニルホスフィン等の第３級有機リン化合物と、アゾジカルボン酸ジエチル、アゾジカルボン酸ジイソプロピル等のアゾジカルボン酸エステルとを触媒として共存させる。 During the reaction, a tertiary organic phosphorus compound such as triphenylphosphine and an azodicarboxylate ester such as diethyl azodicarboxylate or diisopropyl azodicarboxylate are present as catalysts.
反応溶剤としては、テトラヒドロフラン等のエーテル溶剤を用いることができる。 An ether solvent such as tetrahydrofuran can be used as the reaction solvent.
工程２、３、７について
工程２、３、７では、化合物（ａ－２）、化合物（ｃ）又は化合物（ｊ）と、化合物（ｄ）と、化合物（ｅ）とを反応させることにより、イミダゾール環を形成し、それぞれ、化合物（ｆ）、化合物（１）又は化合物（ｋ）を得ることができる。
Regarding steps 2, 3, and 7: In steps 2, 3, and 7, compound (a-2), compound (c), or compound (j) is reacted with compound (d) and compound (e) to form an imidazole ring, thereby obtaining compound (f), compound (1), or compound (k), respectively.
前記反応時、１，４－ジアザビシクロ［２．２．２］オクタン等の触媒を共存させる。 During the reaction, a catalyst such as 1,4-diazabicyclo[2.2.2]octane is present.
反応溶剤としては、工程２、７では、メタノール、エタノール、イソプロピルアルコール、ブタノール等のアルコール溶剤を用いることができ、工程３では、氷酢酸等を用いることができる。 As the reaction solvent, in steps 2 and 7, alcohol solvents such as methanol, ethanol, isopropyl alcohol, and butanol can be used, and in step 3, glacial acetic acid, etc. can be used.
工程４について
工程４では、化合物（ｆ）と、化合物（ｇ－１）又は化合物（ｇ－２）とを反応させることにより、化合物（ｆ）のカルボキシ基と化合物（ｇ－１）の水酸基、又は、化合物（ｆ）のカルボキシ基と化合物（ｇ－２）の環状エーテルとが反応し、化合物（１）を得ることができる。
Regarding step 4: In step 4, compound (f) is reacted with compound (g-1) or compound (g-2) to react a carboxy group of compound (f) with a hydroxyl group of compound (g-1), or a carboxy group of compound (f) with a cyclic ether of compound (g-2), thereby obtaining compound (1).
前記反応時、触媒を共存させる。化合物（ｇ－１）と反応させる場合は、トリフェニルホスフィン等の第３級有機リン化合物と、アゾジカルボン酸ジエチル、アゾジカルボン酸ジイソプロピル等のアゾジカルボン酸エステルとを触媒として用いる。反応溶剤としては、ジメチルホルムアミド、ジメチルアセトアミド等のアミド溶剤を用いることができる。 During the reaction, a catalyst is allowed to coexist. When reacting with compound (g-1), a tertiary organic phosphorus compound such as triphenylphosphine and an azodicarboxylate ester such as diethyl azodicarboxylate or diisopropyl azodicarboxylate are used as catalysts. As the reaction solvent, an amide solvent such as dimethylformamide or dimethylacetamide can be used.
また、化合物（ｇ－２）と反応させる場合は、テトラブチルアンモニウムクロリド等の触媒を用いることができる。反応溶剤としては、ジメチルホルムアミド等のアミド溶剤を用いることができる。 When reacting with compound (g-2), a catalyst such as tetrabutylammonium chloride can be used. As the reaction solvent, an amide solvent such as dimethylformamide can be used.
工程６について
工程６では、化合物（ｉ）のエステル結合を加水分解することにより、化合物（ｊ）を得ることができる。
Regarding Step 6: In step 6, compound (j) can be obtained by hydrolyzing the ester bond of compound (i).
前記反応時、水酸化カリウム等のアルカリ触媒を共存させてもよい。反応溶剤としては、エタノール等のアルコール溶剤を用いることができる。 During the reaction, an alkaline catalyst such as potassium hydroxide may be present. An alcohol solvent such as ethanol may be used as the reaction solvent.
工程８について
工程８では、化合物（ｋ）と化合物（ｌ）とを反応させることで、化合物（１）を得ることができる。
Regarding Step 8: In step 8, compound (k) is reacted with compound (l) to obtain compound (1).
前記反応時、トリエタノールアミン等のアミン触媒を用いることができる。反応溶剤としては、テトラヒドロフラン等のエーテル溶剤を用いることができる。 During the reaction, an amine catalyst such as triethanolamine can be used. As the reaction solvent, an ether solvent such as tetrahydrofuran can be used.
本発明のイミダゾール化合物は、樹脂合成時の原料への溶解性と、樹脂中における二量化－開裂反応の反応性が良好であり、樹脂へのフォトクロミック性付与剤、ラジカル重合開始剤、フォトクロミック色素等として有用である。 The imidazole compound of the present invention has good solubility in the raw materials used in resin synthesis and good reactivity in the dimerization-cleavage reaction in the resin, making it useful as a photochromic agent for resins, a radical polymerization initiator, a photochromic dye, etc.
以下、実施例を挙げて本発明をより具体的に説明する。本発明はもとより下記実施例によって制限を受けるものではなく、前・後記の趣旨に適合し得る範囲で適当に変更を加えて実施することも勿論可能であり、それらはいずれも本発明の技術的範囲に包含される。 The present invention will be described in more detail below with reference to examples. The present invention is not limited to the following examples, and can of course be modified as appropriate within the scope of the above and below-mentioned aims, and all such modifications are within the technical scope of the present invention.
