JPH01190652A - Novel fluorine-containing aromatic compound and production thereof - Google Patents
Novel fluorine-containing aromatic compound and production thereofInfo
- Publication number
- JPH01190652A JPH01190652A JP63012660A JP1266088A JPH01190652A JP H01190652 A JPH01190652 A JP H01190652A JP 63012660 A JP63012660 A JP 63012660A JP 1266088 A JP1266088 A JP 1266088A JP H01190652 A JPH01190652 A JP H01190652A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- containing aromatic
- general formula
- aromatic compound
- bis
- 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
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims description 13
- 229910052731 fluorine Inorganic materials 0.000 title claims description 13
- 239000011737 fluorine Substances 0.000 title claims description 13
- 150000001491 aromatic compounds Chemical class 0.000 title claims description 6
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 7
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002798 polar solvent Substances 0.000 claims abstract description 6
- -1 aromatic dinitro compound Chemical class 0.000 claims description 13
- 150000005182 dinitrobenzenes Chemical class 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 11
- 150000001875 compounds Chemical class 0.000 abstract description 9
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000004952 Polyamide Substances 0.000 abstract description 4
- 239000004642 Polyimide Substances 0.000 abstract description 4
- 229920002647 polyamide Polymers 0.000 abstract description 4
- 229920001721 polyimide Polymers 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000002585 base Substances 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 150000004985 diamines Chemical class 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 150000004984 aromatic diamines Chemical class 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen 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
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-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
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- QZADIXWDDVQVKM-UHFFFAOYSA-N 1,3-dinitro-5-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=CC(C(F)(F)F)=C1 QZADIXWDDVQVKM-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 239000008096 xylene Substances 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、新規な含フツ素芳香族ジニトロ化合物および
ジアミンに関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel fluorine-containing aromatic dinitro compound and diamine.
ジアミンは縮重合高分子材料のモノマーとして重要な化
合物であり、ポリイミド、ポリアミド、あるいはポリア
ミドイミドなどの塩基成分として用いられる。殊に全芳
香族縮合高分子材料は、耐熱性を要求される構造材料・
電子材料などとしてン主目されており、これらへのパー
フルオロアルキルらすことから、特に電子材料用途には
好ましい物性の付与が期待できる．本発明は上記観点か
らなされたもので、パーフルオロアルキル基を置換基と
して有する新規な芳香族ジアミンおよびその原料として
のジニトロ化合物を提供するものである。Diamine is an important compound as a monomer of condensation polymer materials, and is used as a base component of polyimide, polyamide, polyamideimide, etc. In particular, wholly aromatic condensation polymer materials are used as structural materials and materials that require heat resistance.
They are mainly used as electronic materials, and because they contain perfluoroalkyl, they can be expected to impart favorable physical properties, especially for electronic material applications. The present invention was made from the above viewpoint, and provides a novel aromatic diamine having a perfluoroalkyl group as a substituent and a dinitro compound as a raw material thereof.
［従来技術］
従来、パーフルオロアルキル基を置換基として有する含
フツ素芳香族ジアミンについては特開昭５９−１８９１
２２号公報に２．２−ビス（４−［２−（）リフルオロ
メチル）−４−アミノフェノキシ］フェニル）へキサフ
ルオロプロパンが示されているが、その具体的な製造例
が示されていない．また、本従来技術に示される化合物
は一４位にアミノ基を有するものであり、−３位アミノ
置換体は全く知られていない。[Prior Art] Conventionally, fluorine-containing aromatic diamines having perfluoroalkyl groups as substituents have been disclosed in Japanese Patent Application Laid-Open No. 59-1891.
Publication No. 22 discloses 2.2-bis(4-[2-()lifluoromethyl)-4-aminophenoxy]phenyl)hexafluoropropane, but does not provide a specific example of its production. do not have. Further, the compound shown in this prior art has an amino group at the 1-4th position, and an amino substituted product at the -3rd position is not known at all.
