JPS5942376A - Thiophene compound and its preparation - Google Patents
Thiophene compound and its preparationInfo
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- JPS5942376A JPS5942376A JP15169482A JP15169482A JPS5942376A JP S5942376 A JPS5942376 A JP S5942376A JP 15169482 A JP15169482 A JP 15169482A JP 15169482 A JP15169482 A JP 15169482A JP S5942376 A JPS5942376 A JP S5942376A
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Abstract
Description
【発明の詳細な説明】
本発明は染料または農薬などの中間体とじて重要なチオ
フェン系化合物又はその製造法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thiophene compound which is important as an intermediate for dyes or agricultural chemicals, and a method for producing the same.
さらに詳しくは本発明
（１）式
（式中、Ｒは水素又はホルミルを示し、Ｘはシアン又は
低級カルボアルコキシを示し、Ｙは水素又はニトロを示
す）
で示されるチオフェン系化合物。More specifically, a thiophene compound of the present invention represented by the formula (1) (wherein R represents hydrogen or formyl, X represents cyan or lower carbalkoxy, and Y represents hydrogen or nitro).
（２）式
％式％（２）
（式中、Ｒ□は低級アルキルを示す）
で示される化合物と式
％式％（３）
（式中、Ｘハシアノ又ハＣ０ｏＲ１ヲ示シ、Ｔ（１は前
記と同じものを意味する）で示される化合物を縮合・閉
環して式
（式中、Ｘは前記と同じものを意味する。）で示される
化合物を得、ついでこの化合物を式
％式％（５）
（式中、Ｒ２は低級アルキルを示す）
で示されるジアルキルホルムアミド中オキシ塩化燐を作
用せしめて式
（式中、 Ｒ２は低級アルキルを示し、Ｘは前記と同じ
ものを意味する）
で示される化合物を得、ついでこの化合物を加水分解す
るか又はニトロ化した後加水分解することを特徴とする
式
（式中、Ｒは水素又はホルミルを示し、Ｘ及びＹは前記
と同じものを意味する）
で示されるチオフェン系化合物の製造法。(2) Formula %Formula %(2) (In the formula, R□ represents lower alkyl) Compounds represented by the formula %Formula %(3) (In the formula, X represents C0oR1, T(1 means the same thing as above) to obtain a compound represented by the formula (wherein, X means the same thing as above), and then convert this compound into the formula %formula% (5) (In the formula, R2 represents a lower alkyl) by reacting phosphorus oxychloride in a dialkylformamide represented by the formula (In the formula, R2 represents a lower alkyl, and X means the same as above) A compound represented by the formula (wherein R represents hydrogen or formyl, and X and Y have the same meanings as above) is obtained by hydrolyzing or nitrating and then hydrolyzing this compound. ) A method for producing a thiophene compound shown in
（３）式
（式中、Ｘはシアノ又はＣ０ＯＲ，を示し、Ｒ１は低級
アルキルを示す）
で示される化合物を式
％式％（５）
（式中、Ｒ２は低級アルキルを示す）
で示されるジアルキルホルムアミド中オキシ塩化燐を作
用せしめて式
（式中、Ｘ及び馬は前記と同じものを意味する）で示さ
れる化合物を得、ついでこの化合物を加水分解するか又
はニトロ化した後加水分解することを特徴とする式
（式中、Ｒ，Ｘ及びＹは前記と同じものを意味する）
で示されるチオフェン系化合物の製造法。(3) (In the formula, X represents cyano or C0OR, and R1 represents lower alkyl) A compound represented by the formula %Formula % (5) (In the formula, R2 represents lower alkyl) The reaction with phosphorus oxychloride in dialkylformamide gives a compound of the formula (wherein X and H have the same meanings as above), which is then hydrolyzed or nitrated and then hydrolyzed. A method for producing a thiophene compound represented by the formula (wherein R, X and Y have the same meanings as above), characterized in that:
（４）式
％式％（２）
（式中、几１は低級アルキルを示す）
で示される化合物と式
％式％（３１
（式中、Ｘはシアノ又はＣ０ＯＲ，を示し、馬は前記と
同じものを意味する）
で示される化合物を縮合・閉環することを特徴とする式
（式中、Ｘは前記と同じものを意味する）で示される化
合物の製造法に関する。(4) A compound represented by the formula % formula % (2) (wherein 1 represents lower alkyl) and the formula % formula % (31 (wherein, X represents cyano or C0OR, and horse is the same as the above) The present invention relates to a method for producing a compound represented by the formula (wherein, X means the same as described above), which is characterized by condensing and ring-closing the compound represented by
本発明の式（１）のチオフェン系化合物は新規であり以
下の方法によって製造することができる。The thiophene compound of formula (1) of the present invention is novel and can be produced by the following method.
先ず式（４）の化合物を製造するには式（２）の化合物
と式（３）の化合物をメタノール、エタノール等のアル
コール中トリエチルアミン、ジエチルアミン、ピリジン
等の塩基を触媒として例えばＬｏＣ〜８０Ｃで加温攪拌
することにより容易に縮合・閉環し水で希釈後、酸で中
和することによ析出せしめて涙取することが出来る。First, to produce the compound of formula (4), the compound of formula (2) and the compound of formula (3) are added in an alcohol such as methanol or ethanol using a base such as triethylamine, diethylamine, or pyridine as a catalyst at, for example, LoC to 80C. It can be easily condensed and ring-closed by warm stirring, and after dilution with water, it can be precipitated and removed by neutralization with acid.
次に、式（６）の化合物は例えば以下のようにして得る
。すなわち式（４）の化合物を式（５）の化合物で加熱
攪拌すると容易に式（６）の化合物が生成するので氷水
中に反応液を注加し、アルカリで中和して上記化合物を
析出させて戸数する。本工程に於いてオキシ塩化燐は１
モル当量が適当であって、２〜４モル当量のオキシ塩化
燐を使用すると式
であって、１モルのオキシ塩化燐の使用では殆ど純粋な
式（６）の化合物が得られることは、驚くべきことであ
る。Next, the compound of formula (6) can be obtained, for example, as follows. That is, when the compound of formula (4) is heated and stirred with the compound of formula (5), the compound of formula (6) is easily generated, so the reaction solution is poured into ice water and neutralized with alkali to precipitate the above compound. Let's count the number of houses. In this process, phosphorus oxychloride is 1
It is surprising that the molar equivalents are appropriate and that using 2 to 4 molar equivalents of phosphorus oxychloride gives an almost pure compound of formula (6), whereas using 1 mole of phosphorus oxychloride gives an almost pure compound of formula (6). It is the right thing to do.
９−
次に式（６）の化合物から式（１）の化合物を得るには
以下のようにする。すなわち式（６）の化合物を例えば
低級アルコール中硫酸水溶液又は塩酸を用いて酸性で加
熱（例えば５０Ｄ〜アルコールの沸点）すると容易に加
水分解して２−アミノ−チオフェン誘導体（式（１）に
おいてＲ＝水素の化合物）を得ることができる。文武（
６）の化合物は低級アルコール中アルカリの水溶液を使
用して例えば５０〜１００Ｃに加熱して加水分解すると
２−ホルミルアミノ−チオフェン誘導体（式（１）にお
いてＲがＣＨＯである化合物）を得ることができる。さ
らに式（１）においてＹがニトロ基の化合物は、公知の
方法例えば式（６）の化合物を硫酸に溶解し、これに混
酸を滴下しＯ±５Ｃで攪°拌してニトロ化する。（使用
する、混酸中の硝酸の量は約１モル当量でよい）。次に
反応液を氷水中に注加し析出するニトロ化合物を涙取す
る。最後にアルコール中、上記のように酸性で加水分解
すると２−アミノ−５−ニトロチオフェン誘導体が、又
アルカリ性で加水分解す１０−
ると２−ホルミルアミノ−５−ニトロチオフェン誘導体
が得られる。9- Next, to obtain the compound of formula (1) from the compound of formula (6), proceed as follows. That is, when the compound of formula (6) is heated in acidic conditions (for example, from 50D to the boiling point of alcohol) using an aqueous solution of sulfuric acid or hydrochloric acid in a lower alcohol, it is easily hydrolyzed to form a 2-amino-thiophene derivative (R in formula (1)). = hydrogen compound) can be obtained. Bunmu (
When the compound 6) is hydrolyzed using an aqueous alkali solution in a lower alcohol and heated to, for example, 50 to 100 C, a 2-formylamino-thiophene derivative (a compound in which R is CHO in formula (1)) can be obtained. can. Further, a compound in which Y in formula (1) is a nitro group can be nitrated by a known method, for example, by dissolving the compound of formula (6) in sulfuric acid, adding a mixed acid dropwise thereto, and stirring at O±5C. (The amount of nitric acid in the mixed acid used may be about 1 molar equivalent). Next, the reaction solution is poured into ice water to remove the precipitated nitro compound. Finally, acidic hydrolysis in alcohol as described above yields a 2-amino-5-nitrothiophene derivative, and alkaline hydrolysis yields a 2-formylamino-5-nitrothiophene derivative.
次に本発明に用いられる式（２）の化合物としては例え
ば５ＨＣＨ２ＣＯＯＣＨ３，５ＨＣＨ２ＣＯＯＣ２Ｈ，
、５ＨＣＨ２ＣＯＯＣ３Ｈ７，５ＨＣＨ２ＣＯＯＣ４Ｈ
９などを挙げることができる。また式（３）の化合物と
してはＮＣＣＨ２ＣＮ、 ＮＣＣｌ−ｌ２ＣＯＯＣＨ３
，ＮＣＣＨ２ＣＯＯＣ２Ｈ５，ＮＣＣＨ２Ｃ００Ｃ３Ｈ
，、ＮＣＣｌ−ｌ２ＣＯＯＣ４Ｈ９などを挙げることが
できる。さらに式（５）の化合物としては例えばジメチ
ルホルムアミド又はジエチルホルムアミドなどを挙げる
ことができる。Next, as the compound of formula (2) used in the present invention, for example, 5HCH2COOCH3, 5HCH2COOC2H,
,5HCH2COOC3H7,5HCH2COOC4H
9 etc. can be mentioned. Further, as the compound of formula (3), NCCH2CN, NCCl-l2COOCH3
,NCCH2COOC2H5,NCCH2C00C3H
, , NCCl-12COOC4H9 and the like. Furthermore, examples of the compound of formula (5) include dimethylformamide and diethylformamide.
本発明の式（１）の化合物は赤〜青色系アゾ染料のジア
ゾ成分として又農薬の中間体として有用なものである。The compound of formula (1) of the present invention is useful as a diazo component of red to blue azo dyes and as an intermediate for agricultural chemicals.
次に実施例をあげ本発明を詳述するが「部」及び「％」
は「重量部」及び「重量％」を示す。Next, the present invention will be described in detail with reference to Examples.
indicates "parts by weight" and "% by weight".
実施例１． エタノール４０部、マロンニ） ＩＪル
１３．２部、メルカプト醋酸エチル２４部を攪拌溶解し
、１５Ｃ以下でトリエチルアミン１５部を３０分で滴下
する。１５±２Ｃで１時間半、１１−
１更に４０±２°で１時間攪拌して縮合せしめる。Example 1. 40 parts of ethanol, 13.2 parts of mercaptoethyl acetate, and 24 parts of ethyl mercaptoacetate are dissolved with stirring, and 15 parts of triethylamine is added dropwise over 30 minutes at a temperature below 15C. The mixture was stirred at 15±2° C. for 1.5 hours, and 11-1 was further stirred at 40±2° for 1 hour to effect condensation.
