JP2002338583A - Organic silicon compound having protected catechol group and method for producing the same - Google Patents
Organic silicon compound having protected catechol group and method for producing the sameInfo
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- JP2002338583A JP2002338583A JP2001153237A JP2001153237A JP2002338583A JP 2002338583 A JP2002338583 A JP 2002338583A JP 2001153237 A JP2001153237 A JP 2001153237A JP 2001153237 A JP2001153237 A JP 2001153237A JP 2002338583 A JP2002338583 A JP 2002338583A
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- same
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Links
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 5
- 150000003377 silicon compounds Chemical class 0.000 title abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 11
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 50
- 238000006243 chemical reaction Methods 0.000 claims description 28
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- -1 silane compound Chemical class 0.000 claims description 13
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 3
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 238000010276 construction Methods 0.000 claims 1
- 125000001424 substituent group Chemical group 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 6
- 229920005989 resin Polymers 0.000 abstract description 5
- 239000011347 resin Substances 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 238000004381 surface treatment Methods 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- HEWZVZIVELJPQZ-UHFFFAOYSA-N 2,2-dimethoxypropane Chemical compound COC(C)(C)OC HEWZVZIVELJPQZ-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229940079877 pyrogallol Drugs 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000005370 alkoxysilyl group Chemical group 0.000 description 2
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 2
- GGNQRNBDZQJCCN-UHFFFAOYSA-N benzene-1,2,4-triol Chemical compound OC1=CC=C(O)C(O)=C1 GGNQRNBDZQJCCN-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000002170 ethers Chemical class 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
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- OXQHJIGWZNIQDS-UHFFFAOYSA-N 2,2-dimethoxybutane Chemical compound CCC(C)(OC)OC OXQHJIGWZNIQDS-UHFFFAOYSA-N 0.000 description 1
- DMAYBPBPEUFIHJ-UHFFFAOYSA-N 4-bromobut-1-ene Chemical compound BrCCC=C DMAYBPBPEUFIHJ-UHFFFAOYSA-N 0.000 description 1
- HBLFGOQZEVMJKU-UHFFFAOYSA-N 5,5-dimethoxynonane Chemical compound CCCCC(OC)(OC)CCCC HBLFGOQZEVMJKU-UHFFFAOYSA-N 0.000 description 1
- UPOBJNRMUDPATE-UHFFFAOYSA-N 5-chloropent-1-ene Chemical compound ClCCCC=C UPOBJNRMUDPATE-UHFFFAOYSA-N 0.000 description 1
- BLMIXWDJHNJWDT-UHFFFAOYSA-N 6-chlorohex-1-ene Chemical compound ClCCCCC=C BLMIXWDJHNJWDT-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- HFEHLDPGIKPNKL-UHFFFAOYSA-N allyl iodide Chemical compound ICC=C HFEHLDPGIKPNKL-UHFFFAOYSA-N 0.000 description 1
- FSIJKGMIQTVTNP-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C=C)C=C FSIJKGMIQTVTNP-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- OPTDDWCXQQYKGU-UHFFFAOYSA-N diphenyldichloromethane Chemical compound C=1C=CC=CC=1C(Cl)(Cl)C1=CC=CC=C1 OPTDDWCXQQYKGU-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000002524 organometallic group Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000002444 silanisation Methods 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 125000005371 silicon functional group Chemical group 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Landscapes
- Silicon Polymers (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、新規な有機ケイ素
化合物に関し、さらに詳しくは、有機置換基により保護
されたカテコール基を有するアルコキシシランに関す
る。The present invention relates to a novel organosilicon compound, and more particularly to an alkoxysilane having a catechol group protected by an organic substituent.
【０００２】[0002]
【従来の技術】フェノール性水酸基が有機置換基によっ
て保護された、下記式［５］、［５'］に示す有機ケイ
素化合物は知られている。2. Description of the Related Art Organic silicon compounds represented by the following formulas [5] and [5 '] in which a phenolic hydroxyl group is protected by an organic substituent are known.
【０００３】[0003]
【化５】 Embedded image
【０００４】（式中、Ｒ6、Ｒ7及びＲ8は、炭素数１〜
６のアルキル基であり、Ｚはビニル基又はハロゲンであ
る。）(Wherein R 6 , R 7 and R 8 each have 1 to 1 carbon atoms)
And Z is a vinyl group or a halogen. )
【０００５】[0005]
【化６】 Embedded image
【０００６】（式中、Ｒ9、Ｒ10、Ｒ11、Ｒ12は炭素数
１〜６のアルキル基である。） しかし、カテコール基を有する有機基の末端炭素原子に
アルコキシシリル基のようなケイ素官能基が結合し、か
つ、カテコール基の水素原子が有機置換基で保護された
有機ケイ素化合物は知られていない。(Wherein R 9 , R 10 , R 11 , and R 12 are alkyl groups having 1 to 6 carbon atoms.) However, an organic group having a catechol group has a terminal carbon atom such as an alkoxysilyl group. An organosilicon compound in which a silicon functional group is bonded and a hydrogen atom of the catechol group is protected by an organic substituent is not known.
