JPH02164854A - 5-(perfluorononenyloxy) isophthalic acid bis(nitrophenylester) and production thereof - Google Patents
5-(perfluorononenyloxy) isophthalic acid bis(nitrophenylester) and production thereofInfo
- Publication number
- JPH02164854A JPH02164854A JP31881288A JP31881288A JPH02164854A JP H02164854 A JPH02164854 A JP H02164854A JP 31881288 A JP31881288 A JP 31881288A JP 31881288 A JP31881288 A JP 31881288A JP H02164854 A JPH02164854 A JP H02164854A
- Authority
- JP
- Japan
- Prior art keywords
- perfluorononenyloxy
- isophthalic acid
- formula
- acid
- nitrophenol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- ULSMOZVJXVYNDX-UHFFFAOYSA-N 5-(1,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluoronon-1-enoxy)benzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)=CC(C(O)=O)=C1 ULSMOZVJXVYNDX-UHFFFAOYSA-N 0.000 title claims description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 10
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims abstract description 8
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 claims abstract description 4
- -1 nitrophenyl ester Chemical class 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052731 fluorine Inorganic materials 0.000 abstract description 7
- 239000004952 Polyamide Substances 0.000 abstract description 6
- 239000004642 Polyimide Substances 0.000 abstract description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract description 6
- 229920002647 polyamide Polymers 0.000 abstract description 6
- 229920001721 polyimide Polymers 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 6
- 150000004984 aromatic diamines Chemical class 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 abstract description 3
- RRPVUVFTFFPAND-UHFFFAOYSA-N 5-(1,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluoronon-1-enoxy)benzene-1,3-dicarbonyl chloride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)=C(F)OC1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 RRPVUVFTFFPAND-UHFFFAOYSA-N 0.000 abstract description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract description 3
- RTZZCYNQPHTPPL-UHFFFAOYSA-N 3-nitrophenol Chemical compound OC1=CC=CC([N+]([O-])=O)=C1 RTZZCYNQPHTPPL-UHFFFAOYSA-N 0.000 abstract description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011737 fluorine Substances 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 238000004811 liquid chromatography Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- QNVNLUSHGRBCLO-UHFFFAOYSA-N 5-hydroxybenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(O)=CC(C(O)=O)=C1 QNVNLUSHGRBCLO-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- VJRSWIKVCUMTFK-UHFFFAOYSA-N 1,1,2,3,3,3-hexafluoroprop-1-ene Chemical compound FC(F)=C(F)C(F)(F)F.FC(F)=C(F)C(F)(F)F.FC(F)=C(F)C(F)(F)F VJRSWIKVCUMTFK-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- 101100020289 Xenopus laevis koza gene Proteins 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- CHDFNIZLAAFFPX-UHFFFAOYSA-N ethoxyethane;oxolane Chemical compound CCOCC.C1CCOC1 CHDFNIZLAAFFPX-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、ポリイミド、ポリアミドの原料として有用な
含フツ素芳香族ジアミンの中間体である５−（パーフル
オロノネニルオキシ）イソフタル酸ビス（ニトロフェニ
ルエステル）及びその製造法に関する。Detailed Description of the Invention [Industrial Application Field] The present invention relates to 5-(perfluorononenyloxy)isophthalic acid bis( (nitrophenyl ester) and its production method.
芳香族ジニトロ化合物は、電子材料分野に使用されてい
るポリイミド、ポリアミドなどの原料である芳香族ジア
ミンの中間体として有用である。Aromatic dinitro compounds are useful as intermediates for aromatic diamines, which are raw materials for polyimides, polyamides, and the like used in the field of electronic materials.
で示されるイソフタル酸ビス（アミノフェニルエステル
）は、ポリイミド、ポリアミドの原料として用いられて
きた（例えば、特公昭５９−１４９９２８号公報）。こ
のジアミンはイソフタル酸ビス（二１〜口フェニルアミ
ド）を還元して得られる。Isophthalic acid bis(aminophenyl ester) represented by has been used as a raw material for polyimide and polyamide (for example, Japanese Patent Publication No. 59-149928). This diamine is obtained by reducing bis-isophthalic acid (21-phenylamide).
