JPH0522697B2 - - Google Patents
Info
- Publication number
- JPH0522697B2 JPH0522697B2 JP18817184A JP18817184A JPH0522697B2 JP H0522697 B2 JPH0522697 B2 JP H0522697B2 JP 18817184 A JP18817184 A JP 18817184A JP 18817184 A JP18817184 A JP 18817184A JP H0522697 B2 JPH0522697 B2 JP H0522697B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- methylbenzylidene
- phenylpropionitrile
- amino
- water
- 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 - Fee Related
Links
- -1 2-(α-methylbenzylidene)amino-3-phenylpropionitrile Chemical compound 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 description 5
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 5
- 229940073608 benzyl chloride Drugs 0.000 description 5
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- SCLCDBISIMXAPM-UHFFFAOYSA-N 2-(benzylideneamino)propanenitrile Chemical compound N#CC(C)N=CC1=CC=CC=C1 SCLCDBISIMXAPM-UHFFFAOYSA-N 0.000 description 4
- ACRWYXSKEHUQDB-UHFFFAOYSA-N 3-phenylpropionitrile Chemical compound N#CCCC1=CC=CC=C1 ACRWYXSKEHUQDB-UHFFFAOYSA-N 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 230000002152 alkylating effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000003444 phase transfer catalyst Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- DDOYWSXVQGNRIK-UHFFFAOYSA-N 2-(benzhydrylideneamino)-3-phenylpropanenitrile Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)=NC(C#N)CC1=CC=CC=C1 DDOYWSXVQGNRIK-UHFFFAOYSA-N 0.000 description 1
- YVDSUPOAMPCYSC-UHFFFAOYSA-N 2-amino-3,3-diphenylprop-2-enenitrile Chemical compound C1(=CC=CC=C1)C(C1=CC=CC=C1)=C(C#N)N YVDSUPOAMPCYSC-UHFFFAOYSA-N 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- DFNYGALUNNFWKJ-UHFFFAOYSA-N aminoacetonitrile Chemical compound NCC#N DFNYGALUNNFWKJ-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- VBEKGXAPCZTFJW-UHFFFAOYSA-N benzene;octane Chemical compound C1=CC=CC=C1.CCCCCCCC VBEKGXAPCZTFJW-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- LTYRAPJYLUPLCI-UHFFFAOYSA-N glycolonitrile Chemical compound OCC#N LTYRAPJYLUPLCI-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
イ 産業上の利用分野
本発明は新規化合物２−（α−メチルベンジリ
デン）アミノ−３−フエニルプロピオニトリルお
よびその製造法に関する。DETAILED DESCRIPTION OF THE INVENTION A. Field of Industrial Application The present invention relates to a novel compound 2-(α-methylbenzylidene)amino-3-phenylpropionitrile and a method for producing the same.
新規化合物２−（α−メチルベンジリデン）ア
ミノ−３−フエニルプロピオニトリルはα−アミ
ン酸の１種であるフエニルアラニン製造用中間体
であり、加水分解を受けることにより、２−アミ
ノ−３−フエニルプロピオニトリルを経由して、
フエニルアラニンへ転換しうる化合物である。 The new compound 2-(α-methylbenzylidene)amino-3-phenylpropionitrile is an intermediate for the production of phenylalanine, which is a type of α-amic acid. Via 3-phenylpropionitrile,
It is a compound that can be converted to phenylalanine.
ロ 従来の技術
フエニルアラニンを合成する方法として種々の
中間体を経由する方法が提案されている。B. Prior Art Methods for synthesizing phenylalanine using various intermediates have been proposed.
しかしながら反応ステツプ数、総合収率、原料
の価格などの点で満足しうる方法は少なく新しい
プロセスが望まれている。 However, there are few methods that are satisfactory in terms of the number of reaction steps, overall yield, cost of raw materials, etc., and a new process is desired.
最近フエニルアラニン製造の中間体として、
（ジフエニルメチレン）−アミノアセトニトリルを
塩化ベンジルでアルキル化した２−（ジフエニル
メチレン）アミノ−３−フエニルプロピオニトリ
ルを用いる例があるが〔Tetrahedron Letters
4625（1975）〕、原料ケトンのベンゾフエノンが高
価である欠点を有する。本発明の新規化合物２−
（α−メチルベンジリデン）アミノ−３−フエニ
ルプロピオニトリルはより安価なアセトフエノン
を原料とするもので経済性の高い化合物である。
しかしながら、今までに合成を試みた報告は見当
らない。 Recently, as an intermediate for the production of phenylalanine,
There is an example of using 2-(diphenylmethylene)amino-3-phenylpropionitrile, which is obtained by alkylating (diphenylmethylene)-aminoacetonitrile with benzyl chloride [Tetrahedron Letters]
4625 (1975)], the raw material ketone benzophenone has the disadvantage of being expensive. Novel compound of the present invention 2-
(α-Methylbenzylidene)amino-3-phenylpropionitrile is a highly economical compound that is made from cheaper acetophenone.
However, there have been no reports of attempted synthesis so far.
ハ 問題を解決するための手段
本発明者は、アセトフエノンとグリシノニトリ
ルを原料とするシツク塩基を、ハロゲン化ベンジ
ルでアルキル化した。２−（α−メチルベンジリ
デン）アミノ−３−フエニルプロピオニトリル
（以下PSBと略す）がフエニルアラニン合成用中
間体として有用な化合物であることを見出し、ま
たこのPSBの合成方法を鋭意研究したところ、
収率よく、経済的に、PSBを合成する方法を見
出し、本発明に到達した。C. Means for Solving the Problem The present inventor alkylated a basic base made from acetophenone and glycinonitrile with a benzyl halide. Discovered that 2-(α-methylbenzylidene)amino-3-phenylpropionitrile (hereinafter abbreviated as PSB) is a compound useful as an intermediate for the synthesis of phenylalanine, and also conducted intensive research on the method for synthesizing this PSB. Then,
We have discovered a method for synthesizing PSB in a high yield and economically, and have arrived at the present invention.
本発明はα−メチルベンジリデンアミノアセト
ニトリル（以下SBと略す）とハロゲン化ベンジ
ルを水と共沸する非水溶媒中で水酸化アルカリの
存在下反応させ、生成した水を共沸蒸留により系
外に除することにより達成される。 The present invention involves reacting α-methylbenzylidene aminoacetonitrile (hereinafter abbreviated as SB) with a benzyl halide in the presence of an alkali hydroxide in a non-aqueous solvent that is azeotropic with water, and removing the generated water from the system by azeotropic distillation. This is achieved by dividing.
SBのようなアミノ酸のシツク塩基誘導体をハ
ロゲン化アルキルでアルキル化する方法として
非水溶媒中、リチウムジイソプロピルアシド
のような中和により水を生成しない塩基を用い
る方法（Tetrahedron Letters No.302641
（1978））、
相間移動触媒を用い、有機溶媒と水の混合溶
媒中で塩基の存在下で反応させる方法（前出文
献）
がある。 A method for alkylating thick base derivatives of amino acids such as SB with alkyl halides is a method using a base that does not produce water upon neutralization, such as lithium diisopropyl acid, in a nonaqueous solvent (Tetrahedron Letters No. 302641).
(1978)), and a method in which the reaction is carried out using a phase transfer catalyst in the presence of a base in a mixed solvent of an organic solvent and water (reference cited above).
の方法は反応条件が厳しく、操作が繁雑であ
る、高価な塩基溶媒を使う等の欠点があり、実用
性に乏しい。 This method has disadvantages such as severe reaction conditions, complicated operations, and the use of expensive basic solvents, and is therefore impractical.
の方法はシツク塩基のケトンとしてベンゾフ
エノンを用いる場合には有用であるが、相間移動
触媒の後処理が困難であることの他に、より安価
なアセトフエノンを用いる本反応にこの方法を用
いてもSBの反応が遅く、SBが水による分解を受
けやすいためアルキル化反応中にSBが分解し、
反応収率が上らない。従つて、この方法を本反応
に用いられない。 This method is useful when benzophenone is used as the ketone of the basic base, but in addition to the difficulty in post-treatment of the phase transfer catalyst, even if this method is used in this reaction using cheaper acetophenone, SB The reaction is slow and SB is easily decomposed by water, so SB decomposes during the alkylation reaction.
The reaction yield does not increase. Therefore, this method cannot be used in this reaction.
本発明者らは以上の理由からSBを、ハロゲン
化ベンジルでアルキル化する方法を鋭意研究し、
相間移動触媒を、用いない経済的方法を見出し
た。 For the above reasons, the present inventors have diligently researched a method of alkylating SB with benzyl halide,
We have found an economical method that does not use phase transfer catalysts.
その方法を具体的に説明すると、水と共沸する
非水系溶媒中で水酸化アルカリの存在下に反応さ
せ、生成する水を共沸させて、系外に除去するこ
とにより収率よくPSBを合成する。 To explain the method specifically, PSB is produced in high yield by reacting in the presence of alkali hydroxide in a non-aqueous solvent that is azeotropic with water, and azeotropically removing the generated water from the system. Synthesize.
以下にさらに具体的に説明する。 This will be explained in more detail below.