【０００７】[0007]
【発明が解決しようとする課題】本発明の課題は、有機
置換基により保護されたカテコール基を有するアルコキ
シシランを提供し、そのことによって、有機合成その他
の分野で新規な合成方法や、新規樹脂の製造、材料表面
処理方法および樹脂改質等の分野に資することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide an alkoxysilane having a catechol group protected by an organic substituent, whereby a novel synthesis method in organic synthesis and other fields and a novel resin are provided. In the fields of manufacturing, material surface treatment method and resin modification.
【０００８】[0008]
【課題を解決するための手段】本発明者は、このような
有機ケイ素化合物が、一方では１個のケイ素官能基を有
し、他方では有機置換基で保護された炭素官能基を有す
るために、有機合成などの中間原料や各種材料のカップ
リング剤として有用であることを見出し、その知見に基
いて本発明を完成するに至った。即ち、本発明は、保護
されたカテコール基を有し、下記一般式［１］で表され
る有機ケイ素化合物である。SUMMARY OF THE INVENTION The present inventors have determined that such organosilicon compounds have a single silicon function on the one hand and a carbon function protected by an organic substituent on the other. The present invention was found to be useful as an intermediate material for organic synthesis and the like and as a coupling agent for various materials, and based on the findings, the present invention was completed. That is, the present invention is an organosilicon compound having a protected catechol group and represented by the following general formula [1].
【０００９】[0009]
【化７】 Embedded image
【００１０】（式中、Ｒ1、Ｒ2およびＲ3は炭素数１か
ら６のアルキル基、フェニル基またはアルコキシ基であ
り、互いに同じであっても異なっていても良く、Ｒ1、
Ｒ2またはＲ3の少なくとも１つはアルコキシ基である。
Ｒ5およびＲ6は炭素数１から６のアルキル基またはフェ
ニル基を示し、互いに同じであっても異なっていても良
い。Ｒ4は炭素数２から６のアルキレン基を示す）[0010] (wherein, R 1, R 2 and R 3 is an alkyl group, a phenyl group or an alkoxy group having 1 to 6 carbon atoms, may be different be the same as each other, R 1,
At least one of R 2 or R 3 is an alkoxy group.
R 5 and R 6 represent an alkyl group having 1 to 6 carbon atoms or a phenyl group, and may be the same or different. R 4 represents an alkylene group having 2 to 6 carbon atoms)
【００１１】以下、本発明について詳述する。本発明の
有機ケイ素化合物を表す上記一般式［１］において、Ｒ
1、Ｒ2およびＲ3は炭素数１から６のアルキル基、フェ
ニル基またはアルコキシ基であり、互いに同じであって
も異なっていても良く、Ｒ1、Ｒ2またはＲ3の少なくと
も１つはアルコキシ基である。炭素数１から６のアルキ
ル基及びアルコキシ基の具体例として、メチル基、エチ
ル基、プロピル基、イソプロピル基、ブチル基、イソブ
チル基、ペンチル基、ヘキシル基、メトキシ基、エトキ
シ基、プロピルオキシ基、ブチルオキシ基、ペンチルオ
キシ基、ヘキシルオキシ基等があり、直鎖状でも分岐状
でも差し支えない。上記一般式［１］において、Ｒ4は
炭素数２から６のアルキレン基で、直鎖状、分岐状のい
ずれでもよく、具体例として、ジメチレン基、トリメチ
レン基、テトラメチレン基、ペンタメチレン基、ヘキサ
メチレン基、２−メチルトリメチレン基、３−メチルト
リメチレン基等がある。上記一般式［１］において、Ｒ
5およびＲ6は炭素数１から６のアルキル基またはフェニ
ル基であり、好ましい具体例として、メチル基、エチル
基、プロピル基、ブチル基、ペンチル基、ヘキシル基及
びフェニル基がある。Ｒ5およびＲ6は、直鎖状又は分岐
状の何れでも良く、また環状であっても差し支えない。
Ｒ1〜Ｒ6において好ましいものは、原料が得易く、本発
明の化合物の合成が容易なことから、Ｒ1、Ｒ2およびＲ
3についてはエトキシ基であり、Ｒ4については炭素数が
３の直鎖状炭化水素であり、Ｒ5およびＲ6についてはメ
チル基である。アルコキシシリル基の存在位置として
は、 有機置換基により保護されたカテコール基に対し
て、オルト位又はメタ位のいずれでも構わない。このよ
うな本発明の化合物の具体例はいくつか例示されるが、
上記のことを考慮すると、もっとも好ましいものは、下
記［２］式で表される化合物である。Hereinafter, the present invention will be described in detail. In the above general formula [1] representing the organosilicon compound of the present invention, R
1 , R 2 and R 3 are an alkyl group having 1 to 6 carbon atoms, a phenyl group or an alkoxy group, which may be the same or different, and at least one of R 1 , R 2 or R 3 is It is an alkoxy group. Specific examples of the alkyl group and the alkoxy group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, methoxy group, ethoxy group, propyloxy group, There are a butyloxy group, a pentyloxy group, a hexyloxy group and the like, which may be linear or branched. In the general formula [1], R 4 is an alkylene group having 2 to 6 carbon atoms, which may be linear or branched. Specific examples include a dimethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, There are a hexamethylene group, a 2-methyltrimethylene group and a 3-methyltrimethylene group. In the above general formula [1], R
5 and R 6 are an alkyl group having 1 to 6 carbon atoms or a phenyl group, and preferred specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and a phenyl group. R 5 and R 6 may be linear or branched, and may be cyclic.
