JPH05230071A - Dibenzoylmethane derivative - Google Patents
Dibenzoylmethane derivativeInfo
- Publication number
- JPH05230071A JPH05230071A JP4034744A JP3474492A JPH05230071A JP H05230071 A JPH05230071 A JP H05230071A JP 4034744 A JP4034744 A JP 4034744A JP 3474492 A JP3474492 A JP 3474492A JP H05230071 A JPH05230071 A JP H05230071A
- Authority
- JP
- Japan
- Prior art keywords
- group
- compound
- analysis
- formula
- mol
- 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.)
- Pending
Links
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical class C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 title description 9
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000004104 aryloxy group Chemical group 0.000 claims abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 21
- 239000003960 organic solvent Substances 0.000 abstract description 12
- 238000007259 addition reaction Methods 0.000 abstract description 10
- 229910052697 platinum Inorganic materials 0.000 abstract description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 abstract description 9
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 229920001296 polysiloxane Polymers 0.000 abstract description 4
- ICFRVXBXPFMEST-UHFFFAOYSA-N 2-butyl-1,3-diphenylpropane-1,3-dione Chemical compound C=1C=CC=CC=1C(=O)C(CCCC)C(=O)C1=CC=CC=C1 ICFRVXBXPFMEST-UHFFFAOYSA-N 0.000 abstract description 2
- 229930195733 hydrocarbon Natural products 0.000 abstract description 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- 238000004458 analytical method Methods 0.000 description 40
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
- -1 methoxyethoxy group Chemical group 0.000 description 33
- 239000007788 liquid Substances 0.000 description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 23
- 238000010521 absorption reaction Methods 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000000126 substance Substances 0.000 description 17
- 238000000862 absorption spectrum Methods 0.000 description 16
- 238000004811 liquid chromatography Methods 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- 238000005481 NMR spectroscopy Methods 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000001819 mass spectrum Methods 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000005711 Benzoic acid Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 235000010233 benzoic acid Nutrition 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- BLAHXQHYMANQBP-UHFFFAOYSA-N 1-(4-prop-2-enoxyphenyl)ethanone Chemical compound CC(=O)C1=CC=C(OCC=C)C=C1 BLAHXQHYMANQBP-UHFFFAOYSA-N 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 229910000077 silane Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 230000008033 biological extinction Effects 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- UPIJOAFHOIWPLT-UHFFFAOYSA-N methyl 4-tert-butylbenzoate Chemical compound COC(=O)C1=CC=C(C(C)(C)C)C=C1 UPIJOAFHOIWPLT-UHFFFAOYSA-N 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000002210 silicon-based material Substances 0.000 description 4
- 229920002545 silicone oil Polymers 0.000 description 4
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 229940073735 4-hydroxy acetophenone Drugs 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 150000008062 acetophenones Chemical class 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 235000011181 potassium carbonates Nutrition 0.000 description 3
- 238000010183 spectrum analysis Methods 0.000 description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- WZJUBBHODHNQPW-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2$l^{3},4$l^{3},6$l^{3},8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)O[Si](C)O[Si](C)O1 WZJUBBHODHNQPW-UHFFFAOYSA-N 0.000 description 2
- XJFZOSUFGSANIF-UHFFFAOYSA-N 3-chloro-2-(chloromethyl)prop-1-ene Chemical compound ClCC(=C)CCl XJFZOSUFGSANIF-UHFFFAOYSA-N 0.000 description 2
- 238000003512 Claisen condensation reaction Methods 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 125000002933 cyclohexyloxy group Chemical group C1(CCCCC1)O* 0.000 description 2
- 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 2
- 125000003438 dodecyl 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])C([H])([H])C([H])([H])* 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 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 2
- 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 2
- 239000005457 ice water Substances 0.000 description 2
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 2
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 239000010446 mirabilite Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 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 2
- 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 2
- 239000012074 organic phase Substances 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 2
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- VMAWODUEPLAHOE-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 VMAWODUEPLAHOE-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- BDHXXBPPYQRWMC-UHFFFAOYSA-N 3-bromo-2-(bromomethyl)prop-1-ene Chemical compound BrCC(=C)CBr BDHXXBPPYQRWMC-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- WEAFESPXUBTSGL-UHFFFAOYSA-N diethyl(hydroxy)silane Chemical compound CC[SiH](O)CC WEAFESPXUBTSGL-UHFFFAOYSA-N 0.000 description 1
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- DRUOQOFQRYFQGB-UHFFFAOYSA-N ethoxy(dimethyl)silicon Chemical compound CCO[Si](C)C DRUOQOFQRYFQGB-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- NYMPGSQKHIOWIO-UHFFFAOYSA-N hydroxy(diphenyl)silicon Chemical compound C=1C=CC=CC=1[Si](O)C1=CC=CC=C1 NYMPGSQKHIOWIO-UHFFFAOYSA-N 0.000 description 1
- LFEMHZIYNMLNEB-UHFFFAOYSA-N hydroxy-methyl-phenylsilane Chemical compound C[SiH](O)C1=CC=CC=C1 LFEMHZIYNMLNEB-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- VZSYMWXUKVEIHW-UHFFFAOYSA-N methyl(diphenoxy)silane Chemical compound C=1C=CC=CC=1O[SiH](C)OC1=CC=CC=C1 VZSYMWXUKVEIHW-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【発明の技術分野】本発明は、ジベンゾイルメタン誘導
体に関し、特にシリコーン系材料に高配合が可能である
と共に、紫外線吸収性能の高い新規なジベンゾイルメタ
ン誘導体およびその中間体に関する。TECHNICAL FIELD The present invention relates to a dibenzoylmethane derivative, and more particularly to a novel dibenzoylmethane derivative which can be highly blended with a silicone material and has a high ultraviolet absorption property, and an intermediate thereof.
【０００２】[0002]
【発明の技術的背景とその問題点】従来より、４−（ｔ
−ブチル）−4'−メトキシジベンゾイルメタンなどのジ
ベンゾイルメタン骨格を有する化合物は、化粧品、各種
プラスチック用の紫外線吸収剤として有効であることが
知られている（特公昭61−16258 号公報参照）。しかし
ながら、当該化合物は化粧品材料、各種プラスチックへ
の溶解性、分散性があまり良くないために、配合量に制
限があったり、分散性に劣ることからブリーディングが
生じたりして、結果的に期待された紫外線吸収性能が発
揮されないなどの欠点があった。また、化粧品など様々
な分野で、シリコーンオイル、シリコーンレジンなどの
シリコーン系材料が用いられているにもかかわらず、従
来のジベンゾイルメタン化合物は、特にシリコーン系材
料に対する溶解性が悪いという欠点があった。TECHNICAL BACKGROUND OF THE INVENTION AND ITS PROBLEMS Conventionally, 4- (t
Compounds having a dibenzoylmethane skeleton such as -butyl) -4'-methoxydibenzoylmethane are known to be effective as an ultraviolet absorber for cosmetics and various plastics (see JP-B-61-16258). ). However, since the compound has poor solubility and dispersibility in cosmetic materials and various plastics, the compounding amount is limited, and bleeding occurs due to poor dispersibility, which is expected as a result. Moreover, there were drawbacks such as the fact that the ultraviolet absorption performance was not exhibited. Further, although silicone-based materials such as silicone oil and silicone resin are used in various fields such as cosmetics, conventional dibenzoylmethane compounds have a drawback that they have particularly poor solubility in silicone-based materials. It was
【０００３】[0003]
【発明の目的】本発明の目的は、以上のような課題を解
決し、シリコーン材料に対して優れた溶解性を有すると
共に、紫外線吸収性能の高い新規なジベンゾイルメタン
誘導体およびそれを製造するための中間体を提供するこ
とである。It is an object of the present invention to solve the above problems and to produce a novel dibenzoylmethane derivative having excellent solubility in a silicone material and high ultraviolet absorption performance, and to produce the same. It is to provide an intermediate of.
