JPS60156690A - Preparation of soluble salt of porphyrin compound - Google Patents
Preparation of soluble salt of porphyrin compoundInfo
- Publication number
- JPS60156690A JPS60156690A JP1138084A JP1138084A JPS60156690A JP S60156690 A JPS60156690 A JP S60156690A JP 1138084 A JP1138084 A JP 1138084A JP 1138084 A JP1138084 A JP 1138084A JP S60156690 A JPS60156690 A JP S60156690A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- metal salt
- porphyrin compound
- salt
- protoporphyrin
- 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.)
- Granted
Links
Abstract
Description
【発明の詳細な説明】
本発明は？ルフイリン化合物の可溶性塩、更に詳細には
水に易溶女医の一般式（１）、級アルキル基を示す）を
示す〕
で表わ゛されるポルフィリン化合物のモノアル、、、□
。[Detailed Description of the Invention] What is the invention? A soluble salt of a porphyrin compound, more specifically a monoalkyl compound of a porphyrin compound represented by the general formula (1) (indicating a class alkyl group) which is easily soluble in water, ,, □
.
カリ金属塩の製造法に関する。This invention relates to a method for producing potassium metal salts.
（１、Ｅ ’Ｐ Ｒｓ ＃Ｚ ｅ Ｌ−ｋ ２！Ｓ ”
Ｃ’ 表ｂ ｉ ｈ ；！ｙ ’ｆ ’ｏ ） ｙ３ｅ
ルフイリンはすでに公知の化合物で、肝臓機能治療剤と
して使用されているものであり、またプロトポルフィリ
ンの３位のビニル基がアルコリシスされた３−アルコキ
シ′エテルー８−ピニルーデュウテロ式ルフイリンは本
発明者によって合成された新規化合物で、優れたレーザ
ー光増感作用を有する腫瘍の治療剤として有用な化合物
でおる。(1, E 'P Rs #Z e L-k 2!S"
C' table b i h ;! y'f'o) y3e
Lufirin is already a known compound and is used as a liver function treatment agent, and the 3-alkoxy' ether-8-pinyl-deutero-type lufirin, in which the vinyl group at the 3-position of protoporphyrin is alcoholysed, is a compound of the present invention. This is a novel compound synthesized by a researcher, and is a useful compound as a tumor therapeutic agent with excellent laser photosensitizing activity.
しかしながら、（Ｉ）式のポルフィリン化合物及びその
シアルカリ金属塩は水に難溶であシ、特にプロ）ｙｌｅ
ｌフルリンは注射剤として使用されるため、これが製剤
化の大きな障害となそこで、従来、ゾロトールフィリン
の注射液を調製するには、プロトポルフィリンを苛性ソ
ーダ水溶液に溶解し、ｐＨを調整する方法がとられてい
た。しか′シ、この方法では、プロトポルフィリン自体
を為純度のものとして得ることができないこと並びにｐ
ｉｔを一定−に調整するのが困難なことから品質を一定
に保持することができなかった。However, the porphyrin compound of formula (I) and its sialkali metal salt are sparingly soluble in water, especially pro)yle.
Since Flurin is used as an injection, this is a major obstacle in formulating it. Conventionally, to prepare an injection solution of zolotorphyrin, protoporphyrin is dissolved in an aqueous solution of caustic soda and the pH is adjusted. It had been taken. However, with this method, protoporphyrin itself cannot be obtained in a pure form, and
Since it was difficult to adjust it to a constant value, it was not possible to maintain the quality at a constant level.
本発明者は、先にゾロトｊｅルフィリンのジアルカリ金
属塩な；高純度に精製したプ・・トールフィリンジメチ
ルエステルから定量的に得ることに成功したが、ゾロト
ールフィリンのシアルカリ金属塩は當温では水に難溶で
ある。而して当該シアルカリ金属塩を水に懸濁し、超音
波を施しながら加温すると透明に溶・ 解するが、放冷
すると再び懸濁状態にな□るた・ め、これも注射剤と
す′るには不適当であった。The present inventor had previously succeeded in quantitatively obtaining the dialkali metal salt of zolotorphyrin from highly purified protein dimethyl ester; Slightly soluble in water. When the sialkali metal salt is suspended in water and heated while applying ultrasound, it becomes transparent and dissolved, but when it is allowed to cool, it becomes suspended again, so it is also used as an injection. It was inappropriate for him to do so.