Preferred among R 1 to R 6 are those in which R 1 , R 2 , R 3 and R 4 can be easily obtained and the compound of the present invention can be easily synthesized.
3 is an ethoxy group, R 4 is a straight-chain hydrocarbon having 3 carbon atoms, and R 5 and R 6 are methyl groups. The position of the alkoxysilyl group may be either the ortho position or the meta position with respect to the catechol group protected by the organic substituent. Some specific examples of such compounds of the present invention are illustrated,
In view of the above, the most preferable are compounds represented by the following formula [2].
【００１２】[0012]
【化８】 Embedded image
【００１３】（式中、Ｍｅはメチル基であり、Ｅｔはエ
チル基である。）(In the formula, Me is a methyl group, and Et is an ethyl group.)
【００１４】本発明の化合物は、例えば以下の反応工程
（１）〜（３）により容易に製造することができる。 工程（１）：少なくとも２個の水酸基がオルト位にある
トリヒドロキシベンゼンとカテコール基の保護用化合物
とを反応させて下記式［３］で表される化合物［３］を
得る。The compound of the present invention can be easily produced, for example, by the following reaction steps (1) to (3). Step (1): A compound [3] represented by the following formula [3] is obtained by reacting trihydroxybenzene having at least two hydroxyl groups at the ortho position with a compound for protecting a catechol group.
【００１５】[0015]
【化９】 Embedded image
【００１６】（式中においてＲ5およびＲ6は上記一般式
［１］における意味と同義である。）(In the formula, R 5 and R 6 have the same meanings as in the above general formula [1].)
【００１７】工程（２）：上記化合物［３］とハロゲン
化アルケン（但し、一方の分子末端に炭素二重結合を有
する以外は上記一般式［１］におけるＲ4と同じ炭素骨
格を有し、他方の分子末端にハロゲンを有する。）とを
反応させて下記式［４］で表される化合物［４］を得
る。Step (2): The compound [3] and a halogenated alkene (provided that they have the same carbon skeleton as R 4 in the above general formula [1] except that they have a carbon double bond at one molecular terminal, With a halogen at the other molecular terminal) to obtain a compound [4] represented by the following formula [4].
【００１８】[0018]
【化１０】 Embedded image
【００１９】（式中、Ｒ7は、ハロゲン化アルケンにお
けるハロゲンを除いた残基であり、末端に炭素二重結合
を有する。）(In the formula, R 7 is a residue obtained by removing a halogen in a halogenated alkene, and has a carbon double bond at a terminal.)
【００２０】工程（３）：上記化合物［４］とシラン化
合物Ｒ1Ｒ2Ｒ3ＳｉＨ（但し、Ｒ1、Ｒ 2およびＲ3は上記
一般式［１］における意味と同義である。）とをヒドロ
シリレーション反応させて本発明の化合物を得る。Step (3): silanization with the above compound [4]
Compound R1RTwoRThreeSiH (however, R1, R TwoAnd RThreeIs above
It has the same meaning as in general formula [1]. ) And the hydro
The compound of the present invention is obtained by a silylation reaction.
【００２１】以下に（１）〜（３）の各反応工程につい
て更に詳しく説明する。 ［工程（１）］工程（１）におけるトリヒドロキシベン
ゼンは、少なくとも２個の水酸基がオルト位にあるもの
であり、好ましい例として、ピロガロール、1,2,4-トリ
ヒドロキシベンゼンがある。カテコール基の保護用化合
物は、分子中に、Ｒ5、Ｒ6及びカテコール基に対する反
応性基を有する化合物である（但し、Ｒ5、Ｒ6は上記一
般式［１］における意味と同義。以下同じ。）。Ｒ5及
びＲ6がアルキル基である場合、カテコール基に対する
好ましい反応性基はアルコキシ基であり、より好ましい
反応性基はメトキシ基である。Ｒ5又はＲ6がフェニル基
である場合、カテコール基に対する好ましい反応性基は
ハロゲンであり、より好ましくは塩素である。カテコー
ル基の保護用化合物として以下の化合物が好ましく、Hereinafter, the respective reaction steps (1) to (3) will be described in more detail. [Step (1)] Trihydroxybenzene in the step (1) has at least two hydroxyl groups at the ortho position, and preferable examples include pyrogallol and 1,2,4-trihydroxybenzene. The compound for protecting a catechol group is a compound having a reactive group for R 5 , R 6 and a catechol group in a molecule (provided that R 5 and R 6 have the same meanings as in the above formula [1]. the same.). When R 5 and R 6 are alkyl groups, a preferred reactive group for the catechol group is an alkoxy group, and a more preferred reactive group is a methoxy group. When R 5 or R 6 is a phenyl group, the preferred reactive group for the catechol group is halogen, more preferably chlorine. The following compounds are preferable as the compound for protecting the catechol group,
【００２２】[0022]
【化１１】 Embedded image
【００２３】[0023]
【化１２】 Embedded image
【００２４】その例として、2,2-ジメトキシブタン、3,
3-ジメトキシペンタン、5,5-ジメトキシノナン、ジフェ
ニルジクロロメタン等がある。Examples are 2,2-dimethoxybutane, 3,2
Examples include 3-dimethoxypentane, 5,5-dimethoxynonane, diphenyldichloromethane, and the like.