合成例１：化合物Ａの合成 Synthesis Example 1: Synthesis of Compound A
攪拌装置、温度計及び還流冷却管を取り付けた１００ｍＬの四つ口フラスコに、４－ヒドロキシブチルアクリレート（４ＨＢＡ〔商品名〕、大阪有機化学社製）を１４．１７ｇ（９８．２６ｍｍｏｌ）、テトラヒドロフラン（ＴＨＦ）１４０ｇ、トリフェニルホスフィン（Ｐｈ３Ｐ）２５．７７ｇ（９８．２６ｍｍｏｌ）、４－ヒドロキシベンズアルデヒド１０．００ｇ（８１．８９ｍｍｏｌ）を入れ攪拌した。薄黄色透明溶液であった。続いて、氷浴下、テトラヒドロフラン２０ｇに希釈したアゾジカルボン酸ジイソプロピル（ＤＩＡＤ）１９．８７ｇ（９８．２６ｍｍｏｌ）を３０分かけ、滴下した。橙色透明の反応溶液を、室温で１０時間攪拌した。反応溶液にヘキサンを加え、トリフェニルホスフィン等の副生成物を析出除去した後、クロロホルムで抽出を行い、水、飽和食塩水で洗浄した後、硫酸マグネシウムで乾燥した。エバポレーターで溶媒を留去し、得られた赤色粘稠液体をカラムクロマトグラフィー（展開溶媒として、ｎ－ヘキサン：酢酸エチル＝８０：２０）にて精製し、目的物である化合物Ａを１３．６２ｇ、収率６７．０％で得た。 14.17g (98.26mmol) of 4-hydroxybutyl acrylate (4HBA [trade name], manufactured by Osaka Organic Chemical Industry Co., Ltd.), 140g of tetrahydrofuran (THF), 25.77g (98.26mmol) of triphenylphosphine (Ph3P), and 10.00g (81.89mmol) of 4-hydroxybenzaldehyde were added to a 100mL four-neck flask equipped with a stirrer, thermometer, and reflux condenser and stirred. A pale yellow transparent solution was obtained. Next, 19.87g (98.26mmol) of diisopropyl azodicarboxylate (DIAD) diluted in 20g of tetrahydrofuran was added dropwise over 30 minutes in an ice bath. The orange transparent reaction solution was stirred at room temperature for 10 hours. Hexane was added to the reaction solution, and by-products such as triphenylphosphine were precipitated and removed, followed by extraction with chloroform, washing with water and saturated saline, and drying with magnesium sulfate. The solvent was removed using an evaporator, and the resulting red viscous liquid was purified by column chromatography (developing solvent: n-hexane:ethyl acetate = 80:20) to obtain 13.62 g of the target compound A in a yield of 67.0%.
実施例１：化合物１の合成 Example 1: Synthesis of Compound 1
攪拌装置、温度計及び還流冷却管を取り付けた１００ｍＬの四つ口フラスコに、化合物Ａを４．８７ｇ（１９．６２ｍｍｏｌ）、メタノール（ＭｅＯＨ）１５ｇ、１，４－ジアザビシクロ［２．２．２］オクタン（ＤＡＢＣＯ）０．００１５４ｇ（０．１３７ｍｍｏｌ）、ベンジル４．９４８ｇ（２３．５４ｍｍｏｌ）、酢酸アンモニウム（ＮＨ4ＯＡｃ）３．６２９ｇ（４７．０８ｍｍｏｌ）メトキノン１５００ｐｐｍ、ＢＨＴ５００ｐｐｍを入れ、上から窒素ガスをブロー、液中から空気をバブリングし６５℃２４時間攪拌した。徐々に赤褐色溶液になり、数時間後に、壁に黄色の固体が析出した。室温付近まで冷却後、酢酸エチルで抽出を行い、水、飽和食塩水で洗浄した後、硫酸マグネシウムで乾燥した。エバポレーターで溶媒を留去し、得られた赤色粘稠液体をカラムクロマトグラフィー（展開溶媒として、ｎ－ヘキサン：酢酸エチル＝８０：２０）にて精製し、目的化合物１を３．３１ｇ、収率３８．５％で得た。 In a 100mL four-neck flask equipped with a stirrer, a thermometer, and a reflux condenser, 4.87g (19.62mmol) of compound A, 15g of methanol (MeOH), 0.00154g (0.137mmol) of 1,4-diazabicyclo[2.2.2]octane (DABCO), 4.948g (23.54mmol) of benzil, 3.629g (47.08mmol) of ammonium acetate (NH 4 OAc), 1500ppm of methoquinone, and 500ppm of BHT were placed, and nitrogen gas was blown from above, air was bubbled through the liquid, and the mixture was stirred at 65°C for 24 hours. The mixture gradually became a reddish brown solution, and after several hours, a yellow solid precipitated on the wall. After cooling to around room temperature, the mixture was extracted with ethyl acetate, washed with water and saturated saline, and then dried over magnesium sulfate. The solvent was removed by distillation using an evaporator, and the resulting red viscous liquid was purified by column chromatography (developing solvent: n-hexane:ethyl acetate=80:20) to obtain 3.31 g of target compound 1 in a yield of 38.5%.
〔構造の同定方法〕
生成物（ロフィン化合物）の構造同定は、下記条件にて測定した１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ、ＭＡＬＤＩ－ＭＳにて行った。1Ｈ－ＮＭＲスペクトルを図１に、13Ｃ－ＮＭＲスペクトルを図２に、ＭＡＬＤＩ－ＭＳスペクトルを図３に示す。
[Method of identifying structure]
The structure of the product (lophine compound) was identified by 1 H-NMR, 13 C-NMR, and MALDI-MS measured under the following conditions. The 1 H-NMR spectrum is shown in FIG. 1, the 13 C-NMR spectrum in FIG. 2, and the MALDI-MS spectrum in FIG.
１Ｈ－ＮＭＲはＪＥＯＬ ＲＥＳＯＮＡＮＣＥ製「ＪＮＭ－ＥＣＭ４００Ｓ」を用い、下記条件により測定した。 1 H-NMR was measured using a JEOL RESONANCE "JNM-ECM400S" under the following conditions.
磁場強度：４００ＭＨｚ
積算回数：１６回
溶媒：重水素化クロロホルム
試料濃度：２ｍｇ／０．５ｍｌ
Magnetic field strength: 400MHz
Number of times of accumulation: 16 Solvent: Deuterated chloroform Sample concentration: 2 mg/0.5 ml
13Ｃ－ＮＭＲはＪＥＯＬ ＲＥＳＯＮＡＮＣＥ製「ＪＮＭ－ＥＣＭ４００Ｓ」を用い、下記条件により測定した。 13 C-NMR was measured using a JEOL RESONANCE "JNM-ECM400S" under the following conditions.
磁場強度：１００ＭＨｚ
積算回数：１０００回
溶媒：重水素化クロロホルム
試料濃度：２ｍｇ／０．５ｍｌ
Magnetic field strength: 100MHz
Number of times of accumulation: 1000 Solvent: Deuterated chloroform Sample concentration: 2 mg/0.5 ml
ＭＡＬＤＩ－ＭＳは島津製作所／ＫＲＡＴＯＳ製「ＡＸＩＭＡ－ＱＩＴ」を用い、下記条件により測定した。
装置名：ＡＸＩＭＡ－ＱＩＴ
メーカー：島津製作所製
The MALDI-MS was performed using Shimadzu Corporation/KRATOS "AXIMA-QIT" under the following conditions.