本発明の方法は、用いる原材料はいずれも安価
なものであり、出発原料のSBはアセトフエノン
とグリンクニトリルとの脱水反応により得られ
る。もう一方の原料であるハロゲン化ベンジルは
通常塩化ベンジルが用いられる。溶媒は、水と共
沸し、かつ適当な共沸温度を有し、水の溶解度の
小さいものが好ましく、ベンゼン、トルエン、シ
クロヘキサン等が用いられる。 In the method of the present invention, all the raw materials used are inexpensive, and the starting material SB is obtained by a dehydration reaction between acetophenone and glyconitrile. The other raw material, benzyl halide, is usually benzyl chloride. The solvent is preferably one that is azeotropic with water, has a suitable azeotropic temperature, and has low solubility in water, and benzene, toluene, cyclohexane, etc. are used.
用いるSBとハロゲン化ベンジルの比率は、
１：1.0〜5.0（モル比）、好ましくは１：1.05〜2.0
（モル比）である。 The ratio of SB to benzyl halide used is
1:1.0-5.0 (molar ratio), preferably 1:1.05-2.0
(molar ratio).
水酸化アルカリは、アルカリ金属水酸化物、ア
ルカリ土類金属水酸化物が用いられ、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、水酸化カルシウム等である。 As the alkali hydroxide, an alkali metal hydroxide or an alkaline earth metal hydroxide is used, and specifically, sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, etc. are used.
加える水酸化アルカリの量はSBに対して１：
1.0〜20（当量比）、好ましくは１：1.05〜2.0（当量
比）である。 The amount of alkali hydroxide added is 1 for SB:
The ratio is 1.0 to 20 (equivalent ratio), preferably 1:1.05 to 2.0 (equivalent ratio).
用いる水酸化アルカリは通常の商品形態のも
の、例えば、水溶液状態のものでも事前に脱水操
作を行なえば使用可能であるが、無水の状態（粒
状またはフレーク状）のものが好ましく用いられ
る。 The alkali hydroxide to be used is in the form of a normal commercial product, for example, an aqueous solution can be used as long as it is dehydrated beforehand, but an anhydrous form (granules or flakes) is preferably used.
反応温度は20°〜150℃、好ましくは50°〜100℃
である。反応圧力は、常圧、加圧、減圧いずれも
とりうるが、共沸温度を変えるために圧の操作す
ることも通常とりうる手段である。反応時間は、
１〜30時間、通常２〜15時間が用いられる。 Reaction temperature is 20°~150°C, preferably 50°~100°C
It is. The reaction pressure can be normal pressure, increased pressure, or reduced pressure, but manipulating the pressure in order to change the azeotropic temperature is also a commonly available means. The reaction time is
A time period of 1 to 30 hours, usually 2 to 15 hours is used.
実施例 １
α−メチルベンジリデンアミノアセトニトリル
15.8ｇ（0.1モル）をベンゼン100ｇに溶解し、塩
化ベンジル16.5ｇ（0.13モル）、水酸化ナトリウ
ム（粒状）5.2ｇ（0.13モル）を加え、還流下、
水分定量器で水を分離しながら反応させた。６時
間後ガスクロマトグラフで反応液を分析したとこ
ろ２−（α−メチルベンジリデン）アミノ−３−
フエニルプロピオニトリルが収率95％で生成して
いた。Example 1 α-methylbenzylidene aminoacetonitrile
Dissolve 15.8 g (0.1 mol) in 100 g of benzene, add 16.5 g (0.13 mol) of benzyl chloride and 5.2 g (0.13 mol) of sodium hydroxide (granular), and under reflux,
The reaction was carried out while separating water using a water meter. After 6 hours, the reaction solution was analyzed by gas chromatography, and it was found that 2-(α-methylbenzylidene)amino-3-
Phenylpropionitrile was produced with a yield of 95%.
反応液を冷却後、析出無機塩類を別し、ベン
ゼンを減圧留去した。得られた溶液にｎ−オクタ
ン200mlを加え、沈殿を析出させ粗結晶を取し
た。この粗結晶をベンゼン−ｎ−オクタン混合溶
媒から再結晶させ、精製結晶を得た。このものの
物性値を次に示す。 After cooling the reaction solution, precipitated inorganic salts were separated, and benzene was distilled off under reduced pressure. 200 ml of n-octane was added to the obtained solution to precipitate and obtain crude crystals. The crude crystals were recrystallized from a benzene-n-octane mixed solvent to obtain purified crystals. The physical properties of this material are shown below.
