DE3636125A1 - METHOD FOR PRODUCING DIETHYLENE GLYCOLESTERS - Google Patents
METHOD FOR PRODUCING DIETHYLENE GLYCOLESTERSInfo
- Publication number
- DE3636125A1 DE3636125A1 DE19863636125 DE3636125A DE3636125A1 DE 3636125 A1 DE3636125 A1 DE 3636125A1 DE 19863636125 DE19863636125 DE 19863636125 DE 3636125 A DE3636125 A DE 3636125A DE 3636125 A1 DE3636125 A1 DE 3636125A1
- Authority
- DE
- Germany
- Prior art keywords
- amino
- benzene
- acid
- hydroxyethoxy
- dichlorophenyl
- 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.)
- Ceased
Links
- 238000004519 manufacturing process Methods 0.000 title description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical class OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 17
- -1 diethylene glycol ester Chemical class 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- DCOPUUMXTXDBNB-UHFFFAOYSA-N diclofenac Chemical compound OC(=O)CC1=CC=CC=C1NC1=C(Cl)C=CC=C1Cl DCOPUUMXTXDBNB-UHFFFAOYSA-N 0.000 claims description 4
- 125000004494 ethyl ester group Chemical group 0.000 claims description 4
- MRPZLXMWCIWOGP-UHFFFAOYSA-N 2,3-dimethyl-n-phenylaniline Chemical compound CC1=CC=CC(NC=2C=CC=CC=2)=C1C MRPZLXMWCIWOGP-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- WJCRAVDPIMWFPG-UHFFFAOYSA-N n-phenyl-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC=CC(NC=2C=CC=CC=2)=C1 WJCRAVDPIMWFPG-UHFFFAOYSA-N 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- SLPAPGNFCSVQKP-UHFFFAOYSA-N 2,6-dichloro-3-methyl-n-phenylaniline Chemical compound CC1=CC=C(Cl)C(NC=2C=CC=CC=2)=C1Cl SLPAPGNFCSVQKP-UHFFFAOYSA-N 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- HDUUZPLYVVQTKN-UHFFFAOYSA-N 2,6-dichloro-n-phenylaniline Chemical compound ClC1=CC=CC(Cl)=C1NC1=CC=CC=C1 HDUUZPLYVVQTKN-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/21—Esters, e.g. nitroglycerine, selenocyanates
- A61K31/215—Esters, e.g. nitroglycerine, selenocyanates of carboxylic acids
Landscapes
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Pharmacology & Pharmacy (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von Diethylenglykolestern.The invention relates to a method for producing Diethylene glycol esters.
Es sind verschiedene Verfahren zur Herstellung von Diethylenglykolestern bekannt. Diese Verfahren weisen die Nachteile auf, daß sie in mehreren Stufen durchgeführt werden oder aber die Hydroxylgruppen des Diethylenglykols geschützt werden müssen.There are various methods of making diethylene glycol esters known. These methods have the disadvantages on that they are carried out in several stages or but protected the hydroxyl groups of diethylene glycol Need to become.
Aufgabe der Erfindung ist es, ein einstufiges Verfahren ohne besonderen Schutz der Hydroxylgruppen des Diethylenglykols zur Verfügung zu stellen.The object of the invention is a one-step process without special protection of the hydroxyl groups of diethylene glycol to provide.
Erfindungsgemäß wird diese Aufgabe dadurch gelöst, daß
man Diethylenglykol direkt mit einer Säure der allgemeinen
Formel (1)
worin
n = 0 oder 1
R1 = Cl, H oder CH3,
R2 = H, CF3 oder CH3,
und
R3 = Cl oder H
gilt, umsetzt.According to the invention, this object is achieved in that diethylene glycol is reacted directly with an acid of the general formula (1) wherein
n = 0 or 1
R 1 = Cl, H or CH 3 ,
R 2 = H, CF 3 or CH 3 ,
and
R 3 = Cl or H
applies, implements.
Anstelle der Säure kann auch ein entsprechendes Natrium- oder Kaliumsalz verwendet werden.Instead of the acid, a corresponding sodium or potassium salt can be used.
In einer bevorzugten Ausführungsform wird dem Reaktionsgemisch Thionylchlorid in einer stöchiometrischen oder größeren Menge (bezogen auf die Säure) zugesetzt.In a preferred embodiment, the reaction mixture Thionyl chloride in a stoichiometric or larger Amount (based on the acid) added.
Die Reaktionstemperatur wird beim erfindungsgemäßen Verfahren im Bereich zwischen der Zimmertemperatur und der Temperatur eines erhitzten Wasserbades gehalten.The reaction temperature in the invention Procedures in the range between room temperature and the temperature of a heated water bath.
Erfindungsgemäß werden als Säuren beispielsweise die 2-[(2,6-Dichlorphenyl-)amino]-benzolessigsäure, die 2-[(3-Trifluormethylphenyl)amino]-benzolsäure, die 2-(2,6-Dichlor-3-methylphenyl)amino]-benzolsäure oder die 2-[(2,3-Dimethylphenyl)amino]-benzolsäure eingesetzt.According to the invention, for example, the 2 - [(2,6-dichlorophenyl) amino] benzene acetic acid, the 2 - [(3-trifluoromethylphenyl) amino] benzene acid, the 2- (2,6-dichloro-3-methylphenyl) amino] benzene acid or the 2 - [(2,3-dimethylphenyl) amino] benzene acid is used.
Die durch Umsetzung der Säure mit dem Diethylenglykol
hergestellten Diethylenglykolester sind beispielsweise
der 2-[(2,6-Dichlorphenyl)amino]-essigsäure-2-(2-hydroxyethoxy)-
ethylester,
der 2-[(3-Trifluormethylphenyl)amino]-benzolsäure-
2-(2-hydroxyethoxy)-ethylester,
der 2-[(2,6-Dichlor-3-methylphenyl)amino]-benzolsäure-
2-(2-hydroxyethoxy)-ethylester,
der 2-[(2,3-Dimethylphenyl)amino]-benzolsäure-2-(2-hydroxyethoxy)-
ethylester,
der 2-[(2,6-Dichlorphenyl)amino]-benzolessigsäure-
2-(2-hydroxyethoxy)-ethylester oder
der 2-[(2,6-Dichlorphenyl)amino]-benzolessigsäure-
2-(2,6-hydroxyethoxy)ethylester.The diethylene glycol esters produced by reacting the acid with the diethylene glycol are, for example
the 2 - [(2,6-dichlorophenyl) amino] acetic acid 2- (2-hydroxyethoxy) ethyl ester,
2- (2-hydroxyethoxy) ethyl 2 - [(3-trifluoromethylphenyl) amino] benzene,
2- (2-hydroxyethoxy) ethyl 2 - [(2,6-dichloro-3-methylphenyl) amino] benzene,
the 2 - [(2,3-dimethylphenyl) amino] benzene acid 2- (2-hydroxyethoxy) ethyl ester,
the 2 - [(2,6-dichlorophenyl) amino] benzene acetic acid 2- (2-hydroxyethoxy) ethyl ester or
the 2 - [(2,6-dichlorophenyl) amino] benzene acetic acid 2- (2,6-hydroxyethoxy) ethyl ester.
Nach Umsetzung werden die Reaktionsprodukte durch Zugabe von Wasser und Ethylester abgetrennt. Die Reaktionsprodukte lösen sich in der Esterphase, die eingedampft wird. Der Rückstand wird durch eine mit Silikagel gefüllte Säule unter Verwendung von Chloroform als Eluationsmittel geschickt. Nach der Reinigung durch Säulenchromatographie weisen die Reaktionsprodukte im Dünnschicht-Chromatogramm lediglich einen Flecken auf. Bei Verwendung von Silikagel 60 F254 und Entwicklung mit Chloroform lassen sich die Flecke bei Licht von 254 nm sichtbar machen. Auch bei der Hochdruck-Chromatographie wird ein einzelner Peak erhalten. Die NMR-Spektren stimmen mit den theoretischen Spektren überein. Ferner taucht in den IR-Spektren jeweils die Bande für die Estergruppe auf.After the reaction, the reaction products are separated off by adding water and ethyl ester. The reaction products dissolve in the ester phase, which is evaporated. The residue is passed through a column filled with silica gel using chloroform as the eluent. After purification by column chromatography, the reaction products only show one spot in the thin-layer chromatogram. When using silica gel 60 F 254 and developing with chloroform, the spots can be made visible in light of 254 nm. A single peak is also obtained in high pressure chromatography. The NMR spectra agree with the theoretical spectra. The band for the ester group also appears in the IR spectra.
Die nach dem erfindungsgemäßen Verfahren hergestellten Diethylenglykolester sind wertvolle entzündungshemmende Mittel.The diethylene glycol esters produced by the process according to the invention are valuable anti-inflammatory Medium.
Die folgenden Beispiele erläutern die Erfindung:The following examples illustrate the invention:
180 ml wasserfreies Diethylenglykol werden mit 4 ml Thionylchlorid vermischt. Sodann werden 15 g 2-[(2,6-Dichlorphenyl)- amino]-benzolsäurenatriumacetat zugesetzt. Das Gemisch wird bei Zimmertemperatur geschüttelt und anschließend mit 200 ml Wasser und 250 ml Ethylester versetzt. Es bilden sich beim Schütteln zwei Phasen, wovon die wässrige Phase abgetrennt wird. Die organische Phase wird nacheinander mit Wasser, verdünnter Lauge und erneut mit Wasser gewaschen. Die Etherlösung wird abgetrennt, der Ether durch Destillation entfernt und der Rückstand über Natriumsulfat getrocknet. Es verbleibt eine viskose ölige Flüssigkeit, welche auf eine mit Silikagel gepackte Chromatographiesäule gegeben und mit Chloroform eluiert wird. Nach Abdampfen des Lösungsmittels wird das Produkt in Form eines hellgelben Öls in einer Ausbeute von 16,5 g (86%) gewonnen. Esternachweis: 1.720 cm-1. 180 ml of anhydrous diethylene glycol are mixed with 4 ml of thionyl chloride. Then 15 g of 2 - [(2,6-dichlorophenyl) amino] benzene acid sodium acetate are added. The mixture is shaken at room temperature and then mixed with 200 ml of water and 250 ml of ethyl ester. Two phases form upon shaking, from which the aqueous phase is separated. The organic phase is washed successively with water, dilute alkali and again with water. The ether solution is separated off, the ether is removed by distillation and the residue is dried over sodium sulfate. A viscous oily liquid remains, which is placed on a chromatography column packed with silica gel and eluted with chloroform. After evaporation of the solvent, the product is obtained in the form of a light yellow oil in a yield of 16.5 g (86%). Ester detection: 1,720 cm -1 .
Zu 80 l wasserfreien Diethylglykols werden 3 l Thionylchlorid und 10 kg 2-[(3-Trifluormethylphenyl)amino]benzolsäure gegeben. Das Gemisch wird 6 Stunden auf einem Wasserbad erhitzt. Die erhaltene dunkelgrüne Lösung wird abgekühlt und mit einer wässrigen Lösung von Ethylether versetzt. Das Produkt wird entsprechend der Beschreibung in Beispiel 1 aufgearbeitet. Nach Reinigung werden 7,8 kg (59%) eines hellgelben Öls erhalten. Esternachweis: 1.683 cm-1.3 l of thionyl chloride and 10 kg of 2 - [(3-trifluoromethylphenyl) amino] benzene acid are added to 80 l of anhydrous diethyl glycol. The mixture is heated on a water bath for 6 hours. The dark green solution obtained is cooled and an aqueous solution of ethyl ether is added. The product is worked up as described in Example 1. After cleaning, 7.8 kg (59%) of a light yellow oil are obtained. Evidence of ester: 1,683 cm -1 .
Claims (6)
n = 0 oder 1,
R1 = Cl, H oder CH3,
R2 = H; CF3 oder CH3,
und R3 = Cl oder H
gilt, oder mit einem Natrium- oder Kaliumsalz dieser Säure umsetzt. 1. A process for the preparation of diethylene glycol esters, characterized in that diethylene glycol directly with an acid of the general formula (1) wherein
n = 0 or 1,
R 1 = Cl, H or CH 3 ,
R 2 = H; CF 3 or CH 3 ,
and R 3 = Cl or H
applies, or with a sodium or potassium salt of this acid.
der 2-[(2,6-Dichlorphenyl)amino]-essigsäure-2-(2- hydroxyethoxy)-ethylester,
der 2-[(3-Trifluormethylphenyl)amino]-benzolsäure- 2- (2-hydroxyethoxy)-ethylester,
der 2-[(2,6-Dichlor-3-methylphenyl)amino]-benzolsäure- 2-(2-hydroxyethoxy)-ethylester,
der 2-[(2,3-Dimethylphenyl)amino]-benzolsäure- 2-(2-hydroxyethoxy)-ethylester,
der 2-[(2,6-Dichlorphenyl)amino]-benzolessigsäure- 2-(2-hydroxyethoxy)-ethylester oder
der 2-[(2,6-Dichlorphenyl)amino]-benzolessigsäure- 2-(2,6-hydroxyethoxy)ethylester
ist.6. The method according to any one of the preceding claims, characterized in that the diethylene glycol ester produced
the 2 - [(2,6-dichlorophenyl) amino] acetic acid 2- (2-hydroxyethoxy) ethyl ester,
2- (2-hydroxyethoxy) ethyl 2 - [(3-trifluoromethylphenyl) amino] benzene,
2- (2-hydroxyethoxy) ethyl 2 - [(2,6-dichloro-3-methylphenyl) amino] benzene,
2- (2-hydroxyethoxy) ethyl 2 - [(2,3-dimethylphenyl) amino] benzene,
the 2 - [(2,6-dichlorophenyl) amino] benzene acetic acid 2- (2-hydroxyethoxy) ethyl ester or
the 2 - [(2,6-dichlorophenyl) amino] benzene acetic acid 2- (2,6-hydroxyethoxy) ethyl ester
is.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ES548226A ES8605220A1 (en) | 1985-10-25 | 1985-10-25 | Esters of diethylene glycol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE3636125A1 true DE3636125A1 (en) | 1987-04-30 |
Family
ID=8490031
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19863636125 Ceased DE3636125A1 (en) | 1985-10-25 | 1986-10-23 | METHOD FOR PRODUCING DIETHYLENE GLYCOLESTERS |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS62106064A (en) |
| BE (1) | BE905666A (en) |
| CH (1) | CH676238A5 (en) |
| DE (1) | DE3636125A1 (en) |
| ES (1) | ES8605220A1 (en) |
| FR (1) | FR2589151B1 (en) |
| GB (1) | GB2182041B (en) |
| IT (1) | IT1197255B (en) |
| PT (1) | PT81505B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0336147A3 (en) * | 1988-03-31 | 1991-03-20 | Merckle GmbH | Diethylene glycol monoesters, process for their preparation and their use as medicines |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9217066B2 (en) | 2008-03-31 | 2015-12-22 | Ford Global Technologies, Llc | Structural polymer insert and method of making the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2834167A1 (en) * | 1978-08-04 | 1980-02-21 | Troponwerke Gmbh & Co Kg | Hydroxy-ethoxy-ethyl-N-tri:fluoromethyl-phenyl anthranilate prodn. - by direct esterification of acid with di:ethylene glycol, useful as pharmaceutical |
| EP0112130A1 (en) * | 1982-12-09 | 1984-06-27 | Teva Pharmaceutical Industries Limited | Ethoxycarbonyloxy ethyl esters of non-steroidal anti-inflammatory carboxylic acids, their preparation and use |
| DE3407507A1 (en) * | 1984-03-01 | 1985-09-05 | A. Nattermann & Cie GmbH, 5000 Köln | Novel o-(2,6-dichloroanilino)phenylacetic acid esters, process for their preparation, and pharmaceutical preparations containing them |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1939112C3 (en) * | 1969-08-01 | 1975-03-06 | Troponwerke Dinklage & Co, 5000 Koeln | Esters of N- (3-trifluoromethylphenyl) anthranilic acid, process for their preparation and pharmacologically active preparations thereof |
| DE2735569A1 (en) * | 1977-08-06 | 1979-02-15 | Troponwerke Gmbh & Co Kg | Antiinflammatory and antirheumatic agent prodn. - esp. N-tri:fluoro:methyl-phenyl-anthranilic acid hydroxy-ethoxy-ethyl ester |
| DE2834169C2 (en) * | 1978-08-04 | 1984-02-09 | Troponwerke GmbH & Co KG, 5000 Köln | Process for the preparation of 2- (2-hydroxyethoxy) ethyl-N- (alpha, alpha, alpha -trifluoro-m-tolyl) anthranilate |
| DE2834168C2 (en) * | 1978-08-04 | 1984-02-09 | Troponwerke GmbH & Co KG, 5000 Köln | Process for the preparation of 2- (2-hydroxyethoxy) ethyl-N - (α, α, α-trifluoro-m-tolyl) anthranilate |
| DE2926472A1 (en) * | 1979-06-30 | 1981-01-15 | Thomae Gmbh Dr K | NEW BENZOYL DERIVATIVES, THEIR PRODUCTION AND THEIR USE AS MEDICINAL PRODUCTS |
| EP0132690B1 (en) * | 1983-07-21 | 1989-02-01 | Troponwerke GmbH & Co. KG | Thermoplastics containing antiphlogistics |
| US4694105A (en) * | 1983-12-20 | 1987-09-15 | Ciba-Geigy Corporation | Herbicidal alkoxyamino- and polyalkoxyaminodiphenyl ethers |
-
1985
- 1985-10-25 ES ES548226A patent/ES8605220A1/en not_active Expired
- 1985-11-15 PT PT81505A patent/PT81505B/en not_active IP Right Cessation
-
1986
- 1986-09-19 IT IT21774/86A patent/IT1197255B/en active
- 1986-10-22 CH CH3810/86A patent/CH676238A5/de not_active IP Right Cessation
- 1986-10-23 DE DE19863636125 patent/DE3636125A1/en not_active Ceased
- 1986-10-24 GB GB8625481A patent/GB2182041B/en not_active Expired
- 1986-10-24 JP JP61252159A patent/JPS62106064A/en active Pending
- 1986-10-27 FR FR868614922A patent/FR2589151B1/en not_active Expired - Lifetime
- 1986-10-27 BE BE0/217337A patent/BE905666A/en not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2834167A1 (en) * | 1978-08-04 | 1980-02-21 | Troponwerke Gmbh & Co Kg | Hydroxy-ethoxy-ethyl-N-tri:fluoromethyl-phenyl anthranilate prodn. - by direct esterification of acid with di:ethylene glycol, useful as pharmaceutical |
| EP0112130A1 (en) * | 1982-12-09 | 1984-06-27 | Teva Pharmaceutical Industries Limited | Ethoxycarbonyloxy ethyl esters of non-steroidal anti-inflammatory carboxylic acids, their preparation and use |
| DE3407507A1 (en) * | 1984-03-01 | 1985-09-05 | A. Nattermann & Cie GmbH, 5000 Köln | Novel o-(2,6-dichloroanilino)phenylacetic acid esters, process for their preparation, and pharmaceutical preparations containing them |
Non-Patent Citations (2)
| Title |
|---|
| Helv.Chim.Acta, Bd. 36, 1953, S. 1109-1115 * |
| HOLLEMANN-WIBERG: Lehrbuch der Anorganischen Chemie, Verlag Walter de Gruyter, Berlin, New York 1985, S. 507 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0336147A3 (en) * | 1988-03-31 | 1991-03-20 | Merckle GmbH | Diethylene glycol monoesters, process for their preparation and their use as medicines |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2182041B (en) | 1989-09-20 |
| FR2589151A1 (en) | 1987-04-30 |
| BE905666A (en) | 1987-02-16 |
| CH676238A5 (en) | 1990-12-28 |
| IT8621774A0 (en) | 1986-09-19 |
| JPS62106064A (en) | 1987-05-16 |
| ES8605220A1 (en) | 1986-03-16 |
| FR2589151B1 (en) | 1990-05-18 |
| PT81505A (en) | 1985-12-01 |
| GB2182041A (en) | 1987-05-07 |
| ES548226A0 (en) | 1986-03-16 |
| GB8625481D0 (en) | 1986-11-26 |
| IT1197255B (en) | 1988-11-30 |
| PT81505B (en) | 1987-11-11 |
| IT8621774A1 (en) | 1988-03-19 |
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| Date | Code | Title | Description |
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| 8181 | Inventor (new situation) |
Free format text: ORJALES VENERO, AURELIO MOSQUERA PESTANA, RAMON, LEJONA, VIZCAYA, ES |
|
| 8128 | New person/name/address of the agent |
Representative=s name: BERENDT, T., DIPL.-CHEM. DR. LEYH, H., DIPL.-ING. |
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| 8110 | Request for examination paragraph 44 | ||
| 8131 | Rejection |