JPH05320126A - Production of 2-amino-5-nitrothiobenzamide - Google Patents
Production of 2-amino-5-nitrothiobenzamideInfo
- Publication number
- JPH05320126A JPH05320126A JP4168156A JP16815692A JPH05320126A JP H05320126 A JPH05320126 A JP H05320126A JP 4168156 A JP4168156 A JP 4168156A JP 16815692 A JP16815692 A JP 16815692A JP H05320126 A JPH05320126 A JP H05320126A
- Authority
- JP
- Japan
- Prior art keywords
- amine
- amino
- reaction
- catalyst
- hydrogen sulfide
- 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
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
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、顔染料の中間体として
有用な２−アミノ−５−ニトロチオベンズアミドの製造
法に関するものである。TECHNICAL FIELD The present invention relates to a process for producing 2-amino-5-nitrothiobenzamide useful as an intermediate for facial dyes.
【０００２】[0002]
【従来の技術】従来、２−アミノ−５−ニトロチオベン
ズアミド（以下ＴＢＡと記す）の製造法としてはジメチ
ルフオルムアミドを反応溶媒として２−アミノ−５ニト
ロベンゾニトリル（以下ＢＮと記す）と硫化アンモニウ
ムを反応させる方法（特許：Ｃｚｅｃｈ．ＣＳ ２５６
２１５号）、イソプロパノ−ルを反応溶媒にＢＮと硫化
アンモニウムを反応させる方法（特許：Ｐｏｌ．ＰＬ
１１８６０４号）等が知られているが、これらの方法は
多量の水を使用しており、叉水溶性の反応溶媒を用いて
いるため排水処理が不可欠であり更にはその回収にも多
大な費用が必要で工業的製法としては問題がある。2. Description of the Related Art Conventionally, as a method for producing 2-amino-5-nitrothiobenzamide (hereinafter referred to as TBA), dimethylformamide was used as a reaction solvent and 2-amino-5nitrobenzonitrile (hereinafter referred to as BN) and sulfurization. Method of reacting ammonium (Patent: Czech. CS 256
215), a method of reacting BN and ammonium sulfide with isopropanol as a reaction solvent (Patent: Pol. PL.
No. 118604) is known, but since these methods use a large amount of water and use a water-soluble reaction solvent, wastewater treatment is indispensable, and further, the recovery of the wastewater is very expensive. Is necessary and there is a problem as an industrial manufacturing method.
【０００３】[0003]
【発明の解決しようとする課題】本発明は、従来の技術
が有していた前述の問題点を解決しようとするものであ
る。DISCLOSURE OF THE INVENTION The present invention is intended to solve the above-mentioned problems of the prior art.
【０００４】[0004]
【問題点を解決するための手段】本発明者等は、前述の
問題点を解決するため鋭意研究した結果、本発明を完成
するに至ったものである。即ち、本発明は、ＢＮと硫化
水素を反応溶媒中で反応させＴＢＡを製造する際、触媒
としてアミンの存在下に反応させる事を特徴とするＴＢ
Ａの製造法を提供するものである。[Means for Solving the Problems] The inventors of the present invention have completed the present invention as a result of intensive research for solving the above-mentioned problems. That is, the present invention is characterized in that when BN and hydrogen sulfide are reacted in a reaction solvent to produce TBA, they are reacted in the presence of an amine as a catalyst.
A method for producing A is provided.
【０００５】即ち、本発明の方法によれば、ＢＮと硫化
水素を反応溶媒中触媒の存在下に反応させた後、橙色の
結晶を含有した反応生成物を濾過する事により、結晶を
簡単に分離回収する事が出来る。また反応溶媒は濾過母
液から常法により蒸留にて回収出来、更にこの回収され
た反応溶媒は分折後不足分の触媒のアミンを追加し次回
の反応に再使用できる事から工業的に有利な製造法であ
る。That is, according to the method of the present invention, BN and hydrogen sulfide are reacted in the reaction solvent in the presence of a catalyst, and then the reaction product containing orange crystals is filtered to easily form crystals. Can be separated and collected. Further, the reaction solvent can be recovered from the filtered mother liquor by distillation by a conventional method, and the recovered reaction solvent can be reused for the next reaction by adding an insufficient amount of catalyst amine after the fractionation, which is industrially advantageous. It is a manufacturing method.
【０００６】本発明においては、反応溶媒として炭素数
１〜４の低級アルコールが使用できるがメタノール、イ
ソプロパノールが好ましい。又その使用量は反応系のス
ラリー濃度等よりＢＮに対して４〜５倍量（重量）が好
ましい。本発明における触媒のアミンは第２級アミン、
第３級アミンであり例えばジメチルアミン、ジエチルア
ミン、ジプロピルアミン、トリメチルアミン、トリエチ
ルアミン、トリプロピルアミン等が挙げられるが特にジ
エチルアミン、トリエチルアミンが好ましい。本発明に
おける触媒の使用量は、ＢＮに対して５〜３０重量％、
好ましくは１０〜２０重量％である。この範囲より少な
いと反応時間が延長し好ましくなく又この範囲より多く
ても何等得策ではない。In the present invention, a lower alcohol having 1 to 4 carbon atoms can be used as a reaction solvent, but methanol and isopropanol are preferable. Further, the amount used is preferably 4 to 5 times (weight) with respect to BN in view of the slurry concentration of the reaction system and the like. The amine of the catalyst in the present invention is a secondary amine,
Examples of tertiary amines include dimethylamine, diethylamine, dipropylamine, trimethylamine, triethylamine, tripropylamine, and the like, with diethylamine and triethylamine being particularly preferable. The amount of the catalyst used in the present invention is 5 to 30% by weight based on BN,
It is preferably 10 to 20% by weight. If it is less than this range, the reaction time is prolonged, which is not preferable, and if it is more than this range, it is not a good idea.
【０００７】本発明における反応温度は３０〜８０℃好
ましくは５０〜６０℃でありこの範囲より低い温度では
収率及び品位の低下をきたし好ましくない。本発明にお
けるＢＮに対する硫化水素の使用モル比は大気圧下で実
施する場合は１．０〜２．０、好ましくは１．１〜１．
５であり又加圧下の場合は１．０〜２．０、好ましくは
１．２〜１．５である。この範囲より少ないと取率及び
品位の低下をきたし好ましくなくこの範囲より多くても
何等利点はない。The reaction temperature in the present invention is 30 to 80 ° C., preferably 50 to 60 ° C., and a temperature lower than this range undesirably lowers yield and quality. The molar ratio of hydrogen sulfide to BN used in the present invention is 1.0 to 2.0, preferably 1.1 to 1.
5 and 1.0 to 2.0, preferably 1.2 to 1.5 under pressure. If it is less than this range, the yield and quality will be deteriorated and it is not preferable, and if it is more than this range, there is no advantage.
【０００８】[0008]
【実施例】以下実施例により本発明について詳細に説明
するが、本発明がこれにより何等限定されるものでない
事は勿論である。EXAMPLES The present invention will be described in detail below with reference to Examples, but it goes without saying that the present invention is not limited to these.
【０００９】実施例−１ 温度計、冷却コンデンサー、攪拌装置、硫化水素ガス導
入管を装着した３００ｍｌ容量の４つ口フラスコにＢＮ
５０ｇｒ（０．３０７モル）、イソプロパノール（以下
ＩＰＡと記す）２００ｇｒ、触媒としてジエチルアミン
８．８ｇｒを仕込んだ後、内温を５０℃に昇温しこの温
度を保ちながら硫化水素ガス１５ｇｒ（０．４４１モ
ル）を３時間を要して反応系に導入した。一部未反応で
フリーパスする硫化水素ガスはコンデンサーの塔頂部よ
り水酸化ナトリウム水溶液を仕込んである吸収トラップ
に吸収した。導入終了後同温度下に１時間の後撹拌を行
い反応を完結させた後内温を１５℃まで冷却し橙色の結
晶を濾過し少量のＩＰＡで洗浄後乾燥して５５．１ｇｒ
のＴＢＡを得た。使用したＢＮに対して９１．１％の収
率に相当する。この物の融点は１７０．５〜１７４．５
℃、又高速液体クロマトグラフィによる純度は９９．０
％であった。更に濾過母液及び洗浄母液を合し蒸留によ
りジエチルアミンを７ｇｒ含んだ２００ｇｒのＩＰＡを
回収した。Example 1 BN was placed in a four-necked flask having a capacity of 300 ml equipped with a thermometer, a cooling condenser, a stirrer, and a hydrogen sulfide gas introduction tube.
