JPH049387A - 4-hydroxyphenylmethyloxazopyrroloquinolines - Google Patents
4-hydroxyphenylmethyloxazopyrroloquinolinesInfo
- Publication number
- JPH049387A JPH049387A JP10735790A JP10735790A JPH049387A JP H049387 A JPH049387 A JP H049387A JP 10735790 A JP10735790 A JP 10735790A JP 10735790 A JP10735790 A JP 10735790A JP H049387 A JPH049387 A JP H049387A
- Authority
- JP
- Japan
- Prior art keywords
- hydroxyphenylmethyl
- salts
- tyrosine
- pqq
- salt
- 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
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 8
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 abstract description 14
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 abstract description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- MMXZSJMASHPLLR-UHFFFAOYSA-N pyrroloquinoline quinone Chemical compound 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 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 244000005700 microbiome Species 0.000 abstract description 3
- 208000030507 AIDS Diseases 0.000 abstract description 2
- 241001465754 Metazoa Species 0.000 abstract description 2
- 229940124428 anticataract agent Drugs 0.000 abstract description 2
- 239000007952 growth promoter Substances 0.000 abstract description 2
- 230000007198 pollen germination Effects 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 208000019423 liver disease Diseases 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- -1 4-hydroxyphenylmethyl Chemical group 0.000 description 24
- 229960004441 tyrosine Drugs 0.000 description 12
- 150000003863 ammonium salts Chemical class 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 230000001766 physiological effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229920005654 Sephadex Polymers 0.000 description 2
- 239000012507 Sephadex™ Substances 0.000 description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 125000000168 pyrrolyl group Chemical group 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-O triethanolammonium Chemical class OCC[NH+](CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-O 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical class CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 238000002211 ultraviolet spectrum Methods 0.000 description 2
- 238000001429 visible spectrum Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 150000008553 L-tyrosines Chemical class 0.000 description 1
- 206010067125 Liver injury Diseases 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 231100000234 hepatic damage Toxicity 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000008818 liver damage Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000008057 potassium phosphate buffer Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- UQDJGEHQDNVPGU-UHFFFAOYSA-N serine phosphoethanolamine Chemical compound [NH3+]CCOP([O-])(=O)OCC([NH3+])C([O-])=O UQDJGEHQDNVPGU-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000003357 wound healing promoting agent Substances 0.000 description 1
Landscapes
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、４−ヒドロキシフェニルメチルオキサゾピロ
ロキノリン類に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to 4-hydroxyphenylmethyloxazopyrroquinolines.
〔従来の技術、発明が解決しようとする問題点〕オキサ
ゾピロロキノリン化合物としては、今まで２． ８．
１０−）リカルボキシー１Ｈ−オキサゾ［５，４−ｈ］
−ピロロ［２，３−ｆ］キノリンのみが知られているが
、その生理活性は、実用するにはまだ十分なものではな
い。そこで生理活性がよりすぐれているオキサゾピロロ
キノリン系化合物の開発が望まれていた。[Prior art and problems to be solved by the invention] Until now, oxazopyrroquinoline compounds have been classified into 2. 8.
10-) Licarboxy 1H-oxazo[5,4-h]
Only -pyrrolo[2,3-f]quinoline is known, but its physiological activity is not yet sufficient for practical use. Therefore, it has been desired to develop oxazopyrroquinoline compounds that have better physiological activity.
〔問題点を解決するための手段、作用〕本発明者らは、
生理活性の高いオキサゾピロロキノリン系化合物につい
て鋭意研究を重ねた過程において、ピロロキノリンキノ
ン（以下ＰＱＱと記す）とチロシンとを反応させること
により新規なオキサゾピロロキノリン化合物が得られる
ことを見出し、本発明を完成した。[Means and effects for solving the problem] The present inventors,
In the course of intensive research into highly physiologically active oxazopyrroquinoline compounds, we discovered that a novel oxazopyrroquinoline compound can be obtained by reacting pyrroloquinoline quinone (hereinafter referred to as PQQ) with tyrosine. The invention has been completed.
すなわち、本発明は、５−（４−ヒドロキシフェニルメ
チル）−２，８，１０−トリカルボキシ−ＬＨ−オキサ
ゾ［５，４−ｈ］−ピロロ［２゜３−ｆ’ｌキノリンお
よびその塩である。That is, the present invention provides 5-(4-hydroxyphenylmethyl)-2,8,10-tricarboxy-LH-oxazo[5,4-h]-pyrrolo[2°3-f'l quinoline and its salts. be.
しかるに、この化合物は、式 で表される。However, this compound has the formula It is expressed as
５−（４−ヒドロキシフェニルメチル）−２゜８．１０
−トリカルボキシ−１Ｈ−オキサゾ［５４−ｈ］−ピロ
ロ［２，３−ｆ］キノリン（以下、４−ヒドロキシフェ
ニルメチルＯＰＱと記ス。5-(4-hydroxyphenylmethyl)-2゜8.10
-tricarboxy-1H-oxazo[54-h]-pyrrolo[2,3-f]quinoline (hereinafter referred to as 4-hydroxyphenylmethyl OPQ).
）の塩、すなわち、４−ヒドロキシフェニルメチル○Ｐ
Ｑ塩としては、アルカリ金属塩、アルカリ土類金属塩、
アンモニウム塩および置換アンモニウム塩などがある（
４−ヒドロキシフェニルメチル○ＰＱＪよび４−ヒドロ
キシフェニルメチル○ＰＱ塩を総称して以下４−ヒドロ
キシフェニルメチルｏＰＱ類と記すこともある。）。), i.e., 4-hydroxyphenylmethyl○P
Q salts include alkali metal salts, alkaline earth metal salts,
These include ammonium salts and substituted ammonium salts (
4-hydroxyphenylmethyl oPQJ and 4-hydroxyphenylmethyl oPQ salts may be collectively referred to as 4-hydroxyphenylmethyl oPQs below. ).
置換アンモニウム塩には、たとえば、アルキル置換アン
モニウム塩およびヒドロキシアルキル置換アンモニウム
塩などがある。Substituted ammonium salts include, for example, alkyl-substituted ammonium salts and hydroxyalkyl-substituted ammonium salts.
本発明の４−ヒドロキシフェニルメチルＯＰＱ塩の代表
例としては、ナトリウム塩、カリウム塩、マグネシウム
塩、カルシウム塩、アンモニウム塩、トリメチルアンモ
ニウム塩、トリエチルアンモニウム塩、トリエタノール
アンモニウム塩などがある。Representative examples of the 4-hydroxyphenylmethyl OPQ salts of the present invention include sodium salts, potassium salts, magnesium salts, calcium salts, ammonium salts, trimethylammonium salts, triethylammonium salts, triethanolammonium salts, and the like.
本発明の４−ヒドロキシフェニルメチルＯＰＱ類を得る
方法としては、合成法および微生物を用いる発酵法など
があるが、ＰＱＱとチロシンあるいはＰＱＱ塩とチロシ
ンから合成する方法が比較的簡単であり、しかも、実用
的である。Methods for obtaining the 4-hydroxyphenylmethyl OPQs of the present invention include synthetic methods and fermentation methods using microorganisms, but the method of synthesizing from PQQ and tyrosine or PQQ salt and tyrosine is relatively simple, and It's practical.
ＰＱＱとチロシンあるいはＰＱＱ塩とチロシンから合成
する場合には、使用されるＰＱＱまたはＰＱＱ塩（ＰＱ
ＱとＰＱＱ塩とを総称して以下ＰＱＱ類と記すこともあ
る。）は、発酵生産品あるいは合成品のいずれでも良い
。ＰＱＱ塩には、たとえば、ナトリウム塩およびカリウ
ム塩などのアルカリ金属塩、マグネシウム塩およびカル
シウム塩などのアルカリ土類金属塩、アンモニウム塩、
トリメチルアンモニウム塩およびトリエチルアンモニウ
ム塩などのアルキル置換アンモニウム塩ならびにトリエ
タノールアンモニウム塩などのヒドロキシアルキル置換
アンモニウム塩などがある。When synthesizing from PQQ and tyrosine or PQQ salt and tyrosine, the PQQ or PQQ salt (PQQ) used is
Q and PQQ salts may be collectively referred to as PQQs below. ) may be either a fermented product or a synthetic product. PQQ salts include, for example, alkali metal salts such as sodium and potassium salts, alkaline earth metal salts such as magnesium and calcium salts, ammonium salts,
These include alkyl-substituted ammonium salts such as trimethylammonium salts and triethylammonium salts, and hydroxyalkyl-substituted ammonium salts such as triethanolammonium salts.
また、チロシンは、Ｄ体、Ｌ体およびこれらの混合物の
いずれでもよい。Furthermore, tyrosine may be in the D-form, L-form, or a mixture thereof.
これらのＰＱＱ類およびチロシンは、いずれも市販品を
使用することができる。Commercially available products can be used for both of these PQQs and tyrosine.
チロシンの使用量は、化学量論量以上であればよいが、
実用上、通常はＰＱＱ類に対して１モル倍以上、好まし
くは１〜１０００モル倍程度とされる。The amount of tyrosine used may be more than the stoichiometric amount, but
Practically speaking, the amount is usually 1 mole or more, preferably about 1 to 1000 times the mole of PQQs.
この反応は溶媒を使用した液相で行われる。この溶媒の
代表例として水およびメタノールなどの低級脂肪族アル
コールなどがある。This reaction is carried out in the liquid phase using a solvent. Representative examples of this solvent include water and lower aliphatic alcohols such as methanol.
反応液中におけるＰＱＱ類の濃度範囲は、特に制限され
ず、溶媒の種類および反応条件などによって異なり、−
概に特定し得ないが、実用上、通常は、０．１〜５０［
ＤＭが好ましい。The concentration range of PQQs in the reaction solution is not particularly limited and varies depending on the type of solvent and reaction conditions.
Although it cannot be generally specified, in practice it is usually 0.1 to 50[
DM is preferred.
本発明における４−ヒドロキシフェニルメチルＯＰＱ類
を得る反応には酸素が必要であり、そのためには、反応
液に酸素を供給することが必要である。Oxygen is required for the reaction to obtain 4-hydroxyphenylmethyl OPQs in the present invention, and for that purpose, it is necessary to supply oxygen to the reaction solution.
４−ヒドロキシフェニルメチル○ＰＱ塩は、般に４−ヒ
ドロキシフェニルメチルＯＰＱを含む溶液に、目的とす
る４−ヒドロキシフェニルメチル○ＰＯ塩に対応するア
ルカリを添加することによっても得られる。4-Hydroxyphenylmethyl○PQ salt can also generally be obtained by adding an alkali corresponding to the desired 4-hydroxyphenylmethyl○PO salt to a solution containing 4-hydroxyphenylmethylOPQ.
このようにして得られた反応液から４−ヒドロキシフェ
ニルメチルＯＰＱ類を分離精製する方法としては種々あ
る。たとえば、４−ヒドロキシフェニルメチルＯＰＱ類
を吸着する樹脂担体を用いた方法、有機溶媒抽出法、沈
澱法、洗浄法および限外ろ適法などがあり、これらの方
法を単独あるいは組み合わせて、４−ヒドロキシフェニ
ルメチルＯＰＱ類を分離、精製することができる。There are various methods for separating and purifying 4-hydroxyphenylmethyl OPQ from the reaction solution thus obtained. For example, there are methods using resin carriers that adsorb 4-hydroxyphenylmethyl OPQs, organic solvent extraction methods, precipitation methods, washing methods, and ultrafiltration methods. Phenylmethyl OPQs can be separated and purified.
