FI66585C - FOERFARANDE FOER FRAMSTAELLNING AV SAERSKILT VID BEHANDLING AVSORIASIS ANVAENDBARA 1,8-DIHYDROXI-10-ACYL-9-ANTRONER - Google Patents
FOERFARANDE FOER FRAMSTAELLNING AV SAERSKILT VID BEHANDLING AVSORIASIS ANVAENDBARA 1,8-DIHYDROXI-10-ACYL-9-ANTRONER Download PDFInfo
- Publication number
- FI66585C FI66585C FI831739A FI831739A FI66585C FI 66585 C FI66585 C FI 66585C FI 831739 A FI831739 A FI 831739A FI 831739 A FI831739 A FI 831739A FI 66585 C FI66585 C FI 66585C
- Authority
- FI
- Finland
- Prior art keywords
- acyl
- avsoriasis
- antroner
- dihydroxi
- saerskilt
- Prior art date
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Classifications
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- 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
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- 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)
Description
1 665851 66585
Menetelmä erityisesti psoriasiksen hoitoon käytettävien 1,fl-dihydroksi-10-asyyli-9_antronien valmistamiseksi Tämä keksintö koskee menetelmää 1,Θ-dihydroksi-10-asyyli-5 9-antronien valmistamiseksi. 10-asemassa substituoituja 1.8- dihydroksi-9-antroneja on käytetty muutamien vuosien ajan korvaamaan jo vuodesta 1916 tunnettu psoriasiksen hoitoon käytetty, voimakkaasti ihoa ja vaatteita värjäävä ja ihoa voimakkaasti tulehduttava ditranoli.The present invention relates to a process for the preparation of 1,1'-dihydroxy-10-acyl-59-anthrones. 10-Substituted 1,8-dihydroxy-9-anthrons have been used for several years to replace ditranol, which has been known since 1916 for the treatment of psoriasis and is a strong skin and clothing dye and highly inflamed skin.
10 1.8- dihydroksi-10-asyyli~9-antronin rakennekaava on seuraava:The structural formula of 1,8-dihydroxy-10-acyl-9-anthrone is as follows:
CO-RCO-R
20 jossa R on 2-4 hiiliatomia sisältävä alkyyli ryhmä. Yhdisteitä on valmistettu suomalaisen patenttijulkaisun FI 57743 mukaan saattamalla antraliini reagoimaan kiehuvassa bent-seenissä happokloridin kanssa, jolloin läsnä on myös pyri-diiniä. Happokloridia käytetään 20 %:n ylimäärä. Reaktio-25 seosta keitetään palautusjäähdyttäen 10 tunnin ajan ja tuote kiteytetään etikkahaposta. Saanto on kyseessä olevassa menetelmässä esim. vain 25,5 % teoreettisesta.20 wherein R is an alkyl group having 2 to 4 carbon atoms. The compounds have been prepared according to Finnish patent publication FI 57743 by reacting anthralin in boiling Bentene with an acid chloride, in which case pyridine is also present. An excess of 20% of acid chloride is used. The reaction mixture is refluxed for 10 hours and the product is crystallized from acetic acid. The yield in the method in question is, for example, only 25.5% of theory.
Tämän keksinnön tarkoituksena on aikaansaada menetelmä, 30 jonka avulla voidaan saavuttaa huomattavia etuja. Reaktio-lämpötila voidaan alentaa jopa -10°C:een ja joka tapauksessa voidaan käyttää varsin alhaisia reaktio lämpötiloja, esimerkiksi huoneenlämpötilaa. Lisäksi voidaan välttää voimakkaasti karsinogeenista bentseeniä ja käyttää esimer-35 kiksi vähemmän haitallista tolueenia. Vielä saadaan saanto nousemaan 2-3-kertaiseksi suomalaisen patentin FI 57743 menetelmään verrattuna.It is an object of the present invention to provide a method by which considerable advantages can be obtained. The reaction temperature can be reduced to as low as -10 ° C, and in any case, rather low reaction temperatures, for example room temperature, can be used. In addition, highly carcinogenic benzene can be avoided and less harmful toluene, for example, can be used. The yield is further increased 2-3 times compared to the method of the Finnish patent FI 57743.
2 665852 66585
Edellä mainitut edut on saavutettu menetelmällä, jonka tunnusomaiset piirteet on annettu oheisessa patenttivaatimuksessa 1.The above advantages are achieved by a method, the characteristic features of which are given in the appended claim 1.
5 Keksintö perustuu siihen huomioon, että pyridiinin korvaaminen 2,6-dimetyylipyridiinillä aikaansaa sen, että reaktio-lämpötilaa voidaan alentaa, että bentseenin tilalla voidaan käyttää tolueenia, ksyleeniä tai kloorattuja hiilivetyjä, kuten dikloorimetaania tai tetrakloorieteeniä ja että saanto 10 jopa kolminkertaistuu tunnettuun menetelmään verrattuna. Jos lisäksi happokloridia käytetään 100 %:n ylimäärä, saadaan reaktio menemään loppuun kahdessa tunnissa.The invention is based on the fact that the replacement of pyridine with 2,6-dimethylpyridine makes it possible to lower the reaction temperature, to use toluene, xylene or chlorinated hydrocarbons such as dichloromethane or tetrachlorethylene instead of benzene and to even triple the yield compared to the known process. In addition, if 100% excess of acid chloride is used, the reaction is completed in two hours.
Edellä mainitusta alhaisesta reaktiolämpötilasta, joka voi 15 olla esimerkiksi -10°C - +20°C, seuraa, että valmiiseen 1,8-dihydroksi-10-asyyli-9-antroniin joutuvien epäpuhtauksien määrä on vähäinen. Niinpä puhdistus on yksinkertainen toimenpide verrattuna tunnetun menetelmän vastaavaan toimenpiteeseen. Uudelleenkiteytysliuottimena sopivat käytettä-20 väksi etikkahapon ohessa tai sijasta asetonitriili tai 2-propanoli.It follows from the above-mentioned low reaction temperature, which may be, for example, -10 ° C to + 20 ° C, that the amount of impurities entering the finished 1,8-dihydroxy-10-acyl-9-anthrone is small. Thus, the purification is a simple operation as compared with the corresponding operation of the known method. Suitable recrystallization solvents are acetonitrile or 2-propanol in addition to or instead of acetic acid.
Keksinnön mukaisesti valmistettuja yhdisteitä voidaan käyttää esimerkiksi vaseliini- tai paraffiinipohjaisissa 25 ihovoiteissa 0,5 - 5 %sn pitoisuuksina, ihonhoitoon tarkoitetuissa puikoissa esim 2 - Θ %:n pitoisuuksina ja geeleissä sekä kalvon muodostavissa liuoksissa.The compounds according to the invention can be used, for example, in petrolatum or paraffin-based skin creams in concentrations of 0.5 to 5% sn, in skin care needles, for example in concentrations of 2 to Θ%, and in gels and film-forming solutions.
Seuraavat esimerkit kuvaavat keksintöä tarkemmin.The following examples illustrate the invention in more detail.
3030
Esimerkki 1Example 1
Seokseen, jossa oli 2500 ml tolueenia, 225 g (1,0 mol) 1,B-dihydroksi-9-antronia ja 232 ml (214 g, 2,0 mol) 35 2,6-dimetyylipyridiiniä, lisättiin alle 0°C lämpötilassa 3 66585 2 tunnin aikana 207 ml (213 g, 2,0 mol) voihappokloridia. Seosta sekoitettiin alle 0 C lämpötilassa lisäyksen jälkeen vielä kahden tunnin ajan.To a mixture of 2500 ml of toluene, 225 g (1.0 mol) of 1,2-dihydroxy-9-anthrone and 232 ml (214 g, 2.0 mol) of 2,6-dimethylpyridine were added below 0 ° C. 3,66585 207 mL (213 g, 2.0 mol) of butyric chloride over 2 hours. The mixture was stirred at a temperature below 0 ° C after the addition for a further two hours.
5 Seos lämmitettiin tämän jälkeen +40oC:een, 2,6-dimBtyylipyridiinin hydrokloridi suodatettiin pois ja pääosa tolueenista haihdutettiin pois alennetussa paineessa. Jäännökseen lisättiin 2300 ml isopropanolia, seos jäähdytettiin -10°C:een ja sakka otettiin talteen suodattamalla. Suori-10 tettiin uudelleenkiteytys ase tönitrii1 istä, jolloin saannoksi saatiin 222 g 1,8-dihydroksi-10-butyryyli-9-antronia. Tämä oli 75 % teoreettisesta.The mixture was then warmed to + 40 ° C, the 2,6-dimethylpyridine hydrochloride was filtered off and most of the toluene was evaporated off under reduced pressure. 2300 ml of isopropanol were added to the residue, the mixture was cooled to -10 ° C and the precipitate was collected by filtration. Recrystallization from acetonitrile was carried out to give 222 g of 1,8-dihydroxy-10-butyryl-9-anthrone. This was 75% of theory.
Esimerkki 2 15Example 2 15
Meneteltiin täysin analogisella tavalla kuin esimerkissä 1, mutta tolueenin sijasta käytettiin ksyleeniä. Saanto oli sama kuin esimerkissä 1 eli 75 %.The procedure was completely analogous to Example 1, but xylene was used instead of toluene. The yield was the same as in Example 1, i.e. 75%.
20 Esimerkki 320 Example 3
Seokseen, jossa oli 1200 ml tolueenia, 113 g (0,5 mol) 1.8- dihydroksi-9-antronia ja 116 ml (107 g, 1 mol) 2,6-dimetyylipyridiiniä lisättiin alle 0°C lämpötilassa noin 25 2 tunnin aikana 86,9 ml (92,5 g, 1 mol) propionyylikloridia.To a mixture of 1200 mL of toluene, 113 g (0.5 mol) of 1,8-dihydroxy-9-anthrone and 116 mL (107 g, 1 mol) of 2,6-dimethylpyridine was added below 0 ° C over about 2 hours 86 , 9 mL (92.5 g, 1 mol) of propionyl chloride.
Sekoittamista jatkettiin lisäyksen jälkeen vielä kaksi tun tia.Stirring was continued for another two hours after the addition.
Tuloksena saadun 1,B-dihydroksi-10-propionyyli-9-antronin 30 erottaminen suoritettiin esimerkissä 1 esitetyllä tavalla. Saanto oli (120 g) 82 % teoreettisesta.Separation of the resulting 1,2β-dihydroxy-10-propionyl-9-anthrone 30 was performed as described in Example 1. The yield (120 g) was 82% of theory.
Esimerkki 4 35 Lähtien 1,8~dihydroksi-9-antronista ja valeryylikloridista ja käyttäen valeryylikloridia 100 % ylimäärin, sekä menetellen muuten samoin kuin esimerkissä 1, saatiin tuloksena 1.8- dihy droksi - 10-valeryyli-9-antronia, jolloin saanto oli 53 %.Example 4 Starting from 1,8-dihydroxy-9-anthrone and valeryl chloride and using 100% excess valeryl chloride, and proceeding otherwise as in Example 1, 1,8-dihydroxy-10-valeryl-9-anthrone was obtained in 53% yield. .
Claims (3)
Priority Applications (31)
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 |
NZ207592A NZ207592A (en) | 1983-05-18 | 1984-03-22 | Method for the production of 1,8-dihydroxy-10-acyl-9-anthrone,and pharmaceutical compositions |
AU25998/84A AU560079B2 (en) | 1983-05-18 | 1984-03-22 | 1,8-dihydroxy-10-acyl-9-anthrones |
IT20213/84A IT1173473B (en) | 1983-05-18 | 1984-03-23 | PROCEDURE FOR THE PREPARATION OF 1,8-DIHYDROXY-10-ACYL-9-ANTRONES, IN PARTICULAR FOR USE IN THE TREATMENT OF PSORIASIS |
ZA842223A ZA842223B (en) | 1983-05-18 | 1984-03-26 | Method for the preparation of 1,8-dihydroxy-10-acyl-9-anthrones,especially for use in the treatment of psoriasis |
IN209/CAL/84A IN156115B (en) | 1983-05-18 | 1984-03-29 | |
DK173584A DK154207C (en) | 1983-05-18 | 1984-03-30 | METHOD FOR PREPARING 1,8-DIHYDROXY-10-ACYL-9 ANTHRONS |
GB08408666A GB2140007B (en) | 1983-05-18 | 1984-04-04 | 1,8-dihydroxy-10-acyl-9-anthrones |
NL8401074A NL8401074A (en) | 1983-05-18 | 1984-04-04 | PROCESS FOR PREPARING 1,8-DIHYDROXY-10-ACYL-9 ANTHRONES, ESPECIALLY FOR USE IN THE TREATMENT OF PSORIASIS. |
IL71446A IL71446A (en) | 1983-05-18 | 1984-04-05 | Process for the preparation of 1,8-dihydroxy-10-alkanoyl-9-anthrones |
BE0/212698A BE899334A (en) | 1983-05-18 | 1984-04-05 | PROCESS FOR THE PREPARATION OF 1,8-DIHYDROXY-10-ACYL-9-ANTHRONES, PARTICULARLY FOR USE IN THE TREATMENT OF PSORIASIS. |
