JPS6147175B2 - - Google Patents
Info
- Publication number
- JPS6147175B2 JPS6147175B2 JP5006379A JP5006379A JPS6147175B2 JP S6147175 B2 JPS6147175 B2 JP S6147175B2 JP 5006379 A JP5006379 A JP 5006379A JP 5006379 A JP5006379 A JP 5006379A JP S6147175 B2 JPS6147175 B2 JP S6147175B2
- Authority
- JP
- Japan
- Prior art keywords
- general formula
- lower alkyl
- alkyl group
- formula
- naphtholactam
- 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
Links
- 239000003054 catalyst Substances 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- -1 inorganic acid halide Chemical class 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 238000006482 condensation reaction Methods 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 3
- 239000000981 basic dye Substances 0.000 claims description 3
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229920003002 synthetic resin Polymers 0.000 claims description 3
- 239000000057 synthetic resin Substances 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000000975 dye Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- GPYLCFQEKPUWLD-UHFFFAOYSA-N 1h-benzo[cd]indol-2-one Chemical compound C1=CC(C(=O)N2)=C3C2=CC=CC3=C1 GPYLCFQEKPUWLD-UHFFFAOYSA-N 0.000 description 1
- KHABYXGVKDDLGT-UHFFFAOYSA-N 6-bromo-1-ethylbenzo[cd]indol-2-one Chemical compound C1=CC(N(CC)C2=O)=C3C2=CC=CC3=C1Br KHABYXGVKDDLGT-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 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
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- DVHTZYZBKUFUOA-UHFFFAOYSA-N n-(2-ethoxyethyl)-n-ethylaniline Chemical compound CCOCCN(CC)C1=CC=CC=C1 DVHTZYZBKUFUOA-UHFFFAOYSA-N 0.000 description 1
- MKEXQAIUIWQDQV-UHFFFAOYSA-N n-(2-ethoxyethyl)-n-methylaniline Chemical compound CCOCCN(C)C1=CC=CC=C1 MKEXQAIUIWQDQV-UHFFFAOYSA-N 0.000 description 1
- IBRLRCIVUSLMRB-UHFFFAOYSA-N n-(2-methoxyethyl)-n-methylaniline Chemical compound COCCN(C)C1=CC=CC=C1 IBRLRCIVUSLMRB-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- UXCDUFKZSUBXGM-UHFFFAOYSA-N phosphoric tribromide Chemical compound BrP(Br)(Br)=O UXCDUFKZSUBXGM-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Coloring (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Description
本発明は塩基性染料の製造方法に関するもので
ある。下記一般式〔〕
（式中、R1は水素原子、低級アルキル基、シアノ
低級アルキル基、又はカルボキシル基もしくはカ
ルバモイル基で置換された低級アルキル基、R2
及びR3は低級アルキル基又は低級アルコキシア
ルキル基を示し、Ｘは水素原子又はハロゲン原
子、Ｙは陰イオンを示す）で表わされるナフトス
チリル系の塩基性染料は主にアクリル繊維用の染
料として優れており広く利用されている。通常、
この染料を製造する場合には、下記一般式〔〕
（式中、R1及びＸは前示一般式と同じ意義を有す
る）で表わされる化合物と下記一般式〔〕
（式中、R2〜R3は前示一般式と同じ意義を有す
る）で表わされる化合物とを無機酸ハライドを縮
