CA1161842A - Manufacture of 4-amino-5-chloro-1-phenylpyridaz-6one - Google Patents
Manufacture of 4-amino-5-chloro-1-phenylpyridaz-6oneInfo
- Publication number
- CA1161842A CA1161842A CA000373691A CA373691A CA1161842A CA 1161842 A CA1161842 A CA 1161842A CA 000373691 A CA000373691 A CA 000373691A CA 373691 A CA373691 A CA 373691A CA 1161842 A CA1161842 A CA 1161842A
- Authority
- CA
- Canada
- Prior art keywords
- phenylpyridaz
- reaction
- amino
- chloro
- ammonia
- 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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- Pyridine Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
O.Z. 0050/034048 ABSTRACT OF THE DISCLOSURE: The manufacture of substantially pure 4-amino-5-chloro-1-phenylpyridaz-6-one by reaction of 4,5-dichloro-1-phenylpyridaz-6-one with ammonia in the pre-sence of phenol-4-sulfonic acid.
Description
- l - O.Z. 0050/03~048 Manufacture of 4-amino-5-chloro-l-phenylpyridaz-6-one - The present in~ention relates to a process ~or the manu facture o~ substantially pure 4-amino-5-chloro-1-phenylpyridaz--6-one by reaction of 4~5-dichloro-1-phenylpyridaz-6-one with ammonia in the presence of phenol-4-sulfonic acid.
~ he use o~ 4-amino-~ chloro-1-phenylpyridaz-6-one as a herbicide, especially ~or the selective control of weeds in s~g~rbeets, haæ been disclosed. The compound is manu~actured in accordance with ~ritish 871,674 by reaction o~ 4,5-dichloro--l-phenylpyridaz-6-one with aqueous ~mmonia at ~uperatmospheric pressure and elevated temperatures. A mixtuxe is obtained o~
~hich about 80 % (wt %) i9 4-amino-5-chloro-l~phenylpyridaz--6-one and about 20 % is the isomeric 5-amino-4-chloro-1 -phenylpyridaz-6-one~ which is not such a good herbicide.
In order to manu~acture crop protection agents containing a~ much biologic~lly active mgredient as possible, tech-nical-grade active ingredients o~ the maximum obtainable purity re required. German Laid-Open Application DE-OS ly~20,186 disclo~es the substantial remo~al of the undesired isomeric compound ~rom ~he mixture obtai~ed on m2nu~acture by extraction with nonpolar solvents ~rom the group of aromatic and hydroaromatic hydrocarbons.
It has further been disclosed to carry out the reaction o~ the 4,5-~ichlorophenylp~ridazone with ammonia in organic solvents, a product of high puri~y being obtained ~German Democratic RepubliG DD 1~1,172)~ ~owe~er, the use o~ organic 501vent~ is a drawback.
~ he use o~ 4-amino-~ chloro-1-phenylpyridaz-6-one as a herbicide, especially ~or the selective control of weeds in s~g~rbeets, haæ been disclosed. The compound is manu~actured in accordance with ~ritish 871,674 by reaction o~ 4,5-dichloro--l-phenylpyridaz-6-one with aqueous ~mmonia at ~uperatmospheric pressure and elevated temperatures. A mixtuxe is obtained o~
~hich about 80 % (wt %) i9 4-amino-5-chloro-l~phenylpyridaz--6-one and about 20 % is the isomeric 5-amino-4-chloro-1 -phenylpyridaz-6-one~ which is not such a good herbicide.
In order to manu~acture crop protection agents containing a~ much biologic~lly active mgredient as possible, tech-nical-grade active ingredients o~ the maximum obtainable purity re required. German Laid-Open Application DE-OS ly~20,186 disclo~es the substantial remo~al of the undesired isomeric compound ~rom ~he mixture obtai~ed on m2nu~acture by extraction with nonpolar solvents ~rom the group of aromatic and hydroaromatic hydrocarbons.
It has further been disclosed to carry out the reaction o~ the 4,5-~ichlorophenylp~ridazone with ammonia in organic solvents, a product of high puri~y being obtained ~German Democratic RepubliG DD 1~1,172)~ ~owe~er, the use o~ organic 501vent~ is a drawback.
- 2 - o.zO 0050~0340~8 - We ha~e now found that 4-ami~o-~ chlororl-phenylpyridaz- ~i -~-one is readily obtained in excellen~ yields and h~ h p~rit~
when 4,5-dichloro-1-phe~ylpyridaz 6-o~e is reacte.d with an aqueous solution o~ ammonia at from 20 to 200C and ~rom 1 to ~0 bars in the presence of p~enol~4-sul*onic acidO
.The process according to th~ invention has two esser.tial ad~antag~s. The first is that, as a result of the use of water as reactio~ medi~m~ the process is exceedin~ly simple and there~ore eco~omical, because the water-insoluble end lo product can be ~parated Yrem the reaction mixture by simple . uction filtration; at the ~ame time, the readily water--soluble ammoni~m salt o~ phenol-4-sulfonic acid is sepa-rated ~rom t~e end product. The second advantage is that the phenol-4-3ul~0nic acid i~fluenc~s the isomer ratio d~ing tbe reaction direct, whereas i~l the prior art processes the unde~ired isomeric compound is ~ormed and is removed by employing organic solvents.
~ n contrast to thes~ prior art processes, the process accardins to the i~ention ~i~es, muc~ more simply and ec.onomlcally, the desired 4-aminopyrida20ne deri~ati~e in about ~0 ~ yield and g5 to 99 ~ purity.
The reaction may be carried out for instance as follows.
4,5-Dichloro-l-phen~lpyrida3-6-ane, aqu~ous ammonia solution and phenol-4 sul~onic acid are introduced into a pressure vessel, the ~essel is closed and the mixture is heated to the desired reaction temperature and kept at this t~mperature ~or several hours. Ad~antageously, the reaction components are mixed" ~or exampl~ by stirring. Upon completion o~ the reaction J
_ 3 _ o~z. OoSo/034048 the reaction mixture is cooled~ and the solid is filtered off g washed with water and dried. The use o~ a 5~ to 20-fold molar e~cess o~ ammonia, ~ith reference to the 4,5-dichloro compound, and o~ a 5 to 3~ ~ (wt ~) strength a~ueous ammonia solution has proved-to be ad~antageous. In the reactio~ with ammonia~
the phenol-4 sulfo~ic acid is in the form of its ammonium ~alt. The term "phenol-4-~ulfonic acid" ~hould, there~oreg ~or th~ purposes of the invention, also be taXen to mean its ammo~ium salt~
The reaction i~ carried out at from 20 to 200C, preferably at least 80C, advantageously at from 100 to 150C, and particularly at ~rom 110 to 130C.
~ xpediently, the process is carried out in the presence of ~rom 1 to 100 mole% of pl~enol-4-sulfonic acid, based on the 4,5-dichloro compound, preferably at least 10 mole~, adYantageously Prom 20 to 70 mole%, and ~specially Prom 30 t~ 50 mole%.
me reaction is effected at superatmospheric pressure (1 bar to 50 bars), preferably at ~rom 3 to 10 bars~ and especially at the autogenous pressure in the closed reaction ~es~el when the reaction temperature is reached. It is also possible to increase the pressure in the closed ves~el durin~
the reaction by pressuring ammonia in. Some o~ the ammonia thus introduced dissol~es in the aqueous ammonia solution.
The process according to the invention is non-pollutîng, because the mother liquor obtained on separation o~ the reaction product can, i~ desired a~ter the additio~ of ammcnia, aqueous ammonia solution or phenol-4-sul~onic acid, be employed again ~.~61~
- 4 - o.Z. 0050~034048 ~or reaction with further 4,5-dichloro compound. The mother liquor ~ay therefore be recycled in whole or in part.
The ~llowing examples illustrate the sImplicity and reliability o~ the process according to ~he invention.
85 parts by Yol~me of 15 % (wt ~) strangth aqueous ammonia, .
12.05 parts by ~ei~ht o~ 4,5-dichloro-1-phenylpyridaz-6-one and 6. 2 parts by weight of a 70 ~ strength aqueous solution o~ phenol-4~3ulfonic acid (parts by volume bearing the same relationship to part3 by weight as the liter to the kilogram) are introduc~d into a jacketed pressure ves el having a capa-city o~ 300 part3 by volume. The reaction mixture is heated to 130C while stirring and kept for 4 hours at this tempe-rature, while still stirrin~. ~he autogenous pressure which i~ hereupon generated is 6 b~rs. The reaction mixture is then allowed to cool to r~om tamperature (20C) and the mother li~uor is completely filtered off. The solid reaction product is washed with water and dried in vacuo at lOaC.