本発明の化合物は、この骨格構造がＰＱＱと共通である
ことがらＰＱＱと同様の生理活性を有し、ＰＱＱと同様
の用途、たとえば、微生物に対する生育促進剤、動物に
あける肝障害改善剤、組織修復促進作用による創傷癒合
剤、酵素阻害作用による抗エイズ剤および抗白内障剤、
植物における花粉発芽促進剤および花粉管伸長促進剤な
どとして使用し得るものと推察される。The compound of the present invention has the same skeletal structure as PQQ, so it has the same physiological activity as PQQ, and can be used in the same ways as PQQ, such as a growth promoter for microorganisms, a liver damage improving agent for animals, and a tissue Wound healing agent with repair promoting effect, anti-AIDS agent and anti-cataract agent with enzyme inhibiting effect,
It is presumed that it can be used as a pollen germination promoter and pollen tube elongation promoter in plants.
以下、本発明を実施例によってさらに具体的に説明する
が、本発明はこれらの実施例に限定されるものではない
。EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.
実施例
Ｌ−チロシン４．４ｇを蒸留水４００−に添加し、ＩＮ
塩酸にてｐ）１４．０に調整してＬ−チロシン懸濁液を
得た。Example L - Add 4.4 g of tyrosine to 400 g of distilled water and add IN
The p) was adjusted to 14.0 with hydrochloric acid to obtain an L-tyrosine suspension.
このＬ−チロシン懸濁液にＰ ＱＱ ８００ｍｇを添加
し、空気を通気しながら強く機械撹はんしつつ、６０℃
にて２４時間反応させた。この反応生成液を５℃に冷却
して析出したし一チロシンをろ過した。ろ液を６Ｎ塩酸
にてｐｌｉｌ、 ０に調整し、５℃に冷却して４ヒドロ
ギシフエニルメチルＯＰＱを沈澱さ゛せた。800 mg of PQQ was added to this L-tyrosine suspension, and the mixture was heated at 60°C with strong mechanical stirring while aerating air.
The reaction was carried out for 24 hours. This reaction product solution was cooled to 5° C. to precipitate tyrosine, which was then filtered. The filtrate was adjusted to 0 prill with 6N hydrochloric acid and cooled to 5°C to precipitate 4-hydroxyphenylmethyl OPQ.
この沈澱を遠心分離によって回収し、この沈澱に蒸留水
１５０ＷＬ１．を加え、この液を５Ｎ Ｎａ０）１にて
ｐ）１７．３とし、沈澱を溶解した。This precipitate was collected by centrifugation, and 150 liters of distilled water was added to the precipitate. was added, and the solution was adjusted to p)17.3 with 5N Na0)1 to dissolve the precipitate.
得られた溶液に陰イオン交換担体であるＤＲＡＢセファ
デックスＡ−２５５０ｍｆｆを加え十分に撹はんし、４
−ヒドロキシフェニルメチルＯＰＱをこの担体に吸着さ
せた後静置し、上清を除いて、この担体を分離・回収し
た。DRAB Sephadex A-2550mff, an anion exchange carrier, was added to the obtained solution, stirred thoroughly, and
-Hydroxyphenylmethyl OPQ was adsorbed onto this carrier, and then allowed to stand, the supernatant was removed, and the carrier was separated and collected.
５０ｍｍφカラムに新しいＤＢＡＩＥ−セファデックス
Ａ−２５７５ｍｌ、を充填し、その上に、回収した担体
を充填した。A 50 mmφ column was filled with 2,575 ml of new DBAIE-Sephadex A, and the recovered carrier was packed thereon.
このカラムに蒸留水５００πＪを流して洗浄した後、０
．４Ｍ食塩水３７００ｍＡを流し、引き続いてさらに０
６Ｍ食塩水６０００ｍＡを流した。この時、担体に吸着
されていた４−ヒドロキシフェニルメチル○ＰＱは、０
．６Ｍ食塩水の溶出画分に存在した。After washing this column with 500πJ of distilled water,
．． Flow 3700mA of 4M saline solution, then further
6000 mA of 6M saline was flowed. At this time, 4-hydroxyphenylmethyl○PQ adsorbed on the carrier was reduced to 0.
