JPH0222058B2 - - Google Patents
Info
- Publication number
- JPH0222058B2 JPH0222058B2 JP61067595A JP6759586A JPH0222058B2 JP H0222058 B2 JPH0222058 B2 JP H0222058B2 JP 61067595 A JP61067595 A JP 61067595A JP 6759586 A JP6759586 A JP 6759586A JP H0222058 B2 JPH0222058 B2 JP H0222058B2
- Authority
- JP
- Japan
- Prior art keywords
- structural formula
- chemical structural
- formula
- represented
- 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
- 150000001875 compounds Chemical class 0.000 claims description 7
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical class COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- OLZFZIXORGGLLS-UHFFFAOYSA-N 4-tert-butylcalix[8]arene Chemical compound C1C(C=2O)=CC(C(C)(C)C)=CC=2CC(C=2O)=CC(C(C)(C)C)=CC=2CC(C=2O)=CC(C(C)(C)C)=CC=2CC(C=2O)=CC(C(C)(C)C)=CC=2CC(C=2O)=CC(C(C)(C)C)=CC=2CC(C=2O)=CC(C(C)(C)C)=CC=2CC(C=2O)=CC(C(C)(C)C)=CC=2CC2=CC(C(C)(C)C)=CC1=C2O OLZFZIXORGGLLS-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 239000009719 polyimide resin Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229920006015 heat resistant resin Polymers 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- FYFDQJRXFWGIBS-UHFFFAOYSA-N 1,4-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=C([N+]([O-])=O)C=C1 FYFDQJRXFWGIBS-UHFFFAOYSA-N 0.000 description 1
- ZDFBKZUDCQQKAC-UHFFFAOYSA-N 1-bromo-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Br)C=C1 ZDFBKZUDCQQKAC-UHFFFAOYSA-N 0.000 description 1
- PWKNBLFSJAVFAB-UHFFFAOYSA-N 1-fluoro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1F PWKNBLFSJAVFAB-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012772 electrical insulation material Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Substances [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002076 thermal analysis method Methods 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
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Enzymes And Modification Thereof (AREA)
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は機能性高分子材料、人工酵素などの広
範な分野に用いられるカリクスアレン類の新規誘
導体及びその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel derivative of calixarenes used in a wide range of fields such as functional polymer materials and artificial enzymes, and a method for producing the same.
（従来の技術）
近年、電気・電子機器には多種類の高分子材料
が使用されている。特に耐熱性材料に対する要望
はますます増大し、応用範囲も電気絶縁材料、構
造材料、回路基板など多方面に展開されている。
なかでもポリイミド樹脂が新しい耐熱性高分子材
料として応用分野が著しく進展している。このポ
リイミド樹脂の原料となるものには、４，4′―ジ
アミノジフエニルスルホン（DDS）、４，4′―ジ
アミノジフエニルエーテルなどが存在し、これら
はそれぞれ対応するニトロ化合物の還元によつて
製造される。(Prior Art) In recent years, many types of polymer materials have been used in electrical and electronic devices. In particular, the demand for heat-resistant materials is increasing, and the range of applications is expanding to various fields such as electrical insulation materials, structural materials, and circuit boards.
Among these, polyimide resin is being used as a new heat-resistant polymer material, and its field of application is making remarkable progress. Raw materials for this polyimide resin include 4,4'-diaminodiphenyl sulfone (DDS) and 4,4'-diaminodiphenyl ether, which can be produced by reducing the corresponding nitro compounds. Manufactured.
（発明が解決しようとする問題）
しかしながら、これらを原料とする上記ポリイ
ミド樹脂は加工性に難点があつた。〔今井淑夫、
高分子、34、204（1985）〕その原因の一つとして
使用する上記ジアミンの構造は鎖状でかつ硬直な
ためであると考えられる。本発明は上記難点を解
決することを目的として開発された化合物及びそ
の製造方法を提供することにある。(Problems to be Solved by the Invention) However, the above-mentioned polyimide resins made from these raw materials have problems in processability. [Yoshio Imai,
Kobunshi, 34 , 204 (1985)] One of the reasons for this is thought to be that the structure of the diamine used is chain-like and rigid. The object of the present invention is to provide a compound developed for the purpose of solving the above-mentioned difficulties and a method for producing the same.
（問題点を解決するための手段）
そこで、本発明はアルキル基が適当に導入さ
れ、かつ、柔軟性を持つた化合物としてカリクス
アレン類を選びだし、耐熱性樹脂の原料として有
用であることを見出した。(Means for Solving the Problems) Therefore, the present invention has selected calixarenes as compounds in which alkyl groups have been appropriately introduced and has flexibility, and has found that they are useful as raw materials for heat-resistant resins. Ta.
