JPH03145492A - Pyrroloquinolinequinone ester - Google Patents
Pyrroloquinolinequinone esterInfo
- Publication number
- JPH03145492A JPH03145492A JP27979889A JP27979889A JPH03145492A JP H03145492 A JPH03145492 A JP H03145492A JP 27979889 A JP27979889 A JP 27979889A JP 27979889 A JP27979889 A JP 27979889A JP H03145492 A JPH03145492 A JP H03145492A
- Authority
- JP
- Japan
- Prior art keywords
- pqq
- ester
- publication
- pyrrolo
- dioxo
- 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
- MMXZSJMASHPLLR-UHFFFAOYSA-N coenzyme pyrroloquinoline quinone Natural products C12=C(C(O)=O)C=C(C(O)=O)N=C2C(=O)C(=O)C2=C1NC(C(=O)O)=C2 MMXZSJMASHPLLR-UHFFFAOYSA-N 0.000 title claims abstract description 55
- -1 Pyrroloquinolinequinone ester Chemical class 0.000 title claims abstract description 14
- 239000000126 substance Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 abstract description 15
- 239000002798 polar solvent Substances 0.000 abstract description 4
- 239000003905 agrochemical Substances 0.000 abstract description 3
- 239000013543 active substance Substances 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 2
- 239000005515 coenzyme Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000001766 physiological effect Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- 206010001557 Albinism Diseases 0.000 description 1
- 102000016912 Aldehyde Reductase Human genes 0.000 description 1
- 108010053754 Aldehyde reductase Proteins 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 108020005199 Dehydrogenases Proteins 0.000 description 1
- 241000206602 Eukaryota Species 0.000 description 1
- PSJQCAMBOYBQEU-UHFFFAOYSA-N Glyoxalase I Natural products CC=CC(=O)OCC1=CC(O)C(O)C(O)C1=O PSJQCAMBOYBQEU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 102100034343 Integrase Human genes 0.000 description 1
- 102000014017 Lactoylglutathione lyase Human genes 0.000 description 1
- 108010050765 Lactoylglutathione lyase Proteins 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 108090000854 Oxidoreductases Proteins 0.000 description 1
- 102000004316 Oxidoreductases Human genes 0.000 description 1
- 108010092799 RNA-directed DNA polymerase Proteins 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 108010048916 alcohol dehydrogenase (acceptor) Proteins 0.000 description 1
- 230000003266 anti-allergic effect Effects 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 230000004663 cell proliferation Effects 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002554 disease preventive effect Effects 0.000 description 1
- 238000002265 electronic spectrum Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 208000019423 liver disease Diseases 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000029663 wound healing Effects 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
本発明は、新規なピロロキノリンキノンエステルに関し
、さらに詳細には、「４，５−ジヒドロ−４，５−ジオ
キソ−ＩＨ−ピロロ［２，３−ｆ］キノリン−２，７，
９−）リカルボン酸トリベンジルエステル」 （以下
ＰＱＱ）リベンジルエステルと記す）である。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel pyrroloquinoline quinone ester, more specifically, "4,5-dihydro-4,5-dioxo-IH-pyrrolo[2, 3-f]quinoline-2,7,
9-) Ricarboxylic acid tribenzyl ester” (hereinafter
PQQ) Ribenzyl ester).
ＰＱＱ）リベンジルエステルは、１９７９年に、メタノ
ール資化性細菌のメタノール脱水素酵素の補酵素として
見いだされたピロロキノリンキノン（以下 ＰＱＱと記
す）の誘導体の一種であり、今後、医薬品あるいは農薬
として開発しうる重要な物質である。PQQ) Ribenzyl ester is a type of derivative of pyrroloquinoline quinone (hereinafter referred to as PQQ), which was discovered in 1979 as a coenzyme for methanol dehydrogenase in methanol-assimilating bacteria, and is expected to be developed as a pharmaceutical or agricultural chemical in the future. It is an important substance that can
［従来ρ技術およびその問題点］
ＰＱＱは、細菌に限らず、真核生物であるカビ、酵母、
植物体および動物体にも存在し、脱水素酵素および酸化
酵素のそれぞれの補酵素として重要な働きを担っている
。さらに近年までに、細胞の増殖促進作用（たとえば時
開 昭６１−５８５８４号公報、時開 昭６３−２３３
７８３号公報〉。[Conventional ρ technology and its problems] PQQ is applicable not only to bacteria but also to eukaryotes such as mold, yeast,
It also exists in plants and animals, and plays an important role as a coenzyme for dehydrogenases and oxidases. Furthermore, in recent years, cell proliferation promoting effects (for example, Tokikai Publication No. 58584/1984, Tokikai Publication No. 63/233
Publication No. 783>.