融点 75〜77℃
元素分析値（C17H16N2）
Ｈ％ Ｃ％ Ｎ％
実測値 6.51 82.17 11.31
計算値 6.49 82.23 11.281
H核磁気共鳴スペクトル（CDCl3溶媒中）
2.08ppm （3H）
4.59 （1H）
3.22、3.34 （2H）
7.2〜7.8 （10H）
実施例 ２
α−メチルベンジリデンアミノアセトニトリル
15.8ｇ（0.1モル）をシクロヘキサン100ｇに溶解
し、塩化ベンジル16.5ｇ（0.13モル）、水酸化カ
リウム（粒状）6.2ｇ（0.11モル）を加え、還流
下、水分定量器で水を分離しながら反応させた。
４時間後ガスクロマトグラフで反応液を分析した
ところ２−（α−メチルベンジリデン）アミノ−
３−フエニルプロピオニトリルが収率87％で生成
していた。Melting point 75-77℃ Elemental analysis value (C 17 H 16 N 2 ) H% C% N% Actual value 6.51 82.17 11.31 Calculated value 6.49 82.23 11.28 1H nuclear magnetic resonance spectrum (in CDCl 3 solvent) 2.08ppm (3H) 4.59 (1H) 3.22, 3.34 (2H) 7.2-7.8 (10H) Example 2 α-methylbenzylidene aminoacetonitrile
Dissolve 15.8 g (0.1 mol) in 100 g of cyclohexane, add 16.5 g (0.13 mol) of benzyl chloride and 6.2 g (0.11 mol) of potassium hydroxide (granules), and react under reflux while separating water with a water meter. I let it happen.
After 4 hours, the reaction solution was analyzed by gas chromatography, and it was found that 2-(α-methylbenzylidene)amino-
3-phenylpropionitrile was produced in a yield of 87%.
実施例 ３
α−メチルベンジリデンアミノアセトニトリル
15.8ｇ（0.1モル）をトルエン100ｇに溶解し、塩
化ベンジル16.5ｇ（0.13モル）、水酸化ナトリウ
ム（フレーク状）5.2ｇ（0.13モル）を加え、減
圧下（320mmHg）還流させ、生成水を水分定量器
で分離しながら反応させた。3.2時間後、反応液
を冷却し、ガスクロマトグラフで分析したところ
２−（α−メチルベンジリデン）アミノ−３−フ
エニルプロピオニトリルが収率91％で生成してい
た。Example 3 α-methylbenzylidene aminoacetonitrile
Dissolve 15.8 g (0.1 mol) in 100 g of toluene, add 16.5 g (0.13 mol) of benzyl chloride, and 5.2 g (0.13 mol) of sodium hydroxide (flake), reflux under reduced pressure (320 mmHg), and evaporate the resulting water. The reaction was carried out while being separated using a quantitative meter. After 3.2 hours, the reaction solution was cooled and analyzed by gas chromatography, and it was found that 2-(α-methylbenzylidene)amino-3-phenylpropionitrile had been produced in a yield of 91%.
２−（α−メチルベンジリデン）アミノ−３−
フエニルプロピオニトリルのマススペクトルと核
磁気共鳴スペクトルを図１、図２に示す。
2-(α-methylbenzylidene)amino-3-
The mass spectrum and nuclear magnetic resonance spectrum of phenylpropionitrile are shown in FIGS. 1 and 2.
Claims (1)
リデン）アミノ−３−フエニルプロピオニトリ
ル。 ２ α−メチルベンジリデンアミノアセトニトリ
ルとハロゲン化ベンジルとを水酸化アルカリの存
在下、非水溶媒中で反応させ、生成した水を共沸
蒸留により除去することを特徴とする２−（α−
メチルベンジリデン）アミノ−３−フエニルプロ
ピオニトリルの製造法。[Scope of Claims] 1. 2-(α-methylbenzylidene)amino-3-phenylpropionitrile represented by the following formula. 2-(α-
Method for producing methylbenzylidene)amino-3-phenylpropionitrile.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18817184A JPS6165857A (en) | 1984-09-10 | 1984-09-10 | 2-(alpha-methylbenzylidene)amino-3-phenlpropio-nitrile and its production |
| DE19853531084 DE3531084A1 (en) | 1984-08-30 | 1985-08-30 | Process for the preparation of phenylalanine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18817184A JPS6165857A (en) | 1984-09-10 | 1984-09-10 | 2-(alpha-methylbenzylidene)amino-3-phenlpropio-nitrile and its production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6165857A JPS6165857A (en) | 1986-04-04 |
| JPH0522697B2 true JPH0522697B2 (en) | 1993-03-30 |
Family
ID=16218997
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18817184A Granted JPS6165857A (en) | 1984-08-30 | 1984-09-10 | 2-(alpha-methylbenzylidene)amino-3-phenlpropio-nitrile and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6165857A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015072567A1 (en) | 2013-11-18 | 2015-05-21 | 日立造船株式会社 | Denitration catalyst and method for producing same |
-
1984
- 1984-09-10 JP JP18817184A patent/JPS6165857A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015072567A1 (en) | 2013-11-18 | 2015-05-21 | 日立造船株式会社 | Denitration catalyst and method for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6165857A (en) | 1986-04-04 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |