CS240373B1 - Method of s-triazines' physico-chemically stable mixture production - Google Patents
Method of s-triazines' physico-chemically stable mixture production Download PDFInfo
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- CS240373B1 CS240373B1 CS841455A CS145584A CS240373B1 CS 240373 B1 CS240373 B1 CS 240373B1 CS 841455 A CS841455 A CS 841455A CS 145584 A CS145584 A CS 145584A CS 240373 B1 CS240373 B1 CS 240373B1
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- triazine
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- methylthio
- alkylamino
- triazines
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- 239000000203 mixture Substances 0.000 title claims description 20
- 238000000034 method Methods 0.000 title claims description 9
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical class C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 title description 2
- 238000004519 manufacturing process Methods 0.000 title description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 239000007864 aqueous solution Substances 0.000 claims description 15
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 12
- 150000003973 alkyl amines Chemical class 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 3
- 239000012454 non-polar solvent Substances 0.000 claims description 3
- 239000003495 polar organic solvent Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 13
- 239000011541 reaction mixture Substances 0.000 description 11
- MWPZLWRHHPWTFS-UHFFFAOYSA-N 2,4-dichloro-6-methylsulfanyl-1,3,5-triazine Chemical compound CSC1=NC(Cl)=NC(Cl)=N1 MWPZLWRHHPWTFS-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 8
- IROINLKCQGIITA-UHFFFAOYSA-N terbutryn Chemical compound CCNC1=NC(NC(C)(C)C)=NC(SC)=N1 IROINLKCQGIITA-UHFFFAOYSA-N 0.000 description 6
- FZXISNSWEXTPMF-UHFFFAOYSA-N terbutylazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)(C)C)=N1 FZXISNSWEXTPMF-UHFFFAOYSA-N 0.000 description 6
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- RQVYBGPQFYCBGX-UHFFFAOYSA-N ametryn Chemical compound CCNC1=NC(NC(C)C)=NC(SC)=N1 RQVYBGPQFYCBGX-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000002051 biphasic effect Effects 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
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- Plural Heterocyclic Compounds (AREA)
Description
(54) Sposob výroby fyzikálno-chemicky stále) zmesi s-triazinov(54) Process for producing a physicochemically stable mixture of s-triazines
II
Vynález sa týká sposobu výroby fyzikálno-chemicky stálej zmesi 2,4-bis-alkylamíno-6-chlór-s-triazínu s 2,4-bis-alkylamíno-6-metyltto-s-triazínom reakciou zmesi kyanurchloridu s 2,4-dichlór-6-metyltio-s-triazínom v nepolárnom organickom rozpúšťadle s rovnakým látkovým množstvom alkylamínu všeobecného vzorca IThe present invention relates to a process for the preparation of a physicochemically stable mixture of 2,4-bis-alkylamino-6-chloro-s-triazine with 2,4-bis-alkylamino-6-methyltto-s-triazine by reacting a mixture of cyanuric chloride with 2,4-dichloro -6-methylthio-s-triazine in a non-polar organic solvent with the same amount of alkylamine of formula I
R4NH2 (I) a s rovnakým látkovým množstvom alkylamínu všeobecného vzorca IIR 4 NH 2 (I) and with the same amount of alkylamine of the formula II
R2NH2 (II) kdeR 2 NH 2 (II) wherein
R* 1 (II) a R2 majú význam uvedený v opise,., vždy v přítomnosti hydroxidu sodného ako chlorovodík viažúceho činidla a po odstránení nepolárného rozpúšťadla sa fyzikálno-chemicky stála zmes získá kryštalizáciou z 20 až 25 %-ného vodného roztoku alifatického ketonu. Zbytky R4 a R2 možu byť rovnaké alebo rožne. R 1 (II) and R @ 2 are as defined in the description., Each in the presence of sodium hydroxide as a hydrogen chloride binding agent and, after removal of non-polar solvent, the physico-chemical cost was obtained by crystallisation from 20 to 25% strength aqueous solution of an aliphatic ketone . The radicals R 4 and R 2 may be the same or different.
Vynález sa týká sposobu výroby fyzikálno-chemicky stálej zmesi 2,4-bis-alkylamíno-6-chlór-s-triazínu s 2,4-bis-alkylamíno-6-rnetyltio-s-triazínom.The invention relates to a process for the preparation of a physically-chemically stable mixture of 2,4-bis-alkylamino-6-chloro-s-triazine with 2,4-bis-alkylamino-6-methylthio-s-triazine.