Device name: AXIMA-QIT
Manufacturer: Shimadzu Corporation
測定範囲：ｍ／ｚ＝５０．００～２０００．００
変化率：２５．６ｍＡ／ｍｉｎ
最終電流値：４０ｍＡ
カソード電圧：－１０ｋＶ
・測定モード
ｍ／ｚ ～３００：ｅｘｔｒａＬｏｗ
３００～７５０：Ｌｏｗ
７５０～：Ｍｉｄ
Measurement range: m / z = 50.00 to 2000.00
Rate of change: 25.6mA/min
Final current value: 40mA
Cathode voltage: -10 kV
Measurement mode m/z ~300: extraLow
300-750: Low
750～:Mid
合成例２：化合物Ｂの合成 Synthesis Example 2: Synthesis of Compound B
４－ヒドロキシブチルアクリレートの代わりに、ヒドロキシエチルアクリレート（ＨＥＡ〔商品名〕、大阪有機化学社製）を用いた以外は合成例１と同様に行い、上記構造式で表される化合物Ｂを１２．１１ｇ、収率６７．１５％で得た。 The same procedure as in Synthesis Example 1 was carried out except that hydroxyethyl acrylate (HEA [product name], manufactured by Osaka Organic Chemical Industry Co., Ltd.) was used instead of 4-hydroxybutyl acrylate, and 12.11 g of compound B represented by the above structural formula was obtained in a yield of 67.15%.
実施例２：化合物２の合成 Example 2: Synthesis of compound 2
化合物Ａの代わりに、化合物Ｂを用いた以外は実施例１と同様に行い、上記構造式で表される目的化合物２を３．９２ｇ、収率４２．１％で得た。 The same procedure as in Example 1 was carried out except that compound B was used instead of compound A, and 3.92 g of target compound 2 represented by the above structural formula was obtained in a yield of 42.1%.
合成例３：化合物Ｃの合成 Synthesis Example 3: Synthesis of Compound C
４－ヒドロキシブチルアクリレートの代わりに、メタクリル酸２－ヒドロキシエチル（ＨＥＭＡ〔商品名〕、日本触媒社製）を用いた以外は合成例１と同様に行い、上記構造式で表される化合物Ｃを１３．８３ｇ、収率７２．１％で得た。 The same procedure as in Synthesis Example 1 was carried out except that 2-hydroxyethyl methacrylate (HEMA [trade name], manufactured by Nippon Shokubai Co., Ltd.) was used instead of 4-hydroxybutyl acrylate, and 13.83 g of compound C represented by the above structural formula was obtained in a yield of 72.1%.
実施例３：化合物３の合成 Example 3: Synthesis of compound 3
化合物Ａの代わりに、化合物Ｃを用いた以外は実施例１と同様に行い、上記構造式で表される目的化合物３を４．０２ｇ、収率４４．４％で得た。 The same procedure as in Example 1 was carried out except that compound C was used instead of compound A, and 4.02 g of target compound 3 represented by the above structural formula was obtained in a yield of 44.4%.
合成例４：化合物Ｄの合成 Synthesis Example 4: Synthesis of Compound D
４－ヒドロキシブチルアクリレートの代わりに、アクリル酸２－ヒドロキシプロピル（ＨＰＡ〔商品名〕、日本触媒社製）を用いた以外は合成例１と同様に行い、上記構造式で表される化合物Ｄを１１．１１ｇ、収率５７．９％で得た。 The same procedure as in Synthesis Example 1 was carried out except that 2-hydroxypropyl acrylate (HPA [product name], manufactured by Nippon Shokubai Co., Ltd.) was used instead of 4-hydroxybutyl acrylate, and 11.11 g of compound D represented by the above structural formula was obtained in a yield of 57.9%.
実施例４：化合物４の合成 Example 4: Synthesis of compound 4
化合物Ａの代わりに、化合物Ｄを用いた以外は実施例１と同様に行い、上記構造式で表される目的化合物４を２．９０ｇ、収率３２．０％で得た。 The same procedure as in Example 1 was carried out except that compound D was used instead of compound A, and 2.90 g of target compound 4 represented by the above structural formula was obtained in a yield of 32.0%.
合成例５：化合物Ｅの合成 Synthesis Example 5: Synthesis of Compound E
４－ヒドロキシブチルアクリレートの代わりに、２－ヒドロキシブチルアクリレート（ライトアクリレートＨＯＢ－Ａ〔商品名〕、共栄社化学社製）を用いた以外は合成例１と同様に行い、上記構造式で表される化合物Ｅを１１．３６ｇ、収率５５．９％で得た。 The same procedure as in Synthesis Example 1 was carried out except that 2-hydroxybutyl acrylate (Light Acrylate HOB-A [product name], manufactured by Kyoeisha Chemical Co., Ltd.) was used instead of 4-hydroxybutyl acrylate, and 11.36 g of compound E represented by the above structural formula was obtained in a yield of 55.9%.
実施例５：化合物５の合成 Example 5: Synthesis of compound 5
化合物Ａの代わりに、化合物Ｅを用いた以外は実施例１と同様に行い、上記構造式で表される目的化合物５を１．９９ｇ、収率２２．５％で得た。 The procedure was carried out in the same manner as in Example 1, except that compound E was used instead of compound A, and 1.99 g of target compound 5 represented by the above structural formula was obtained in a yield of 22.5%.
合成例６：化合物Ｆの合成 Synthesis Example 6: Synthesis of Compound F
４－ヒドロキシブチルアクリレートの代わりに、ジエチレングリコールモノアクリレートを用いた以外は合成例１と同様に行い、上記構造式で表される化合物Ｆを１５．５７ｇ、収率７２．０％で得た。 The same procedure as in Synthesis Example 1 was carried out except that diethylene glycol monoacrylate was used instead of 4-hydroxybutyl acrylate, and 15.57 g of compound F represented by the above structural formula was obtained in a yield of 72.0%.
実施例６：化合物６の合成 Example 6: Synthesis of compound 6
化合物Ａの代わりに、化合物Ｆを用いた以外は実施例１と同様に行い、上記構造式で表される目的化合物６を２．６７ｇ、収率３１．０％で得た。 The same procedure as in Example 1 was carried out except that compound F was used instead of compound A, and 2.67 g of target compound 6 represented by the above structural formula was obtained in a yield of 31.0%.
合成例７：化合物Ｇの合成 Synthesis Example 7: Synthesis of Compound G
４－ヒドロキシブチルアクリレートの代わりに、ポリプロピレングリコール-モノアクリレート（ブレンマーＡＰ－４００〔商品名〕、日油社製）を用いた以外は合成例１と同様に行い、上記構造式で表される化合物Ｇを３０．２９ｇ、収率７０．５％で得た。 The same procedure as in Synthesis Example 1 was carried out except that polypropylene glycol monoacrylate (Blenmer AP-400 [product name], manufactured by NOF Corp.) was used instead of 4-hydroxybutyl acrylate, and 30.29 g of compound G represented by the above structural formula was obtained in a yield of 70.5%.
実施例７：化合物７の合成 Example 7: Synthesis of compound 7
化合物Ａの代わりに、化合物Ｇを用いた以外は実施例１と同様に行い、上記構造式で表される目的化合物７を２．８６ｇ、収率２８．６％で得た。 The procedure was carried out in the same manner as in Example 1, except that compound G was used instead of compound A, and 2.86 g of target compound 7 represented by the above structural formula was obtained in a yield of 28.6%.