After charging 50 gr (0.307 mol), isopropanol (hereinafter referred to as IPA) 200 gr, and diethylamine 8.8 gr as a catalyst, the internal temperature was raised to 50 ° C. and hydrogen sulfide gas 15 gr (0.441) was maintained while maintaining this temperature. Mol) was introduced into the reaction system over 3 hours. Partially unreacted free-passing hydrogen sulfide gas was absorbed from the top of the condenser into an absorption trap containing an aqueous sodium hydroxide solution. After completion of the introduction, the mixture was stirred at the same temperature for 1 hour to complete the reaction, then the internal temperature was cooled to 15 ° C., orange crystals were filtered, washed with a small amount of IPA, dried and then 55.1 gr.
TBA was obtained. This corresponds to a yield of 91.1% based on the BN used. This product has a melting point of 170.5-174.5
℃, purity by high performance liquid chromatography 99.0
%Met. Further, the filtered mother liquor and the washed mother liquor were combined and distilled to recover 200 gr of IPA containing 7 gr of diethylamine.
【００１０】実施例−２ 実施例−１で回収されたＩＰＡ２００ｇｒにジエチルア
ミンを１．８ｇｒ追加し、実施例−１と同様に反応及び
処理して融点１７０．５〜１７４．５℃、純度９９．１
％のＴＢＡを５５．３ｇｒ得た。収率は９１．４％に相
当する。Example-2 1.8 gr of diethylamine was added to 200 gr of IPA recovered in Example-1, reacted and treated in the same manner as in Example-1, melting point 170.5-174.5 ° C, purity 99. 1
55.3 gr of% TBA was obtained. The yield corresponds to 91.4%.
【００１１】実施例−３ ＩＰＡの代わりにメタノ−ル２００ｇｒを使用した以外
は実施例−１と同様に行った。融点１６９〜１７２℃、
純度は９８．１％のＴＢＡを４８．４ｇｒ得た。これは
８０％の収率に相当する。Example-3 The procedure of Example-1 was repeated except that 200 gr of methanol was used instead of IPA. Melting point 169-172 ° C,
48.4 gr of TBA having a purity of 98.1% was obtained. This corresponds to a yield of 80%.
【００１２】実施例−４ ジエチルアミンの代わりにトリエチルアミン８．８ｇｒ
を使用した以外は実施例−１と同様に実施し融点１６
９．５〜１７３℃、純度９８．６％のＴＢＡ５３ｇｒを
得た。これは８７．６％の収率に相当する。Example 4 8.8 gr of triethylamine instead of diethylamine
Was carried out in the same manner as in Example 1 except that
TBA53gr having a purity of 98.6% at 9.5 to 173 ° C. was obtained. This corresponds to a yield of 87.6%.
【００１３】実施例−５ 攪拌機及びガス導入管を付した１０００ｍ１容量のオー
トクレーブに、ＢＮを８１．５ｇｒ（０．５モル）、ジ
エチルアミン１３．６ｇｒ及びＩＰＡ３２６ｇｒを仕込
み内温を５０℃まで昇温した後この温度を保ちながら１
時間を要して硫化水素ガスを３０ｇｒ（０．８８モル）
導入した。その後更に３時間の後撹拌を行って反応を完
結させた後（この間の内圧は１〜４ｋｇ／ｃｍ２を示し
た）反応生成物を常温まで冷却し、未反応で残留してい
る硫化水素ガスを水酸化ナトリウム水溶液を仕込んであ
るトラップにて捕集後、橙色の結晶を濾別した。更に少
量のＩＰＡで洗浄し乾燥して８８ｇｒのＴＢＡを得た。
これは８９．３％の収率に相当し融点及び純度は１６
９．５〜１７３．５℃、９８．６％であった。Example 5 In an autoclave of 1000 ml capacity equipped with a stirrer and a gas introduction tube, 81.5 gr (0.5 mol) of BN, 13.6 gr of diethylamine and 326 gr of IPA were charged and the internal temperature was raised to 50 ° C. Later while maintaining this temperature 1
It takes 30 gr (0.88 mol) of hydrogen sulfide gas over time.
