DD220603A1 - PROCESS FOR PREPARING 2- (1- (ALKYL, ARYL) -2-ACYL-HYDRAZINO) -4,6 - ((ALKYL, ARYL) -OXY) -1,3,5-TRIAZINENE - Google Patents

Abstract

The invention relates to a production process for new chemical compounds. According to the synthesis of the invention, two ether groups are combined with an acylated alkyl or arylhydrazino substituent on a triazine ring. For this purpose, in a simple reaction, 3,5-disubstituted 2-imino-1,3,4-oxadiazolines are reacted with cyanic acid esters to give the target compounds. The compounds according to the invention can be used as herbicides, fungicides, bactericides, viricides or as medicaments. formula

Description

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Process for the preparation of 2- / Ί- (alkyl, aryl) -2-acyl-hydrazino / 4,6 - / (alkyl, aryl) -oxy / -1, 3,5-triazines · ···

Field of application of the invention. , _:

The invention relates to compounds which can be used as growth regulators, fungicides, bactericides and Pharrnaca. - '._'

Characteristic of the known technical solutions

2,4,6-Substituted s-triazines with the substituent combination according to the invention have not been described. The construction of the compounds by exchange of the three chlorine atoms in cyanuric chloride is not possible. The reaction of cyanuric aryl esters with acyl - (aryl, alkyl) hydrazines to give the target compounds is also unsatisfactory. The described preparation method for acyl-alkylhydrazino-1,3,5-triazines / bovlatyan, khachatryan: CA. 78 (1973) 13-84325, 19-124548 / hardly allows the incorporation of two 'aryloxy groups. /

2-Irnino-1,3,4-oxadiazolines were obtained by the reaction of cyanic acid esters with N'-substituted carboxylic acid hydrazides, but no derivatives with a triazine structure were described / lethal, Zinner: Arch. Pharm. ( ^T .- / heim) .313 (1980) 867-876 /. '. , . ''/

From cyanic acid esters and amines it is easy to prepare 2-amino-4,6-di-aryloxy-1,3,5-triazines / Grigat, Pütter: DAS 1,201,847 (1964) j Martin, Titelbach, Rapolol: J. pralct , Chem. 323 (4) (Ί 931) 694-699 /. However, the compounds according to the invention are not according to analogous methods

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accessible. With the corresponding acylhydrazines, the 2-imino-1,3,4-oxadiazolines are formed primarily. The replacement of aryl ether groups on the cyanuric acid ester by substituted acylhydrazides proceeds very unevenly,

Aim of the invention; · ','

The invention aims at the preparation of triazine derivatives which, in addition to an aromatic- or alidhatically-substituted acylhydrazido group, still possess two ether groups as substituents. The coupling of these groups is expected to increase their impact. The process according to the invention provides the target compounds under simple conditions in good yield and large. Purity.

Explanation of the essence of the invention

In the process of the present invention, cyanic acid esters are reacted with 2-imino-3- (alkyl, aryl) -5- (alkyl, aryl) -1,3,4-oxadiazolines or, more conveniently, with their salts and an equivalent amount of base, e.g. Triethylamine or alkali hydrogencarbonate reacted; It is favorable to use a solvent for the cyanic acid ester. The addition reaction takes place at room temperature, followed by the splitting of the oxadiazoline ring and the cyclization, to the corresponding 1,3,5-triazine. The reaction products usually precipitate out as waxy precipitates or are isolated by concentration of the solvent. They crystallize after a short time and are recrystallized from ethanol. However, the crude products are already largely free of by-products when using equivalent amounts of the reactants:

..N-NR ² " 2 * -

RC C = NH + 2R ^ -OCN- * R ¹ -C-NH-NC ^ - ^ COR

oR ⁵

, ·, · 3 - "

The preparation of the target compounds is particularly characterized it facilitates, * 'neither employed nor the cyanate ester 2-Iminq-1,3,4-oxadiazolines ^from: must be separated each synthetic precursors or cleaned. The reaction is hardly affected by the solvent. Diethyl ether, tetrahydrofuran, chloroform, acetone and ethanol may be used, among others. The solvent and possibly used triethylamine can be worked up for the most part again for further approaches.

The. Reaction proceeds relatively quickly. But it is favorable to complete the conversion to Stir- 2 to '4 hours at 40 to 80 ⁰ C. '.