アルドース還元酵素阻害効果−抗白内症作用（たとえば
時開 昭６３−４１４２１号公報、特開昭６３−４８２
１５号公報、時開 昭６４−２９３１３号公報）、肝臓
疾患予防治療作用（たとえば時開 昭６３−１９２７１
７号公報）、創傷治癒作用（たとえば時開 昭６３−１
５２３０９号公報）、抗アレルギー作用（たとえば時開
昭６３−１７４９３１号公報）、逆転写酵素阻害作用
（たとえば時開 昭６３−１５６７２４号公報。Aldose reductase inhibitory effect - anti-albinism effect (for example, Tokikai Publication No. 63-41421, JP-A No. 63-482)
15 Publication, Jikai Publication No. 64-29313), liver disease preventive and therapeutic effects (for example, Jikai Publication No. 1987-19271)
No. 7 Publication), wound healing effect (for example, Tokikai Sho 63-1)
No. 52309), anti-allergic action (for example, Jikai Publication No. 174931/1988), and reverse transcriptase inhibitory action (for example, Publication No. 156724/1982).
平０１−２９３１３号公報）およびグリオキサラーゼＩ
阻害作用−制癌作用（たとえば時開 昭６３−２１５６
２８号公報、時開 平０ｌ−２９３１３）効果などの多
くの生理活性が明らかにされている。ＰＱＱ・エステル
化合物としては、ＰＱＱ・トリメチルエステルおよびＰ
ＱＱ・ジメチルエチルエステルのみが知られているが、
その生理活性は、まだ十分なものではない。そこで、よ
り新規なＰＱＱ・エステルの開発が望まれていた。Publication No. 01-29313) and glyoxalase I
Inhibitory action - anticancer action (for example, Tokikai 1986-2156)
Many physiological activities have been clarified, such as the effects (No. 28, Jikai Hei 01-29313). Examples of PQQ/ester compounds include PQQ/trimethyl ester and PQQ/trimethyl ester.
Only QQ dimethylethyl ester is known, but
Its physiological activity is still not sufficient. Therefore, it has been desired to develop a newer PQQ ester.
［問題を解決するための手段２作用］
本発明者らは、新規なＰＱＱ・エステルを得るべく種々
検討したところ、ＰＱＱとハロゲン化ベンジルを塩基の
存在下で、非プロトン極性溶媒中で反応させることによ
り、下記の式で示される新規なＰＱＱ・トリベンジルエ
ステルが得られることを見出し、本発明を完成した。[Means for Solving the Problem 2 Effects] The present inventors conducted various studies to obtain a new PQQ ester, and found that PQQ and a benzyl halide were reacted in an aprotic polar solvent in the presence of a base. It was discovered that a novel PQQ tribenzyl ester represented by the following formula could be obtained by doing this, and the present invention was completed.
すなわち、本発明は、下記の式ニ
ルエステルを製造する方法としては、いろいろな方法が
考えられるが、ＰＱＱをハロゲン化ベンジルと塩基の存
在下、非プロトン極性溶媒中で反応させる方法が好まし
い。That is, in the present invention, various methods can be considered for producing the nyl ester of the following formula, but a method in which PQQ is reacted with a benzyl halide in the presence of a base in an aprotic polar solvent is preferred.
ＰＱＱとしては、ＰＱＱはもちろん、ＰＱＱのナトリウ
ム塩およびＰＱＱのカリウム塩などのＰＱＱ塩類を使用
することが出来る。ハロゲン化ベンジルとしては、ベン
ジルクロライド、ベンジルブロマイド、ベンジルヨード
を用いることが出来る。塩基としては、ヒドロキシイオ
ンのアルカリ金属塩、炭酸イオンのアルカリ金属塩、お
よび四級化されにくい、エチルジイソプロピルアミン等
の３級アミンが用いられる。また、非プロトン極性溶媒
としては、ジメチルホルムアミド、ヘキサメチルホスホ
リルトリアミド、ジメチルスルホキシド、ジメチルアセ
トアミド、ジメチルイミダゾリジノン等が用いられる。As PQQ, not only PQQ but also PQQ salts such as sodium salt of PQQ and potassium salt of PQQ can be used. As the benzyl halide, benzyl chloride, benzyl bromide, and benzyl iodo can be used. As the base, alkali metal salts of hydroxy ions, alkali metal salts of carbonate ions, and tertiary amines such as ethyldiisopropylamine, which are not easily quaternized, are used. Further, as the aprotic polar solvent, dimethylformamide, hexamethylphosphoryltriamide, dimethylsulfoxide, dimethylacetamide, dimethylimidazolidinone, etc. are used.
なお、反応は室温で行なうことが出来るが、１００℃以
下で加熱することがより好ましい。Although the reaction can be carried out at room temperature, it is more preferable to heat the reaction at a temperature of 100° C. or lower.
反応液中からのＰＱＱ）リベンジルエステルの抽出・分
離は、溶媒抽出法、再結晶およびカラムクロマトグラフ
ィーなどの常法によることができる。Extraction and separation of PQQ)ribenzyl ester from the reaction solution can be carried out by conventional methods such as solvent extraction, recrystallization, and column chromatography.
ＰＱＱ）リベンジルエステルの同定には、元素分析、核
磁気共鳴スペクトル、赤外吸収スペクトル質量分析など
の手段が用いられる。PQQ) Ribenzyl esters are identified by means such as elemental analysis, nuclear magnetic resonance spectroscopy, infrared absorption spectrometry, and mass spectrometry.
また、ＰＱＱ）リベンジルエステルの定量は、高速液体
クロマトグラフィーにより行なうことが出来る。In addition, the quantitative determination of PQQ)ribenzyl ester can be performed by high performance liquid chromatography.
［実施例］
以下、実施例によって本発明をさらに具体的に説明する
。[Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples.
［実施例１コ
ＰＱＱ６００ｍｇを２０ｍ１の乾燥ジメチルホルムアミ
ドに溶かし、これに１．３８ｇの炭酸カリウムを加えた
。この懸）１５液に３．０８ｇのベンジルブロマイドを
加え、窒素気流下、２５°Ｃで攪拌しながら反応を５日
間行なった。[Example 1] 600 mg of PQQ was dissolved in 20 ml of dry dimethylformamide, and 1.38 g of potassium carbonate was added thereto. 3.08 g of benzyl bromide was added to this suspension) 15, and the reaction was carried out for 5 days with stirring at 25°C under a nitrogen stream.
反応液全量を２Ｎ塩酸水溶液１００ｍ１に入れ、混合し
た。この混合液にクロロホルム・四塩化炭素・酢酸エチ
ル（１：１：１容量比）３０ｍｌを加え、振盪し、クロ
ロホルム−四塩化炭素−酢酸エチル層を回収した。この
抽出操作を３回行なった。このクロロホルム・四塩化炭
素・酢酸エチル液を０．ＩＮ塩酸および水で洗浄した後
、硫酸すトリウム５ｇを加え、脱水した。濾過により硫
酸ナトリウムを除いた後、減圧下で濃縮し、残渣をシリ
カゲルクロマトグラフィー（展開液、エチルエーテル：
クロロホルム＝５：９５）を行ない、粗ＰＱＱ〜トリベ
ンジルエステル画分を得、濃縮乾固した。この乾固物を
エチルエーテル２０ｍ１に溶解し、５℃で１０時間放置
し、結晶を析出させ、乾燥させた。ＰＱＱ＼トリベンジ
ルエステルを５３０ ｍ ｇ得た。ＰＱＱに対するＰＱ
Ｑ）リベンジルエステルの収率は、４８％（ｍｏｌ）で
あった。The entire amount of the reaction solution was poured into 100 ml of 2N aqueous hydrochloric acid solution and mixed. To this mixture, 30 ml of chloroform/carbon tetrachloride/ethyl acetate (1:1:1 volume ratio) was added and shaken, and a chloroform/carbon tetrachloride/ethyl acetate layer was collected. This extraction operation was performed three times. Add this chloroform/carbon tetrachloride/ethyl acetate solution to 0. After washing with IN hydrochloric acid and water, 5 g of sodium sulfate was added and dehydrated. After removing sodium sulfate by filtration, it was concentrated under reduced pressure, and the residue was subjected to silica gel chromatography (developing solution, ethyl ether:
A crude PQQ to tribenzyl ester fraction was obtained and concentrated to dryness. This dried product was dissolved in 20 ml of ethyl ether and left at 5° C. for 10 hours to precipitate crystals, which were then dried. 530 mg of PQQ\tribenzyl ester was obtained. PQ to PQQ
Q) The yield of ribenzyl ester was 48% (mol).
得られた化合物の融点は、２３３〜２３６℃で、メタノ
ール、エタノール、アセトンなどに極めて溶けやすく、
水にはほとんど溶けなかった。The melting point of the obtained compound is 233-236°C, and it is extremely soluble in methanol, ethanol, acetone, etc.
