CS259207B1 - Method of 4-amino-1-phenyl-5-chloro-6-oxo-1h-pyridazine insulation - Google Patents
Method of 4-amino-1-phenyl-5-chloro-6-oxo-1h-pyridazine insulation Download PDFInfo
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- CS259207B1 CS259207B1 CS851679A CS167985A CS259207B1 CS 259207 B1 CS259207 B1 CS 259207B1 CS 851679 A CS851679 A CS 851679A CS 167985 A CS167985 A CS 167985A CS 259207 B1 CS259207 B1 CS 259207B1
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- pyridazine
- oxo
- phenyl
- chloro
- amino
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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 abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 9
- 238000009413 insulation Methods 0.000 title 1
- 238000010533 azeotropic distillation Methods 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- 238000002955 isolation Methods 0.000 claims abstract description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 17
- 239000008096 xylene Substances 0.000 claims description 17
- 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 11
- 239000007900 aqueous suspension Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- HAKJEHJYRKVCIU-UHFFFAOYSA-N 4-amino-5-chloro-2-phenylpyridazin-3-one Chemical compound O=C1C(N)=C(Cl)C=NN1C1=CC=CC=C1 HAKJEHJYRKVCIU-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- AAILEWXSEQLMNI-UHFFFAOYSA-N 1h-pyridazin-6-one Chemical compound OC1=CC=CN=N1 AAILEWXSEQLMNI-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 13
- 239000000725 suspension Substances 0.000 description 6
- 238000005576 amination reaction Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000004563 wettable powder Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- 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
- ZIBQCQDAFOPHBJ-UHFFFAOYSA-N 4-chloro-3-phenyl-1h-pyridazin-6-one Chemical compound ClC1=CC(=O)NN=C1C1=CC=CC=C1 ZIBQCQDAFOPHBJ-UHFFFAOYSA-N 0.000 description 1
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical class NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 241000219310 Beta vulgaris subsp. vulgaris Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-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
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 230000003254 anti-foaming effect Effects 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000013020 final formulation Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
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- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Riešenie sa týká spósobu izolácie 4-amino-l-fenyl-5-chlór-6-oxo-lH-pyridazínu vyrobeného reakciou 4,5-dichlór-l-fenyl- -6-oxo-lH-pyridazínu s plynným amoniakem za použitia povrchovoaktívnych látok, ktoré sa pridávajú před azeotropickou destiláciou a/alebo před filtráciou v množstve 0,05 až' 3 % hmot.The solution relates to the method of isolation 4-amino-l-phenyl-5-chloro-6-oxo-pyridazine by the reaction of 4,5-dichloro-1-phenyl- With 6-oxo-1H-pyridazine with ammonia gas using surfactants, which are added before azeotropic distillation and / or before filtration in quantity 0.05 to 3 wt.
Description
259207·259207 ·
Vynález sa týká spósobu izolácie 4-amino-l-fenyl-5-chlór-6-oxo-lH-pyridazínu za přítomnosti povrchovo aktívnej látky.The invention relates to a process for the isolation of 4-amino-1-phenyl-5-chloro-6-oxo-1H-pyridazine in the presence of a surfactant.
4-amino-l-fenyl-5-chlčr-6-oxo-lH-pyridazín je herbicid určený predovšetkým na selektívne ničenie burín v cukrovéj repe /Burex, Pyramín/.4-Amino-1-phenyl-5-chloro-6-oxo-1H-pyridazine is a herbicide intended primarily for the selective control of weeds in sugar beet (Burex, Pyramine).
Doteraz sú známe viaceré spósoby výroby 4-amino-l-fenyl-5-chlór-6-oxo-lH-pyridazíntr. Predmetom GB 871 674 je spósob výroby 4-amino-l-fenyl-5-chlór-6-oxo-lH-pyridazínu reakciou 4,5-dichlór-l-fenyl-6-oxo-lH-pyridazínu s vodným roztokom amoniaku za tlaku pri zvýšenej teplote. Týmto postupom sa získá produkt s obsahom cca 80 % hmotnostných 4-amino-l-fenyl-5-chlór-6-oxo-lH-pyridazínu. Ďalej sú známe reakcie 4,5-dichlčr-l-fehyl-6-oxo-lH-pyridazínu s vodným roztokem amoniaku za tlaku v přítomnosti katalyzátorat/EP 28 až 359, CS 214 843 a 226 250/, pri ktorých sa získá produkt s vysokou čistotou.Several methods for the preparation of 4-amino-1-phenyl-5-chloro-6-oxo-1H-pyridazine are known to date. GB 871 674 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 aqueous ammonia solution under pressure at elevated temperature. This gives a product containing about 80% by weight of 4-amino-1-phenyl-5-chloro-6-oxo-1H-pyridazine. Further, it is known to react 4,5-dichloro-1-phenyl-6-oxo-1H-pyridazine with aqueous ammonia solution under pressure in the presence of a catalyst ( EP 28-359, CS 214 843 and 226 250) to give the product with high purity.