氷水３００ ＊ｇｐ加し１５係塩酸を加えて結晶を析出
せしめる。炉別し水洗乾燥すると式（イ）の２−イミノ
−３−シアノ−２，３，４，５−テトラヒドロチオフェ
ン（−４）２５．８部を得る。Add 300*gp of ice water and add 15% hydrochloric acid to precipitate crystals. After separating in a furnace, washing with water and drying, 25.8 parts of 2-imino-3-cyano-2,3,4,5-tetrahydrothiophene (-4) of formula (A) are obtained.
ｍ、ｐ、１８９−１９ ＩＣ
ジメチルホルムアミド１２０部に上記イミノ一体２１部
を加え攪拌溶解せしめＩｏｎ以下でオキシ塩化燐２４．
０部を約２０分を要して滴下する。１５Ｃ±２°で１時
間４０±５Ｃで１時間攪拌した後氷水１３００部に注加
する。１５％苛性ソーダ液約１１０部を加えｐＨ＝５−
６迄中和する。３時間１０±２Ｃで攪拌し析出した結晶
を炉別水洗する。m, p, 189-19 IC Add 21 parts of the above imino monomer to 120 parts of dimethylformamide, stir and dissolve. Phosphorous oxychloride 24.
Add 0 parts dropwise over a period of about 20 minutes. After stirring for 1 hour at 15C±2° and 1 hour at 40±5C, the mixture was poured into 1300 parts of ice water. Add approximately 110 parts of 15% caustic soda solution to pH = 5-
Neutralize up to 6. The mixture was stirred at 10±2C for 3 hours, and the precipitated crystals were washed in a separate furnace with water.
下記式仲）のアミジン誘導体２２部が得られる。22 parts of an amidine derivative of the following formula (N) are obtained.
ｍ、ｐ、８６−８８ ’Ｃ
マススペクトルの親ピークは２１３を示し、下記式（ロ
）と一致する。m, p, 86-88'C The parent peak of the mass spectrum shows 213, which matches the following formula (b).
上記アミジン誘導体１５部をエタノ−シマ０部忙溶解し
濃硫酸（９６％）７部を加え約１時間還流せしめる。そ
の後氷水４００部に注加し、苛性ソーダ水溶液を加えて
ｐＨ＝＝７−８まで中和する。この水溶液よりエーテル
を用いて抽出し無水芒硝で乾燥後、減圧下にエーテルを
除去する。下記式（ハ）の２−アミノ−３−シアノ−４
−クロル−チオフェン１０部が油状物として得られる。15 parts of the above-mentioned amidine derivative were dissolved in 0 parts of ethanol, and 7 parts of concentrated sulfuric acid (96%) was added thereto, followed by refluxing for about 1 hour. Thereafter, the mixture was poured into 400 parts of ice water and neutralized to pH=7-8 by adding an aqueous solution of caustic soda. This aqueous solution is extracted with ether, dried over anhydrous sodium sulfate, and then the ether is removed under reduced pressure. 2-amino-3-cyano-4 of the following formula (c)
10 parts of -chloro-thiophene are obtained as an oil.
マススペクトルの親ピークは１５８で下記式（ハ）に一
致し、ＩＲスペクトルは（７４０，、，８５０゜９００
．１０９５，１２６０，１４００，１４９０，１６００
゜１７３０．２２００，２９５０，３１５０，３３００
．３４００ｃｍ−”）に吸収を示す。又ｐ−ジメチルベ
ンズアルデヒドとアルコール中、ペビリジン触媒で縮合
すると下記式に）のシッフ塩基が得られｍ、ｐ。The parent peak of the mass spectrum is 158, which corresponds to the following formula (c), and the IR spectrum is (740,,,850°900
．． 1095, 1260, 1400, 1490, 1600
゜1730.2200,2950,3150,3300
．． When p-dimethylbenzaldehyde and p-dimethylbenzaldehyde are condensed in alcohol with a peviridine catalyst, the Schiff base of the following formula is obtained (m, p).
１８２−１８４Ｃを示す。182-184C is shown.
