BG98889A - Method for the preparation of 2-cyano-n-[(ethylamino)-carbonyl]-2-(methoxyimino) acetamide - Google Patents

Abstract

By the method 2-cyano-N-[(athylamino) carbonyl]-2-(methoxyimino) acetamide is produced in the methilation of 2-xyano-N'[(ethylamino)-carbonyl]-2-hydroxyimino) acetamide with dimethylsulphate and sodium bicarbonate in aqeous medium. The initial free oxime is produced in two stages - condensation of cyanoacetic acid and ethylcarbamide in medium of acetic anhydride at reaction mixture temperature from 45 to 60°C until the production of 1-/1-cyanoacetel/3-ethylcarbamide and subsequent treatment of the latter with sodium nitrite and hydrochloric acid in aqueous medium.

Description

METHOD FOR PREPARATION OF 2 - CYANO-Λ / (ETHYLAMINO) - CARBONIA] - 2 - (METOXY

IMINO) ACETAMID

A process for the preparation of 2-cyano-N- (ethylamino) -carbonyl-2- (methoxyimino) acetamide (1), characterized in that by methylation of 2- cyano-N- (ethylamino) -carbonyl] 2- (chloroxyimino) acetamide (2) with dimethyl sulfate and sodium bicarbonate in aqueous medium gave 2-cyano-N- (ethylamino) -carbonyl] -2- (methoxyimino) acetamide (1). Source free oksym (2) was prepared in two cyanoacetic acid (3) and urea, hydride, at a temperature of the reaction stage - the condensation of (4) is a medium of the mixture 45-60 ^by C. Preparation of 1 - (1-cyanoacetyl) - 3 - ethylacobamide (5) acetic acid to semi and subsequent treatment of (5) with sodium nitrite and hydrochloric acid in aqueous medium.

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The invention relates to

2- cyano - (systemic) carbonyl 2- (methoxyimino) acetamyl fungicide with systemic actionAltvHa.) In tomatoes and potatoes

1G0 - 129 g active substance (1), which is applicable as

For vines () and lp. , in the amount of hectare p '].

It is known to prepare (1) by methylation of oxoime (2) with diazomethane in diethyl ether. The free eye (2) is obtained by nitrosation of 1-cyanoacetyl-3-ethidocobyl with sodium nitrite in a medium with dilute acetic acid *

U

- With Ch

Oh

-s

And

-C-0A7 »/ fd-OC

C? Nc'C -C-C - OSC ⁱⁿ If if y / <C? 0 fjOC'4 ^ ai

Si

The methylation process can be carried out with the oasis free oxime (2) 3 dimethylformamide, a stoichiometric amount of sodium methylate is added to convert the whole amount of oxime into the corresponding sodium salt, and methyl iodide is added to the reaction mixture. The reaction is carried out at room temperature and with a slight excess of methylation. • Schill can be used and methyl boomide (1) is obtained by methylation of (2) with an agent instead of methyl

0J. According to another method, they have methylsulfate and potassium carbonate in acetone free. The reaction was carried out at reflux of the reaction mixture and 1ϋ Vew excess of dimethyl sulfate PJ.

pane is the use of expensive methylation agents, the glass of the process in Opel, an organic solvent that imposes a sex on the bed and its associated

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9999 «e ο ···

9 · · · ·

Oh

9 • 9 · 0

999 9999

99 ·

3.

juice extraction and purity. For this purpose, in addition to the methylation process, all other stages of the synthesis of (1) were also investigated.

/ —V

According to the invention 2-Cisno-N- (ethylamino) -Nyl-2- (methoxyimino) acetamyl (1) is prepared by the following reaction scheme:

o = e (mHz

CWUg o - c '

and. I'ho

Mysh

...