本発明のカリクスアレン類新規誘導体は化学構
造式
で示されるｐ―tert―ブチルカリクス〔８〕アレ
ンのペンタキス（ｐ―ニトロフエニル）誘導体で
ある。 The new calixarene derivatives of the present invention have the chemical structural formula: It is a pentakis (p-nitrophenyl) derivative of p-tert-butylcalix[8]arene represented by
（作用）
本発明による新規化合物は次の化学構造式
（）
で示されるｐ―tert―ブチルカリクス〔８〕アレ
ンを金属ナトリウム、水酸化ナトリウム、炭酸ナ
トリウム、炭酸カリウムのようなアルカリ金属化
合物存在下、一般式（）
（式中、Ｘはハロゲン原子、及びニトロ基より
なる群から選択された置換基を示す。）
で示される化合物と反応させることにより合成さ
れる。(Function) The new compound according to the present invention has the following chemical structural formula () p-tert-butylcalix[8]arene represented by the general formula () in the presence of an alkali metal compound such as sodium metal, sodium hydroxide, sodium carbonate, or potassium carbonate (In the formula, X represents a substituent selected from the group consisting of a halogen atom and a nitro group.) It is synthesized by reacting with the compound shown below.
この反応はジメチルスルホキシド、スルホラン
などのような非水性極性溶媒中で行う。この反応
に使用する温度は160℃〜180℃が好ましい。これ
より低温で反応を行うと収率が著しく低下する。 This reaction is carried out in a non-aqueous polar solvent such as dimethyl sulfoxide, sulfolane, etc. The temperature used for this reaction is preferably 160°C to 180°C. If the reaction is carried out at a lower temperature than this, the yield will drop significantly.
本発明の反応成分である前記一般式（）で示
される置換ニトロベンゼンの例としては、、ｐ―
フルオロニトロベンゼン、ｐ―クロロニトロベン
ゼン、ｐ―ブロモニトロベンゼン、及びｐ―ジニ
トロベンゼンなどがあげられる。 Examples of the substituted nitrobenzene represented by the general formula (), which is a reaction component of the present invention, include p-
Examples include fluoronitrobenzene, p-chloronitrobenzene, p-bromonitrobenzene, and p-dinitrobenzene.
（実施例） 次に本発明の実施例を示す。(Example) Next, examples of the present invention will be shown.
実施例 １
ｐ―tert―ブチルカリクス〔８〕アレン1.3ｇ
（0.001モル）、ｐ―クロロニトロベンゼン1.5ｇ
（0.0095モル）、炭酸カリウム1.15ｇ（0.0083モル）
の混合物をジメチルスルホキシド20ml中、165℃
で６時間かきまぜた。反応混合物を1N―塩酸10
mlに注いだ。析出した固体をろ別し、乾燥した後
シリカゲルカラムクロマトグラフイーを行つた。
ベンゼンで展開すると、
次式
を有する化合物が780mg得られた。ベンゼン／ヘ
キサンで再結晶した。Example 1 p-tert-butylcalix [8] arene 1.3g
(0.001 mol), p-chloronitrobenzene 1.5 g
(0.0095 mol), potassium carbonate 1.15g (0.0083 mol)
in 20 ml of dimethyl sulfoxide at 165°C.
I stirred it for 6 hours. The reaction mixture was diluted with 1N-hydrochloric acid 10
Pour into ml. The precipitated solid was filtered off, dried, and then subjected to silica gel column chromatography.
Expanding with benzene, the following formula 780 mg of a compound having . Recrystallized from benzene/hexane.
収率 49％
融点 333℃（分解点、熱分析）
特性赤外線吸収（OH構造、3420cm-1）
（ON2構造、1520cm-1、1340cm-1）
元素分析
測定値 炭素74.14％、水素6.90％，
窒素3.63％，
計算値（C118H127N5O18）
炭素74.46％、水素6.73％，
窒素3.68％，
実施例 ２
溶媒としてジメチルスルホキシドの代わりにス
ルホランを用い実施例１と同様な操作を行い、実
施例１で記載した構造式を有する化合物を収率25
％で得た。 Yield 49% Melting point 333℃ (decomposition point, thermal analysis) Characteristic infrared absorption (OH structure, 3420cm -1 ) (ON 2 structure, 1520cm -1 , 1340cm -1 ) Elemental analysis measurements Carbon 74.14%, hydrogen 6.90%, Nitrogen 3.63%, Calculated value (C 118 H 127 N 5 O 18 ) Carbon 74.46%, Hydrogen 6.73%, Nitrogen 3.68%, Example 2 The same operation as Example 1 was performed using sulfolane instead of dimethyl sulfoxide as the solvent. , the compound having the structural formula described in Example 1 was obtained in a yield of 25
Obtained in %.
