JPH0517227B2 - - Google Patents
Info
- Publication number
- JPH0517227B2 JPH0517227B2 JP1140684A JP1140684A JPH0517227B2 JP H0517227 B2 JPH0517227 B2 JP H0517227B2 JP 1140684 A JP1140684 A JP 1140684A JP 1140684 A JP1140684 A JP 1140684A JP H0517227 B2 JPH0517227 B2 JP H0517227B2
- Authority
- JP
- Japan
- Prior art keywords
- tcdc
- epoxy
- acid
- compound
- present
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- FBZANWBJFUBGEF-UHFFFAOYSA-N 4-oxatetracyclo[6.2.1.02,7.03,5]undecane-9,10-dicarboxylic acid Chemical compound C12C3OC3CC2C2C(C(=O)O)C(C(O)=O)C1C2 FBZANWBJFUBGEF-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 description 7
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 125000003700 epoxy group Chemical group 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 3
- 150000001451 organic peroxides Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- XYPISWUKQGWYGX-UHFFFAOYSA-N 2,2,2-trifluoroethaneperoxoic acid Chemical compound OOC(=O)C(F)(F)F XYPISWUKQGWYGX-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 description 1
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 1
- ITDQHLYEMHBLAN-UHFFFAOYSA-N CCC=CCCCC(C(C)C(=O)O)C(=O)O Chemical compound CCC=CCCCC(C(C)C(=O)O)C(=O)O ITDQHLYEMHBLAN-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- SIOVKLKJSOKLIF-UHFFFAOYSA-N bis(trimethylsilyl)acetamide Chemical compound C[Si](C)(C)OC(C)=N[Si](C)(C)C SIOVKLKJSOKLIF-UHFFFAOYSA-N 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 108700039708 galantide Proteins 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- LULAYUGMBFYYEX-UHFFFAOYSA-N metachloroperbenzoic acid Natural products OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
- Epoxy Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Description
本発明は、構造式〔１〕で表される
３，４−エポキシ−トリシクロ〔５，２，１，
02、6〕デカン−８，９−ジカルボン酸（以下Ｅ
−TCDCと略称する）に関するものである。本発
明の化合物は、新規化合物で分子内に反応性に富
むエポキシ基と二つのカルボキシル基を同時に有
する事を特徴としており、耐熱性に有利なトリシ
クロデカン骨格が存在する為エポキシ樹脂、エポ
キシ硬化剤、ポリエステル樹脂その他新しい型の
多官能性モノマーとして新規な性能が期待され
る。更に農医薬の新規な中間体としての用途にも
興味が持たれる。
本化合物の利用法としては
(1) 単独重合によるポリエステル樹脂とする方法
(2) エポキシ基を先に重合させてカルボキシル基
を持つ高分子を作り、これを利用する方法
(3) カルボキシル基を使用した重合を先に行いエ
ポキシ基をもつ高分子を作り、これを利用する
方法
等が考えられる。何れの方法で得られる高分子も
架橋密度の高いものが期待される。
本化合物の製造方法は、次頁のスキームで示さ
れる。
即ち、出発物質であるジシクロペンタジエン
（以下DCPDと略称する）からトリシクロ〔５，
１，02.6〕デセ−３−エン−８，９−ジカルボン
酸（以下TCDCと略称する）を得る方法は、本発
明者らが既に特許出願している。（特願昭57−
190429）
このTCDCのエポキシ化によるＥ−TCDCの製
造には酸素酸化、金属酸化物酸化、過酸化水素酸
化、有機過酸化物その他の方法が適用出来る。然
し、これらの中では目的物の収率の面から有機過
酸化物酸化法が好ましい。
有機過酸化物としては過安息香酸、メタクロロ
過安息香酸、過ギ酸、過酢酸、トリフルオロ過酢
酸等が挙げられるが、実用的には過酢酸が好まし
い。
更に目的Ｅ−TCDCエポキサイド環がジオール
に水和開裂する事を抑制する為にリン酸水素二ナ
トリウムのような塩基を共存させると目的Ｅ−
TCDCの収率は向上する。又反応温度は50℃以下
で行う事が好ましい。
以下実施例によつて本発明を詳細に説明する
が、本発明はこれらによつて何等制限されるもの
ではない。
実施例
TCDC22.2ｇ（0.1Mo1）、１，４−ジオキサン
60ｇ、リン酸水素二ナトリウム５ｇを200ml四口
フラスコに仕込み、マグネチツクスタラーで撹拌
しながら、40％過酢酸28.5ｇ（0.15Mol）を５〜
10℃で30分間で滴下した。滴下後徐々に室温に戻
しながら更に４時間撹拌した。
反応後、反応液を50℃以下で減圧濃縮し粗結晶
を得た。この結晶に水30ｇを加え、しばらく撹拌
後濾過し結晶を分離した。次に60℃で４時間減圧
乾燥し白色結晶18.9ｇを得た。
この結晶をジメチルホルムアマイドに溶解しガ
スクロマトグラフイイによる分析の結果は、原料
TCDCとは異なる単一ピークが出現した。
この結晶について、以下の分析を行つた。
マススペクトル〔ビス（トリメチルシリル）ア
セトアミドでシリル化して測定〕〔ｍ／ｅ（％）〕
367（Ｍ−15）（53）、261（40）、147（100）
融 点
191〜193℃13
C−NMRスペクトル（P.P.M）
174.231、173.961、60.357、58.786、46.921、
44.267、44.104、43.779、43.292、41.558、
37.387、27.527
赤外スペクトル
3170、2930、1720〜1700、1220、920、835（cm
-1）
元素分析
C12H14O5＝238.24として
The present invention is represented by structural formula [1] 3,4-epoxy-tricyclo[5,2,1,
0 2 , 6 ] Decane-8,9-dicarboxylic acid (hereinafter referred to as E
- abbreviated as TCDC). The compound of the present invention is a new compound and is characterized by simultaneously having a highly reactive epoxy group and two carboxyl groups in the molecule.The compound of the present invention is characterized by having a highly reactive epoxy group and two carboxyl groups at the same time in the molecule, and because it has a tricyclodecane skeleton that is advantageous for heat resistance, it can be used for epoxy resin, epoxy curing, etc. It is expected to have novel performance as a new type of polyfunctional monomer such as additives, polyester resins, and other new types of polyfunctional monomers. Furthermore, there is interest in its use as a novel intermediate for agricultural medicines. Methods of using this compound include (1) producing polyester resin through homopolymerization; (2) polymerizing epoxy groups first to create a polymer with carboxyl groups; and (3) using carboxyl groups. One possible method is to first conduct polymerization to create a polymer with epoxy groups, and then utilize this. Polymers obtained by either method are expected to have a high crosslinking density. The method for producing this compound is shown in the scheme on the next page. That is, the starting material dicyclopentadiene (hereinafter abbreviated as DCPD) is converted to tricyclo[5, The present inventors have already filed a patent application for a method for obtaining dec-3-ene-8,9- dicarboxylic acid (hereinafter abbreviated as TCDC). (Special application 1987-