【００２５】工程（１）の反応は、トリヒドロキシベン
ゼンに溶媒を加え、加熱還流下でカテコール基の保護用
化合物を滴下することにより行う。この反応はトリヒド
ロキシベンゼンとカテコール基の保護用化合物との等モ
ル反応であるが、副生するアルコールと共に反応系外へ
一部溜出するため、通常後者を過剰に供給して反応を行
う。反応系内で副生するアルコール又はハロゲン化水素
を反応系外へ流出させ、反応を完結させる。好ましい溶
媒として、ｎ−ペンタン、ｎ−ヘキサン、シクロヘキサ
ン、石油エーテル、トルエン、キシレン、ガソリン、リ
グロインのような炭化水素類；ジエチルエーテル、ジイ
ソプロピルエーテル、テトラヒドロフランのようなエー
テル類がある。上記の反応が終了後、溶媒および揮発成
分を減圧下留去することにより下記化合物［３］を得
る。この化合物［３］において、カテコール基は有機置
換基［（Ｒ5）（Ｒ6）Ｃ＝］により保護されている。The reaction of the step (1) is carried out by adding a solvent to trihydroxybenzene and dropping a compound for protecting a catechol group under heating and reflux. Although this reaction is an equimolar reaction between trihydroxybenzene and a compound for protecting a catechol group, a part thereof is distilled out of the reaction system together with a by-produced alcohol, so that the latter is usually supplied in excess to carry out the reaction. Alcohol or hydrogen halide by-produced in the reaction system is allowed to flow out of the reaction system to complete the reaction. Preferred solvents include hydrocarbons such as n-pentane, n-hexane, cyclohexane, petroleum ether, toluene, xylene, gasoline and ligroin; ethers such as diethyl ether, diisopropyl ether and tetrahydrofuran. After the completion of the above reaction, the solvent and volatile components are distilled off under reduced pressure to obtain the following compound [3]. In this compound [3], the catechol group is protected by an organic substituent [(R 5 ) (R 6 ) C =].
【００２６】[0026]
【化１３】 Embedded image
【００２７】［工程（２）］工程（２）におけるハロゲ
ン化アルケンは、一方の分子末端に炭素二重結合を有す
る以外は上記一般式［１］におけるＲ4と同じ炭素骨格
を有し、他方の分子末端にハロゲンを有する化合物であ
る。好ましいハロゲン化アルケンは、２−クロロ−１−
エテン、４−ブロモ−１−ブテン、５−クロロ−１−ペ
ンテン、６−クロロ−１−ヘキセン等である。工程
（２）の反応は、工程（１）で得た化合物［３］に溶
媒、塩基を加え、加熱還流下、ハロゲン化アルケンを滴
下することにより行う。[Step (2)] The alkene halide in the step (2) has the same carbon skeleton as R 4 in the above general formula [1] except that it has a carbon double bond at one molecular terminal. Is a compound having a halogen at the molecular terminal. Preferred halogenated alkenes are 2-chloro-1-
Ethene, 4-bromo-1-butene, 5-chloro-1-pentene, 6-chloro-1-hexene and the like. The reaction of the step (2) is performed by adding a solvent and a base to the compound [3] obtained in the step (1), and dropwise adding an alkene halide under reflux with heating.
【００２８】好ましい溶媒は、メタノール、エタノー
ル、イソプロパノール、ブタノールのようなアルコール
類、ジエチルエーテル、ジイソプロピルエーテル、テト
ラヒドロフランのようなエーテル類、水、アセトン、ジ
メチルホルムアミドのような極性溶媒である。好ましい
塩基は、水酸化ナトリウム、水酸化カリウム、炭酸カリ
ウム等である。化合物［３］とハロゲン化アルケンとの
反応が終了後、溶媒および揮発成分を減圧下留去し、減
圧蒸留によって下記化合物［４］を単離する。Preferred solvents are alcohols such as methanol, ethanol, isopropanol and butanol, ethers such as diethyl ether, diisopropyl ether and tetrahydrofuran, and polar solvents such as water, acetone and dimethylformamide. Preferred bases are sodium hydroxide, potassium hydroxide, potassium carbonate and the like. After the reaction of the compound [3] with the halogenated alkene is completed, the solvent and volatile components are distilled off under reduced pressure, and the following compound [4] is isolated by distillation under reduced pressure.
【００２９】[0029]
【化１４】 Embedded image
【００３０】［工程（３）］工程（２）で得た上記化合
物［４］とシラン化合物（Ｒ1Ｒ2Ｒ3ＳｉＨ）との反応
は、通常、触媒の存在下で行う。好ましい触媒として、
コバルト、ニッケル、ルテニウム、ロジウム、パラジウ
ム、イリジウム、白金等の第８属から第１０属金属の単
体、有機金属錯体、金属塩、金属酸化物等がある。これ
らの中で、白金系の触媒が特に好ましい。白金系触媒と
しては、塩化白金酸六水和物（H2PtCl6・６H2O）、cis-
PtCl2(PhCN)2、白金カーボン、ジビニルテトラメチルジ
シロキサンが配位した白金錯体(PtDVTMDS)等がある。な
お、Phはフェニル基を表わす。触媒の好ましい使用量
は、化合物［４］の量に対して、0.1ｐｐｍから1,000ｐ
ｐｍである。[Step (3)] The reaction of the compound [4] obtained in the step (2) with the silane compound (R 1 R 2 R 3 SiH) is usually carried out in the presence of a catalyst. As a preferred catalyst,
There is a simple substance of Group 8 to Group 10 metals such as cobalt, nickel, ruthenium, rhodium, palladium, iridium, platinum and the like, organometallic complexes, metal salts, metal oxides and the like. Of these, platinum-based catalysts are particularly preferred. The platinum-based catalyst, chloroplatinic acid hexahydrate (H 2 PtCl 6 · 6H 2 O), cis-
Examples include PtCl 2 (PhCN) 2 , platinum carbon, a platinum complex coordinated with divinyltetramethyldisiloxane (PtDVTMDS), and the like. Ph represents a phenyl group. The preferred amount of the catalyst used is 0.1 ppm to 1,000 p based on the amount of the compound [4].
pm.
【００３１】また、反応温度の制御操作は、外部からの
加熱およびシラン化合物の供給速度に依存するため、一
概に決められないが、通常、反応温度を室温〜１１０℃
の範囲に保持することで、ヒドロシリレーション反応を
円滑に継続させることができる。反応終了後、溶媒およ
び揮発成分を減圧下留去することにより本発明の化合物
を得る。The control operation of the reaction temperature depends on external heating and the supply rate of the silane compound, and thus cannot be unconditionally determined.
By keeping in the range, the hydrosilylation reaction can be smoothly continued. After completion of the reaction, the compound of the present invention is obtained by distilling off the solvent and volatile components under reduced pressure.
【００３２】本発明の化合物の内、好ましい化合物
［２］の場合、次のようにして製造することができる。
即ち、少なくとも２個の水酸基がオルト位にあるトリヒ
ドロキシベンゼンと2,2-ジメトキシプロパンを脱メタノ
ールさせながら反応させ、下記式［５］で表される化合
物［５］を得る。この化合物［５］は有機置換基［（Ｍ
ｅ）2Ｃ＝］により保護されたカテコール基を有する化
合物である。In the case of the preferred compound [2] among the compounds of the present invention, it can be produced as follows.
That is, trihydroxybenzene having at least two hydroxyl groups at the ortho position is reacted with 2,2-dimethoxypropane while removing methanol to obtain a compound [5] represented by the following formula [5]. This compound [5] has an organic substituent [(M
e) A compound having a catechol group protected by 2 C =].
【００３３】[0033]
【化１５】 Embedded image
【００３４】反応は、トリヒドロキシベンゼンに溶媒を
加え、加熱還流下で2,2-ジメトキシプロパンを滴下する
ことにより行う。反応系内で生成されるメタノールを反
応系外へ流出させ、反応を完結させる。好ましい溶媒
は、上記工程（１）において例示したものである。トリ
ヒドロキシベンゼンと2,2-ジメトキシプロパンとの反応
が終了後、溶媒および揮発成分を減圧下留去することに
より上記化合物［５］を得る。続けて化合物［５］を塩
基存在下、ハロゲン化アリルと反応させることにより、
下記式［６］で表される化合物［６］を得る。The reaction is carried out by adding a solvent to trihydroxybenzene and adding 2,2-dimethoxypropane dropwise under reflux with heating. Methanol generated in the reaction system is allowed to flow out of the reaction system to complete the reaction. Preferred solvents are those exemplified in the above step (1). After the reaction of trihydroxybenzene with 2,2-dimethoxypropane is completed, the solvent and volatile components are distilled off under reduced pressure to obtain the above compound [5]. Subsequently, by reacting compound [5] with allyl halide in the presence of a base,
A compound [6] represented by the following formula [6] is obtained.
【００３５】[0035]
【化１６】 Embedded image
【００３６】化合物［５］とハロゲン化アリルとの反応
は、化合物［５］に溶媒、塩基を加え、加熱還流下、ハ
ロゲン化アリルを滴下することにより行う。好ましい溶
媒及び好ましい塩基は、上記工程（２）で例示したもの
である。好ましいハロゲン化アリルは、塩化アリル、臭
化アリル、ヨウ化アリル等である。化合物［５］とハロ
ゲン化アリルとの反応が終了後、溶媒および揮発成分を
減圧下留去し、減圧蒸留によって化合物［６］を単離す
る。The reaction of the compound [5] with the allyl halide is carried out by adding a solvent and a base to the compound [5], and dropping the allyl halide under reflux with heating. Preferred solvents and preferred bases are those exemplified in the above step (2). Preferred allyl halides are allyl chloride, allyl bromide, allyl iodide and the like. After the reaction of the compound [5] with the allyl halide is completed, the solvent and volatile components are distilled off under reduced pressure, and the compound [6] is isolated by distillation under reduced pressure.