［問題点を解決するための手段］
本発明者らは、ポリイミド、ポリアミド、などの塩基成
分として有用な化合物について検討の結果パーフルオロ
アルキル基を置換基として有し、−３位にアミノ基を有
する新規な含フツ素芳香族ジアミンおよびその原料とし
ての新規な含フツ素芳香族ジニトロ化合物を得、本発明
に至った．すなわち本発明は、一般式
（式中、Ｒｆは炭素数１〜１０のパーフルオロアルキル
基である）で表わされる新規な含フツ素芳香族ジニトロ
化合物および一ＮＯ，基を一ＮＢ，基に変えた新規な含
フツ素芳香族ジアミンであり、２．２−ビス（４−ヒド
ロキシフェニル）へキサフルオロプロパンと一般式
（式中、Ｒｆは前記と同じ）で表わされるジニトロベン
ゼン類を非プロトン性極性溶媒中、塩基の存在下で縮合
させ、一般式（りで表わされるジニトロ化合物を得、次
いで還元することにより一般式（Ｉ［ｌ）
（式中、Ｒｆは前記と同じ）で表わされるジアミンを得
ることができる．ここで用いられるジニトロベンゼンＩ
（ＩＩ）は、５−パーフルオロアルキル−１、３−ジニ
トロベンゼンであって、具体的には５−トリフルオロメ
チル−１．３−ジニトロベンゼン、５−ノナフルオロブ
チル−１．３−ジニトロベンゼン等が使用できる．使用
量は２．２−ビス（４−ヒドロキシフェニル）へキサフ
ルオロプロパンに対して１，０５〜１。[Means for Solving the Problems] The present inventors investigated compounds useful as base components for polyimide, polyamide, etc., and found that they have a perfluoroalkyl group as a substituent and an amino group at the -3 position. The present invention has been accomplished by obtaining a novel fluorine-containing aromatic diamine having the following properties and a novel fluorine-containing aromatic dinitro compound as a raw material thereof. That is, the present invention provides a novel fluorine-containing aromatic dinitro compound represented by the general formula (wherein Rf is a perfluoroalkyl group having 1 to 10 carbon atoms) and a compound in which -NO, group is replaced with -NB, group. It is a novel fluorine-containing aromatic diamine that combines 2,2-bis(4-hydroxyphenyl)hexafluoropropane and dinitrobenzenes represented by the general formula (wherein Rf is the same as above) into an aprotic A diamine represented by the general formula (I[l) (wherein Rf is the same as above) is obtained by condensation in a polar solvent in the presence of a base to obtain a dinitro compound represented by the general formula (RI), and then reduced. The dinitrobenzene I used here can be obtained.
(II) is 5-perfluoroalkyl-1,3-dinitrobenzene, specifically 5-trifluoromethyl-1,3-dinitrobenzene, 5-nonafluorobutyl-1,3-dinitrobenzene etc. can be used. The amount used is 1,05-1 based on 2,2-bis(4-hydroxyphenyl)hexafluoropropane.
２０倍であることが好ましい。Preferably, it is 20 times larger.
使用される塩基としては、アルカリ金属の水酸化物、炭
酸塩、炭酸水素塩、水素化物などであって、具体的には
水酸化ナトリウム、水酸化カリウム、水酸化リチウム、
炭酸カリウム、炭酸ナトリウム、炭酸水素カリウム、炭
酸水素ナトリウム、水素化ナトリウムなどが例示できる
。塩基の量は２、２−ビス（４−ヒドロキシフェニル）
へキサフルオロプロパンに対して１〜５倍当量好ましく
は１〜３倍当量である。The bases used include alkali metal hydroxides, carbonates, hydrogen carbonates, hydrides, etc., specifically sodium hydroxide, potassium hydroxide, lithium hydroxide,
Examples include potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, and sodium hydride. The amount of base is 2,2-bis(4-hydroxyphenyl)
The amount is 1 to 5 times equivalent, preferably 1 to 3 times equivalent, relative to hexafluoropropane.
使用される非プロトン性極性溶媒としては、アミド、ス
ルホキシド、スルホン、ニトリルなどであって、具体的
にはＮ−メチルホルムアミド、Ｎ。The aprotic polar solvents used include amides, sulfoxides, sulfones, nitriles, and specifically N-methylformamide, N-methylformamide, and N-methylformamide.
Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトア
ミド、ジメチルスルホキシド、ジメチルスルホン、スル
ホラン、１−メチル−２−ピロリジノン、ベンゾニトリ
ルなどが例示できる。溶媒の量は原料に対して１〜１帽
１倍が用いられる。Examples include N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, dimethylsulfone, sulfolane, 1-methyl-2-pyrrolidinone, and benzonitrile. The amount of solvent used is 1 to 1 times the amount of the raw material.
