JPH0555513B2 - - Google Patents
Info
- Publication number
- JPH0555513B2 JPH0555513B2 JP6562788A JP6562788A JPH0555513B2 JP H0555513 B2 JPH0555513 B2 JP H0555513B2 JP 6562788 A JP6562788 A JP 6562788A JP 6562788 A JP6562788 A JP 6562788A JP H0555513 B2 JPH0555513 B2 JP H0555513B2
- Authority
- JP
- Japan
- Prior art keywords
- diamino
- diphenyl
- acid
- bisthiazole
- benzo
- 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
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims description 10
- HVXLKRWRWNFGBA-UHFFFAOYSA-N 2,5-diaminobenzene-1,4-dithiol;dihydrochloride Chemical compound Cl.Cl.NC1=CC(S)=C(N)C=C1S HVXLKRWRWNFGBA-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229960004050 aminobenzoic acid Drugs 0.000 claims description 4
- 125000005605 benzo group Chemical group 0.000 claims description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- JWLNXHODHNBWPR-UHFFFAOYSA-N [1,3]thiazolo[5,4-f][1,3]benzothiazole Chemical compound C1=C2SC=NC2=CC2=C1N=CS2 JWLNXHODHNBWPR-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000012429 reaction media Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 4
- 229940098779 methanesulfonic acid Drugs 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000137 polyphosphoric acid Polymers 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 239000012264 purified product Substances 0.000 description 2
- JRNVQLOKVMWBFR-UHFFFAOYSA-N 1,2-benzenedithiol Chemical compound SC1=CC=CC=C1S JRNVQLOKVMWBFR-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、２，６−（４，4′−ジアミノ−ジフ
エニル）ベンゾ〔１，２−ｄ：４，５−d′〕ビス
チアゾールの合成法に関するものである。Detailed Description of the Invention (Industrial Application Field) The present invention relates to the use of 2,6-(4,4'-diamino-diphenyl)benzo[1,2-d:4,5-d']bisthiazole. It concerns synthesis methods.
（従来の技術）
２，６−（４，4′−ジアミノ−ジフエニル）ベ
ンゾ〔１，２−ｄ：４，５−d′〕ビスチアゾール
（）は対称性の良いジアミンである。(Prior Art) 2,6-(4,4'-diamino-diphenyl)benzo[1,2-d:4,5-d']bisthiazole () is a diamine with good symmetry.
化合物（）を単量体として他の酸成分と反応
させることにより、高弾性率で且つ耐熱性に優れ
た芳香族複素環ポリマーを容易に合成することが
出来るため、産業上重要な化合物として期待され
ている。 By reacting compound () as a monomer with other acid components, aromatic heterocyclic polymers with high elastic modulus and excellent heat resistance can be easily synthesized, so it is expected to be an industrially important compound. has been done.
従来から、上記化合物（）は、２，５−ジア
ミノ−１，４ベンゼンジチオール二塩酸塩をポリ
リン酸を反応媒体とする中で脱塩酸して得られ
る、２，５−ジアミノ−１，４−ベンゼンジチオ
ールと、ｐ−アミノ安息香酸とを反応させて製造
する方法が知られている。（公開60−101123号公
報）
この反応は、次のような反応と考えられる。 Conventionally, the above compound (2) is 2,5-diamino-1,4- which is obtained by dehydrochlorinating 2,5-diamino-1,4 benzenedithiol dihydrochloride in polyphosphoric acid as a reaction medium. A method of producing it by reacting benzenedithiol with p-aminobenzoic acid is known. (Publication No. 60-101123) This reaction is considered to be as follows.
（発明が解決しようとする課題）
しかし、この方法は、反応媒体に粘度の高いポ
リリン酸が用いられる一方、脱塩酸速度は脱泡可
能な範囲にとどめる必要があるため、必然的に、
この工程に長時間を要することとなり、製造上非
能率を指適されていた。 (Problem to be Solved by the Invention) However, in this method, while polyphosphoric acid with high viscosity is used as the reaction medium, the dehydrochloric acid rate must be kept within a range that allows defoaming, so inevitably,
This process took a long time, leading to manufacturing inefficiency.
（課題を解決するための手段）
すなわち、本発明は、２，５−ジアミノ−１，
４−ベンゼンジチオール二塩酸塩とｐ−アミノ安
息香酸とを反応させて、２，６−（４，4′−ジア
ミノ−ジフエニル）ベンゾ〔１，２−ｄ：４，５
−d′〕ビスチアゾールを製造する方法において、
反応媒体としてメタンスルホン酸と五酸化リンを
含有する混合物を用いることを特徴とする、２，
６−（４，4′−ジアミノ−ジフエニル）ベンゾ
〔１，２−ｄ：４，５−d′〕ビスチアゾールの製
造法を要旨とするものである。(Means for solving the problem) That is, the present invention provides 2,5-diamino-1,
4-benzenedithiol dihydrochloride and p-aminobenzoic acid are reacted to produce 2,6-(4,4'-diamino-diphenyl)benzo[1,2-d:4,5
-d′] A method for producing bisthiazole,
2, characterized in that a mixture containing methanesulfonic acid and phosphorus pentoxide is used as the reaction medium;
The gist is a method for producing 6-(4,4'-diamino-diphenyl)benzo[1,2-d:4,5-d']bisthiazole.
本発明に反応媒体として使用するメタンスルホ
ン酸と五酸化リンの混合物としては、重量比で、
20／１〜２／１、更に好ましくは20／１〜５／１
の範囲を挙げることができる。 The mixture of methanesulfonic acid and phosphorus pentoxide used as a reaction medium in the present invention has a weight ratio of:
20/1 to 2/1, more preferably 20/1 to 5/1
The range of
本発明は、２，５−ジアミノ−１，４−ベンゼ
ンジチオール二塩酸塩とｐ−アミノ安息香酸とを
反応させて、２，６−（４，4′−ジアミノ−ジフ
エニル）ベンゾ〔１，２−ｄ：４，５−d′〕ビス
チアゾールを製造する方法において、反応媒体と
してメタンスルホン酸と五酸化リンを含有する混
合物を用いることを特徴とする、２，６−（４，
4′−ジアミノ−ジフエニル）ベンゾ〔１，２−
ｄ：４，５−d′〕ビスチアゾールの製造方法を要
旨とするものであるが、本発明の反応終了後は、
常法により中和、ろ過を行ない粗生成物を得るこ
とができる。粗生成物は、再結晶し、精製物を得
ることができるが、この際１，３−ジメチル−２
−イミダゾリジノン（以下DMIと略称する。）を
再結晶溶剤として使用することができる。 In the present invention, 2,6-(4,4'-diamino-diphenyl)benzo[1,2 -d:4,5-d'] bisthiazole, characterized in that a mixture containing methanesulfonic acid and phosphorus pentoxide is used as the reaction medium.
4′-diamino-diphenyl)benzo[1,2-
d:4,5-d′] The gist of this is a method for producing bisthiazole, and after the reaction of the present invention is completed,
A crude product can be obtained by neutralization and filtration using conventional methods. The crude product can be recrystallized to obtain a purified product, but in this case, 1,3-dimethyl-2
-Imidazolidinone (hereinafter abbreviated as DMI) can be used as a recrystallization solvent.
（実施例）
次に比較例及び実施例により本発明を更に説明
するが、本発明はこれら比較例及び実施例に限定
されるものではない。(Example) Next, the present invention will be further explained with reference to Comparative Examples and Examples, but the present invention is not limited to these Comparative Examples and Examples.
比較例 １
２，５−ジアミノ−１，４−ベンゼンジチオー
ル二塩酸塩60ｇ（0.245モル）をポリリン酸3000
ｇに溶解させた。窒素下常温で30時間、50℃で15
時間、さらに減圧下、80℃で５時間撹拌を続け脱
塩酸反応を行なうと、溶液は透明、淡緑色となつ
た。さらに、常圧窒素下で、これにパラアミノ安
息香酸74ｇ（0.539モル）を加え、110℃で２時
間、150℃で4.5時間、200℃で10時間反応させた。
反応後、アンモニア水で生成物を析出させ、水洗
を繰り返し、真空乾燥して黄褐色の化合物（）
粗製物を得た。収率は71％であつた。更に窒素気
流下でこの様にして得られる粗製物100ｇを
DMI500mlに80℃で溶解し、不溶部をろ別しろ液
を室温下で徐冷し一昼夜静置したところ、黄色の
針状結晶が析出した。結晶をろ過回収してメタノ
ールでDMIを洗浄除去した後80℃で真空乾燥し
た。収率は50％であつた。Comparative Example 1 60 g (0.245 mol) of 2,5-diamino-1,4-benzenedithiol dihydrochloride was mixed with 3000 g of polyphosphoric acid.
It was dissolved in g. 30 hours at room temperature under nitrogen, 15 hours at 50℃
After further stirring for 5 hours at 80° C. under reduced pressure to carry out the dehydrochlorination reaction, the solution became transparent and pale green in color. Furthermore, 74 g (0.539 mol) of para-aminobenzoic acid was added to this under normal pressure of nitrogen, and the mixture was reacted at 110°C for 2 hours, at 150°C for 4.5 hours, and at 200°C for 10 hours.
After the reaction, the product is precipitated with aqueous ammonia, washed repeatedly with water, and dried in vacuum to form a yellow-brown compound ().
A crude product was obtained. The yield was 71%. Furthermore, 100 g of the crude product obtained in this way was added under a nitrogen stream.
It was dissolved in 500 ml of DMI at 80°C, the insoluble portion was filtered off, and the filtrate was slowly cooled at room temperature and left to stand overnight, resulting in the precipitation of yellow needle-like crystals. The crystals were collected by filtration, washed to remove DMI with methanol, and then dried under vacuum at 80°C. The yield was 50%.
実施例 １
２，５−ジアミノ−１，４−ベンゼンジチオー
ル二塩酸塩60ｇ（0.245モル）を、メタンスルホ
ン酸320ｇおよび五酸化リン32ｇから成る均一溶
液中に徐々に塩酸の発生状況をみながら加えた。Example 1 60 g (0.245 mol) of 2,5-diamino-1,4-benzenedithiol dihydrochloride was gradually added to a homogeneous solution consisting of 320 g of methanesulfonic acid and 32 g of phosphorus pentoxide while monitoring the generation of hydrochloric acid. Ta.
加え終つて30分で塩酸の発生は終了し、この段
階で淡緑色の均一溶液となつた。 The generation of hydrochloric acid stopped 30 minutes after the addition, and at this stage the solution became a pale green homogeneous solution.
70℃に昇温し、ｐ−アミノ安息香酸74ｇ
（0.539モル）を加え30分間この温度に保持した。
その間に溶液はオレンジ色に変わつた。その後10
℃／時間の速度で昇温させ、最終的に150℃で10
時間反応させた。この間に溶液は赤褐色を呈し
た。反応終了后、比較例１に示される処法を以つ
て再結晶精製物を得た。収率は50％であつた。 Raise the temperature to 70℃ and add 74g of p-aminobenzoic acid.
(0.539 mol) was added and held at this temperature for 30 minutes.
During this time the solution turned orange. then 10
The temperature was increased at a rate of ℃/hour, and finally at 150℃ for 10
Allowed time to react. During this time the solution took on a reddish-brown color. After the reaction was completed, a recrystallized purified product was obtained using the process shown in Comparative Example 1. The yield was 50%.
（発明の効果）
本発明によれば高純度の２，６−（４，4′−ジ
アミノ−ジフエニル）ベンゾ〔１，２−ｄ：４，
５−d′〕ビスチアゾールを効率よく得ることが出
来る。(Effect of the invention) According to the present invention, high purity 2,6-(4,4'-diamino-diphenyl)benzo[1,2-d:4,
5-d'] bisthiazole can be obtained efficiently.
上記比較例と実施例とを比較すれば明らかなよ
うに、化合物（）の収率の点では相違はない
が、比較例での緩慢な加熱条件に対し、本発明の
急速な加熱は、生成する塩酸の除去速度が非常に
早いことを示すものである。 As is clear from comparing the Comparative Examples and Examples above, there is no difference in the yield of compound (), but the rapid heating of the present invention is more effective than the slow heating conditions of the Comparative Examples. This shows that the removal rate of hydrochloric acid is extremely fast.
Claims (1)
ール・二塩酸塩とｐ−アミノ安息香酸とを反応さ
せて、２，６−（４，4′−ジアミノ−ジフエニル）
ベンゾ〔１，２−ｄ：４，５−d′〕ビスチアゾー
ルを製造する方法において、反応媒体としてメタ
ンスルホン酸と五酸化リンを含有する混合物を用
いることを特徴とする、２，６−（４，4′−ジア
ミノ−ジフエニル）ベンゾ〔１，２−ｄ：４，５
−d′〕ビスチアゾールの製造方法。[Claims] 1 2,6-(4,4'-diamino-diphenyl) is produced by reacting 2,5-diamino-1,4-benzenedithiol dihydrochloride with p-aminobenzoic acid.
2,6-( 4,4′-diamino-diphenyl)benzo[1,2-d:4,5
−d′] Method for producing bisthiazole.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6562788A JPH01316386A (en) | 1988-03-22 | 1988-03-22 | Production of 2,6-(4,4'-diamino-diphenyl)benzo(1,2-d:4,5-d')bisthiazole |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6562788A JPH01316386A (en) | 1988-03-22 | 1988-03-22 | Production of 2,6-(4,4'-diamino-diphenyl)benzo(1,2-d:4,5-d')bisthiazole |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01316386A JPH01316386A (en) | 1989-12-21 |
| JPH0555513B2 true JPH0555513B2 (en) | 1993-08-17 |
Family
ID=13292445
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6562788A Granted JPH01316386A (en) | 1988-03-22 | 1988-03-22 | Production of 2,6-(4,4'-diamino-diphenyl)benzo(1,2-d:4,5-d')bisthiazole |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01316386A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07220930A (en) * | 1994-02-07 | 1995-08-18 | Mosutetsuku:Kk | Lead frame body |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5766510A (en) * | 1995-08-25 | 1998-06-16 | Dai Nippon Printing Co., Ltd. | Liquid crystalline compound and use thereof |
-
1988
- 1988-03-22 JP JP6562788A patent/JPH01316386A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07220930A (en) * | 1994-02-07 | 1995-08-18 | Mosutetsuku:Kk | Lead frame body |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01316386A (en) | 1989-12-21 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |