JPS58150520A - Ring-opening of bicyclic compound - Google Patents
Ring-opening of bicyclic compoundInfo
- Publication number
- JPS58150520A JPS58150520A JP57033637A JP3363782A JPS58150520A JP S58150520 A JPS58150520 A JP S58150520A JP 57033637 A JP57033637 A JP 57033637A JP 3363782 A JP3363782 A JP 3363782A JP S58150520 A JPS58150520 A JP S58150520A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- acid
- water
- organic acid
- ring
- 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.)
- Granted
Links
- -1 bicyclic compound Chemical class 0.000 title abstract description 7
- 238000007142 ring opening reaction Methods 0.000 title abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 150000007524 organic acids Chemical class 0.000 claims abstract description 17
- 238000010494 dissociation reaction Methods 0.000 claims abstract description 8
- 230000005593 dissociations Effects 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 7
- 235000013305 food Nutrition 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 6
- 210000000214 mouth Anatomy 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 2
- 125000002619 bicyclic group Chemical group 0.000 abstract 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 abstract 2
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 abstract 1
- 125000000962 organic group Chemical group 0.000 description 8
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 235000005985 organic acids Nutrition 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 210000003323 beak Anatomy 0.000 description 2
- 239000005548 dental material Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- DILXLMRYFWFBGR-UHFFFAOYSA-N 2-formylbenzene-1,4-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(S(O)(=O)=O)C(C=O)=C1 DILXLMRYFWFBGR-UHFFFAOYSA-N 0.000 description 1
- TVEXGJYMHHTVKP-UHFFFAOYSA-N 6-oxabicyclo[3.2.1]oct-3-en-7-one Chemical compound C1C2C(=O)OC1C=CC2 TVEXGJYMHHTVKP-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical class ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 241000254158 Lampyridae Species 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 210000004907 gland Anatomy 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
【発明の詳細な説明】 本発−はビシクー化合物のｍｓ方法に関する。[Detailed description of the invention] The present invention relates to a ms method for biscicou compounds.
詳しくはビシクー化合物を開部するに際し、酸解離定数
（ＦＫａ）が１．５以上の有機酸と水とを触媒として用
いるビシタロ化合物のｌｌ５１方法である。Specifically, this is the 1151 method for biscicou compounds, in which an organic acid with an acid dissociation constant (FKa) of 1.5 or more and water are used as catalysts to open the biscicou compound.
ビシクロ化合物は従来塩化ビニル樹脂の安定剤、瞭草剤
勢の用途に種々の種類の化合物が使用されさることが知
られている。またこれらの公知の方法でビシタロ化合物
をａｍする場合は開数ＫＢ Ｐｇ ０１ ｔｇ 、Ｐシ
イＯν５ＢＯｓＮ 勢の触媒が使用される。これらの
触媒は確かにビシクロ化食物の一１１Ｋ有効であるが該
ビシクロ化合物の用途によっては使用出来ない場合があ
る１例えば本発明者勢はビシクロ化合物を歯科用材料と
して使用することを試みた。しかしながら従来公知の触
媒を口腔内で使用することが出来ず実質的に歯科用材料
として使用することは出来なかった。It is known that various types of bicyclo compounds have been conventionally used as stabilizers for vinyl chloride resins and as herbicides. In addition, when a bisitalo compound is amperated by these known methods, a catalyst having a numerical aperture of KB Pg 01 tg and PsiOv5BOsN is used. Although these catalysts are certainly effective in preparing bicyclo-converted foods, they may not be usable depending on the use of the bicyclo compound.For example, the inventors of the present invention attempted to use the bicyclo compound as a dental material. However, conventionally known catalysts could not be used in the oral cavity and could not be used as dental materials.
そのために１本発明の闘的は口腔内でも十分に使用出来
るビシクー化合物のＷｓｌｌ触謀をｅｕｉすることにあ
る。上記目的の達成のため本発明看勢は鋭意触媒の一発
研究を行つて来た。その結果、特定の有機−と水とより
なる触媒が優れたビシクロ化合物の開法反応のための触
媒となることを見出し本ｇＩｋ嘴を完成するに至うた。To this end, one advantage of the present invention is to utilize the Wsll action of a biscicou compound that can be used satisfactorily even in the oral cavity. In order to achieve the above object, the inventors of the present invention have been conducting intensive research on catalysts. As a result, they found that a catalyst consisting of a specific organic compound and water is an excellent catalyst for open-method reactions of bicyclo compounds, and completed the book GIk Beak.
