JPS63112530A - Production of 1,4,5,8-tetramethoxynaphthalene - Google Patents
Production of 1,4,5,8-tetramethoxynaphthaleneInfo
- Publication number
- JPS63112530A JPS63112530A JP25555086A JP25555086A JPS63112530A JP S63112530 A JPS63112530 A JP S63112530A JP 25555086 A JP25555086 A JP 25555086A JP 25555086 A JP25555086 A JP 25555086A JP S63112530 A JPS63112530 A JP S63112530A
- Authority
- JP
- Japan
- Prior art keywords
- expressed
- formula
- raw material
- shikonin
- naphthazarin
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- SWNROPPWBFHVCS-UHFFFAOYSA-N 1,4,5,8-tetramethoxynaphthalene Chemical compound C1=CC(OC)=C2C(OC)=CC=C(OC)C2=C1OC SWNROPPWBFHVCS-UHFFFAOYSA-N 0.000 title claims description 4
- RQNVIKXOOKXAJQ-UHFFFAOYSA-N naphthazarin Chemical compound O=C1C=CC(=O)C2=C1C(O)=CC=C2O RQNVIKXOOKXAJQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims abstract description 7
- 230000011987 methylation Effects 0.000 claims description 5
- 238000007069 methylation reaction Methods 0.000 claims description 5
- NEZONWMXZKDMKF-JTQLQIEISA-N Alkannin Chemical compound C1=CC(O)=C2C(=O)C([C@@H](O)CC=C(C)C)=CC(=O)C2=C1O NEZONWMXZKDMKF-JTQLQIEISA-N 0.000 abstract description 8
- 241001071917 Lithospermum Species 0.000 abstract description 8
- UNNKKUDWEASWDN-UHFFFAOYSA-N alkannin Natural products CC(=CCC(O)c1cc(O)c2C(=O)C=CC(=O)c2c1O)C UNNKKUDWEASWDN-UHFFFAOYSA-N 0.000 abstract description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 229930192627 Naphthoquinone Natural products 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 4
- 150000002791 naphthoquinones Chemical class 0.000 abstract description 4
- 230000003110 anti-inflammatory effect Effects 0.000 abstract description 3
- 229940079593 drug Drugs 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000259 anti-tumor effect Effects 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 3
- SCIUCADXFKAPEB-INIZCTEOSA-N Echinone Chemical compound O=C1C=CC(=O)C2=C1C(O)=CC([C@H](CC=C(C)C)OC(C)=O)=C2OC SCIUCADXFKAPEB-INIZCTEOSA-N 0.000 abstract 1
- SCIUCADXFKAPEB-UHFFFAOYSA-N Echinone Natural products O=C1C=CC(=O)C2=C1C(O)=CC(C(CC=C(C)C)OC(C)=O)=C2OC SCIUCADXFKAPEB-UHFFFAOYSA-N 0.000 abstract 1
- 229910004878 Na2S2O4 Inorganic materials 0.000 abstract 1
- 230000000845 anti-microbial effect Effects 0.000 abstract 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 230000001035 methylating effect Effects 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- KKZJGLLVHKMTCM-UHFFFAOYSA-N mitoxantrone Chemical compound O=C1C2=C(O)C=CC(O)=C2C(=O)C2=C1C(NCCNCCO)=CC=C2NCCNCCO KKZJGLLVHKMTCM-UHFFFAOYSA-N 0.000 description 3
- 229960001156 mitoxantrone Drugs 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- LQQKULWAVYAOBB-UHFFFAOYSA-N 1,2,3,4-tetramethoxynaphthalene Chemical compound C1=CC=CC2=C(OC)C(OC)=C(OC)C(OC)=C21 LQQKULWAVYAOBB-UHFFFAOYSA-N 0.000 description 1
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000118 anti-neoplastic effect Effects 0.000 description 1
- 229940034982 antineoplastic agent Drugs 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012022 methylating agents Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は１，４，５．８−テトラメトキシナフタレンの
製造法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing 1,4,5,8-tetramethoxynaphthalene.
（従来の技術）
Ｌ４，５．８−テトラメトキシナフタレンは、抗ｎ重瘍
性、抗菌性、抗炎信性作用を持つ構造式で表わされるシ
コニン、構造式、
で表わされるエチノン、および構造式、で表わされるミ
トザントロンなどの重要なナフトキノン系医薬合成に出
発原料あるいは中間体として用いられる。(Prior art) L4,5.8-tetramethoxynaphthalene has anti-neoplastic, antibacterial, and anti-inflammatory properties; shikonin, which has the structural formula; ethynon, which has the structural formula; and It is used as a starting material or intermediate in the synthesis of important naphthoquinone drugs such as mitoxantrone, which is represented by .
また本発明者等によって提案されたシコニン製造法（特
開昭５９−１７５４４９号）とシコニン合成中間体の製
造法（特開昭６１−２０４１５３号）と共に、シコニン
の工業的合成に関連する重要な一系路を構成するもので
ある。すなわち、本発明者は嚢に、下記反応式、
で示されるように、１，５−ナフタレンジオール（４）
から出発して、１．５−ジメトキシナフタレン（５）を
臭素化して４．８−ジブロモ−１，，５−ジメトキシナ
フタレン（６）を得、触媒として新しくわれわれが開発
したヨウ化銅の存在下でナトリウムメトキシドにより、
目的物Ｌ４，５．８−テトラメトキシナフタレン（７）
へ導く改良合成法を発表した（Ｊ、Ｃｈｅｍ、Ｓｏｃ。In addition to the method for producing shikonin (Japanese Unexamined Patent Publication No. 59-175449) and the method for producing intermediates for shikonin synthesis (Japanese Patent Unexamined Patent Application No. 204153-1988) proposed by the present inventors, important information related to the industrial synthesis of shikonin has been proposed. This constitutes one route. That is, the present inventor added 1,5-naphthalenediol (4) to the capsule as shown in the following reaction formula:
Starting from with sodium methoxide,
Target L4,5.8-tetramethoxynaphthalene (7)
published an improved synthetic method leading to (J, Chem, Soc.
Ｃｈｅｍ、Ｃｏｍｍｕｎ、、 １９８３．９８７）。こ
のように従前の（６）−（７）の報告の収率１９％〔八
、Ｚｗｅｉｇ＋Ａ、Ｈ，Ｍａｕｒｅｒａｎｄ Ｒｏｂｅ
ｒｔｓ、Ｊ、Ｏｒｇ、Ｃｈｅｍ、、 ３２．１３３２（
１９６７））であったものを８４％に改良したものの、
３工程を要し、（４）から（７）への通算した総数率は
３３％であった。従ってこの工程の短縮化による合理化
の必要性は頗る望まれるところであった。Chem, Commun, 1983.987). Thus, the yield of previous reports (6)-(7) was 19% [8, Zweig + A, H, Maureland Robe
rts, J, Org, Chem,, 32.1332 (
Although it was improved from 1967) to 84%,
Three steps were required, and the total number rate from (4) to (7) was 33%. Therefore, it is highly desirable to streamline this process by shortening it.
（発明が解決しようとする問題点）
一方、ナフタザリン、すなわち５．８−ジヒドロキシ−
１，４−ナフトキノンは、希硫酸媒質中で亜鉛をもって
還元すればＬ４，５．８−テトラヒドロキシナフタレン
となることは周知である。（Ｓ、Ｃｏｆｆｅｙ １８Ｒ
ｏｄｄ’ｓ Ｃｈｅｍｉｓｔｒｙ ｏｆ Ｃａｒｂｏｎ
ｃｏｍｐｏｕｎｄｓ＋ｖｏ１． ＩｆｆＰａｒｔ Ｇ
、Ｅｌｓｅｖｉｅｒ Ｓｃｉ、Ｐｕｂｌ、Ｃｏ、＋ １
９７８＋ ｐ、２３６）そこで本発明者はこの反応に着
目して、ナフタザリンをメタノール中でスズと塩化水素
ガスとで還元しながらメチル化を試みたが、好結果を生
じなかった。すなわち、途中までメチル化を進めること
はできるが４つの水酸基を全部メチル化して（７）とす
ることには成功しなかった。(Problems to be solved by the invention) On the other hand, naphthazarine, i.e., 5,8-dihydroxy-
It is well known that 1,4-naphthoquinone can be reduced to L4,5,8-tetrahydroxynaphthalene with zinc in dilute sulfuric acid medium. (S, Coffee 18R
odd's Chemistry of Carbon
compounds+vol1. If Part G
, Elsevier Sci, Publ, Co, +1
978+ p., 236) Therefore, the present inventor focused on this reaction and attempted methylation of naphthazarine while reducing it with tin and hydrogen chloride gas in methanol, but no good results were obtained. That is, although it was possible to proceed with methylation halfway, it was not possible to methylate all four hydroxyl groups to form (7).
本発明者等は更に鋭意研究の結果、アルカリ媒質中で還
元すると同時にメチル化を進めることによって目的とす
るＬ４，５．８−テトラメトキシナフタレンを一挙に取
得することに成功し本発明を完成したものである。As a result of further intensive research, the present inventors succeeded in obtaining the target L4,5.8-tetramethoxynaphthalene at once by proceeding with reduction and methylation in an alkaline medium, and completed the present invention. It is something.