【０００４】[0004]
【発明の構成】即ち、本発明は、一般式That is, the present invention has the general formula
【０００５】[0005]
【化３】 [Chemical 3]
【０００６】（式中、R1は水素原子、アルキル基または
アルコキシ基、R2は置換または非置換の１価の炭化水素
基、Y はアルコキシ基、アリールオキシ基または水酸基
であり、a は１または２、n は０〜３の整数を示す）で
表されるジベンゾイルメタン誘導体、及び該ジベンゾイ
ルメタン誘導体の合成に有用な中間体である一般式(Wherein R 1 is a hydrogen atom, an alkyl group or an alkoxy group, R 2 is a substituted or unsubstituted monovalent hydrocarbon group, Y is an alkoxy group, an aryloxy group or a hydroxyl group, and a is 1 Or 2, n represents an integer of 0 to 3), and a general formula which is an intermediate useful for the synthesis of the dibenzoylmethane derivative and the dibenzoylmethane derivative.
【０００７】[0007]
【化４】 [Chemical 4]
【０００８】（式中、R1およびa は前記と同じである）
で表される化合物である。(Wherein R 1 and a are the same as above)
Is a compound represented by.
【０００９】本発明の化合物（Ｉ）において、R1は水素
原子、アルキル基またはアルコキシ基である。R1として
は、例えば水素原子；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、ドデシル基のような
アルキル基；メトキシ基、エトキシ基、プロポキシ基、
イソプロポキシ基、メトキシエトキシ基、ブトキシ基、
sec−ブトキシ基、イソブトキシ基、ｔ−ブトキシ基、
シクロヘキシルオキシ基、２−エチルヘキシルオキシ基
のようなアルコキシ基が例示される。これらの中でも、
原料の入手、紫外線吸収性能の面から、とりわけブチル
基が好ましい。本発明の化合物（Ｉ）において、R2は置
換または非置換の１価の炭化水素基である。R2として
は、例えばメチル基、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、ドデシル基のようなアルキル
基；シクロペンチル基、シクロヘキシル基のようなシク
ロアルキル基；２−フェニルエチル基、２−フェニルプ
ロピル基のようなアラルキル基；フェニル基、トリル基
のようなアリール基；ビニル基、アリル基のようなアル
ケニル基；およびこれらの１価の炭化水素基の炭素原子
に結合した水素原子が部分的にハロゲン原子、アミノ
基、シアノ基などで置換されたクロロメチル、クロロフ
ェニル、 3,3,3−トリフルオロプロピル、アミノエチ
ル、シアノエチルのような置換炭化水素基が例示され
る。これらの中でも、原料の入手および合成が容易なこ
とから炭素数１〜４の飽和炭化水素、とりわけメチル基
が好ましい。本発明の化合物（Ｉ）において、Y として
は、例えばメトキシ基、エトキシ基、プロポキシ基、イ
ソプロポキシ基、メトキシエトキシ基、ブトキシ基、 s
ec−ブトキシ基、イソブトキシ基、ｔ−ブトキシ基、シ
クロヘキシルオキシ基のようなアルコキシ基；フェノキ
シ基のようなアリールオキシ基；および水酸基が例示さ
れる。これらの中でも、合成の容易さ、安定性、適度な
反応性などの観点からメトキシ基、エトキシ基が特に好
ましい。本発明の化合物（Ｉ）において、a は１または
２であり、n は０〜３の整数である。硬化性シリコーン
材料に配合した場合、ブリードが少なくなることから n
は２〜３が好ましい。In the compound (I) of the present invention, R 1 is a hydrogen atom, an alkyl group or an alkoxy group. R 1 is, for example, hydrogen atom; methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group,
Alkyl groups such as octyl group, nonyl group, decyl group, dodecyl group; methoxy group, ethoxy group, propoxy group,
Isopropoxy group, methoxyethoxy group, butoxy group,
sec-butoxy group, isobutoxy group, t-butoxy group,
Examples thereof include alkoxy groups such as cyclohexyloxy group and 2-ethylhexyloxy group. Among these,
A butyl group is particularly preferable from the viewpoint of availability of raw materials and ultraviolet absorption performance. In the compound (I) of the present invention, R 2 is a substituted or unsubstituted monovalent hydrocarbon group. R 2 is, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group or a dodecyl group; a cyclopentyl group or a cyclohexyl group. Such as cycloalkyl group; aralkyl group such as 2-phenylethyl group and 2-phenylpropyl group; aryl group such as phenyl group and tolyl group; alkenyl group such as vinyl group and allyl group; and monovalent thereof. Such as chloromethyl, chlorophenyl, 3,3,3-trifluoropropyl, aminoethyl, cyanoethyl in which the hydrogen atom bonded to the carbon atom of the hydrocarbon group of is partially substituted with a halogen atom, amino group, cyano group, etc. Examples of such substituted hydrocarbon groups are: Among these, a saturated hydrocarbon having 1 to 4 carbon atoms, particularly a methyl group, is preferable because the raw materials can be easily obtained and synthesized. In the compound (I) of the present invention, examples of Y include methoxy group, ethoxy group, propoxy group, isopropoxy group, methoxyethoxy group, butoxy group, s
Examples include an ec-butoxy group, an isobutoxy group, a t-butoxy group, an alkoxy group such as a cyclohexyloxy group; an aryloxy group such as a phenoxy group; and a hydroxyl group. Among these, a methoxy group and an ethoxy group are particularly preferable from the viewpoints of ease of synthesis, stability, appropriate reactivity, and the like. In the compound (I) of the present invention, a is 1 or 2 and n is an integer of 0-3. When compounded in a curable silicone material, bleeding is reduced, so n
Is preferably 2 to 3.
【００１０】本発明の化合物（Ｉ）の製法を以下に説明
する。すなわち、本発明の化合物（Ｉ）は一般式（II）
で示される本発明の他の化合物と一般式(III) で表され
るシラン化合物とを付加反応させることにより得られ
る。この化学反応式を式(1) に示す。The production method of the compound (I) of the present invention is explained below. That is, the compound (I) of the present invention has the general formula (II)
It can be obtained by the addition reaction of the other compound of the present invention represented by and the silane compound represented by the general formula (III). This chemical reaction formula is shown in formula (1).