．． It was present in the 6M saline elution fraction.
この４−ヒドロキシフェニルメチル○Ｐ Ｑ溶出画分を
６Ｎ塩酸にてｐＨ１，０とし、５℃にて４−ヒドロキシ
フェニルメチル○ＰＱを沈澱させた。得られた沈澱を遠
心分離により回収し、メタノールに溶解させ、これを濃
縮乾固した。これにジエチルエーテルを加え、生じた沈
澱をろ過した。得られた沈澱を真空下約７０℃で乾燥し
て３５７ｍｇの４−ヒドロキシフェニルメチルＯＰＱを
得た。This 4-hydroxyphenylmethyl○PQ elution fraction was adjusted to pH 1.0 with 6N hydrochloric acid, and 4-hydroxyphenylmethyl○PQ was precipitated at 5°C. The resulting precipitate was collected by centrifugation, dissolved in methanol, and concentrated to dryness. Diethyl ether was added to this, and the resulting precipitate was filtered. The resulting precipitate was dried under vacuum at about 70°C to obtain 357 mg of 4-hydroxyphenylmethyl OPQ.
得うれた４−ヒドロキシフェニルメチル０ＰＱＯ色は、
赤茶色であり、２６３〜２６８℃から徐々に分解し、明
確な融点を示さなかった。また水に溶けやすく、中性お
よびアルカリ性下では極めて溶けやすかった。また低級
アルコールにも溶けたがアセトンおよびジエチルエーテ
ルには溶けなかった。The obtained 4-hydroxyphenylmethyl 0PQO color is
It was reddish brown in color, gradually decomposed from 263 to 268°C, and showed no clear melting point. It was also easily soluble in water, and extremely soluble under neutral and alkaline conditions. It was also soluble in lower alcohols, but not in acetone and diethyl ether.
また、この４−ヒドロキシフェニルメチルＯＰＯの水溶
液の色は、４−ヒドロキシフェニルメチルＯＰＱの濃度
および水溶液のｐＨによって異なるが、約１０ｍｇ／ｍ
Ａの４−ヒドロキシフェニルメチル０ＰＱ水溶液は、水
溶液のｐＨが中性からアルカリ性では淡黄色であり、酸
性では赤みがかった淡黄色であった。The color of this aqueous solution of 4-hydroxyphenylmethyl OPO varies depending on the concentration of 4-hydroxyphenylmethyl OPQ and the pH of the aqueous solution, but it is approximately 10 mg/m
The 4-hydroxyphenylmethyl 0PQ aqueous solution A was pale yellow when the pH of the aqueous solution was neutral to alkaline, and reddish pale yellow when the pH of the aqueous solution was acidic.
０の元素分析値、ＩＲスペクトル、廿−ＮＭＲスペクト
ルおよび可視・紫外部スペクトルを示す。The elemental analysis value, IR spectrum, 廿-NMR spectrum, and visible/ultraviolet spectrum of 0 are shown.
１）元素分析値： Ｃ２２Ｈ１３Ｎ ｓＯａ・Ｈ２０＜
ＭＷ ４６５．３７）
理論値（％）：Ｃ５６，７８Ｈ３，２５Ｎ ９．０３実
測値（％）：Ｃ５６，５１Ｈ３，５２Ｎ ８．８７２）
ＩＲスペクトル（νｍａｘ値、 ｃｍ −’） ： （
ＫＢｒ）２８１０’、 ２５２０’＝ ”、 １５９０
’、 １５００’、 １４１５”。1) Elemental analysis value: C22H13N sOa・H20<
MW 465.37) Theoretical value (%): C56,78H3,25N 9.03 Actual value (%): C56,51H3,52N 8.872)
IR spectrum (νmax value, cm −'): (
KBr)2810', 2520'='', 1590
', 1500', 1415''.