しかし、近年、電子機器の高密度化、高性能化に伴い、
それらに使用されているポリイミ１−．ボリアミ１くな
どの絶縁材料に、耐熱性、耐湿性の向上などが強く要求
されており、従来の芳香族ジアミン化合物を原料とした
ポリイミド、ポリアミドなどでは、これらの要求に十分
満足するものは得られなかった。However, in recent years, with the increasing density and performance of electronic devices,
Polyimide 1-. There is a strong demand for improved heat resistance and moisture resistance for insulating materials such as polyamide 1, and conventional polyimides and polyamides made from aromatic diamine compounds cannot fully satisfy these demands. I couldn't.
この様な要求に対処するには１分子構造中にフッ素原子
を含む置換基を導入することが有効であると考えられる
。。In order to meet such requirements, it is considered effective to introduce a substituent containing a fluorine atom into the single molecule structure. .
そこで本発明者らは、従来から用いられているイソフタ
ル酸ビス（アミノフェニルエステル）の構造にフッ素原
子を含む置換基を導入すべく、先ず、その中間体となる
新規化合物５−（パーフルオロノネニルオキシ）イソフ
タル酸ビス（ニトロフェニルエステル）及びその製造法
を提供するものである。Therefore, in order to introduce a substituent containing a fluorine atom into the structure of conventionally used isophthalic acid bis(aminophenyl ester), the present inventors first developed a new compound 5-(perfluoronone The present invention provides bis(nitrophenyloxy)isophthalate and a method for producing the same.
本発明における新規化合物は一般式（Ｉ）（ただし、式
中、−Ｃ，Ｆ□７基は二重結合を］個有し、適宜分岐し
ていてもよい）で示される５（パーフルオロノネニルオ
キシ）イソフタル酸ビスにトロフェニルエステル）であ
る。上記−Ｃ，Ｆ□７基は、例えば、ヘキサフルオロプ
ロペン３量体に基づいて導入されたものがある。The novel compound of the present invention is a 5 (perfluoronone compound) represented by the general formula (I) (in the formula, -C,F□7 groups have a double bond and may be branched as appropriate). trophenyl ester). The above -C,F□7 group is, for example, introduced based on a hexafluoropropene trimer.
上記化合物は５−（パーフルオロノネニルオキシ）イソ
フタル酸又はその酸クロライドとニトロフェノール（オ
ルト−、メタ−又はパラ−ニトロフェノール）とを反応
させることにより製造することができる。The above compound can be produced by reacting 5-(perfluorononenyloxy)isophthalic acid or its acid chloride with nitrophenol (ortho-, meta- or para-nitrophenol).
５−（パーフルオロノネニルオキシ）イソフタル酸とニ
トロフェノールを反応させる場合には、新実験化学講座
１４巻〔■〕 （丸善（株）昭和５２年１２月２０日発
行）第１００２頁以下に示される様な公知の方を採用す
ることができる。例えば、ベンゼン、トルエンを溶媒と
し、生成する水を共沸留去する方法、無水硫酸マグネシ
ウム。When 5-(perfluorononenyloxy)isophthalic acid and nitrophenol are reacted, the reaction shown in New Experimental Chemistry Course Volume 14 [■] (published by Maruzen Co., Ltd. December 20, 1978), pages 1002 onwards. Any known person may be employed. For example, a method in which benzene or toluene is used as a solvent and the water produced is azeotropically distilled off, anhydrous magnesium sulfate.
モレキュラーシーブスなどの乾燥剤を用いる方法などが
ある。There is a method using a desiccant such as molecular sieves.