合剤として触媒の存在下、縮合反応させることに
より製造されている。この反応は無機酸ハライド
の金属腐蝕性のため通常ガラスないし耐蝕性樹脂
でライニングされた反応器中で行われている。
本発明者等は前示一般式〔〕の化合物と前示
一般式〔〕の化合物とを反応させるための新規
な触媒を得ることを目的として種々検討した結
果、ある特定の金属が触媒として有効であること
を見い出し本発明を完成した。
すなわち、本発明の要旨は、下記一般式〔〕
（式中、R1は水素原子、低級アルキル基、シアノ
低級アルキル基、又はカルボキシル基もしくはカ
ルバモイル基で置換された低級アルキル基を示
し、Ｘは水素原子又はハロゲン原子を示す）で表
わされる化合物と下記一般式〔〕
（式中、R2及びR3は低級アルキル基又は低級アル
コキシアルキル基を示す）で表わされる化合物と
を、少くとも内壁がガラス又は耐蝕性合成樹脂で
構成された反応器を用い、無機酸ハライドの存在
下、縮合反応させて下記一般式〔〕
（式中、R1〜R3及びＸは前示一般式と同じ意義を
有し、Ｙは陰イオンを示す）で表わされる塩基性
染料を製造するに当り、亜鉛、銅及び鉄から選ば
れた少なくとも一種の金属触媒を使用することを
特徴とする塩基性染料の製造方法に存する。
以下、本発明を詳細に説明する。
本発明で対象となる前示一般式〔〕で表わさ
れる化合物の具体例としては、例えば、１・８−
ナフトラクタム、４−ブロム−１・８−ナフトラ
クタム、Ｎ−メチル−１・８−ナフトラクタム、
Ｎ−エチル−１・８−ナフトラクタム、Ｎ−プロ
ピル−１・８−ナフトラクタム、Ｎ−シアノメチ
ル−１・８−ナフトラクタム、Ｎ−シアノエチル
−１・８−ナフトラクタム、Ｎ−シアノプロピル
−１・８−ナフトラクタム、４−ブロム−Ｎ−メ
チル−１・８−ナフトラクタム、４−ブロム−Ｎ
−エチル−１・８−ナフトラクタム、４−ブロム
−Ｎ−シアノメチル−１・８−ナフトラクタム、
４−ブロム−Ｎ−シアノエチル−１・８−ナフト
ラクタム、４−クロル−１・８−ナフトラクタ
ム、４−クロル−Ｎ−エチル−１・８−ナフトラ
クタム、４−クロル−Ｎ−シアノエチル−１・８
−ナフトラクタム、４−ヨード−Ｎ−プロピル−
１・８−ナフトラクタム、４−ヨード−Ｎ−シア
ノエチル−１・８−ナフトラクタム、Ｎ−β−カ
ルボキシエチル−１・８−ナフトラクタム、Ｎ−
β−カルバモイルエチル−１・８−ナフトラクタ
ムなどが挙げられる。
一方、前示一般式〔〕で表わされる化合物と
しては、例えば、Ｎ・Ｎ−ジメチル−アニリン、
Ｎ・Ｎ−ジエチル−アニリン、Ｎ・Ｎ−ジ−ｎ−
プロピル−アニリン、Ｎ・Ｎ−ジ−イソ−プロピ
ル−アニリン、Ｎ・Ｎ−ジ−メトキシエチル−ア
ニリン、Ｎ−Ｎ−ジ−エトキシエチル−アニリ
ン、Ｎ・Ｎ−ジ−メトキシ−ｎ−プロピル−アニ
リン、Ｎ・Ｎ−ジ−エトキシ−イソ−プロピル−
アニリン、Ｎ−メチル−Ｎ−メトキシエチル−ア
ニリン、Ｎ−メチル−Ｎ−エトキシエチル−アニ
リン、Ｎ−エチル−Ｎ−エトキシエチル−アニリ
ン、Ｎ−ｎ−プロピル−Ｎ−メトキシエチル−ア
ニリンなどが挙げられる。
前示一般式〔〕と前示一般式〔〕との化合
物の使用割合は通常、0.5〜1.5モル倍程度であ
り、好ましくは等モル付近である。
本発明の反応で縮合剤として使用する無機酸ハ
ライドとしては、例えば、オキシ塩化リン、オキ
シ臭化リン、三塩化リン、三臭化リン、チオニル
クロライドなどが挙げられる。この無機酸ハライ
ドを選ぶことにより前示一般式〔〕のＹが決定
される。無機酸ハライドの使用量は通常、前示一
般式〔〕の化合物に対し、２〜20モル倍、好ま
しくは３〜７モル倍である。本発明では無機酸ハ
ライドを使用するため、反応器としてはガラス又
はフエノール樹脂、メラミン樹脂などの合成樹脂
ライニングを施したものが使用される。
上述のような前示一般式〔〕と前示一般式
〔〕の化合物を無機酸ハライドの存在下で縮合
反応させるが、本発明ではこの反応に当り、亜
鉛、銅及び鉄から選ばれた少くとも一種の金属触
媒を使用することを必須の要件とするものであ
る。
これら金属触媒は触媒としての使用に適した形
態であればよく例えば網状、線状、粉末状等種々
の形態のものが使用できるが、粉末状のものを使
用するのが簡便である。これら金属は、縮合反応
を損わない適当な担体に担持させた担持金属触媒
として使用することもできる。
金属触媒の使用量は通常、前示一般式〔〕の
化合物に対して、0.1〜５モル倍、好ましくは0.3
〜１モル倍である。触媒量があまり少ないと反応
が良好に行なわれず、また、あまり多すぎても効
果の著しい向上はなく経済的でないので好ましく
ない。
本発明での反応温度は通常、20〜120℃、好ま
しくは60〜90℃であり、反応時間は通常、２〜20
時間、好ましくは４〜10時間である。本発明の反
応は通常、反応原料、縮合剤及び触媒の全てを仕
込み反応を行なうか又は予め、前示一般式〔〕
の化合物と縮合剤、触媒を反応器に仕込み反応温
度に加温したのち、撹拌下、前示一般式〔〕の
化合物を滴下することにより行なわれる。また、
本発明では不活性希釈剤を使用して反応を行なつ
てもよいが、通常、無機酸ハライドを過剰に使用
することにより溶媒としての効果を兼ねるのが好
ましい。
反応終了後の混合物は常法に従い、先ず、過剰
の無機酸ハライドを十分に加水分解できる多量の
水と混合処理したのち、苛性ソーダ水溶液を添加
して混合物のPHを0.5〜５程度に調節することに
より前示一般式〔〕の化合物の結晶を析出させ
る。
次に、本発明を実施例により更に詳細に説明す
るが、本発明はその要旨を超えない限り以下の実
施例に限定されるものではない。
実施例 １
Ｎ−シアノエチル−１・８−ナフトラクタム
0.05モル（11.1ｇ）、Ｎ・Ｎ−ジエチルアニリン
0.075モル（11.2ｇ）、オキシ塩化リン0.3モル（45
ｇ）及び第１表に示す金属粉末（和光純薬製、試