１１８０”、 ９９０”−”、 ８２０ｗ−Ｓｈ、 ７
６０’″、 ７３０’″、６７０°・ゝ１３） ’Ｈ
−ＮＭＲスペクトル （δ値、 ｐｐｍ） ：（ＤＭＳ
Ｏ−ｄ、、内部標準：ＴＭＳ）４、５４（ｓ、 ２Ｈ，
Ｃ，ｉｉ、−Ｃ６Ｈ，０ｔｌ）。1180", 990"-", 820w-Sh, 7
60''', 730''', 670°・ゝ13) 'H
-NMR spectrum (δ value, ppm): (DMS
O-d,, internal standard: TMS) 4, 54 (s, 2H,
C,ii, -C6H,0tl).
６、６４ （ｄ、 ２Ｈ，Ｊ＝８．６）１ｚ、 ＣＨ，
側ベンゼン環Ｃ−１１）６、８１ （ｄ、 ２Ｈ，Ｊ＝
８．１Ｈｚ、 ＯＨ側ベンゼン環Ｃ−ｆｌ）７、３１
（ｄ、 Ｉｔ（、ピロール環Ｃ−ｊ、 Ｊ＝２．０Ｈｚ
） 。6, 64 (d, 2H, J=8.6) 1z, CH,
Side benzene ring C-11) 6, 81 (d, 2H, J=
8.1Hz, OH side benzene ring C-fl)7, 31
(d, It(, pyrrole ring C-j, J=2.0Hz
).
７、９４ （ｓ、 ＬＨ，ピリジン環Ｃ−Ｈ） 。7,94 (s, LH, pyridine ring C-H).
１３、０１ （ｂｒｓ、 １Ｈ，ピロール環Ｎ−１（、
）４）可視・紫外部スペクトル（λ１１８値、 ｎｍ）
：（１０ｍＭ リン酸カリウム緩衝液ｐ）１７．０）
２５６、２７０”４２０
〔発明の効果〕
本発明の新規化合物は、新規なオキサゾピロロキノリン
化合物であり、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。13,01 (brs, 1H, pyrrole ring N-1(,
)4) Visible/ultraviolet spectrum (λ118 value, nm)
: (10mM potassium phosphate buffer p)17.0)
256, 270''420 [Effects of the Invention] The novel compound of the present invention is a novel oxazopyrroquinoline compound, and is expected to be used as a new physiologically active substance, as a medicine or as an agrochemical.
特許出願人 三菱瓦斯化学株式会社 代表者 画用 禮二Patent applicant: Mitsubishi Gas Chemical Co., Ltd. Representative: Painter: Reiji
Claims (1)
−トリカルボキシ−１Ｈ−オキサゾ［５，４−ｈ］−ピ
ロロ［２，３−ｆ］キノリンおよびその塩。5-(4-hydroxyphenylmethyl)-2,8,10
-Tricarboxy-1H-oxazo[5,4-h]-pyrrolo[2,3-f]quinoline and salts thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10735790A JPH049387A (en) | 1990-04-25 | 1990-04-25 | 4-hydroxyphenylmethyloxazopyrroloquinolines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10735790A JPH049387A (en) | 1990-04-25 | 1990-04-25 | 4-hydroxyphenylmethyloxazopyrroloquinolines |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH049387A true JPH049387A (en) | 1992-01-14 |
Family
ID=14457022
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10735790A Pending JPH049387A (en) | 1990-04-25 | 1990-04-25 | 4-hydroxyphenylmethyloxazopyrroloquinolines |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH049387A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0670321A1 (en) * | 1994-03-03 | 1995-09-06 | Mitsubishi Gas Chemical Company, Inc. | Oxazopyrroloquinoline deivatives and use thereof |
-
1990
- 1990-04-25 JP JP10735790A patent/JPH049387A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0670321A1 (en) * | 1994-03-03 | 1995-09-06 | Mitsubishi Gas Chemical Company, Inc. | Oxazopyrroloquinoline deivatives and use thereof |
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