Th~re i~ obtained 9.8 parts by weight (89 % o~ theor~J) of ~-amino-~-chloro-1-phenylpyridaz-6~one o~ melting point 205-206C. ~he amount o~ 5-amino-4 -chloro- 1-phenylpyridaz--6-o~e is determined gas-chromatographically and ~ound to be 1 ~, and the amo.unt o~ 4~amino derivati~e ~9 Z.
The mother liquor se~rated in E~ample 1, 12.05 parts by weight of 4,5-dichloro~l~phenylpyridaz- 6-one and 15 parts by volume of 15 ~ streng~h aqueous ammonia are mixed, and kept, as des-cribed i~ Example 1, at 1~0C ~or 6 hours. ~ter working up 4~
_ 5 _ o.z~ 0050/V34048 there is o~tained 10.1 part~ by ~eight (91 p of theory) o~
4-amino~ chloro-1-phenylpyridaz-6-one of melting point 202-204C. The amount of 5-amino-4-chloro-l~phenylpyridaz--6-one was determined gas-chromatographically and ~ound to be 2-3 ~, and the amount of 4-amino derivative 96 ~.
when 4,5-dichloro-1-phe~ylpyridaz 6-o~e is reacte.d with an aqueous solution o~ ammonia at from 20 to 200C and ~rom 1 to ~0 bars in the presence of p~enol~4-sul*onic acidO
.The process according to th~ invention has two esser.tial ad~antag~s. The first is that, as a result of the use of water as reactio~ medi~m~ the process is exceedin~ly simple and there~ore eco~omical, because the water-insoluble end lo product can be ~parated Yrem the reaction mixture by simple . uction filtration; at the ~ame time, the readily water--soluble ammoni~m salt o~ phenol-4-sulfonic acid is sepa-rated ~rom t~e end product. The second advantage is that the phenol-4-3ul~0nic acid i~fluenc~s the isomer ratio d~ing tbe reaction direct, whereas i~l the prior art processes the unde~ired isomeric compound is ~ormed and is removed by employing organic solvents.
~ n contrast to thes~ prior art processes, the process accardins to the i~ention ~i~es, muc~ more simply and ec.onomlcally, the desired 4-aminopyrida20ne deri~ati~e in about ~0 ~ yield and g5 to 99 ~ purity.
The reaction may be carried out for instance as follows.
4,5-Dichloro-l-phen~lpyrida3-6-ane, aqu~ous ammonia solution and phenol-4 sul~onic acid are introduced into a pressure vessel, the ~essel is closed and the mixture is heated to the desired reaction temperature and kept at this t~mperature ~or several hours. Ad~antageously, the reaction components are mixed" ~or exampl~ by stirring. Upon completion o~ the reaction J
_ 3 _ o~z. OoSo/034048 the reaction mixture is cooled~ and the solid is filtered off g washed with water and dried. The use o~ a 5~ to 20-fold molar e~cess o~ ammonia, ~ith reference to the 4,5-dichloro compound, and o~ a 5 to 3~ ~ (wt ~) strength a~ueous ammonia solution has proved-to be ad~antageous. In the reactio~ with ammonia~
the phenol-4 sulfo~ic acid is in the form of its ammonium ~alt. The term "phenol-4-~ulfonic acid" ~hould, there~oreg ~or th~ purposes of the invention, also be taXen to mean its ammo~ium salt~
The reaction i~ carried out at from 20 to 200C, preferably at least 80C, advantageously at from 100 to 150C, and particularly at ~rom 110 to 130C.
~ xpediently, the process is carried out in the presence of ~rom 1 to 100 mole% of pl~enol-4-sulfonic acid, based on the 4,5-dichloro compound, preferably at least 10 mole~, adYantageously Prom 20 to 70 mole%, and ~specially Prom 30 t~ 50 mole%.
me reaction is effected at superatmospheric pressure (1 bar to 50 bars), preferably at ~rom 3 to 10 bars~ and especially at the autogenous pressure in the closed reaction ~es~el when the reaction temperature is reached. It is also possible to increase the pressure in the closed ves~el durin~
the reaction by pressuring ammonia in. Some o~ the ammonia thus introduced dissol~es in the aqueous ammonia solution.
The process according to the invention is non-pollutîng, because the mother liquor obtained on separation o~ the reaction product can, i~ desired a~ter the additio~ of ammcnia, aqueous ammonia solution or phenol-4-sul~onic acid, be employed again ~.~61~
- 4 - o.Z. 0050~034048 ~or reaction with further 4,5-dichloro compound. The mother liquor ~ay therefore be recycled in whole or in part.
The ~llowing examples illustrate the sImplicity and reliability o~ the process according to ~he invention.
85 parts by Yol~me of 15 % (wt ~) strangth aqueous ammonia, .
12.05 parts by ~ei~ht o~ 4,5-dichloro-1-phenylpyridaz-6-one and 6. 2 parts by weight of a 70 ~ strength aqueous solution o~ phenol-4~3ulfonic acid (parts by volume bearing the same relationship to part3 by weight as the liter to the kilogram) are introduc~d into a jacketed pressure ves el having a capa-city o~ 300 part3 by volume. The reaction mixture is heated to 130C while stirring and kept for 4 hours at this tempe-rature, while still stirrin~. ~he autogenous pressure which i~ hereupon generated is 6 b~rs. The reaction mixture is then allowed to cool to r~om tamperature (20C) and the mother li~uor is completely filtered off. The solid reaction product is washed with water and dried in vacuo at lOaC.
Th~re i~ obtained 9.8 parts by weight (89 % o~ theor~J) of ~-amino-~-chloro-1-phenylpyridaz-6~one o~ melting point 205-206C. ~he amount o~ 5-amino-4 -chloro- 1-phenylpyridaz--6-o~e is determined gas-chromatographically and ~ound to be 1 ~, and the amo.unt o~ 4~amino derivati~e ~9 Z.
The mother liquor se~rated in E~ample 1, 12.05 parts by weight of 4,5-dichloro~l~phenylpyridaz- 6-one and 15 parts by volume of 15 ~ streng~h aqueous ammonia are mixed, and kept, as des-cribed i~ Example 1, at 1~0C ~or 6 hours. ~ter working up 4~
_ 5 _ o.z~ 0050/V34048 there is o~tained 10.1 part~ by ~eight (91 p of theory) o~
4-amino~ chloro-1-phenylpyridaz-6-one of melting point 202-204C. The amount of 5-amino-4-chloro-l~phenylpyridaz--6-one was determined gas-chromatographically and ~ound to be 2-3 ~, and the amount of 4-amino derivative 96 ~.
Claims (2)
1. A process for the manufacture of substantially pure 4-amino-5-chloro-1-phenylpyridaz-6-one by reaction of 4,5--dichloro-1-phenylpyridaz-6-one with ammonia, wherein the reaction is carried out with an aqueous solution of ammonia, at from 20° to 200°C and from 1 to 20 bars, in the presence of phenol-4-sulfonic acid.
2. A process as claimed in claim 1, wherein the 4-amino--5-chloro-1-phenylpyridaz-6-one is separated from the reaction mixture after the reaction, and the remaining mother liquor is, if desired after the addition of ammonia, aqueous ammonia solution or phenol-4-sulfonic acid, employed again for reac-tion with further 4,5-dichloro-1-phenylpyridaz-6-one.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000373691A CA1161842A (en) | 1981-03-24 | 1981-03-24 | Manufacture of 4-amino-5-chloro-1-phenylpyridaz-6one |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000373691A CA1161842A (en) | 1981-03-24 | 1981-03-24 | Manufacture of 4-amino-5-chloro-1-phenylpyridaz-6one |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1161842A true CA1161842A (en) | 1984-02-07 |
Family
ID=4119519
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000373691A Expired CA1161842A (en) | 1981-03-24 | 1981-03-24 | Manufacture of 4-amino-5-chloro-1-phenylpyridaz-6one |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1161842A (en) |
-
1981
- 1981-03-24 CA CA000373691A patent/CA1161842A/en not_active Expired
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