【００１１】[0011]
【化５】 [Chemical 5]
【００１２】（式中、R1、R2、Y 、a およびn は前記と
同じである） ここに、原料として使用するシラン化合物(III) として
は、例えばトリメトキシシラン、トリエトキシシラン、
メチルジメトキシシラン、ジメチルエトキシシランのよ
うなモノハイドロジェンアルコキシシラン；メチルジフ
ェノキシシランのようなモノハイドロジェンフェノキシ
シラン；およびジエチルシラノール、ジフェニルシラノ
ール、メチルフェニルシラノールのようなモノハイドロ
ジェンシラノールが挙げられる。これらの中でも、原料
の入手、合成の容易さ、反応性などの点で、トリメトキ
シシラン、トリエトキシシランが特に好ましい。付加反
応式(1) において、中間体（II）とシラン化合物(III)
との使用割合は特に限定されないが、中間体（II）のビ
ニル基１モルに対してシラン化合物(III) のヒドロシリ
ル基１モルが反応するので、等モル量を使用し反応させ
ることが経済上好ましい。式(1) の付加反応の触媒とし
ては、オレフィンのシロキサン誘導体をリガンドとする
白金錯体が好ましく、中でも 1,3,5,7−テトラビニル−
1,3,5,7−テトラメチルシクロテトラシロキサンをリガ
ンドとする白金錯体が特に好ましい。白金錯体の使用量
は特に限定されないが、中間体（II）の使用量に対して
白金原子として２ppm 以上、2000ppm 未満の範囲が好ま
しい。２ppm 未満では反応が遅く、短時間に良好な収率
をあげることができない。また、2000ppm 以上用いても
特に加えただけの効果がない。付加反応式(1) におい
て、有機溶媒の使用は必須とするものではないが、中間
体（II）の融点が常温より著しく高い場合、これを溶解
させる有機溶媒を使用することが、反応制御上好まし
い。このような有機溶媒としては、反応物質に対して不
活性なものが望ましく、例えばベンゼン、トルエン、キ
シレンのような芳香族炭化水素；ヘキサン、ヘプタンの
ような脂肪族炭化水素；シクロヘキサンのような脂環式
炭化水素；ジブチルエーテルのようなエーテル類；およ
び 1,2−ジクロロエタンのようなハロゲン化炭化水素；
メチルエチルケトンのようなケトン類などが挙げられ
る。これらの有機溶媒は、単独でも、２種以上を混合し
て使用してもよい。有機溶媒の使用量は特に限定されな
いが、反応物質の合計重量に対して10重量％以上、1000
重量％以下の範囲とすることが好ましい。また、この付
加反応は、反応容器に中間体（II）、触媒および有機溶
媒を仕込み、所要の温度に加熱して中間体（II）を溶解
させた後、これらにシラン化合物(III) を滴下し反応さ
せる方法により行うことが、反応制御上好ましい。この
付加反応の温度は18〜200 ℃、より好ましくは40〜120
℃の範囲である。反応時間は触媒使用量、反応温度、原
料モル比などにより 0.1〜100 時間の範囲で変えること
が可能である。この反応は常圧下または加圧下のいずれ
でも実施することが可能である。(In the formula, R 1 , R 2 , Y, a and n are the same as above.) Examples of the silane compound (III) used as a raw material include trimethoxysilane, triethoxysilane,
Mention may be made of monohydrogenalkoxysilanes such as methyldimethoxysilane and dimethylethoxysilane; monohydrogenphenoxysilanes such as methyldiphenoxysilane; and monohydrogensilanols such as diethylsilanol, diphenylsilanol and methylphenylsilanol. Among these, trimethoxysilane and triethoxysilane are particularly preferable in terms of availability of raw materials, ease of synthesis, reactivity, and the like. In the addition reaction formula (1), the intermediate (II) and the silane compound (III)
There is no particular limitation on the use ratio with, but since 1 mol of the hydrosilyl group of the silane compound (III) reacts with 1 mol of the vinyl group of the intermediate (II), it is economical to use an equimolar amount. preferable. As the catalyst for the addition reaction of the formula (1), a platinum complex having a siloxane derivative of olefin as a ligand is preferable, and among them, 1,3,5,7-tetravinyl-
A platinum complex having 1,3,5,7-tetramethylcyclotetrasiloxane as a ligand is particularly preferable. The amount of platinum complex used is not particularly limited, but is preferably in the range of 2 ppm or more and less than 2000 ppm in terms of platinum atom relative to the amount of the intermediate (II) used. If it is less than 2 ppm, the reaction is slow and a good yield cannot be obtained in a short time. Moreover, even if it is used at 2000 ppm or more, there is no particular effect. In the addition reaction formula (1), the use of an organic solvent is not essential, but when the melting point of the intermediate (II) is significantly higher than room temperature, it is recommended to use an organic solvent that dissolves it in order to control the reaction. preferable. As such an organic solvent, those which are inert to the reactants are desirable, for example, aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as hexane and heptane; and aliphatic hydrocarbons such as cyclohexane. Cyclic hydrocarbons; ethers such as dibutyl ether; and halogenated hydrocarbons such as 1,2-dichloroethane;
Examples thereof include ketones such as methyl ethyl ketone. These organic solvents may be used alone or in combination of two or more. The amount of the organic solvent used is not particularly limited, but 10% by weight or more based on the total weight of the reactants, 1000
It is preferably in the range of not more than wt%. In addition, in this addition reaction, the intermediate (II), the catalyst and the organic solvent are charged into a reaction vessel, heated to a required temperature to dissolve the intermediate (II), and then the silane compound (III) is added dropwise thereto. It is preferable to carry out the reaction in order to control the reaction. The temperature of this addition reaction is 18 to 200 ° C, more preferably 40 to 120 ° C.
It is in the range of ° C. The reaction time can be changed within the range of 0.1 to 100 hours depending on the amount of catalyst used, reaction temperature, raw material molar ratio and the like. This reaction can be carried out either under normal pressure or under pressure.
【００１３】このようにして得られた反応混合物からの
本発明の化合物（Ｉ）の単離および精製は、有機合成化
学の分野で一般に使用されている手法によって行うこと
ができ、例えば有機溶媒などの低沸点成分を蒸留により
除去し、さらに必要に応じて溶媒抽出、再結晶、カラム
クロマトグラフィーなどの精製手段を用いることによっ
て化合物（Ｉ）を単離することが可能である。Isolation and purification of the compound (I) of the present invention from the reaction mixture thus obtained can be carried out by a method generally used in the field of synthetic organic chemistry, such as an organic solvent. The compound (I) can be isolated by removing the low-boiling point component of (1) by distillation and, if necessary, using a purification means such as solvent extraction, recrystallization, column chromatography and the like.
【００１４】本発明の化合物（Ｉ）の製造に使用する、
本発明の他の化合物である中間体（II）は、以下の方法
で合成される。即ち、アシル化剤である安息香酸エステ
ル（IV）と活性メチル基含有化合物であるアセトフェノ
ン誘導体（Ｖ）とを、強塩基、例えばナトリウムアミ
ド、ナトリウムメチラート、ナトリウムエチラートなど
の存在下にClaisen 縮合させることにより得られる。一
例として、塩基としてナトリウムアミドを使用した場合
の化学反応式を式(2) に示す。Used for the preparation of the compound (I) of the present invention,
The intermediate (II) which is another compound of the present invention is synthesized by the following method. That is, benzoic acid ester (IV) which is an acylating agent and acetophenone derivative (V) which is an active methyl group-containing compound are subjected to Claisen condensation in the presence of a strong base such as sodium amide, sodium methylate or sodium ethylate. It is obtained by As an example, the chemical reaction formula when sodium amide is used as a base is shown in formula (2).