合成例８：化合物Ｈの合成 Synthesis Example 8: Synthesis of Compound H
４－ヒドロキシブチルアクリレートの代わりに、ペンタエリトリトールトリアクリレートを用いた以外は合成例１と同様に行い、上記構造式で表される化合物Ｈを１４．２０ｇ、収率４３．１％で得た。 The same procedure as in Synthesis Example 1 was carried out except that pentaerythritol triacrylate was used instead of 4-hydroxybutyl acrylate, and 14.20 g of compound H represented by the above structural formula was obtained in a yield of 43.1%.
実施例８：化合物８の合成 Example 8: Synthesis of compound 8
化合物Ａの代わりに、化合物Ｈを用いた以外は実施例１と同様に行い、上記構造式で表される目的化合物８を１．４４４ｇ、収率９．８１％で得た。 The procedure was carried out in the same manner as in Example 1, except that compound H was used instead of compound A, and 1.444 g of the target compound 8 represented by the above structural formula was obtained in a yield of 9.81%.
合成例９：化合物Ｉの合成 Synthesis Example 9: Synthesis of Compound I
４－ヒドロキシブチルアクリレートの代わりに、グリセリンジメタクリレート（７０１〔商品名〕、新中村化学社製）を用いた以外は合成例１と同様に行い、上記構造式で表される化合物Ｉを１４．１８ｇ、収率５２．１％で得た。 The same procedure as in Synthesis Example 1 was carried out except that glycerin dimethacrylate (701 [product name], manufactured by Shin-Nakamura Chemical Co., Ltd.) was used instead of 4-hydroxybutyl acrylate, and 14.18 g of compound I represented by the above structural formula was obtained in a yield of 52.1%.
（実施例９） (Example 9)
化合物Ａの代わりに、化合物Ｉを用いた以外は実施例１と同様に行い、上記構造式で表される目的化合物９を２．１４ｇ、収率１３．６％で得た。 The procedure of Example 1 was repeated except that compound I was used instead of compound A, and 2.14 g of target compound 9 represented by the above structural formula was obtained in a yield of 13.6%.
合成例１０：化合物Ｊの合成 Synthesis Example 10: Synthesis of Compound J
攪拌装置、温度計及び還流冷却管を取り付けた５００ｍＬの四つ口フラスコに、テレフタルアルデヒド酸を１７．８５ｇ（１１８．９１ｍｍｏｌ）、氷酢酸２８５ｇ、１，４－ジアザビシクロ［２．２．２］オクタン（ＤＡＢＣＯ）０．０９３４ｇ（０．８３２ｍｍｏｌ）、ベンジル２５．００ｇ（１１８．９１ｍｍｏｌ）、酢酸アンモニウム２７．５０ｇ（３５６．７５ｍｍｏｌ）を入れ、１０５℃６時間攪拌した。室温付近まで冷却後、氷水に添加し、得られた固体を濾取、クロロホルムで洗浄し、目的化合物Ｊを３８．４５ｇ、収率９５．０％で得た。 17.85 g (118.91 mmol) of terephthalaldehyde acid, 285 g of glacial acetic acid, 0.0934 g (0.832 mmol) of 1,4-diazabicyclo[2.2.2]octane (DABCO), 25.00 g (118.91 mmol) of benzil, and 27.50 g (356.75 mmol) of ammonium acetate were placed in a 500 mL four-neck flask equipped with a stirrer, thermometer, and reflux condenser, and stirred at 105°C for 6 hours. After cooling to near room temperature, the mixture was added to ice water, and the resulting solid was filtered and washed with chloroform to obtain 38.45 g of the target compound J in a yield of 95.0%.
実施例１０ Example 10
攪拌装置、温度計及び還流冷却管を取り付けた２００ｍＬの四つ口フラスコに、化合物Ｊを１５．００ｇ（４４．０７ｍｍｏｌ）、ジメチルホルムアミド（ＤＭＦ）９０ｇ、テトラブチルアンモニウムクロリド（ＴＢＡＣｌ）０．３１８４ｇ（１．１４６ｍｍｏｌ）、グリシジルメタクリレート（ＧＭＡ）６．６２ｇ（４４．０７ｍｍｏｌ）、メトキノン１５００ｐｐｍ、ＢＨＴ５００ｐｐｍを入れ、上から窒素ガスをブロー、液中から空気をバブリングし８５℃４０時間攪拌した。室温付近まで冷却後、酢酸エチルで抽出を行い、水、飽和食塩水で洗浄した後、硫酸マグネシウムで乾燥した。エバポレーターで溶媒を留去し、得られた赤色粘稠液体をカラムクロマトグラフィー（展開溶媒：ｎ－ヘキサン：酢酸エチル＝９０：１０）にて精製し、室温付近まで冷却後、氷水に添加し、得られた固体を濾取、クロロホルムで洗浄し、目的化合物１０を１２．５ｇ、収率５８．８％で得た。 15.00 g (44.07 mmol) of compound J, 90 g of dimethylformamide (DMF), 0.3184 g (1.146 mmol) of tetrabutylammonium chloride (TBACl), 6.62 g (44.07 mmol) of glycidyl methacrylate (GMA), 1500 ppm of methoquinone, and 500 ppm of BHT were placed in a 200 mL four-neck flask equipped with a stirrer, a thermometer, and a reflux condenser, and nitrogen gas was blown from above to bubble air through the liquid and the mixture was stirred at 85°C for 40 hours. After cooling to near room temperature, the mixture was extracted with ethyl acetate, washed with water and saturated saline, and then dried over magnesium sulfate. The solvent was removed using an evaporator, and the resulting red viscous liquid was purified by column chromatography (developing solvent: n-hexane:ethyl acetate = 90:10), cooled to near room temperature, and then added to ice water. The resulting solid was filtered and washed with chloroform to obtain 12.5 g of the target compound 10 in a yield of 58.8%.
実施例１１：化合物１１の合成 Example 11: Synthesis of compound 11
ＧＭＡの代わりに、サイクロマーＭ－１００（ダイセル化学社製）を用いた以外は実施例１０と同様に行い、上記構造式で表される目的化合物１１を１１．５２ｇ、収率４８．７％で得た。 The same procedure as in Example 10 was carried out except that Cyclomer M-100 (manufactured by Daicel Chemical Industries, Ltd.) was used instead of GMA, and 11.52 g of the target compound 11 represented by the above structural formula was obtained in a yield of 48.7%.
実施例１２：化合物１２の合成 Example 12: Synthesis of compound 12
攪拌装置、温度計及び還流冷却管を取り付けた１００ｍＬの四つ口フラスコに、化合物Ｊを５．００ｇ（１４．６８９ｍｍｏｌ）、４ＨＢＡ２．５４ｇ（１７．６３ｍｍｏｌ）、トリフェニルホスフィン４．６２ｇ（１７．６３ｍｍｏｌ）、ＤＭＦ１５．６６ｇを入れ攪拌した。薄黄色透明溶液であった。続いて、氷浴下、ＤＭＦ３．５６ｇに希釈したアゾジカルボン酸ジイソプロピル３．５６ｇ（１７．６３ｍｍｏｌ）を３０分かけ、滴下した。橙色透明の反応溶液を、室温で１０時間攪拌した。反応溶液をドライアップし、クロロホルムとヘキサンを加え、トリフェニルホスフィン等の副生成物を析出除去した後、クロロホルムで抽出を行い、水、飽和食塩水で洗浄した後、硫酸マグネシウムで乾燥した。エバポレーターで溶媒を留去し、得られた赤色粘稠液体をカラムクロマトグラフィー（展開溶媒：ｎ－ヘキサン：酢酸エチル＝８０：２０）にて精製し、目的化合物１２を５．２４ｇ、収率７６．４４％で得た。 5.00 g (14.689 mmol) of compound J, 2.54 g (17.63 mmol) of 4HBA, 4.62 g (17.63 mmol) of triphenylphosphine, and 15.66 g of DMF were added to a 100 mL four-neck flask equipped with a stirrer, a thermometer, and a reflux condenser, and stirred. A pale yellow transparent solution was obtained. Next, 3.56 g (17.63 mmol) of diisopropyl azodicarboxylate diluted in 3.56 g of DMF was added dropwise over 30 minutes in an ice bath. The orange transparent reaction solution was stirred at room temperature for 10 hours. The reaction solution was dried up, chloroform and hexane were added, and by-products such as triphenylphosphine were precipitated and removed, followed by extraction with chloroform, washing with water and saturated saline, and drying with magnesium sulfate. The solvent was removed using an evaporator, and the resulting red viscous liquid was purified by column chromatography (developing solvent: n-hexane:ethyl acetate = 80:20) to obtain 5.24 g of the target compound 12 in a yield of 76.44%.
実施例１３：化合物１３の合成 Example 13: Synthesis of compound 13
４ＨＢＡの代わりに、ＨＥＡを用いた以外は実施例１２と同様に行い、上記構造式で表される目的化合物１３を５．１６ｇ、収率８０．１２％で得た。 The procedure was carried out in the same manner as in Example 12, except that HEA was used instead of 4HBA, and 5.16 g of the target compound 13 represented by the above structural formula was obtained in a yield of 80.12%.
実施例１４：化合物１４の合成 Example 14: Synthesis of compound 14
４ＨＢＡの代わりに、ＨＥＭＡを用いた以外は実施例１２と同様に行い、上記構造式で表される目的化合物１４を５．３８ｇ、収率８１．０１％で得た。 The procedure was carried out in the same manner as in Example 12, except that HEMA was used instead of 4HBA, and 5.38 g of the target compound 14 represented by the above structural formula was obtained in a yield of 81.01%.
実施例１５：化合物１５の合成 Example 15: Synthesis of compound 15
４ＨＢＡの代わりに、ＨＰＡを用いた以外は実施例１２と同様に行い、上記構造式で表される目的化合物１５を４．３８ｇ、収率６５．９７％で得た。 The procedure was carried out in the same manner as in Example 12, except that HPA was used instead of 4HBA, and 4.38 g of the target compound 15 represented by the above structural formula was obtained in a yield of 65.97%.
実施例１６：化合物１６の合成 Example 16: Synthesis of compound 16
４ＨＢＡの代わりに、ライトエステルＨＯＰ（共栄社化学）を用いた以外は実施例１２と同様に行い、上記構造式で表される目的化合物１６を３．９５ｇ、収率５７．６５％で得た。 The same procedure as in Example 12 was carried out except that Light Ester HOP (Kyoeisha Chemical) was used instead of 4HBA, and 3.95 g of the target compound 16 represented by the above structural formula was obtained in a yield of 57.65%.
実施例１７：化合物１７の合成 Example 17: Synthesis of compound 17
４ＨＢＡの代わりに、ライトエステルＨＯＢＡ（共栄社化学）を用いた以外は実施例１２と同様に行い、上記構造式で表される目的化合物１７を３．８６ｇ、収率５６．３２％で得た。 The same procedure as in Example 12 was carried out except that light ester HOBA (Kyoeisha Chemical) was used instead of 4HBA, and 3.86 g of the target compound 17 represented by the above structural formula was obtained in a yield of 56.32%.
実施例１８：化合物１８の合成 Example 18: Synthesis of compound 18
４ＨＢＡの代わりに、ライトエステルＨＯＢＡ（共栄社化学）を用いた以外は実施例１２と同様に行い、上記構造式で表される目的化合物１８を３．９１ｇ、収率５５．４２％で得た。 The same procedure as in Example 12 was carried out except that light ester HOBA (Kyoeisha Chemical) was used instead of 4HBA, and 3.91 g of the target compound 18 represented by the above structural formula was obtained in a yield of 55.42%.
実施例１９：化合物１９の合成 Example 19: Synthesis of compound 19
４ＨＢＡの代わりに、ブレンマーＡＥ－９０Ｕ（日油）を用いた以外は実施例１２と同様に行い、上記構造式で表される目的化合物１９を６．９９ｇ、収率７２．１９％で得た。 The same procedure as in Example 12 was carried out except that Blenmar AE-90U (NOF Corp.) was used instead of 4HBA, and 6.99 g of the target compound 19 represented by the above structural formula was obtained in a yield of 72.19%.
実施例２０：化合物２０の合成 Example 20: Synthesis of compound 20
４ＨＢＡの代わりに、ブレンマーＰＥ－９０（日油）を用いた以外は実施例１２と同様に行い、上記構造式で表される目的化合物２０を５．２６ｇ、収率５３．２１％で得た。 The same procedure as in Example 12 was carried out except that Blenmar PE-90 (NOF Corp.) was used instead of 4HBA, and 5.26 g of the target compound 20 represented by the above structural formula was obtained in a yield of 53.21%.
実施例２１：化合物２１の合成 Example 21: Synthesis of compound 21
４ＨＢＡの代わりに、ブレンマーＡＰ－２００（日油）を用いた以外は実施例１２と同様に行い、上記構造式で表される目的化合物２１を７．４６ｇ、収率６８．３２％で得た。 The same procedure as in Example 12 was carried out except that Blenmar AP-200 (NOF Corp.) was used instead of 4HBA, and 7.46 g of the target compound 21 represented by the above structural formula was obtained in a yield of 68.32%.