Je známe, že zmesi 2,4-bis-alkylamíno-6chlór-s-triazíhov s 2,4-bis-alkylamíno-6-metyltio-s-triazínmi sú zložkami mnohých významných herbicídnych prípravkov. Známe sú najmá zmesi 2-etylamíno-4-chlór-6-terc.-butylamíno-s-triazínu (terbutylazínu) s 2-etylamíno-4-metyltio-6-terc.butylamíno-s-triazínom (terbutrýnom), 2-etylamíno-4-chlór-6-izopropylamíno-s-triazínu (atrazínu) s 2-etylamíno-4-izopropylamíno-6-meťyltio-s-triazínom (ametrynomj a pod. Uvedené kombinované preparáty sa obvykle upravujú do formy dispergovatelných práškov a suspenzných koncentrátov.Mixtures of 2,4-bis-alkylamino-6-chloro-s-triazines with 2,4-bis-alkylamino-6-methylthio-s-triazines are known to be ingredients of many important herbicidal formulations. The most known are mixtures of 2-ethylamino-4-chloro-6-tert-butylamino-s-triazine (terbutylazine) with 2-ethylamino-4-methylthio-6-tert-butylamino-s-triazine (terbutyrene), 2-ethylamino 4-Chloro-6-isopropylamino-s-triazine (atrazine) with 2-ethylamino-4-isopropylamino-6-methylthio-s-triazine (ametrynine, etc.).
Úprava kombinovaných preparátov na báze 2,4-bis-alkylamíno-6-chlór-s-triazínov sTreatment of 2,4-bis-alkylamino-6-chloro-s-triazines
2,4-bis-alkylamíno-6-metyltio-s-triazínmi představuje tečhnický problém, lebo přípravky získané fyzikálnym zmiešaním oboch aktívnych látok a upravením takto získanej zmesi majú nevyhovujúcu stálost fyzikálnych vlastností pri skladovaní.The 2,4-bis-alkylamino-6-methylthio-s-triazines present a technical problem since the preparations obtained by physically mixing the two active substances and modifying the mixture thus obtained have an inadequate storage stability of the physical properties.
Z Čs. pat. 194 660 je známe, že fyzikálno-chemicky stálu zmes týchto zlúčenín možno získat například stavením oboch zložiek a pomalým ochladzovaním a očkováním chladnúcej taveniny alebo kryštalizáciou zmesi tesne pod teplotou topenia. Tentoi sposob je nevýhodný, lebo vyžaduje izoláciu oboch zložiek v čistom stave, zariadenie na roztavenie zložiek, dlhé časy krýštalizácie (ochladzovanie o 0,01 až 0,2°C/min) a tuhý blok intramolekulárnej zlúčeniny je potřebné drvit a mlieť. Další spQsob přípravy stálej Intramolekulárnej zlúčeniny spočívá v kryštalizácii oboch zložiék z bezvodých rozpúšťadiel ako· sú nitrily, amidy, alkoholy alebo ketony, připadne ich zmesi s uhlovodíkmi. Táto kryštalizácia dává však velmi nízké výtažky (v případe metanolu 60 %, v případe zmesi hexán.: aceton 1:1 40 %).Z Čs. pat. No. 194,660, it is known that a physicochemically stable mixture of these compounds can be obtained, for example, by quenching both components and slowly cooling and seeding the cooling melt, or crystallizing the mixture just below the melting point. This method is disadvantageous because it requires the isolation of both components in a pure state, a melting component, long crystallization times (cooling at 0.01 to 0.2 ° C / min) and a solid block of the intramolecular compound to be crushed and ground. Another method for preparing a stable intramolecular compound is to crystallize both components from anhydrous solvents such as nitriles, amides, alcohols or ketones, or mixtures thereof with hydrocarbons. However, this crystallization yields very low yields (60% in the case of methanol, 40% in the case of hexane: acetone 1: 1).
