CA1241665A - Process for the preparation of chloro-o-nitroanilines - Google Patents
Process for the preparation of chloro-o-nitroanilinesInfo
- Publication number
- CA1241665A CA1241665A CA000489641A CA489641A CA1241665A CA 1241665 A CA1241665 A CA 1241665A CA 000489641 A CA000489641 A CA 000489641A CA 489641 A CA489641 A CA 489641A CA 1241665 A CA1241665 A CA 1241665A
- Authority
- CA
- Canada
- Prior art keywords
- chloro
- formula
- ammonia
- reaction
- temperatures
- 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
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/10—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Abstract of the disclosure A process for the preparation of chloro-o-nitroanilines of the formula (1) (1) in which R1 and R2 are hydrogen or chlorine atoms, by reaction of chloronitrobenzenes of the formula (2) (2) in which R1 and R2 have the meanings given above, with ammonia at an elevated temperature, by effecting the reaction at temperatures from about 120 to 200°C with anhydrous ammonia in the presence of aromatic hydrocarbons of the formula (3) (3)
Description
HOECHST AKtIENGESELLSCHAFT HOE 84/~ 198 ~r.M~/S~
_rocess for the preparat;on of chloro-o-n~_r an7l;nes The invent;on relates to a process for the preparation of chloro-o-n;troanilines in h;gh pur;ty and yield ~;th-out addit;onal purif;cat;on operat;ons by react;ng chloro-nitrobenzenes, for example 2,4-dichloron;trobenzene, ~;th anhydrous ammonia.
As is known, chloron;troan;lines are valuable precursors and ;ntermed;ates for the preparat;on of dyes, pharma-ceut;cals and plant protect;on agents.
It is known to prepare, for example, 5-chloro-2-n;tro-aniline by reacting 2,4-dichloronitrobenzene in ethanolic solution with ammon;a (A. 1B2 (1876) 94, 109; RecueiL 72, 44 et seq. S1953)). Hoover the drawbacks involved in this procedure, above all because of the unlimited m;sc;-b;l;ty of ethanol w;th water and with the ammonia always present in excess, are so considerable that industr;al utilization of this process is out of the question. An analogous process method kith a solution of ammonia ;n other ~ater-soLuble lou-molecular alkanols or gLycol ethers, such as, for exampleO methanol, isopropanol~
tert.-butanol or d;ethylene glycol dimethyl ether, which , have to be m;xed with water in the ~ork;ng-up of the reaction mixture obta;ned and then l;kew;se m;x ~;th water ;n unl;m;ted quantities, ;s also ;mposs;ble indus-trially, for the reasons given.
In the preparation of 5-chloro-2-nitroanil;ne by ammonolys;s in aqueous systems (Recueil 72, 44 et seq. (1953)), con-siderable quant;ties of 3-chloro-4-nitroanil;ne and 5-amino-2-nitroan;line Sd;am;ne) are always also formed in add;t;on, ;n fact largely ;ndependently of the reaction condit;ons, and unconverted start;ng product can also st;ll be present ;n the case of very mild reaction condit;ons.
'I
f
_rocess for the preparat;on of chloro-o-n~_r an7l;nes The invent;on relates to a process for the preparation of chloro-o-n;troanilines in h;gh pur;ty and yield ~;th-out addit;onal purif;cat;on operat;ons by react;ng chloro-nitrobenzenes, for example 2,4-dichloron;trobenzene, ~;th anhydrous ammonia.
As is known, chloron;troan;lines are valuable precursors and ;ntermed;ates for the preparat;on of dyes, pharma-ceut;cals and plant protect;on agents.
It is known to prepare, for example, 5-chloro-2-n;tro-aniline by reacting 2,4-dichloronitrobenzene in ethanolic solution with ammon;a (A. 1B2 (1876) 94, 109; RecueiL 72, 44 et seq. S1953)). Hoover the drawbacks involved in this procedure, above all because of the unlimited m;sc;-b;l;ty of ethanol w;th water and with the ammonia always present in excess, are so considerable that industr;al utilization of this process is out of the question. An analogous process method kith a solution of ammonia ;n other ~ater-soLuble lou-molecular alkanols or gLycol ethers, such as, for exampleO methanol, isopropanol~
tert.-butanol or d;ethylene glycol dimethyl ether, which , have to be m;xed with water in the ~ork;ng-up of the reaction mixture obta;ned and then l;kew;se m;x ~;th water ;n unl;m;ted quantities, ;s also ;mposs;ble indus-trially, for the reasons given.
In the preparation of 5-chloro-2-nitroanil;ne by ammonolys;s in aqueous systems (Recueil 72, 44 et seq. (1953)), con-siderable quant;ties of 3-chloro-4-nitroanil;ne and 5-amino-2-nitroan;line Sd;am;ne) are always also formed in add;t;on, ;n fact largely ;ndependently of the reaction condit;ons, and unconverted start;ng product can also st;ll be present ;n the case of very mild reaction condit;ons.
'I
f
2 --The purif;cation of such mixtures can be carried out ;ndustrially only with considerable effort and with a reduction in yield, al o associated with significant environmental problems. moreover, as compared with pure 5-chloro-2-nitroanil;ne, react;on mixtures obta;ned ;n this Jay have greatly reduced thermal stabil;t;es, so that safety engineering problems arise when such processes are carr;ed out on an ;ndustr;al scale.
According to European Patent Appl;cat;on 0,057,861 (U.S.
Patent 4,421,694), 5-chloro-2-nitroan;line is obta;ned in y;elds of up to about 95X and purit;es of up to 96X by reacting 2,4-d;chloron;trobenzene ~;th ammonia in chlorinated aromatic hydrocarbons. Even though the selec-t;v;ty is ;mproved by comparison ~;th the abovekno~n pro-cesses, it ;s not yet sat;sfactory and there are also reser-vat;ons regarding the use of rhlor;nated hydrocarbons under the aspect of occupational hyg;eneO Thus, for example, the values of the max;mum allowable workplace concentration for chLorobenzene and the d;chlorobenzenes are remarkably lo, at 50 ppm. There is a general trend to restrict the use of chlor;nated hydrocarbons to the absolutely necessary minimum, in order to reduce health risks.
It has nou been found surprisingly, that chloro-o-nitro-anilines of the general formula (1) ~H2 (1 ) in which R1 and R2 are hydrogen atoms or chlorine atoms, can be prepared ;n an almcsst quantitative y;eld and almost 100% pur;ty by react;ng chloron;trobenzenes of the general formula t2) Cl (2 Cl in which R1 and R2 have tha meanings given above, at temperatures from about 1Z0 to Z00C, preferably 150 to 18QC, with anhydrous ammonia in the presence of aromatic hydrocarbons of the general formula ~3) (3 in which R3 is a C1-C4-alkyl group, such as, for example, a methyl, ethyl, n-butyl~ iso-butyl, tert.-butyl, propyl or iso-propyl group and R4 and R5~ are hydrogen atoms or Cl-c4-alkyl groups.
As chloronitrobenzenes of the said general formula (2), 2,3,4- and 2~,5-trichloronitrobenzene, 2,3,$,5-tetra-chloronitrobenzene and especially 2,4-dichloronitrobenz-ene may be mentioned as examples.
The chlorine atom, which is in the p-position relative to the nitro group in each case and is also activated as is `
known, virtually does not enter the reaction under the conditions of the process according to the invention.
As aromatic hydrocarbons of the said general formula (3), toluene, ethylbenzene, xylenes and mesitylene may be men-tioned as examples, toluene and xylenes being used preferably.
Mixtures of hydrocarbons of the said general formula (3) can also be used.
The aromat;c hydrocarbons of the general formula ~3), which are preferably used according to the process, are l jÇ t j generally available, are inexpens;ve and raise fewer prob-lems than the chlorinated aromatic hydrocarbons under the aspect of occupational hygiene.
Roth the ammonia to be used and the aromat;c hydrocarbons used must be anhydrous as far as possible, since, with increas;ng presence of water, the selective replacement of the activated chlorine atom in the o-position relative to the n;tro group is suppressed by the amino group in the starting products of the said general formula t2).
However, the quantities of water, which remain dissolved in the aromatic hydrocarbons when the reaction mixture obtained is worked up, are not harmful to the prscess according to the invention The quantity of the aromatic hydrocarbons can be varied within wide limits. Advantageously, the quantitative ratios are selected such that, after cooling of the resulting reaction mixture, suspensions are obtained wh;ch can still read;ly be stirred and flow freely.
The parameters determ;n;ng the rate and completeness of conversion are the react;on temperature and the quant;ty of the ammon;a employed. Even thoush the sto;ch;ometric quantity of 2 mol of NH3 per mol of chloron;trobenzene of the formula (2) is suffic;ent in princ;ple, it is advant-ageous to use a quantity wh;ch exceeds th;s rat;o. The molar ratio of starting product ammonia can vary here from about 1:3 to 1:12, a molar ratio of 1:6 to 1:8 being chosen with advantage. Unconsumed ammonia can be reco-vered by conventional methods and re-used.
The reaction temperature can move within a wide range.
Advantageously, temperatures between about 120 and 200C
are chosen; preferably, the reaction is carried out at temperatures of 150-180C. Together with a correspond-ingly large excess of ammonia, reaction times of about
According to European Patent Appl;cat;on 0,057,861 (U.S.
Patent 4,421,694), 5-chloro-2-nitroan;line is obta;ned in y;elds of up to about 95X and purit;es of up to 96X by reacting 2,4-d;chloron;trobenzene ~;th ammonia in chlorinated aromatic hydrocarbons. Even though the selec-t;v;ty is ;mproved by comparison ~;th the abovekno~n pro-cesses, it ;s not yet sat;sfactory and there are also reser-vat;ons regarding the use of rhlor;nated hydrocarbons under the aspect of occupational hyg;eneO Thus, for example, the values of the max;mum allowable workplace concentration for chLorobenzene and the d;chlorobenzenes are remarkably lo, at 50 ppm. There is a general trend to restrict the use of chlor;nated hydrocarbons to the absolutely necessary minimum, in order to reduce health risks.
It has nou been found surprisingly, that chloro-o-nitro-anilines of the general formula (1) ~H2 (1 ) in which R1 and R2 are hydrogen atoms or chlorine atoms, can be prepared ;n an almcsst quantitative y;eld and almost 100% pur;ty by react;ng chloron;trobenzenes of the general formula t2) Cl (2 Cl in which R1 and R2 have tha meanings given above, at temperatures from about 1Z0 to Z00C, preferably 150 to 18QC, with anhydrous ammonia in the presence of aromatic hydrocarbons of the general formula ~3) (3 in which R3 is a C1-C4-alkyl group, such as, for example, a methyl, ethyl, n-butyl~ iso-butyl, tert.-butyl, propyl or iso-propyl group and R4 and R5~ are hydrogen atoms or Cl-c4-alkyl groups.
As chloronitrobenzenes of the said general formula (2), 2,3,4- and 2~,5-trichloronitrobenzene, 2,3,$,5-tetra-chloronitrobenzene and especially 2,4-dichloronitrobenz-ene may be mentioned as examples.
The chlorine atom, which is in the p-position relative to the nitro group in each case and is also activated as is `
known, virtually does not enter the reaction under the conditions of the process according to the invention.
As aromatic hydrocarbons of the said general formula (3), toluene, ethylbenzene, xylenes and mesitylene may be men-tioned as examples, toluene and xylenes being used preferably.
Mixtures of hydrocarbons of the said general formula (3) can also be used.
The aromat;c hydrocarbons of the general formula ~3), which are preferably used according to the process, are l jÇ t j generally available, are inexpens;ve and raise fewer prob-lems than the chlorinated aromatic hydrocarbons under the aspect of occupational hygiene.
Roth the ammonia to be used and the aromat;c hydrocarbons used must be anhydrous as far as possible, since, with increas;ng presence of water, the selective replacement of the activated chlorine atom in the o-position relative to the n;tro group is suppressed by the amino group in the starting products of the said general formula t2).
However, the quantities of water, which remain dissolved in the aromatic hydrocarbons when the reaction mixture obtained is worked up, are not harmful to the prscess according to the invention The quantity of the aromatic hydrocarbons can be varied within wide limits. Advantageously, the quantitative ratios are selected such that, after cooling of the resulting reaction mixture, suspensions are obtained wh;ch can still read;ly be stirred and flow freely.
The parameters determ;n;ng the rate and completeness of conversion are the react;on temperature and the quant;ty of the ammon;a employed. Even thoush the sto;ch;ometric quantity of 2 mol of NH3 per mol of chloron;trobenzene of the formula (2) is suffic;ent in princ;ple, it is advant-ageous to use a quantity wh;ch exceeds th;s rat;o. The molar ratio of starting product ammonia can vary here from about 1:3 to 1:12, a molar ratio of 1:6 to 1:8 being chosen with advantage. Unconsumed ammonia can be reco-vered by conventional methods and re-used.
The reaction temperature can move within a wide range.
Advantageously, temperatures between about 120 and 200C
are chosen; preferably, the reaction is carried out at temperatures of 150-180C. Together with a correspond-ingly large excess of ammonia, reaction times of about
3-6 hours then result. The very high selectivity is not significantly affected either by the level of the tem-perature or by the quantity of the ammon;a employed. The comb;nat;on of these parameters only determ;nes the com-pleteness of the convers;on or the requ;red react;on per;od.
In deta;l, the process accord;ng to the ;nvent;on can be carr;ed out ;n such a Jay that the start;ng product (chloron;trobenzene of the general formula t2)) ;s intro-duced into an autoclave together with the aromat;c hydrocarbon of the formula (3?, and the anhydrous amnonia is metered in all at unce or ;n port;ons.
The react;on product is isolated by conventional methods.
Thus, for example, after depressuriz;ng the autoclave -the excess ammonia can then be recovered and fed to another batch - and cooling of the reaction mixture obtained, the product can be f;ltered off from the result-ing crystal suspension and the ammon;um chloride, which has also prec;pitated, can be washed out ~;th water. The f;ltrate ~h;ch ;s predominantly composed of the aromat;c hydrocarbon, can be re-used ~;thout further measures. In 3 a particularly advantageous ~ork;ng-up method, the aro-matic hydrocarbon ;s removed by steam distillation and the product is filtered off from the aqueous suspensionY
Here again, the hydrocarbon can be re-used directly for subsequent batches, after the water has been separated off. In th;s case the traces of water d;ssolved in the hydrocarbon do not interfere ;n the sense of the process accord;ng to the ;nvent;on.
A part;cular advantage of the process according to the ;nvention over the processes belonging to the state of the art is the high selectiv;ty with which the react;on proceeds. At almost quantitative convers;on, there ;s v;rtually no d;am;nation, so that expensive purification operations are not necessary. The react;on is uncritical over do ranges of temperature and concentration and requires only generally available and ;nexpensive aromatic hydrocarbons as the reaction medium. As a resu!t of avo;d;ng the formation of diaminonitrobenzenes, a greatly enhanced thermal stability is obtained and the tendency to uncontrolled decomposition reactions, uhich is present ;n the m;xtures obtained by the known processes, is suppressed.
In the examples which follow, the process accord;ng to the ;nvention is illustrated more clearly, without being restricted thereto. Percentage data relate to the weight.
Example 1 1~2 9 (1 mol) of 2,4-d;chloronitrobenzene and 40û g of xylene are introduced into a steel autoclave. After seaL-;ng the autocLave, 136 g t8 mol) of ammonia gas are ;njec-ted and the m;xture ;s heated at 17ûC for 5 hours, a pressure of about 70 bar being established. The autoclave is then cooled and depressurized, and the xylene is str;pped out with steam. The product is obtained from the aqueous crystal suspension by filtration and is vashed with water until free of chloride.
Th;s gives 171 9 of 5-chLoro-2-nitroaniline of melt;ng po;nt 924.2C, corresponding to a yield of 99% of the-ory. According to analys;s by gas chromatography, the 5-chloro-2-nitroaniline content is 98.8X (diamine content ~0.2%).
Example 2 If the batch is heated for 3 hours at 180C instead of 5 hours at 170C and the procedure ;s in other respects as described on Example 1, 5-chloro-2-nitroaniline is obtained in the same yield and purity as according to Example 1.
Example 3 192 9 tl mol) of 2,4-dichloronitrobenzene are introduced together with 300 9 of toluene into a steel autoclave.
After inject;on of 102 9 ~6 mol) of ammon;a, the batch is heated for 6 hours to 170C. After the ~ork;ng-up of the result;n~ react;on mixture, as described in Ex 3 mple 1, ~-chloro-2-n;troan;line ;s obtained ;n the same yield and purity as according to Example 1.
In deta;l, the process accord;ng to the ;nvent;on can be carr;ed out ;n such a Jay that the start;ng product (chloron;trobenzene of the general formula t2)) ;s intro-duced into an autoclave together with the aromat;c hydrocarbon of the formula (3?, and the anhydrous amnonia is metered in all at unce or ;n port;ons.
The react;on product is isolated by conventional methods.
Thus, for example, after depressuriz;ng the autoclave -the excess ammonia can then be recovered and fed to another batch - and cooling of the reaction mixture obtained, the product can be f;ltered off from the result-ing crystal suspension and the ammon;um chloride, which has also prec;pitated, can be washed out ~;th water. The f;ltrate ~h;ch ;s predominantly composed of the aromat;c hydrocarbon, can be re-used ~;thout further measures. In 3 a particularly advantageous ~ork;ng-up method, the aro-matic hydrocarbon ;s removed by steam distillation and the product is filtered off from the aqueous suspensionY
Here again, the hydrocarbon can be re-used directly for subsequent batches, after the water has been separated off. In th;s case the traces of water d;ssolved in the hydrocarbon do not interfere ;n the sense of the process accord;ng to the ;nvent;on.
A part;cular advantage of the process according to the ;nvention over the processes belonging to the state of the art is the high selectiv;ty with which the react;on proceeds. At almost quantitative convers;on, there ;s v;rtually no d;am;nation, so that expensive purification operations are not necessary. The react;on is uncritical over do ranges of temperature and concentration and requires only generally available and ;nexpensive aromatic hydrocarbons as the reaction medium. As a resu!t of avo;d;ng the formation of diaminonitrobenzenes, a greatly enhanced thermal stability is obtained and the tendency to uncontrolled decomposition reactions, uhich is present ;n the m;xtures obtained by the known processes, is suppressed.
In the examples which follow, the process accord;ng to the ;nvention is illustrated more clearly, without being restricted thereto. Percentage data relate to the weight.
Example 1 1~2 9 (1 mol) of 2,4-d;chloronitrobenzene and 40û g of xylene are introduced into a steel autoclave. After seaL-;ng the autocLave, 136 g t8 mol) of ammonia gas are ;njec-ted and the m;xture ;s heated at 17ûC for 5 hours, a pressure of about 70 bar being established. The autoclave is then cooled and depressurized, and the xylene is str;pped out with steam. The product is obtained from the aqueous crystal suspension by filtration and is vashed with water until free of chloride.
Th;s gives 171 9 of 5-chLoro-2-nitroaniline of melt;ng po;nt 924.2C, corresponding to a yield of 99% of the-ory. According to analys;s by gas chromatography, the 5-chloro-2-nitroaniline content is 98.8X (diamine content ~0.2%).
Example 2 If the batch is heated for 3 hours at 180C instead of 5 hours at 170C and the procedure ;s in other respects as described on Example 1, 5-chloro-2-nitroaniline is obtained in the same yield and purity as according to Example 1.
Example 3 192 9 tl mol) of 2,4-dichloronitrobenzene are introduced together with 300 9 of toluene into a steel autoclave.
After inject;on of 102 9 ~6 mol) of ammon;a, the batch is heated for 6 hours to 170C. After the ~ork;ng-up of the result;n~ react;on mixture, as described in Ex 3 mple 1, ~-chloro-2-n;troan;line ;s obtained ;n the same yield and purity as according to Example 1.
Claims (5)
1. A process for the preparation of chloro-o-nitroanilines of the formula (1) (1) in which R1 and R2 are hydrogen atoms or chlorine atoms, by reaction of chloronitrobenzenes of the formula (2) (2) in which R1 and R2 have the meanings given above, with ammonia at an elevated temperatures which com-prises effecting the reaction at temperatures from about 120 to 200°C with anhydrous ammonia in the pre-sence of aromatic hydrocarbons of the formula (3) (3) in which R3 is a C1-C4-alkyl group and R4 and R5 are hydrogen atoms or C1-C4-alkyl groups.