Introduced. Then, after stirring for another 3 hours to complete the reaction (internal pressure during this time was 1 to 4 kg / cm 2 ), the reaction product was cooled to room temperature, and hydrogen sulfide gas remaining unreacted Was collected by a trap containing an aqueous sodium hydroxide solution, and then orange crystals were separated by filtration. Further, it was washed with a small amount of IPA and dried to obtain 88 gr of TBA.
This corresponds to a yield of 89.3%, a melting point and a purity of 16
It was 9.5 to 173.5 ° C and 98.6%.
【００１４】実施例−６ 硫化水素ガスを２１ｇｒ（０．６２モル）、反応圧力を
１〜２ｋｇ／ｃｍ２にした以外は実施例−５と同様に実
施し９０．４ｇｒのＴＢＡを得た。９１．８％の収率に
相当する。この物の融点及び純度は１７０．５〜１７
４．５℃、９９．０％であったExample-6 90.4 gr of TBA was obtained in the same manner as in Example-5 except that the hydrogen sulfide gas was 21 gr (0.62 mol) and the reaction pressure was 1-2 kg / cm 2 . This corresponds to a yield of 91.8%. This product has a melting point and purity of 170.5 to 17
It was 4.5 ° C and 99.0%
【００１５】比較例 触媒のジエチルアミンを使用しない以外は実施例−１と
同様に行った。水酸化ナトリウムトラップで１４．４ｇ
ｒの硫化水素が回収され、殆ど反応せず得られた目的物
はわずか０．６ｇｒであった。Comparative Example The procedure of Example 1 was repeated except that the catalyst, diethylamine, was not used. 14.4g with sodium hydroxide trap
The hydrogen sulfide of r was recovered, and the target product obtained with almost no reaction was only 0.6 gr.
【００１６】[0016]
【発明の効果】本発明の方法によれば、排水が出ず又使
用反応溶媒は簡単に回収出来、更には次回の反応に反復
使用され従来になく工業的に極めて有利に製造する事が
出きる。EFFECTS OF THE INVENTION According to the method of the present invention, no waste water is emitted and the reaction solvent used can be easily recovered, and further, the reaction solvent is repeatedly used in the next reaction, which is unprecedented and industrially extremely advantageous. Wear.
Claims (4)
硫化水素を反応溶媒中で反応させ２−アミノ−５−ニト
ロチオベンズアミドを製造する際、触媒としてアミンの
存在下に反応させる事を特徴とする２−アミノ−５−ニ
トロチオベンズアミドの製造法。1. When 2-amino-5-nitrobenzonitrile and hydrogen sulfide are reacted in a reaction solvent to produce 2-amino-5-nitrothiobenzamide, the reaction is carried out in the presence of an amine as a catalyst. A method for producing 2-amino-5-nitrothiobenzamide.
ルである請求項１記載の製造法。2. The method according to claim 1, wherein the reaction solvent is a lower alcohol having 1 to 4 carbon atoms.
は第３級アミンである請求項１記載の製造法。3. The process according to claim 1, wherein the catalyst amine is a secondary amine and / or a tertiary amine.
求項１記載の製造法。4. The production method according to claim 1, wherein the reaction is carried out under atmospheric pressure or pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4168156A JPH05320126A (en) | 1992-05-19 | 1992-05-19 | Production of 2-amino-5-nitrothiobenzamide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4168156A JPH05320126A (en) | 1992-05-19 | 1992-05-19 | Production of 2-amino-5-nitrothiobenzamide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05320126A true JPH05320126A (en) | 1993-12-03 |
Family
ID=15862856
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4168156A Pending JPH05320126A (en) | 1992-05-19 | 1992-05-19 | Production of 2-amino-5-nitrothiobenzamide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05320126A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000229920A (en) * | 1999-02-12 | 2000-08-22 | Otsuka Pharmaceut Co Ltd | Production of amide derivative |
| JP2002053546A (en) * | 2000-08-10 | 2002-02-19 | Sumitomo Seika Chem Co Ltd | Method for producing thiobenzamide compounds |
-
1992
- 1992-05-19 JP JP4168156A patent/JPH05320126A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000229920A (en) * | 1999-02-12 | 2000-08-22 | Otsuka Pharmaceut Co Ltd | Production of amide derivative |
| JP2002053546A (en) * | 2000-08-10 | 2002-02-19 | Sumitomo Seika Chem Co Ltd | Method for producing thiobenzamide compounds |
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