すなわち本発明の目的はナフタザリンよリー工程をもっ
て収率良＜ １．４，５．８−テトラメトキシナフタレ
ンを製造せんとするにあり、終掻の目的は、シコニン、
エチノン、ミトザントロンなどの合成法を合理化するこ
とにある。That is, the purpose of the present invention is to produce 1.4,5.8-tetramethoxynaphthalene in good yield using a naphthazarin filtration process, and the purpose of the final stage is to produce shikonin,
The aim is to rationalize the synthesis method of ethinones, mitoxantrone, etc.
（問題点を解決するための手段）
上記目的は、ナフタザリンに亜ジチオン酸ナトリウムを
作用させながらジメチル硫酸でメチル化することを特徴
とする１、４，５．８−テトラメトキシナフタレンの製
造法によって達成される。(Means for solving the problem) The above object is achieved by a method for producing 1,4,5,8-tetramethoxynaphthalene, which is characterized in that naphthazarin is methylated with dimethyl sulfate while acting with sodium dithionite. achieved.
本発明においては、出発原料は市販のナフタザリン（８
）を用い、還元剤としてこれも安価なハイドロサルファ
イド、すなわち亜ジチオン酸ナトリウムを用いて還元し
つつ、これも普通のメチル化剤であるジメチル硫酸で一
挙にメチル化を進めて目的物１，４，５．８−テトラメ
トキシナフタレン（７）が−工程で得られる。これを反
応式で示せば次の通りである。In the present invention, the starting material is commercially available naphthazarin (8
) and using hydrosulfide, which is also an inexpensive reducing agent, i.e., sodium dithionite, to proceed with the methylation at once with dimethyl sulfate, which is also a common methylating agent, to obtain the target compounds 1 and 4. , 5.8-tetramethoxynaphthalene (7) is obtained in step -. The reaction formula for this is as follows.
反応は室温で進行し、ある実験例においては、収率は４
４％にも達した。The reaction proceeds at room temperature, and in some examples the yield is 4
It reached 4%.
さらにこの反応系の反応試剤に不活性で反応系に生じる
化合物を良く溶かす有機溶剤、例えばエーテル、テトラ
ヒドロフランなどを共存せしめると、より反応を円滑に
進めることができる。Furthermore, the reaction can proceed more smoothly if an organic solvent such as ether, tetrahydrofuran, etc., which is inert and dissolves well the compounds generated in the reaction system, is coexisting with the reaction reagent in the reaction system.
（実施例） 次に実施例を示してさらに詳細に説明する。(Example) Next, a more detailed explanation will be given with reference to examples.
実施例１
ナフタザリン０．１９０ ｇ （１ｍｍｏｆ） とエー
テル４０ｍ１を１００ ｍｌの四つロフラスコに入れ、
室温で激しくかきまぜながらハイドロサルファトナトリ
ウム（亜ジチオン酸ナトリウム） １．０６ｇを水２０
ｍ ｌに溶かしたものの半量を添加してゆくと反応液は
無色になる。次に水酸化ナトリウムＬｏｇを水２０ｍ
ｌに溶かしたものの半量を加え、１５ｇのジメチル硫酸
の半量を滴下して室温で３時間反応させる。次に水酸化
ナトリウムの残量を滴下、ハイドロサルファト液の残量
を加え、さらにジメチル硫酸の残りを滴下し、再び１２
時間室温で反応を続けた。希塩酸を加えて酸性とし、ク
ロロホルムで抽出、水洗して乾燥する。Ｌ４，５．８−
テトラメトキシナフタレンの白色結晶０．１０’９ ｇ
（４４％）を得る。融点は１６７〜１６８℃を示し、
赤外分析、元素分析の結果とも一致した（融点１６８．
５〜１６９℃、Ａ、Ｈ，Ｃａｒｔｅｒ、Ｅ。Example 1 0.190 g (1 mmof) of naphthazarin and 40 ml of ether were placed in a 100 ml four-loaf flask.
Add 1.06 g of sodium hydrosulfate (sodium dithionite) to 20 g of water while stirring vigorously at room temperature.
When half of the amount dissolved in ml is added, the reaction solution becomes colorless. Next, add sodium hydroxide Log to 20 m of water.
Add half of the solution dissolved in 1 liter of water, dropwise add half of 15 g of dimethyl sulfate, and let the mixture react at room temperature for 3 hours. Next, the remaining amount of sodium hydroxide was added dropwise, the remaining amount of hydrosulfate solution was added, and the remaining amount of dimethyl sulfate was added dropwise.
