DK166411B1 - METHOD OF PREPARING 2,4-DICHLOR-5-FLUORO-BENZOIC ACID - Google Patents
METHOD OF PREPARING 2,4-DICHLOR-5-FLUORO-BENZOIC ACID Download PDFInfo
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- DK166411B1 DK166411B1 DK436685A DK436685A DK166411B1 DK 166411 B1 DK166411 B1 DK 166411B1 DK 436685 A DK436685 A DK 436685A DK 436685 A DK436685 A DK 436685A DK 166411 B1 DK166411 B1 DK 166411B1
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- Prior art keywords
- fluoro
- dichloro
- benzoic acid
- reaction
- process according
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 16
- 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 title claims description 9
- 239000000460 chlorine Substances 0.000 claims description 18
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 11
- 229910052801 chlorine Inorganic materials 0.000 claims description 11
- 230000010933 acylation Effects 0.000 claims description 10
- 238000005917 acylation reaction Methods 0.000 claims description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- BDJZCCWUSOZUQG-UHFFFAOYSA-N 2,4-dichloro-1-fluorobenzene Chemical compound FC1=CC=C(Cl)C=C1Cl BDJZCCWUSOZUQG-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims description 6
- 239000012346 acetyl chloride Substances 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 5
- 239000003085 diluting agent Substances 0.000 claims description 5
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 5
- 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 description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000002955 isolation Methods 0.000 claims description 3
- 238000007796 conventional method Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 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
- 238000002360 preparation method Methods 0.000 description 5
- 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
- -1 aliphatic carboxylic acid halides Chemical class 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 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
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 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
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 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
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material 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)
Description
i DK 166411 B1 oin DK 166411 B1 o
Den foreliggende opfindelse angår en særlig fremgangsmåde til fremstilling af 2,4-dichlor-5-fluor-benzoe-syre, et mellemprodukt til fremstillingen af antibakteriel-le midler.The present invention relates to a particular process for the preparation of 2,4-dichloro-5-fluoro-benzoic acid, an intermediate for the preparation of antibacterial agents.
5 Det er allerede kendt, at trihalogenbenzoesyrer.5 It is already known that trihalobenzoic acids.
kan fremstilles ved forsæbning af trihalogen-trihalogen-methyl-benzen. Således dannes der ved forsæbningen af 2,4--dichlor-5-fluor-trichlormethylbenzen 2,4-dichlor-5-fluor--benzoesyre, jvf. EP nr. 78.362.can be prepared by saponification of trihalo-trihalo-methyl-benzene. Thus, by the saponification of 2,4 - dichloro-5-fluoro-trichloromethylbenzene, 2,4-dichloro-5-fluoro - benzoic acid is formed, cf. EP No. 78,362.
10 Endvidere er det kendt, at acyleringen med alipha- tiske carboxylsyrehalogenider ved dihalogenbenzener er særdeles vanskelig og ikke skal finde sted ved trihalogenben-zener, jvf. Methoden der organischen Chemie (Houben-Weyl-Miil-ler) bind 7/2a, 43 (1973), Thieme-Verlag, Stuttgart.Furthermore, it is known that the acylation with aliphatic carboxylic acid halides by dihalogenbenzenes is extremely difficult and should not take place in trihalogenbenzenes, cf. the method of Organic Chemie (Houben-Weyl-Miiller) Volume 7/2a, 43 ( 1973), Thieme-Verlag, Stuttgart.
15 Desuden er det kendt, at man ved acyleringen med carboxylsyreanhydrider, såsom eddikesyreanhydrid, ud fra 2.4- dichlorfluorbenzen, i nærværelse af aluminiumtrichlo-rid, får 2,4-dichlor-5-fluor-acetophenon i dårligt udbytte, jvf. CA 58, 11243 g.In addition, it is known that in the acylation with carboxylic anhydrides, such as acetic anhydride, from 2,4-dichlorofluorobenzene, in the presence of aluminum trichloride, 2,4-dichloro-5-fluoroacetophenone is obtained in poor yield, cf. CA 58, 11243 g.
20 Overraskende har det nu vist sig, at man får 2,4- -dichlor-5-fluorbenzoesyre med formlenSurprisingly, it has now been found that 2,4- dichloro-5-fluorobenzoic acid of the formula
Cl-//\\-C00HCl - // \\ - C00H
r 25 i særdeles godt udbytte og høj renhed ved, at man omsætter 2.4- dichlor-fluorbenzen med acetylchlorid, i nærværelse af acyleringskatalysatorer og eventuelt i nærværelse af fortyndingsmidler, ved temperaturer mellem 10°C og 150°C, og omsætter det på denne måde dannede reaktionsprodukt 30 2,4-dichlor-5-fluor-acetophenon med formlenr 25 in very good yield and high purity by reacting 2.4-dichlorofluorobenzene with acetyl chloride, in the presence of acylation catalysts and optionally in the presence of diluents, at temperatures between 10 ° C and 150 ° C, and reacting in this way reaction product formed 2,4-dichloro-5-fluoroacetophenone of the formula
Cl-Ø-CQ-CH, (II) 35 eventuelt efter isolering, med en natriumhypochloritopløs-ning (i form af den såkaldte chlorlud), ved en temperatur mellem 0°C og 140°C.Optionally after isolation, with a sodium hypochlorite solution (in the form of the so-called chlorine liquor), at a temperature between 0 ° C and 140 ° C.
OISLAND
DK 166411 B1 2DK 166411 B1 2
Det lykkes overraskende, ved hjælp af fremgangsmåden ifølge opfindelsen, at udføre en acylering af 2,4-dichlor--fluorbenzen med et carboxylsyrechlorid i meta-stilling til det mere elektronegative halogen med højt udbytte og 5 selektivitet. Dette er så meget mere overraskende, da man ifølge teknikkens stade ved acyleringen af halogenbenzener måtte have forventet en acylering i ortho- eller para-stil-ling af det mere elektronegative halogen, jvf. Methoden der organischen Chemie (Houben-Weyl-Miiller) bind 7/2a 43 (1973) , 10 Thieme-Verlag, Stuttgart.Surprisingly, by the process of the invention, we succeed in performing an acylation of 2,4-dichlorofluorobenzene with a carboxylic acid chloride in meta position to the more electronegative halogen with high yield and selectivity. This is all the more surprising, since according to the state of the art, when acylating halogen benzenes, one would have expected an acylation in the ortho or para position of the more electronegative halogen, cf. the method of the Organic Chemie (Houben-Weyl-Miiller) 7 / 2a 43 (1973), 10 Thieme-Verlag, Stuttgart.
De ovennævnte kendte fremgangsmåder har en række ulemper. Således fremstilles der ved fremstillingen af 2,4-dichlor-5-fluor-trichlormethylbenzen som mellemprodukt en triazen, som kun vanskeligt lader sig håndtere på grund 15 af sine ugunstige fysiologiske egenskaber.The above known methods have a number of disadvantages. Thus, in the preparation of 2,4-dichloro-5-fluoro-trichloromethylbenzene, an intermediate is produced a triazene which is difficult to handle only because of its unfavorable physiological properties.
Endvidere er flere trin nødvendige ved denne fremgangsmåde til fremstillingen af 2,4-dichlor-5-fluor-benzoe-syre.Furthermore, several steps are required in this process for the preparation of 2,4-dichloro-5-fluoro-benzoic acid.
Ved den i litteraturen beskrevne acylering af 2,4-20 -dichlor-5-fluorbenzen i nærværelse af eddikesyreanhydrid er udbyttet af reaktionsprodukt særdeles ringe.In the acylation of 2,4-20-dichloro-5-fluorobenzene described in the literature in the presence of acetic anhydride, the yield of reaction product is extremely poor.
Anvender man 2,4-dichlor-fluorbenzen og acetyl-chlorid som udgangsstoffer, aluminiumchlorid som katalysator og chlorlud, kan reaktionsforløbet gengives således 25 ved det følgende reaktionsskema:If 2,4-dichlorofluorobenzene and acetyl chloride are used as starting materials, aluminum chloride as catalyst and chlorine liquor, the course of the reaction can thus be represented by the following reaction scheme:
Cl -Cl ♦ CHj-CO-Cl A1Cls— > Cl-^^-CO-CHj 30 - —Cl -Cl ♦ CH2-CO-Cl A1Cls—> Cl - ^^ - CO-CHj 30 - -
Chlorlud-> Cl-^^COOHChlorlud-> Cl - ^^ COOH
2,4-Dichlor-fluorbenzen er en kendt forbindelse i 35 den organiske kemi.2,4-Dichlorofluorobenzene is a known compound in organic chemistry.
OISLAND
DK 166411 B1 3DK 166411 B1 3
Reaktionstemperaturen kan varieres inden for et større område. Man arbejder ved acyleringen almindeligvis således ved temperaturer mellem 10°C og lSO^C, fortrinsvis mellem 20°C og 130°C, især mellem 80°C og 130°C. Den føl-5 gende oxidation med den såkaldte chlorlud gennemføres almindeligvis ved temperaturer mellem 0°C og 140°C, fortrinsvis mellem 20°C og 120°C. Reaktionen gennemføres almindeligvis ved normalt tryk.The reaction temperature can be varied within a larger range. Thus, the acylation is generally employed at temperatures between 10 ° C and 10 ° C, preferably between 20 ° C and 130 ° C, especially between 80 ° C and 130 ° C. The subsequent oxidation with the so-called chlorine liquor is generally carried out at temperatures between 0 ° C and 140 ° C, preferably between 20 ° C and 120 ° C. The reaction is usually carried out under normal pressure.
Fremgangsmåden ifølge opfindelsen gennemføres for-10 trinsvis uden fortyndingsmidler.The process of the invention is preferably carried out without diluents.
Som katalysator kommer på tale til fremgangsmåden ifølge opfindelsen acyleringskatalysatorer, såsom jern-III--chlorid/ zinkchlorid eller alminiumchlorid, fortrinsvis alminiumchlorid.As the catalyst, the process of the invention is acylation catalysts such as ferric III chloride / zinc chloride or alminium chloride, preferably alminium chloride.
15 Som oxidationsmiddel kommer i betragtning til frem gangsmåden ifølge opfindelsen den såkaldte chlorlud, en na-triumhypochlorit-opløsning i vand.As the oxidizing agent, the so-called chlorine liquor, a sodium hypochlorite solution in water, is considered in the present invention.
Ved gennemføringen af fremgangsmåden ifølge opfindelsen anvender man almindeligvis pr. mol 2,4-dichlor-fluor-20 benzen fra 1 til 3 mol acetylchlorid og fra 1 til 3 mol al-uminiumchlorid. Efter at reaktionen er tilendebragt, sættes reaktionsblandingen til is og tages op i et med vand ikke--blandbart fortyndingsmiddel, såsom methylenchlorid eller chloroform. Reaktionsproduktet kan imidlertid også skilles 25 fra uden anvendelse af fortyndingsmidler. Eventuelt efter fjerhelse af ekstraktionsmidlet oxideres remanensen i nærværelse af fra 2 til 4 liter, fortrinsvis fra 2,1 til 3,3 liter chlorlud (150 g aktivt chlor pr. liter) pr. mol udgangsprodukt. Derpå fældes 2,4-dichlor-5-fluor-benzoesyren 30 ud med en mineralsyre, såsom saltsyre, og skilles derpå fra ved sugning.In carrying out the method according to the invention, one is usually used per moles of 2,4-dichlorofluorobenzene from 1 to 3 moles of acetyl chloride and from 1 to 3 moles of aluminum chloride. After the reaction is complete, the reaction mixture is added to ice and taken up in a water immiscible diluent such as methylene chloride or chloroform. However, 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 from 2 to 4 liters, preferably from 2.1 to 3.3 liters of chlorine liquor (150 g of active chlorine per liter) per liter. moles of starting product. The 2,4-dichloro-5-fluoro-benzoic acid 30 is then precipitated with a mineral acid such as hydrochloric acid and then separated by suction.
Den ved fremgangsmåden ifølge opfindelsen let tilgængelige 2,4-dichlor-5-fluor-benzoesyre lader sig eksempelvis anvende til syntese af antibakterielle midler. Man 35 kan således ud fra denne syre fremstille de substituerede oxoquinolincarboxylsyrer, forbindelser med højt baktericid potens, ifølge følgende ligninger, jvf. eksempelvis EP nr. 78.362: DK 166411 B1 4 oThe 2,4-dichloro-5-fluoro-benzoic acid readily available in the process of the invention can be used, for example, for the synthesis of antibacterial agents. Thus, from this acid, the substituted oxoquinoline carboxylic acids, compounds of high bactericidal potency, can be prepared according to the following equations, cf., for example, EP No. 78.362: DK 166411 B1 4 o
Cl^COOH SOCI2—> C1^C0CI CH?(C00C2H5)2—> f3—f F' 5 /-rcl . /-^1Cl 2 COOH SOCl 2 -> C 1 C0Cl CH 2 (C00 C 2 H 5) 2 -> f 3 - f F '5 / -rcl. / - ^ 1
Cl -y'^V-CO-CH( COOC2H5 )2 --> Ciy/_\\-C0-CH2-C00C2H5 p3—' F3—' OC2H5 HCtOCiiHfiJa > ci-^ioi-cooc2H5 > HN-O 0Cl -y '^ V-CO-CH (COOC2H5) 2 -> Ciy / _ \\ - C0-CH2-C00C2H5 p3—' F3— 'OC2H5 HCtOCiiHfiJa> ci- ^ ioi-cooc2H5> HN-O 0
Cl CH J.CDOC2H5 ci-^^-cd-i!-cooc2H5 ^Β£ί—> i^T 1 -> k 20 0 oCl CH J.CDOC2H5 ci - ^^ - cd-i! -Cooc2H5 ^ Β £ ί—> i ^ T 1 -> k 20 0 o
RN NH F -^XnOOHRN NH F - ^ XnOOH
~\,&0~ \, & 0
1 RN N J1 RN N J
Å w Å 25 R = H, Alkyl FremstillingseksempelÅ w Å 25 R = H, Alkyl Preparation Example
C1-/^V)-C00HC 1 - / V ^) -C00H
30 F'- ^30 F'- ^
Til en blanding af 33 g (0,2 mol) 2,4-dichlor-fluor-benzen og 66,8 g (0,5 mol) aluminiumchlorid ved fra 20°C til 40°C sættes der 23,6 g (0,3 mol) acetyichlorid, og der omrøres derpå i 2 timer ved 120°C. Den endnu varme blanding sættes 35 til 250 g is, og den olie, som udskiller sig, tages op i methylenclorid. Opløsningsmidlet bortdampes, og der sættes 450 ml chlorlud (150 g aktivt chlor pr. liter) til remanen- 5 DK 1 6ό4ί Ί ΒΊ Ο sen og omrøres først i 1 time uden opvarmning og koges derpå i 2 timer ved tilbagesvaling. Efter fraskillelse af den dannede chloroform tilsætter man 300 ml vand, der tilsættes 10 ml 40%'s natriumhydrogensulfit-opløsning og derpå 5 koncentreret saltsyre, indtil man opnår en pH-værdi på 1.To a mixture of 33 g (0.2 mole) of 2,4-dichlorofluorobenzene and 66.8 g (0.5 mole) of aluminum chloride at from 20 ° C to 40 ° C is added 23.6 g (0 (3 moles) of acetylchloride and then stirred for 2 hours at 120 ° C. The still hot mixture is added 35 to 250 g of ice and the oil separating is taken up in methylene chloride. The solvent is evaporated and 450 ml of chlorine liquor (150 g of active chlorine per liter) is added to the residue and first stirred for 1 hour without heating and then boiled for 2 hours at reflux. After separation of the chloroform formed, 300 ml of water is added, 10 ml of 40% sodium hydrogen sulfite solution and then 5 concentrated hydrochloric acid are added until a pH of 1 is reached.
Man får på denne måde 33,5 g (80% af teorien) 2,4--dichlor-5-flour-benzoesyre som farveløst pulver med et smeltepunkt på 139°C.This gives 33.5 g (80% of theory) of 2,4-dichloro-5-fluorobenzoic acid as a colorless powder, mp 139 ° C.
10 15 20 25 30 3510 15 20 25 30 35
Claims (5)
Applications Claiming Priority (2)
| 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 |
| DE3435392 | 1984-09-27 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK436685D0 DK436685D0 (en) | 1985-09-26 |
| DK436685A DK436685A (en) | 1986-03-28 |
| DK166411B1 true DK166411B1 (en) | 1993-05-17 |
Family
ID=6246450
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK436685A DK166411B1 (en) | 1984-09-27 | 1985-09-26 | METHOD OF PREPARING 2,4-DICHLOR-5-FLUORO-BENZOIC ACID |
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 |
-
1984
- 1984-09-27 DE DE19843435392 patent/DE3435392A1/en not_active Withdrawn
-
1985
- 1985-09-11 UA UA3950798A patent/UA8020A1/en unknown
- 1985-09-11 SU SU853950798A patent/SU1470175A3/en active
- 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 EP EP85111789A patent/EP0176026B1/en not_active Expired
- 1985-09-18 DE DE8585111789T patent/DE3561054D1/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 FI FI853686A patent/FI86413C/en not_active IP Right Cessation
- 1985-09-25 CA CA000491506A patent/CA1255330A/en not_active Expired
- 1985-09-26 ES ES547345A patent/ES8605462A1/en not_active Expired
- 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 DD DD85281050A patent/DD239591A5/en not_active IP Right Cessation
- 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 PH PH32852A patent/PH24252A/en unknown
- 1985-09-26 ZA ZA857432A patent/ZA857432B/en unknown
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