LU85292A1 - PROCESS FOR THE PREPARATION OF 1,8-DIHYDROXY-10-ACYL-9-ANTHRONES, IN PARTICULAR FOR USE IN THE TREATMENT OF PSORIASIS - Google Patents
PROCESS FOR THE PREPARATION OF 1,8-DIHYDROXY-10-ACYL-9-ANTHRONES, IN PARTICULAR FOR USE IN THE TREATMENT OF PSORIASIS Download PDFInfo
- Publication number
- LU85292A1 LU85292A1 LU85292A LU85292A LU85292A1 LU 85292 A1 LU85292 A1 LU 85292A1 LU 85292 A LU85292 A LU 85292A LU 85292 A LU85292 A LU 85292A LU 85292 A1 LU85292 A1 LU 85292A1
- Authority
- LU
- Luxembourg
- Prior art keywords
- dihydroxy
- anthrone
- acyl
- acid chloride
- psoriasis
- Prior art date
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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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Pharmacology & Pharmacy (AREA)
- Animal Behavior & Ethology (AREA)
- Dermatology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Bioinformatics & Cheminformatics (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)
- Cosmetics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
Description
La présente invention est relative à un procédé , pour la préparation de 1,8-dihydroxy-10-acyl-9-anthrones.The present invention relates to a process for the preparation of 1,8-dihydroxy-10-acyl-9-anthrones.
On a utilisé des 1,8-dihydroxy-S-anthrones substituées en position 10 depuis quelques années pour remplacer le di-5 thranol, connu depuis 1916 et utilisé pour le traitement du psoriasis et qui tache fortement la peau et les vêtements et induit de fortes inflammations cutanées.We have used 1,8-dihydroxy-S-anthrones substituted in position 10 for a few years to replace di-5 thranol, known since 1916 and used for the treatment of psoriasis and which strongly stains the skin and clothes and induces severe skin inflammation.
La formule structurale des 1,8-dihydroxy-10-acyl-9-anthrones est la suivante : 10The structural formula of 1,8-dihydroxy-10-acyl-9-anthrones is as follows: 10
HO O OHHO O OH
êyàêyà
CO-RHORN
dans laquelle R est un groupe alcoyle ayant 2 à 4 atomes de carbone. On a préparé ces composés selon le Brevet Finnois FI 57743 en faisant réagir de l'anthraline dans du 20 benzène, à ébullition avec un chlorure d'acide, en présence de pyridine également. Le chlorure d'acide est utilisé en un excès de 20 %. Le mélange réactionnel est chauffé à reflux pendant 10 heures et le produit est séparé par cristallisation à partir de l'acide acétique. Avec cette méthode 25 le- rendement n'est, par exemple, que de 25,50 %.wherein R is an alkyl group having 2 to 4 carbon atoms. These compounds were prepared according to Finnish Patent FI 57743 by reacting anthralin in benzene, boiling with an acid chloride, also in the presence of pyridine. The acid chloride is used in a 20% excess. The reaction mixture is heated at reflux for 10 hours and the product is separated by crystallization from acetic acid. With this method, the yield is, for example, only 25.50%.
La présente invention a pour objet de fournir un procédé permettant d'obtenir d'importants avantages. La température de réaction peut être réduite jusqu'à une valeur aussi basse que -10eC et dans tous les cas, il est 30 possible d'utiliser de très faibles températures de réaction, par exemple, la température ambiante. De plus, on peut éviter l'utilisation du benzène, fortement carcinogène et employer par exemple du toluène qui est moins nocif. De plus, le rendement peut être doublé ou triplé par rap-35 port à celui que donne la méthode du Brevet Finnois FI 57743.The object of the present invention is to provide a method making it possible to obtain significant advantages. The reaction temperature can be reduced to as low as -10 ° C and in any case it is possible to use very low reaction temperatures, for example, room temperature. In addition, we can avoid the use of benzene, which is highly carcinogenic, and use, for example, toluene, which is less harmful. In addition, the yield can be doubled or tripled compared to that given by the method of the Finnish Patent FI 57743.
22
On peut obtenir les avantages décrits plus haut, , grâce au procédé conforme à la présente invention qui met en oeuvre de la 2,6-diméthyl-pyridine.The advantages described above can be obtained, thanks to the process according to the present invention which uses 2,6-dimethyl-pyridine.
La présente invention repose sur l'observation 5 selon laquelle le remplacement de la pyridine par la 2,6-diméthyl-pyridine permet d'abaisser la température de réaction, d'utiliser du toluène, du xylène ou des hydrocarbures chlorés, comme du dichlorométhane et du tétrachloroéthane à la place du benzène et même de tripler le rendement par 10 rapport au rendement fourni par la méthode connue. Si de plus, le chlorure d'acide est mis en oeuvre en un excès de 100 %, la réaction peut être achevée en deux heures.The present invention is based on the observation that the replacement of pyridine by 2,6-dimethyl-pyridine makes it possible to lower the reaction temperature, to use toluene, xylene or chlorinated hydrocarbons, such as dichloromethane and tetrachloroethane in place of benzene and even triple the yield compared to the yield provided by the known method. If, in addition, the acid chloride is used in an excess of 100%, the reaction can be completed in two hours.
Grâce à la faible température de réaction indiquée plus haut, qui peut par exemple, être comprise entre 15 —10°C et +20°C, il en résulte que la quantité d'impuretés passant dans la 1,8-dihydroxy-10-acyl-9-anthrone, est faible. La purification est donc une procédure simple par rapport à celle qui est impliquée dans la méthode connue. On peut utiliser de 1'acëtonitrile ou du 2-propanol en tant 20 que solvant de recristallisation, avec l'acide acétique ou à la place de celui-ci.Thanks to the low reaction temperature indicated above, which can for example be between 15 -10 ° C and + 20 ° C, it follows that the amount of impurities passing into the 1,8-dihydroxy-10- acyl-9-anthrone, is weak. Purification is therefore a simple procedure compared to that which is involved in the known method. Acetonitrile or 2-propanol can be used as the recrystallization solvent, with or in place of acetic acid.
Les composés préparés conformément à la présente invention peuvent être utilisés, par exemple, dans des crèmes pour la peau, à base de vaseline ou de paraffine, 25 à des concentrations de 0,5 à 5 %, dans des bâtons pour les soins de la peau, à des concentrations de, par exemple, 2 à 8 % et dans des gels et des solutions filmogènes. EXEMPLE 1 . On ajoute du chlorure de butyryle à raison de 30 207 ml (213 g, 2,0 moles) en une période de deux heures, à une température inférieure à 0°C, à un mélange qui contient 2500 ml de toluène, 226 g /1,0 mole) de 1,8-dihydroxy-9-anthrone et 232 ml (214 g, 2,0 moles) de 2,6-diméthylpyri-dine.The compounds prepared in accordance with the present invention can be used, for example, in skin creams, based on petrolatum or paraffin, in concentrations of 0.5 to 5%, in sticks for the care of the skin. skin, at concentrations of, for example, 2 to 8% and in gels and film-forming solutions. EXAMPLE 1. Butyryl chloride is added at a rate of 30,207 ml (213 g, 2.0 moles) over a period of two hours, at a temperature below 0 ° C, to a mixture which contains 2,500 ml of toluene, 226 g / 1.0 mole) of 1,8-dihydroxy-9-anthrone and 232 ml (214 g, 2.0 moles) of 2,6-dimethylpyri-dine.
35 Le mélange est agité à une température inférieure 3 à 0°C, pendant 2 heures supplémentaires après l'addition.The mixture is stirred at a temperature below 3 ° to 0 ° C. for an additional 2 hours after the addition.
* Le mélange est chauffé ensuite à +4Q*C, le chlo rhydrate de la 2,6-dimëthylpyridine est séparé par filtration et la plus grande partie du toluène est évaporée sous 5 pression réduite. On ajoute 2300 ml d'isopropanol au résidu, on refroidit le mélange à -10°C et récupère le précipité , en le filtrant. Une recristallisation est effectuée à par tir d'acétonitrile et fournit 222 g de 1,8-dihydroxy-10-* butyryl-9-anthrone. Cela constitue un rendement de 75 %.* The mixture is then heated to + 4Q * C, the 2,6-dimethylpyridine hydrochloride is separated by filtration and most of the toluene is evaporated under reduced pressure. 2300 ml of isopropanol are added to the residue, the mixture is cooled to -10 ° C and the precipitate is recovered, by filtering. Recrystallization is carried out using acetonitrile and provides 222 g of 1,8-dihydroxy-10- * butyryl-9-anthrone. This constitutes a yield of 75%.
10 EXEMPLE 210 EXAMPLE 2
On répète la procédure qui est décrite dans l'Exemple 1, sauf que l'on utilise du xylène à la place du toluène. Le rendement est le même que celui de l'Exemple 1, à savoir 75 %.The procedure which is described in Example 1 is repeated, except that xylene is used in place of toluene. The yield is the same as that of Example 1, namely 75%.
15 EXEMPLE 315 EXAMPLE 3
Du chlorure de propionyle en une quantité de 86,9 ml (92,5 g , 1 mole) est ajouté en une période de 2 heures environ, à une température inférieure à 0°C, à un * mélange contenant 1200 ml de toluène, 113 g (0,5 mole) de 20 1,8-dihydroxy-9-anthrone et 116 ml (107 g, 1 mole) de 2,6-diméthylpyridine. L'agitation est poursuivie pendant 2 heures supplémentaires après l'addition.Propionyl chloride in an amount of 86.9 ml (92.5 g, 1 mole) is added over a period of approximately 2 hours, at a temperature below 0 ° C., to a mixture containing 1200 ml of toluene, 113 g (0.5 mole) of 1,8-dihydroxy-9-anthrone and 116 ml (107 g, 1 mole) of 2,6-dimethylpyridine. Stirring is continued for an additional 2 hours after the addition.
La l,8-dihydroxy-10-propionyl-9-anthrone ainsi obtenue est séparée selon la procédure qui est décrite dans 25 l'Exemple 1. Le rendement est de 120 g (82 %).The 1,8-dihydroxy-10-propionyl-9-anthrone thus obtained is separated according to the procedure which is described in Example 1. The yield is 120 g (82%).
EXEMPLE 4 • A partir de 1,8-dihydroxy-9-anthrone et de chlo rure de valéryle en un excès de 100 % et en procédant par ailleurs selon la méthode qui est décrite dans l’Exemple 1, 30 on obtient la 1,8—dihydroxy-10-Valéry1-9-anthrone avec un rendement de 53 %.EXAMPLE 4 • From 1,8-dihydroxy-9-anthrone and valeryl chloride in excess of 100% and by proceeding further according to the method which is described in Example 1, 30 is obtained 1, 8 — dihydroxy-10-Valéry1-9-anthrone with a yield of 53%.
EXEMPLE 5EXAMPLE 5
On préparé des compositions pharmaceutiques à partir des constituants suivants, avec les quantités indi-35 quées.Pharmaceutical compositions are prepared from the following constituents, with the amounts indicated.
4 paraffine liquide 40 - 60 % paraffine solide 40 - 60 % cire microcristalline 0,5 - 5 %4 liquid paraffin 40 - 60% solid paraffin 40 - 60% microcrystalline wax 0.5 - 5%
De plus, on mélange environ 2 à 8 % de 1,8-dihy-5 àroxy-10-butyryl-9-anthrone avec la composition support présentée ci-dessus. On moule des bâtons conçus pour les soins de la peau à partir de ce mélange et l'on observe » que les propriétés d'utilisation des bâtons sont bonnes et î que de plus, le médicament contenu dans les bâtons demeure 10 inchangé, en particulier, il n'est pas oxydé.In addition, approximately 2 to 8% of 1,8-dihy-5 to hydroxy-10-butyryl-9-anthrone is mixed with the support composition presented above. Sticks designed for skin care are molded from this mixture and it is observed that the properties of use of the sticks are good and that, moreover, the medicament contained in the sticks remains unchanged, in particular , it is not oxidized.
Ainsi que cela ressort de ce qui précède, l'invention ne se limite nullement à ceux de ses modes de mise en oeuvre,-de réalisation et d'application qui viennent d'être décrits de façon plus explicite ; elle en embrasse au 15 contraire toutes les variantes qui peuvent venir à l'esprit du technicien en la matière, sans s'écarter du cadre, ni de la portée, de la présente invention.As is apparent from the above, the invention is in no way limited to those of its modes of implementation, of embodiment and of application which have just been described in a more explicit manner; on the contrary, it embraces all the variants which may come to the mind of the technician in the field, without departing from the framework, or the scope, of the present invention.
ss
Claims (6)
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 |
|---|---|
| LU85292A1 true LU85292A1 (en) | 1984-10-26 |
Family
ID=8517222
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| 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 |
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 |
| 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 |
| 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 |
| 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 AU AU25998/84A patent/AU560079B2/en not_active Ceased
- 1984-03-22 NZ NZ207592A patent/NZ207592A/en unknown
- 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 BE BE0/212698A patent/BE899334A/en not_active IP Right Cessation
- 1984-04-05 IS IS2902A patent/IS2902A7/en unknown
- 1984-04-05 GR GR74318A patent/GR79971B/el 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 NO NO841965A patent/NO157099C/en unknown
- 1984-05-16 PH PH30686A patent/PH20038A/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 PL PL1984247724A patent/PL141866B1/en unknown
- 1984-05-17 HU HU841908A patent/HUT36076A/en unknown
- 1984-05-17 CA CA000454593A patent/CA1212943A/en not_active Expired
- 1984-05-17 CH CH2431/84A patent/CH659464A5/en not_active IP Right Cessation
- 1984-05-17 PT PT78603A patent/PT78603B/en unknown
- 1984-05-17 DD DD84263131A patent/DD223702A5/en unknown
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