FR2589151A1 - PROCESS FOR THE PREPARATION OF DIETHYLENE GLYCOL ESTERS - Google Patents
PROCESS FOR THE PREPARATION OF DIETHYLENE GLYCOL ESTERS Download PDFInfo
- Publication number
- FR2589151A1 FR2589151A1 FR8614922A FR8614922A FR2589151A1 FR 2589151 A1 FR2589151 A1 FR 2589151A1 FR 8614922 A FR8614922 A FR 8614922A FR 8614922 A FR8614922 A FR 8614922A FR 2589151 A1 FR2589151 A1 FR 2589151A1
- Authority
- FR
- France
- Prior art keywords
- amino
- diethylene glycol
- ethyl
- hydroxyethoxy
- acid
- 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.)
- Granted
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- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical class OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 14
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000002148 esters Chemical class 0.000 claims abstract description 6
- 239000011734 sodium Substances 0.000 claims abstract description 5
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 5
- 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 abstract description 4
- -1 2,3-dimethylphenyl Chemical group 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 150000007513 acids Chemical class 0.000 claims description 7
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- YCNFHQIOFCOXNJ-UHFFFAOYSA-N [2-(2,6-dichloroanilino)phenyl] acetate Chemical compound CC(=O)OC1=CC=CC=C1NC1=C(Cl)C=CC=C1Cl YCNFHQIOFCOXNJ-UHFFFAOYSA-N 0.000 claims description 2
- DCOPUUMXTXDBNB-UHFFFAOYSA-N diclofenac Chemical compound OC(=O)CC1=CC=CC=C1NC1=C(Cl)C=CC=C1Cl DCOPUUMXTXDBNB-UHFFFAOYSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims 2
- 235000010233 benzoic acid Nutrition 0.000 claims 2
- DNUPYEDSAQDUSO-UHFFFAOYSA-N diethylene glycol monobenzoate Natural products OCCOCCOC(=O)C1=CC=CC=C1 DNUPYEDSAQDUSO-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 159000000001 potassium salts Chemical class 0.000 claims 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Substances ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- XXXFZKQPYACQLD-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl acetate Chemical compound CC(=O)OCCOCCO XXXFZKQPYACQLD-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- UQFHJDVUQSAVOQ-UHFFFAOYSA-N (2-aminophenyl) acetate Chemical compound CC(=O)OC1=CC=CC=C1N UQFHJDVUQSAVOQ-UHFFFAOYSA-N 0.000 description 1
- OUNPIOSIKLGJER-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethane-1,1-diol Chemical compound OCCOCC(O)O OUNPIOSIKLGJER-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- SBDNJUWAMKYJOX-UHFFFAOYSA-N Meclofenamic Acid Chemical compound CC1=CC=C(Cl)C(NC=2C(=CC=CC=2)C(O)=O)=C1Cl SBDNJUWAMKYJOX-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- SBDNJUWAMKYJOX-UHFFFAOYSA-M meclofenamic acid(1-) Chemical compound CC1=CC=C(Cl)C(NC=2C(=CC=CC=2)C([O-])=O)=C1Cl SBDNJUWAMKYJOX-UHFFFAOYSA-M 0.000 description 1
- HYYBABOKPJLUIN-UHFFFAOYSA-N mefenamic acid Chemical compound CC1=CC=CC(NC=2C(=CC=CC=2)C(O)=O)=C1C HYYBABOKPJLUIN-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229940049953 phenylacetate Drugs 0.000 description 1
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 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
- 238000003756 stirring Methods 0.000 description 1
- 238000004809 thin layer chromatography 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)
Abstract