本発明はビシクロ化合物を開渡するＫＩＩＬ、酸鱗離定
数（ＰＫａ）が１．Ｓ以上の有＊＊と水とを触媒として
用い番ことを畳黴とするビシクロ化合物の開衰方渋であ
る一
本発明の対象となるビシクロ化合物はビシクる化合物で
あれば４１Ｋｌｌ定されるものではない。The present invention has a KIIL which releases a bicyclo compound, and an acid scale separation constant (PKa) of 1. This is the development and deterioration process of bicyclo compounds that use S or higher and water as a catalyst, and the bicyclo compounds that are the subject of the present invention are those that are defined as 41 Kll if they are bicyclo compounds that are subject to the present invention. isn't it.
（式中、員１％ １１ は同種又は異種の水素又は−
価の有機基を示す）で示されゐビシクー化合物が最も代
表的なものである。上記−価の有機基は％Ｋｌｌ定され
ず如何なるものを用いてもよい。(In the formula, the member 1% 11 is the same or different hydrogen or -
The most typical example is the ibisicu compound, which is represented by (representing a valent organic group). The above-mentioned -valent organic group is not specified in %Kll, and any group may be used.
に例示すれば、０Ｈｓ−１Ｏｓ Ｈｓ−１Ｒ−Ｏｓ Ｈ
ｌ−１ｉｅ。For example, 0Hs-1Os Hs-1R-Os H
l-1ie.
−Ｃｍ ｌｌｖ −、、ｎ−０４Ｈｅ ＋、ｉｓｏ −
Ｏｗ Ｈｕ −％ ０ｎＨｔ＋−等の飽和炭化水素残基
：ｉ、０−０Ｈ−基、０ｆｌｓ−ＯＨ−Ｃト基、［３−
基等を有する不飽和炭化水素残基；ｙｕ、−１ＯＨｍＮ
Ｅ−１０−Ｍト勢の７々）基を會む有機基： ＣＴｌａ
０Ｏ１ｉＨ−１ＯＨＩ ｍＨｃｏｙｉ−、（３−００
輩■−勢のアンド基を含む有機基：０１ｌｓｌＨ０００
Ｃｆ Ｈ＠−１ＯＨａ （！ Ｈ−側００００迅−勢の
ウレタン基を含む有機基；Ｃｍ嘗−０１０００−１ＯＨ
，１＝ｏ（ＯＲ，）０００−１ＯＨｓ口０ＨＯＯＯＯ迅
−１ＯＨ，露０（０１１ｍ ） ００００Ｍｔ−１Ｏ１
ｉｌ＠ ｍｏ（Ｏｌｌｓ ）０００（ＯＨｔ ＯＨＩ
Ｏ）ｍｌ 、ＯＨ菅リす＃勢の残基；これらの有機基
で、一部叉は全部の水嵩原子がハｐゲン原子、ヒトレキ
７等で置換されている有機基等である。-Cmllv-,,n-04He+,iso-
Saturated hydrocarbon residues such as Ow Hu -% 0nHt+-: i, 0-0H- group, 0fls-OH-Cto group, [3-
Unsaturated hydrocarbon residue having groups, etc.; yu, -1OHmN
Organic group meeting E-10-M group 7): CTla
0O1iH-1OHI mHcoyi-, (3-00
Organic group containing the and group: 01lslH000
Cf H@-1OHa (! Organic group containing a urethane group with 0000 rapidity on the H- side; Cm嘗-01000-1OH
,1=o(OR,)000-1OHs 口0HOOOO quick-1OH, dew 0(011m) 0000Mt-1O1
il@mo(Olls)000(OHt OHI
O) ml, OH kaniri group residues; These organic groups include organic groups in which some or all of the water bulk atoms are substituted with Hapgen atoms, Hitoreki 7, etc.
本発明の最大め特徴は前記ビシクー化合物な一讃するに
際し、使用する触＊にある。即ち本発明の触媒は酸解離
定数（ＰＩａ）が１．１以上の有＊＊と水とよりなるも
のである。The most important feature of the present invention lies in the method used when evaluating the biscicou compound. That is, the catalyst of the present invention is composed of a compound having an acid dissociation constant (PIa) of 1.1 or more and water.