上記反応は有機溶媒中で行われることが好ましい。この
際使用される有機溶媒としては、カルボン酸、フェノー
ルと反応性のないものであれば良く、トルエン、ベンゼ
ン、テトラヒドロフラン。The above reaction is preferably carried out in an organic solvent. The organic solvent used in this case may be one that is not reactive with carboxylic acid or phenol, such as toluene, benzene, and tetrahydrofuran.
ジクロロエタンなどが用いられ、互いに相溶すれば２種
以上を混合して用いても良い。Dichloroethane or the like is used, and two or more types may be used in combination as long as they are compatible with each other.
５−（パーフルオロノネニルオキシ）イソフタル酸の酸
クロライドと二１−口フエノールを反応させる場合は、
上記と同様、新化学講座１４巻〔１〕第１０１２頁以下
に示される様な公知の方法を採用することができる。例
えば、低温下、窒素雰囲気中で反応させ、生成する塩酸
を捕獲するためにピリジン、トリエチルアミン、ジメチ
ルアニリンなどの塩基を用いることが好ましい。When reacting the acid chloride of 5-(perfluorononenyloxy)isophthalic acid with 21-phenol,
Similarly to the above, a known method such as that shown in Shin Kagaku Koza volume 14 [1] page 1012 et seq. can be adopted. For example, it is preferable to carry out the reaction at a low temperature in a nitrogen atmosphere and to use a base such as pyridine, triethylamine, or dimethylaniline to capture the generated hydrochloric acid.
塩基の使用量は、生成する塩酸に対して１モル当量〜３
モル当量用いることが好ましい。１モル当量より少ない
と塩酸の捕獲が不十分であり、３モル当量より多いと副
反応などにより収率が低下する場合がある。」二記反応
は、有機溶媒中で行われることが好ましい。用いること
のできる溶媒としては、１−ルエン、ベンゼン、テトラ
ヒドロフランジエチルエーテルなど酸クロライド、フェ
ノールと反応性のない有機溶媒が使用される。これら有
機溶媒は、互いに相溶すれば２種以上を混合して用いて
も良い。使用する有機溶媒は充分に脱水したものを用い
ることが好ましい。反応系中に水分が存在すると酸クロ
ライドが分解するため収率が低下することがある。The amount of base used is 1 molar equivalent to 3 molar equivalents to the hydrochloric acid to be generated.
Preferably, molar equivalents are used. If it is less than 1 molar equivalent, the capture of hydrochloric acid will be insufficient, and if it is more than 3 molar equivalents, the yield may decrease due to side reactions. It is preferable that the reaction described above is carried out in an organic solvent. As the solvent that can be used, there are used organic solvents that are not reactive with acid chloride and phenol, such as 1-toluene, benzene, and tetrahydrofuran diethyl ether. Two or more of these organic solvents may be used in combination as long as they are compatible with each other. It is preferable that the organic solvent used be sufficiently dehydrated. If moisture is present in the reaction system, the acid chloride may decompose, resulting in a decrease in yield.
５−（パーフルオロノネニルオキシ）イソフタル酸の酸
クロライドは５−（パーフルオロノネニルオキシ）イソ
フタル酸を塩化チオニル、五塩化リン、三塩化リンなど
を用いる酸クロライド合成の公知の方法によって反応さ
せることにより得られる。反応条件については用いる試
薬により異なり特に限定されるものではない。Acid chloride of 5-(perfluorononenyloxy)isophthalic acid is obtained by reacting 5-(perfluorononenyloxy)isophthalic acid by a known method for acid chloride synthesis using thionyl chloride, phosphorus pentachloride, phosphorus trichloride, etc. It can be obtained by Reaction conditions vary depending on the reagent used and are not particularly limited.
前記の５−（パーフルオロノネニルオキシ）イソフタル
酸は、一般式（ｎ）
（たたし、式中−〇ｑＦ１７基は二重結合を１個含み、
適宜分岐していてもよい）で示される化合物である。The above-mentioned 5-(perfluorononenyloxy)isophthalic acid has the general formula (n) (wherein the -〇qF17 group contains one double bond,
This is a compound represented by the following formula (which may be branched as appropriate).
