CS261415B1

CS261415B1 - 2-phenyl-4-acetamido-5-dialkylamino-3-oxo-2H-pyridazines and methods for their preparation

Info

Publication number: CS261415B1
Application number: CS873119A
Authority: CS
Inventors: Vaclav Rndr Csc Konecny; Stefan Doc Dr Ing Csc Kovac
Original assignee: Konecny Vaclav; Kovac Stefan
Priority date: 1987-05-04
Filing date: 1987-05-04
Publication date: 1989-02-10
Also published as: CS311987A1

Abstract

Riešenie sa týká 2-fenyl-4-acetamido-5-dialkylamíno-3-oxo-2H-pyridazínov všeobecného vzorca I, v ktorom R* 1 znamená sekundárnu amínoskupinu všeobecného vzorca II, v ktorom R2 a R3 znamenajú rovnaký alebo rozny alkyl s 1 až 4 atómami uhlíka alebo alyl, alebo vytvárajú s atómom dusíka šesťčlánkový heterocyklický kruh, připadne s kyslíkom ako dalším heteroatómom, ktoré sa pripravujú reakciou 2-fenyl-4-substituovaný amíno-5-chlór-3-oxo-2H pyridazínu všeobecného vzorca III, v ktorom R4 znamená vodík alebo skupinu CH3CO— a R5 znamená skupinu CHsCO—, s amínom všeobecného vzorca IV, v ktorom R2 a R3 majú už uvedený význam, v přítomnosti organického rozpúšťadla pri teplote 40 až 140 °C, s výhodou. 80 až 110 °C. Zlúčeniny sú využitelné v chemickom priemysle ako medziprodukty pri výrobě pesticídov.The solution concerns 2-phenyl-4-acetamido-5-dialkylamino-3-oxo-2H-pyridazines of the general formula I, in which R* 1 denotes a secondary amino group of the general formula II, in which R2 and R3 denote the same or different alkyl with 1 to 4 carbon atoms or allyl, or form a six-membered heterocyclic ring with a nitrogen atom, optionally with oxygen as another heteroatom, which are prepared by the reaction of 2-phenyl-4-substituted amino-5-chloro-3-oxo-2H pyridazine of general formula III, in which R4 denotes hydrogen or the group CH3CO— and R5 denotes the group CHsCO—, with the amine of general formula IV, in which R2 and R3 have the previously mentioned meaning, in the presence of an organic solvent at a temperature of 40 to 140 °C, preferably. 80 to 110 °C. The compounds are useful in the chemical industry as intermediate products in the production of pesticides.

Description

3 4 261415

The invention relates to 2-phenyl-4-acetamido-5-di-alkylamino-3-oxo-2H-pyridazines and to processes for their preparation. Said compounds serve as intermediates in the production of foliage.

2-phenyl-5-dimethyl-amine (morpholino) -3-oxo-2H-pyridazines are known from the literature, such as 2-phenyl-4-bromo-5-dimethylamino (morpholino) -3-oxo-2H-pyridazines [Helv. Chim. Acta, 37, 529 (1954)]. Also known are 2-substituted-4-chloro-5-amino (alkylamino, dialkylamino) -3-oxo-2H-pyridazine of general formula V

wherein R 6 and R 7 are hydrogen or alkyl, R 8 is alkyl, cycloalkyl or aryl. Chem. 77, 282 (1965)].

We have now found 2-phenyl-4-acetamido-5-substituted-3-oxo-2H-pyridazines, general formula I

O (/,

wherein R 1 is a secondary amino group of formula II R 2

From R 3 (Π) in which R 2 and R 3 are the same butborane alkyl of 1 to 4 carbon atoms or alkyl or form a six-membered heterocyclic ring with the nitrogen atom, it will be like an additional heteroatom.

A method for preparing compounds of formula I by reacting 2-phenyl-4-substituted amino-5-chloro-3-oxo-2H-pyridazine of formula III has also been found.

R "0 <ll!"

wherein R 4 is hydrogen or CH 3 CO "and R 5 is CH 3 CO", by self-formula IV R 2

NH

From R 3 (IV) in which R 2 and R 3 are as defined above, in the presence of an organic solvent a temperature of 40 to 140 ° C, preferably 80 to 110 ° C.

The following examples illustrate but do not limit the invention. Example 1 2-phenyl-4-acetamido-5-dimethylamino-3-oxo-2H-pyridazine To 9.3 g of 2-phenyl-4-acetamino-5-chloro-3-oxo-2H-pyridazine (0, Of 2.8 g of dimethylamine 10.06 mol during 2 hours under stirring at boiling temperature. After completion and cooling, the precipitated solid was collected by filtration, dried, crushed in a water-quencher. , separated by filtration, washed with water on the filter and dried. 7.8 g of a white solid were obtained with mp: 206.7 ° C.

Analysis: For C14H1 & N4O2 (M.H .: 272.18) .Example / Found: 61.75 / 61.89% C, 5.92 / 6.14% N, 20.57 / 20.71 % N. IC (CHCl 3), ν / cnr 1: 1700, 3,269, 3,389. UV (methanol), λ / nm, (log ε): 244 (3.39), 308 (3.07). Example 2 2-Phenyl-4-acetamido-5-piperidino-3-oxo-2H-pyridazine To 18.3 g of 2-phenyl-4-diacetylamino-5-chloro-3-oxo-2H-pyridazine (0, 10 mole was added with 120 mole of toluene under stirring at 20 ° C. piperidine in 20 cm 3 of toluene. The reaction mixture was stirred at reflux for 4 h, cooled. The precipitated solid was collected by filtration, the filter solid was crushed with water, collected by filtration. After drying, the bolsuric product purified by column chromatography using toluene was added acetone. This gave 16.4 g of white solid, mp 172.3 ° C.

Analysis for C 17 H 20 N 4 O 2 (M.H .: 312.36).

Claims

S B Off / C .: 67.28% C, 6.46 θ / δ H, 17.94 θ / ο N. IR (CHCl 3), v / cm -1; 1,701, 3,268, 3,374. UV (methanol), A / nm, (log ε): 251 (3.41), 313 (3.11). Example 3 2-phenyl-4-acetamido-5-diethylamino-3-oxo-2H-pyridazine To 13.2 g of 2-phenyl-4-acetamido-5-chloro-3-oxo-2H-pyridazine (0, Of a solution in 100 cm @ 3 of toluene was added 3.7 g of diethylamine 10.05 mol of 20 ml of toluene under stirring at 2 DEG C. with stirring. The reaction mixture was stirred at reflux for 4 h. After cooling, Example 1 was worked up. 14.1 g of a white solid was obtained with m.p .: 166.7 ° C. Analysis for C 16 H 20 N 4 OS (M.H .: 300.32). C / N: 63.99 / 64.21% C, 6.71 / 6.80% H, 18.66 / 19.01% N. IR (CHCl3), p / cnr1: 1700, 3,270 , 389. UV (methanol), λ / nm, (loge): 256 (3.21), 305 (2.84). Following a similar procedure, the following compounds were prepared: 4. 2-Phenyl-4-acetamido-5-dipropylamino-3-oxo-2H-pyridazine mp 148.6 ° C 5. 2-Phenyl-4-acetamine-5- dialylamino-3-oxo-2H-pyridazine, mp 136.4 ° C. 6. 2-Phenyl-4-acetamido-5- (N-ethyl-N-butyl) amino-3-oxo-2H-pyridazine, mp 113.0 CC, 7. 2-Phenyl-acetamido-5-diisobutylamino-3-oxo-2H-pyridazine, mp 162.1 ° C. -oxo-2H-pyridazine, mp 205.0 ° C. OBJECT OF THE INVENTION 1. 2-Phenyl-4-acetamido-5-substituted-3-oxo-2H-pyridazines of Formula I I having the Formula I wherein the 2-phenyl-4-substituted amino-5-chloro The 3-oxo-2H-pyridazine of the general formula III. wherein R 1 is a secondary amine of formula II R 2 N—

(h '/ J in which R 4 is hydrogen or CH 3 CO- and R 5 is CH 3 CO 2, with an amine of formula IV R 3 (1) Nil wherein R 2 and R 3 are the same butborane alkyl of 1 to 4 carbon atoms or are taken together with with a nitrogen atom, a 6-membered heterocyclic ring, is attributable to a halo as another heteroatom.

2. A process for the preparation of compounds according to R3 (IV) wherein R2 and R3 are as defined above, in an organic solvent environment at a temperature of 40 DEG to 140 DEG C., preferably 80 DEG to 110 DEG.