上ｌｅ酸解離定款（ＰＫａ）が１．６以上となる有＊＊
は例えば化学便ｔｉ＆費−１，＠１（１４〜館１０６１
１頁（１８１Ｅ１４１年！月２ｓ日、丸善株式金社発行
）Ｋｌｅ載されているよ５な有機酸が特Ｋｌｌ定されず
用いられる。４１に好適に１１１！用される該有機酸を
具体＃に挙げれば、例えば酢酸、メタクリル酸、アク亨
ル駿、Ｐ−トルエンスルフィン酸、ビニルネス７オン１
１１、Ｆ−）ルエンＸＳネン駿、ｔ−Ｈｓ酸、ンクロヘ
キナンカルメン酸、ダリコール蒙、プロピオン酸、漉石
酸、クエン酸、アジピン酸、プハタ歇譬の有機のカルダ
ン酸、リン酸、スルホン酸化音物である。Pleated acid dissociation articles (PKa) are 1.6 or higher**
For example, chemical mail ti&cost-1, @1 (14~Kan 1061
Page 1 (181E141! Month 2s, published by Maruzen Co., Ltd. Kinsha) The organic acids listed in Kle are used without being specified. 111 suitable for 41! Specific examples of the organic acids used include acetic acid, methacrylic acid, acrylic acid, P-toluenesulfinic acid, vinylnes 7-one 1
11, F-) Luene It is an oxidized sound.
本実１１１に１にける触媒は上記特定の有機酸化合物が
存在することが必要であるが鋏有機軟化会物のみしか存
在しない場合はｗＩＩ記ビシクー化合物が１ｌｌｉＩ！
ｊｔ応を生起することが出来ない０本発明にあっては上
記有機酸化金物の他に水が反応系にを在することが必要
である。The catalyst in Honjitsu 111-1 requires the presence of the above-mentioned specific organic acid compound, but if only the scissor organic softening compound is present, the biscicou compound described in wII is 1lliI!
In the present invention, in which the jt reaction cannot occur, it is necessary that water be present in the reaction system in addition to the above-mentioned organic metal oxide.
本発明の触媒系に凝げる上記水の裏奄がビシ！諺化会物
のＷａＩＩＫどのように作用をするのかその機構は明ら
かで＆家ない０本発明者勢は該水の存在によって有機酸
の解離が促進されるため、ビッタ固化合物のｌｌ１１反
応が生起すると識定している。The lining of the water that condenses in the catalyst system of the present invention is amazing! The mechanism of how WaIIK works is clear and the present inventors believe that the presence of water promotes the dissociation of organic acids, which causes the II11 reaction of the Bitta solid compound. Then it is identified.
本発明の触媒は前記のよ５に水が存在することが必要で
あるが水の存在は必ずしもビシクー化合物のＷＲ衰反応
後の生成物の処１１に好適とは言えない、そのために反
応系に存在する水の量は少ない程好ましい、従ってビシ
クロ化合物の１ｌＩｆＩＡと反応条件に応じて予め必要
な有機酸と水の量を決定しておくのが好ましい、一般に
はビシクロ化合物に対して有機酸及び水をそれぞれｏ、
ｏ １〜！Ｏ−好ｔシ＜ｓｔｏ、１−１０％＃）ｌｌｓ
となるよ５に選べば好適である。The catalyst of the present invention requires the presence of water in the above-mentioned 5, but the presence of water is not necessarily suitable for the treatment 11 of the product after the WR decay reaction of the biscou compound. The smaller the amount of water present, the better. Therefore, it is preferable to determine the amounts of organic acid and water required in advance according to the 1lIfIA of the bicyclo compound and the reaction conditions. o, respectively.
o 1~! O-liketshi<sto, 1-10%#)lls
It is preferable to select 5.
本実−におけるビシクロ化合物０ＩＩＩ１１方法は籍に
ｌＫ定されず、公知の方法が採用される。一般にはビシ
クー化合物が液状であればそのま一１固体状であればメ
チルメタクリレート、メデルアタνレート等の適轟な溶
媒にｍｓした後、餉配有機酸及び水を添加混食すればよ
い。また反応は如何なる態様で実施してもよいが一般に
は部枠中で、或いはプレート間に流込み中ヤスティンダ
ｙ＃式で１！論する書味がしばしば好適に採用される。The method for preparing the bicyclo compound 0III11 in this work is not specified in the book, and a known method is employed. In general, if the biscou compound is in liquid form, it may be left as is; if it is in solid form, it may be mixed with a suitable solvent such as methyl methacrylate or medel ata ν-late, and then mixed with the organic acid and water. The reaction may be carried out in any manner, but generally it is carried out in a frame or in a Yastin die while being poured between plates. A style of writing that discusses is often preferred.