IS2902A IS2902A7 (en) | 1983-05-18 | 1984-04-05 | Method for the preparation of 1,8-dihydroxy-10-acyl-9-anthrones, especially for the treatment of psoriasis |
GR74318A GR79971B (en) | 1983-05-18 | 1984-04-05 | |
LU85292A LU85292A1 (en) | 1983-05-18 | 1984-04-06 | PROCESS FOR THE PREPARATION OF 1,8-DIHYDROXY-10-ACYL-9-ANTHRONES, IN PARTICULAR FOR USE IN THE TREATMENT OF PSORIASIS |
CS842911A CS256379B2 (en) | 1983-05-18 | 1984-04-18 | Method of 1,8-dihydroxy-10-acyl-9-anthrones production |
ES531760A ES8505167A1 (en) | 1983-05-18 | 1984-04-18 | 1,8-dihydroxy-10-acyl-9-anthrones |
KR1019840002278A KR840009059A (en) | 1983-05-18 | 1984-04-27 | Manufacturing method of 1,8-dihydroxy-10-acyl-9-anthrones |
FR8406790A FR2546162B1 (en) | 1983-05-18 | 1984-05-02 | PROCESS FOR THE PREPARATION OF 1,8-DIHYDROXY-10-ACYL-9-ANTHRONES, IN PARTICULAR FOR USE IN THE TREATMENT OF PSORIASIS |
JP59090047A JPS59212443A (en) | 1983-05-18 | 1984-05-04 | Manufacture of 1,8-dihydroxy-10-acyl-9-anthrone |
SU843735603A SU1240351A3 (en) | 1983-05-18 | 1984-05-08 | Method of producing 1,8-dioxy-10-acyl-9-anthrone |
YU00817/84A YU81784A (en) | 1983-05-18 | 1984-05-10 | Process for making 1,8-dihydroxy-10-acyl-9-antrone, active against psoriasis |
SE8402649A SE453827B (en) | 1983-05-18 | 1984-05-16 | PROCEDURE FOR THE PREPARATION OF 1,8-DIHYDROXY-10-ACYL-9 ANTRONES |
PH30686A PH20038A (en) | 1983-05-18 | 1984-05-16 | A process for the preparation of 1,8-dihydroxy-10-acyl-9-anthrone |
NO841965A NO157099C (en) | 1983-05-18 | 1984-05-16 | PROCESS FOR THE MANUFACTURE OF 1,8-DIHYDROXY-10-ACYL-9-ANTHRON DERIVATIVES. |
PL1984247724A PL141866B1 (en) | 1983-05-18 | 1984-05-17 | Method of obtaining 1,8-dihydroxy-10-ocyl-9-antrones |
PT78603A PT78603B (en) | 1983-05-18 | 1984-05-17 | Process for preparing 1,8-dihidroxy-10-acyl-9-anthrones especially for use in the treatment of psoriasis |
CH2431/84A CH659464A5 (en) | 1983-05-18 | 1984-05-17 | METHOD FOR PRODUCING 1,8-DIHYDROXY-10-ACYL-9-ANTHRONES. |
HU841908A HUT36076A (en) | 1983-05-18 | 1984-05-17 | Improved process for production of 1,8-dihidroxi-10-acil-9-antrons |
DE19843418382 DE3418382A1 (en) | 1983-05-18 | 1984-05-17 | METHOD FOR THE PRODUCTION OF 1,8-DIHYDROXY-10-ACYL-9-ANTHRONES |
CA000454593A CA1212943A (en) | 1983-05-18 | 1984-05-17 | Method for the preparation of 1,8-dihydroxy-10-acyl-9- anthrones, especially for use in the treatment of psoriasis |
DD84263131A DD223702A5 (en) | 1983-05-18 | 1984-05-17 | PROCESS FOR THE PREPARATION OF 1,8-DIHYDROXY-10-ACYL-9-ANTHRONES |
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 (3)
Publication Number | Publication Date |
---|---|
FI831739A0 FI831739A0 (en) | 1983-05-18 |
FI66585B FI66585B (en) | 1984-07-31 |
FI66585C true FI66585C (en) | 1984-11-12 |
Family
ID=8517222
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
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 |
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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