【００３７】このようにして得られた化合物［６］を、
トリエトキシシランとヒドロシリレーション反応させ、
本発明の化合物［２］を得る。The compound [6] thus obtained is
Hydrosilylation reaction with triethoxysilane,
The compound [2] of the present invention is obtained.
【００３８】[0038]
【発明の効果】本発明によって、有機置換基により保護
されたカテコール基を有する新規なアルコキシシランが
提供される。本発明の新規な有機ケイ素化合物は、ケイ
素原子に結合した加水分解性のアルコキシ基が存在する
ため、他の有機ケイ素化合物（ポリマーを含む）との反
応によりシロキサン結合を形成したり、無機化合物中の
シラノール基とカップリング反応させることができる。
また、３官能性アルコキシシランは、（ＳｉＯＳｉ）の
架橋反応を利用することができるので、シリコーンレジ
ン又はシルセスキオキサン等の製造用原料として有用で
ある。一方、本発明の化合物における保護されたカテコ
ール基は、酸性条件下で加水分解により容易に保護基を
脱離して、フリーのカテコール基となり、炭素官能性基
またはアルカリ水溶性基として機能する。フリーのカテ
コール基により、本発明の化合物は、１分子当たり２個
のヒドロキシル基を有することになり、フェノール基が
保護された従来の化合物に比較して、アルカリ水溶性は
格段に大きいという特徴がある。また、この際脱離する
成分は通常揮発性に富むケトンであり、容易に揮散させ
ることができる。この特性は、本発明の化合物を用いる
合成反応や樹脂の製造において、不純分をできるだけ少
なくする目的に有利である。フリーのカテコール基は極
性官能基と強い水素結合を形成するので、本発明の有機
珪素化合物は、水素結合を利用した有機−無機ハイブリ
ッド材料へも利用できる。上記の通り、本発明の化合物
は、ケイ素官能性および保護された炭素官能性をもつ複
反応性ケイ素化合物として機能するので、有機合成の中
間原料、ポリマー樹脂の合成原料、ポリマーの改質剤、
無機化合物の表面処理剤として有用である。According to the present invention, there is provided a novel alkoxysilane having a catechol group protected by an organic substituent. Since the novel organosilicon compound of the present invention has a hydrolyzable alkoxy group bonded to a silicon atom, it reacts with another organosilicon compound (including a polymer) to form a siloxane bond, Can be coupled with a silanol group.
Further, trifunctional alkoxysilane can be used as a raw material for producing a silicone resin or silsesquioxane since a crosslinking reaction of (SiOSi) can be utilized. On the other hand, the protected catechol group in the compound of the present invention easily releases the protecting group by hydrolysis under acidic conditions to become a free catechol group, and functions as a carbon functional group or an alkali water-soluble group. Due to the free catechol group, the compound of the present invention has two hydroxyl groups per molecule, and is characterized by a significantly higher alkali water solubility than the conventional compound in which the phenol group is protected. is there. The component to be eliminated at this time is usually a ketone with high volatility, and can be easily volatilized. This property is advantageous for the purpose of minimizing impurities in a synthetic reaction or resin production using the compound of the present invention. Since the free catechol group forms a strong hydrogen bond with the polar functional group, the organosilicon compound of the present invention can be used for an organic-inorganic hybrid material using a hydrogen bond. As described above, since the compound of the present invention functions as a double-reactive silicon compound having a silicon functionality and a protected carbon functionality, an intermediate material for organic synthesis, a synthetic material for a polymer resin, a polymer modifier,
It is useful as a surface treatment agent for inorganic compounds.
【００３９】[0039]
【実施例】以下、本発明を参考例および実施例によって
具体的に説明する。EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples and Examples.