更Ｋまた前記ビシクロ化合物の開法反応の条件は特Ｋ［
定されず適宜選択して採用すればよいが、過１１Ｏ℃〜
２００℃好ましくは３０’Ｃ〜１３１Ｃの温度下に数分
〜歇呻間で反応させればよい。Moreover, the conditions for the opening reaction of the bicyclo compound are specified below.
Although it is not specified and can be selected and adopted as appropriate,
The reaction may be carried out at a temperature of 200°C, preferably 30'C to 131C, for several minutes to a few minutes.
本発明０触謀は前記酸解離定数が１，５以上の有機酸が
好適に使用されるが、４１にビシクロ化合物の一積反応
を歯科用材料として口腔中で実施する場合は鋏酸郷離定
数が２．０以上好ましくは墨、ｆ１以上更に好ましくは
４．０以上のものを使用するととによって好適にｌＩＩ
施出来る。従って従来日腺中でａｍ出来る触ｍがなかっ
たため歯科用等の用途に使Ｍ出来なかったビシクロ化合
物を新しい素材として使用可能にした本発明の寄与は幹
わめて大きいものである。In the present invention, an organic acid having an acid dissociation constant of 1.5 or more is preferably used. It is preferable to use a constant of 2.0 or more, preferably black, f1 or more, more preferably 4.0 or more.
It can be done. Therefore, the contribution of the present invention is extremely large, as it has made it possible to use bicyclo compounds as new materials, which could not be used for dental purposes or the like due to the lack of atom formation in the glands.
本発明の実施ＫＩＩし、質東−科業界で公知の充填剤、
接着剤勢に本ＩＡ嘴で得られる重合体を混合して用いる
ことも、また本発明の反応に際し、歯科用に使用される
ことが公知の重合性単量体を混合して用いることかで館
る。特に混合に好適な重合性単量体を例示すると、メチ
ルメタクやし一ト、アクリレート、ヒドロキシエチルア
タリレート、ヒドロキシエチルアタリレート、エテレン
ダリコールメタクリレート、シー又はトリー又はテトラ
ーエチレングリコールジアタνレート、ビスフヮノール
ムジアクリレート、！、！’−ビス（メタアク９ａキシ
エトキシ７、ニル）プロパン、２．２′−ビス（ｒ−メ
タアクリＩ＋Ｉ命シー！−ヒトμキシグロボキタフ、ニ
ル）プ！パン、Ｍ、菖−ジメチルアミノエチルメタタリ
レート、ダリシジルメタアタリレーＦ１スチレン、酢酸
ビニＬル勢である。また反応時の粘度や硬化速度等を調
節するためポリエチルメタクリレート、ポリエチルメタ
クリレート、ボザヌテレン、不飽和ポリエステル樹脂、
エポキシアクツレ−）１１１１等の高分子９化合物の添
ｍも有効である。According to the implementation of the present invention, fillers known in the field of quality and technology,
It is also possible to mix and use the polymer obtained with the present IA beak in the adhesive, or to mix and use a polymerizable monomer known to be used for dentistry in the reaction of the present invention. House. Examples of particularly suitable polymerizable monomers for mixing include methyl methacrylate, acrylate, hydroxyethyl acylate, hydroxyethyl acylate, eterenda glycol methacrylate, cy-, tri-, or tetra-ethylene glycol diathrate, Bisphenol acrylate! ,! '-bis(methacrylic 9a xyethoxy7, nil)propane, 2,2'-bis(r-methacrylic I+I life sea!-human μxyglobokitav, nil)p! Pan, M, irises-dimethylaminoethyl metatarylate, dalicidyl metatarylate F1 styrene, vinyl acetate L group. In addition, polyethyl methacrylate, polyethyl methacrylate, bozanutelene, unsaturated polyester resin, etc. are used to adjust the viscosity and curing speed during the reaction.
It is also effective to add 9 polymeric compounds such as epoxy Acturay) 1111.
本発明を更に具体的Ｋｌ［するため以下実施例を挙げて
説明するが本発明けこれらの実施例に＠定されるもので
はない。In order to make the present invention more specific, the present invention will be described below with reference to Examples, but the present invention is not limited to these Examples.
実施例１〜７、比ｌ２Ｉｌ１１〜！
１．４−ジエチル−Ｌ Ａ、 ７−トリオキサビシクロ
（ｔ、２．２）オクタン器１ｔ−ｓ−の封管用アングル
Ｋ１１ｌ１人した。これに、下記第１表に示す有機酸及
び水を添ｔＩｓ１１ただちにドライアイス中で凍結させ
た。その後＃１分閾脱気し封管した。Examples 1-7, ratio l2Il11~! 1.4-diethyl-LA, 7-trioxabicyclo (t, 2.2) octane container 1t-s- Angle for sealing tube K11l 1 person. To this, an organic acid and water shown in Table 1 below were added and immediately frozen in dry ice. Thereafter, the tube was degassed for #1 minute and sealed.
反応はアンプ身中の混合物を溶解後、６７℃で２０峙闘
行なうた。The reaction was carried out at 67°C for 20 hours after dissolving the mixture in the amplifier body.
触媒能の指針とな奄ビシクー獄の開票率は反応前の１．
４−ジエチル−２，！、 ７−ドリオキナビシクロ（２
，！、！ ）オクタン及び反応螢の混合物の”Ｈ−ＭＭ
Ｒスベタトルから計算した０反応前後ノヒシター瀧の６
つのメチレンゲ四トンＫｌ＆づ＜ａｍ強度をそれぞれ１
、ａ′その倫のプロトンに基づくｌｌ教＊＊を１．１′
とすると一事率Ｉ■は次式で表わすことができる。The voting rate of the Ambishiku prison, which is a guideline for catalytic ability, is 1.
4-diethyl-2,! , 7-Drioquinabicyclo (2
，! ,! ) “H-MM” of a mixture of octane and reactive fireflies
Nohisiter Taki's 6 before and after 0 reaction calculated from R Subetator
Four methylene chlorides each have a strength of 1
, a'1.1'
Then, the event rate I can be expressed by the following equation.
上記測定により得られた結果を下記第１表に示す。又、
比較として１．４−ジエチル−２，６，７−ドリオキナ
ビシクロ（２，２，２）オクタンにビシクロａｍ触媒Ｅ
して公知のＢ’ｌ！ｓ ＠Ｏ）！ｔｓを添加した場合及
び有機酸のみを添加した場合につき上記と同様の測定を
行ない、その結果を下記第１表に併記した。The results obtained from the above measurements are shown in Table 1 below. or,
For comparison, 1,4-diethyl-2,6,7-dolioquinabicyclo(2,2,2)octane was treated with bicycloam catalyst E.
The well-known B'l! s @O)! Measurements similar to those described above were carried out when ts was added and when only organic acid was added, and the results are also listed in Table 1 below.
実施例１〜７で用いた１、４−ジエチル−２，６゜７−
トリオキサビシクロ（２，２，２）オクタンを１−エチ
ｋ −４−メタクリルキシメチル−２，６゜７−トリオ
キナビシクロ（２，！、りオクタンに変え、反応温度を
７０’ＣＫした以外は実施１１１〜７と同様な実験を行
なった結果をＩＩｔｍｌＫ示した。また、ビアクロｍ１
ｌｌ触謙として公知のＢν巻・０１ｔｓを添加した場食
に９１上記と同様の実験を行ない、その結果を第２１！
ｌ！に併記した。1,4-diethyl-2,6°7- used in Examples 1 to 7
Except that trioxabicyclo(2,2,2)octane was changed to 1-ethylk-4-methacryloxymethyl-2,6°7-trioxabicyclo(2,!,rioctane) and the reaction temperature was changed to 70'CK. IItmlK showed the results of experiments similar to those in Examples 111 to 7.
91 An experiment similar to the above was conducted on a field food containing Bν volume/01ts, which is known as ll.
l! Also listed.
