DD239591A5 - PROCESS FOR THE PREPARATION OF 2,4-DICHLOR-5-FLUORO BENZOESAEURE - Google Patents
PROCESS FOR THE PREPARATION OF 2,4-DICHLOR-5-FLUORO BENZOESAEURE Download PDFInfo
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- DD239591A5 DD239591A5 DD85281050A DD28105085A DD239591A5 DD 239591 A5 DD239591 A5 DD 239591A5 DD 85281050 A DD85281050 A DD 85281050A DD 28105085 A DD28105085 A DD 28105085A DD 239591 A5 DD239591 A5 DD 239591A5
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- German Democratic Republic
- Prior art keywords
- dichloro
- fluoro
- formula
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- optionally
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- 238000000034 method Methods 0.000 title claims description 19
- 238000002360 preparation method Methods 0.000 title claims description 7
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 title 1
- 239000000460 chlorine Substances 0.000 claims abstract description 15
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000010933 acylation Effects 0.000 claims abstract description 12
- 238000005917 acylation reaction Methods 0.000 claims abstract description 12
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 12
- KZCWJHUTTSVCRO-UHFFFAOYSA-N 2,4-dichloro-5-fluorobenzoic acid Chemical compound OC(=O)C1=CC(F)=C(Cl)C=C1Cl KZCWJHUTTSVCRO-UHFFFAOYSA-N 0.000 claims abstract description 10
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012346 acetyl chloride Substances 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 4
- 238000002955 isolation Methods 0.000 claims abstract description 4
- FAKJFAMIABOKBW-UHFFFAOYSA-N 1-(2,4-dichloro-5-fluorophenyl)ethanone Chemical compound CC(=O)C1=CC(F)=C(Cl)C=C1Cl FAKJFAMIABOKBW-UHFFFAOYSA-N 0.000 claims abstract description 3
- BDJZCCWUSOZUQG-UHFFFAOYSA-N 2,4-dichloro-1-fluorobenzene Chemical compound FC1=CC=C(Cl)C=C1Cl BDJZCCWUSOZUQG-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000003085 diluting agent Substances 0.000 claims description 5
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000007796 conventional method Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 125000004201 2,4-dichlorophenyl group Chemical group [H]C1=C([H])C(*)=C(Cl)C([H])=C1Cl 0.000 abstract 1
- 239000007884 disintegrant Substances 0.000 abstract 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 11
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- NDBIFEJDDYXFGA-UHFFFAOYSA-N 3,5-dichloro-2-fluoro-5-(trichloromethyl)cyclohexa-1,3-diene Chemical compound ClC1(CC=C(C(=C1)Cl)F)C(Cl)(Cl)Cl NDBIFEJDDYXFGA-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- -1 aliphatic carboxylic acid halides Chemical class 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- NPXCSDPOOVOVDQ-UHFFFAOYSA-N 1,2-dichloro-3-fluorobenzene Chemical compound FC1=CC=CC(Cl)=C1Cl NPXCSDPOOVOVDQ-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000005171 halobenzenes Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- AYNNSCRYTDRFCP-UHFFFAOYSA-N triazene Chemical compound NN=N AYNNSCRYTDRFCP-UHFFFAOYSA-N 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/46—Friedel-Crafts reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/29—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with halogen-containing compounds which may be formed in situ
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Die vorliegende Erfindung betrifft ein neues Verfahren zur Herstellung von 2,4-Dichlor-5-fluorbenzoesaeure der Formel (I), welches dadurch gekennzeichnet ist, dass man 2,4-Dichlorflourbenzol mit Acetylchlorid, in Gegenwart von Acylierungskatalysatoren und gegebenenfalls in Gegenwart von Verduennungsmitteln, bei Temperaturen zwischen 10C und 150C umsetzt und das auf diese Weise entstandene Reaktionsprodukt 2,4-Dichlor-5-fluor-acetophenon der Formel (II), gegebenenfalls nach Isolierung, mit einer Natriumhypochloritloesung (in Form der sogenannten Chlorlauge), bei einer Temperatur zwischen 0C und 140C umsetzt. Formeln I und IIThe present invention relates to a novel process for preparing 2,4-dichloro-5-fluorobenzoic acid of the formula (I), which comprises reacting 2,4-dichlorophenyl borobenzene with acetyl chloride in the presence of acylation catalysts and optionally in the presence of disintegrants , Reacted at temperatures between 10C and 150C and the resulting reaction product 2,4-dichloro-5-fluoro-acetophenone of the formula (II), optionally after isolation, with a Natriumhypochloritloesung (in the form of the so-called chlorine solution), at a temperature between 0C and 140C. Formulas I and II
Description
λ Berlin, den 23. 9. 1985 65 885/11 λ Berlin, 23 September 1985 65 885/11
Verfahren zur Herstellung von 2,4-Dichlor-5-fluor-benzoesäureProcess for the preparation of 2,4-dichloro-5-fluoro-benzoic acid
Zwischenprodukt für die Herstellung von antibakteriellen Mitteln.Intermediate for the production of antibacterial agents.
Es ist bereits bekannt, daß Trihalogenbenzoesäuren durch Verseifung von Trihalogen-trihalogenmethyl-benzol hergestellt werden können· So wird bei der Verseifung von 2,4-Dichlor-5-fluor-trichlormethylbenzol, 2,4-Dlchlor-5-fluorbenzoesäure gebildet (EP-OS 78 362).It is already known that trihalobenzoic acids can be prepared by saponification of trihalogeno-trihalomethyl-benzene. Thus, in the saponification of 2,4-dichloro-5-fluoro-trichloromethylbenzene, 2,4-dichloro-5-fluorobenzoic acid is formed (EP- OS 78,362).
Weiterhin ist bekannt, daß die Acylierung mit aliphatischen Carbonsäurehalogeniden bei Dihalogenbenzolen sehr schwierig ist und bei Trihalogenbenzolen nicht stattfinden soll (vgl. Methoden der organischen Chemie (Houben-VVeyl-Müller) Band 7/2a, 43 (1973), Thieme-Verlag, Stuttgart).Furthermore, it is known that acylation with aliphatic carboxylic acid halides is very difficult with dihalobenzenes and should not take place with trihalogenobenzenes (compare Methods of Organic Chemistry (Houben-Vleyl-Muller) Vol 7 / 2a , 43 (1973), Thieme-Verlag, Stuttgart ).
Außerdem ist bekannt, daß bei der Acylierung mit Carbonsäureanhydriden, wie z. B. Essigsäureanhydrid, aus 2,4-It is also known that in the acylation with carboxylic anhydrides, such as. Acetic anhydride, from 2,4-
.» - r r»R
2 39 59 I2 39 59 I
Dichlorfluorbenzol, in Gegenwart von Aluminiumtrichlorid, in schlechter Ausbeute 2,4-Dichlor-5-flupr-acetophenon erhalten wird (vgl. CA 58, 11243 g).Dichlorofluorobenzene, in the presence of aluminum trichloride, is obtained in poor yield 2,4-dichloro-5-flupr-acetophenone (see CA 58, 11243 g).
Ziel der Erfindung Purpose of the invention
Überraschenderweise wurde nun gefunden, daß man 2,4-Dichlor-5-fluorbenzoesäure der Formel (I)Surprisingly, it has now been found that 2,4-dichloro-5-fluorobenzoic acid of the formula (I)
ClCl
Cl_/Tw_COOH (I) *Cl_ / Tw_COOH (I) *
in sehr guter Ausbeute und hoher Reinheit erhält, wenn man 2,4-Dichlor-fluorbenzol mit Acetylchlorid, in Gegenwart von Acylierungskatalysatoren und gegebenenfalls in Gegenwart von Verdünnungsmitteln, bei Temperaturen zwischen 10 C und 150 0C umsetzt und das auf diese Weise entstandene Reaktions· produkt 2,4-Dichlor-5-fluor-acetophenon der Formel (II)in very good yield and high purity, when reacting 2,4-dichloro-fluorobenzene with acetyl chloride, in the presence of acylation catalysts and optionally in the presence of diluents, at temperatures between 10 C and 150 0 C and the resulting reaction · Product 2,4-dichloro-5-fluoro-acetophenone of the formula (II)
(II)(II)
gegebenenfalls nach Isolierung, mit einer Natriumhypochlo· ritlösung (in Form der sogenannten Chlorlauge), bei einer Temperatur zwischen 0 0C und 140 0C umsetzt.optionally after isolation, with a sodium hypochlorite solution (in the form of the so-called chlorine liquor), at a temperature between 0 0 C and 140 0 C reacted.
Überraschenderweise gelingt es, mit Hilfe des erfindungsgemäßen Verfahrens eine Acylierung von 2,4-Dichlorfluorbenzol mit einem Carbonsäurechlorid in meta-Stellung zumSurprisingly, it is possible with the aid of the inventive method, an acylation of 2,4-dichlorofluorobenzene with a carboxylic acid chloride in the meta position to
elektronegativeren Halogen in hoher Ausbeute und Selektivität durchzuführen. Dies ist umso überraschender, als nach dem Stand der Technik bei der Acylierung von Halogenbenzolen die Acylierung in ortho- oder para-Stellung vom elektronegativeren Halogen hätte erwartet werden müssen (vergl. Methoden der organischen Chemie (Houben-Weyl-Müller) Band 7/2a 43 (1973), Thieme-Verlag, Stuttgart).perform electronegativeren halogen in high yield and selectivity. This is all the more surprising since in the acylation of halobenzenes according to the prior art, the acylation in the ortho or para position of the electronegativeren halogen should have been expected (see Methods of Organic Chemistry (Houben-Weyl-Müller) Volume 7 / 2a 43 (1973), Thieme Verlag, Stuttgart).
Die oben genannten bekannten Verfahren besitzen eine Reihe von Nachteilen. So wird bei der Herstellung von 2,4-Dichlor-5-fluor-trichlormethvlbenzol als Zwischenprodukt ein Triazen hergestellt, das sich wegen seiner ungünstigen physiologischen Eigenschaften nur schwierig handhaben läßt.The above known methods have a number of disadvantages. Thus, in the preparation of 2,4-dichloro-5-fluoro-trichloromethvlbenzol a triazene is produced as an intermediate, which is difficult to handle because of its unfavorable physiological properties.
Weiterhin sind nach diesem Verfahren für die Herstellung von 2,4-Dichlor-5-fluor-benzoesäure mehrere Stufen erforderlich.Furthermore, several steps are required by this process for the preparation of 2,4-dichloro-5-fluoro-benzoic acid.
Bei der in der Literatur beschriebenen Acylierung von 2,4-Dichlor-5-fluorbenzol in Gegenwart von Essigsäureanhydrid ist die Ausbeute an Reaktionsprodukt sehr gering.In the acylation of 2,4-dichloro-5-fluorobenzene described in the literature in the presence of acetic anhydride, the yield of reaction product is very low.
Verwendet man 2,4-Dichlor-fluorbenzol und Acetylchlorid als Ausgangsstoffe, Aluminiumchlorid als Katalysator und Chlorlauge, so kann der Reaktionsverlauf durch das folgende Forme!schema wiedergegeben werden:If 2,4-dichloro-fluorobenzene and acetyl chloride are used as starting materials, aluminum chloride as catalyst and chlorine liquor, the course of the reaction can be represented by the following formula:
+ CH3-CO-Cl+ CH 3 -CO-Cl
AlCl,AlCl,
2,4-Dichlor-fluorbenzol ist eine bekannte Verbindung der organischen Chemie.2,4-dichloro-fluorobenzene is a known compound of organic chemistry.
Die Reaktionstemperatur kann in einem größeren Bereich variiert werden. So arbeitet man bei der Acylierung im allgemeinen bei Temperaturen zwischen 100C und 1500C, vorzugsweise zwischen 2O0C und 13O0C, insbesondere zwischen 8O0C und 13O0C. Die anschließende Oxidation mit der sogenannten Chlorlauge wird im allgemeinen bei Temperaturen zwischen 00C und 14O0C, vorzugsweise zwischen 2O0C und 12O0C durchgeführt. Die Reaktion wird im allgemeinen bei Normaldruck durchgeführt.The reaction temperature can be varied within a wide range. So you work in the acylation generally at temperatures between 10 0 C and 150 0 C, preferably between 2O 0 C and 13O 0 C, in particular between 8O 0 C and 13O 0 C. The subsequent oxidation with the so-called chlorine is generally at Temperatures between 0 0 C and 14O 0 C, preferably carried out between 2O 0 C and 12O 0 C. The reaction is generally carried out at atmospheric pressure.
Das erfindungsgemäße Verfahren wird vorzugsweise ohne Verdünnungsmittel durchgeführt.The process according to the invention is preferably carried out without a diluent.
Als Katalysator kommen für das erfindungsgemäße Verfahren Acylierungskatalysatoren in Frage wie z.B. Eisen-(III)-Chlorid, Zinkchlorid oder Aluminiumchlorid, vorzugsweise Aluminiumchlorid.Suitable catalysts for the process according to the invention are acylation catalysts, such as, for example, Iron (III) chloride, zinc chloride or aluminum chloride, preferably aluminum chloride.
Als Oxidationsmittel kommt für das erfindungsgemäße Verfahren die sogenannte Chlorlauge, eine Natriumhypochloritlösung in Wasser in Betracht.Suitable oxidizing agents for the process according to the invention are the so-called chlorine liquor, a sodium hypochlorite solution in water.
Bel der Durchführung des erfindüngsgemäBen Verfahrens setzt man im allgemeinen auf 1 Mol 2,4-Dichlor-fluorbenzol, 1 bis 3 Mol Acetylchlorid und 1 bis 3 Mol Aluminiumchlorid ein. Nach beendeter Reaktion wird das Reaktions-gemisch auf Eis gegeben und in einem mit Wasser nicht mischbaren Verdünnungsmittel, wie z.B. Methylenchlorid oder Chloroform, aufgenommen. Das Reaktionsprodukt kann aber auch ohne Verwendung von Verdünnungsmitteln abgetrennt werden. Gegebenenfalls nach Entfernen des Extrak-tionsmittel wird der Rückstand in Gegenwart von 2 bis 4 1, vorzugsweise 2,1 bis 3,3 1 Chlorlauge (150 g aktives Chlor/1) pro Mol Ausgangsprodukt oxidiert. Anschließend wird die 2,4-Dichlor-5-fluor-benzolsäure mit einer Mineralsäure, wie z.B. Salzsäure, ausgefällt und dann abge-saugt.In carrying out the erfindüngsgemäBen method is generally used to 1 mole of 2,4-dichloro-fluorobenzene, 1 to 3 moles of acetyl chloride and 1 to 3 moles of aluminum chloride. After completion of the reaction, the reaction mixture is poured on ice and dissolved in a water-immiscible diluent, such as e.g. Methylene chloride or chloroform. The reaction product can also be separated without the use of diluents. Optionally, after removal of the extractant, the residue is oxidized in the presence of 2 to 4 l, preferably 2.1 to 3.3 l of chlorine solution (150 g of active chlorine / l) per mole of starting material. Subsequently, the 2,4-dichloro-5-fluoro-benzoic acid is treated with a mineral acid, e.g. Hydrochloric acid, precipitated and then sucked off.
Die nach dem erfindungsgemäßen Verfahren leicht zugängliche 2,4-Dichlor-5-fluor-benzoesäure läßt sich beispielsweise zur Synthese von antibakteriellen Mitteln einsetzen. So lassen sich aus dieser Säure z.B. gemäß folgenden Gleichungen, die substituierten Oxochinolincarbonsäuren, Verbindungen mit hoher bakteriziden Potenz, herstellen (vgl. z.B. EP-OS 78 362):The readily available by the process according to the invention 2,4-dichloro-5-fluoro-benzoic acid can be used for example for the synthesis of antibacterial agents. Thus, from this acid, e.g. according to the following equations producing substituted oxoquinolinecarboxylic acids, compounds having high bactericidal potency (see for example EP-OS 78 362):
Xlxl
soc_i2—> nV/\Vcocisoc_i2-> nV / \ Vcoci
OC2H5 OC 2 H 5
,Cl CH Ci-^W)-CO-U-COOC2H5 , Cl CH Ci- ^ W) -CO-U-COOC 2 H 5
Cl CH CO-U-COOC2H5 Cl CH CO-U-COOC 2 H 5
R = H, AlkylR = H, alkyl
(i)(I)
Eine Mischung aus 33 g (0,2 Mol) 2,4-Dichlor-fluorbenzol und 66,8 g (0,5 Mol) Aluroiniumchlorid wird bei 2O0C bis400C mit 23,6 g (0,3 Mol) Acetylchlorid versetzt und dann 2 Stunden bei 1200C gerührt. Die noch heiße Mischung wird auf 250 g Eis gegeben und das sich abscheidende 01 in Methylenchlorid aufgenommen. Das Lösungsmittel wird abgedampft und der Rückstand wird mit 450 ml Chlorlauge (150 σaktives Chlor/1) versetzt und erst 1 Stunde ohne Heizung gerührt und dann 2 Stunden unter Rückfluß gekocht. Nach Abtrennen des entstandenen Chloroforms gibt man 300 ml Wasser zu, versetzt mit 10 ml 40 %iger Natriumhydrogensulfit-Lösung und anschließend mit konzentrierter SaIz-säure bis ein pH-Wert 1 erreicht wird.A mixture of 33 g (0.2 mol) of 2,4-dichloro-fluorobenzene and 66.8 g (0.5 mol) of aluminum chloride is added at 2O 0 C to 40 0 C with 23.6 g (0.3 mol) of acetyl chloride and then stirred for 2 hours at 120 0 C stirred. The still hot mixture is added to 250 g of ice and the precipitating 01 taken up in methylene chloride. The solvent is evaporated and the residue is mixed with 450 ml of chlorine solution (150 active chlorine / 1) and stirred for 1 hour without heating and then boiled under reflux for 2 hours. After separating the resulting chloroform are added to 300 ml of water, mixed with 10 ml of 40% sodium bisulfite solution and then with concentrated hydrochloric acid until a pH of 1 is reached.
Man erhält auf diese Weise 33,5 g (80 % der Theorie) 2,4-Dichlor-5-fluor-benzoesäure als farbloses Pulver vom Schmelzpunkt 139°C.Obtained in this way 33.5 g (80% of theory) of 2,4-dichloro-5-fluoro-benzoic acid as a colorless powder of melting point 139 ° C.
Claims (5)
Natriumhypochloritlösung (Chlorlauge) umgesetzt wird.5. The method according to item 1 to 4, characterized in that the resulting in the course of the process 2,4-dichloro ^ - fluoro-acetophenone without isolation with the
Sodium hypochlorite solution (chlorine liquor) is reacted.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19843435392 DE3435392A1 (en) | 1984-09-27 | 1984-09-27 | METHOD FOR THE PRODUCTION OF 2,4-DICHLOR-5-FLUOR-BENZOESAEEURE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DD239591A5 true DD239591A5 (en) | 1986-10-01 |
Family
ID=6246450
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DD85281050A DD239591A5 (en) | 1984-09-27 | 1985-09-26 | PROCESS FOR THE PREPARATION OF 2,4-DICHLOR-5-FLUORO BENZOESAEURE |
Country Status (21)
| Country | Link |
|---|---|
| EP (1) | EP0176026B1 (en) |
| JP (1) | JPH0647568B2 (en) |
| KR (1) | KR910008936B1 (en) |
| AU (1) | AU569176B2 (en) |
| CA (1) | CA1255330A (en) |
| DD (1) | DD239591A5 (en) |
| DE (2) | DE3435392A1 (en) |
| DK (1) | DK166411B1 (en) |
| ES (1) | ES8605462A1 (en) |
| FI (1) | FI86413C (en) |
| GR (1) | GR852346B (en) |
| HU (1) | HU193345B (en) |
| IE (1) | IE72493B1 (en) |
| IL (1) | IL76466A (en) |
| NO (1) | NO159080C (en) |
| NZ (1) | NZ213599A (en) |
| PH (1) | PH24252A (en) |
| PT (1) | PT81144B (en) |
| SU (1) | SU1470175A3 (en) |
| UA (1) | UA8020A1 (en) |
| ZA (1) | ZA857432B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4791225A (en) * | 1986-01-20 | 1988-12-13 | Kyorin Pharmaceutical Co., Ltd. | Halogenobenzoic acid derivatives and their preparation |
| DE3641099A1 (en) * | 1986-12-02 | 1988-06-09 | Hoechst Ag | METHOD FOR PRODUCING 4- (2'-CHLORETHYL) BENZOESIC ACID |
| DE3840371A1 (en) * | 1988-11-30 | 1990-05-31 | Lentia Gmbh | Process for the preparation of 2,4,5-trifluorobenzoic acid |
| US4996355A (en) * | 1989-04-14 | 1991-02-26 | Mallinckrodt, Inc. | Novel intermediates for the production of 2,4,5-trifluorobenzoyl fluoride |
| DE3925036A1 (en) * | 1989-07-28 | 1991-01-31 | Riedel De Haen Ag | METHOD FOR PRODUCING FLUORINATED BENZOESAURS |
| GB9107684D0 (en) * | 1991-04-11 | 1991-05-29 | Berge Richard | Panel system |
| DE19617558A1 (en) * | 1996-05-02 | 1997-11-06 | Hoechst Ag | Process for the preparation of 4,5-dichloro-2-methylbenzoic acid |
| DE19733243A1 (en) | 1997-08-01 | 1999-02-04 | Bayer Ag | Process for the preparation of 3-cyano-2,4-dihalogen-5-fluoro-benzoic acid |
| RU2155185C1 (en) * | 1999-03-24 | 2000-08-27 | Новосибирский институт органической химии им. Н.Н. Ворожцова СО РАН | Method of preparing partially fluorinated benzoic acids |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2412855C2 (en) * | 1974-03-18 | 1983-03-31 | Basf Ag, 6700 Ludwigshafen | Process for the production of carboxylic acids |
| DE3035355A1 (en) * | 1980-09-19 | 1982-04-29 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING 3-BROMO-4-FLUORO-BENZOESIC ACID |
| DE3248505A1 (en) * | 1982-12-29 | 1984-07-05 | Bayer Ag, 5090 Leverkusen | 1-CYCLOPROPYL-6-FLUOR-1,4-DIHYDRO-4-OXO-7 (4- (OXOALKYL) -1-PIPERAZINYL / -3-QUINOLINE CARBONIC ACIDS AND THEIR DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF, AND THEIR CONTAINERS |
| DE3248506A1 (en) * | 1982-12-29 | 1984-07-05 | Bayer Ag, 5090 Leverkusen | 1-CYCLOPROPYL-6-FLUOR-1,4-DIHYDRO-4-OXO-7 (ALKYL-1-PIPERAZINYL) -3-CHINOLINE CARBONIC ACIDS, METHOD FOR THE PRODUCTION THEREOF AND THEIR CONTAINING ANTIBACTERIAL AGENTS |
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1984
- 1984-09-27 DE DE19843435392 patent/DE3435392A1/en not_active Withdrawn
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1985
- 1985-09-11 SU SU853950798A patent/SU1470175A3/en active
- 1985-09-11 UA UA3950798A patent/UA8020A1/en unknown
- 1985-09-13 NO NO853605A patent/NO159080C/en not_active IP Right Cessation
- 1985-09-17 PT PT81144A patent/PT81144B/en not_active IP Right Cessation
- 1985-09-18 DE DE8585111789T patent/DE3561054D1/en not_active Expired
- 1985-09-18 EP EP85111789A patent/EP0176026B1/en not_active Expired
- 1985-09-23 IL IL76466A patent/IL76466A/en not_active IP Right Cessation
- 1985-09-24 NZ NZ213599A patent/NZ213599A/en unknown
- 1985-09-24 JP JP60209034A patent/JPH0647568B2/en not_active Expired - Lifetime
- 1985-09-24 KR KR1019850006988A patent/KR910008936B1/en not_active Expired
- 1985-09-25 AU AU47924/85A patent/AU569176B2/en not_active Ceased
- 1985-09-25 CA CA000491506A patent/CA1255330A/en not_active Expired
- 1985-09-25 FI FI853686A patent/FI86413C/en not_active IP Right Cessation
- 1985-09-26 IE IE238085A patent/IE72493B1/en not_active IP Right Cessation
- 1985-09-26 HU HU853691A patent/HU193345B/en not_active IP Right Cessation
- 1985-09-26 ES ES547345A patent/ES8605462A1/en not_active Expired
- 1985-09-26 DD DD85281050A patent/DD239591A5/en not_active IP Right Cessation
- 1985-09-26 PH PH32852A patent/PH24252A/en unknown
- 1985-09-26 GR GR852346A patent/GR852346B/el unknown
- 1985-09-26 DK DK436685A patent/DK166411B1/en not_active IP Right Cessation
- 1985-09-26 ZA ZA857432A patent/ZA857432B/en unknown
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Legal Events
| Date | Code | Title | Description |
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| A5 | Published as prov. exclusive patent | ||
| ENJ | Ceased due to non-payment of renewal fee |