It was almost insoluble in water.
次に得られたＰＱＱ）リベンジルエステルの特性値を示
す。Next, the characteristic values of the obtained PQQ)ribenzyl ester are shown.
（１）元素分析値： Ｃ３ｓＨ２ａＮ２０ｅ （間６０
０．５９）理論値（％） ： Ｃ；７０．００．Ｈ；４
．０３．Ｎ；４．６６実測値（％） ： Ｃ；７０．３
０．Ｈ；３．８５．Ｎ；４．８２（２）融点：２３３〜
２３６℃
（３）溶解性：メタノール、クロロホルム、アセトンな
どに極めて溶けやすく、水にはほとんど溶けない。(1) Elemental analysis value: C3sH2aN20e (between 60
0.59) Theoretical value (%): C; 70.00. H;4
．． 03. N; 4.66 Actual value (%): C; 70.3
0. H; 3.85. N; 4.82 (2) Melting point: 233~
236℃ (3) Solubility: Extremely soluble in methanol, chloroform, acetone, etc., and almost insoluble in water.
（４）水素核磁気共鳴スペクトル（ＤＭＳＯ−ｄ６中、
テトラメチルシラン内部標準）；δ５．３９（ｓ、 ２
Ｈ） 、 ５．４３ （ｓ、 ２Ｈ） 、 ５．４７
（ｓ、 ２Ｈ）、７．４（ｍ、１６Ｈ）、８．６５（
Ｓ、ＩＨ）。(4) Hydrogen nuclear magnetic resonance spectrum (in DMSO-d6,
Tetramethylsilane internal standard); δ5.39 (s, 2
H), 5.43 (s, 2H), 5.47
(s, 2H), 7.4 (m, 16H), 8.65 (
S, IH).
１２．５６ （ｂ ｒ、 Ｉ Ｈ） ｐｐｍ。12.56 (br, IH) ppm.
（５）電子スペクトル； １ｍａＸ （ＣＨ３０Ｈ）２
０６．２５４，３７８ｎｍ。(5) Electronic spectrum; 1maX (CH30H)2
06.254,378nm.
（６）赤外吸収スペクトル（ＫＢｒ）： ｖｍａｘ３０
２０’、 １７００”、 １７８０ｖｓ、 １７６５”
’、 １３６５’、 １２３０ｖｓ１１８０’ツ、 ９
７０’、 ８３０’、 ７４０’、 ６８５５ｃｍ”（
以下余白）
［発明の効果］
本発明の新規化合物は、新規なＰＱＱ誘導体であるので
、新しい生理活性物質として、医薬あるいは農薬として
の用途が期待される。(6) Infrared absorption spectrum (KBr): vmax30
20', 1700", 1780vs, 1765"
', 1365', 1230vs1180'tsu, 9
70', 830', 740', 6855cm" (
(Left below) [Effects of the Invention] Since the novel compound of the present invention is a novel PQQ derivative, it is expected to be used as a new physiologically active substance, as a medicine or as an agrochemical.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27979889A JPH03145492A (en) | 1989-10-30 | 1989-10-30 | Pyrroloquinolinequinone ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27979889A JPH03145492A (en) | 1989-10-30 | 1989-10-30 | Pyrroloquinolinequinone ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03145492A true JPH03145492A (en) | 1991-06-20 |
Family
ID=17616064
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27979889A Pending JPH03145492A (en) | 1989-10-30 | 1989-10-30 | Pyrroloquinolinequinone ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03145492A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008029907A1 (en) | 2006-09-08 | 2008-03-13 | Kyowa Hakko Bio Co., Ltd. | Hypertension-ameliorating agent |
| WO2008035686A1 (en) | 2006-09-19 | 2008-03-27 | Kyowa Hakko Bio Co., Ltd. | Agent for improving insulin resistance |
| CN112042642A (en) * | 2020-07-27 | 2020-12-08 | 湖南省蔬菜研究所 | Use of PQQ as pesticide safener and method of use |
-
1989
- 1989-10-30 JP JP27979889A patent/JPH03145492A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008029907A1 (en) | 2006-09-08 | 2008-03-13 | Kyowa Hakko Bio Co., Ltd. | Hypertension-ameliorating agent |
| WO2008035686A1 (en) | 2006-09-19 | 2008-03-27 | Kyowa Hakko Bio Co., Ltd. | Agent for improving insulin resistance |
| CN112042642A (en) * | 2020-07-27 | 2020-12-08 | 湖南省蔬菜研究所 | Use of PQQ as pesticide safener and method of use |
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