反応方法としては、塩基として水酸化物を用いる場合に
は、水が生成するため、２．２−ビス（４−ヒドロキシ
フェニル）へキサフルオロプロパンと、ベンゼン、トル
エン、キシレン、クロロベンゼン等の溶媒を仕込み、２
．２−ビス（４−ヒドロキシフェニル）へキサフルオロ
プロパンのアルカリ金属塩を調整し、生ずる水を溶媒と
の共沸混合物として除去したのち、溶媒を非プロトン性
極性溶媒に変換し、ジニトロベンゼン類と縮合させる方
法と、塩基として水酸化物以外を用いる場合には、２．
２−ビス（４−ヒドロキシフェニル）へキサフルオロプ
ロパン、ジニトロベンゼン類と、塩基、非プロトン性極
性溶媒すべてを仕込み１段で縮合を行わせる２通りの方
法がある。As for the reaction method, when using hydroxide as a base, water is produced, so 2,2-bis(4-hydroxyphenyl)hexafluoropropane and a solvent such as benzene, toluene, xylene, or chlorobenzene are used. Preparation, 2
．． After preparing the alkali metal salt of 2-bis(4-hydroxyphenyl)hexafluoropropane and removing the resulting water as an azeotrope with the solvent, the solvent is converted to an aprotic polar solvent and dinitrobenzenes and 2. Condensation method and when using a base other than hydroxide.
There are two methods in which 2-bis(4-hydroxyphenyl)hexafluoropropane, dinitrobenzenes, a base, and an aprotic polar solvent are all charged and the condensation is carried out in one step.
反応温度は１００〜１５０°Ｃで好ましくは１２０〜１
４０″Ｃである。The reaction temperature is 100-150°C, preferably 120-1
It is 40″C.
また反応時間は１〜２時間で十分である。Further, a reaction time of 1 to 2 hours is sufficient.
反応終了後、塩基、生成したハロゲン化アルカリを除去
し、反応液中に水を加えるか、溶媒留去によりジニトロ
化合物が得られる。After the reaction is completed, the base and the generated alkali halide are removed, and a dinitro compound is obtained by adding water to the reaction solution or by distilling off the solvent.
このジニトロ化合物の接触還元により、容易にジアミン
が合成できる。Diamines can be easily synthesized by catalytic reduction of this dinitro compound.
還元反応の溶媒としてはジニトロ化合物が可溶で原料、
生成物に不活性なものであれば特に限定されるものでは
なく、アルコール類、エーテル類、エステル類で、具体
的にはメタノール、エタノール、エーテル、テトラヒド
ロフラン、酢酸エチル、酢酸ブチル等が挙げられる。The dinitro compound is soluble as a solvent for the reduction reaction, and the raw material,
It is not particularly limited as long as it is inert to the product, and alcohols, ethers, and esters include methanol, ethanol, ether, tetrahydrofuran, ethyl acetate, butyl acetate, and the like.
触媒としては、一般に接触還元に用いられる金属触媒を
用いればよく、工業的にはパラジウム触媒を使用するの
が好ましい、使用量はジニトロ化合物に対して０．１〜
５重量％である。As a catalyst, a metal catalyst generally used for catalytic reduction may be used, and it is preferable to use a palladium catalyst industrially.
It is 5% by weight.
反応温度は４０〜１００°Ｃの範囲が好ましく、反応圧
は４〜１０ｋｇ／ｃｄの範囲が好ましい。The reaction temperature is preferably in the range of 40 to 100°C, and the reaction pressure is preferably in the range of 4 to 10 kg/cd.
反応は、原料、触媒、溶媒を仕込み、所定の温度で撹拌
下で水素を導入して反応を行う。反応の終点は水素吸収
量によって決定できる。The reaction is carried out by charging raw materials, a catalyst, and a solvent, and introducing hydrogen at a predetermined temperature with stirring. The end point of the reaction can be determined by the amount of hydrogen absorbed.
反応終了後、触媒を口割し、溶媒を留去するとジアミン
が得られる。After the reaction is completed, the catalyst is cut into pieces and the solvent is distilled off to obtain the diamine.
以下、実施例により本発明の詳細な説明する。Hereinafter, the present invention will be explained in detail with reference to Examples.