斯かる実情において、本発明者は鋭意絣究を行った結果
、（Ｉ）式の？ｌフルリン化合物の・モノアルカリ金属
塩が水に易溶性で一冷所に保存しても沈澱を生じないこ
と、並びにこの可溶性塩は、当該ポルフィリン化合物の
シアルカリ金属塩を当モルの酸性物質で中和処理するこ
とによって得られることを見出し、本発明を完成した。Under such circumstances, the inventor of the present invention has conducted intensive research on Kasuri, and as a result, the formula (I)? l The mono-alkali metal salt of the porphyrin compound is easily soluble in water and does not form a precipitate even when stored in a cool place, and this soluble salt is obtained by dissolving the sial alkali metal salt of the porphyrin compound in equimolar amounts of an acidic substance. The present invention was completed based on the discovery that it can be obtained by Japanese processing.
すなわち、本発明は、（Ｉ）式で表わされるポルフィリ
ン化合物のゾ□アルカリ金属塩の溶液に−ｅルフイリン
化合物と当モルの酸性物質を加えて処理し、−ルフ□イ
リン化合物のモノアルカリ金属塩として収得することを
特徴とするポルフィリン化合物の可溶性塩の製造法であ
る゛。That is, in the present invention, a solution of a monoalkali metal salt of a porphyrin compound represented by formula (I) is treated by adding an acidic substance in the same molar amount as the -e ruphyrin compound, to obtain a monoalkali metal salt of the porphyrin compound represented by the formula (I). This is a method for producing a soluble salt of a porphyrin compound, which is characterized in that it is obtained as a porphyrin compound.
本発明を実施するには、先ず？ルフイリン化合物山のシ
アルカリ金属塩を水に懸濁し、超音波を施しながら、７
０〜９０−℃に加温して溶解させる１次いでこれに攪拌
下酸性物質を加え、シアルカリ金属塩の半分を中和する
。First, how to implement the present invention? Suspend the sialkali metal salt of the lufirin compound in water and apply ultrasonic waves for 70 minutes.
The mixture is heated to 0 to 90° C. to dissolve it. Then, an acidic substance is added thereto under stirring to neutralize half of the sialkali metal salt.
酸性物質としては倒れのものでも使用できるが、弱酸性
イオン交換樹脂、酢酸、クエン酸等の弱い酸が好ましい
。酸性物質は叡ルフイリン化合物ａ＞と当モルあるいは
や＼過剰になるように加え、反応は２〜５時間行うのが
好ましい。反応後、反応混合物を凍結乾燥等によって乾
燥す・れば、？ｌフルリン化合物の可溶性塩が得られる
。・この可溶性塩は後述の実施例に示すようにポルフィ
リン化合物のモノアルカリ金属塩であシ、常温あるいは
低温において水及び生理食塩水等に易溶であり、例えは
注射剤を製造する場合に極めて便利である。Although any acidic substance can be used, weak acids such as weakly acidic ion exchange resins, acetic acid, and citric acid are preferable. It is preferable that the acidic substance is added in an equimolar amount or slightly in excess of the olephilin compound a>, and the reaction is carried out for 2 to 5 hours. After the reaction, what if the reaction mixture is dried by freeze-drying? A soluble salt of the l-flurin compound is obtained.・This soluble salt is a monoalkali metal salt of a porphyrin compound, as shown in the examples below, and is easily soluble in water, physiological saline, etc. at room temperature or low temperature, and is extremely useful when manufacturing injections. It's convenient.
次に参考例及び実施例を挙げて説明する。Next, reference examples and examples will be given and explained.