【００１５】[0015]
【化６】 [Chemical 6]
【００１６】（式中、R1およびa は前記と同じであり、
R3はメチル基またはエチル基である） 反応式(2) において、原料として使用する安息香酸エス
テル（IV）は公知物質であり、相当する安息香酸に硫酸
触媒下、メチルアルコールまたはエチルアルコールを作
用させることにより容易に得られることが知られてい
る。このような安息香酸エステル（IV）としては、例え
ば安息香酸メチル、安息香酸エチル、ｔ−ブチル安息香
酸メチル、ｔ−ブチル安息香酸エチルなどが挙げられ
る。これらの中でも、工業的な入手の容易さ、紫外線吸
収性能の面からｔ−ブチル安息香酸メチルが特に好まし
い。また、反応式(2) において、原料として使用するア
セトフェノン誘導体（Ｖ）は、ヒドロキシアセトフェノ
ンと一般式（VI）で表されるハロゲン化アリルとを、ア
セトン中で炭酸カリウムの存在下に脱ハロゲン化水素反
応させることにより容易に得られる。この化学反応式を
式(3) に示す。(Wherein R 1 and a are the same as above,
R 3 is a methyl group or an ethyl group) In reaction formula (2), the benzoic acid ester (IV) used as a raw material is a known substance, and methyl alcohol or ethyl alcohol is reacted with the corresponding benzoic acid under a sulfuric acid catalyst. It is known that this can be easily obtained. Examples of such benzoic acid ester (IV) include methyl benzoate, ethyl benzoate, methyl t-butyl benzoate, ethyl t-butyl benzoate and the like. Among these, methyl t-butyl benzoate is particularly preferable in terms of industrial availability and ultraviolet absorption performance. Further, in the reaction formula (2), the acetophenone derivative (V) used as a raw material is a dehalogenation product of hydroxyacetophenone and an allyl halide represented by the general formula (VI) in acetone in the presence of potassium carbonate. It can be easily obtained by reacting with hydrogen. This chemical reaction formula is shown in formula (3).
【００１７】[0017]
【化７】 [Chemical 7]
【００１８】（式中、a は前記と同じであり、X はハロ
ゲン原子、B は第三アミンである） ここで、ヒドロキシアセトフェノンおよびハロゲン化ア
リル（VI）は公知物質である。ハロゲン化アリル（VI）
としては、例えばアリルクロライド、アリルブロマイ
ド、３−クロロ−２−クロロメチルプロペン、３−ブロ
モ−２−プロモメチルプロペンなどが挙げられる。反応
式(2) のClaisen 縮合は、当該反応に対して不活性な有
機溶媒中において、強塩基の存在下、安息香酸エステル
（IV）とアセトフェノン誘導体（Ｖ）とを加熱すること
により行うことができる。反応物質の使用割合は特に限
定されないが、化学量論的使用量が経済上好ましい。こ
の反応は常圧で、温度40〜110 ℃の範囲で行うのが、反
応制御上好ましい。また、この反応に用いる有機溶媒と
しては、ベンゼン、トルエン、キシレンのような芳香族
炭化水素；ヘキサン、ヘプタンのような脂肪族炭化水
素；シクロヘキサンのような脂環式炭化水素；ジブチル
エーテル、テトラヒドロフランのようなエーテル類を挙
げることができ、これらの中でも反応制御上の安全性の
面から、とりわけトルエンが好ましい。また、これらの
有機溶媒は単独でも、２種以上を混合して使用してもよ
い。有機溶媒の使用量は特に限定されないが、反応物質
の合計重量に対して10重量％以上、1000重量％以下の範
囲とすることが好ましい。さらに、この反応混合物から
の中間体（II）の単離および精製は、塩酸の添加および
水洗により中和し、必要に応じて付加反応式(1) で説明
した、単離および精製に関する事項を適用することがで
きる。(In the formula, a is the same as above, X is a halogen atom, and B is a tertiary amine.) Here, hydroxyacetophenone and allyl halide (VI) are known substances. Allyl halide (VI)
Examples thereof include allyl chloride, allyl bromide, 3-chloro-2-chloromethylpropene, and 3-bromo-2-bromomethylpropene. The Claisen condensation of the reaction formula (2) can be performed by heating the benzoic acid ester (IV) and the acetophenone derivative (V) in the presence of a strong base in an organic solvent inert to the reaction. it can. The ratio of the reactant used is not particularly limited, but a stoichiometric amount is economically preferable. This reaction is preferably carried out at normal pressure and at a temperature in the range of 40 to 110 ° C. in terms of reaction control. The organic solvent used in this reaction includes aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as hexane and heptane; alicyclic hydrocarbons such as cyclohexane; dibutyl ether and tetrahydrofuran. Such ethers can be mentioned, and among these, toluene is particularly preferable from the viewpoint of safety in controlling the reaction. These organic solvents may be used alone or in combination of two or more. The amount of the organic solvent used is not particularly limited, but it is preferably in the range of 10% by weight or more and 1000% by weight or less based on the total weight of the reactants. Further, isolation and purification of the intermediate (II) from this reaction mixture are performed by neutralizing by addition of hydrochloric acid and washing with water, and if necessary, the isolation and purification described in the addition reaction formula (1) is performed. Can be applied.
【００１９】[0019]
【発明の効果】本発明の化合物（Ｉ）は、その分子構造
にジベンゾイルメタン骨格を有するため紫外線吸収性能
が高く、しかもシリル基を有するため、シリコーンオイ
ルなどのシリコーン系材料に対する溶解性が非常に優れ
ている特徴がある。さらに、本発明の化合物（Ｉ）のシ
リル基は加水分解性であるため、シリコーン系材料のガ
ラス、金属、プラスチックなどの基材に対する密着性の
付与、また紫外線吸収機能をもつシリコーンオイルの製
造原料としても有用である。INDUSTRIAL APPLICABILITY The compound (I) of the present invention has a dibenzoylmethane skeleton in its molecular structure, so that it has high ultraviolet absorption performance, and since it has a silyl group, its solubility in silicone-based materials such as silicone oil is extremely high. There is a feature that is excellent. Further, since the silyl group of the compound (I) of the present invention is hydrolyzable, it provides the silicone-based material with adhesion to a substrate such as glass, metal or plastic, and a raw material for producing a silicone oil having an ultraviolet absorbing function. Is also useful as
【００２０】[0020]
【実施例】以下に、実施例を掲げ、本発明をさらに詳し
く説明する。なお、本発明の範囲は以下の実施例のみに
限定されるものではない。 合成例１ ４−ｔ−ブチル安息香酸メチルの合成 撹拌機、温度計、滴下漏斗、還流冷却器、ディーンスタ
ーク水分離器およびオイルバスを備えた内容積１リット
ルのフラスコに、４−ｔ−ブチル安息香酸 178ｇ(1.0モ
ル) 、メタノール38.4ｇ(1.2モル) およびトルエン 300
ｇを仕込み、撹拌を開始した。徐々に加熱して、エステ
ル化反応により副生する水をディーンスターク水分離器
で除去しながら、液温95〜105 ℃で７時間加熱還流させ
た。EXAMPLES The present invention will be described in more detail below with reference to examples. The scope of the present invention is not limited to the following examples. Synthesis Example 1 Synthesis of methyl 4-t-butylbenzoate 4-t-butyl was added to a flask having an internal volume of 1 liter equipped with a stirrer, a thermometer, a dropping funnel, a reflux condenser, a Dean Stark water separator and an oil bath. Benzoic acid 178 g (1.0 mol), methanol 38.4 g (1.2 mol) and toluene 300
g was charged and stirring was started. While gradually heating, the water by-produced by the esterification reaction was removed by a Dean-Stark water separator, and the mixture was heated under reflux at a liquid temperature of 95 to 105 ° C for 7 hours.
【００２１】次いで、室温まで冷却後、飽和炭酸水素ナ
トリウム水で中和し、さらに飽和食塩水で水洗して、無
水芒硝で乾燥した。乾燥後、減圧蒸留により沸点 119〜
120 ℃／９Torrの留分を分取した結果、無色透明液状の
４−ｔ−ブチル安息香酸メチル 165.1ｇ（収率86.0％、
純度99％）を得た。このものの分子構造は元素分析、赤
外吸収スペクトル分析、1H核磁気共鳴吸収分析および質
量スペクトル分析により、次式と一致することを確認し
た。Next, after cooling to room temperature, the mixture was neutralized with saturated aqueous sodium hydrogen carbonate, washed with saturated saline, and dried over anhydrous sodium sulfate. After drying, boiling point 119-by vacuum distillation
As a result of fractionating a fraction of 120 ° C / 9 Torr, 165.1 g of methyl 4-t-butylbenzoate in a colorless transparent liquid (yield 86.0%,
Purity 99%) was obtained. It was confirmed by elemental analysis, infrared absorption spectrum analysis, 1 H nuclear magnetic resonance absorption analysis and mass spectrum analysis that the molecular structure of this product was in agreement with the following formula.
