JPS59212443A - Manufacture of 1,8-dihydroxy-10-acyl-9-anthrone - Google Patents
Manufacture of 1,8-dihydroxy-10-acyl-9-anthroneInfo
- Publication number
- JPS59212443A JPS59212443A JP59090047A JP9004784A JPS59212443A JP S59212443 A JPS59212443 A JP S59212443A JP 59090047 A JP59090047 A JP 59090047A JP 9004784 A JP9004784 A JP 9004784A JP S59212443 A JPS59212443 A JP S59212443A
- Authority
- JP
- Japan
- Prior art keywords
- anthrone
- dihydroxy
- formula
- acyl
- represented
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
- C07C49/703—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups
- C07C49/723—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups polycyclic
- C07C49/727—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups polycyclic a keto group being part of a condensed ring system
- C07C49/737—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups polycyclic a keto group being part of a condensed ring system having three rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
- C07C49/703—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups
- C07C49/747—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups containing six-membered aromatic rings
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P17/00—Drugs for dermatological disorders
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Pharmacology & Pharmacy (AREA)
- Animal Behavior & Ethology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dermatology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Pyridine Compounds (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Cosmetics (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
本発明は式（１）；
（式中、Ｒは炭素数２〜４のアルキル基である）で示さ
れる１、８−ジヒドロキシ−１０−アシル−９−アンス
ロン（ａｎｔｈｒｏｎｅ ）の製造法に関する。Detailed Description of the Invention The present invention provides 1,8-dihydroxy-10-acyl-9-anthrone represented by formula (1); (wherein R is an alkyl group having 2 to 4 carbon atoms) ).
１０位の置換された１、８−ジヒド田キシー９−アンス
四ンがここ数年来ジスラノール（ｄｉｔｈｒａｎｏｌ
）に代わって用いられている。ジスラノールは１９１６
年に見出され、以来乾癖−（ｐｓｏｒｉａｅｉｓ ）の
治療に用いられてきたが、このものは皮膚や衣服を強く
染色し、また皮膚に強い炎症を与える。In recent years, 1,8-dihydro-9-anthine substituted at the 10th position has been used as dithranol.
) is used instead of. Githranol is 1916
It was discovered in 1997 and has since been used to treat psoriasis, but it strongly stains the skin and clothing and causes severe irritation to the skin.
式（Ｉ）で示される化合物はすでにフィンランド特許１
１５７７４５号明細書の方法にしたがって、アンスラリ
ン（ａｎｔｈｒａｌｉｎｅ ）の沸騰べ、ンゼン中でピ
リジンの存在下に酸クロライドと反応させるこ、とによ
り製造されている。しかしながら、かかる方法において
は２０％過剰の酸クロライドが必要であり、反応混合物
をリターンコンデンセイシ田ン（ｒｅｔｕｒｎ ｏｏｎ
ｄｅｎｓａｔｉｏｎ ）を用いて１０時間沸騰させ、生
成物を酢酸から結晶化する。かくしてえられる目的物の
収率は理論値の２５．５％にすぎない。The compound of formula (I) has already been granted a Finnish patent 1.
No. 157,745, by reacting anthraline with an acid chloride in boiling water in the presence of pyridine. However, such a method requires a 20% excess of acid chloride and the reaction mixture is returned to the condensate tank.
densation) for 10 hours and the product is crystallized from acetic acid. The yield of the target product thus obtained is only 25.5% of the theoretical value.
本発明め目的はきわめて有利に式（１） ：ｃ示される
１、８−ジヒド冒キシー１０−アシケー９−アンスロン
を製造する方法を提供することにあ、る。The object of the present invention is to provide a very advantageous process for preparing 1,8-dihydrooxy-10-acyl-9-anthrone of the formula (1):c.
すなわち、本発明は式（１）：
で示すれる１、８−ジヒドロキシ−９−アンスロンと式
（釦：
ＲＯＯＯ／ （１）（式中、Ｒ
は前記と同じ）で示される。酸りシライドとを２，６−
シメチルビリジンの存在下に反応させることを特徴とす
る式（Ｉ）：
（式中、Ｒは前記と同じ）で示される１、８−ジヒドロ
キシ−１０−アシル−９−アンスロンの製造法に関する
。That is, the present invention relates to 1,8-dihydroxy-9-anthrone represented by the formula (1): and the formula (button: ROOO/ (1) (in the formula, R
is the same as above). acid silide and 2,6-
The present invention relates to a method for producing 1,8-dihydroxy-10-acyl-9-anthrone represented by formula (I): (wherein R is the same as above), which is characterized by carrying out the reaction in the presence of dimethylpyridine.
本発明の方法によれば、反応温度を−１，０００程度ま
で下げることができ、いかなるばあいにも非常に低い反
応温度、たとえば室温で反応を行なうことができる。さ
らに、発癌性のきわめて強いベンゼンの使用を避けるこ
とができ、その代わりに危険性の低い、たとえばトルエ
ンなどを用いることができる。さらに、前記フィンラン
ド特許ＦＩ ５７７４５号に比して収率を２〜３倍増加
させることもできる。According to the method of the present invention, the reaction temperature can be lowered to about -1,000, and in any case the reaction can be carried out at a very low reaction temperature, for example at room temperature. Furthermore, the use of benzene, which is highly carcinogenic, can be avoided and instead less dangerous substances such as toluene can be used. Moreover, the yield can be increased by 2-3 times compared to the Finnish patent FI 57745.
、本発明の基礎は、ピリジンに代えて２，６−シメチル
ピリジンを用いることにより反応温度を下げることがで
き、ベンゼンの代わりにトルエン、キシレンまたは塩素
化炭化水素、たとえばジクｐロメタンやテトラクロ田エ
タンを用いることができるようになり、さらに公知の方
法に比して収率を６倍はど高めることができるようにな
った点にある。さらに、１００％過剰の酸クロライドを
用いると、反応は２時間で完了する。, the basis of the invention is that by using 2,6-dimethylpyridine instead of pyridine, the reaction temperature can be lowered, and instead of benzene, toluene, xylene or chlorinated hydrocarbons, such as dichloromethane or tetrachloride, can be used. Ethane can now be used and the yield can be increased six times compared to known methods. Additionally, with 100% excess acid chloride, the reaction is complete in 2 hours.
前記のごとく、反応温度が低い、たとえば−１０°〜２
０°０であることから、目的物の１，８−ジヒド田キシ
−１０−アシル−９−アンスロンに混入する不純物の量
は少ないｏしたがって、精製の操作が公知の方法に比し
て単純である。再結晶溶媒としては、酢酸とともにある
いは酢酸に代えてアセトニトリルまたは２−プロパツー
ルを用いるのが好ましい。As mentioned above, the reaction temperature is low, for example -10° to 2°
0°0, the amount of impurities mixed into the target 1,8-dihydro-10-acyl-9-anthrone is small. Therefore, the purification operation is simpler than known methods. be. As the recrystallization solvent, it is preferable to use acetonitrile or 2-propanol together with acetic acid or in place of acetic acid.
本発明の方法によりえられる化合物（Ｉ）は、たとえば
ワセリンまたはパラフィンを基剤として化合物ＣＩ）の
濃度０．５〜５重量％で皮膚用クリ−ムに、また濃度２
〜８重量％でスティック状にして皮膚医療（５ｌｃｉｎ
ｃａｒｅ ）用に、さらにはゲル状、フィルム形成溶
液（ｆｉｌｍ−ｆｏｎｎｉｎｇ ５ｏｌｕｔｉｏｎ）に
して用いることができる。Compound (I) obtained by the process of the invention can be used in skin creams, for example in petrolatum or paraffin bases, in concentrations of 0.5 to 5% by weight of compound CI), and in concentrations of 2 to 5% by weight.
~8% by weight for skin treatment (5lcin) in the form of a stick
It can also be used in the form of a gel or film-forming solution.
つぎに実施例をあげて本発明をさらに詳しく説明するが
、本発明はかかる実施例のみに限定されるものではない
。Next, 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１
プチリルク算ライド２０７ｍ１ （２１Ｓ９．２．０モ
ル）をトルエン２５００ｍ１ｓ Ｌ８−ジヒドロキシ−
９−アンスロン２２６９Ｃ１−０モル）および２，６−
シメチルビリジン２５２ｍｊ （２１４ｇ、２．０モル
）の混合物に０°０より低い温度で２時間かけて加えた
。Example 1 207 ml of petyryl trichloride (9.2.0 mol of 21S) was mixed with 2500 ml of toluene L8-dihydroxy-
9-Anthrone 2269C1-0 mol) and 2,6-
Added to a mixture of 252 mj (214 g, 2.0 mol) of dimethylpyridine at a temperature below 0°0 over 2 hours.
添加終了後、反応混合物をｏ ’ａより低い温度でさら
に２時間攪拌した。After the addition was complete, the reaction mixture was stirred for a further 2 hours at a temperature below o'a.
ついで、えられた反応混合物を４０°Ｃまで加熱し、２
．６−シメチルビリジンの塩酸塩を戸別し、減圧下にト
ルエンをほとんど蒸発させた。残渣にイソプ四パノール
２ｉＳＯＯｍｌを加え、反応混合物を−１０００まで冷
却し、沈殿を泊過して回収した。The resulting reaction mixture was then heated to 40°C and
．． The hydrochloride of 6-dimethylpyridine was taken from door to door, and most of the toluene was evaporated under reduced pressure. 2 iSOOml of isoptetrapanol was added to the residue, the reaction mixture was cooled to -1000, and the precipitate was collected by filtration.
アセジニトリルから再結晶して目的とする１、８−ジヒ
ドロキシ−１０−ブチリル−９−アンスロン２２２りを
えた。収率ニア５％
実施例２
トルエンに代えてキシレンを用いたほかは実施例１と同
様にして目的化合物をえた。収率ニア５％
実施例６
プロビオニルクロライド８６．９ｍｌ （９２，５９，
１モル）をトルエン１２００ｍ１．１ 、Ｂ−ジヒドロ
キシ−９−アンスロン１１６り（０，５モル）および２
，６−シメチルピリジン１１６ｍ１（１０７ｇ、１モル
）の混合物に０°Ｏより低い温度で、約２時間かけて加
えた。添加終了後、さらに２時間攪拌を続けた。えられ
た反応混合物を実施例１と同様に処理して目的とする１
、８−ジヒドロキシ−１０−プロピオニル−９−アンス
ロン１２０９をえた。収率：８２％
実施例４
１．８−ジヒドロ、キシ−９−アンスロンおよび１００
％過剰のバレリルク四ライドを出発物質として用いたほ
かは実施例１と同様にして１，８−ジヒドロキシ−１０
−バレリル−９−アンスロンをえた。収率：５３％
実施例５
つぎに示す各成分を用いて医薬組成物を調製した。The desired product 1,8-dihydroxy-10-butyryl-9-anthrone 222 was obtained by recrystallization from acedinitrile. Yield near 5% Example 2 The target compound was obtained in the same manner as in Example 1 except that xylene was used instead of toluene. Yield near 5% Example 6 Probionyl chloride 86.9ml (92,59,
1 mol), 1200 ml of toluene, 116 ml of B-dihydroxy-9-anthrone (0.5 mol) and 2
,6-dimethylpyridine (107 g, 1 mol) at a temperature below 0 DEG O. over about 2 hours. After the addition was complete, stirring was continued for an additional 2 hours. The obtained reaction mixture was treated in the same manner as in Example 1 to obtain the desired product 1.
, 8-dihydroxy-10-propionyl-9-anthrone 1209 was obtained. Yield: 82% Example 4 1.8-dihydro, xy-9-anthrone and 100
1,8-dihydroxy-10 was prepared as in Example 1 except that % excess of valeryl chloride was used as the starting material.
- Valeryl-9-anthrone was obtained. Yield: 53% Example 5 A pharmaceutical composition was prepared using each component shown below.
液体パラフィン ４０〜６０重ｆｉ％固
体パラフィン ４０〜６０重量％微小結
晶クリスタリン ０．５〜５重量％さらに
、およそ２〜８％の１，８−ジヒドロキシ−１０−ブチ
ル−９−アンスロンを前記のキャリヤー成分と混合した
。かがる混合物から皮膚医療用のスティックを成形した
。かがるスティックの使用性は良好であり、さらにこれ
を医療に用いたばあい変化がなく、とくに酸化されなか
った。Liquid paraffin 40-60% by weight Solid paraffin 40-60% by weight Microcrystalline crystalline 0.5-5% by weight Additionally, approximately 2-8% 1,8-dihydroxy-10-butyl-9-anthrone is added to the carrier as described above. mixed with ingredients. A dermatological stick was formed from the darning mixture. The usability of the darning stick was good, and when it was used medically, there was no change, especially no oxidation.
Claims (1)
（■）： ｎｏｔ （Ｉ［） （式中、Ｒは炭素数２〜４のアルキル基である）で示さ
れる酸り四ライドとを２，６−シメチルビリジンの存在
下に反応させることを特徴とする式（１）： （式中、Ｒは前記と同じ）で示される１、８−ジヒドロ
キシ−１０−アシル−９−アンスロンの製造法０ ２ 溶媒としてトルエン、キシレンまたは塩素化炭化水
素を用いる特許請求の範囲第１項記載の方法。 ３ 前記塩素化炭化水素がジクロロメタンまたはテトラ
クロロエタンである特許請求の範囲第１項記載の方法。 ４ 反応温度が一１０〜２０°０で、酸クロライドを２
時間かけて加え、さらに２時間攪拌を続けて反応を行な
う特許請求の範囲第１項記載の方法。 ５ １．８−ジヒドロキシ−１０−アシル−９−アンス
ロン ２〜８重量％液体パラフィ
ン ４０〜６０重量％固体パラフィン
４０〜６０３１１１％微結晶性ワックス
０．５〜５重量％からなる医薬組成物。[Claims] 1 1,8-dihydroxy-9-anthrone represented by formula (II): and formula (■): not (I[) (wherein, R is an alkyl group having 2 to 4 carbon atoms) Formula (1) is characterized by reacting the acid tetralide represented by the formula (1) with the acid tetralide represented by (in the formula, R is the same as above) in the presence of 2,6-dimethylpyridine -Production method of dihydroxy-10-acyl-9-anthrone 0 2 The method according to claim 1, wherein toluene, xylene or a chlorinated hydrocarbon is used as the solvent. 3. The method according to claim 1, wherein the chlorinated hydrocarbon is dichloromethane or tetrachloroethane. 4 At a reaction temperature of 110 to 20 °0, add 2 acid chlorides.
The method according to claim 1, wherein the reaction is carried out by adding over a period of time and stirring for an additional 2 hours. 5 1,8-dihydroxy-10-acyl-9-anthrone 2-8% by weight liquid paraffin 40-60% by weight solid paraffin
40-603111% Microcrystalline wax 0.5-5% by weight of a pharmaceutical composition.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI831739A FI66585C (en) | 1983-05-18 | 1983-05-18 | FOERFARANDE FOER FRAMSTAELLNING AV SAERSKILT VID BEHANDLING AVSORIASIS ANVAENDBARA 1,8-DIHYDROXI-10-ACYL-9-ANTRONER |
| FI831739 | 1983-05-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS59212443A true JPS59212443A (en) | 1984-12-01 |
Family
ID=8517222
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59090047A Pending JPS59212443A (en) | 1983-05-18 | 1984-05-04 | Manufacture of 1,8-dihydroxy-10-acyl-9-anthrone |
Country Status (31)
| Country | Link |
|---|---|
| JP (1) | JPS59212443A (en) |
| KR (1) | KR840009059A (en) |
| AU (1) | AU560079B2 (en) |
| BE (1) | BE899334A (en) |
| CA (1) | CA1212943A (en) |
| CH (1) | CH659464A5 (en) |
| CS (1) | CS256379B2 (en) |
| DD (1) | DD223702A5 (en) |
| DE (1) | DE3418382A1 (en) |
| DK (1) | DK154207C (en) |
| ES (1) | ES8505167A1 (en) |
| FI (1) | FI66585C (en) |
| FR (1) | FR2546162B1 (en) |
| GB (1) | GB2140007B (en) |
| GR (1) | GR79971B (en) |
| HU (1) | HUT36076A (en) |
| IL (1) | IL71446A (en) |
| IN (1) | IN156115B (en) |
| IS (1) | IS2902A7 (en) |
| IT (1) | IT1173473B (en) |
| LU (1) | LU85292A1 (en) |
| NL (1) | NL8401074A (en) |
| NO (1) | NO157099C (en) |
| NZ (1) | NZ207592A (en) |
| PH (1) | PH20038A (en) |
| PL (1) | PL141866B1 (en) |
| PT (1) | PT78603B (en) |
| SE (1) | SE453827B (en) |
| SU (1) | SU1240351A3 (en) |
| YU (1) | YU81784A (en) |
| ZA (1) | ZA842223B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2492372A1 (en) * | 1980-10-21 | 1982-04-23 | Cird | 1,8-DIHYDROXY-9-ANTHRONES SUBSTITUTED IN POSITION 10 AND THEIR USE IN HUMAN OR VETERINARY MEDICINE AND IN COSMETICS |
| FR2591222B1 (en) * | 1985-12-11 | 1988-07-22 | Cird | MONO, DI AND TRI-ESTERS OF 1,8-DIHYDROXY PHENYL-10 ANTHRONE-9 OR ANTHRANOL-9, THEIR PREPARATION PROCESS AND THEIR USE IN HUMAN OR VETERINARY MEDICINE AND IN COSMETICS |
| US4843097A (en) * | 1984-06-13 | 1989-06-27 | Groupement D'interet Economique Dit: Centre International De Recherches Dermatologiques C.I.R.D. | 10-aryl-1,8-dihydroxy-9-anthrones and their esters, process for preparing same, and use of same in human and veterinary medicine and in cosmetics |
| FR2566772B1 (en) * | 1984-06-29 | 1986-11-14 | Cird | DIACYLOXY-1,8 ACYL-10 ANTHRONES, THEIR PREPARATION PROCESS AND THEIR USE IN HUMAN OR VETERINARY MEDICINE AND IN COSMETICS |
| FR2580631B1 (en) * | 1985-04-17 | 1987-05-29 | Cird | HYDROXY-1 ACYLOXY-8 ACYL-10 ANTHRONES, THEIR PREPARATION PROCESS AND THEIR USE IN HUMAN OR VETERINARY MEDICINE AND IN COSMETICS |
| DE69223723T2 (en) * | 1991-10-04 | 1998-04-16 | Fisher & Paykel | humidifier |
| DE4231636A1 (en) * | 1992-09-22 | 1994-03-24 | Beiersdorf Ag | New anthrone and anthracene derivatives substituted in the 10-position, processes for their preparation, pharmaceutical or cosmetic compositions containing these compounds and their use |
| US5426197A (en) * | 1993-07-19 | 1995-06-20 | Teva Pharmaceutical Industries, Ltd. | 10-substituted 1,8-dihydroxy-9(10H) anthracenone pharmaceuticals |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI57743C (en) * | 1979-03-29 | 1980-10-10 | Orion Yhtymae Oy | FREQUENCY REQUIREMENT FOR NYA 1,8-DIHYDROXI-10-ACYL-9-ANTRONER MOT PSORIASIS |
-
1983
- 1983-05-18 FI FI831739A patent/FI66585C/en not_active IP Right Cessation
-
1984
- 1984-03-22 NZ NZ207592A patent/NZ207592A/en unknown
- 1984-03-22 AU AU25998/84A patent/AU560079B2/en not_active Ceased
- 1984-03-23 IT IT20213/84A patent/IT1173473B/en active
- 1984-03-26 ZA ZA842223A patent/ZA842223B/en unknown
- 1984-03-29 IN IN209/CAL/84A patent/IN156115B/en unknown
- 1984-03-30 DK DK173584A patent/DK154207C/en active IP Right Grant
- 1984-04-04 GB GB08408666A patent/GB2140007B/en not_active Expired
- 1984-04-04 NL NL8401074A patent/NL8401074A/en not_active Application Discontinuation
- 1984-04-05 IL IL71446A patent/IL71446A/en not_active IP Right Cessation
- 1984-04-05 GR GR74318A patent/GR79971B/el unknown
- 1984-04-05 BE BE0/212698A patent/BE899334A/en not_active IP Right Cessation
- 1984-04-05 IS IS2902A patent/IS2902A7/en unknown
- 1984-04-06 LU LU85292A patent/LU85292A1/en unknown
- 1984-04-18 CS CS842911A patent/CS256379B2/en unknown
- 1984-04-18 ES ES531760A patent/ES8505167A1/en not_active Expired
- 1984-04-27 KR KR1019840002278A patent/KR840009059A/en not_active Application Discontinuation
- 1984-05-02 FR FR8406790A patent/FR2546162B1/en not_active Expired
- 1984-05-04 JP JP59090047A patent/JPS59212443A/en active Pending
- 1984-05-08 SU SU843735603A patent/SU1240351A3/en active
- 1984-05-10 YU YU00817/84A patent/YU81784A/en unknown
- 1984-05-16 PH PH30686A patent/PH20038A/en unknown
- 1984-05-16 NO NO841965A patent/NO157099C/en unknown
- 1984-05-16 SE SE8402649A patent/SE453827B/en not_active IP Right Cessation
- 1984-05-17 DE DE19843418382 patent/DE3418382A1/en not_active Withdrawn
- 1984-05-17 PT PT78603A patent/PT78603B/en unknown
- 1984-05-17 CH CH2431/84A patent/CH659464A5/en not_active IP Right Cessation
- 1984-05-17 HU HU841908A patent/HUT36076A/en unknown
- 1984-05-17 CA CA000454593A patent/CA1212943A/en not_active Expired
- 1984-05-17 DD DD84263131A patent/DD223702A5/en unknown
- 1984-05-17 PL PL1984247724A patent/PL141866B1/en unknown
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