実施例１
（＋） ゾロトボルフイリンゾナトリウム（純度９９％
以上）１０ｆを蒸留水３．５ｔに懸濁させ、これに超音
波振動棒を挿入し、８０℃に加温した。該懸濁液は３０
分で透明な溶液となった。この溶液に、攪拌下、弱酸性
イオン交換樹脂（アンノ層−ライトＩＲＣ−５０：オル
ガノ株式会社）を活性化したもの５−を加え、３時間攪
拌した。反応液からイオン交換樹脂をＦ別し、Ｆ液を０
．２Ｐのメンブランフィルタ−を通過させ、凍結乾燥し
てプロトポルフィリンの可溶性塩９ｆを得た。Example 1 (+) Zolotoborfirinzosodium (purity 99%
(above) 10f was suspended in 3.5 t of distilled water, an ultrasonic vibrating rod was inserted into the suspension, and the mixture was heated to 80°C. The suspension is 30
It became a clear solution in minutes. To this solution was added 5-, an activated weakly acidic ion exchange resin (Anno Layer Light IRC-50: Organo Co., Ltd.) under stirring, and the mixture was stirred for 3 hours. Separate the ion exchange resin from the reaction solution and remove the F solution.
．． The mixture was passed through a 2P membrane filter and lyophilized to obtain protoporphyrin soluble salt 9f.
（ｉ） この凍結乾燥物５１２ｑ（水分３％）を蒸留水
５０−に溶かし、これに０．ＩＮ酢酸５〇−を加え、析
出するプロトポルフィリンを炉別した。このＦ液５０−
を正確にとシ、フェノールフタレイン試薬を３滴加え、
０．１Ｎ苛性ソーダで逆滴定したところ、７．９−を消
費した。従ってこの凍結乾燥物は３．９５％のす１
トリウムを含み、プロトポルフィリンモノナトリウムで
あることが確認された。(i) Dissolve 512q of this freeze-dried product (water content 3%) in 50% of distilled water, and add 0.0% to this. 50% of IN acetic acid was added, and the precipitated protoporphyrin was filtered out. This F liquid 50-
Add exactly 3 drops of phenolphthalein reagent,
When back titrated with 0.1N caustic soda, 7.9- was consumed. Therefore, this freeze-dried product contained 3.95% monothorium and was confirmed to be protoporphyrin monosodium.
実施例２
＜１） 実施例１の（１）と同様にして調製したプロト
ポルフィリンシナトリウムの水溶液に、攪拌下９９％酢
酸１．０ｆ（１，１０モル）を加え、３時間攪拌した。Example 2 <1) To an aqueous solution of protoporphyrin sinodium prepared in the same manner as in Example 1 (1), 1.0 f (1.10 mol) of 99% acetic acid was added with stirring, and the mixture was stirred for 3 hours.
以下実施例１と同様にして凍結乾燥し、プロトポルフィ
リンの可溶性塩９．５ｆを得た。Thereafter, freeze-drying was carried out in the same manner as in Example 1 to obtain 9.5f of a soluble salt of protoporphyrin.
（ｉｉ） この凍結乾燥物３４Ｍｇを１０％塩酸含有メ
タノール１００−に溶かし１．この溶液１〇−□
を２５ｔａ容のメスフラスコにとり、トリエチルアミン
２ｄを加えて中和し、これにジクロルエタンを加えて２
５ｍとした。この液１０μｔを高速液体クロマトグラフ
ィーに付したとζろ、ゾロト緻ルフイリンゾメチルエス
テルと同一の保持時間にピークが認められ、他にピーク
社認められなかった。(ii) Dissolve 34 Mg of this freeze-dried product in 100% methanol containing 10% hydrochloric acid. Take 10-□ of this solution in a 25 ta volumetric flask, add 2d of triethylamine to neutralize it, add dichloroethane to it, and add 2d of triethylamine to neutralize it.
It was set to 5m. When 10 .mu.t of this solution was subjected to high performance liquid chromatography, a peak was observed at the same retention time as that of zetafiltration and zorotofilinzomethyl ester, and no other peaks were observed.