_z MM-C- ₄ ⁱⁿ W

In

JCAiHa practice is a three-step synthesis, then the quality of the final product (1) and the amount of yield obtained are limited by the successful passage of the first stage of the chavan? on 1- (1-cyanoacetate.) - 5 ethylurea (5). The direct production method ng (') is based on the interaction of anacetic acid (3) with ethylcobamide (4) in a medium at a temperature of 75-85 ° C, despite the comparative production technology of (5), the yields of the target laboratory conditions n-s poaii-leazt 70-75 semi ^! lazy:

on the acetic acid zhnil ^r carried the product yaooi n l g

4.

adverse reactions take place and a significant amount of undesirable impurities such as N-ethylacetylcapbamyl is obtained.

<Used as 'output' by our requirements

I:

duct technical ethylcobanide with a purity of VP%, of

- 17% and moisture content - 1,5 I; and cyanoacetic acid - crystal, with a purity of 98%.

According to the invention, the synthesis is conducted in a fusion manner - a reaction mixture of equimolar amounts is prepared

ethylcyrbacid and cisanoic acid (3). The amount of acetic anhydride required is determined in order to allow for the presence and release of the oxide. The resulting slurry was heated at 40-45 ° C for 5 hours and at 50 * C for 4 hours. The reaction is exothermic, so the reaction mixture is heated carefully with warm water. After the reaction time, the heating is stopped and stirred for one hour until the temperature drops to room temperature - 25 ° C. At the end of the process, the reaction mixture is viscous and difficult to digest.

According to the proposed method, reactions (a) and (c), respectively, of cyanacetylation of ethylurea and subsequent nitrosiration to oxane (2) are eliminated in one step without removing the intermediate 1- (1-niacacetyl) -3-ethylurea ( 5). As a result, a certain amount of methanol is added to the viscose produced. With continuous stirring and at a temperature of 25-35 ° C, a solution of sodium nitrile solution was added dropwise over a period of 2 hours. More foam formation is possible, since unreacted ethylcapamyl reacts with sodium nmtoite. Pa. op ве op p p op op op op op op op op op op op op op op op op op op y?

AND HE'- 'Π AND HHG' - Ηΐ Π T Π ^r T · · ^ ·· ·· «· ·· ··

hydrochloric acid. Addition time 2 hours, at the end of the process the reaction mixture was pH 2.0 - 2.5. A pale yellowish precipitate is obtained by otoxime (2), the reaction mixture is stirred for another 1/2 hour, filtered and washed with a certain amount of ox, o pH-6.0-6.5 The oxime thus obtained does not need to be dried as it agrees method of the invention, the next step of methylation was carried out g 'ί &

in an aquatic environment.

The resulting oxide from step (c) was quenched for methylation with the required amount of water, and the calculated amount of sodium bicarbonate was added to the suspension thus obtained. The reaction is slightly exothermic and the reaction temperature of 35-40 ° C is successfully maintained by adjusting the speed and amount of dimethyl sulfate. In this phase of the process the end product is not ^kd discredited and at temperatures up to 65 ° C, but this vapoeki recommend observing the said temperature conditions (35-40 ° C). After the required amount of dimethyl sulfate was added, the reaction mixture was stirred for 1 hour at 40 ° C and for 1 hour at 20-25 ° C. The resulting pale pink precipitate from 2-cyano-N- (ectylamino) carbonyl -2- (methoxyimino) acetamide (1) was centrifuged, washed with ox and shi.

The advantages of the process according to the invention are the translation of pose methylation in an aqueous medium, which allows the use of hodminm oxime to be used maliciously without slow drying, which is particularly economically advantageous; simple technological equipment is used. According to the process of the invention, all the stages of the process are carried out at the optimum reaction temperature and state, and I guarantee the final '' solution; (Ί) high e-mise and high purity.

jig i

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Example 1 A / B Enamelled Reactor (V-2.5 m3) 357 l of acetic anhydride 6.99%, 204 kg were charged sequentially. cyanoacetic acid and 260 kg. ethylcarbamyl with composition - 80% ethylcarbamide, 18% sodium nitrate, 1.5% water and 0.5% ethanol. With continuous stirring, the reaction mixture was heated to 49 ° C and held for 3 hours at 40-45 ° C and 5 hours at 55-60 ° C. The heating is then stopped and the mixture is stirred 0 '

1-1.5 hours, with the temperature spontaneously decreasing to 25

30 ° C. At the end of the process, the reaction mixture is viscous and difficult to stir. 201 p are added to it. methanol and temperature with?

sets in the range of 25-28 ° C. At this temperature ^{, a} pre-prepared solution of 186 kg was added to the reaction mixture. of triez nitrite 6.98% and 412l of aqueous condensate for a period of 2 hours.