Z čs. autorského osvedčenia č. 226 627 je známe, že 1 mól 2,4-dlchlór-6-metyltio-s-triazínu (MDTJ reaguje s 1 mólom aminu v přítomnosti 1 mólu vodného roztoku hydroxidu sodného prakticky adiabaticky. Pre nahradenie chlóru v 2-alkylamíno-4-chlór-6-metyltio-s-triazínoch ďalšou alkylamínoskupinou je potřebné zvýšit teplotu reakčnej zmesi na 60 až 70 °C počas 2 až 5 hodin, a to aj v prostředí acetonu (čs. pat. 145 197J.Z čs. of the author's certificate no. 226,627, it is known that 1 mole of 2,4-dichloro-6-methylthio-s-triazine (MDTJ reacts with 1 mole of amine in the presence of 1 mole aqueous sodium hydroxide solution practically adiabatically. To replace chlorine in 2-alkylamino-4-chlorine 6-methylthio-s-triazines with another alkylamino group it is necessary to raise the temperature of the reaction mixture to 60-70 ° C for 2 to 5 hours, even in acetone (U.S. Pat. No. 145,197J).
Ďalej je známe, že kyanurchlorid reaguje s alkylamínml v přítomnosti hydroxidu sodného v dvojfázovom vodn,o-organickom prostředí prakticky za adiabatických podmienok (Čs. pat. 156 446). Je tiež známe, že chlór v 2,4-bis-alkylamíno-6-chlór-s-triazínoch je len obtiažne nukleofilne vyměnitelný.It is further known that cyanuric chloride reacts with alkylamine in the presence of sodium hydroxide in a biphasic aqueous, o-organic medium practically under adiabatic conditions (U.S. Pat. 156,446). It is also known that chlorine in 2,4-bis-alkylamino-6-chloro-s-triazines is difficult to exchange nucleophilically.
Vačšinu nedoetatkou přípravy fyzikálno-chemicky stálej zmesi 2,4-bis-alkylamíno-6-chlór-s-triazínov s 2,4-bis-alkylamíno-6-metyltio-s-triazínmi vo vzájomnom hmotnostnom pomere 1: 9 až 9 : 1 odstraňuje spósob výroby podlá vynálezu.Most of the lack of preparation of a physicochemically stable mixture of 2,4-bis-alkylamino-6-chloro-s-triazines with 2,4-bis-alkylamino-6-methylthio-s-triazines in a weight ratio of 1: 9 to 9: 1 eliminates the production method of the invention.
Podstata vynálezu spočívá v tom, že zmes kyanurchloridu s 2,4-dichlór-6-metyltio-s-triazínom v nepolárnom organickém rozpúšťadle sa nechá zreagovat s rovnakým látkovým množstvom alkylamínu všeobecného vzorca IThe present invention consists in reacting a mixture of cyanuric chloride with 2,4-dichloro-6-methylthio-s-triazine in a non-polar organic solvent with an equal amount of alkylamine of the formula I
R4NH2 (I) v ktoromR 4 NH 2 (I) wherein
R1 znamená alkylskupinu s 1 až 5 atómami uhlíka a rovnakým látkovým množstvom alkylamínu všeobecného vzorca IIR 1 represents an alkyl group having 1 to 5 carbon atoms and an equal amount of an alkylamine of the formula II
R2NH2 (II) v ktoromR 2 NH 2 (II) wherein
R2 znamená alkylskupinu s 1 až 5 atómami uhlíka vždy v přítomnosti hydroxidu sodného ako chlorovodík viažúceho činidla a po odstránení nepolárného rozpúštadla sa fyzikálno-chemicky stála zmes získá kryštalizáciou z 20 až 50 %-ného vodného roztoku alifatického ketonu. Ak R1 — R2, potom látkové množstvo alkylamínu je dvojnásobné, oproti látkovému množstvu zmesi kyanurchloridu a 2,4-dichlór-6-metyltio-s-triazínu.R 2 is C 1 -C 5 alkyl in the presence of sodium hydroxide as the hydrogen chloride-binding agent and, after removal of the non-polar solvent, the physicochemically stable mixture is obtained by crystallization from a 20 to 50% aqueous solution of an aliphatic ketone. If R 1 -R 2 , the amount of alkylamine is twice the amount of the mixture of cyanuric chloride and 2,4-dichloro-6-methylthio-s-triazine.