【００４０】参考例１ 攪拌機、精留塔及び冷却管を備えた反応器を乾燥窒素雰
囲気下にして、ピロガロール100.0g（793mmol）、トル
エン300mLを仕込み、加熱還流させた。2,2-ジメトキシ
プロパン82.6g (793 mmol)を徐々に滴下させると、塔頂
温度約６０℃でメタノールが流出した。流出が止まった
ら、同量の2,2-ジメトキシプロパン82.6g(793 mmol)を
滴下させ、滴下終了後、加熱還流３時間行った。ガスク
ロマトグラフィーを用いてピロガロールが反応系内から
消失したのを確認し、溶媒を減圧下で留去することによ
り、褐色粘性液体を得た。この粘性液体をエタノール50
0mLに溶かし、還流管を備えた２口フラスコに仕込ん
だ。続けて水酸化ナトリウム66.7g(1190 mmol)を仕込
み、加熱還流させた。反応系に臭化アリル144g (1190 m
mol)を徐々に滴下させ、滴下終了後、加熱還流３時間行
った。エタノールを減圧下留去後、トルエン200mLを加
えた。トルエンに不溶の塩をろ別後、減圧蒸留によっ
て、沸点110〜112℃/707Paの無色透明の液体86.0g(53
%)を得た。この液体について270MHzの1Ｈ-ＮＭＲの測定
を行ったところ、第１図のスペクトルを得た。δ値とそ
の帰属は第１表のとおりであり、この同定結果により、
上記で得られた液体は、有機置換基により保護されたカ
テコールを含有する下記化合物［７］であることが確認
できた。REFERENCE EXAMPLE 1 A reactor equipped with a stirrer, a rectification tower and a condenser was placed under a dry nitrogen atmosphere, and 100.0 g (793 mmol) of pyrogallol and 300 mL of toluene were charged and heated to reflux. When 82.6 g (793 mmol) of 2,2-dimethoxypropane was gradually added dropwise, methanol flowed out at a top temperature of about 60 ° C. When the outflow stopped, 82.6 g (793 mmol) of the same amount of 2,2-dimethoxypropane was added dropwise, and after completion of the addition, the mixture was heated under reflux for 3 hours. It was confirmed by gas chromatography that pyrogallol had disappeared from the reaction system, and the solvent was distilled off under reduced pressure to obtain a brown viscous liquid. Add this viscous liquid to ethanol 50
It was dissolved in 0 mL and charged in a two-necked flask equipped with a reflux tube. Subsequently, 66.7 g (1190 mmol) of sodium hydroxide was charged and heated to reflux. Allyl bromide 144 g (1190 m
mol) was gradually added dropwise, and after completion of the addition, the mixture was heated under reflux for 3 hours. After ethanol was distilled off under reduced pressure, 200 mL of toluene was added. After filtering off salts insoluble in toluene, 86.0 g of a colorless and transparent liquid having a boiling point of 110 to 112 ° C / 707 Pa (53
%). When this liquid was measured by 1 H-NMR at 270 MHz, the spectrum shown in FIG. 1 was obtained. The δ values and their assignments are as shown in Table 1, and from this identification result,
The liquid obtained above was confirmed to be the following compound [7] containing catechol protected by an organic substituent.
【００４１】[0041]
【表１】 [Table 1]
【００４２】[0042]
【化１７】 Embedded image
【００４３】実施例１ 攪拌機、温度計及び冷却管を備えた反応器を乾燥窒素雰
囲気下にして、参考例１で合成した化合物［７］2.7g
（13.1mmol）、トリエトキシシラン3.23g（19.7mmol ）
を仕込み、系内を攪拌させながらオイルバスで加熱し
た。内温度が90℃に達したところで、白金触媒であるPt
DVTMDSのキシレン溶液(1μl,0.0001mmol)を加えた。触
媒滴下後、１時間、90℃で攪拌放置した。その後、減圧
下、揮発成分を留去し無色透明の液体4.37g(90%)を得
た。この液体について270MHzの1Ｈ-ＮＭＲの測定を行っ
たところ、第２図のスペクトルを得た。δ値とその帰属
は第２表のとおりであった。これにより得られた液体
は、有機置換基により保護されたカテコールを含有する
下記化合物［８］であることが確認できた。Example 1 2.7 g of the compound [7] synthesized in Reference Example 1 was placed in a reactor equipped with a stirrer, a thermometer and a condenser under a dry nitrogen atmosphere.
(13.1 mmol), 3.23 g (19.7 mmol) of triethoxysilane
And heated in an oil bath while stirring the inside of the system. When the internal temperature reaches 90 ° C, the platinum catalyst Pt
A xylene solution of DVTMDS (1 μl, 0.0001 mmol) was added. After the addition of the catalyst, the mixture was left to stir at 90 ° C. for 1 hour. Thereafter, volatile components were distilled off under reduced pressure to obtain 4.37 g (90%) of a colorless and transparent liquid. When this liquid was subjected to 1 H-NMR measurement at 270 MHz, the spectrum shown in FIG. 2 was obtained. The δ values and their assignments are as shown in Table 2. The obtained liquid was confirmed to be the following compound [8] containing catechol protected by an organic substituent.
【００４４】[0044]
【表２】 [Table 2]
【００４５】[0045]
【化１８】 Embedded image
【図1】第１図は参考例１で得られた生成物の1H-NMRス
ペクトルを示す。FIG. 1 shows the 1 H-NMR spectrum of the product obtained in Reference Example 1.
【図2】第２図は実施例１で得られた生成物の1H-NMRス
ペクトルを示す。FIG. 2 shows a 1 H-NMR spectrum of the product obtained in Example 1.