【００２２】[0022]
【化８】 [Chemical 8]
【００２３】合成例２ ４−アリロキシアセトフェノン
の合成 撹拌機、温度計、滴下漏斗、還流冷却器およびオイルバ
スを備えた内容積１リットルのフラスコに、４−ヒドロ
キシアセトフェノン89.5ｇ (0.50モル）、炭酸カリウム
69.0ｇ (0.50モル）およびアセトン 200ｇを仕込み、撹
拌を開始し、液温35℃に加熱した。これに、アリルブロ
マイド60.5ｇ (0.50モル）を滴下漏斗より、液温35〜40
℃で20分かけて滴下した。滴下終了後、液温54℃で15時
間加熱撹拌し、ガスクロマトグラフィー分析により４−
ヒドロキシアセトフェノンのピークが消失し、そのアリ
ル化誘導体である４−アリロキシアセトフェノンが生成
していることを確認した。次に、室温まで冷却後、副生
した臭化カリウムおよび炭酸水素カリウムの沈殿を濾別
し、さらにこの濾液にトルエン 150ｇ、市水 100ｇを添
加して、４−アリロキシアセトフェノンを抽出したの
ち、２回水洗を行い、無水芒硝を入れて乾燥した。乾燥
後、減圧蒸留により沸点 135〜137 ℃／５Torrの留分を
分取した結果、無色透明液状の４−アリロキシアセトフ
ェノン71.6ｇ（収率80.0％、純度99％）を得た。このも
のの分子構造は元素分析、赤外吸収スペクトル分析、1H
核磁気共鳴吸収分析および質量スペクトル分析により、
次式と一致することを確認した。Synthesis Example 2 Synthesis of 4-allyloxyacetophenone In a flask having an internal volume of 1 liter equipped with a stirrer, thermometer, dropping funnel, reflux condenser and oil bath, 89.5 g (0.50 mol) of 4-hydroxyacetophenone, Potassium carbonate
69.0 g (0.50 mol) and 200 g of acetone were charged, stirring was started, and the solution was heated to 35 ° C. 60.5 g (0.50 mol) of allyl bromide was added to this via a dropping funnel at a liquid temperature of 35-40.
It was added dropwise at 20 ° C. over 20 minutes. After completion of the dropping, the mixture was heated and stirred at a liquid temperature of 54 ° C. for 15 hours, and analyzed by gas chromatography for 4-
It was confirmed that the peak of hydroxyacetophenone disappeared and that its allylated derivative, 4-allyloxyacetophenone, was produced. Next, after cooling to room temperature, the precipitates of by-produced potassium bromide and potassium hydrogen carbonate were filtered off, and 150 g of toluene and 100 g of city water were added to this filtrate to extract 4-allyloxyacetophenone, It was washed twice with water, and anhydrous Glauber's salt was added to dry it. After drying, a fraction having a boiling point of 135 to 137 ° C./5 Torr was collected by distillation under reduced pressure, and as a result, 71.6 g (yield 80.0%, purity 99%) of 4-allyloxyacetophenone was obtained as a colorless transparent liquid. The molecular structure of this product is elemental analysis, infrared absorption spectrum analysis, 1 H
By nuclear magnetic resonance absorption analysis and mass spectrum analysis,
It was confirmed that the following equation was met.
【００２４】[0024]
【化９】 [Chemical 9]
【００２５】合成例３ ２−メチレン−1,3 −ジ（４−
アセチルフェノキシ）プロパンの合成 撹拌機、温度計、滴下漏斗、還流冷却器およびオイルバ
スを備えた内容積１リットルのフラスコに、４−ヒドロ
キシアセトフェノン69.5ｇ (0.50モル）、炭酸カリウム
69.0ｇ (0.50モル）およびアセトン 200ｇを仕込み、撹
拌を開始し、液温40℃に加熱した。次いで、滴下漏斗よ
り、純度50％の３−クロロ−２−クロロメチルプロペン
62.5ｇ (0.25モル）を液温40〜50℃で20分かけて滴下
し、さらに液温54℃で24時間加熱撹拌し、液体クロマト
グラフィー分析により、４−ヒドロキシアセトフェノン
のピークがほぼ消失し、反応生成物である２−メチレン
−1,3 −ジ（４−アセチルフェノキシ）プロパンが生成
していることを確認した。次に、室温まで冷却後、塩化
カリウムおよび炭酸水素カリウムの沈殿を濾別し、さら
にこの濾液に市水 100ｇを添加して、粗結晶を析出させ
た。さらに、この結晶を 120mlのエタノールから再結晶
し、室温で５時間減圧乾燥した。この結果、２−メチレ
ン−1,3 −ジ（４−アセチルフェノキシ）プロパン57.8
ｇ（収率70.0％）を得た。このものの分子構造は元素分
析、赤外吸収スペクトル分析、1H核磁気共鳴吸収分析お
よび質量スペクトル分析により、次式と一致することを
確認した。Synthesis Example 3 2-methylene-1,3-di (4-
Acetylphenoxy) propane synthesis In a flask with an internal volume of 1 liter equipped with a stirrer, a thermometer, a dropping funnel, a reflux condenser and an oil bath, 69.5 g (0.50 mol) of 4-hydroxyacetophenone and potassium carbonate were added.
69.0 g (0.50 mol) and 200 g of acetone were charged, stirring was started, and the solution was heated to 40 ° C. Then, from the dropping funnel, 3-chloro-2-chloromethylpropene with a purity of 50% was used.
62.5 g (0.25 mol) was added dropwise at a liquid temperature of 40 to 50 ° C. over 20 minutes, and the mixture was heated and stirred at a liquid temperature of 54 ° C. for 24 hours, and by liquid chromatography analysis, the peak of 4-hydroxyacetophenone almost disappeared, It was confirmed that 2-methylene-1,3-di (4-acetylphenoxy) propane, which was a reaction product, was produced. Next, after cooling to room temperature, the precipitates of potassium chloride and potassium hydrogen carbonate were filtered off, and 100 g of city water was added to this filtrate to precipitate crude crystals. Further, the crystals were recrystallized from 120 ml of ethanol and dried under reduced pressure at room temperature for 5 hours. As a result, 2-methylene-1,3-di (4-acetylphenoxy) propane 57.8
g (yield 70.0%) was obtained. It was confirmed by elemental analysis, infrared absorption spectrum analysis, 1 H nuclear magnetic resonance absorption analysis and mass spectrum analysis that the molecular structure of this product was in agreement with the following formula.
【００２６】[0026]
【化１０】 [Chemical 10]
【００２７】実施例１ ４−アリロキシ−4'−ｔ−ブチルジベンゾイルメタンの
合成 撹拌機、温度計、滴下漏斗、還流冷却器およびオイルバ
スを備えた内容積 500mlのフラスコに、純度90％のナト
リウムアミド10.8ｇ (0.25モル）およびトルエン 150ｇ
を仕込み、撹拌を開始し、液温50℃に加熱した。これ
に、４−アリロキシアセトフェノン40.0ｇ(0.227モル）
を滴下漏斗より液温50〜52℃で15分かけて滴下した。次
いで、４−ｔ−ブチル安息香酸メチル43.6ｇ(0.227モ
ル）を滴下漏斗より、液温50〜54℃で15分かけて滴下し
た。滴下終了後、液温50〜65℃で１時間、さらに液温90
〜95℃で２時間加熱撹拌し、液体クロマトグラフィー分
析により原料のピークが消失し、Claisen 縮合物である
４−アリロキシ−4'−ｔ−ブチルジベンゾイルメタンが
生成していることを確認した。次に、室温まで冷却後、
氷水 100ｇ、塩酸24mlを加えて中和・分液し、さらに有
機相を飽和食塩水 200mlで２回水洗した後、無水芒硝を
入れて乾燥した。乾燥後、トルエンなどの低沸点成分を
蒸留により除去して、赤色の粗結晶を得た。さらに、こ
の粗結晶を 100mlのエタノールから再結晶し、室温で10
時間減圧乾燥した。この結果、淡黄色粒状の４−アリロ
キシ−4'−ｔ−ブチルジベンゾイルメタンの精製結晶6
0.3ｇ（収率79.0％）を得た。このものの液体クロマト
グラフィー分析、融点測定、赤外吸収スペクトル分析、
1H核磁気共鳴吸収分析、紫外−可視吸収スペクトル分析
および質量スペクトル分析の結果は後記の通りであり、
次式の分子構造であることを確認した。Example 1 Synthesis of 4-allyloxy-4'-t-butyldibenzoylmethane A flask having an internal volume of 500 ml and equipped with a stirrer, a thermometer, a dropping funnel, a reflux condenser and an oil bath was prepared to have a purity of 90%. Sodium amide 10.8g (0.25mol) and toluene 150g
Was charged, stirring was started, and the liquid temperature was heated to 50 ° C. 40.0 g (0.227 mol) of 4-allyloxyacetophenone
Was dropped from the dropping funnel at a liquid temperature of 50 to 52 ° C over 15 minutes. Then, 43.6 g (0.227 mol) of methyl 4-t-butylbenzoate was added dropwise from a dropping funnel at a liquid temperature of 50 to 54 ° C over 15 minutes. After the dropping is completed, the liquid temperature is 50 to 65 ° C for 1 hour, and the liquid temperature is 90.
The mixture was heated and stirred at ˜95 ° C. for 2 hours, and it was confirmed by liquid chromatography analysis that the peak of the raw material disappeared and 4-Aryloxy-4′-t-butyldibenzoylmethane, which was a Claisen condensate, was produced. Next, after cooling to room temperature,
100 g of ice water and 24 ml of hydrochloric acid were added for neutralization and liquid separation, and the organic phase was washed twice with 200 ml of saturated saline and dried by adding anhydrous Glauber's salt. After drying, low boiling point components such as toluene were removed by distillation to obtain crude red crystals. Furthermore, this crude crystal was recrystallized from 100 ml of ethanol, and the crystal was recrystallized at room temperature for 10 minutes.
It was dried under reduced pressure for an hour. As a result, a pale yellow granular purified crystal of 4-allyloxy-4′-t-butyldibenzoylmethane 6
0.3 g (yield 79.0%) was obtained. Liquid chromatography analysis, melting point measurement, infrared absorption spectrum analysis,
The results of 1 H nuclear magnetic resonance absorption analysis, ultraviolet-visible absorption spectrum analysis and mass spectrum analysis are as described below.
It was confirmed to have the following molecular structure.
【００２８】[0028]
【化１１】 [Chemical 11]
【００２９】・液体クロマトグラフィー分析（ＵＶ検出
器；254nm)：主成分純度98.7％ ・融点測定：72℃ ・赤外吸収スペクトル分析（液膜法）： 波数（cm-1) 帰属 2940 C−H 1705 C＝O 1595 C＝C ・1H核磁気共鳴吸収分析（90MHz 、CDCl3 中）：所望の
分子構造に合致するスペクトル ・紫外−可視吸収スペクトル分析（溶媒；エタノー
ル）： 吸収極大波長 λmax＝360nm モル吸光係数 εmax＝3.40×104dm3 mol-1cm-1 ・質量スペクトル分析(m/e) ：336 (M+ピーク) 実施例２ ４−トリエトキシシリルプロピルオキシ−4'−ｔ−ブチ
ルジベンゾイルメタンの合成 撹拌機、温度計、滴下漏斗、還流冷却器およびオイルバ
スを備えた内容積 100mlのフラスコに、４−アリロキシ
−4'−ｔ−ブチルジベンゾイルメタン20.2ｇ(0.06 モ
ル）を仕込み、撹拌を開始した。75℃に加熱して液状化
させ、触媒として1,3,5,7 −テトラビニル−1,3,5,7 −
テトラメチルシクロテトラシロキサンをリガンドとする
白金錯体（白金含有量２％）0.04ｇを添加した。これ
に、滴下漏斗よりトリエトキシシラン10.9ｇ (0.06モ
ル）を液温75〜84℃で15分かけて滴下した。滴下終了
後、液温82〜96℃で１時間加熱撹拌し、液体クロマトグ
ラフィー分析により原料のピークが消失し、付加反応物
が生成していることを確認した。放冷後、白金触媒を除
去するために活性炭 0.2ｇを加えて30分撹拌し、吸引濾
過して、黄色透明液状の４−トリエトキシシリルプロピ
ルオキシ−4'−ｔ−ブチルジベンゾイルメタン29.8ｇ
（収率96.0％）を得た。このもののガスクロマトグラフ
ィー分析、赤外吸収スペクトル分析、1H核磁気共鳴吸収
分析、紫外−可視吸収スペクトル分析および質量スペク
トル分析の結果は後記の通りであり、次式の分子構造で
あることを確認した。Liquid chromatography analysis (UV detector; 254 nm): Purity of main component: 98.7% Melting point measurement: 72 ° C. Infrared absorption spectrum analysis (liquid film method): Wave number (cm -1 ) attribution 2940 C-H 1705 C = O 1595 C = C ・1 H nuclear magnetic resonance absorption analysis (90 MHz, in CDCl 3 ): spectrum matching desired molecular structure ・ UV-visible absorption spectrum analysis (solvent; ethanol): absorption maximum wavelength λmax = 360 nm molar extinction coefficient εmax = 3.40 x 10 4 dm 3 mol -1 cm -1 · mass spectrum analysis (m / e): 336 (M + peak) Example 2 4-triethoxysilylpropyloxy-4'-t- Synthesis of butyldibenzoylmethane In a flask with an internal volume of 100 ml equipped with a stirrer, thermometer, dropping funnel, reflux condenser and oil bath, 20.2 g (0.06 mol) of 4-allyloxy-4'-t-butyldibenzoylmethane was added. Was charged and stirring was started. Liquefied by heating to 75 ℃, 1,3,5,7-tetravinyl-1,3,5,7-catalyst
0.04 g of a platinum complex having tetramethylcyclotetrasiloxane as a ligand (platinum content 2%) was added. To this, 10.9 g (0.06 mol) of triethoxysilane was added dropwise from a dropping funnel at a liquid temperature of 75 to 84 ° C over 15 minutes. After completion of dropping, the mixture was heated and stirred at a liquid temperature of 82 to 96 ° C. for 1 hour, and it was confirmed by liquid chromatography analysis that the peak of the raw material disappeared and an addition reaction product was formed. After cooling, 0.2 g of activated carbon was added to remove the platinum catalyst, and the mixture was stirred for 30 minutes, suction filtered, and 49.8 g of 4-triethoxysilylpropyloxy-4'-t-butyldibenzoylmethane as a yellow transparent liquid.
(Yield 96.0%) was obtained. The results of gas chromatography analysis, infrared absorption spectrum analysis, 1 H nuclear magnetic resonance absorption analysis, ultraviolet-visible absorption spectrum analysis and mass spectrum analysis of this product are as described below and confirmed to be the molecular structure of the following formula. did.
【００３０】[0030]
【化１２】 [Chemical 12]
【００３１】・液体クロマトグラフィー分析（ＵＶ検出
器；254nm)：94.8％ ・赤外吸収スペクトル分析（液膜法）： 波数（cm-1) 帰属 2960 C−H 1705 C＝O 1100〜1080 Si−OCH2 ・1H核磁気共鳴吸収分析（90MHz 、CDCl3 中）：所望の
分子構造に合致するスペクトル ・紫外−可視吸収スペクトル分析（溶媒；エタノー
ル）： 吸収極大波長 λmax＝361nm モル吸光係数 εmax＝3.43×104dm3 mol-1cm-1 ・質量スペクトル分析(m/e) ：500 (M+) 実施例３Liquid chromatography analysis (UV detector; 254 nm): 94.8% Infrared absorption spectrum analysis (liquid film method): Wave number (cm -1 ) attribution 2960 C-H 1705 C = O 1100 to 1080 Si- OCH 2 - 1 H nuclear magnetic resonance analysis (90 MHz, in CDCl 3): spectrum ultraviolet matches the desired molecular structure - visible absorption spectral analysis (solvent: ethanol): absorption maximum wavelength .lambda.max = 361 nm molar extinction coefficient .epsilon.max = 3.43 × 10 4 dm 3 mol -1 cm -1 · mass spectrum analysis (m / e): 500 (M + ) Example 3
【００３２】[0032]
【化１３】 [Chemical 13]
【００３３】撹拌機、温度計、滴下漏斗、還流冷却器お
よびオイルバスを備えた内容積 500mlのフラスコに、純
度90％のナトリウムアミド10.8ｇ (0.25モル) およびト
ルエン 150ｇを仕込み、撹拌を開始し、液温50℃に加熱
した。これに、２−メチレン−1,3 −ジ（４−アセチル
フェノキシ）プロパン41.3ｇ(0.125モル）をトルエン60
ｇに溶解した混合溶液を、滴下漏斗より液温50〜55℃で
45分かけて滴下した。次いで、４−ｔ−ブチル安息香酸
メチル45.3ｇ (0.25モル) を滴下漏斗より、液温50〜55
℃で15分かけて滴下した。滴下終了後、液温50〜67℃で
２時間、さらに液温90〜100 ℃で５時間加熱撹拌し、液
体クロマトグラフィー分析により原料のピークが消失
し、目的とするClaisen 縮合物が生成していることを確
認した。次に、室温まで冷却後、氷水 100ｇ、塩酸24ml
を加えて中和・分液し、さらに有機相を飽和食塩水 300
mlで３回水洗した後、無水芒硝を入れて乾燥した。乾燥
後、トルエンなどの低沸点成分を蒸留により除去して、
赤色の粗結晶を得た。さらに、この粗結晶を 100mlのエ
タノールから再結晶し、室温で10時間減圧乾燥した。こ
の結果、淡黄色粒状の目的化合物の精製結晶49.2ｇ（収
率60.0％）を得た。このものの液体クロマトグラフィー
分析、赤外吸収スペクトル分析、1H核磁気共鳴吸収分
析、紫外−可視吸収スペクトル分析および質量スペクト
ル分析の結果は後記の通りであり、次式の分子構造であ
ることを確認した。A flask having an inner volume of 500 ml equipped with a stirrer, a thermometer, a dropping funnel, a reflux condenser and an oil bath was charged with 10.8 g (0.25 mol) of sodium amide having a purity of 90% and 150 g of toluene, and stirring was started. The solution was heated to 50 ° C. To this, 41.3 g (0.125 mol) of 2-methylene-1,3-di (4-acetylphenoxy) propane was added in 60 parts of toluene.
The mixed solution dissolved in g at a liquid temperature of 50-55 ℃ from the dropping funnel.
It was added dropwise over 45 minutes. Then, 45.3 g (0.25 mol) of methyl 4-t-butylbenzoate was added from a dropping funnel at a liquid temperature of 50 to 55.
It was added dropwise at 15 ° C over 15 minutes. After completion of the dropping, the mixture was heated and stirred at a liquid temperature of 50 to 67 ° C for 2 hours and further at a liquid temperature of 90 to 100 ° C for 5 hours, and the raw material peak disappeared by liquid chromatography analysis, and the desired Claisen condensate was formed. I confirmed that. Next, after cooling to room temperature, 100 g of ice water and 24 ml of hydrochloric acid
To neutralize and separate the solution, and then add the organic phase to saturated saline solution 300
After washing with water three times in ml, anhydrous sodium sulfate was added and dried. After drying, remove low boiling point components such as toluene by distillation,
Crude red crystals were obtained. Further, the crude crystals were recrystallized from 100 ml of ethanol and dried under reduced pressure at room temperature for 10 hours. As a result, 49.2 g (yield 60.0%) of pale yellow granular purified crystals of the target compound were obtained. The results of liquid chromatography analysis, infrared absorption spectrum analysis, 1 H nuclear magnetic resonance absorption analysis, ultraviolet-visible absorption spectrum analysis and mass spectrum analysis of this product are as described below, and it was confirmed that they have the molecular structure of the following formula. did.
【００３４】[0034]
【化１４】 [Chemical 14]
【００３５】・液体クロマトグラフィー分析（ＵＶ検出
器；254nm)：主成分純度95.7％ ・赤外吸収スペクトル分析（液膜法）： 波数（cm-1) 帰属 2940 C−H 1705 C＝O 1595 C＝C ・1H核磁気共鳴吸収分析（90MHz 、CDCl3 中）：前記の
分子構造に合致するスペクトル ・紫外−可視吸収スペクトル分析（溶媒；エタノー
ル）： 吸収極大波長 λmax＝361nm モル吸光係数 εmax＝3.50×104dm3 mol-1cm-1 ・質量スペクトル分析(m/e) ：656 (M+ピーク) 実施例４Liquid chromatography analysis (UV detector; 254 nm): Purity of main component 95.7% Infrared absorption spectrum analysis (liquid film method): Wave number (cm -1 ) attribute 2940 C-H 1705 C = O 1595 C = C · 1 H nuclear magnetic resonance analysis (90 MHz, in CDCl 3): the spectral ultraviolet matches the molecular structure - visible absorption spectral analysis (solvent: ethanol): absorption maximum wavelength .lambda.max = 361 nm molar extinction coefficient .epsilon.max = 3.50 × 10 4 dm 3 mol −1 cm −1 · mass spectrum analysis (m / e): 656 (M + peak) Example 4
【００３６】[0036]
【化１５】 [Chemical 15]
【００３７】撹拌機、温度計、滴下漏斗、還流冷却器お
よびオイルバスを備えた内容積 100mlのフラスコに、実
施例３で得られたObtained in Example 3 in a 100 ml internal volume flask equipped with stirrer, thermometer, dropping funnel, reflux condenser and oil bath.