一般式（ＩＩ）において、−Ｃ，Ｆ、、、基は、例えば
、ヘキサフルオロプロペンの３量体に基づいて導入され
たものかある９゜
−・般式（Ｉ１）で示される化合物は、例えば、特開昭
６０−５１１４６ 号公報に示されるよう１こ、ハキフ
ルオロプロペン３量体と５−ヒドロキシイソフタル酸を
反応させることにより得ることができる。In the general formula (II), the -C,F,... group is, for example, one introduced based on the trimer of hexafluoropropene.9゜-.The compound represented by the general formula (I1) is: For example, as shown in JP-A-60-51146, it can be obtained by reacting a hakifluoropropene trimer with 5-hydroxyisophthalic acid.
反応は、非プロ１〜ン性極性溶媒中、室温以下で塩基触
媒の存在十に行なわれ、下記式（ＩＩＩ ）で示さ」し
る構造式の化合物が得られる。The reaction is carried out in an aprotic polar solvent at room temperature or below in the presence of a basic catalyst to obtain a compound having the structural formula shown by the following formula (III).
式（Ｉｌｌ）
本発明に係る一般式（Ｉ）で示される化合物はポリイミ
ド、ポリアミドの原料として有用な含フツ素芳香族ジア
ミンの中間体として有用である。Formula (Ill) The compound represented by the general formula (I) according to the present invention is useful as an intermediate for a fluorine-containing aromatic diamine useful as a raw material for polyimide and polyamide.
以下、本発明を実施例により説明するが１本発明はこの
実施例により特に限定されるものではない。The present invention will be explained below with reference to Examples, but the present invention is not particularly limited by these Examples.
実施例
（Ｉ）５−（パーフルオロノネニルオキシ）イソフタル
酸ジクロライドの合成温度計、還流冷却管。Example (I) Synthesis of 5-(perfluorononenyloxy)isophthalic acid dichloride Thermometer, reflux condenser.
塩化カルシウム管、かくはん装置を備えた四ツ［ロフラ
スコに５−（パーフルオロノネニルオキシ）イソフタル
酸６１．２ ｇ （０，１モル）、塩化チオニル１２０
ｇ （Ｉ，０モル）を入れ８０℃で加熱した。約１２時
間後、反応系は均一な溶液となる。過剰の塩化チオニル
を減圧留人後。5-(perfluorononenyloxy)isophthalic acid 61.2 g (0.1 mol), thionyl chloride 120
g (I, 0 mol) was added thereto and heated at 80°C. After about 12 hours, the reaction system becomes a homogeneous solution. After removing excess thionyl chloride in vacuo.
減圧蒸留を行い、５−（パーフルオロノネニルオキシ）
イソフタル酸ジクロライドを得た。これの収率は５１％
、沸点は１４０℃／ ３ ｍｎ Ｉ−Ｉ ｇであった。Perform vacuum distillation to obtain 5-(perfluorononenyloxy)
Isophthalic acid dichloride was obtained. The yield of this is 51%
, the boiling point was 140°C/3 mn I-I g.
なお、上記５−（パーフルオロノネニルオキシ）イソフ
タル酸は前記式（［１）の化合物を使用した。In addition, the compound of the said formula ([1) was used as said 5-(perfluorononenyloxy) isophthalic acid.
一
（２）５−（パーフルオロノネニルオキシ）イソフタル
酸ビス（二１〜口フェニルエステル）の合成温度３１．
還流冷却管、窒素導入管、乾燥管、かくはん装置を備え
た四ツ目フラスコに、Ｐ−ニトロフェノール２．７８ｇ
（２０ミリモル）ピリジン１．７４ｇ（２２ミリモル）
、脱水精製したテ１〜ラヒトロフラン４０ｍＱを仕込み
、Ｏ℃水浴中窒素気流下て５−（パーフルオロノネニル
オキシ）イソフタル酸シクロライド６．４９ ｇ（Ｉ０
ミリモル）伝説水精製したテ１〜ラヒドロフランｌ ５
ｍ Ｑに溶解したものをゆっくりと滴下した。滴下す
るに従い反応系は白濁してきた。Synthesis temperature of 1(2)5-(perfluorononenyloxy)isophthalic acid bis(21-phenyl ester) 31.
2.78 g of P-nitrophenol was placed in a four-eye flask equipped with a reflux condenser, nitrogen introduction tube, drying tube, and stirring device.
(20 mmol) Pyridine 1.74 g (22 mmol)
, 40 mQ of dehydrated and purified Te1-lahitorofuran was charged, and 6.49 g of 5-(perfluorononenyloxy)isophthalic acid cyclolide (I0
mmol) Legendary Water Purified Te 1 ~ Lahydrofuran 5
The solution dissolved in mQ was slowly added dropwise. As the solution was added dropwise, the reaction system became cloudy.
滴下終了後水浴をはずし、室温で約１時間反応サセ、更
に、／ｌＯ℃で約３０分、５０℃で約３０分、７０°Ｃ
で約１時間反応させた。反応終了後、析出した白色沈殿
をろ別し、ろ液を１Ｑの水に注いだ。得られた淡黄色結
晶を水で洗浄し、減圧乾燥を行った。得られた結晶は、
Ｎ、Ｎ−ジメチルホルｊ１アミド、水の混合イ容媒から
再結晶した。得られた結晶の収率、物性は次のとおりで
ある。After the dropwise addition was completed, the water bath was removed and the reaction was incubated at room temperature for about 1 hour.
The reaction was carried out for about 1 hour. After the reaction was completed, the precipitated white precipitate was filtered off, and the filtrate was poured into 1Q water. The obtained pale yellow crystals were washed with water and dried under reduced pressure. The obtained crystal is
It was recrystallized from a mixed medium of N,N-dimethylformamide and water. The yield and physical properties of the obtained crystals are as follows.
収率８２％
融点］−３３°Ｃ（示差走査熱量計による）赤外吸収ス
ペクトル １７６０ａｎ−” （Ｃ＝Ｏ，エステル）１
５３０ｃｍ−’ （Ｎｏ２）
１、５５５ａｎ ” （ＮＨ−Ｒ，アミド）１２５０、
１２００訓−’ （Ｃ−Ｆ）’ Ｉ（−Ｎ Ｍ Ｒスペ
ク１ヘル ８．７３，８．４．１〜８．３５゜８．０８
（ＣＨ，芳香族）
また得られた結晶は液体クロマトグラフィ分析では単一
ピークであった。Yield 82% Melting point] -33°C (by differential scanning calorimeter) Infrared absorption spectrum 1760 an-" (C=O, ester) 1
530cm-' (No2) 1, 555an'' (NH-R, amide) 1250,
1200 Lessons-'(C-F)' I(-N M R Spec 1 Hell 8.73, 8.4.1~8.35°8.08
(CH, aromatic) Furthermore, the obtained crystal showed a single peak when analyzed by liquid chromatography.
分析条件
示差走査熱量計 ：パーキンエルマー社製ＤＳＣ−７
型昇温速度 ２ 、０ ’Ｃ／ ｍｉｎ
赤外吸収スペクｌ−ル：日立製作所 ＩＲ２７０−５０
ＫＢｒ錠剤法
”Ｈ−ＮＭＲスペク１−ル プルカー（株）ｉｉｊＡｃ
−２５０溶媒 ジメチルスルホキシ＋ニーｄ。Analysis conditions Differential scanning calorimeter: PerkinElmer DSC-7
Mold heating rate 2,0'C/min Infrared absorption spectrum: Hitachi IR270-50
KBr tablet method "H-NMR spectrum 1-ru Pulcar Co., Ltd. iijAc
-250 solvent dimethyl sulfoxy + needle d.