190429) Oxygen oxidation, metal oxide oxidation, hydrogen peroxide oxidation, organic peroxide, and other methods can be applied to the production of E-TCDC by epoxidizing TCDC. However, among these methods, the organic peroxide oxidation method is preferred from the viewpoint of yield of the target product. Examples of the organic peroxide include perbenzoic acid, metachloroperbenzoic acid, performic acid, peracetic acid, trifluoroperacetic acid, etc., but peracetic acid is preferred from a practical standpoint. Furthermore, in order to suppress the hydration cleavage of the objective E-TCDC epoxide ring to the diol, if a base such as disodium hydrogen phosphate is present in the coexistence, objective E-
The yield of TCDC is improved. Further, the reaction temperature is preferably 50°C or lower. EXAMPLES The present invention will be explained in detail below with reference to Examples, but the present invention is not limited by these in any way. Example TCDC22.2g (0.1Mo1), 1,4-dioxane
60g of disodium hydrogen phosphate and 5g of disodium hydrogen phosphate were placed in a 200ml four-necked flask, and while stirring with a magnetic stirrer, 5 to 28.5g (0.15Mol) of 40% peracetic acid was added.
The mixture was added dropwise at 10°C for 30 minutes. After the dropwise addition, the mixture was further stirred for 4 hours while gradually returning to room temperature. After the reaction, the reaction solution was concentrated under reduced pressure at 50°C or lower to obtain crude crystals. 30 g of water was added to the crystals, stirred for a while, and then filtered to separate the crystals. Next, it was dried under reduced pressure at 60° C. for 4 hours to obtain 18.9 g of white crystals. The results of dissolving these crystals in dimethylformamide and analyzing them using gas chromatography show that the raw material
A single peak different from TCDC appeared. The following analysis was performed on this crystal. Mass spectrum [measured by silylation with bis(trimethylsilyl)acetamide] [m/e (%)] 367 (M-15) (53), 261 (40), 147 (100) Melting point 191-193℃ 13 C- NMR spectrum (PPM) 174.231, 173.961, 60.357, 58.786, 46.921,
44.267, 44.104, 43.779, 43.292, 41.558,
37.387, 27.527 Infrared spectrum 3170, 2930, 1720~1700, 1220, 920, 835 (cm
-1 ) Elemental analysis C 12 H 14 O 5 = 238.24
【表】
以上より本化合物は、構造式〔１〕で示される
３，４−エポキシ−トリシクロ〔５，２，１，
02、6〕デカン−８，９−ジカルボン酸である事
が判明した。[Table] From the above, this compound is 3,4-epoxy-tricyclo[5,2,1,
0 2 , 6 ] decane-8,9-dicarboxylic acid.
Claims (1)
02、6〕デカン−８，９−ジカルボン酸。[Claims] 1 Represented by structural formula [1] 3,4-epoxy-tricyclo[5,2,1,
0 2 , 6 ] Decane-8,9-dicarboxylic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1140684A JPS60156682A (en) | 1984-01-25 | 1984-01-25 | 3,4-epoxy-tricyclo(5,2,1,02,6)decane-8,9-dicarboxylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1140684A JPS60156682A (en) | 1984-01-25 | 1984-01-25 | 3,4-epoxy-tricyclo(5,2,1,02,6)decane-8,9-dicarboxylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60156682A JPS60156682A (en) | 1985-08-16 |
| JPH0517227B2 true JPH0517227B2 (en) | 1993-03-08 |
Family
ID=11777135
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1140684A Granted JPS60156682A (en) | 1984-01-25 | 1984-01-25 | 3,4-epoxy-tricyclo(5,2,1,02,6)decane-8,9-dicarboxylic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60156682A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4539791B2 (en) * | 2000-05-19 | 2010-09-08 | 日産化学工業株式会社 | Acrylate compound and production method thereof |
| US9447240B2 (en) * | 2011-04-28 | 2016-09-20 | Nissan Chemical Industries, Ltd. | Polyimide precursor modified with dicarboxylic acid anhydride, imidized polyimide and liquid crystal aligning agent using it |
-
1984
- 1984-01-25 JP JP1140684A patent/JPS60156682A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60156682A (en) | 1985-08-16 |
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