実施例１
温度計、攪拌器、冷却管を備えた５０ｍ１四ツ目フラス
コに２．２−ビス（４−ヒドロキシフェニル）へキサフ
ルオロプロパン３．３６ｇ （０，０１モル）、５−ト
リフルオロメチル−１，３−ジニトロベンゼン５．２ｇ
（０，０２２モル）、炭酸カリウム３．３６ｇ、Ｎ、Ｎ
ジメチルアセトアミド１５ｍ ｌを仕込み、約１時間で
１３０°Ｃまで昇温させ、このままの温度で１時間反応
させた。室温まで冷却後、塩を口割した。ｔ８媒を減圧
下に留去したのち、メタノール１７０■ｌを加え攪拌し
ながら加温溶解させた０次いで水浴により冷却し、析出
した結晶を０別乾燥し、２．２−ビス［４−（３−ニト
ロ−５−トリフルオロメチルフェノキシ）フェニル］ヘ
キサフルオロプロパンの黄色結晶を得た。収１９．８ｇ
（収率６８．７％）、純度９６．９％この化合物の赤外
吸収スペクトルを第１図に示した。Example 1 3.36 g (0.01 mol) of 2,2-bis(4-hydroxyphenyl)hexafluoropropane and 5-trifluoromethyl were placed in a 50 ml four-eye flask equipped with a thermometer, stirrer, and condenser. -1,3-dinitrobenzene 5.2g
(0,022 mol), potassium carbonate 3.36 g, N, N
15 ml of dimethylacetamide was charged, the temperature was raised to 130°C in about 1 hour, and the reaction was continued at this temperature for 1 hour. After cooling to room temperature, the salt was cracked. After distilling off the t8 medium under reduced pressure, 170 μl of methanol was added and dissolved by heating with stirring.Then, the mixture was cooled in a water bath, and the precipitated crystals were dried separately to give 2.2-bis[4-( Yellow crystals of 3-nitro-5-trifluoromethylphenoxy)phenyl]hexafluoropropane were obtained. Yield: 19.8g
(yield: 68.7%), purity: 96.9% The infrared absorption spectrum of this compound is shown in FIG.
この２．２−ビス［４−（３−ニトロ−５−トリフルオ
ロメチルフェノキシ）フェニル］へキサフルオロプロパ
ン１．７ｇ（０，００２モル）、５％Ｐｄ／ Ｃｏ、
Ｉｇ、酢酸エチル１０ｇを５０ｍ ｌ Ｓ Ｕ Ｓ耐圧
反応器に仕込み、８０°Ｃまで昇温した０反応圧５にｇ
／−で水素を吹き込み、所定量の水素′が消費されるま
で２時間反応を行った。室温まで冷却後、触媒を口割し
、溶媒を留去して、２，２−ビス［４−（３−アミノ−
５−トリフルオロメチルフェノキシ）フェニル］へキサ
フルオロプロパンの黄色ワックス状物を得た。収量１．
５ｇ（収−６４，４６ｐｐｍ（Ｓ、６Ｆ、−ＣＦ３）こ
の化合物の赤外吸収スペクトルを第２図に示した。This 2.2-bis[4-(3-nitro-5-trifluoromethylphenoxy)phenyl]hexafluoropropane 1.7 g (0,002 mol), 5% Pd/Co,
Ig, 10 g of ethyl acetate was charged into a 50 ml SUS pressure reactor, and the temperature was raised to 80°C.
Hydrogen was blown in at /-, and the reaction was carried out for 2 hours until a predetermined amount of hydrogen' was consumed. After cooling to room temperature, the catalyst was cut into pieces and the solvent was distilled off to give 2,2-bis[4-(3-amino-
A yellow waxy substance of 5-trifluoromethylphenoxy)phenyl]hexafluoropropane was obtained. Yield 1.
5 g (yield: -64.46 ppm (S, 6F, -CF3)) The infrared absorption spectrum of this compound is shown in FIG.
［発明の効果］
本発明の新規な含フツ素芳香族化合物はポリイミド、ポ
リアミド等の原料として優れたものであり、これにより
得られる重合体は、耐熱性に優れ、耐湿性の向上、誘電
率の低下をはかることができ、溶剤溶解性に優れるため
成形が容易であり、工業的に極めて有用なものである。[Effect of the invention] The novel fluorine-containing aromatic compound of the present invention is excellent as a raw material for polyimide, polyamide, etc. The polymer obtained thereby has excellent heat resistance, improved moisture resistance, and a low dielectric constant. It has excellent solvent solubility and is easy to mold, making it extremely useful industrially.
第１図、第２図は、本発明の新規な化合物の赤外吸収ス
ペクトルのチャートを示すものである。FIGS. 1 and 2 show charts of infrared absorption spectra of the novel compound of the present invention.
Claims (4)
基である）で表わされる新規な含フッ素芳香族化合物。(1) A novel fluorine-containing aromatic compound represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (wherein, Rf is a perfluoroalkyl group having 1 to 10 carbon atoms).
フルオロプロパンと一般式 ▲数式、化学式、表等があります▼（II） （式中、Ｒｆは一般式（ I ）の場合と同じ意味である
）で表わされるジニトロベンゼン類を非プロトン性極性
溶媒中、塩基の存在下で縮合させることを特徴とする一
般式（ I ）で表わされる新規な含フッ素芳香族化合物
の製造方法。(2) 2,2-bis(4-hydroxyphenyl)hexafluoropropane and the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, Rf has the same meaning as in the general formula (I) 1. A method for producing a novel fluorine-containing aromatic compound represented by general formula (I), which comprises condensing dinitrobenzenes represented by formula (I) in an aprotic polar solvent in the presence of a base.
）で表わされる新規な含フッ素芳香族化合物。(3) A novel fluorine-containing aromatic compound represented by the general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (III) (In the formula, Rf has the same meaning as in the general formula (I)).
トロ化合物を還元することを特徴とする一般式（III）
で表わされる新規な含フッ素芳香族化合物の製造方法。(4) General formula (III) characterized by reducing the fluorine-containing aromatic dinitro compound represented by general formula (I)
A method for producing a novel fluorine-containing aromatic compound represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63012660A JPH01190652A (en) | 1988-01-25 | 1988-01-25 | Novel fluorine-containing aromatic compound and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63012660A JPH01190652A (en) | 1988-01-25 | 1988-01-25 | Novel fluorine-containing aromatic compound and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01190652A true JPH01190652A (en) | 1989-07-31 |
Family
ID=11811517
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63012660A Pending JPH01190652A (en) | 1988-01-25 | 1988-01-25 | Novel fluorine-containing aromatic compound and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01190652A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5145999A (en) * | 1991-04-04 | 1992-09-08 | E. I. Du Pont De Nemours And Company | Perfluoroalkylated amines, and polymers made therefrom |
| US5177179A (en) * | 1991-04-04 | 1993-01-05 | E. I. Du Pont De Nemours And Company | Perfluoroalkylated diaminomesitylene and polyimides therefrom |
| US5296635A (en) * | 1989-12-28 | 1994-03-22 | Mitsui Toatsu Chemicals, Inc. | Preparation of bis(3-nitrophenoxy) compound |
| US5354839A (en) * | 1992-04-07 | 1994-10-11 | Mitsui Toatsu Chemicals, Incorporated | Polyimide and preparation process of same |
| US5470943A (en) * | 1994-01-07 | 1995-11-28 | Mitsui Toatsu Chemicals, Inc. | Polyimide |
-
1988
- 1988-01-25 JP JP63012660A patent/JPH01190652A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5296635A (en) * | 1989-12-28 | 1994-03-22 | Mitsui Toatsu Chemicals, Inc. | Preparation of bis(3-nitrophenoxy) compound |
| US5145999A (en) * | 1991-04-04 | 1992-09-08 | E. I. Du Pont De Nemours And Company | Perfluoroalkylated amines, and polymers made therefrom |
| US5177179A (en) * | 1991-04-04 | 1993-01-05 | E. I. Du Pont De Nemours And Company | Perfluoroalkylated diaminomesitylene and polyimides therefrom |
| US5280103A (en) * | 1991-04-04 | 1994-01-18 | E. I. Du Pont De Nemours And Company | Perfluoroalkylated amines, and polymers made therefrom |
| US5354839A (en) * | 1992-04-07 | 1994-10-11 | Mitsui Toatsu Chemicals, Incorporated | Polyimide and preparation process of same |
| US5470943A (en) * | 1994-01-07 | 1995-11-28 | Mitsui Toatsu Chemicals, Inc. | Polyimide |
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