手続補正書
昭和５７年３月３１日
特許庁長官 島 １）春 樹 殿
１、事件の表示 特願昭５７− うろｚａ７２、発
明（Ｄ名称 ｌ：／シフｏ４ｔ：、珍杓ｎ用課力毛
３、補正をする者
事件との関係 特許出願人
住 所 山口県徳山市御影町１番１号名
称 （３１８）徳山曹達株式会社代表者福田克己
４、代理人
郵便番号 １０５
居 所 東京都港区西新橋１丁目４番５号５゜
補正の対象
願１及び明細書全文
６゜補正の内容
願書及び明細書の浄書（内容に変更なし）手続補正型
昭和５７年５月Ｉ２−日
特許庁長官 島 １）春 樹 殿
１、事件の表示 特島暢５７−３３６３７月２、発
明の名称 ビシクロ化合物の開環方法な説明」の欄
５、補正の内容
（１） 明細書第１頁
特許請求の範囲を別紙のとおり補正する。Procedural amendment March 31, 1980 Commissioner of the Japan Patent Office Shima 1) Haruki Tono 1, Indication of the case Patent application 1982-Uroza72, Invention (D name l:/Shifu o4t:, Charge hair for rare scoop n) 3. Relationship with the case of the person making the amendment Patent applicant address: 1-1 Mikage-cho, Tokuyama City, Yamaguchi Prefecture
Name (318) Tokuyama Soda Co., Ltd. Representative Katsumi Fukuda 4 Agent postal code 105 Address 1-4-5 Nishi-Shinbashi, Minato-ku, Tokyo 5゜Application subject to amendment 1 and full text of the specification 6゜Application for contents of amendment and the engraving of the specification (no change in content), procedural amendment May 12, 1980, Commissioner of the Japan Patent Office Shima 1) Haruki Tono 1, indication of the case Noburu Tokushima 57-3363 July 2, title of the invention Bicyclo compound Column 5, "Explanation of Ring Opening Method", Contents of Amendment (1) The claims on page 1 of the specification are amended as shown in the attached sheet.
（３） 同 第６頁１４行（２ケ所） 補正する。(3) Same page 6, line 14 (2 locations) to correct.
以上
別 紙
補正後の特許請求の範囲
「（１） ビシクロ化合物を開環するに際し、酸解離定
数（ＰＫａ ）が１．５以上の有機酸と水とを触媒とし
て用いることを特徴とするビシクロ化合物の開環方法。Claims as amended above (1) A bicyclo compound characterized in that an organic acid with an acid dissociation constant (PKa) of 1.5 or more and water are used as a catalyst in ring-opening the bicyclo compound. ring-opening method.
（２） ビシクロ化合物が一般式、
（式中、Ｒ＋ 、Ｒｔは同種又は異種の水素又は−価の
有機基を示す）で示されるビシクロ化合物である特許請
求の範囲（１）記載の方法。(2) The method according to claim (1), wherein the bicyclo compound is a bicyclo compound represented by the general formula: (wherein R+ and Rt represent the same or different hydrogen or -valent organic group).
（３） 有機酸及び水がビシクロ化合物に対してそれぞ
れ０．０１〜２０ｗｔ％、使用される特許請求の範囲（
１）記載の方法。 」
＝１６(3) The scope of the claim (
1) The method described. ” = 16
Claims (2)
数（ＰＫａ）が１．ｉｋＬ上の有機酸と水とを触媒とし
て用いることを特徴とするビシクロ化合物の−ｓ″ｊ５
法。(1) When counting the bisicou compound, the acid dissociation constant (PKa) is 1. -s″j5 of a bicyclo compound characterized by using an organic acid on ikL and water as a catalyst
Law.
機基を示す）で示されるビシクロ化合物である譬許請求
のａｍθ）Ｉｅ載の方法。 （！Ｉ） 有機酸及び水がビシクロ化合物に対してそ
れぞれ口、・１〜２０チ、使用される特許四求の颯１１
（１）記載の１機。(2) The amθ) Ie of the claim in which the bicyclo-containing food is a bicyclo compound represented by the general formula: Method. (!I) Patent No. 4 No. 11 in which organic acid and water are used in an amount of 1 to 20%, respectively, for a bicyclo compound.
(1) One aircraft mentioned.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57033637A JPS58150520A (en) | 1982-03-02 | 1982-03-02 | Ring-opening of bicyclic compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57033637A JPS58150520A (en) | 1982-03-02 | 1982-03-02 | Ring-opening of bicyclic compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58150520A true JPS58150520A (en) | 1983-09-07 |
| JPH0116250B2 JPH0116250B2 (en) | 1989-03-23 |
Family
ID=12391962
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57033637A Granted JPS58150520A (en) | 1982-03-02 | 1982-03-02 | Ring-opening of bicyclic compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58150520A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7850228B2 (en) | 2004-09-21 | 2010-12-14 | Toyota Jidosha Kabushiki Kaisha | Vehicle front structure |
-
1982
- 1982-03-02 JP JP57033637A patent/JPS58150520A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7850228B2 (en) | 2004-09-21 | 2010-12-14 | Toyota Jidosha Kabushiki Kaisha | Vehicle front structure |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0116250B2 (en) | 1989-03-23 |
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