液体クロマトグラフィ カラム 東洋曹達製ＴＳＫ−
ｇｅＱ Ｇ２０００ＨＸＬ］−本＋Ｇ１０００ＨＸＬ
１本
溶媒 テトラヒドロフラン
流量 １ ｍ Ｑ ／ｍｉｎ
検出器ＵＶ
第１図に赤外吸収スペク１ヘル、第２図に゛Ｈ−ＮＭＲ
スペクトルの一部拡大図（横方向拡大）及び第３図に液
体クロマトグラフィーのチャートを示す。Liquid chromatography column TSK- manufactured by Toyo Soda
geQ G2000HXL]-Book+G1000HXL
1 solvent Tetrahydrofuran flow rate 1 mQ/min Detector UV Figure 1 shows infrared absorption spectrum, Figure 2 shows H-NMR.
A partially enlarged view of the spectrum (horizontal enlargement) and a liquid chromatography chart are shown in FIG.
なお、 １Ｈ−ＮＭＲスペクトルには、他に水に基づ＜
３．３４ｐｐｍの大きなピーク及び溶媒に基づく２．４
９ｐｐｍの小さなピークがあった。In addition, in the 1H-NMR spectrum, there is also a water-based
3.34 ppm large peak and 2.4 based on solvent
There was a small peak at 9 ppm.
以上より、前記で得られた結晶は、式（ＶＩ）香族ジア
ミンの中間体として有用である。From the above, the crystals obtained above are useful as intermediates for the aromatic diamine of formula (VI).
第１図は、実施例で得られた化合物の赤外線吸収スペク
トル、第２図は該化合物の１Ｈ−ＮＭＲスペクトルの一
部拡大図及び第３図は該化合物の液体クロマトグラフィ
ーのチャートを示す。FIG. 1 shows an infrared absorption spectrum of the compound obtained in the Examples, FIG. 2 shows a partially enlarged view of the 1H-NMR spectrum of the compound, and FIG. 3 shows a liquid chromatography chart of the compound.
Claims (1)
個含み、適宜分岐していてもよい）で示される５−（パ
ーフルオロノネニルオキシ）イソフタル酸ビスにトロフ
エニルエステル）。 ２、５−（パーフルオロノネニルオキシ）イソフタル酸
、又は、その酸クロライドとニトロフェノールを反応さ
せることを特徴とする５−（パーフルオロノネニルオキ
シ）イソフタル酸ビス（ニトロフエニルエステル）の製
造法。[Claims] 1. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (However, in the formula, the -C_9F_1_7 group has one double bond.
5-(perfluorononenyloxy)isophthalic acid bis-trophenyl ester). Production of 5-(perfluorononenyloxy)isophthalic acid bis(nitrophenyl ester), which is characterized by reacting 2,5-(perfluorononenyloxy)isophthalic acid or its acid chloride with nitrophenol. Law.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31881288A JPH02164854A (en) | 1988-12-16 | 1988-12-16 | 5-(perfluorononenyloxy) isophthalic acid bis(nitrophenylester) and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31881288A JPH02164854A (en) | 1988-12-16 | 1988-12-16 | 5-(perfluorononenyloxy) isophthalic acid bis(nitrophenylester) and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02164854A true JPH02164854A (en) | 1990-06-25 |
Family
ID=18103220
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31881288A Pending JPH02164854A (en) | 1988-12-16 | 1988-12-16 | 5-(perfluorononenyloxy) isophthalic acid bis(nitrophenylester) and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02164854A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5270438A (en) * | 1990-04-03 | 1993-12-14 | Hitachi Chemical Company, Ltd. | Fluorine-containing polyimides and precursors thereof |
-
1988
- 1988-12-16 JP JP31881288A patent/JPH02164854A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5270438A (en) * | 1990-04-03 | 1993-12-14 | Hitachi Chemical Company, Ltd. | Fluorine-containing polyimides and precursors thereof |
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