2. The process as claimed in claim 1, wherein the reac-tion is carried out at temperatures from 150 to 180°C
3. The process as claimed in claim 1, wherein the chloro-nitrobenzenes of the said formula (2) and the ammonia are employed in a molar ratio of 1:3 to 1:12.
4, The process as claimed in claim 1, wherein the chloro-nitrobenzenes of the said formula (2) and the ammonia are employed in a molar ratio of 1:6 to 1:8.
5. The process as claimed in claim 1, wherein the reac-tion is carried out in the presence of toluene or xylenes.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3431827.5 | 1984-08-30 | ||
| DE19843431827 DE3431827A1 (en) | 1984-08-30 | 1984-08-30 | METHOD FOR PRODUCING CHLORINE-O-NITROANILINE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1241665A true CA1241665A (en) | 1988-09-06 |
Family
ID=6244230
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000489641A Expired CA1241665A (en) | 1984-08-30 | 1985-08-29 | Process for the preparation of chloro-o-nitroanilines |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0173202B1 (en) |
| JP (1) | JPS6160637A (en) |
| BR (1) | BR8504162A (en) |
| CA (1) | CA1241665A (en) |
| DD (1) | DD236520A5 (en) |
| DE (2) | DE3431827A1 (en) |
| MX (1) | MX159907A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6479703B1 (en) | 1998-12-17 | 2002-11-12 | Aventis Cropscience Sa | Method for preparing polyhalogenated paratrifluoromethylanilines |
| US6552230B1 (en) | 1998-07-01 | 2003-04-22 | Bayer Aktiengesellschaft | Method for preparing 2-nitro-5-(phenylthio)-anilines |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3922036A1 (en) * | 1989-07-05 | 1991-01-31 | Hoechst Ag | METHOD FOR PRODUCING 4,5-DICHLOR-2-NITRO-ANILINE |
| JP4945840B2 (en) * | 2000-11-29 | 2012-06-06 | 井関農機株式会社 | Combine |
| CN102531923A (en) * | 2012-02-21 | 2012-07-04 | 南通市东昌化工有限公司 | Method for producing 5-chloro-2-nitroaniline |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2305573A (en) * | 1941-07-07 | 1942-12-15 | American Cyanamid Co | Preparation of nitrophenyl amines |
| US3002998A (en) * | 1959-05-13 | 1961-10-03 | Lloyd A Kaplan | Preparation of 1,3,5-triamino-2,4,6-trinitrobenzene |
| DE3104310A1 (en) * | 1981-02-07 | 1982-08-19 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING 5-CHLORINE-2-NITROANILINE |
-
1984
- 1984-08-30 DE DE19843431827 patent/DE3431827A1/en not_active Withdrawn
-
1985
- 1985-08-19 EP EP85110345A patent/EP0173202B1/en not_active Expired - Lifetime
- 1985-08-19 DE DE8585110345T patent/DE3576816D1/en not_active Expired - Fee Related
- 1985-08-29 BR BR8504162A patent/BR8504162A/en not_active IP Right Cessation
- 1985-08-29 JP JP60188733A patent/JPS6160637A/en active Granted
- 1985-08-29 DD DD85280119A patent/DD236520A5/en not_active IP Right Cessation
- 1985-08-29 CA CA000489641A patent/CA1241665A/en not_active Expired
- 1985-08-29 MX MX206458A patent/MX159907A/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6552230B1 (en) | 1998-07-01 | 2003-04-22 | Bayer Aktiengesellschaft | Method for preparing 2-nitro-5-(phenylthio)-anilines |
| US6479703B1 (en) | 1998-12-17 | 2002-11-12 | Aventis Cropscience Sa | Method for preparing polyhalogenated paratrifluoromethylanilines |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6160637A (en) | 1986-03-28 |
| EP0173202B1 (en) | 1990-03-28 |
| DE3431827A1 (en) | 1986-03-13 |
| JPH0580464B2 (en) | 1993-11-09 |
| MX159907A (en) | 1989-09-29 |
| EP0173202A3 (en) | 1986-12-03 |
| BR8504162A (en) | 1986-06-24 |
| DD236520A5 (en) | 1986-06-11 |
| EP0173202A2 (en) | 1986-03-05 |
| DE3576816D1 (en) | 1990-05-03 |
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