薬１級）４ｇを反応器（ガラス製）に仕込み、撹
拌下、90℃にて４時間反応を行なつた。
反応終了後、混合物を０℃の氷水1100ｇ中に放
出し撹拌処理したのち、25％苛性ソーダ水溶液を
PHが2.5になるまで加え、青色の染料結晶を析出
させた。
染料結晶を過し、洗浄、乾燥し、得られた染
料結晶の収率を計算し、第１表に示す結果を得
た。
The present invention relates to a method for producing basic dyes. General formula below [] (In the formula, R 1 is a hydrogen atom, a lower alkyl group, a cyano lower alkyl group, or a lower alkyl group substituted with a carboxyl group or a carbamoyl group, R 2
and R 3 represents a lower alkyl group or a lower alkoxyalkyl group; It is widely used. usually,
When producing this dye, the following general formula [] (In the formula, R 1 and X have the same meanings as in the above general formula) and the following general formula [] (In the formula, R 2 to R 3 have the same meanings as in the general formula above) are produced by condensation reaction using an inorganic acid halide as a condensing agent in the presence of a catalyst. This reaction is usually carried out in a reactor lined with glass or corrosion-resistant resin because of the corrosive nature of inorganic acid halides. The present inventors have conducted various studies aimed at obtaining a new catalyst for reacting the compound of the above general formula [] with the compound of the above general formula [], and have found that a certain specific metal is effective as a catalyst. We have discovered that this is the case and have completed the present invention. That is, the gist of the present invention is the following general formula [] (In the formula, R 1 represents a hydrogen atom, a lower alkyl group, a cyano lower alkyl group, or a lower alkyl group substituted with a carboxyl group or a carbamoyl group, and X represents a hydrogen atom or a halogen atom) General formula below [] (In the formula, R 2 and R 3 represent a lower alkyl group or a lower alkoxyalkyl group) using a reactor whose inner wall is made of glass or corrosion-resistant synthetic resin, an inorganic acid halide A condensation reaction is carried out in the presence of the following general formula [] (In the formula, R 1 to R 3 and X have the same meanings as in the above general formula, and Y represents an anion.) The present invention relates to a method for producing a basic dye characterized by using at least one metal catalyst. The present invention will be explained in detail below. Specific examples of compounds represented by the above general formula [] that are the object of the present invention include, for example, 1,8-
Naphtholactam, 4-bromo-1,8-naphtholactam, N-methyl-1,8-naphtholactam,