Podlá CS 120 858 výroba 4-amino-l-fenyl-5-chlór-6-oxo-lH-pyridazínu s.a uskutoční amináciou 4,5-dichlór-l-fenyl-6-oxo-lH-pyridazínu plynným amoniakem pri teplote udržujúcej reakčnú zmes vo formě taveniny. Takto získaný technický produkt s obsahom 70 až 75 % 4-amino-l-fenyl-5-chlór-6-oxo-lH-pyridazínu sa podrobí extrakcii s xylénom /CS 122 103/, pričom sa odstráni nežiadúci izomér 5-amino-l-fenyl-4-chlór-6-oxo-lH-pyridazín. Z izolovaného xylénového koláča 4-amino-l-fenylr-5-chlór-6-oxo-lH-pyridazínu sa odstráni rozpúšťadlo azeotropickou destiláciou s vodou. Produkt sa z vodnej suspenzie získá filtrácioxi na odstředivkách.According to CS 120 858, the preparation of 4-amino-1-phenyl-5-chloro-6-oxo-1H-pyridazine is carried out by amination of 4,5-dichloro-1-phenyl-6-oxo-1H-pyridazine with ammonia gas at a temperature maintaining the reaction temperature. melt blend. The technical product thus obtained containing 70 to 75% of 4-amino-1-phenyl-5-chloro-6-oxo-1H-pyridazine is subjected to extraction with xylene (CS 122 103), removing the undesired 5-amino-1 isomer. phenyl-4-chloro-6-oxo-pyridazine. The isolated 4-amino-1-phenyl-5-chloro-6-oxo-1H-pyridazine xylene cake was removed by azeotropic distillation with water. The product is recovered from the aqueous suspension by filtration on centrifuges.
Nevýhodou uvedeného postupu - okrem tvorby spenenej suspenzie, ku ktorej dochádza pri azeotropickej destilácii xylénového koláča - je, že pri aminácii menej čistého 4,5-dichlór-l-fenyl-6-oxo-lH-pyridazinu sa získá technický produkt 4-amino-l-fenyl-5-chlór-6-oxo-lH-pyridazínu znečistěný sprievodnými nečistotami, čím vznikajú ťažkosti pri filtrácii vodnej suspenzie na odstředivkách v dósledku zmien fyzikálnych vlastností produktu /lepkavost, spekavost/ a dochádza ku stratám. Nežiadúce změny fyzikálnych vlastností produktu majú za následok aj zhoršenú suspendovatelnost finálneho přípravku po úpravě na zmáčatelný prášok.The disadvantage of this process - besides the formation of a foamed suspension which occurs during azeotropic distillation of the xylene cake - is that amination of the less pure 4,5-dichloro-1-phenyl-6-oxo-1H-pyridazine yields the technical product 4-amino- 1-phenyl-5-chloro-6-oxo-1H-pyridazine contaminated with concomitant impurities, which causes difficulty in filtering the aqueous suspension on centrifuges due to changes in the physical properties of the product (stickiness, caking) and losses. Undesirable changes in the physical properties of the product also result in impaired suspendability of the final formulation after being made into a wettable powder.
Ďalšou nevýhodou je to, že po azeotropickej destilácii část xylénu zostáva v spekaných častiach produktu a pri sušeni produktu dochádza k jeho úniku do ovzdušia, čo sa prejavuje zhoršením pracovného prostredia.A further disadvantage is that after azeotropic distillation, part of the xylene remains in the sintered portions of the product and leaks to the atmosphere when the product is dried, resulting in a deterioration of the working environment.
Teraz sa zistil spósob izolácie 4-amino-l-fenyl-5-chlór-6-oxo-lH-pyridazínu vyrobeného reakciou 4,5-dichlór-l-fenyl-6-oxo-lH-pyridazínu s plynným amoniakom pri teplote 170 až 220 °C, následnou extrakciou přítomného neaktlvneho 5-amino-l-fenyl-4-chlór-6-oxo-lH-pyridazínu a nezreagovaného, 4,5-dichlór-l-fenyl-6-oxo-lH-pyridazínu s xylénom, ďalej odstránením rozpúštadla z xylénového koláča produktu azeotropickou destiláciou s vodou a filtráciou 4-amíno-l-fenyl-5-chlór-6-oxo-lH-pyridazínu z vodnej suspenzie podía vynálezu. Podstata vynálezu spočívá v tom, že ku xylénovému koláčů sa před azeotropickou destiláciou a/alebo před filtráciou přidá povrchovo aktívna látka v množstve 0,05 až 3 % hmotnostných v pomere k technickému 4-amino-l-fenyl-5-chlór-6-oxo-lH-pyridazínu.We have now found a process for the isolation of 4-amino-1-phenyl-5-chloro-6-oxo-1H-pyridazine produced by reacting 4,5-dichloro-1-phenyl-6-oxo-1H-pyridazine with ammonia gas at 170 to 170 ° C. 220 ° C, followed by extraction of the present inactive 5-amino-1-phenyl-4-chloro-6-oxo-1H-pyridazine and unreacted 4,5-dichloro-1-phenyl-6-oxo-1H-pyridazine with xylene, further removing the solvent from the xylene cake of the product by azeotropic distillation with water and filtering 4-amino-1-phenyl-5-chloro-6-oxo-1H-pyridazine from the aqueous suspension of the invention. SUMMARY OF THE INVENTION The surfactant is added to the xylene cakes prior to azeotropic distillation and / or filtration in an amount of 0.05 to 3% by weight relative to the technical 4-amino-1-phenyl-5-chloro-6- oxo-pyridazine.
Povrchovoaktívnymi látkami móžu byt Spolion založený na báze dialkylsulfojantaranu, Abeson” na báze kombinácii alkalickej soli kyseliny ďodecylbenzénsulfónovej, alkylpolyglykolétersulfátu alkalického s obsahom rozpúšťadiel, Odpeňovač T na báze živičných kyselin a etylénoxidu a pod.The surfactants may be Spolion based on dialkylsulfosuccinate, Abeson 'based on a combination of an alkali salt of dodecylbenzenesulfonic acid, an alkali-containing alkylpolyglycol ether sulfate, a T-foam based on bitumen acids and ethylene oxide and the like.
Výhodou postupu podía vynálezu - okrem známého účinku odpeňovacích prostriedkov, ktorý spočívá v zamedzení penenia reakčnej zmesi pri azeotropickej destilácii - je tá skutočnost, že aj v případe použitia menej čistého 4,5-dichlór-l-fenyl-6-oxo-lH-pyridazínu ako východiskového produktu pri aminácii sa získá po azeotropickej destilácii technický produkt 4-amino-l-fenyl-5-chlór-6-oxo-IH-pyridazínu s vysokou čistotou. Produkt je lahko filtrovatelný, neobsahuje zvyšky xylénu a nečistoty lepkavého charakteru, ktoré bývajú příčinou mechanických strát pri filtrácii. Ďalšia výhoda spočívá v zlepšení fyzikálnych vlastností Účinnej látky, čo sa prejavuje hlavně v zlepšení suspendovatelnosti finálneho přípravku upraveného na zmáčatelný prášok.The advantage of the process according to the invention - in addition to the known anti-foaming effect of avoiding foaming of the reaction mixture in azeotropic distillation - is that, even if less pure 4,5-dichloro-1-phenyl-6-oxo-1H-pyridazine is used as a starting material in the amination, after azeotropic distillation, the technical product of high purity 4-amino-1-phenyl-5-chloro-6-oxo-1H-pyridazine is obtained. The product is easily filterable and does not contain any xylene residues and sticky impurities, which cause mechanical filtration losses. A further advantage lies in the improvement of the physical properties of the active substance, which is manifested mainly in the improvement of the suspendability of the final wettable powder-formulated formulation.
Následujúce příklady ozrejmujú, ale neobmedzujú predmet vynálezu.The following examples illustrate but do not limit the scope of the invention.
Příklad 1Example 1
Do reaktora sa předložilo 630 kg 4,5-dichlór-l-fenyl-6-oxo-lH-pyridazínu 96 %-ného ku ktorému sa přidalo 15 kg technického sulfitového výluhu /šlempy/ a 10 kg kyseliny benzoovéj. Do reakčnej zmesi sa zavádzal za miešania plynný amoniak pri teplote 200 °C. Po skončení aminácie· sa reakčná zmes vo formě taveniny vypustilo do 3 100 kg xylénu předloženého v extrakčnom kotli. Po 1 hodinovej extrakcii pri 60 °C xylénová suspenzia sa odfiltrovala. Polovica získaného xylénového koláča 4-amino-l-fenyl-5-chlór-6-oxo-lH-pyridazínu sa vniesla do kotlá s 900 1 vody.630 kg of 4,5-dichloro-1-phenyl-6-oxo-1H-pyridazine 96% were charged to the reactor, to which 15 kg of technical sulphite liquor (slurry) and 10 kg of benzoic acid were added. Ammonia gas was introduced into the reaction mixture with stirring at 200 ° C. After the amination was complete, the melt reaction mixture was discharged into the 3,100 kg of xylene submitted in the extraction boiler. After extraction at 60 ° C for 1 hour, the xylene suspension was filtered off. Half of the obtained 4-amino-1-phenyl-5-chloro-6-oxo-1H-pyridazine xylene cake was charged to a 900 L water boiler.
K zmesi sa přidalo 0,5 kg Spolionu a xylén sa jednoducho azeotropicky vydestiloval, pričom nedochádzalo ku kypeniu. Po vydestilovaní xylénu. sa produkt izoloval z vodnej suspenzie filtráciou na odstředivkách. Odtekajúci filtrát prakticky neobsahoval nerozpustný podiel 4-amino-l-fenyl-5-chlór-6-oxo-lH-pyridazínu. Podobným postupom sa spracovala druhá polovica xylénového koláča. Získalo sa 4 714 kg 4-amino-l-fenyl-5-chlór-6-oxo-lH-pyridazfnu o čistotě 93,2 %.0.5 kg of Spolione was added to the mixture and the xylene was simply distilled off azeotropically without causing any seizure. After distilling off xylene. the product was isolated from the aqueous suspension by centrifugation. The effluent filtrate was substantially free of insoluble 4-amino-1-phenyl-5-chloro-6-oxo-1H-pyridazine. The second half of the xylene cake was treated in a similar manner. 4,714 kg of 4-amino-1-phenyl-5-chloro-6-oxo-1H-pyridazine having a purity of 93.2% were obtained.
Příklad 2Example 2
Postupom popísaným v příklade 1 s tým rozdielom, že miesto Spolionu sa použilo 1 kg Odpeňovača T, získalo sa 479,5 kg 4-amino-l-fenyl-5-chlór-6-oxo-lH-pyridazínu o čistotě 93,6 %.Using the procedure described in Example 1, except that 1 kg of Teaser T was used instead of Spolion, 479.5 kg of 4-amino-1-phenyl-5-chloro-6-oxo-1H-pyridazine of 93.6% purity were obtained. .
Porovnanie čistoty 4-amino-l-fenyl-5-chlór-6-oxo-lH-pyridazínu /PCA/ získaného za použitia povrchovoaktívnej látky na báze dialkylsulfojantaranu pri azeotropickej destilácii a bez použitia povrchovoaktívnej látky je uvedené v tabulke 1.A comparison of the purity of 4-amino-1-phenyl-5-chloro-6-oxo-1H-pyridazine (PCA) obtained using a dialkylsulfosuccinate-based surfactant in azeotropic distillation and without surfactant is shown in Table 1.
Reakcie boli uskutočnené postupom uvedeným v příklade 1 s tým rozdielom, že východiskový 4,5-dichlór-l-fenyl-6-oxo-lH-pyridazín bol čistoty 91,8 %The reactions were carried out as described in Example 1 except that the starting 4,5-dichloro-1-phenyl-6-oxo-1H-pyridazine was 91.8% pure
Tabulka 1Table 1
Vplyv Spolionu na čistotu PCAEffect of Spolion on PCA purity
Porovnanie stálosti suspenzie finálneho přípravku upraveného na zmáčatelný prášok za použitia Spolionu pri azeotropickej destilácii a bez jeho použitia je uvedené v tabulke 2.A comparison of the suspension stability of the finished wettable powder formulation using Spolion with and without azeotropic distillation is shown in Table 2.
Sledovala sa stálost 1 %-nej vodnej suspenzie zmáčatelného prášku po dobu 30 minút vo vodě 30 °N tvrdej.The stability of a 1% aqueous wettable powder suspension for 30 minutes in 30 ° N hard water was monitored.
Pokus 6Experiment 6
Stálost suspenzieSuspension stability
So SpolionomWith Spolion
Tabulka 2Table 2
Vplyv Spolionu na stálost suspenzieEffect of Spolion on suspension stability
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS851679A CS259207B1 (en) | 1985-03-11 | 1985-03-11 | Method of 4-amino-1-phenyl-5-chloro-6-oxo-1h-pyridazine insulation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS851679A CS259207B1 (en) | 1985-03-11 | 1985-03-11 | Method of 4-amino-1-phenyl-5-chloro-6-oxo-1h-pyridazine insulation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CS167985A1 CS167985A1 (en) | 1988-02-15 |
| CS259207B1 true CS259207B1 (en) | 1988-10-14 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS851679A CS259207B1 (en) | 1985-03-11 | 1985-03-11 | Method of 4-amino-1-phenyl-5-chloro-6-oxo-1h-pyridazine insulation |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS259207B1 (en) |
-
1985
- 1985-03-11 CS CS851679A patent/CS259207B1/en unknown
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| Publication number | Publication date |
|---|---|
| CS167985A1 (en) | 1988-02-15 |
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