実施例３
３−メトキ′１チに−８−ｉ＝↑−デ゛ウテロ？ルフイ
リン（ＭＶＤ ）ゾ町トリ、ラム１０ｔを５００−の蒸
留水に懸濁し、これに弱酸性イオン交換樹脂（実施例１
に同じ）を活性化したもの５ｄを加え、３竺間攪拌した
。イオン変換樹脂なＦ去し、Ｆ液を０．２μのタンブラ
４ンフイルターを通過させた後、凍結乾燥して３−メト
キシエチル−８−ビニル、−デュウテロ鑓、ルフイリン
？可溶性塩９．２ｆを得た。実施例１の（１）と同様に
して測定したととろ、モノナトリウム塩でめった。Example 3 3-Methoki'1 to -8-i=↑-Deutero? 10 tons of Rufirin (MVD) Zomachi Tori and Lamb were suspended in 500-liter distilled water, and a weakly acidic ion exchange resin (Example 1
Activated product 5d (same as above) was added and stirred for 3 minutes. After removing F from the ion conversion resin, the F solution was passed through a 0.2 μm tumbler filter, and then lyophilized to give 3-methoxyethyl-8-vinyl, -deutero, and lufilin. 9.2f of soluble salt was obtained. Measurement was made in the same manner as in Example 1 (1).
参考例
［りツロト？ルフイリンシメチルエステル１ｆム
をメタノール５００−に懸濁し、これに塩化水素ガスを
導入して飽和させ、３時間煮沸した。これを１０％炭酸
アンモニウム水溶液１ｔに注加し、ジクロルエタン２０
０ｄで抽出し、抽出液を水洗後、硫酸ナトリウムで乾燥
した。この抽出液を、予めジクロルエタンで洗浄したシ
リカゲルカラムに注加して吸着させ、ジクロルエタンで
溶出を行った。最初に原料のゾロト？ルフイリンゾメテ
ルエステルが溶出された。Reference example [Rituroto? Rufilin methyl ester 1f was suspended in 500 methanol, hydrogen chloride gas was introduced into the suspension to saturate the suspension, and the suspension was boiled for 3 hours. This was poured into 1 t of 10% ammonium carbonate aqueous solution, and 20 ml of dichloroethane was added.
The extract was washed with water and then dried over sodium sulfate. This extract was poured onto a silica gel column that had been previously washed with dichloroethane to be adsorbed, and elution was performed with dichloroethane. First raw material Zoroto? Lufilin zometer ester was eluted.
（ｉ）第２に溶出されるフラクション（ＴＬＣで単一ス
？ットであることを確認）を集め、溶媒を留去し、残留
物をトルエンよシ再結晶して、ＭＶＤゾメチルエステル
０．１３ ｆ （取高１３％）を得た。(i) The second eluted fraction (confirmed to be a single cut by TLC) was collected, the solvent was distilled off, the residue was recrystallized from toluene, and the MVD zomethyl ester .13 f (13% of proceeds) was obtained.
元素分析値 Ｃｓｙ Ｈａｓ Ｎ４０ｓ計算値〜： ｃ
ニア１．３６．ｎ：６．８０ 、Ｎ：９．００実測値（
財）： Ｃニア１．３１ 、 Ｈ： ６．９３ 、 Ｎ
： ９．０２Ｍａｓｓ ： Ｃａ１ｅｄ ６２２ Ｆｏ
ｕｎｄ ６２３（Ｍ＋ １ ）ＮＭＲ（４００ＭＨｚ
、ｉｎ ＣＤＣ４ｇ ） ｐｐｍ１０．５４（ＩＨ，ｍ
、５−０Ｈ）
１０．０８（ＩＨ，ｓ、１Ｏ−ＣＨ）
１０．０６（ＩＨ，ｓ、２Ｏ−ＣＨ）
９．９２（ＩＨ，ｓ、１５−ＣＨ）
８．２７ｅ８．２４．ｔＬ！３，８．２０（ｉｎ、ａ、
８ｌ−ｃｎ）６．３６ ＃ ６．３１ （ＩＨ，ｄ 、
８２−Ｃ馬）６．１６ ｍ ６．１５ （Ｉ Ｈ−ｄ
−５”−ＣＨＩ ）６．１３＊６．１２−６．０６．６
．０４（ＩＨｌｑ−３’−ＣＨ）４．３４，４３２．４
．３０．４．２８（４ｉ１．ｑ、１３’、１７”−ＣＨ
鵞−）３．７２（３Ｈ，ａ−７−ＣＨｌ）
３．６９ （３Ｈ＃ Ｉ −２−ＣＤ４ ）３．６３（
６Ｈａ＠１１３” １１７”エステル−〇ＣＨ３）３．
６０（３）１．＠、３’−ＱＣ旦３）３．５７ （３Ｈ
、’＠、 １２−ＣＨｌ ）３．５２（３Ｈ，ｓ 、１
”８−ＣＨｓ ）’３．２３．３．２２．３．２１ 、
３．２０ （４Ｈ，ｑ；’１３” 、 ｉ’ｙ”−ｃ’
Ｈ，−）’２．２７．２．２５（３Ｋ 山 ３”−ｃｆ
ｓ ）−３，７６（２Ｈ山Ｎ−ＩＩ） ’
（ｉ）（ｉｌ）テｊｈ ｆｃ ＭＶＤ Ｖ メｆルエス
テル１ｔをぎリシン゛５０−に溶か・し、苛性ソーダ２
０ηのメ ・□タノール溶液を加え、９０℃士′２時間
攪拌し ゛た。反ｉ後析出した結晶をＦ□飯し、乾燥し
、・ＭＶＤシナトリウム０．１ｆを得た。： ゛以上
□
手続補正書（自発）
昭和５９年５ 月２ｂ Ｂ
、特許庁長官若杉和夫殿
２、 発廟の名称 □
信ルフイリン化合物の可溶性塩およびその製造法３、
補止をする者
′ ±“”゛°、：九１．−１よ＊ａＴ１２（［３−１
住所
・ 名、称 株式会社 佐藤糸学研冗所代表者佐藤三部
４、′代理尺□
６、補正により増加する発明のａ１
７． 補正の対象
明細書の「発明の名称」、「特許請求の範囲」及び「発
明の詳細な説明」の−
８、補正の自答
（１） 明細書中、「発明の名称」を次の如く訂正する
。Elemental analysis value Csy Has N40s calculated value ~: c
Near 1.36. n: 6.80, N: 9.00 actual value (
Goods): C near 1.31, H: 6.93, N
: 9.02Mass : Caled 622 Fo
und 623 (M+1) NMR (400MHz
, in CDC4g) ppm10.54 (IH, m
, 5-0H) 10.08 (IH, s, 1O-CH) 10.06 (IH, s, 2O-CH) 9.92 (IH, s, 15-CH) 8.27e8.24. tL! 3,8.20(in,a,
8l-cn) 6.36 # 6.31 (IH, d,
82-C horse) 6.16 m 6.15 (I H-d
-5”-CHI)6.13*6.12-6.06.6
．． 04(IHlq-3'-CH)4.34,432.4
．． 30.4.28 (4i1.q, 13', 17"-CH
Goose-) 3.72 (3H, a-7-CHl) 3.69 (3H# I-2-CD4) 3.63 (
6Ha@113” 117” Ester-〇CH3)3.
60(3)1. @, 3'-QCdan 3) 3.57 (3H
,'@, 12-CHl)3.52(3H,s,1
"8-CHs)'3.23.3.22.3.21,
3.20 (4H,q;'13'', i'y''-c'
H, -)'2.27.2.25 (3K mountain 3"-cf
s)-3,76 (2H mountain N-II)' (i) (il) Tejh fc MVD V Dissolve 1 t of methyl ester in 50-glycine, and add 2 ml of caustic soda.
A 0η methanol solution was added and stirred at 90°C for 2 hours. After the incubation, the precipitated crystals were boiled and dried to obtain 0.1f of MVD cinodium. : ゛ or more
□ Procedural amendment (voluntary) May 2b, 1982 B, Kazuo Wakasugi, Commissioner of the Patent Office 2, Name of the temple □ Soluble salt of luciferin compound and its manufacturing method 3,
Person who makes correction′ ±“”゛°：91. -1yo*aT12([3-1
Address/First Name Sato Ito Gakken Kyasho Co., Ltd. Representative Sato Sanbe 4, 'Representative Shaku □ 6, A1 of inventions increased by amendment 7. 8. Self-answer for amendment (1) In the description, the “title of the invention” should be changed as follows: correct.
［ポルフィリン化合物の可溶性塩およびその製造法」
（２） 明細書中、「特許請求の範囲」を別紙の如く訂
正する。[Soluble salt of porphyrin compound and method for producing the same] (2) In the specification, the "Claims" are amended as shown in the attached sheet.