N-ethyl-1,8-naphtholactam, N-propyl-1,8-naphtholactam, N-cyanomethyl-1,8-naphtholactam, N-cyanoethyl-1,8-naphtholactam, N-cyanopropyl-1,8-naphtholactam , 4-bromo-N-methyl-1,8-naphtholactam, 4-bromo-N
-ethyl-1,8-naphtholactam, 4-bromo-N-cyanomethyl-1,8-naphtholactam,
4-bromo-N-cyanoethyl-1,8-naphtholactam, 4-chloro-1,8-naphtholactam, 4-chloro-N-ethyl-1,8-naphtholactam, 4-chloro-N-cyanoethyl-1,8
-naphtholactam, 4-iodo-N-propyl-
1,8-naphtholactam, 4-iodo-N-cyanoethyl-1,8-naphtholactam, N-β-carboxyethyl-1,8-naphtholactam, N-
Examples include β-carbamoylethyl-1,8-naphtholactam. On the other hand, examples of the compound represented by the general formula [] include N.N-dimethyl-aniline,
N・N-diethyl-aniline, N・N-di-n-
Propyl-aniline, N・N-di-iso-propyl-aniline, N・N-di-methoxyethyl-aniline, N-N-di-ethoxyethyl-aniline, N・N-di-methoxy-n-propyl- Aniline, N・N-di-ethoxy-iso-propyl-
Aniline, N-methyl-N-methoxyethyl-aniline, N-methyl-N-ethoxyethyl-aniline, N-ethyl-N-ethoxyethyl-aniline, N-n-propyl-N-methoxyethyl-aniline, etc. It will be done. The ratio of the compounds of the above general formula [] and the above general formula [] to be used is usually about 0.5 to 1.5 moles, preferably about equimolar. Examples of the inorganic acid halide used as a condensing agent in the reaction of the present invention include phosphorus oxychloride, phosphorus oxybromide, phosphorus trichloride, phosphorus tribromide, and thionyl chloride. By selecting this inorganic acid halide, Y in the general formula [] is determined. The amount of the inorganic acid halide to be used is usually 2 to 20 times, preferably 3 to 7 times, the amount of the compound represented by the general formula []. Since an inorganic acid halide is used in the present invention, a reactor lined with glass or a synthetic resin such as phenol resin or melamine resin is used. The above-mentioned general formula [] and the compound of the above-mentioned general formula [] are subjected to a condensation reaction in the presence of an inorganic acid halide. Both require the use of a type of metal catalyst. These metal catalysts may be in various forms as long as they are suitable for use as catalysts, such as net, linear, powder, etc., but it is convenient to use powder. These metals can also be used as supported metal catalysts supported on suitable carriers that do not impair the condensation reaction. The amount of the metal catalyst used is usually 0.1 to 5 moles, preferably 0.3 times the amount of the compound of the general formula [] shown above.