実施例２２：化合物２２の合成 Example 22: Synthesis of compound 22
４ＨＢＡの代わりに、ブレンマーＰＰ－５００（日油）を用いた以外は実施例１２と同様に行い、上記構造式で表される目的化合物２２を４．６８ｇ、収率４２．１０％で得た。 The same procedure as in Example 12 was carried out except that Blenmar PP-500 (NOF Corp.) was used instead of 4HBA, and 4.68 g of the target compound 22 represented by the above structural formula was obtained in a yield of 42.10%.
実施例２３：化合物２３の合成 Example 23: Synthesis of compound 23
４ＨＢＡの代わりに、サートマーＳＲ－４９５（サートマー）を用いた以外は実施例１２と同様に行い、上記構造式で表される目的化合物２３を１．５０ｇ、収率４４．８７％で得た。 The same procedure as in Example 12 was carried out except that Sartomer SR-495 (Sartomer) was used instead of 4HBA, and 1.50 g of the target compound 23 represented by the above structural formula was obtained in a yield of 44.87%.
実施例２４：化合物２４の合成 Example 24: Synthesis of compound 24
４ＨＢＡの代わりに、アロニックスＭ－３０５（東亞合成）を用いた以外は実施例１２と同様に行い、上記構造式で表される目的化合物２４を１．３９ｇ、収率３８．９８％で得た。 The same procedure as in Example 12 was carried out except that Aronix M-305 (Toagosei) was used instead of 4HBA, and 1.39 g of the target compound 24 represented by the above structural formula was obtained in a yield of 38.98%.
実施例２５ Example 25
４ＨＢＡの代わりに、ＮＫエステル７０１Ａ（新中村化学）を用いた以外は実施例１２と同様に行い、上記構造式で表される目的物２５を１．６２ｇ、収率５０．１９％で得た。 The same procedure as in Example 12 was carried out except that NK Ester 701A (Shin-Nakamura Chemical) was used instead of 4HBA, and 1.62 g of the target product 25 represented by the above structural formula was obtained in a yield of 50.19%.
合成例１１：化合物Ｋの合成 Synthesis Example 11: Synthesis of Compound K
４－ヒドロキシブチルアクリレートの代わりに、４－ヒドロキシブチルビニルエーテル（ＨＢＶＥ）〔商品名〕、丸善石油化学社製）を用いた以外は合成例１と同様に行い、上記構造式で表される化合物Ｋを１３．０８ｇ、収率７２．５％で得た。 The same procedure as in Synthesis Example 1 was carried out except that 4-hydroxybutyl vinyl ether (HBVE) (product name, manufactured by Maruzen Petrochemical Co., Ltd.) was used instead of 4-hydroxybutyl acrylate, and 13.08 g of compound K represented by the above structural formula was obtained in a yield of 72.5%.
実施例２６：化合物２６の合成 Example 26: Synthesis of compound 26
化合物Ａの代わりに、化合物Ｋを用いた以外は実施例１と同様に行い、上記構造式で表される目的化合物２６を２．８１ｇ、収率３０．２％で得た。 The procedure of Example 1 was repeated except that compound K was used instead of compound A, and 2.81 g of target compound 26 represented by the above structural formula was obtained in a yield of 30.2%.
合成例１２：化合物Ｌの合成 Synthesis Example 12: Synthesis of Compound L
４－ヒドロキシブチルアクリレートの代わりに、２－ヒドロキシエチルビニルエーテル（ＨＥＶＥ）〔商品名〕、丸善石油化学社製）を用いた以外は合成例１と同様に行い、上記構造式で表される化合物Ｌを１１．４７ｇ、収率７２．９％で得た。 The same procedure as in Synthesis Example 1 was carried out except that 2-hydroxyethyl vinyl ether (HEVE) (product name, manufactured by Maruzen Petrochemical Co., Ltd.) was used instead of 4-hydroxybutyl acrylate, and 11.47 g of compound L represented by the above structural formula was obtained in a yield of 72.9%.
実施例２７：化合物２７の合成 Example 27: Synthesis of compound 27
化合物Ａの代わりに、化合物Ｌを用いた以外は実施例１と同様に行い、上記構造式で表される目的化合物２７を２．９６ｇ、収率２９．８％で得た。 The procedure was carried out in the same manner as in Example 1, except that compound L was used instead of compound A, and 2.96 g of target compound 27 represented by the above structural formula was obtained in a yield of 29.8%.
合成例１３：化合物Ｍの合成 Synthesis Example 13: Synthesis of Compound M
４－ヒドロキシブチルアクリレートの代わりに、３－エチル－３－ヒドロキシメチルオキセタン（オキセタンアルコール）（アロンオキセタンＯＸＴ－１０１（ＯＸＡ）〔商品名〕、東亜合成社製）を用いた以外は合成例１と同様に行い、上記構造式で表される化合物Ｍを１２．６４ｇ、収率７０．１％で得た。 The same procedure as in Synthesis Example 1 was carried out except that 3-ethyl-3-hydroxymethyloxetane (oxetane alcohol) (Aron Oxetane OXT-101 (OXA) [product name], manufactured by Toa Gosei Co., Ltd.) was used instead of 4-hydroxybutyl acrylate, and 12.64 g of compound M represented by the above structural formula was obtained in a yield of 70.1%.
実施例２８：化合物２８の合成 Example 28: Synthesis of compound 28
化合物Ａの代わりに、化合物Ｍを用いた以外は実施例１と同様に行い、上記構造式で表される目的物２８を１１．８５ｇ、収率６３．６％で得た。 The same procedure as in Example 1 was carried out except that compound M was used instead of compound A, and 11.85 g of target compound 28 represented by the above structural formula was obtained in a yield of 63.6%.
合成例１４：化合物Ｎの合成 Synthesis Example 14: Synthesis of Compound N
４－ヒドロキシブチルアクリレートの代わりに、３－エチル－３－（４－ヒドロキシブチルオキシメチル）オキセタン（ＥＴＥＲＮＡＣＯＬＬ（登録商標）ＨＢＯＸ〔商品名〕、宇部興産社製）を用いた以外は合成例１と同様に行い、上記構造式で表される化合物Ｎを９．５６ｇ、収率７９．９％で得た。 The same procedure as in Synthesis Example 1 was carried out except that 3-ethyl-3-(4-hydroxybutyloxymethyl)oxetane (ETERNACOLL (registered trademark) HBOX [product name], manufactured by Ube Industries, Ltd.) was used instead of 4-hydroxybutyl acrylate, and 9.56 g of compound N represented by the above structural formula was obtained in a yield of 79.9%.
実施例２９：化合物２９の合成 Example 29: Synthesis of compound 29
化合物Ａの代わりに、化合物Ｎを用いた以外は実施例１と同様に行い、上記構造式で表される目的化合物２９を５．５５ｇ、収率６７．３％で得た。 The same procedure as in Example 1 was carried out except that compound N was used instead of compound A, and 5.55 g of target compound 29 represented by the above structural formula was obtained in a yield of 67.3%.