（３） 明細豊中、第３負第１〜２行
「モノアルカリ金属塩」とめる次に「及びそ」を挿入す
る。(3) In the specification Toyonaka, in the 3rd negative line 1-2, insert ``andso'' after the ``mono-alkali metal salt'' stop.
１、一般式
〔式中、ｎｉ １ｊ−ＣＨ＝ＣＨ，又は−ｃＨ−ｏｎ（
Ｒａカリ金属塩。1. General formula [wherein, ni 1j-CH=CH, or -cH-on(
Ra potash metal salt.
２、一般式
級アルキル基を示す）を示す〕
で表わされるポルフィリン化合物のシアルカリ金属塩の
溶液にポルフィリン化合物と当モルの敵性物質を加えて
処理し、−ルフィリン化合物のモノアルカリ金属塩とし
て収得することを％徴とするポルフィリン化合物の可溶
性塩の製造法。2. Indicates a general formula alkyl group] A solution of a sialkali metal salt of a porphyrin compound represented by is treated with the porphyrin compound and an equimolar amount of an enemy substance to obtain a monoalkali metal salt of a -ruphyrin compound. A method for producing a soluble salt of a porphyrin compound having the following characteristics.
Claims (1)
ルの酸性物質を加えて処理し、メルフイリン化合物のモ
ノアル、カリ金属塩として収得することを特徴とする？
ルフイリン化合物の可溶性塩の製造法。[Claims] ,! , having the general formula 3゜, representing a class alkyl group). So, gold, in a solution of bird salt? It is characterized in that it is obtained as a monoalkaline or potassium metal salt of a melphyrin compound by adding and treating a melphyrin compound with a specific amount of an acidic substance.
A method for producing a soluble salt of a lufilin compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1138084A JPS60156690A (en) | 1984-01-25 | 1984-01-25 | Preparation of soluble salt of porphyrin compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1138084A JPS60156690A (en) | 1984-01-25 | 1984-01-25 | Preparation of soluble salt of porphyrin compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60156690A true JPS60156690A (en) | 1985-08-16 |
| JPH0421674B2 JPH0421674B2 (en) | 1992-04-13 |
Family
ID=11776402
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1138084A Granted JPS60156690A (en) | 1984-01-25 | 1984-01-25 | Preparation of soluble salt of porphyrin compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60156690A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61186385A (en) * | 1985-02-13 | 1986-08-20 | Sato Yakugaku Kenkyusho:Kk | Deuteroporphyrin derivative and its salt |
| JPS62167783A (en) * | 1986-01-17 | 1987-07-24 | Hamari Yakuhin Kogyo Kk | Porphyrin derivative |
| JPS62205082A (en) * | 1986-03-03 | 1987-09-09 | Hamari Yakuhin Kogyo Kk | Porphyrin derivative |
| JPH02138280A (en) * | 1988-07-14 | 1990-05-28 | Toyo Hatsuka Kogyo Kk | Porphyrin derivative |
| WO2024050694A1 (en) * | 2022-09-06 | 2024-03-14 | 南京百特生物工程有限公司 | Natural porphin salt and use thereof as plant growth regulator and immune resistance inducer |
-
1984
- 1984-01-25 JP JP1138084A patent/JPS60156690A/en active Granted
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61186385A (en) * | 1985-02-13 | 1986-08-20 | Sato Yakugaku Kenkyusho:Kk | Deuteroporphyrin derivative and its salt |
| JPS62167783A (en) * | 1986-01-17 | 1987-07-24 | Hamari Yakuhin Kogyo Kk | Porphyrin derivative |
| JPS62205082A (en) * | 1986-03-03 | 1987-09-09 | Hamari Yakuhin Kogyo Kk | Porphyrin derivative |
| JPH02138280A (en) * | 1988-07-14 | 1990-05-28 | Toyo Hatsuka Kogyo Kk | Porphyrin derivative |
| WO2024050694A1 (en) * | 2022-09-06 | 2024-03-14 | 南京百特生物工程有限公司 | Natural porphin salt and use thereof as plant growth regulator and immune resistance inducer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0421674B2 (en) | 1992-04-13 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |