CA1255330A - Process for the preparation of 2,4-dichloro-5-fluoro- benzoic acid - Google Patents
Process for the preparation of 2,4-dichloro-5-fluoro- benzoic acidInfo
- Publication number
- CA1255330A CA1255330A CA000491506A CA491506A CA1255330A CA 1255330 A CA1255330 A CA 1255330A CA 000491506 A CA000491506 A CA 000491506A CA 491506 A CA491506 A CA 491506A CA 1255330 A CA1255330 A CA 1255330A
- Authority
- CA
- Canada
- Prior art keywords
- fluoro
- dichloro
- benzoic acid
- preparation
- temperature
- 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.)
- Expired
Links
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
Abstract
ABSTRACT
A process for the preparation of 2,4-dichloro-5-fluoro-benzoic acid of the formula which comprises reacting acetyl chloride with 2,4-dichlorofluorobenzene in the presence of an acylation catalyst at a temperature between 10°C
and 150°C to produce 2,4-dichloro-5-fluoro-acetophenone of the formula
A process for the preparation of 2,4-dichloro-5-fluoro-benzoic acid of the formula which comprises reacting acetyl chloride with 2,4-dichlorofluorobenzene in the presence of an acylation catalyst at a temperature between 10°C
and 150°C to produce 2,4-dichloro-5-fluoro-acetophenone of the formula
Description
33~
The present invention relates to a new process for ~he preparation of 2,4-dichloro-5-fluoro~benzoic acid, ~hich is an intermediate product for the preparation of anti-bacterial agents~
It is already known that trihalogenobenzo;c acids can be prepared by saponificat;on of a tr;haLogeno-tri-halogenomethyl~benzene. Thus~ 2,4-dichloro-5-fluoro-benzoic acid is formed ;n the saponi~;ca~;on of 2,4-di-chloro-5-fluoro-trichloro~ethylben~ene (EP-OS (European Published Specification) 78,36Z).
It is also kno~n that acylation with aliphat;c carboxylic acid halides is very difficult ;n the case o~
dihalogenobenzenes, and it is said that it does not pro-ceed in the case of trihalogenobenzenes (co~pared Methoden der or~anisrhen Chem;e CMethods of or~anic chemistry~
(Houben~Weyl-Muller) Volume 7/2a, 43 t1973), Th;eme-Yerlag, Stuttgart).
In addit;on, it i5 known that 2,4-dichloro-5-fluoro-acetophenone ;s obtained in poor yield from 2~4-20 dichLorofluorobenzene in the acylation ~ith carboxylicacid anhydrides, such as, for e~a~ple~ acetic anhydride, in the presence of aluminium trichloride ~co~pare CA 58, 11243 ~
Surprisin3ly, ;t has no~ been found that 2,4~di-chloro-5~fluoro~ben~o;c ~cid of th~ ~or~ul~
Cl ~ COOH lI) is obtained in very 900d y;eld ~nd hi~h purity~ ~hen 2,4-dichlorofluorobenzene is reacted ~;th acetyl chloride~
in the presence of acylation catalysts and optionally in the presence of diluents, at temperatur~s between 10C
and 150C and the reaction product, 2~4--dichloro-5-fluoro-Le A 23 3B5 ~e .. . . .
.
~5~33~
The present invention relates to a new process for ~he preparation of 2,4-dichloro-5-fluoro~benzoic acid, ~hich is an intermediate product for the preparation of anti-bacterial agents~
It is already known that trihalogenobenzo;c acids can be prepared by saponificat;on of a tr;haLogeno-tri-halogenomethyl~benzene. Thus~ 2,4-dichloro-5-fluoro-benzoic acid is formed ;n the saponi~;ca~;on of 2,4-di-chloro-5-fluoro-trichloro~ethylben~ene (EP-OS (European Published Specification) 78,36Z).
It is also kno~n that acylation with aliphat;c carboxylic acid halides is very difficult ;n the case o~
dihalogenobenzenes, and it is said that it does not pro-ceed in the case of trihalogenobenzenes (co~pared Methoden der or~anisrhen Chem;e CMethods of or~anic chemistry~
(Houben~Weyl-Muller) Volume 7/2a, 43 t1973), Th;eme-Yerlag, Stuttgart).