実施例３０：化合物３０の合成 Example 30: Synthesis of compound 30
４ＨＢＡの代わりに、4－ヒドロキシブチルビニルエーテル（ＨＢＶＥ）〔商品名〕、丸善石油化学社製）を用いた以外は実施例１２と同様に行い、上記構造式で表される目的化合物３０を５．０１ｇ、収率７７．７％ｇで得た。 The same procedure as in Example 12 was carried out except that 4-hydroxybutyl vinyl ether (HBVE) (product name, manufactured by Maruzen Petrochemical Co., Ltd.) was used instead of 4HBA, and 5.01 g of the target compound 30 represented by the above structural formula was obtained in a yield of 77.7% g.
実施例３１：化合物３１の合成 Example 31: Synthesis of compound 31
４ＨＢＡの代わりに、２－ヒドロキシエチルビニルエーテル（ＨＥＶＥ）〔商品名〕、丸善石油化学社製）を用いた以外は実施例１２と同様に行い、上記構造式で表される目的化合物３１を４．５５ｇ、収率７５．４％で得た。 The same procedure as in Example 12 was carried out except that 2-hydroxyethyl vinyl ether (HEVE) (product name, manufactured by Maruzen Petrochemical Co., Ltd.) was used instead of 4HBA, and 4.55 g of the target compound 31 represented by the above structural formula was obtained in a yield of 75.4%.
実施例３２：化合物３２の合成 Example 32: Synthesis of compound 32
４ＨＢＡの代わりに、３－エチル－３－ヒドロキシメチルオキセタン（オキセタンアルコール）（アロンオキセタンＯＸＴ－１０１（ＯＸＡ）〔商品名〕、東亜合成社製）を用いた以外は実施例１２と同様に行い、上記構造式で表される目的化合物３２を４．５９ｇ、収率７１．２９％で得た。 The same procedure as in Example 12 was carried out except that 3-ethyl-3-hydroxymethyloxetane (oxetane alcohol) (Aron Oxetane OXT-101 (OXA) [product name], manufactured by Toa Gosei Co., Ltd.) was used instead of 4HBA, and 4.59 g of the target compound 32 represented by the above structural formula was obtained in a yield of 71.29%.
実施例３３：化合物３２の合成 Example 33: Synthesis of compound 32
４ＨＢＡの代わりに、3-エチル-3-(4-ヒドロキシブチルオキシメチル)オキセタン（ＥＴＥＲＮＡＣＯＬＬ（登録商標）ＨＢＯＸ〔商品名〕、宇部興産社製）を用いた以外は実施例１２と同様に行い、上記構造式で表される目的化合物３３を５．２４ｇ、収率６９．８５％で得た。 The same procedure as in Example 12 was carried out except that 3-ethyl-3-(4-hydroxybutyloxymethyl)oxetane (ETERNACOLL (registered trademark) HBOX [product name], manufactured by Ube Industries, Ltd.) was used instead of 4HBA, and 5.24 g of the target compound 33 represented by the above structural formula was obtained in a yield of 69.85%.
合成例１５ Synthesis Example 15
攪拌装置、温度計及び還流冷却管を取り付けた５００ｍＬの四つ口フラスコに、４－ヒドロキシベンズアルデヒド７．００ｇ（５７．３２ｍｍｏｌ）、ＤＭＦ１５０ｇ、炭酸カリウム９．００ｇ（６５．１２ｍｍｏｌ）を添加し、９０℃で撹拌した。次いで、4-クロロブチルアセテート７．９０ｇ（４９．３８ｍｍｏｌ）を３０分かけ、滴下した。滴下終了後、４時間９０℃で反応させた後、室温に冷却し、２Ｌのビーカーに移し、そこに水２５０ｇを加えた。ジエチルエーテルで抽出を行い、１０％水酸化カリウム水溶液１００ｇで洗浄し、飽和食塩水で洗浄した後、硫酸マグネシウムで乾燥した。エバポレーターで溶媒を留去し、目的化合物Оを９．０３ｇ、収率６６．７％で得た。 7.00g (57.32mmol) of 4-hydroxybenzaldehyde, 150g of DMF, and 9.00g (65.12mmol) of potassium carbonate were added to a 500mL four-neck flask equipped with a stirrer, a thermometer, and a reflux condenser, and the mixture was stirred at 90°C. Then, 7.90g (49.38mmol) of 4-chlorobutyl acetate was added dropwise over 30 minutes. After the addition was completed, the mixture was reacted at 90°C for 4 hours, cooled to room temperature, transferred to a 2L beaker, and 250g of water was added thereto. Extraction was performed with diethyl ether, washed with 100g of 10% potassium hydroxide aqueous solution, washed with saturated saline, and then dried with magnesium sulfate. The solvent was removed with an evaporator, and 9.03g of the target compound O was obtained in a yield of 66.7%.
化合物О４．００ｇ（１６．９３ｍｍｏｌ）を２００ｍｌナスフラスコに入れ、エタノール（ＥｔＯＨ）１００ｇ、水酸化カリウム３．００ｇ（５３．４７ｍｍｏｌ）を入れ、４時間加熱還流させた。反応終了後、室温に冷却し、１０％塩酸で中和し、ジエチルエーテルで抽出、飽和食塩水で洗浄した後、硫酸マグネシウムで乾燥した。エバポレーターで溶媒を留去し、得られた粘稠液体をカラムクロマトグラフィー（展開溶媒：ｎ－ヘキサン：酢酸エチル＝６０：４０）にて精製し、目的物である化合物Ｐを２．１１ｇ、収率６４．２％で得た。 4.00 g (16.93 mmol) of compound O was placed in a 200 ml eggplant flask, 100 g of ethanol (EtOH) and 3.00 g (53.47 mmol) of potassium hydroxide were added, and the mixture was heated to reflux for 4 hours. After the reaction was completed, the mixture was cooled to room temperature, neutralized with 10% hydrochloric acid, extracted with diethyl ether, washed with saturated saline, and then dried over magnesium sulfate. The solvent was removed using an evaporator, and the resulting viscous liquid was purified by column chromatography (developing solvent: n-hexane:ethyl acetate = 60:40) to obtain 2.11 g of the target compound P in a yield of 64.2%.
合成例１６：化合物Ｑの合成 Synthesis Example 16: Synthesis of Compound Q
化合物Ａの代わりに、化合物Ｐを用いた以外は実施例１と同様に行い、上記構造式で表される目的化合物Ｑを２．９３ｇ、収率７０．１％で得た。 The procedure was carried out in the same manner as in Example 1, except that compound P was used instead of compound A, and 2.93 g of the target compound Q represented by the above structural formula was obtained in a yield of 70.1%.