L'INVENTION A POUR OBJET UN PROCEDE DE PREPARATION D'ESTERS DU DIETYLENEGLYCOL, OBTENUS EN UNE SEULE ETAPE, C'EST-A-DIRE EN UTILISANT LE DIETHYLENEGLYCOL AVEC L'ACIDE CORRESPONDANT, DE FORMULE : (CF DESSIN DANS BOPI) DANS LAQUELLE N 0 OU 1, R H, CL OU CH, R H, CH OU CF ET R H OU CL OU SON SEL DE SODIUM OU DE POTASSIUM ET EN LUI AJOUTANT DU CHLORURE DE THIONYLE EN QUANTITES STOECHIOMETRIQUES PAR RAPPORT A L'ACIDE OU MEME EN QUANTITES SUPERIEURES, ET EN EFFECTUANT LA REACTION ENTRE LA TEMPERATURE AMBIANTE ET LE BAIN-MARIE. CETTE REACTION S'EFFECTUE SANS BESOIN DE PROTEGER LES HYDROXYLES DU DIETHYLENEGLYCOL.THE SUBJECT OF THE INVENTION IS A PROCESS FOR THE PREPARATION OF DIETYLENEGLYCOL ESTERS, OBTAINED IN A SINGLE STEP, THAT IS TO SAY BY USING DIETHYLENEGLYCOL WITH THE CORRESPONDING ACID, OF FORMULA: (CF DRAWING IN BOPI) IN WHICH N 0 OR 1, RH, CL OR CH, RH, CH OR CF AND RH OR CL OR ITS SODIUM OR POTASSIUM SALT AND ADDING THIONYL CHLORIDE IN STOECHIOMETRIC QUANTITIES IN RELATION TO ACID OR EVEN IN HIGHER QUANTITIES , AND PERFORMING THE REACTION BETWEEN THE AMBIENT TEMPERATURE AND THE WATERBATH. THIS REACTION TAKES PLACE WITHOUT THE NEED TO PROTECT THE HYDROXYLES OF DIETHYLENEGLYCOL.
Description
DESCRIPTION DE L'INVENTIONDESCRIPTION OF THE INVENTION
La présente invention concerne la préparation d'une série de monoesters du diéthytèneglycol, par un procédé courant, aux caractéristiques propres, qui Le rendent avantageux par rapport à The present invention relates to the preparation of a series of monoesters of diethylene glycol, by a common method, with its own characteristics, which make it advantageous with respect to
d'autres procédés. En effet, la préparation de ces esters s'effec- other methods. Indeed, the preparation of these esters is
tue en une seule étape, en utilisant le diéthylèneglycol et l'acide correspondant, et sans besoin de protéger l'un des hydroxyles du diéthylèneglycol. Pour que la réaction évolue favorablement, il faut ajouter, en plus de l'acide et du diéthyltneglycol, qui est utilisé en fort excès, du chlorure de thionyle, en quantité stoechiométrique par rapport à l'acide ou, dans certains cas, kills in a single step, using the diethylene glycol and the corresponding acid, and without the need to protect one of the hydroxyl diethylene glycol. In order for the reaction to progress favorably, it is necessary to add, in addition to the excessively used acid and diethylene glycol, thionyl chloride, in stoichiometric quantities with respect to the acid or, in some cases,
légèrement supérieure.slightly higher.
Il est important de signaler que la réaction s'effectue de la même manière si l'on utilise au lieu de l'acide, un de ses It is important to point out that the reaction is carried out in the same way if, instead of the acid, one of its
sels, par exemple le sel de sodium ou de potassium. salts, for example the sodium or potassium salt.
La température de réaction est comprise entre la tempéra- The reaction temperature is between the temperature
ture ambiante et celle du bain-marie, et elle est évidemment en rapport avec le temps nécessaire pour que La réaction soit complète. Les acides utilisés répondent à la formule générale I, i dans laquelle n= O ou 1, R peut être un atome d'hydrogène ou de chlore ou un groupe méthyle; R2 peut être un atome d'hydrogène ou un groupe méthyle ou trifluorométhyle; et R3 peut être un atome and the temperature of the water bath, and is obviously related to the time required for the reaction to be complete. The acids used have the general formula I, wherein n = O or 1, R may be hydrogen, chlorine or methyl; R2 may be a hydrogen atom or a methyl or trifluoromethyl group; and R3 can be an atom
d'hydrogène ou de chlore.hydrogen or chlorine.
(CH2)n CO2H R3(CH2) n CO2H R3
\/ NH (I)\ / NH (I)
1 21 2
R R2R R2
On a donc fait réagir avec le diéthylèneglycol les acides suivants: acide 2-[(2,6-dichlorophényl)aminoJphénylacetique (n = 1, R = R = Cl, R2 = H), acide 2-[(3-trifluorométhytphényl)amino]benzoique (n = O, R = R = The following acids were thus reacted with diethylene glycol: 2 - [(2,6-dichlorophenyl) amino] phenylacetic acid (n = 1, R = R = Cl, R 2 = H), 2 - [(3-trifluoromethylphenyl) amino acid) ] benzoic (n = O, R = R =
H, R2 = CF3),H, R2 = CF3),
acide 2-[(2,6-dichtoro-3-méthylphényl)amino]benzo;que (n = O, R = R3 = Ct, R2 = CH3), acide 2-[(2,3-diméthylphényl)aminolbenzo;que (n = O, R1 = R2 = CH3, 2 - [(2,6-dichloro-3-methylphenyl) amino] benzoic acid (n = O, R = R 3 = Ct, R 2 = CH 3), 2 - [(2,3-dimethylphenyl) amino) benzoic acid; (n = O, R1 = R2 = CH3,
R3 = H).R3 = H).
Comme on l'a déjà signalé, n'importe lequel des sels As already mentioned, any of the salts
de sodium ou de potassium de ces acides réagit de façon semblable. of sodium or potassium of these acids reacts similarly.
Les esters obtenus par réaction des acides cités plus haut et du diéthylèneglycol en présence du chlorure de thionyle sont les suivants: The esters obtained by reaction of the acids mentioned above and diethylene glycol in the presence of thionyl chloride are the following:
2-f(2,6-dichlorophényl)amino]phénylacétate de 2-(2-hydroxyéthoxy)- 2- (2-hydroxyethoxy) 2- (2,6-dichlorophenyl) amino] phenylacetate
éthyle.ethyl.
2-[(3-trifluorométhylphényl)amino]benzoate de 2-(2-hydroxyéthoxy)- 2 - [(3-trifluoromethylphenyl) amino] benzoate 2- (2-hydroxyethoxy) -
éthyle.ethyl.
2-[(2,6-dichloro-3-méthylphényl)amino]benzoate de 2-(2-hydroxy- 2 - [(2,6-dichloro-3-methylphenyl) amino] benzoate 2- (2-hydroxy-
éthoxy)éthyle.ethoxy) ethyl.
2-[(2,3-diméthylphényl)aminolbenzoate de 2-(2-hydroxyéthoxy)éthyle. 2- (2-hydroxyethoxy) ethyl 2 - [(2,3-dimethylphenyl) aminolbenzoate.
On isole les produits bruts de la réaction du diéthylène- Crude products are isolated from the reaction of diethylene
glycol avec les acides représentés par la formule générale I, dans i 2 3 laquelle n, R1, R et R ont la signification décrite plus haut, en présence du chlorure de thionyle, en ajoutant de l'eau et de l'éther éthylique, puisqu'ils sont très solubles dans le solvant organique. On les purifie en les faisant passer à travers une colonne remplie de gel de silice. Après chromatographie sur colonne, ils présentent une seule tache en chromatographie sur couche mince, lorsque l'on utilise des plaques à support de gel de silice silicagel 60 F254" du chloroforme et que l'on visualise la 254 uctrfree u 'onvsaiet glycol with the acids represented by the general formula I, wherein n, R1, R and R have the meaning described above, in the presence of thionyl chloride, by adding water and ethyl ether, since they are very soluble in the organic solvent. They are purified by passing them through a column filled with silica gel. After column chromatography, they show a single spot in thin layer chromatography, when silica gel silica gel 60 F254-chloroform silica support plates are used and the 254 uctrfree u 'onvsaiet is visualized.
lumière de longueur d'onde 254 nm.light of wavelength 254 nm.
Ils présentent également un pic unique en chromatographie liquide à haute pression. D'autre part, les spectres de RMN de 1H sont ceux que l'on attend pour ces composés. Ils présentent tous la They also have a unique peak in high pressure liquid chromatography. On the other hand, the 1H NMR spectra are those expected for these compounds. They all present the
bande correspondant au groupe ester dans les spectres IR. band corresponding to the ester group in the IR spectra.
Les exemples suivants illustrent l'invention sans toute- The following examples illustrate the invention without any
fois en limiter la portée.limit its scope.
Exemple 1 - Préparation du 2-[(2,6-dichlorophényl)amino]phényLacé- Example 1 - Preparation of 2 - [(2,6-dichlorophenyl) amino] phenylacetate
tate de 2-(2-hydroxyéthoxy)éthyle2- (2-hydroxyethoxy) ethyl acetate
A 180 ml de diéthylèneglycol sec, on ajoute 4 ml de chlo- To 180 ml of dry diethylene glycol, 4 ml of chlorine are added.
rure de thionyle et, peu après, on introduit 15 g de 2-[(2,6-di- of thionyl and shortly thereafter 15 g of 2 - [(2,6-di-
chlorophényL)aminojphénylacétate de sodium. Le mélange est agité à la température ambiante, puis l'on ajoute 200 ml d'eau et 250 ml d'éther éthylique; après avoir agité les deux phases, on sépare la couche aqueuse et on lave la couche organique successivement par l'eau, par la soude aqueuse et par l'eau. On sèche La solution sodium chlorophenyl) aminophenylacetate. The mixture is stirred at room temperature, then 200 ml of water and 250 ml of ethyl ether are added; after stirring the two phases, the aqueous layer is separated and the organic layer is washed successively with water, with aqueous sodium hydroxide and with water. The solution is dried
éthérée sur sulfate de sodium et on élimine l'éther par distilla- ethereal over sodium sulphate and the ether is distilled off
tion. Le résidu obtenu, à l'aspect huileux, est purifié par passage tion. The resulting residue, oily in appearance, is purified by passage
sur une colonne chromatographique garnie de gel de silice et éLu- on a chromatographic column packed with silica gel and
tion par le chloroforme. Apres élimination du solvant, on obtient 16,5 g (86 %) d'une huile légèrement jaune, correspondant au chloroform. After removal of the solvent, 16.5 g (86%) of a slightly yellow oil, corresponding to
produit recherché). (ester) = 1 720 cm-1. sought product). (ester) = 1720 cm-1.
Exemple 2 - Préparation du 2-[(3-trifluorométhylphényl)amino]benzo- Example 2 - Preparation of 2 - [(3-trifluoromethylphenyl) amino] benzoate
ate de 2-(2-hydroxyéthoxy)éthyle A 80 l de diéthylèneglycol sec, on ajoute 3 l de chlorure 2- (2-hydroxyethoxy) ethyl acetate To 80 l of dry diethylene glycol, add 3 l of chloride
de thionyle et 10 kg d'acide 2-[(3-trifluorométhylphényl)amino]- of thionyl and 10 kg of 2 - [(3-trifluoromethylphenyl) amino] -
benzo;que. On chauffe le mélange au bain-marie pendant 6 h. On refroidit la solution obtenue, de couleur vert foncé; on y ajoute alors de l'eau et de l'éther éthylique et on traite le produit de benzo; that. The mixture is heated in a water bath for 6 hours. The solution obtained is cooled to a dark green color; water and ethyl ether are added and the product is treated.
façon semblable à ce qui est décrit à l'exemple 1. Après purifica- similar to that described in Example 1. After purification
tion du produit, on obtient 7,8 kg (59 %) de produit huileux de of the product, 7.8 kg (59%) of oily
couleur jaune clair. (ester) = 1 683 cm-1. light yellow color. (ester) = 1683 cm -1.
