CS229170B1 - Method of preparing 4-amino-1-phenyl-5-chloro-6-oxo-1h-pyridazine - Google Patents
Method of preparing 4-amino-1-phenyl-5-chloro-6-oxo-1h-pyridazine Download PDFInfo
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- CS229170B1 CS229170B1 CS949082A CS949082A CS229170B1 CS 229170 B1 CS229170 B1 CS 229170B1 CS 949082 A CS949082 A CS 949082A CS 949082 A CS949082 A CS 949082A CS 229170 B1 CS229170 B1 CS 229170B1
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- Prior art keywords
- pyridazine
- phenyl
- oxo
- amino
- chloro
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- WYKYKTKDBLFHCY-UHFFFAOYSA-N chloridazon Chemical compound O=C1C(Cl)=C(N)C=NN1C1=CC=CC=C1 WYKYKTKDBLFHCY-UHFFFAOYSA-N 0.000 title claims description 15
- 238000000034 method Methods 0.000 title description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- VKWCOHVAHQOJGU-UHFFFAOYSA-N 4,5-dichloro-2-phenylpyridazin-3-one Chemical compound O=C1C(Cl)=C(Cl)C=NN1C1=CC=CC=C1 VKWCOHVAHQOJGU-UHFFFAOYSA-N 0.000 claims description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 239000011541 reaction mixture Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical class OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- -1 amino-4,5-dichloro-1-phenyl-6-oxo-1H-pyridazine Chemical compound 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229940044652 phenolsulfonate Drugs 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 125000005374 siloxide group Chemical group 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- VUTBELPREDJDDH-UHFFFAOYSA-N 4-amino-5-hydroxymethyl-2-methylpyrimidine Chemical compound CC1=NC=C(CO)C(N)=N1 VUTBELPREDJDDH-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- 241000219310 Beta vulgaris subsp. vulgaris Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- LTNCICGQRAKAQZ-UHFFFAOYSA-N NC=1C=NN(C(C1F)=O)C1=CC=CC=C1 Chemical compound NC=1C=NN(C(C1F)=O)C1=CC=CC=C1 LTNCICGQRAKAQZ-UHFFFAOYSA-N 0.000 description 1
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 235000021536 Sugar beet Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- BYMHXIQVEAYSJD-UHFFFAOYSA-M sodium;4-sulfophenolate Chemical compound [Na+].OC1=CC=C(S([O-])(=O)=O)C=C1 BYMHXIQVEAYSJD-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
Vynález sa týká sposobu výroby 4-smino-1-fenyl-5-chlór-6-oxo-1H-pyridazínu reakciou 4,5-dichlór-1-fenyl-6-oxo-1H-pyridazínu s vodným roztokom amoniaku pri zvýšenej teplote a tlaku za přítomnosti inertaých anorganických a/alebo povrchovoaktívnych látok,The present invention relates to a process for preparing 4-amino-1-phenyl-5-chloro-6-oxo-1H-pyridazine by reacting 4,5-dichloro-1-phenyl-6-oxo-1H-pyridazine with an aqueous ammonia solution at elevated temperature and pressure in the presence of inorganic and / or surface-active substances,
4-amino-1-fenyl-5-chlór-6-oxo-1H-pyridazín je účinnou látkou herbicídneho přípravku na selektívne ničenie burín v cukrové j repe /Pyramín, Burex/.4-Amino-1-phenyl-5-chloro-6-oxo-1 H -pyridazine is an active ingredient of a herbicidal preparation for the selective control of weeds in sugar beet (Pyramine, Burex).
Doteraz sú známe viaceré sposoby výroby 4-amino-1-fenyl-5-chlór-6-oxo-1H-pyridazínu, Podía Čs, pat, 120 858 a čs. AO 189 538 postup výroby 4-amino-1-fenyl-5-chlór-6-oxo-1H-pyridazínu spočívá v amináoii 4,5-dichlór-1-fenyl-6-oxo-1H-pyridazínu plynným amoniakom pri teplote udržujúcej reakčnú zmes vo formě taveniny. Predmetom čs. AO 208 446 je sposob výroby 4-amíno-1-fenyl-5-chlór-6-oxo-1H-pyridazínu už popísáným postupom za přítomnosti močoviny,Several methods for the preparation of 4-amino-1-phenyl-5-chloro-6-oxo-1 H -pyridazine are known to date, according to U.S. Pat. No. 120,858 and U.S. Pat. AO 189 538 A process for the preparation of 4-amino-1-phenyl-5-chloro-6-oxo-1H-pyridazine consists of amino-4,5-dichloro-1-phenyl-6-oxo-1H-pyridazine with ammonia gas at a temperature maintaining the reaction melt blend. Subject of MS. AO 208 446 is a process for the production of 4-amino-1-phenyl-5-chloro-6-oxo-1H-pyridazine as described above in the presence of urea,
Ďalšie známe postupy výroby 4-amino-1-fenyl-5-chlor-6-oxo-1H-pyridazínu spočívajú v amináoii 4,5-ůichlór-i-fenyl-6-oxo-1H-pyridazínu v organických rozpúštadlách /NDR pat. 131 172/ ako aj vo vodnom prostředí za zvýšenej teploty a tlaku /Brit. pat. 871 674; EP 28-359/. Tento postup výroby 4-amino-1-fenyl-5-chlór -6-oxo-1H-pyridazinu pri svojich výhodách ako napr, získanie technického produktu vo vysokéj čistotě, má aj svoje nedostatky pri priemyselnej výrobě. Pri amináoii 4,5-dichlór-1-fenyl-6-oxo-1H-pyridazínu vodným roztokom amoniaku pri zvýšenej teplote a tlaku, reakčná zmes tvoří homogenný roztok v reaktore. Po jeho ochladení vypadává tuhý 4-amino-1-fenyl-5-chlór-6-oxo-1H-pyridazín, ktorý sa usadzuje na chladné steny reaktora t.j. dochádza vOther known processes for the preparation of 4-amino-1-phenyl-5-chloro-6-oxo-1H-pyridazine are based on amino-4,5-chloro-1-phenyl-6-oxo-1H-pyridazine in organic solvents / GDR pat. 131 172 (as well as in an aqueous environment at elevated temperature and pressure). pat. 871 674; EP 28-359]. This process of producing 4-amino-1-phenyl-5-chloro-6-oxo-1H-pyridazine, with its advantages such as obtaining a technical product in high purity, also has its drawbacks in industrial production. With the amino-4,5-dichloro-1-phenyl-6-oxo-1H-pyridazine aqueous solution of ammonia at elevated temperature and pressure, the reaction mixture forms a homogeneous solution in the reactor. Upon cooling, solid 4-amino-1-phenyl-5-chloro-6-oxo-1 H -pyridazine precipitates, which settles on the cold walls of the reactor, i. occurs in
k inkrustáoii. Táto skutečnost stažuje izoláciu technického 4-amino-1-fenyl-5-ehlór-6-oxo-1H-pyridazínu z reaktora.k incrustáoii. This makes it difficult to isolate the technical 4-amino-1-phenyl-5-fluoro-6-oxo-1H-pyridazine from the reactor.
Teraz sa zistil sposob výroby 4-amino-1-fenyl-5-chlór-6229 170The process for producing 4-amino-1-phenyl-5-chloro-6229 170 has now been found
-οχο-ΙΗ-pyridazínu reakciou 4,5-dichlór-l-fenyl-6-oxo-lH-pyridazínu s vodným roztokom amoniaku, připadne v přítomnosti katalyzátora, pri teplote 80 až 200° C a tlaku 0,1 až 5,0 MPa podl’a vynálezu.-οχο-ΙΗ-pyridazine by reacting 4,5-dichloro-1-phenyl-6-oxo-1H-pyridazine with an aqueous ammonia solution, optionally in the presence of a catalyst, at a temperature of 80 to 200 ° C and a pressure of 0.1 to 5.0 MPa according to the invention.
Podstata vynálezu spočívá v tom, že k reakčnej zmesi sa pridajú před reakciou vo vodě nerozpustné anorganické a/álebo povrcho vo aktivně látky v množstve 0,1 až 15% hmot. v pomere k 4,5-dichlór-l-fenyl-6-oxo-lH-pyridazínu. Ako příklady pre vo vodě neroz<· pustne anorganické látky možno uviesť zmes polykremičitých kyselin /silikagél/, prírodný kremičitan hlinitý /kaolín/, siloxid, vápenec, mastenec a pod,.The present invention is characterized in that water-insoluble inorganic and / or surface-active substances are added to the reaction mixture in an amount of 0.1 to 15% by weight before the reaction. in relation to 4,5-dichloro-1-phenyl-6-oxo-1H-pyridazine. Examples of water-insoluble inorganic substances include a mixture of polysilicic acids (silica gel), natural aluminum silicate (kaolin), siloxide, limestone, talc and the like.
Príkladmi pre povrchovo aktivně látky može byť sulfitový výluh, etylénoxidový adukt kyseliny ricínolejověj s počtom etylénoxidových jednotiek 19 až 24 /Slovasol EL/, zmesn^kopolymér propylénoxidu a etylénoxidu v pomere 1 : 0,87 /Slovanik M-640/ ap·.Examples of surfactants include sulphite liquor, ricinoleic acid ethylene oxide adduct having a number of ethylene oxide units of 19 to 24 (Slovasol EL), a propylene oxide / ethylene oxide copolymer of 1: 0.87 (Slovanik M-640 / ap).
Výhodou postupu podlá vynálezu je tá skutočnosť, že pri výrobě 4-amino-l-fenyl-5-chlór-6-oxo-lH-pyridazínu nedochádza vo vodnom prostředí , pri zvýšenej teplote a tlaku, k inkrustácii v reakčnej aparatuře, ktorou može byť disfcontinuálna tlaková nádoba resp. kontinuálny reaktor. To umožní jednoduché vyprázdnenie reakčnej nádoby, fialej je potřebné zdorazniť, že sposobom podlá vynálezu sa ovplyvní veTkosť tvoriacich sa kryštálov 4-amino-l-fenyl-5-chlór-6-oxo-lH-pyridazínu, čo má nemalý vyýznam pri jeho aplikačněj úpravě.The advantage of the process according to the invention is that the production of 4-amino-1-phenyl-5-chloro-6-oxo-1H-pyridazine does not result in an incrustation in the reaction apparatus at elevated temperature and pressure, which may be disfcontinuous pressure vessel resp. continuous reactor. This allows for a simple emptying of the reaction vessel, the violet having to be made clear that the size of the 4-amino-1-phenyl-5-chloro-6-oxo-1H-pyridazine crystals being formed is influenced by the process according to the invention. .
Nasledujúce příklady ozrejmujú, ale neobmedzujú predmet vynálezu.The following examples illustrate but do not limit the scope of the invention.
Příklad. 1Example. 1
Do 21 trepacieho autoklávu sa předložilo 150 g 96,2%-ného150 g of 96.2% were introduced into a 21 shaking autoclave
4,5-dichlór-l-fenyl-6-oxo-lH-pyridazínu, 1075 g 15%-ného vodného roztoku amoniaku, 25 g sodnéj soli 4-fenolsulfonovej kyseliny a 1,5 g silikagélu. Veko tlakovej nádoby sa uzavřelo a reakčná zmes sa udržiavala pri teplote 150°C po dobu 3 h. Po uplynutíreakčnej doby sa reakčná zmes v nádobě ochladila a po otvorení veka sa jednoducho kvantitativné odsala na filtráciu pomocou vývevy. Získalo sa 114 g technického 4-amino-l-feny 1-5-ch3or-6-oxo-lH-pyridazínu o čistotě 93,2%.4,5-dichloro-1-phenyl-6-oxo-1H-pyridazine, 1075 g of 15% aqueous ammonia solution, 25 g of 4-phenolsulfonic acid sodium salt and 1.5 g of silica gel. The lid of the pressure vessel was sealed and the reaction mixture was maintained at 150 ° C for 3 h. After the reaction time, the reaction mixture in the vessel was cooled and, after opening the lid, was simply quantitatively aspirated for filtration by means of a vacuum pump. 114 g of technical 4-amino-1-phenyl-5-chloro-6-oxo-1H-pyridazine having a purity of 93.2% were obtained.
Příklad 2Example 2
229 170229 170
Do tlakovej nádoby, popísanej v příklade 1, sa navážilo 150 g 96,2%-ného 4,5-dichlór-l-fenyl-6-oxo-lH-pyridazínu, 1075 g 15%-ného vodného roztoku amoniaku, 25 g draselnej soli 4-hydroxybenzoovej kyseliny, 1,5 g kaolínu a 5 g Slovasolu EL. Postupom ako v příklade 1 sa získalo 117,2 g technického 4-amino-l-fenyl-5-chlór-6-oxo-lH-pyridazínu o Čistotě 94,8%.150 g of 96.2% 4,5-dichloro-1-phenyl-6-oxo-1H-pyridazine, 1075 g of a 15% aqueous ammonia solution, 25 g of potassium were weighed into the pressure vessel described in Example 1. salts of 4-hydroxybenzoic acid, 1.5 g of kaolin and 5 g of Slovasol EL. Following the procedure of Example 1, 117.2 g of industrial 4-amino-1-phenyl-5-chloro-6-oxo-1H-pyridazine was obtained with a purity of 94.8%.
Příklad 3Example 3
Do tlakovej nádoby popísanej v příklade 1 sa navážilo 150 g 96,2%-ného 4,5-dichlór-l-fenyl-6-oxo-lH-pyridazínu, 1075 g 15%ného vodného roztoku amoniaku, 17 g 4-fenolsulfónanu sodného a 5 g Syntaponu L /sulfát laurylalkoholr/. Postupom ako v příklade 1 sa získalo 119 g technického 4-amino-l-fenyl-5-chlór-6οχο-ΙΗ-pyridazínu o čistotě 93,9%.150 g 96.2% 4,5-dichloro-1-phenyl-6-oxo-1H-pyridazine, 1075 g 15% aqueous ammonia solution, 17 g sodium 4-phenolsulfonate were weighed into the pressure vessel described in Example 1 and 5 g Syntapone L (lauryl alcohol sulfate). As in Example 1, 119 g of industrial 4-amino-1-phenyl-5-chloro-6-oxo-β-pyridazine was obtained with a purity of 93.9%.
Příklad 4Example 4
Do tlakovej nádoby popísanej v příklade 1 sa předložilo 150 g 96,2%-ného 4,5-dichlór-l-fenyl-6-οχο-ΙΗ-pyridazínu, 1050 g 25%-ného vodného roztoku amoniaku, 20 g 4-fenolsulfónanu sodného a 7 g siloxidu /zrážaný SiOg/. Po uzavretí veka tlakovej nádoby sa reakčná zmes 1 h udržovala pri teplote 150°C. Po uplynutí reakčnej doby sa reakčné zmes v tlakovej nádobě ochladila a po otvorení veka sa kvantitativné odsala na filtráciu pomocou vývěvy. Získalo sa 116 g technického 4-amino-l-fenyl-5-chlór-6-οχο-ΙΗ-pyridazínu o čistotě 94,80%.150 g of 96.2% 4,5-dichloro-1-phenyl-6-οχο-ΙΗ-pyridazine, 1050 g of a 25% aqueous ammonia solution, 20 g of 4-phenolsulfonate were charged to the pressure vessel described in Example 1. sodium and 7 g of siloxide (precipitated SiO2). After closing the pressure vessel lid, the reaction mixture was kept at 150 ° C for 1 h. After the reaction time, the reaction mixture was cooled in a pressure vessel and, after opening the lid, was quantitatively aspirated for filtration by means of a vacuum pump. 116 g of technical 4-amino-1-phenyl-5-chloro-6-oxo-pyrid-pyridazine having a purity of 94.80% were obtained.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS949082A CS229170B1 (en) | 1982-12-22 | 1982-12-22 | Method of preparing 4-amino-1-phenyl-5-chloro-6-oxo-1h-pyridazine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS949082A CS229170B1 (en) | 1982-12-22 | 1982-12-22 | Method of preparing 4-amino-1-phenyl-5-chloro-6-oxo-1h-pyridazine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CS229170B1 true CS229170B1 (en) | 1984-06-18 |
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ID=5444993
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS949082A CS229170B1 (en) | 1982-12-22 | 1982-12-22 | Method of preparing 4-amino-1-phenyl-5-chloro-6-oxo-1h-pyridazine |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS229170B1 (en) |
-
1982
- 1982-12-22 CS CS949082A patent/CS229170B1/en unknown
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