Table 1 gives an overview of possible substituent combinations in compounds which can be prepared by the process according to the invention, but without limiting its scope of application. ,

Table 1

No Phenyl _; H ² phenyl Y. . (#) Mp. ( ⁰ o. 1 phenyl phenyl 2-methylphenyl. , 28 182-133 - ; 2 Phenyl. phenyl 2-methoxyphenyl , 93 192-193 3 phenyl phenyl 2-chlorophenyl 78 197-198 4 phenyl phenyl 4-chlorophenyl 42 215-216: VJL 'is phenyl phenyl 4-bromophenyl. .: ' 207-208 "6 Phenyl,. phenyl 2,4-Dichlorpiienyl 36 227-229 7 , phenyl phenyl Naphth-1-yl 1-9 .. 163-1.70 · 8th phenyl Phenyl ' / Naphth-2-yl _: / I ² V 236-238 9 4-nitrophenyl phenyl ..Phenyl " 18. 200- ^ 202. 10 4-nitrophenyl methyl 2-methoxyphenyl. 30 190-195 11 4-nitrophenyl methyl 4-chlorophenyl 31. 160-161 12 4-nitrophenyl methyl 4-bromophenyl .57 294-296 13 methyl methyl Phenyl. 82 ': .. 270-272 14 , ethyl methyl phenyl   73 206-203 15 i-Propyl / methyl Phenyl. 29 "' 135-186 16 i-propyl methyl 4-chlorophenyl 35 190-191 17 i-propyl methyl 4-bromophenyl 94 185-187 18 i-propyl. methyl : 4-nitrophenyl 77 209-211 19 Benzyl. methyl Phenyl; 75. 225-226 20 methyl 70 175-176

Embodiments.

Connection 1

'24 S (o, 2 mo.l) phenyl cyanate are dissolved in acetone 250 ^ml: 24 g (o.1 CEE). 2-imino-3,5-diphenyl-1,3,3,4-oxadiazoline added. The mixture is then heated under reflux for 4 hours, then about 200 ml of acetone are distilled off. After some time, the reaction product can then be separated and recrystallized from ethanol. , . ·. ·

"Connection 14,. ^; ^

30 g of 2-amino-5-niethyl-1,3,4-oxadiazole are added after pulverization and drying with 40 g of dimethyl sulfate and stirred at about 60 ° C until homogenization. After cooling to about 30 ⁰ C, excess of dimethyl sulfate is twice stirred with 50 ml diethyl ether ent- ^(removed. The residue is dissolved in a Getaisch 100 ml of water and 400 ml of ethanol. Then, 63 g Phenyleyanat are added. Is added with stirring then a saturated Kaliumhydrogencarbonatlö'sung at room temperature was added dropwise until the pH ^of:. 8 is reached after the completion of the dropping for 2 hours stirring, the precipitate is filtered off with suction and washed with water is recrystallized from ethanol. '..:

, Instead of the potassium bicarbonate solution can also TrI-. ethylamine be used. ,.

Connection 16.

.6.5 g: 2-amino-5-i-propyl-1,3,4-oxadiazole are stirred with 8 g of dimethyl sulfate at 60 C until homogenization and then freed from excess dimethyl sulfate by treatment with diethyl ether. '.

.6 ml of bromine are covered with 10 ml of water and covered with a. 1 The above sodium cyanide solution is added dropwise with stirring until it is discolored. In this case, the temperature is maintained in the range of 0 to 5 ' ⁰ C by cooling. To. This Bromcyahgemisch now 11g phenol, which was dissolved in 50 ml of chloroform, added. While stirring slowly 11.8 g of triethylamine are added dropwise. After 20 minutes' will

Solution of the phenyl cyanate separated in chloroform and with the prepared from 2-amino-5-i-propyl-1, 3, 4-Qxadiazol and dimethyl sulfate 2-imino-3-methyl-5-i-propyl-1,3,4 Oxadiazolin methyl sulfate added. Further triethylamine is added to this mixture until / to the weakly alkaline reaction. It is stirred for another hour. The precipitate / is washed with water and ethanol. From ethanol is recrystallized.

Claims (1)

Claim of invention. A process for the preparation of 2- / Ί- (alkyl, aryl) -2-acylhydrazine-benz / -4,6-di- / (alkyl, aryl) -oxy / -1, 3,5-triazines, characterized in that 3, 5-disubstituted 2-imino
-1,3,4-oxadiazolines or their salts in the presence of an equivalent amount of base reacted with cyanic acid esters
become.