The reaction was continued at room temperature for an hour. Add dilute hydrochloric acid to make acidic, extract with chloroform, wash with water, and dry. L4, 5.8-
White crystals of tetramethoxynaphthalene 0.10'9 g
(44%). The melting point is 167-168°C,
The results were consistent with infrared analysis and elemental analysis (melting point: 168.
5-169°C, A, H, Carter, E.
Ｒａｃｅ ａｎｄ Ｆ、Ｍ、Ｒｏｗｅ、 Ｊ、Ｃｈｅｍ
、Ｓｏｃ＋ １９４２＋ ２３６）。Race and F, M, Rowe, J, Chem.
, Soc+ 1942+ 236).
元素分析値 Ｃ６７，５０％：Ｈ６，５８％Ｃ＋ｔＨ＋
６０４の計算値 Ｃ６７，７３％：Ｈ６，５０％実施例
２
実施例１と同じ処方で、エーテルの代りにテトラヒドロ
フラン４０ｍ１使用したときの（７）の収率２７％が得
られた。Elemental analysis value C67,50%: H6,58%C+tH+
Calculated value of 604 C67, 73%: H6, 50% Example 2 A yield of 27% of (7) was obtained using the same recipe as in Example 1 but using 40 ml of tetrahydrofuran instead of ether.
赤外分析図、Ｎ）ＩＲ分析図をそれぞれ第１図と第２図
に示す。An infrared analysis diagram and an IR analysis diagram are shown in Figures 1 and 2, respectively.
（発明の効果）
本発明により、抗腫瘍性、抗菌性、抗炎慣性作用を持つ
シコニン（１）、エチノン（２）、ミトザントロン（３
）などの重要なナフトキノン系医薬合成に出発原料ある
いは中間体として用いられる１、４゜５．８−テトラメ
トキシナフタレンが入手容易な市販のナフタザリンより
１工程により収率良く得られるから、従来の多工程が一
挙に短縮され、上記有用物質の合成工程が著しく合理化
されるという顕著な効果を奏する。(Effects of the Invention) The present invention provides shikonin (1), ethinon (2), and mitoxantrone (3), which have antitumor, antibacterial, and antiinflammatory effects.
1,4゜5.8-tetramethoxynaphthalene, which is used as a starting material or intermediate in the synthesis of important naphthoquinone-based pharmaceuticals such as This has the remarkable effect that the steps are shortened all at once, and the synthesis steps for the above-mentioned useful substances are significantly streamlined.
第１図および第２図は本発明方法によって得られた１、
４，５．８−テトラメトキシナフタレンの、それぞれ赤
外分析図およびＮＭＲ分析図である。1 and 2 show 1 obtained by the method of the present invention,
They are an infrared analysis diagram and an NMR analysis diagram, respectively, of 4,5.8-tetramethoxynaphthalene.
Claims (1)
ながらジメチル硫酸でメチル化することを特徴とする１
，４，５，８−テトラメトキシナフタレンの製造法。1. Methylation with dimethyl sulfate while reacting sodium dithionite with naphthazarin 1
, 4,5,8-Tetramethoxynaphthalene manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25555086A JPS63112530A (en) | 1986-10-29 | 1986-10-29 | Production of 1,4,5,8-tetramethoxynaphthalene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25555086A JPS63112530A (en) | 1986-10-29 | 1986-10-29 | Production of 1,4,5,8-tetramethoxynaphthalene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63112530A true JPS63112530A (en) | 1988-05-17 |
| JPH0470292B2 JPH0470292B2 (en) | 1992-11-10 |
Family
ID=17280279
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25555086A Granted JPS63112530A (en) | 1986-10-29 | 1986-10-29 | Production of 1,4,5,8-tetramethoxynaphthalene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63112530A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003099346A2 (en) * | 2002-05-24 | 2003-12-04 | Angiotech International Ag | Compositions and methods for coating medical implants |
| JP2018528859A (en) * | 2016-01-13 | 2018-10-04 | 厦門理工学院 | Method for producing anthraquinone functionalized polyvinylidene fluoride ultrafiltration membrane |
-
1986
- 1986-10-29 JP JP25555086A patent/JPS63112530A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003099346A2 (en) * | 2002-05-24 | 2003-12-04 | Angiotech International Ag | Compositions and methods for coating medical implants |
| WO2003099346A3 (en) * | 2002-05-24 | 2004-03-18 | Angiotech Pharm Inc | Compositions and methods for coating medical implants |
| JP2018528859A (en) * | 2016-01-13 | 2018-10-04 | 厦門理工学院 | Method for producing anthraquinone functionalized polyvinylidene fluoride ultrafiltration membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0470292B2 (en) | 1992-11-10 |
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