In addit;on, it i5 known that 2,4-dichloro-5-fluoro-acetophenone ;s obtained in poor yield from 2~4-20 dichLorofluorobenzene in the acylation ~ith carboxylicacid anhydrides, such as, for e~a~ple~ acetic anhydride, in the presence of aluminium trichloride ~co~pare CA 58, 11243 ~
Surprisin3ly, ;t has no~ been found that 2,4~di-chloro-5~fluoro~ben~o;c ~cid of th~ ~or~ul~
Cl ~ COOH lI) is obtained in very 900d y;eld ~nd hi~h purity~ ~hen 2,4-dichlorofluorobenzene is reacted ~;th acetyl chloride~
in the presence of acylation catalysts and optionally in the presence of diluents, at temperatur~s between 10C
and 150C and the reaction product, 2~4--dichloro-5-fluoro-Le A 23 3B5 ~e .. . . .
.
~5~33~
2 --acetophenone of the for~ula ~II) Cl Cl ~ ~o-CH3 tII) F
formed in th;s way ;s, optionally after ;solation, reacted ~;th a sod;um hypochlor;te solut;on (in the form of the so-called chlorinated soda solut;on) at a temperature between 0C and 140C.
Surprisingly, it is poss;ble by means of the pro-cess according to the invention to effect an acylation of 2,4-dichlorofluorobenzene ~ith a carboxylic acid chloride, in high yield and ~ith a high selectivity, in the m~ta-position relative to the more electronegative halogen.
This is the more surprising since~ acrording to the state of the art, acylation in th~ ortho-position or para-posit;on relative to the ~ore electronegative halogen ~as to be expected in the acylation of halogenoben~enes ~Methoden der organischen Chemie ~Methods of organic chem;stry~ (Houben-Weyl-Muller~ volume 7t2a 43 (1973 Thieme-Verlag, Stuttgart).
The abovementioned known processes have a nu~ber of disadvantages. Thus, in the preparation of 294-di-chloro-5-fluoro-trichloromethylbenzene, a triazene, ~hich is very difficult to handle because of its unfavourable phys;olo~ical properties, ;s prepared as an înternediate product~
~5 Moreover, this process for the preparation of 2,4-dirhloro-S-fluoro-benzoic acid requires several sta~es.
In the acylation~ described in the literature, of 2,4-dichloro-5-fluorobenzene in the presence of acetic anhydride, the yield of reaction product is very low.
If 2~4-dichlorofluoroben~ene and acetyl chloride as startin0 materials, aluminium chloride as the catalyst and chlor;nat*d soda solution are used~ the react;on Le A 23 385 '' ~ ' `
.
' ' ~ '
formed in th;s way ;s, optionally after ;solation, reacted ~;th a sod;um hypochlor;te solut;on (in the form of the so-called chlorinated soda solut;on) at a temperature between 0C and 140C.
Surprisingly, it is poss;ble by means of the pro-cess according to the invention to effect an acylation of 2,4-dichlorofluorobenzene ~ith a carboxylic acid chloride, in high yield and ~ith a high selectivity, in the m~ta-position relative to the more electronegative halogen.
This is the more surprising since~ acrording to the state of the art, acylation in th~ ortho-position or para-posit;on relative to the ~ore electronegative halogen ~as to be expected in the acylation of halogenoben~enes ~Methoden der organischen Chemie ~Methods of organic chem;stry~ (Houben-Weyl-Muller~ volume 7t2a 43 (1973 Thieme-Verlag, Stuttgart).
The abovementioned known processes have a nu~ber of disadvantages. Thus, in the preparation of 294-di-chloro-5-fluoro-trichloromethylbenzene, a triazene, ~hich is very difficult to handle because of its unfavourable phys;olo~ical properties, ;s prepared as an înternediate product~
~5 Moreover, this process for the preparation of 2,4-dirhloro-S-fluoro-benzoic acid requires several sta~es.
In the acylation~ described in the literature, of 2,4-dichloro-5-fluorobenzene in the presence of acetic anhydride, the yield of reaction product is very low.
If 2~4-dichlorofluoroben~ene and acetyl chloride as startin0 materials, aluminium chloride as the catalyst and chlor;nat*d soda solution are used~ the react;on Le A 23 385 '' ~ ' `
.
' ' ~ '
3~3 s~qu~nce can be reproduced by the following set of ~ua~ i OhS:
Cl~> + CH3-CO-CI AlC13 > [c~ CO-C~
Chlor;nated soda solution ~ F ~ COOH
2,4 D;chlorofluorobenzene is a kno~n compnund of organic chemistry.
The reaction temperature can be var;ed with;n ~
fairly wide range. ~hus, temperatures bet~een 10C and 150C, preferably bet~een 20C and 130OCD in particular between 80C and 130c, are ~eneralLy used in the acy-~ation. The subsequent oxidation ~ith the so-called chlo-rinated soda solution is in general carried out at tempera-tures bet~een 0C and 140C, preferably bet~een 20C
and lZ0C~ In general, the reaction is carried out under normal pressure.
The process according to the invention is prefer-ably carried out ~ithout a diluent.
Catalysts ~hich can be used for the process according to the invention are acylation ca~alysts, sush as, for example, irontIII) chloride~ zinc chlor;de or Z0 aluminium chloride~ preferably alum;nium chloride.
So-called chLorinated soda solution~ ~hich ;s a sodium hypochlorite solution in ~ater, can be used as the oxidising a~ent for the process accord;ng to the inven-tionO
~hen carry;ng out the process ac~ording to the ;nvention, 1 to 3 mol of acetyl chloride and 1 to 3 mol of aluminium chloride are in general empLoyed per 1 mol of 2~4-dichlorofluorobenzene. After the reaction has ended, the reaction m;xture is poured onto ice and taken L~ ~ 23_~85 - ' , ' up in a diluent which is immiscible with ~ater, such as, for example, methylene chloride or chloroform. However, the reaction product can also be separated off ~ithout the use of diluents If appropriate after re00val of the extr~ction agent, the residue is oxidised in the presence of 2 to 4 1, preferably 2.1 to 3.3 1, of chlo~;nated soda solut;on (150 g of active chlor;ne/1) per mol of starting mater;al. Subsequently, the 2,4-dichloro-5-fluoro-benzene acid is precipitated with a m;neral acid, such as, for example, hydrochloric ac;d~ and then f;ltered off with suc~ion.
204-Dichloro-5-fluoro-benzoic acid, ~hich ;s read;ly accessible by the process according to the inven-tion~ can be used, for example, for the synthesis of anti-bacterial agents. Thus, substi~ut*d oxoquinsline-carboxy-lic acids, which are compounds of high bac~ericidal potency~ can be prepared from this acid, for example in accordance ~ith the follo~ing equations (compare, for example, EP OS CEuropean Published Spec;f;cat;on) 78,362).
Cl ~ COOH SOCl~ > Cl ~ COCl CH2(COOC2HC)~ >
F F
F ~ C0-CH(COOC2Hs)2 > Cl ~ C0-CH2-COOC2Hs Le A Z3 385 .. . .
::
.
.. ..
, .
.: .
3~
HC(OC2~s)3 > Cl~CO-~-COOC2H5 D~H2 HN~ o Cl CH F~J~Cooc2H5 F~CO-~-COOC2H5 , !ICl~
~.
O ~ O
F ~ COOH RN ~H F - ~ ~COOH
Cl ~ r~~ / ~ N
~ RN~_~N
R = Ho alkyl Cl Cl ~ -COOH ~I) 23.6 9 ~0.3 mol) of acetyl chloride are added at 20C to 40C to a m;xture of 33 g (0.2 mol) of 204-dichlorofluorobenzene and 66.8 ~ (0.5 mol) of aLum;n;um chloride, ~nd the m;xture is then stirred for 2 hours at 120C. While still hot, the mixture is poured onto 250 9 of ice, and the o;l ~hich separates ou~ is taken up in methylene chloride. The solvent is eYaporated off~
450 ~l of chlorinated soda solution ~150 9 of active chlorine/13 are added to the residue and the m;xture ;s first stirred for 1 hour u;thout heat;ng and then bo;led for 2 hours under reflux. After the result;ng chloroform has been separated off, 300 ml of water are added~ and the Le A 23 385 33~) /s mlY~tUre lS treated ~ith 10 Ml of 40 ~ strength sodium bi-su~pnile solution and then with concentrated hydrochloric acid, until a pH value of 1 is reached.
I~l this way, 33.5 ~ (80X of theory) of 204-di-chloro-5-fluoro~benzoic acid ar~ obtained as a colourless po~der of melt;ng point 139C.
Le A 2~ 385 __.
, :
3~2~
~,he e~ dimc-n~s of the inver~tion in which an e~clusiv~ prG~-rty or privilege ~re clai~ed are defined as follows:
1- ~ compound of the formula:
R ~ ( 2 ~ COR4 [wherein n is an integer of 0 to 2; Rl and R3 which may be the same or different each represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group or a nitro group; R~ ;.s a hydroxyl group or the group -NHZ (Z
is a hydro~en atom or a lower alkyl group), e~cepting both the case where n i5 0 or 1, any one of Rl to R3 is 5-chloro, 5-methoxy or 5~nitro and the remainder is a hydrogen atom, and R4 is a hydroxyl group, and the case where n is 0 or 1, any two of Rl to R3 axe 3,5-dichloro or 3,5-dinitro and the remainder is a hydrogen atom, and R4 is a hydroxyl group]
or an alkali metal salt thereof.
2. A compound of the formula R
3 ~ S
R ~ ()n 2 Rl COOH
[wherein n is a~ integer o~ 0 t~ 2; Rl to R3 which may be the same or di~ferent each represents a hydrogen atom, a halo~en atom, a lower alkyl group, a lower alkoxy group or a nitro group, excepting both the case where n is 0 or 1, any one of Rl to R3 is 5-chloro, 5-methoxy or 5-nitro, and the remainder is a hydrogen atom, and the case where n is 0 or 1, two substituents of Rl to R3 are 3,5 dichloro or 3,5-dinitro and the remainder is a hydrogen atom] or an alkali metal salt thereof.
3. A compound of the formula:
CONHZ
R2 ~ (~) Rl CONHZ
~,;
- ~.
.:
~: .
. . .
[wherein n is an integer of 0 to 2; Z is a hydrogen atom or a loweralkyl group; R1 to R3 which may be the same or differen-t each represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group or a nitro group].
Cl~> + CH3-CO-CI AlC13 > [c~ CO-C~
Chlor;nated soda solution ~ F ~ COOH
2,4 D;chlorofluorobenzene is a kno~n compnund of organic chemistry.
The reaction temperature can be var;ed with;n ~
fairly wide range. ~hus, temperatures bet~een 10C and 150C, preferably bet~een 20C and 130OCD in particular between 80C and 130c, are ~eneralLy used in the acy-~ation. The subsequent oxidation ~ith the so-called chlo-rinated soda solution is in general carried out at tempera-tures bet~een 0C and 140C, preferably bet~een 20C
and lZ0C~ In general, the reaction is carried out under normal pressure.
The process according to the invention is prefer-ably carried out ~ithout a diluent.
Catalysts ~hich can be used for the process according to the invention are acylation ca~alysts, sush as, for example, irontIII) chloride~ zinc chlor;de or Z0 aluminium chloride~ preferably alum;nium chloride.
So-called chLorinated soda solution~ ~hich ;s a sodium hypochlorite solution in ~ater, can be used as the oxidising a~ent for the process accord;ng to the inven-tionO
~hen carry;ng out the process ac~ording to the ;nvention, 1 to 3 mol of acetyl chloride and 1 to 3 mol of aluminium chloride are in general empLoyed per 1 mol of 2~4-dichlorofluorobenzene. After the reaction has ended, the reaction m;xture is poured onto ice and taken L~ ~ 23_~85 - ' , ' up in a diluent which is immiscible with ~ater, such as, for example, methylene chloride or chloroform. However, the reaction product can also be separated off ~ithout the use of diluents If appropriate after re00val of the extr~ction agent, the residue is oxidised in the presence of 2 to 4 1, preferably 2.1 to 3.3 1, of chlo~;nated soda solut;on (150 g of active chlor;ne/1) per mol of starting mater;al. Subsequently, the 2,4-dichloro-5-fluoro-benzene acid is precipitated with a m;neral acid, such as, for example, hydrochloric ac;d~ and then f;ltered off with suc~ion.
204-Dichloro-5-fluoro-benzoic acid, ~hich ;s read;ly accessible by the process according to the inven-tion~ can be used, for example, for the synthesis of anti-bacterial agents. Thus, substi~ut*d oxoquinsline-carboxy-lic acids, which are compounds of high bac~ericidal potency~ can be prepared from this acid, for example in accordance ~ith the follo~ing equations (compare, for example, EP OS CEuropean Published Spec;f;cat;on) 78,362).
Cl ~ COOH SOCl~ > Cl ~ COCl CH2(COOC2HC)~ >
F F
F ~ C0-CH(COOC2Hs)2 > Cl ~ C0-CH2-COOC2Hs Le A Z3 385 .. . .
::
.
.. ..
, .
.: .
3~
HC(OC2~s)3 > Cl~CO-~-COOC2H5 D~H2 HN~ o Cl CH F~J~Cooc2H5 F~CO-~-COOC2H5 , !ICl~
~.
O ~ O
F ~ COOH RN ~H F - ~ ~COOH
Cl ~ r~~ / ~ N
~ RN~_~N
R = Ho alkyl Cl Cl ~ -COOH ~I) 23.6 9 ~0.3 mol) of acetyl chloride are added at 20C to 40C to a m;xture of 33 g (0.2 mol) of 204-dichlorofluorobenzene and 66.8 ~ (0.5 mol) of aLum;n;um chloride, ~nd the m;xture is then stirred for 2 hours at 120C. While still hot, the mixture is poured onto 250 9 of ice, and the o;l ~hich separates ou~ is taken up in methylene chloride. The solvent is eYaporated off~
450 ~l of chlorinated soda solution ~150 9 of active chlorine/13 are added to the residue and the m;xture ;s first stirred for 1 hour u;thout heat;ng and then bo;led for 2 hours under reflux. After the result;ng chloroform has been separated off, 300 ml of water are added~ and the Le A 23 385 33~) /s mlY~tUre lS treated ~ith 10 Ml of 40 ~ strength sodium bi-su~pnile solution and then with concentrated hydrochloric acid, until a pH value of 1 is reached.
I~l this way, 33.5 ~ (80X of theory) of 204-di-chloro-5-fluoro~benzoic acid ar~ obtained as a colourless po~der of melt;ng point 139C.
Le A 2~ 385 __.
, :
3~2~
~,he e~ dimc-n~s of the inver~tion in which an e~clusiv~ prG~-rty or privilege ~re clai~ed are defined as follows:
1- ~ compound of the formula:
R ~ ( 2 ~ COR4 [wherein n is an integer of 0 to 2; Rl and R3 which may be the same or different each represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group or a nitro group; R~ ;.s a hydroxyl group or the group -NHZ (Z
is a hydro~en atom or a lower alkyl group), e~cepting both the case where n i5 0 or 1, any one of Rl to R3 is 5-chloro, 5-methoxy or 5~nitro and the remainder is a hydrogen atom, and R4 is a hydroxyl group, and the case where n is 0 or 1, any two of Rl to R3 axe 3,5-dichloro or 3,5-dinitro and the remainder is a hydrogen atom, and R4 is a hydroxyl group]
or an alkali metal salt thereof.
2. A compound of the formula R
3 ~ S
R ~ ()n 2 Rl COOH
[wherein n is a~ integer o~ 0 t~ 2; Rl to R3 which may be the same or di~ferent each represents a hydrogen atom, a halo~en atom, a lower alkyl group, a lower alkoxy group or a nitro group, excepting both the case where n is 0 or 1, any one of Rl to R3 is 5-chloro, 5-methoxy or 5-nitro, and the remainder is a hydrogen atom, and the case where n is 0 or 1, two substituents of Rl to R3 are 3,5 dichloro or 3,5-dinitro and the remainder is a hydrogen atom] or an alkali metal salt thereof.
3. A compound of the formula:
CONHZ
R2 ~ (~) Rl CONHZ
~,;
- ~.
.:
~: .
. . .
[wherein n is an integer of 0 to 2; Z is a hydrogen atom or a loweralkyl group; R1 to R3 which may be the same or differen-t each represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group or a nitro group].
4. A pharmaceu-tical compositlon for controlling infectious diseases, which comprises an effective amount of a compound of the formula:
S ~ >
wherein n ~s an integer of 0 to 2; Rl to R3 which may be the same or different each represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group or a nitro group; and R4 is a hydroxyl group or the group - NHZ, Z being a hydrogen atom or a lower alkyl group or an alkali metal salt thereof, together with a pharmaceutically acceptable carrier.
~P
i ~ '' I I
S ~ >
wherein n ~s an integer of 0 to 2; Rl to R3 which may be the same or different each represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group or a nitro group; and R4 is a hydroxyl group or the group - NHZ, Z being a hydrogen atom or a lower alkyl group or an alkali metal salt thereof, together with a pharmaceutically acceptable carrier.
~P
i ~ '' I I
Claims (6)
1. A process for the preparation of 2,4-dichloro-5-fluoro-benzoic acid of the formula which comprises reacting acetyl chloride with 2,4-dichlorofluorobenzene in the presence of an acylation catalyst at a temperature between 10°C
and 150°C to produce 2,4-dichloro-5-fluoro-acetophenone of the formula and reacting the 2,4-dichloro-fluoro-acetophenone with a sodium hypochlorite solution at a temperature between 0°C and 140°C.
and 150°C to produce 2,4-dichloro-5-fluoro-acetophenone of the formula and reacting the 2,4-dichloro-fluoro-acetophenone with a sodium hypochlorite solution at a temperature between 0°C and 140°C.
2. The process according to claim 1, wherein aluminum trichloride is used as the acylation catalyst.
3. The process according to claim 1, wherein the reaction with acetyl chloride is carried out at a temperature between 20°C and 130°C.
4. The process according to claim 1, wherein the reaction with the sodium hypochlorite solution is carried out at a temperature between 20°C and 120°C.
5. The process according to claim 1, wherein the 2,4-dichloro-5-fluoro-acetophenone formed is, without isolation, reacted with the sodium hypochlorite solution.
6. The process according to claim 1, wherein acylation is effected in the presence of a diluent.
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 |
| DEP3435392.5 | 1984-09-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1255330A true CA1255330A (en) | 1989-06-06 |
Family
ID=6246450
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000491506A Expired CA1255330A (en) | 1984-09-27 | 1985-09-25 | Process for the preparation of 2,4-dichloro-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) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5886218A (en) * | 1996-05-02 | 1999-03-23 | Hoechst Aktiengesellschaft | Process for preparing 4, 5-dichloro-2-methylbenzoic acid |
| US6462218B1 (en) | 1997-08-01 | 2002-10-08 | Bayer Aktiengesellschaft | Method for preparing 3-cyano-2,4-dihalogeno-5-fluoro-Benzoic acid |
Families Citing this family (6)
| 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 |
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 |
| 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 |
| 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 |
-
1984
- 1984-09-27 DE DE19843435392 patent/DE3435392A1/en not_active Withdrawn
-
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 JP JP60209034A patent/JPH0647568B2/en not_active Expired - Lifetime
- 1985-09-24 KR KR1019850006988A patent/KR910008936B1/en not_active IP Right Cessation
- 1985-09-24 NZ NZ213599A patent/NZ213599A/en unknown
- 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 ZA ZA857432A patent/ZA857432B/en unknown
- 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 PH PH32852A patent/PH24252A/en unknown
- 1985-09-26 DD DD85281050A patent/DD239591A5/en not_active IP Right Cessation
- 1985-09-26 DK DK436685A patent/DK166411B1/en not_active IP Right Cessation
- 1985-09-26 GR GR852346A patent/GR852346B/el unknown
- 1985-09-26 IE IE238085A patent/IE72493B1/en not_active IP Right Cessation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5886218A (en) * | 1996-05-02 | 1999-03-23 | Hoechst Aktiengesellschaft | Process for preparing 4, 5-dichloro-2-methylbenzoic acid |
| US6462218B1 (en) | 1997-08-01 | 2002-10-08 | Bayer Aktiengesellschaft | Method for preparing 3-cyano-2,4-dihalogeno-5-fluoro-Benzoic acid |
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