~1 mole times. If the amount of catalyst is too small, the reaction will not be carried out well, and if it is too large, the effect will not be significantly improved and it will be uneconomical, which is not preferable. The reaction temperature in the present invention is usually 20 to 120°C, preferably 60 to 90°C, and the reaction time is usually 2 to 20°C.
time, preferably 4 to 10 hours. The reaction of the present invention is usually carried out by charging all of the reaction raw materials, condensing agent, and catalyst, or by preliminarily preparing the reaction according to the general formula []
The reaction is carried out by charging the compound, the condensing agent, and the catalyst into a reactor and heating it to the reaction temperature, and then adding the compound of the general formula [] dropwise under stirring. Also,
In the present invention, the reaction may be carried out using an inert diluent, but it is usually preferable to use an excess of the inorganic acid halide so that it also serves as a solvent. After the reaction is completed, the mixture is mixed according to a conventional method with a large amount of water that can sufficiently hydrolyze excess inorganic acid halide, and then an aqueous solution of caustic soda is added to adjust the pH of the mixture to about 0.5 to 5. Crystals of the compound of the general formula [] are precipitated by this method. Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. Example 1 N-cyanoethyl-1,8-naphtholactam
0.05 mol (11.1 g), N.N-diethylaniline
0.075 mole (11.2 g), 0.3 mole (45
g) and 4 g of the metal powder shown in Table 1 (manufactured by Wako Pure Chemical Industries, Ltd., reagent grade 1) were charged into a reactor (made of glass), and the reaction was carried out at 90° C. for 4 hours with stirring. After the reaction was completed, the mixture was poured into 1100g of ice water at 0°C and stirred, followed by a 25% aqueous solution of caustic soda.
The solution was added until the pH reached 2.5, and blue dye crystals were precipitated. The dye crystals were filtered, washed and dried, and the yield of the obtained dye crystals was calculated, and the results shown in Table 1 were obtained.
【表】
実施例 ２
実施例１の方法において、反応原料として第２
表に示す化合物及び触媒を使用して実施例１と同
様な反応を行ない、第２表に示す結果を得た。[Table] Example 2 In the method of Example 1, the second
The same reaction as in Example 1 was carried out using the compounds and catalysts shown in the table, and the results shown in Table 2 were obtained.
【表】【table】
Claims (1)
低級アルキル基、又はカルボキシル基もしくはカ
ルバモイル基で置換された低級アルキル基を示
し、Ｘは水素原子又はハロゲン原子を示す）で表
わされる化合物と下記一般式〔〕 （式中、R2及びR3は低級アルキル基又は低級アル
コキシアルキル基を示す）で表わされる化合物と
を少くとも内壁がガラス又は耐蝕性合成樹脂で構
成された反応器を用い、無機酸ハライドの存在
下、縮合反応させて下記一般式〔〕 （式中、R1〜R3及びＸは前示一般式と同じ意義を
有し、Ｙは陰イオンを示す）で表わされる塩基性
染料を製造するに当り、亜鉛、銅及び鉄から選ば
れた少なくとも一種の金属触媒を使用することを
特徴とする塩基性染料の製造方法。[Claims] 1. The following general formula [] (In the formula, R 1 represents a hydrogen atom, a lower alkyl group, a cyano lower alkyl group, or a lower alkyl group substituted with a carboxyl group or a carbamoyl group, and X represents a hydrogen atom or a halogen atom) General formula below [] (In the formula, R 2 and R 3 represent a lower alkyl group or a lower alkoxyalkyl group) using a reactor whose inner wall is made of at least glass or corrosion-resistant synthetic resin, and an inorganic acid halide. A condensation reaction is carried out in the presence of the following general formula [] (In the formula, R 1 to R 3 and X have the same meanings as in the above general formula, and Y represents an anion.) A method for producing a basic dye, comprising using at least one metal catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5006379A JPS55142056A (en) | 1979-04-23 | 1979-04-23 | Preparation of basic dye |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5006379A JPS55142056A (en) | 1979-04-23 | 1979-04-23 | Preparation of basic dye |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS55142056A JPS55142056A (en) | 1980-11-06 |
| JPS6147175B2 true JPS6147175B2 (en) | 1986-10-17 |
Family
ID=12848530
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5006379A Granted JPS55142056A (en) | 1979-04-23 | 1979-04-23 | Preparation of basic dye |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS55142056A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4369188A (en) * | 1981-07-17 | 1983-01-18 | Ayerst, Mckenna & Harrison Inc. | 2-Thioxobenz[cd]indole-1(2H)-acetic acid derivatives |
-
1979
- 1979-04-23 JP JP5006379A patent/JPS55142056A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS55142056A (en) | 1980-11-06 |
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