１３一
式（ロ）のアミジン誘導体５．５部をエタノール４０部
に溶解し１００以下で８％苛性ソーダ水溶液２０部を滴
下する。２５±２０で２時間５０士５Ｃで３０分攪拌し
た後氷水２００部に注加する。後希塩酸を加えて中和し
析出する結晶を炉別する。5.5 parts of the amidine derivative of set 13 (b) is dissolved in 40 parts of ethanol, and 20 parts of an 8% aqueous solution of caustic soda at a concentration of 100% or less is added dropwise. After stirring for 2 hours at 25±20° C. and 30 minutes at 5° C., the mixture was poured into 200 parts of ice water. After that, dilute hydrochloric acid is added to neutralize and the precipitated crystals are separated by furnace.
下記式（ホ））の２−ホルミルアミノ一体が得られマス
スペクトルの親ピークは１８６を示し、ｍ、ｐ、は１０
２−１０４０である。A 2-formylamino monomer of the following formula (e) was obtained, the parent peak of the mass spectrum was 186, and m and p were 10
It is 2-1040.
実施例２゜
シアン醋酸エチル２２．６部、メルカプト醋酸エチル２
４．０部、エタノール４０部を攪拌下Ｌｏｔ：
・以下でトリエチルアミン１５部を滴下する。、１５部
２℃で１時間４５±２Ｃで１時間攪拌する。これを氷水
４００部に注加し、１５部ｇ）塩酸３０部を加えてｐＨ
＝５迄中和すると下記式（へ）の２−イミノ１４−
＝３−カルボエトキシ−２，３，４，５−テトラヒドロ
チオフェノン（−４）が析出するので炉別、水洗、乾燥
する。３３部が得られる。ｍ、ｐ、 １５０−ｉ５２？
：Ｊ
同様にシアン醋酸エチル２２．６部のかわりにシアノ醋
醪メチル１９．８部を使用すると２−イミノ−３−カル
ボメトキシ−２，３，４，５−テトラヒドロチオフェノ
ン（−４）３０部が得られる。ｍ、ｐ、 １７７１７８
Ｃ
ジメチルホルムアミド１００部に上記イミノ一体２８部
を攪拌下溶解し、オキシ塩化燐２４部を１０ｔ）’以下
で約３０分を要して滴下する。１５±２０で１時間、５
０−６００で１時間攪拌した後氷水１３００部に注加す
る。１５％苛性ソーダ約１４０部を加えてｐＨ＝５迄中
和し３時間攪拌する。下記式（ト）のアミジンが油状に
析出し、次にこれを水で洗滌すると約３０部が得られる
。このものはマススペクトルの親ピークは２６０を示し
、式（ト）の化合物と一致する。Example 2 22.6 parts of ethyl cyanacetate, 2 parts of ethyl mercaptoacetate
Lot of 4.0 parts and 40 parts of ethanol under stirring:
- Add 15 parts of triethylamine dropwise below. , 15 parts at 2° C. for 1 hour and stirred at 45±2° C. for 1 hour. Pour this into 400 parts of ice water and add 15 parts g) 30 parts of hydrochloric acid to adjust the pH.
When neutralized to =5, 2-imino 14- =3-carboethoxy-2,3,4,5-tetrahydrothiophenone (-4) of the following formula (2) precipitates, which is separated in a furnace, washed with water, and dried. 33 parts are obtained. m, p, 150-i52?
:J Similarly, when 19.8 parts of methyl cyanoacetate is used instead of 22.6 parts of ethyl cyanacetate, 2-imino-3-carbomethoxy-2,3,4,5-tetrahydrothiophenone (-4) 30 part is obtained. m, p, 177178
C. 28 parts of the above imino monomer is dissolved in 100 parts of dimethylformamide under stirring, and 24 parts of phosphorus oxychloride is added dropwise to the solution under 10 tons over a period of about 30 minutes. 1 hour at 15±20, 5
After stirring at 0-600 for 1 hour, the mixture was poured into 1300 parts of ice water. About 140 parts of 15% caustic soda was added to neutralize the mixture to pH=5, and the mixture was stirred for 3 hours. Amidine of the following formula (g) is precipitated in the form of an oil, which is then washed with water to obtain about 30 parts. The parent peak of this mass spectrum is 260, which is consistent with the compound of formula (g).
上記アミジン１５部をアルコール１００部に溶解し濃硫
酸１０部を加えて１時間還流する。水４００部に性別後
苛性ソーダ液を加えてｐｉ（＝ ５−７迄中和する。こ
の水溶液よりエーテルで抽出しエーテル溶液に無水芒硝
を加えて乾燥後、減圧下エーテルを除去する。下記式（
ホ）のアミノ−チオフェン９．５部が油状で得られる。15 parts of the above amidine was dissolved in 100 parts of alcohol, 10 parts of concentrated sulfuric acid was added, and the mixture was refluxed for 1 hour. After sex, add caustic soda solution to 400 parts of water and neutralize to pi (= 5-7). Extract from this aqueous solution with ether, add anhydrous sodium sulfate to the ether solution, dry, and remove the ether under reduced pressure. The following formula (
9.5 parts of amino-thiophene (e) are obtained in the form of an oil.
マススペクトルの親ピークは２０５で武力に一致し、１
．Ｉ％、スペクトルは（７３０，８５０，９０５，１０
９０，１１９０，１２６０゜１３３０．１．３７０．１
４９０．１５９０，１６５０，１７４０゜２３００．２
９７０．．３１３０．３４５０ｉ”）に吸収を示した。The parent peak of the mass spectrum is 205, which corresponds to force, and 1
．． I%, the spectrum is (730, 850, 905, 10
90,1190,1260゜1330.1.370.1
490.1590, 1650, 1740°2300.2
970. ．． 3130.3450i'').
又上記アミジン１５部をアルコール１００部に溶解し２
０曝苛性ソ一ダ水溶液３０部を加え１時間還流する。こ
の反応液を氷水５００部に注加し、塩酸を加えてｐＨ＝
５迄中和する。上記式（す）のホルミルアミノ一体が析
出するので炉別し、水洗乾燥する。１０．８部が得られ
、マススペクトルの親ピークは２３３を示して式（男に
一致し、ｍ、ｐ、７７−７８ｒを示す。In addition, 15 parts of the above amidine was dissolved in 100 parts of alcohol, and 2
Add 30 parts of aqueous sodium hydroxide solution and reflux for 1 hour. This reaction solution was poured into 500 parts of ice water, and hydrochloric acid was added to adjust the pH to
Neutralize up to 5. Since the formylamino of the above formula (S) is precipitated, it is separated in an oven, washed with water and dried. 10.8 parts were obtained, and the parent peak in the mass spectrum showed 233, corresponding to the formula (m, p, 77-78r).
又上記式（ト）のアミジン１５部をアルコール１００部
に溶解し６６Ｂ１硫酸１０部を加えて１時間還流後冷却
し、更に２０％苛性ソーダ５０部を加えて７５±２Ｃで
４時間加熱する。氷水３００部に注加し、濃塩酸を加え
てｐＨ＝３迄中和する。炉別して残渣を除き、流液から
エーテルで抽出し、減圧下にエーテルを除去する。上記
式評）のチオフェンカルボン醒が得られ、マススペクト
ルの親ピークは１７７を示し、ｍ、ｐ、 １２３°（分
解）を示す。Further, 15 parts of amidine of the above formula (g) is dissolved in 100 parts of alcohol, 10 parts of 66B1 sulfuric acid is added, and the mixture is refluxed for 1 hour and then cooled.Furthermore, 50 parts of 20% caustic soda is added and heated at 75±2C for 4 hours. Pour into 300 parts of ice water, and add concentrated hydrochloric acid to neutralize to pH=3. The residue is removed from the furnace, the flow is extracted with ether, and the ether is removed under reduced pressure. The thiophene carboxylate of the above formula was obtained, and the parent peak in the mass spectrum was 177, with m, p, and 123° (decomposition).
実施例３゜
実施例２記載の式（ト）のアミジン２０部を６６Ｂｉ硫
酸１８０部に加え１０Ｃ以下で攪拌して溶解せ１７−
しめる。濃硝酸４．７部（ｄ＝１．ｓ２）濃硫酸１０部
からなる混酸を一５±２Ｃで約１時間を要し滴下し更に
３０分攪拌する。氷水７００部に性別後ややハルツ状に
析出するニトロ体を分離し、水洗する。これにアルコー
ル１００部を加えて溶解し、濃硫酸１０部を加えて４時
間還流する。その後熱濾過して残査を除き、アルコール
溶液を氷水５００部に注加し食塩２０部を加えて攪拌す
る。Example 3 20 parts of the amidine of formula (g) described in Example 2 was added to 180 parts of 66Bi sulfuric acid and dissolved by stirring at 10C or less. A mixed acid consisting of 4.7 parts of concentrated nitric acid (d=1.s2) and 10 parts of concentrated sulfuric acid was added dropwise at -5±2C over about 1 hour, and the mixture was further stirred for 30 minutes. After sex, the nitro compound which precipitates in a slightly Harz shape is separated and washed with water in 700 parts of ice water. Add 100 parts of alcohol to dissolve the mixture, add 10 parts of concentrated sulfuric acid, and reflux for 4 hours. Thereafter, the residue was removed by hot filtration, and the alcohol solution was poured into 500 parts of ice water, 20 parts of common salt was added, and the mixture was stirred.
や＼ハルツ状の下記式四のニトロチオフェン誘導体が得
られる。メタノール−アセトン（８：２）より再結晶す
るとｍ、ｐ、２１６−２１９０を示す。or \Harz-like nitrothiophene derivatives of the following formula 4 are obtained. Recrystallization from methanol-acetone (8:2) gives m, p, 216-2190.
ニトロチオフェン（ワを常法により、酢酸−プロピオン
酸（４：１）に溶解しニトロシル硫酸を０士２０で加え
てジアゾ化し、ＮＮ−ジエチルーアセトメタミンの水溶
液に加えてカップリングすると下記式（力）のモノアゾ
染料が得られ、λｍａｘ６１８ｎｍ（８５％アンセン溶
液）を示し、ポリエステル繊維を青色に染色する。When nitrothiophene (wa) is dissolved in acetic acid-propionic acid (4:1) by a conventional method, diazotized by adding nitrosyl sulfuric acid at a ratio of 0 to 20, and coupled by adding it to an aqueous solution of NN-diethyl acetomethamine, the following formula is obtained. A monoazo dye of (10%) is obtained which exhibits a λmax of 618 nm (85% Ansen solution) and dyes polyester fibers in blue.
１８− ＮＨＣＯＣＨ３ 特許出願人 日本化薬株式会社 １９−18- NHCOCH3 Patent applicant: Nippon Kayaku Co., Ltd. 19-
Claims (4)
低級カルボアルコキシを示し、Ｙは水素又はニトロを示
す） で示されるチオフェン系化合物。(1) A thiophene compound represented by the formula (wherein R represents hydrogen or formyl, X represents cyano or lower carbalkoxy, and Y represents hydrogen or nitro).
同じものを意味する）で示される化合物を縮合・閉環し
て式 （式中、Ｘは前記と同じものを意味する。）で示される
化合物を得、ついでとの化合物を式 ％式％（５１ （式中、Ｒ２は低級アルキルを示す） で示されるジアルキルホルムアミド中オキシ塩化燐を作
用せしめて式 （式中、Ｒ２は低級アルキルを示し、Ｘは前記と同じも
のを意味する） で示される化合物を得、ついでこの化合物を加水分解す
るか又はニトロ化した後加水分解 ：することを特
徴とする式 （式中、Ｒは水素又はホルミルを示し、Ｘ及びＹは前記
と同じものを意味する） で示されるチオフェン系化合物の製造法。(2) Compounds represented by the formula % formula % (21 (in the formula, R1 represents lower alkyl) and the formula % formula % (31 (in the formula, X represents cyano or C0OR□, R ) is condensed and ring-closed to obtain a compound represented by the formula (wherein, (wherein, R2 represents lower alkyl) A compound represented by the formula (wherein R2 represents lower alkyl and X means the same as above) is obtained by reacting phosphorus oxychloride in dialkylformamide represented by , then this compound is hydrolyzed or nitrated and then hydrolyzed: (wherein R represents hydrogen or formyl, and X and Y have the same meanings as above) A method for producing thiophene-based compounds.
級アルキルを示す） で示される化合物を式 ％式％（５１ （式中、Ｒ２は低級アルキルを示す） で示されるジアルキルホルムアミド中オキシ塩化燐を作
用せしめて式 （式中、Ｘ及びＲ２は前記と同じものを意味する）で示
される化合物を得、ついでこの化合物を加水分解するか
又はニトロ化した後加水分解することを特徴とする式 （式中、Ｒ９Ｘ及びＹは前記と同じものを意味する）で
示されるチオフェン系化合物の製造法。(3) A compound represented by the formula (wherein, X represents sia, ) or C0OR, and R1 represents lower alkyl) is represented by the formula % (51 (wherein, R2 represents lower alkyl)) phosphorus oxychloride in dialkylformamide to obtain a compound represented by the formula (wherein X and R2 have the same meanings as above), which is then hydrolyzed or nitrated and then hydrolyzed. A method for producing a thiophene compound represented by the formula (wherein R9X and Y have the same meanings as described above).
同じものを意味する）で示される化合物を縮合・閉環す
ることを特徴とする式（式中、Ｘは前記と同じものを意
味する）で示される化合物の製造法。(4) Compounds represented by the formula % formula % (21 (in the formula, R1 represents lower alkyl) and the formula % formula % (3) (in the formula, X represents cyano or COOR1, and R1 is the same as above) A method for producing a compound represented by the formula (wherein, X means the same as defined above), which comprises condensing and ring-closing the compound represented by the formula (wherein, X means the same as defined above).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15169482A JPS5942376A (en) | 1982-09-02 | 1982-09-02 | Thiophene compound and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15169482A JPS5942376A (en) | 1982-09-02 | 1982-09-02 | Thiophene compound and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5942376A true JPS5942376A (en) | 1984-03-08 |
| JPH03393B2 JPH03393B2 (en) | 1991-01-07 |
Family
ID=15524217
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15169482A Granted JPS5942376A (en) | 1982-09-02 | 1982-09-02 | Thiophene compound and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5942376A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61212579A (en) * | 1985-03-02 | 1986-09-20 | バスフ アクチェン ゲゼルシャフト | Thiophene derivative |
| US4837269A (en) * | 1986-07-03 | 1989-06-06 | Basf Aktiengesellschaft | 2-aminothiophene radical substituted by an electron withdrawing group |
| US5206375A (en) * | 1985-03-02 | 1993-04-27 | Basf Aktiengesellschaft | Thiophene derivatives |
| US5679800A (en) * | 1984-08-30 | 1997-10-21 | Clariant Finance (Bvi) Limited | 2-Amino-3,5,disubstituted-4-halothiophenes and processes for the synthesis thereof |
-
1982
- 1982-09-02 JP JP15169482A patent/JPS5942376A/en active Granted
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5679800A (en) * | 1984-08-30 | 1997-10-21 | Clariant Finance (Bvi) Limited | 2-Amino-3,5,disubstituted-4-halothiophenes and processes for the synthesis thereof |
| JPS61212579A (en) * | 1985-03-02 | 1986-09-20 | バスフ アクチェン ゲゼルシャフト | Thiophene derivative |
| US5206375A (en) * | 1985-03-02 | 1993-04-27 | Basf Aktiengesellschaft | Thiophene derivatives |
| US4837269A (en) * | 1986-07-03 | 1989-06-06 | Basf Aktiengesellschaft | 2-aminothiophene radical substituted by an electron withdrawing group |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03393B2 (en) | 1991-01-07 |
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