PL141866B1 - Method of obtaining 1,8-dihydroxy-10-ocyl-9-antrones - Google Patents
Method of obtaining 1,8-dihydroxy-10-ocyl-9-antrones Download PDFInfo
- Publication number
- PL141866B1 PL141866B1 PL1984247724A PL24772484A PL141866B1 PL 141866 B1 PL141866 B1 PL 141866B1 PL 1984247724 A PL1984247724 A PL 1984247724A PL 24772484 A PL24772484 A PL 24772484A PL 141866 B1 PL141866 B1 PL 141866B1
- Authority
- PL
- Poland
- Prior art keywords
- dihydroxy
- formula
- anthrone
- hours
- acid chloride
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 22
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 10
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 8
- NUZWLKWWNNJHPT-UHFFFAOYSA-N anthralin Chemical compound C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O NUZWLKWWNNJHPT-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- UYKMGHUKSVDIFU-UHFFFAOYSA-N 1,8-dihydroxy-10-pentanoyl-10h-anthracen-9-one Chemical compound C1=CC=C2C(C(=O)CCCC)C3=CC=CC(O)=C3C(=O)C2=C1O UYKMGHUKSVDIFU-UHFFFAOYSA-N 0.000 description 1
- KRTYVWKREPCSNP-UHFFFAOYSA-N 1,8-dihydroxy-10-propanoyl-10h-anthracen-9-one Chemical compound C1=CC=C2C(C(=O)CC)C3=CC=CC(O)=C3C(=O)C2=C1O KRTYVWKREPCSNP-UHFFFAOYSA-N 0.000 description 1
- AHZXFRRDQXXPJD-UHFFFAOYSA-N 10-butanoyl-1,8-dihydroxy-10h-anthracen-9-one Chemical compound C1=CC=C2C(C(=O)CCC)C3=CC=CC(O)=C3C(=O)C2=C1O AHZXFRRDQXXPJD-UHFFFAOYSA-N 0.000 description 1
- SUJBUFGFNUEIRB-UHFFFAOYSA-N 2,6-dimethylpyridin-1-ium;chloride Chemical compound Cl.CC1=CC=CC(C)=N1 SUJBUFGFNUEIRB-UHFFFAOYSA-N 0.000 description 1
- DVECBJCOGJRVPX-UHFFFAOYSA-N butyryl chloride Chemical compound CCCC(Cl)=O DVECBJCOGJRVPX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- XGISHOFUAFNYQF-UHFFFAOYSA-N pentanoyl chloride Chemical compound CCCCC(Cl)=O XGISHOFUAFNYQF-UHFFFAOYSA-N 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000002884 skin cream Substances 0.000 description 1
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
Description
Przedmiotem wynalazku jest opracowanie sposobu, który umozliwia osiagniecie powaznych korzysci. Temperaturereakcji mozna obnizyc do poziomu tak niskiego jak -10°C, a w kazdym razie mozliwe jest zastosowanie bardzo niskiej temperatury reakcji, np. temperatury pokojowej. W dodatku mozna uniknac stosowania benzenu, i stosowac np. toluen, który jest mniej szkodliwy.Ponadto mozna zwiekszyc wydajnosc 2 do 3-krotnie w porównaniu ze sposobem wedlug finskiego opisu patentowego FI nr 57 743.Sposób wytwarzania l,8-dwuhydroksy-10-acylo-9-antronu, o wzorze 1, w którym R oznacza grupe alkilowa o 2-4 atomach wegla, poprzez reakcje 1,8-dwuhydroksy-9-antronu o wzorze 2 z chlorkiem kwasowym o wzorze RCOC1, w którym R ma wyzej podane znaczenie, wedlug wyna¬ lazku polega na tym, ze w mieszaninie reakcyjnej stosuje sie 2,6-dwumetylopirydyne.Jako rozpuszczalnik stosuje sie korzystnie toluen, ksylen albo chlorowane weglowodory takie jak dwuchlorometan albo czterochloroetan.Chlorek kwasowy stosuje sie korzystne w nadmiarze wynoszacym 100%. Temperaturareakcji wynosi -10 do +20°C, chlorek kwasowy dodaje sie w ciagu dwóch godzin, i mieszanie kontynuuje sie w ciagu dalszych dwóch godzin.Wynalazek oparty jest na obserwacji, ze zastapienie pirydyny przez 2,6-dwumetylopirydyne umozliwia obnizenie temperatury reakcji, zastosowanie toluenu, ksylenu albo chlorowanych weg-1 141 866 iowodorów takich jak dwuchlorometan albo czterochloroetan zamiast benzenu, a nawet potrojenie wydajnosci w porównaniu ze znana metoda. Jesli ponadto stosuje sie chlorek kwasowy w nadmia¬ rze wynoszacym 100ct, reakcje mozna zakonczyc w ciagu dwóch godzin.Z wyzej wymienionej niskiej temperatury reakcji, która moze wynosic np. -10°C do+20°C, wynika, ze ilosc zanieczyszczen przechodzacych do wytworzonego l,8-dwuhydroksy-10-acylo-9- antronu jest niewielka. Oczyszczanie jest zatem prostym postepowaniem w porównaniu z odpo¬ wiednia procedura w znanym sposobie. Acetonitryl albo 2-propanol nadaja sie do zastosowania jako rozpuszczalnik do rekrystalizacji razem z kwasem octowym albo zamiast niego.Zwiazki wytworzone sposobem wedlug wynalazku mozna stosowac np. w kremach do skóry na podstawie wazeliny albo parafiny w stezeniu 0,5-5%, w precikach do pielegnacji skóry w stezeniu np. 2-8% i w galaretkach i roztworach tworzacych blonki.Nastepujace przyklady wyjasniaja szczególy wynalazku.P r z y k l a d I. Chlorek butyrylu w ilosci 207 ml (213 ml), 2,0 mole) dodano w ciagu 2 godzin w temperaturze ponizej 0°C do mieszaniny, która zawierala 2500 ml toluenu, 226 g (1,0 mol) 1,8- dwuhydroksy-9-antronu i 232 ml (214 g, 2,0 mole) 2,6-dwumetylopirydyny.Mieszanine mieszano w temperaturze ponizej 0°C w ciagu dalszych dwóch godzin.Mieszanine ogrzano nastepnie do temperatury+40°C, odsaczono chlorowodorek 2,6-dwu¬ metylopirydyny, i wiekszosc toluenu odparowano pod zmniejszonym cisnieniem. Do pozostalosci dodano 2300 ml izopropanolu, mieszanine oziebiono do temperatury -10°C.Otrzymany po przesaczeniu osad poddano rekrystalizacji z acetronitrylu, uzyskujac 222 g l,8-dwuhydroksy-10-butyrylo-9-antronu, 75% wydajnosci teoretycznej.Przykladll. Postepowano analogicznie jak w przykladzie I, z tym, ze zastosowano ksylen zamiast toleunu. Wydajnosc byla taka sama jak w przykladzie I, to jest 75%.Przyklad III. Chlorek propionylu w ilosci 86,9ml (92,5g, 1 mol) dodano w ciagu okolo 2 godzin w temperaturze ponizej 0°C do mieszaniny, która zawierala 1200 ml toluenu, 113g (0,5 moli) l,8-dwuhydroksy-9-antronu i 116ml (107g, 1 mol) 2,6-dwumetylopirydyny. Mieszanie kon¬ tynuowano w ciagu dalszych dwóch godzin po dodaniu.Otrzymany w wyniku l,8-dwuhydroksy-10-propionylo-9-antron oddzielono w sposób przed¬ stawiony w przykladzie I. Wydajnosc wynosila 120g, to znaczy 82% wydajnosci teoretycznej.Przyklad IV. Przy zastosowaniu 1,8-dwuhydroksy-9-antronu i chlorku walerylu uzytym w nadmiarze wynoszacym 100% oraz postepujac jak w przykladzie I, otrzymano 1,8-dwuhydroksy- 10-walerylo-9-antron z wydajnoscia 53%.Zastrzezenia patentowe 1. Sposób wytwarzania l,8-dwuhydroksy-10-acylo-9-antronu, o wzorze 1, w którym R ozna¬ cza grupe alkilowa o 2-4 atomach wegla, poprzez reakcje 1,8-dwuhydroksy-9-antronu o wzorze 2 z chlorkiem kwasowym o wzorze RCOC1, w którym R ma wyzej podane znaczenie, znamienny tym, ze w mieszaninie reakcyjnej stosuje sie 2,6-dwumetylopirydyne. 2. Sposób wedlug zastrz. 1, znamienny tym, ze jako rozpuszczalnik stosuje sie toluen, ksylen albo chlorowane weglowodory takie jak dwuchlorometan albo czterochloroetan. 3. Sposób wedlug zastrz. 1, znamienny tym, ze chlorek kwasowy stosuje sie w nadmiarze wynoszacym 100%. 4. Sposób wedlug zastrz. 1, znamienny tym, ze stosuje sie temperature reakcji -10 do-l-20oC, chlorek kwasowy dodaje sie w ciagu 2 godzin, i mieszanie kontynuuje sie w ciagu nastepnych dwóch godzin.141866 CO-R WZÓR 1 HO O OH WZCfR 2 PL PL PL PL The subject of the invention is to develop a method that allows achieving significant benefits. The reaction temperature can be lowered to as low as -10°C, and in any case it is possible to use a very low reaction temperature, e.g. room temperature. In addition, you can avoid the use of benzene and use, for example, toluene, which is less harmful. Moreover, you can increase the efficiency by 2 to 3 times compared to the method according to the Finnish patent FI No. 57,743. Method for producing 1,8-dihydroxy-10- acyl-9-anthrone, of formula 1, where R is an alkyl group with 2-4 carbon atoms, by reacting 1,8-dihydroxy-9-anthrone of formula 2 with an acid chloride of formula RCOC1, where R has the above The importance of the invention is that 2,6-dimethylpyridine is used in the reaction mixture. Toluene, xylene or chlorinated hydrocarbons such as dichloromethane or tetrachloroethane are preferably used as the solvent. The acid chloride is preferably used in an excess of 100%. The reaction temperature is -10 to +20°C, the acid chloride is added within two hours, and stirring is continued for a further two hours. The invention is based on the observation that replacing pyridine with 2,6-dimethylpyridine makes it possible to lower the reaction temperature, the use toluene, xylene or chlorinated hydrocarbons such as dichloromethane or tetrachloroethane instead of benzene, and even tripling the efficiency compared to the known method. If, in addition, acid chloride is used in an excess of 100 ct, the reaction can be completed within two hours. From the above-mentioned low reaction temperature, which can be, for example, -10°C to +20°C, it follows that the amount of impurities passing into 1,8-dihydroxy-10-acyl-9- anthrone produced is small. Purification is therefore a simple procedure compared to the corresponding procedure in known methods. Acetonitrile or 2-propanol can be used as a recrystallization solvent together with or instead of acetic acid. The compounds prepared according to the invention can be used, for example, in skin creams based on petroleum jelly or paraffin at a concentration of 0.5-5%, in sticks for skin care in a concentration of e.g. 2-8% and in jellies and film-forming solutions. The following examples explain the details of the invention. EXAMPLE I. Butyryl chloride in an amount of 207 ml (213 ml, 2.0 mol) was added over 2 hours in temperature below 0°C to a mixture that contained 2500 ml of toluene, 226 g (1.0 mol) of 1,8-dihydroxy-9-anthrone and 232 ml (214 g, 2.0 mol) of 2,6-dimethylpyridine. Mixture was stirred at a temperature below 0°C for a further two hours. The mixture was then warmed to +40°C, the 2,6-dimethylpyridine hydrochloride was filtered off, and most of the toluene was evaporated under reduced pressure. 2300 ml of isopropanol were added to the residue, the mixture was cooled to -10°C. The precipitate obtained after filtration was recrystallized from acetronitrile, obtaining 222 g of 1,8-dihydroxy-10-butyryl-9-anthrone, 75% of the theoretical yield. Example 11. The procedure was the same as in Example 1, except that xylene was used instead of toleene. The yield was the same as in example I, i.e. 75%. Example III. Propionyl chloride in an amount of 86.9 ml (92.5 g, 1 mol) was added over about 2 hours at a temperature below 0°C to a mixture that contained 1200 ml of toluene, 113 g (0.5 mol) of 1,8-dihydroxy-9 -anthron and 116ml (107g, 1 mol) 2,6-dimethylpyridine. Stirring was continued for a further two hours after the addition. The 1,8-dihydroxy-10-propionyl-9-anthrone obtained was separated as described in Example 1. The yield was 120 g, i.e. 82% of the theoretical yield. Example IV. Using 1,8-dihydroxy-9-anthrone and valeryl chloride in an excess of 100% and proceeding as in Example I, 1,8-dihydroxy-10-valeryl-9-anthrone was obtained with a yield of 53%. Patent claims 1. A method for preparing 1,8-dihydroxy-10-acyl-9-anthrone of formula 1, in which R is an alkyl group with 2-4 carbon atoms, by reacting 1,8-dihydroxy-9-anthrone of formula 2 with an acid chloride of the formula RCOC1, where R has the above-mentioned meaning, characterized in that 2,6-dimethylpyridine is used in the reaction mixture. 2. The method according to claim The process according to claim 1, characterized in that the solvent is toluene, xylene or chlorinated hydrocarbons such as dichloromethane or tetrachloroethane. 3. The method according to claim 1, characterized in that the acid chloride is used in an excess of 100%. 4. The method according to claim 1, characterized in that the reaction temperature is -10 to -1-20°C, the acid chloride is added within 2 hours, and stirring is continued for another two hours.141866 CO-R FORMULA 1 HO O OH WZCfR 2 PL PL PL PL
Claims (4)
Applications Claiming Priority (1)
| 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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| PL247724A1 PL247724A1 (en) | 1985-06-18 |
| PL141866B1 true PL141866B1 (en) | 1987-09-30 |
Family
ID=8517222
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PL1984247724A PL141866B1 (en) | 1983-05-18 | 1984-05-17 | Method of obtaining 1,8-dihydroxy-10-ocyl-9-antrones |
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) | ES531760A0 (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 |
| EP0535952B1 (en) * | 1991-10-04 | 1997-12-29 | FISHER & PAYKEL LIMITED | 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 |
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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 IS IS2902A patent/IS2902A7/en unknown
- 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
- 1984-04-06 LU LU85292A patent/LU85292A1/en unknown
- 1984-04-18 CS CS842911A patent/CS256379B2/en unknown
- 1984-04-18 ES ES531760A patent/ES531760A0/en active Granted
- 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 SE SE8402649A patent/SE453827B/en not_active IP Right Cessation
- 1984-05-16 PH PH30686A patent/PH20038A/en unknown
- 1984-05-16 NO NO841965A patent/NO157099C/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 DD DD84263131A patent/DD223702A5/en unknown
- 1984-05-17 HU HU841908A patent/HUT36076A/en unknown
- 1984-05-17 DE DE19843418382 patent/DE3418382A1/en not_active Withdrawn
- 1984-05-17 PT PT78603A patent/PT78603B/en unknown
- 1984-05-17 PL PL1984247724A patent/PL141866B1/en unknown
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