Claims (5)
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 (2)
| Publication Number | Publication Date |
|---|---|
| FR2589151A1 true FR2589151A1 (en) | 1987-04-30 |
| FR2589151B1 FR2589151B1 (en) | 1990-05-18 |
Family
ID=8490031
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| FR868614922A Expired - Lifetime FR2589151B1 (en) | 1985-10-25 | 1986-10-27 | PROCESS FOR THE PREPARATION OF DIETHYLENEGLYCOL ESTERS |
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) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3811118C1 (en) * | 1988-03-31 | 1989-10-12 | Merckle Gmbh, 7902 Blaubeuren, De | |
| US9217066B2 (en) | 2008-03-31 | 2015-12-22 | Ford Global Technologies, Llc | Structural polymer insert and method of making the same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| DE2834168A1 (en) * | 1978-08-04 | 1980-02-21 | Troponwerke Gmbh & Co Kg | METHOD FOR PRODUCING 2- (2-HYDROXYAETHOXY) AETHYL-N- (ALPHA, ALPHA, ALPHA -TRIFLUOR-M-TOLYL) ANTHRANILATE |
| 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 |
| DE2834169A1 (en) * | 1978-08-04 | 1980-02-21 | Troponwerke Gmbh & Co Kg | Hydroxy-ethoxy-ethyl N-tri:fluoromethyl-phenyl anthranilate prodn. - by converting corresp. acid to halide, then reaction with di:ethylene glycol |
| EP0149427A1 (en) * | 1983-12-20 | 1985-07-24 | Ciba-Geigy Ag | (Poly-)Oxyalkylamino diphenyl ethers having herbicidal activity |
Family Cites Families (5)
| 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 |
| DE2926472A1 (en) * | 1979-06-30 | 1981-01-15 | Thomae Gmbh Dr K | NEW BENZOYL DERIVATIVES, THEIR PRODUCTION AND THEIR USE AS MEDICINAL PRODUCTS |
| IL67445A (en) * | 1982-12-09 | 1985-11-29 | Teva Pharma | Ethoxycarbonyloxy ethyl esters of non-steroidal anti-inflammatory carboxylic acids |
| DE3476550D1 (en) * | 1983-07-21 | 1989-03-09 | Troponwerke Gmbh & Co Kg | Thermoplastics containing antiphlogistics |
| 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 |
-
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 (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| DE2834168A1 (en) * | 1978-08-04 | 1980-02-21 | Troponwerke Gmbh & Co Kg | METHOD FOR PRODUCING 2- (2-HYDROXYAETHOXY) AETHYL-N- (ALPHA, ALPHA, ALPHA -TRIFLUOR-M-TOLYL) ANTHRANILATE |
| 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 |
| DE2834169A1 (en) * | 1978-08-04 | 1980-02-21 | Troponwerke Gmbh & Co Kg | Hydroxy-ethoxy-ethyl N-tri:fluoromethyl-phenyl anthranilate prodn. - by converting corresp. acid to halide, then reaction with di:ethylene glycol |
| EP0149427A1 (en) * | 1983-12-20 | 1985-07-24 | Ciba-Geigy Ag | (Poly-)Oxyalkylamino diphenyl ethers having herbicidal activity |
Non-Patent Citations (1)
| Title |
|---|
| ARZNEIMITTELFORSCHUNG * |
Also Published As
| Publication number | Publication date |
|---|---|
| IT8621774A0 (en) | 1986-09-19 |
| GB8625481D0 (en) | 1986-11-26 |
| FR2589151B1 (en) | 1990-05-18 |
| IT8621774A1 (en) | 1988-03-19 |
| CH676238A5 (en) | 1990-12-28 |
| GB2182041A (en) | 1987-05-07 |
| GB2182041B (en) | 1989-09-20 |
| DE3636125A1 (en) | 1987-04-30 |
| PT81505A (en) | 1985-12-01 |
| JPS62106064A (en) | 1987-05-16 |
| IT1197255B (en) | 1988-11-30 |
| PT81505B (en) | 1987-11-11 |
| BE905666A (en) | 1987-02-16 |
| ES548226A0 (en) | 1986-03-16 |
| ES8605220A1 (en) | 1986-03-16 |
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| Date | Code | Title | Description |
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| ST | Notification of lapse |