【００３８】[0038]
【化１６】 [Chemical 16]
【００３９】19.7ｇ (0.03モル）、トルエン50ｇ、触媒
として1,3,5,7 −テトラビニル−1,3,5,7 −テトラメチ
ルシクロテトラシロキサンをリガンドとする白金錯体
（白金含有量２％）0.04ｇを仕込み、液温75℃に加熱し
た。これに、滴下漏斗よりトリエトキシシラン 4.9ｇ
(0.03モル) をトルエン10ｇに溶解した混合溶液を液温7
5〜80℃で10分かけて滴下した。滴下終了後、液温82〜1
00 ℃で１時間加熱撹拌し、液体クロマトグラフィー分
析により原料のピークが消失し、付加反応物が生成して
いることを確認した。放冷後、白金触媒を除去するため
に活性炭 0.2ｇを加えて30分撹拌し、吸引濾過し、さら
にトルエンなどの低沸点成分を液温 120℃、減圧度５To
rrの条件で蒸留除去した。この結果、黄色透明液状の目
的化合物23.4ｇ（収率95.0％）を得た。このものの液体
クロマトグラフィー分析、赤外吸収スペクトル分析、1H
核磁気共鳴吸収分析、紫外−可視吸収スペクトル分析お
よび質量スペクトル分析の結果は後記の通りであり、次
式の分子構造であることを確認した。Platinum complex having 19.7 g (0.03 mol), 50 g of toluene and 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane as a catalyst as a ligand (platinum content 2 %) 0.04 g, and heated to a liquid temperature of 75 ° C. Add 4.9 g of triethoxysilane from the dropping funnel.
(0.03 mol) dissolved in 10 g of toluene to prepare a mixed solution at a liquid temperature of 7
It was added dropwise at 5 to 80 ° C over 10 minutes. After dropping, the liquid temperature is 82-1.
The mixture was heated and stirred at 00 ° C. for 1 hour, and it was confirmed by liquid chromatography analysis that the peak of the raw material had disappeared and an addition reaction product had been formed. After cooling, 0.2 g of activated carbon was added to remove the platinum catalyst, stirred for 30 minutes, suction filtered, and low-boiling components such as toluene were added at a liquid temperature of 120 ° C and a decompression degree of 5 To.
It was distilled off under the condition of rr. As a result, 23.4 g (yield 95.0%) of the target compound was obtained as a yellow transparent liquid. Liquid chromatography analysis, infrared absorption spectrum analysis, 1 H
The results of nuclear magnetic resonance absorption analysis, ultraviolet-visible absorption spectrum analysis and mass spectrum analysis are as described below, and it was confirmed that the molecular structure was represented by the following formula.
【００４０】[0040]
【化１７】 [Chemical 17]
【００４１】・液体クロマトグラフィー分析（ＵＶ検出
器；254nm)：92.8％ ・赤外吸収スペクトル分析（液膜法）： 波数（cm-1) 帰属 2960 C−H 1705 C＝O 1100〜1080 Si−OCH2 ・1H核磁気共鳴吸収分析（90MHz 、CDCl3 中）：前記の
分子構造に合致するスペクトル ・紫外−可視吸収スペクトル分析（溶媒；エタノー
ル）： 吸収極大波長 λmax＝362nm モル吸光係数 εmax＝3.63×104dm3 mol-1cm-1 ・質量スペクトル分析(m/e) ：820 (M+ ) 実施例５ 実施例２および実施例４で得られた化合物を各種シリコ
ーンオイルへ10重量％配合したときの25℃での溶解性
（○：可溶、×：不溶）をまとめて表１に示す。比較品
として４−（ｔ−ブチル）−4'−メトキシジベンゾイル
メタンの場合を併記した。Liquid chromatography analysis (UV detector; 254 nm): 92.8% Infrared absorption spectrum analysis (liquid film method): Wave number (cm -1 ) attribution 2960 C-H 1705 C = O 1100 to 1080 Si- OCH 2 - 1 H nuclear magnetic resonance analysis (90 MHz, in CDCl 3): the spectral ultraviolet matches the molecular structure - visible absorption spectral analysis (solvent: ethanol): absorption maximum wavelength .lambda.max = 362 nm molar extinction coefficient .epsilon.max = 3.63 × 10 4 dm 3 mol −1 cm −1 · mass spectrum analysis (m / e): 820 (M + ) Example 5 10% by weight of the compounds obtained in Examples 2 and 4 in various silicone oils The solubility at 25 ° C. when blended (◯: soluble, x: insoluble) is summarized in Table 1. The case of 4- (t-butyl) -4'-methoxydibenzoylmethane is also shown as a comparative product.
【００４２】[0042]
【表１】 [Table 1]
【００４３】*1)４−（ｔ−ブチル）−4'−メトキシジ
ベンゾイルメタン* 1) 4- (t-butyl) -4'-methoxydibenzoylmethane
Claims (2)
基、R2は置換または非置換の１価の炭化水素基、Y はア
ルコキシ基、アリールオキシ基または水酸基であり、a
は１または２、n は０〜３の整数を示す）で表されるジ
ベンゾイルメタン誘導体。1. A general formula: (In the formula, R 1 is a hydrogen atom, an alkyl group or an alkoxy group, R 2 is a substituted or unsubstituted monovalent hydrocarbon group, Y is an alkoxy group, an aryloxy group or a hydroxyl group, and
Is 1 or 2, and n is an integer of 0 to 3).
合物。2. A general formula: (Wherein R 1 and a are the same as defined above).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4034744A JPH05230071A (en) | 1992-02-21 | 1992-02-21 | Dibenzoylmethane derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4034744A JPH05230071A (en) | 1992-02-21 | 1992-02-21 | Dibenzoylmethane derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05230071A true JPH05230071A (en) | 1993-09-07 |
Family
ID=12422837
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4034744A Pending JPH05230071A (en) | 1992-02-21 | 1992-02-21 | Dibenzoylmethane derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05230071A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003081910A (en) * | 2001-09-11 | 2003-03-19 | Chemiprokasei Kaisha Ltd | Dibenzoylmethane derivative, method for producing the same and use thereof |
| FR2869036A1 (en) * | 2004-04-19 | 2005-10-21 | Commissariat Energie Atomique | COMPOUNDS, POROUS ORGANIC-INORGANIC HYBRID MATERIALS MESOSTRUCTURES AND SENSORS USEFUL FOR THE DETECTION OR DETERMINATION OF HALOGENATED GASEOUS COMPOUNDS |
| JP2008045126A (en) * | 2006-08-16 | 2008-02-28 | Wacker Chemie Ag | Chelate polymerization |
-
1992
- 1992-02-21 JP JP4034744A patent/JPH05230071A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003081910A (en) * | 2001-09-11 | 2003-03-19 | Chemiprokasei Kaisha Ltd | Dibenzoylmethane derivative, method for producing the same and use thereof |
| FR2869036A1 (en) * | 2004-04-19 | 2005-10-21 | Commissariat Energie Atomique | COMPOUNDS, POROUS ORGANIC-INORGANIC HYBRID MATERIALS MESOSTRUCTURES AND SENSORS USEFUL FOR THE DETECTION OR DETERMINATION OF HALOGENATED GASEOUS COMPOUNDS |
| WO2005100371A1 (en) * | 2004-04-19 | 2005-10-27 | Commissariat A L'energie Atomique | Porous hybrid organic-inorganic materials for the detection of halogens |
| JP2007532613A (en) * | 2004-04-19 | 2007-11-15 | コミツサリア タ レネルジー アトミーク | Compounds, mesostructured porous hybrid organic-inorganic materials and sensors used for the detection or quantification of halogenated gaseous compounds |
| US7892851B2 (en) | 2004-04-19 | 2011-02-22 | Commissariat A L'energie Atomique | Porous hybrid organic-inorganic materials for the detection of halogens |
| JP2008045126A (en) * | 2006-08-16 | 2008-02-28 | Wacker Chemie Ag | Chelate polymerization |
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