During nitrosation formation of n is possible ^; a certain amount of foam as a result of the reaction of unreacted ethyl urea. When the sodium nitrite is added, the temperature of the reaction mixture is maintained in the range of 18-35 ° C.

the end of the process results in an orange-red crucible which is stirred for another hour at this temperature. The mixture was then cooled to 10-15 [deg.] C and added 2 hours ^of individually prepared solution of 201 l of hydrochloric acid 6345. and 4 ' of aqueous condensate. 3 end of adding hydrochloric acid, Reaki? the mixture has OH = 2.9 - 2.5. Stirring was continued for another 1 hour at T = 10-15. The resulting precipitate was filtered off and washed with water: pH = 6.0 - 6.5 on the wash water. The resulting oxime (2) -2 - Cia - N - ((ethylanino) - carbonyl] -2- (hydroxyimino) acetammyl does not co-exist, moist (c = 20-25%) is used in the next synthetic step. on oxime, based on dry matter, - 325 kg. or 73.6% of the test melting point 198-202 ° C.

· · · · ·. · · · · · · · · · · · · · · · · · 999 9 9 9 99 9 9 • 9 9 9 9 9 9 9 9 9 9999999

9 9 9 9 9 99 9

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B / B stainless reactor (B = 4.0m3) is charged 304 kg. oxime (2) b. 100% and 1600/1. water condensate. At 25 30 ° C, 289 kg were added portionwise to the resulting suspension. sodium bicarbonate 6.97% for a time of 1.5 hours. The resulting solution was stirred for another 1 hour. To it at 30 ° C the addition of 304l begins. dimethyl sulfate 6.99%. The reaction is slightly exothermic, and by adjusting the rate of addition of dimethyl sulphate is easily maintained at a reaction temperature of 35-40 ° C. Dimethyl sulfate addition time - 3 hours. After the addition is complete, reaction! the mixture was stirred for 1 hour at T = 40 ° C and 1 hour at T = 29 - 25 ° C.

The resulting suspension was centrifuged and washed with water; to pH = 7.0 - 7.2 of the wash water. The wet material (w = 5-6 ° was dried in a hot air-drying oven at T = 75-80 ° C.

Yield of (1) - 2- Cyano-N - [(ethylamino) - carbonyl] -2- (methoxyimino) acetamide - 3 Hg. or 94.8% of theoretical

mining.

Melting point 158-162 ° C, purity 98.6% (HP / C).

IR (KBr): 3340cm ¹ (Λ / Η), 3230 - 3160cm ¹ (L 3000cm ' ¹ (CH), 2240cm- ¹ (C ^ L /), 1750-1600cm ¹ (C' - = O) (Me ₂ S 0) 1.1 (£, 3H, CH ₃ ), 3.25 (^, 2H, CH ₂ ),

4.32 ($, H, CH ₃ 0), 7,71 (£, H, / VH), 10,2 ($ , D / H). Elemental analysis: for

Calculated,%: C, 42, 40; H, 5, 09; N, 28, 28

Found,%: C, 42, 46; H, 5, 17; / V ', 25, 40.

Claims (2)

1. Method for the Preparation of 2- Cyano - // - // Ethylamino / capblnyl 7-2- (mpxypyrimidin) aptamy hapyitroiapayl! Wed sodium bicarbonate in aqueous medium at 35-40 ° C, resulting in (1) high yield and purity. A method according to claim 1, characterized in that for the preparation of (2) 2- Cyano - / - // ethylamino-carbonyl -2- (hydroxyimino / acetamide) technical ethyl urea is used, with a basic substance content of 75% and 18% sodium nitrate, the condensation being carried out in a temperature range of 45-60 ° C.