実施例３４：化合物３４の合成 Example 34: Synthesis of compound 34
攪拌装置、温度計及び還流冷却管を取り付けた１００ｍＬの四つ口フラスコに、Ｑ２．００ｇ（５．２０ｍｍｏｌ）、無水ＴＨＦ４０ｇ、トリエチルアミン（ＴＥＡ）１．００ｇ（９．８８ｍｍｏｌ）を加え撹拌した。氷浴下、シリンジでゆっくり塩化アクリロイル１．１０ｇ（１０．５２ｍｍｏｌ）を添加した。添加終了後、室温で１６時間反応させた。反応終了後、クロロホルムで抽出、飽和食塩水で洗浄した後、硫酸マグネシウムで乾燥した。エバポレーターで溶媒を留去し、得られた粘稠液体をカラムクロマトグラフィー（展開溶媒：クロロホルム：酢酸エチル＝９０：１０）にて精製し、目的物である化合物３４を１．７６ｇ、収率７４．７％で得た。 2.00g (5.20mmol) of Q, 40g of anhydrous THF, and 1.00g (9.88mmol) of triethylamine (TEA) were added to a 100mL four-neck flask equipped with a stirrer, thermometer, and reflux condenser, and the mixture was stirred. 1.10g (10.52mmol) of acryloyl chloride was slowly added with a syringe in an ice bath. After the addition was completed, the mixture was allowed to react at room temperature for 16 hours. After the reaction was completed, the mixture was extracted with chloroform, washed with saturated saline, and then dried with magnesium sulfate. The solvent was removed with an evaporator, and the resulting viscous liquid was purified by column chromatography (developing solvent: chloroform: ethyl acetate = 90:10) to obtain 1.76g of the target compound 34 in a yield of 74.7%.
合成例１６：化合物Ｒの合成 Synthesis Example 16: Synthesis of Compound R
４－ヒドロキシブチルアクリレートの代わりに、エチレングリコールモノアリルエーテルを用いた以外は合成例１と同様に行い、上記構造式で表される化合物Ｒを１１．９４ｇ、収率７０．７％で得た。 The same procedure as in Synthesis Example 1 was carried out except that ethylene glycol monoallyl ether was used instead of 4-hydroxybutyl acrylate, and 11.94 g of compound R represented by the above structural formula was obtained in a yield of 70.7%.
実施例１５：化合物３５の合成 Example 15: Synthesis of compound 35
化合物Ａの代わりに、化合物Ｒを用いた以外は実施例１と同様に行い、上記構造式で表される目的物３５を２．２９ｇ、収率２５．４％で得た。 The same procedure as in Example 1 was carried out except that compound R was used instead of compound A, and 2.29 g of target compound 35 represented by the above structural formula was obtained in a yield of 25.4%.
実施例３６：化合物３６の合成 Example 36: Synthesis of compound 36
４ＨＢＡの代わりに、エチレングリコールモノアリルエーテルを用いた以外は実施例１２と同様に行い、上記構造式で表される目的物３６を４．５４ｇ、収率７２．８％で得た。 The same procedure as in Example 12 was carried out except that ethylene glycol monoallyl ether was used instead of 4HBA, and 4.54 g of the target product 36 represented by the above structural formula was obtained in a yield of 72.8%.
実施例３７：二量体の調製 Example 37: Preparation of dimers
攪拌装置、温度計を取り付けた２００ｍＬの３つ口フラスコに、化合物１を０．５０ｇ（１．１４ｍｍｏｌ）、酢酸エチル１０ｇ、ノルマルヘキサン３０ｇ、イオン交換水３０ｇを入れ、撹拌させた。ついで、氷浴下、水酸化カリウム１．００ｇ（１７．８２ｍｍｏｌ）を入れた。そこに、フェリシアン化カリウム０．４００ｇ（１．２１ｍｍｏｌ）を少量ずつ加えた。加えた直後は、オレンジ、すぐに青色となった。室温下激しく撹拌させ、溶液の色が青色透明から、黄色透明溶液になった時点で反応を終了した。 0.50 g (1.14 mmol) of compound 1, 10 g of ethyl acetate, 30 g of normal hexane, and 30 g of ion-exchanged water were placed in a 200 mL three-neck flask equipped with a stirrer and thermometer, and stirred. Next, 1.00 g (17.82 mmol) of potassium hydroxide was added in an ice bath. 0.400 g (1.21 mmol) of potassium ferricyanide was added in small amounts. Immediately after addition, the solution was orange, and then quickly turned blue. The solution was stirred vigorously at room temperature, and the reaction was terminated when the solution changed from a transparent blue to a transparent yellow solution.
混合物を、分液ロートへ移し、水槽が着色しなくなるまで洗浄した。溶媒をドライアップし、目的の二量体３７を０．９３７６ｇ、収率９４．００％で得た。 The mixture was transferred to a separatory funnel and washed until the water tank was no longer colored. The solvent was dried up to obtain 0.9376 g of the desired dimer 37 in a yield of 94.00%.
生成物について、ＭＡＬＤＩ－ＭＳ測定を行い、化合物１の二量体３７が得られていることを確認した。二量体３７のＭＡＬＤＩ－ＭＳスペクトルを図４に示す。 MALDI-MS measurement was performed on the product, and it was confirmed that dimer 37 of compound 1 was obtained. The MALDI-MS spectrum of dimer 37 is shown in Figure 4.
同様の操作を２～３６の物質でも行ない、二量体３８～７２を得た。 The same procedure was carried out with substances 2 to 36 to obtain dimers 38 to 72.
本発明のイミダゾール化合物は、樹脂合成時の原料への溶解性と、樹脂中における二量化－開裂反応の反応性が良好であり、樹脂へのフォトクロミック性付与剤、ラジカル重合開始剤、フォトクロミック色素等として有用である。 The imidazole compound of the present invention has good solubility in the raw materials used in resin synthesis and good reactivity in the dimerization-cleavage reaction in the resin, making it useful as a photochromic agent for resins, a radical polymerization initiator, a photochromic dye, etc.
Claims (2)
下記式（１－４５）～（１－５６）で表されるイミダゾール化合物。
Ａｒ１は、フェニル基を表す。
Ａｒ２は、フェニル基を表す。
Ａｒ３は、２価のフェニレン基を表す。
Ｌ１は、－Ｏ－、又は－ＣＯＯ－を表す。
Ｌ２は、単結合又は－Ｏ－を表す。
Ｒ１は、置換基を有していてもよい炭素原子数１～５０の２価の炭化水素基を表す。
Ｒａ１は、ビニル基を表す。］
Imidazole compounds represented by the following formulas (1-45) to (1-56) .
Ar 1 represents a phenyl group.
Ar2 represents a phenyl group.
Ar3 represents a divalent phenylene group.
L1 represents —O— or —COO—.
L2 represents a single bond or --O--.
R 1 represents a divalent hydrocarbon group having 1 to 50 carbon atoms which may have a substituent.
R a1 represents a vinyl group.
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