Claims (3)
式［１］で表される有機ケイ素化合物。 【化１】 （式中、Ｒ1、Ｒ2およびＲ3は炭素数１から６のアルキ
ル基、フェニル基またはアルコキシ基であり、互いに同
じであっても異なっていても良く、Ｒ1、Ｒ2またはＲ3
の少なくとも１つはアルコキシ基である。Ｒ5およびＲ6
は炭素数１から６のアルキル基またはフェニル基を示
し、互いに同じであっても異なっていても良い。Ｒ4は
炭素数２から６のアルキレン基を示す）1. An organosilicon compound having a protected catechol group and represented by the following general formula [1]. Embedded image (Wherein, R 1 , R 2 and R 3 are an alkyl group having 1 to 6 carbon atoms, a phenyl group or an alkoxy group, which may be the same or different, and R 1 , R 2 or R 3
At least one is an alkoxy group. R 5 and R 6
Represents an alkyl group having 1 to 6 carbon atoms or a phenyl group, which may be the same or different. R 4 represents an alkylene group having 2 to 6 carbon atoms)
Ｒ1、Ｒ2およびＲ3がエトキシ基であり、Ｒ5およびＲ6
がメチル基であり、Ｒ4が炭素数３の直鎖状のアルキル
基である、下記構造式［２］で表される請求項１記載の
有機ケイ素化合物。 【化２】 （式中、Ｍｅはメチル基であり、Ｅｔはエチル基であ
る。）2. In the general formula [1] according to claim 1,
R 1 , R 2 and R 3 are ethoxy groups, and R 5 and R 6
Is a methyl group, and R 4 is a linear alkyl group having 3 carbon atoms, and is represented by the following structural formula [2]. Embedded image (In the formula, Me is a methyl group and Et is an ethyl group.)
ことを特徴とする請求項１記載の有機ケイ素化合物の製
造方法。 工程（１）：少なくとも２個の水酸基がオルト位にある
トリヒドロキシベンゼンとカテコール基の保護用化合物
とを反応させて下記式［３］で表される化合物［３］を
得る。 【化３】 （式中においてＲ5およびＲ6は上記一般式［１］におけ
る意味と同義である。） 工程（２）：上記化合物［３］とハロゲン化アルケン
（但し、一方の分子末端に炭素二重結合を有する以外は
上記一般式［１］におけるＲ4と同じ炭素骨格を有し、
他方の分子末端にハロゲンを有する。）とを反応させて
下記式［４］で表される化合物［４］を得る。 【化４】 （式中、Ｒ7は、ハロゲン化アルケンにおけるハロゲン
を除いた残基であり、末端に炭素二重結合を有する。） 工程（３）：上記化合物［４］とシラン化合物Ｒ1Ｒ2Ｒ
3ＳｉＨ（但し、Ｒ1、Ｒ 2およびＲ3は上記一般式［１］
における意味と同義である。）とをヒドロシリレーショ
ン反応させる。3. The following reaction steps (1) to (3) are sequentially performed.
The method for producing an organosilicon compound according to claim 1, wherein
Construction method. Step (1): at least two hydroxyl groups are in the ortho position
Compounds for protection of trihydroxybenzene and catechol groups
To give a compound [3] represented by the following formula [3]
obtain. Embedded image(Where RFiveAnd R6In the general formula [1]
Has the same meaning as Step (2): Compound [3] and Halogenated Alkene
(However, except that it has a carbon double bond at one molecular end
R in the above general formula [1]FourHas the same carbon skeleton as
It has a halogen at the other molecular end. ) And react
A compound [4] represented by the following formula [4] is obtained. Embedded image(Where R7Is the halogen in the halogenated alkene
And has a carbon double bond at the end. Step (3): Compound [4] and silane compound R1RTwoR
ThreeSiH (however, R1, R TwoAnd RThreeIs the above general formula [1]
Has the same meaning as ) And the hydrosilation
Reaction.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7402648B2 (en) | 2004-11-05 | 2008-07-22 | Toagosei Co., Ltd. | Method for producing cyclic organic silicon compound and organic silicon resin having alcoholic hydroxyl group |
| US7432387B2 (en) | 2004-08-24 | 2008-10-07 | Toagosei Co., Ltd. | Process for producing organosilicon compound |
| JP2015182977A (en) * | 2014-03-25 | 2015-10-22 | 信越化学工業株式会社 | Organic silicon compound, adhesive composition, and article |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07252272A (en) * | 1994-03-11 | 1995-10-03 | Tatsuya Shono | Organic silicon compound and its production |
| JPH09241267A (en) * | 1996-03-08 | 1997-09-16 | Tatsuya Shono | Organosilicon compound and its production |
-
2001
- 2001-05-22 JP JP2001153237A patent/JP4543577B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07252272A (en) * | 1994-03-11 | 1995-10-03 | Tatsuya Shono | Organic silicon compound and its production |
| JPH09241267A (en) * | 1996-03-08 | 1997-09-16 | Tatsuya Shono | Organosilicon compound and its production |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7432387B2 (en) | 2004-08-24 | 2008-10-07 | Toagosei Co., Ltd. | Process for producing organosilicon compound |
| US7402648B2 (en) | 2004-11-05 | 2008-07-22 | Toagosei Co., Ltd. | Method for producing cyclic organic silicon compound and organic silicon resin having alcoholic hydroxyl group |
| JP2015182977A (en) * | 2014-03-25 | 2015-10-22 | 信越化学工業株式会社 | Organic silicon compound, adhesive composition, and article |
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