（発明の効果）
本発明によれば、４，4′―ジアミノジフエニル
スルホン（DDS）、４，4′―ジアミノジフエニル
エーテルなどを原料とする従来のポリイミド樹脂
のもつ問題点を解決し、加工性が良く、耐熱性樹
脂の原料として有用な効果を奏するものを提供す
ることができる。(Effects of the Invention) According to the present invention, problems with conventional polyimide resins made from 4,4'-diaminodiphenyl sulfone (DDS), 4,4'-diaminodiphenyl ether, etc., are solved, It is possible to provide a product that has good processability and is useful as a raw material for heat-resistant resin.
Claims (1)
ンをアルカリ金属化合物存在下、有機溶媒中で一
般式 （式中、Ｘはハロゲン原子及びニトロ基よりな
る群から選択された置換基を示す。） で示される化合物と反応させることよりなる化学
構造式 で示されるカリクスアレン類の新規誘導体の製造
方法。[Claims] 1. Chemical structural formula A new derivative of calixarenes shown in 2 Chemical structural formula p-tert-butylcalix[8]arene represented by the general formula (In the formula, X represents a substituent selected from the group consisting of a halogen atom and a nitro group.) A chemical structural formula obtained by reacting with a compound represented by A method for producing a new derivative of calixarenes represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61067595A JPS62223156A (en) | 1986-03-25 | 1986-03-25 | Novel derivative of calixarene and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61067595A JPS62223156A (en) | 1986-03-25 | 1986-03-25 | Novel derivative of calixarene and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62223156A JPS62223156A (en) | 1987-10-01 |
| JPH0222058B2 true JPH0222058B2 (en) | 1990-05-17 |
Family
ID=13349420
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61067595A Granted JPS62223156A (en) | 1986-03-25 | 1986-03-25 | Novel derivative of calixarene and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62223156A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5210216A (en) * | 1985-03-28 | 1993-05-11 | Loctite (Ireland) Limited | Calixarene and oxacalixarene derivatives and use thereof of sequestration metals |
| JP5137410B2 (en) * | 2006-06-09 | 2013-02-06 | キヤノン株式会社 | Photosensitive compound, photosensitive composition, resist pattern forming method and substrate processing method |
-
1986
- 1986-03-25 JP JP61067595A patent/JPS62223156A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62223156A (en) | 1987-10-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE2726541C2 (en) | Aromatic diamines and processes for their preparation | |
| US4098825A (en) | Acetylene-substituted aromatic benzils and acetylene-terminated quinoxaline compositions | |
| JPH0222058B2 (en) | ||
| US3956321A (en) | Preparation of 4-fluorophthalic anhydride | |
| KR100225748B1 (en) | Process for producing hexafluorobiphenyl-3,3',4,4'-tetracarboxylic acid precursors | |
| JPH0571582B2 (en) | ||
| JPS6335548A (en) | Production of triarylamine | |
| JPH0358982A (en) | New fluorine-containing tetracarboxylic acid dianhydride and production thereof | |
| JP5874378B2 (en) | Sulfonated arylamine polymer and process for producing the same | |
| JP5178098B2 (en) | Alicyclic vinyl ether compounds | |
| JPH01186865A (en) | Biscitraconimide compound and production thereof | |
| JP3543585B2 (en) | Method for producing 2,2 ', 5,5', 6,6'-hexafluorobiphenyl-3,3 ', 4,4'-tetracarboxylic acid precursor | |
| US4279836A (en) | Hydroxamic acid derivative and method of preparing metoclopramide using same | |
| JPH05170735A (en) | Fluorinated n,n-bisimide | |
| JP2698384B2 (en) | Fluorine-containing pyromellitic anhydride and method for producing the same | |
| JP3265135B2 (en) | Thiophene monomer and polymer having ureido group in side chain | |
| JPS6122034A (en) | Method for producing tetramethylbiphenyl | |
| JPS5852966B2 (en) | Manufacturing method of organic fluorine compounds | |
| JPS62246568A (en) | Crown ether compound and production thereof | |
| JPH075554B2 (en) | Process for producing 5-bromopyridone-3-carboxamide compound | |
| CN118026865A (en) | A method for preparing N-methyl-D-aspartic acid using D-aspartic acid as raw material | |
| JPH05320100A (en) | Aromatic dinitro compound, aromatic diamino compound and its production | |
| JPS63120736A (en) | Production of polyimide thioether | |
| JPS6261954A (en) | Production of phthalic acid derivative | |
| JP2812541B2 (en) | New ether diamine and method for producing the same |