Získaná fyzikálno-chemicky stálu zmes je možné upravovat mletím, zmiešavaním s plnidlami ako kaolín, kysličník křemičitý, s dispergátormi, emulgátormi a podobné na zmáčatelné popraše, ktoré sa móžu skladovat’ až dva roky pri teplote —5 až +30°C bez změny ich fyzikálno-chemických vlastností.The physicochemically stable mixture obtained can be treated by grinding, mixing with fillers such as kaolin, silica, dispersants, emulsifiers and the like for wettable dusts which can be stored for up to two years at a temperature of -5 to +30 ° C without changing their physico-chemical properties.
Uvedené příklady ilustrujú, ale neobmedzujú predmet vynálezu.These examples illustrate but do not limit the scope of the invention.
PřikladlEXAMPLE
V 500 cm3 toluenu sa rozpustilo 9,9 g 2,4-dichlór-6-metyltio-s-triazínu (0,05 mólu) a9.9 g of 2,4-dichloro-6-methylthio-s-triazine (0.05 mol) were dissolved in 500 cm 3 of toluene and
83,8 g kyanurchloridu (0,45 mólu). K roztoku se za miešania přidalo 51,9 g 70,4%-ného vodného roztoku terc.butylamínu (0,50 mólu) a 136,8 g 14,62%-ného vodného roztoku hydroxidu sodného (0,50 mólu), pričom teplota reakčnej zmesi nepřevýšila 50 °C. Po 15-minútovom miešaní sa k reakčnej zmesi přidalo 50,8 g 44,4%-ného vodného roztoku etylamínu (0,50 mčlu) a 137,5 g 14,62%-ného vodného roztoku hydroxidu sodného (0,503 mólu). Reakčná zmes sa ešte 1 hodinu miešala pri teplote varu. Potom sa vědnou parou oddestiloval toluen, k zvyšku sa přidalo 125 cm3 acetónu a reakčná zmes sa za miešania ochladila na 20 °C. Vypadnutý krystalický produkt sa odfiltroval, premyl s83.8 g of cyanuric chloride (0.45 mol). To the solution, 51.9 g of a 70.4% aqueous t-butylamine solution (0.50 mol) and 136.8 g of a 14.62% aqueous sodium hydroxide solution (0.50 mol) were added with stirring, the temperature of the reaction mixture did not exceed 50 ° C. After stirring for 15 minutes, 50.8 g of a 44.4% aqueous solution of ethylamine (0.50 mol) and 137.5 g of a 14.62% aqueous solution of sodium hydroxide (0.503 mol) were added to the reaction mixture. The reaction mixture was stirred at reflux for 1 hour. Thereafter, toluene was distilled off with scientific steam, 125 cm 3 of acetone were added to the residue, and the reaction mixture was cooled to 20 ° C with stirring. The precipitated crystalline product was filtered off, washed with
250 ml vody a vysušil do konstantně] hmotnosti.250 ml of water and dried to constant weight.
Získalo sa 111,5 g produktu, ktorý podía analýzy obsahoval 90,4 % terbuíylázínu a 9,2 % terbutrynu.111.5 g of product were obtained, which, according to analysis, contained 90.4% terbutylamine and 9.2% terbutryne.
P r í k 1 a d 2Example 1 a d 2
Postupovalo sa ako v příklade 1 s tým rozdielom, že k 500 cm3 toluénu sa přidaloThe procedure was as in Example 1 except that 500 cm 3 of toluene was added
46,8 g kyanurchloridu (0,25 molu) a 49,5 gramov 2,4-dichlór-6-metyltio-s-triazínu (0,25 molu). K toluenovému roztoku sa za mieša-. nia přidalo 51,9 g 70,4 %-ného vodného roztoku terc.butylamínu (0,50 molu), 136,8 g 14,62 %-ného vodného . roztoku etylamínu (0,50 molu) a 137,5 g 14,62 %-ného vodného· roztoku hydroxidu sodného (0,503 molu). Po oddestilování toluénu, přidaní acetonu, ochladení, izolovaní a vysušení sa získalo 114 g bieleho až krémovo sfarbeného krystalického produktu s obsahom 49,5 % terbutylazínu a 48,8 % terbutrynu.46.8 g of cyanuric chloride (0.25 mol) and 49.5 grams of 2,4-dichloro-6-methylthio-s-triazine (0.25 mol). The toluene solution was stirred with stirring. 51.9 g of a 70.4% aqueous solution of t-butylamine (0.50 mol), 136.8 g of 14.62% aqueous solution were added. a solution of ethylamine (0.50 mol) and 137.5 g of a 14.62% aqueous sodium hydroxide solution (0.503 mol). After distilling off toluene, adding acetone, cooling, isolating and drying, 114 g of a white to cream colored crystalline product were obtained containing 49.5% terbutylazine and 48.8% terbutryne.
Příklad 3Example 3
a)a)
V 500 cm3 toluénu sa rozpustilo 67,3 g 2,4-dichlór-6-metyltio-s-triazínu (0,34 molu), 28,0 g kyanurchloridu (0,15 molu) a k získanému roztoku sa postupné za „adiabatických“ podmienok přidalo 51,9 g 70,4 %-ného vodného roztoku terc.butylamínu (0,50 molu), 136,8 g 14,62 %-ného hydroxidu sodného· (0,50 mólu) a po 15 min. miešaní 50,8 gramov 44,4 %-ného vodného roztoku etylamínu (0,50 mólu) a 137,5 g 14,62 %-ného vodného roztoku hydroxidu sodného (0,503 mólu). Po hodinovom miešaní reakčnej zmesi pri teplote varu sa vodnou parou oddestiloval toluén, k zvyšku sa přidalo 150 ml acetonu a po ochladení, odfiltrovaní, premytí a vysušení sa získalo 119 g produktu, ktorý obsahoval 67,8 % terbutrynu a 30,9 % terbutylazínu.67.3 g of 2,4-dichloro-6-methylthio-s-triazine (0.34 mol), 28.0 g of cyanuric chloride (0.15 mol) were dissolved in 500 cm @ 3 of toluene and successively adiabatic in solution. 51.9 g of a 70.4% aqueous solution of tert-butylamine (0.50 mol), 136.8 g of 14.62% sodium hydroxide (0.50 mol) and after 15 min. stirring 50.8 grams of a 44.4% aqueous solution of ethylamine (0.50 mol) and 137.5 g of a 14.62% aqueous solution of sodium hydroxide (0.503 mol). After stirring the reaction mixture for 1 hour at the boiling point, toluene was distilled off with steam, 150 ml of acetone were added to the residue, and after cooling, filtering, washing and drying, 119 g of a product containing 67.8% terbutryne and 30.9% terbutylazine were obtained.
b)b)
V 2 500 cm3 toluénu sa rozpustilo 336,3 g336.3 g were dissolved in 2500 cm 3 of toluene
2,4-dichlór-6-metyltio-s-triazínu (1,72 mólu) a 139,7 g kyanurchloridu (0,76 mólu). K získanému roztoku sa za miešania „adiabaticky“ přidalo 256,9 g 71,16 %-ného vodného roztoku terc.butylamínu (2,50 mólu), 687,4 gramov 14,62 %-ného vodného roztoku hydroxidu sodného (2,51 mólu). Reakčná zmes sa potom udržiavaia 1 hodinu pri teplote varu, vodná vrstva sa oddělila a z toluenového· roztoku sa rozpúšťadlo oddestilovalo vodnou parou. K zvyšku sa přidalo 1 000 cm3 acetonu, zmes sa chladila ve 29 °C, tuhá krystalická látka sa odfiltrovala, premyla s 500 cm3 vody a vysušila do konstantně) hmotnosti. Získalo sa 560 g produktu, ktorý obsahoval 72,1 % terbutrynu a 27,3 % terbutylazínu.2,4-dichloro-6-methylthio-s-triazine (1.72 mol) and 139.7 g of cyanuric chloride (0.76 mol). 256.9 g of a 71.16% aqueous solution of t-butylamine (2.50 moles), 687.4 grams of a 14.62% aqueous sodium hydroxide solution (2.51 moles) were added adiabatically to the obtained solution. mol). The reaction mixture was then kept at reflux for 1 hour, the aqueous layer was separated and the solvent was distilled off with water vapor from the toluene solution. 1000 cm 3 of acetone was added to the residue, the mixture was cooled at 29 ° C, the solid crystalline material was filtered off, washed with 500 cm 3 of water and dried to constant weight. 560 g of a product containing 72.1% terbutryne and 27.3% terbutylazine were obtained.
Příklad 4Example 4
Postupovalo sa ako· v příklade 1 s tým rozdielom, že k 500 cm3 toluénu sa přidalo 88,23 g 2,4-dichlór-6-metyltlo-s-triazínu (0,45 mólu), 9,3 g kyanurchloridu (0,05 mólu),The procedure was as in Example 1 except that 88.23 g of 2,4-dichloro-6-methyltlo-s-triazine (0.45 mol) and 9.3 g of cyanuric chloride (0) were added to 500 cm 3 of toluene. , 05 mole),
51,9 g 70,4 %-ného vodného roztoku terc.butylamínu (0,5 mólu), 136,8 g 14,62 %-ného vodného roztoku hydroxidu sodného (0,5 mólu). Po oddestilování toluénu, přidaní acetonu a ďalšom obvyklom spracovaní sa získalo 120,0 g produktu s obsahom 11,4 % terbutylazínu a 88 % terbutrynu.51.9 g of a 70.4% aqueous solution of t-butylamine (0.5 mol), 136.8 g of a 14.62% aqueous sodium hydroxide solution (0.5 mol). After distilling off toluene, addition of acetone and further conventional work-up, 120.0 g of product were obtained containing 11.4% terbutylazine and 88% terbutryne.
P r í k 1 a d 5Example 5
V 500 cm3 toluénu sa rozpustilo 49,02 g49.02 g were dissolved in 500 cm 3 of toluene
2,4-dichlór-6-metyltio-s-triazínu (0,25 molu), 46,1 g kyanurchloridu (0,25 molu) a za miešania sa k roztoku přidalo 49,1 g 60,2 %-ného vodného roztoku izopropylamínu (0,5 molu) a 133,4 g 15,0 %-ného vodného roztoku hydroxydu sodného (0,5 molu). Po 30 minútach miešaní sa k reakčnej zmesi přidalo 53,7 g 42,0 %-ného vodného roztoku etylamínu (0,5 molu) a 133,4 g 15,0 %-ného vodného roztoku hydroxidu sodného (0,5 molu). Reakčná zmes sa potom miešala ešte 1 h pri teplote varu reakčnej zmesi. Potom sa vodnou parou oddestiloval toluén, k zvyšku sa přidalo 125 cm3 acetonu, reakčná zmes sa za miešania ochladila na 20 °C, vypadnutý krystalický produkt sa odfiltroval, premyl s 250 ml vody a vysušil do konštantnej hmotnosti.2,4-dichloro-6-methylthio-s-triazine (0.25 mol), 46.1 g of cyanuric chloride (0.25 mol) and 49.1 g of a 60.2% aqueous solution were added with stirring. isopropylamine (0.5 mol) and 133.4 g of a 15.0% aqueous sodium hydroxide solution (0.5 mol). After stirring for 30 minutes, 53.7 g of a 42.0% aqueous solution of ethylamine (0.5 mol) and 133.4 g of a 15.0% aqueous solution of sodium hydroxide (0.5 mol) were added to the reaction mixture. The reaction mixture was then stirred for an additional 1 hour at the boiling point of the reaction mixture. Thereafter, toluene was distilled off with water, 125 cm 3 of acetone were added to the residue, the reaction mixture was cooled to 20 ° C with stirring, the precipitated crystalline product was filtered off, washed with 250 ml of water and dried to constant weight.
Získalo sa 107,5 g produktu, ktorý podía analýzy obsahoval 49,3 % atrazínu a 49,4 '% a 49,4 % ametrynu.107.5 g of product were obtained which, according to analysis, contained 49.3% atrazine and 49.4% and 49.4% amethylene.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS841455A CS240373B1 (en) | 1984-03-01 | 1984-03-01 | Method of s-triazines' physico-chemically stable mixture production |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS841455A CS240373B1 (en) | 1984-03-01 | 1984-03-01 | Method of s-triazines' physico-chemically stable mixture production |
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| Publication Number | Publication Date |
|---|---|
| CS145584A1 CS145584A1 (en) | 1985-07-16 |
| CS240373B1 true CS240373B1 (en) | 1986-02-13 |
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| Application Number | Title | Priority Date | Filing Date |
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| CS841455A CS240373B1 (en) | 1984-03-01 | 1984-03-01 | Method of s-triazines' physico-chemically stable mixture production |
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| CS (1) | CS240373B1 (en) |
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| CS145584A1 (en) | 1985-07-16 |
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