RU2086547C1 - 4-methyl-4-(1,1-dichloro-2-cyclopropylmethoxyethyl)-1,3-dioxane having herbicide activity - Google Patents

Abstract

FIELD: agriculture. SUBSTANCE: synthesis of 4-methyl-4-(1,1-dichloro-2-cyclopropylmethoxyethyl)-1,3-dioxane is carried out in two steps. At the first step interaction of 4-methyl-4-hydroxyethyl-1,3-dioxane with allyl chloride is carried out, the process takes place at 60-70 C in the presence of sodium hydroxide and phase transfer catalyst, triethylbenzylammonium chloride being used as said catalyst. At the second step 4-methyl-4-allyl oxyethyl-1,3-dioxane prepared at the first step interacts with chloroform, the process is carried out at 10-20 C in the presence of NaOH and catalytic amounts of triethylbenzylammonium chloride. EFFECT: searched novel biologically active compounds being derivatives of 1,3-dioxane. 2 tbl

Description

обладающему гербицидной активностью.The invention relates to a new chemical compound, specifically to 4-methyl-4- (1,1-dichloro-2-cyclopropylmethoxyethyl) -1,3-dioxane of the formula

possessing herbicidal activity.

 Due to the biological properties exhibited, the new compound may find application in agriculture as a herbicide. The inventive compound, its properties, the production method is not described in the literature.

где A алкил, алкенил;
B водород, низший алкил;
Y водород, низший алкил;
A и B вместе могут образовывать циклогексил, замещенный алкиламин, обладающие терапевтической активностью [1]
Известно применение 4-изопропил-5,5-диметил-1,3-диосана формулы

где R₁, R₂ водород, алкил, циклоалкил,
в качестве душистого вещества [2]
Известно соединение 2-н. бутил-4,4,6-триметил-1,3-диоксан, которое предлагается использовать в качестве активного ингредиента в душистых составах [3]
Известны 5-алкил-5-аралкокси-1,3-диоксаны формулы

где R галоидалкил;
R₁ водород, низший алкил,
обладающие гербицидной активностью [4]
Известны замещенные 1,3-диоксаны формулы

где R₁ фенил, фурил, пиридил, тиенил, замещенный хлором, фтором, метилом фенил;
R₂ водород, алкил, галоидалкил и др.Known derivatives of the general formula

where A is alkyl, alkenyl;
B hydrogen, lower alkyl;
Y is hydrogen, lower alkyl;
A and B together can form cyclohexyl, substituted alkylamine, having therapeutic activity [1]
The use of 4-isopropyl-5,5-dimethyl-1,3-diosan of the formula is known

where R ₁ , R ₂ hydrogen, alkyl, cycloalkyl,
as a fragrance [2]
Compound 2-n is known. butyl-4,4,6-trimethyl-1,3-dioxane, which is proposed to be used as an active ingredient in aromatic compositions [3]
Known 5-alkyl-5-aralkoxy-1,3-dioxanes of the formula

where R is haloalkyl;
R ₁ hydrogen, lower alkyl,
possessing herbicidal activity [4]
Substituted 1,3-dioxanes of the formula are known

where R ₁ phenyl, furyl, pyridyl, thienyl substituted with chlorine, fluorine, methyl phenyl;
R ₂ hydrogen, alkyl, haloalkyl, etc.

R ₃ hydrogen, or R ₂ + R ₃ form a divalent polymethylene with 2-6 carbon atoms;
R ₄ alkyl, haloalkyl, cyanoalkyl;
R ₅ hydrogen, alkyl;
R ₆ hydrogen, alkyl, haloalkyl, cyanoalkyl,
possessing herbicidal activity [5] prototype.

 The aim of the invention is the search for new compounds in a series of derivatives of 1,3-dioxanes exhibiting herbicidal activity.

 This goal is achieved by the synthesis of 4-methyl-4- (1,1-di-chloro-2-cyclopropylmethoxyethyl) -1,3-dioxane, which is carried out by the interaction of 4-methyl-4-hydroxyethyl-1,3-dioxane with alkyl chloride and by the reaction of the obtained product with chloroform, both stages take place in the presence of sodium hydroxide and catalytic amounts of TEBAH (triethylbenzylammonium chloride).

 Example 1. Obtaining 4-methyl-4- (1,1-dichloro-2-cyclopropylmethoxyethyl) -1,3-dioxane. The production method consists of two stages.

В трехгорлую круглодонную колбу, снабженную механической мешалкой, обратным холодильником и капельной воронкой загружают 146 г (1 моль) 4-метил-4-гидроксиэтил-1,3-диоксана, 60 г (1,5 моль) порошкообразной гидроокиси натрия и каталитическое количество (1 г) ТЭБАХ. Смесь при перемешивании разогревают на водяной бане до 60-70^oC и начинают прикапывать 134 г (1,75 моль) аллила хлористого. По окончании прикапывания (30 45 мин) смесь перемешивают при 60-70^oC еще в течение 1 ч. Затем баню убирают, дают реакционной смеси охладиться до комнатной температуры и экстрагируют диэтиловым эфиром 3 раза по 100 мл. Экстракт высушивают прокаленным сульфатом магния, отгоняют эфир и остаток перегоняют в вакууме. Выход 167 г 4-метил-4-аллилоксиэтил-1,3-диоксана, что составляет 90% на взятый 4-метил-4-гидроксиэтил-1,3-диоксан.

In a three-necked round bottom flask equipped with a mechanical stirrer, reflux condenser and dropping funnel, 146 g (1 mol) of 4-methyl-4-hydroxyethyl-1,3-dioxane, 60 g (1.5 mol) of powdered sodium hydroxide and a catalytic amount ( 1 g) TEBAH. The mixture is heated with stirring in a water bath to 60-70 ^° C and 134 g (1.75 mol) of allyl chloride are added dropwise. Upon completion of the dropwise addition (30–45 min), the mixture was stirred at 60-70 ^° C for another 1 hour. The bath was then removed, the reaction mixture was allowed to cool to room temperature and extracted with diethyl ether 3 times in 100 ml each. The extract was dried with calcined magnesium sulfate, ether was distilled off, and the residue was distilled in vacuo. Yield 167 g of 4-methyl-4-allyloxyethyl-1,3-dioxane, which is 90% of the taken 4-methyl-4-hydroxyethyl-1,3-dioxane.

В трехгорлую колбу, снабженную механической мешалкой, обратным холодильником, капельной воронкой и термометром, загружают 167 г (0,9 моль) 4-метил-4-аллилоксиэтил-1,3-диоксана, 100 г (2,5 моль) порошкообразной гидроокиси натрия и каталитическое количество (1 г) ТЭБАХ. Затем в реакционную массу добавляют 100 мл хлористого метилена в качестве растворителя, начинают прикапывать 357 г (3 моль) хлороформа с интенсивным перемешиванием и охлаждением до поддержания температуры в реакционной смеси 10-20^oC. По окончании прикапывания смесь продолжит перемешивать в течение 30 мин, после чего реакционную массу промывают водой. Полученный раствор экстрагируют 3 раза по 150 мл диэтиловым эфиром. Эфирный слой отделяют и сушат над прокаленным сульфатом магния. После вакуумной перегонки получают 133 г 4-метил-4-(1,1-дихлоро-2-циклопропилметоксиэтил)1,3-диоксана, что составляет 55% на взятый 4-метил-4-аллилоксиэтил-1,3-диоксан.

A three-necked flask equipped with a mechanical stirrer, reflux condenser, dropping funnel and thermometer is charged with 167 g (0.9 mol) of 4-methyl-4-allyloxyethyl-1,3-dioxane, 100 g (2.5 mol) of powdered sodium hydroxide and a catalytic amount (1 g) of TEBAH. Then, 100 ml of methylene chloride as a solvent is added to the reaction mass, 357 g (3 mol) of chloroform are added dropwise with vigorous stirring and cooling to maintain the temperature in the reaction mixture 10-20 ^o C. After completion of the dropping, the mixture will continue to mix for 30 minutes, after which the reaction mass is washed with water. The resulting solution was extracted 3 times with 150 ml of diethyl ether. The ether layer was separated and dried over calcined magnesium sulfate. After vacuum distillation, 133 g of 4-methyl-4- (1,1-dichloro-2-cyclopropylmethoxyethyl) 1,3-dioxane is obtained, which is 55% of the taken 4-methyl-4-allyloxyethyl-1,3-dioxane.

 The structure of the synthesized compounds is established on the basis of the following data.

4-Methyl-4-allyloxyethyl-1,3-dioxane C ₉ H ₁₆ O ₃ . T. bale. 75 76 (3). ¹ H NMR spectrum (HMDS, CCl ₄ ) 1.2 s (3H, CH ₃ ); 1.3 2.0 m (4H, -CH ₂ CH ₂ ); 1.7 m (2H, CH ₂ ); 3.4 t (2H, CH ₂ C =); 3.78 m (2H, OCH ₂ ); 4.68 s (2H, OCH ₂ O); 4.9 5.3 m (2H, CH ₂ -); 5.6 6.0 m (2H, -CH ₂ =).

4-Methyl-4- (1,1-dichloro-2-cyclopropylmethoxyethyl) -1,3-dioxane C ₁₁ H ₁₈ Cl ₂ O ₃ . T. bale. 150 152 ^o C at 3 mm RT. Art. n $\genfrac{}{}{0ex}{}{\text{twenty}}{\text{<figure-callout id="1" label="D" filenames="00000009.png,00000010.png" state="{{state}}">D</figure-callout>}}$ 1,4808, ρ $\genfrac{}{}{0ex}{}{\text{twenty}}{\text{4}}$ 1.1451. ¹ H NMR spectrum (HMDS, CCl ₄ ) 1.02 - 1.34 m (3H, CH ₃ ); 1.34 1.68 m (3H, CH ₂ , CH); 1.68 1.92 m (4H, CH ₂ , CH ₂ ); 3.48 t (2H, CH ₂ O); 4.68 m (2H, CH ₂ ). ¹³ C NMR spectrum (δ ppm) 22.97 q (1C, CH ₃ ), 24.66 t (1C, CH ₂ ), 30.03 d (1C, CH), 35.66 t (1C, CH ₂ ), 39.61 t (1C, CH ₂ ), 60.39 s (1C, OC), 62.27 t (1C, CH ₂ ), 66.02 t (1C, CH ₂ ), 69.64 t (1C, CH ₂ ), 71.59 s (1C, CCl ₂ ), 87.25 t (1C, OCH ₂ O).

The result of elemental analysis of C ₁₁ H ₁₈ Cl ₂ O ₃ .

 Calculated, C 49.08, H 6.74, Cl 26.34.

 Found C 49.00, H 6.21, Cl 26.12.

 The biological activity of the claimed compounds is confirmed by the following examples.

Example 2. In the laboratory, previously germinated seeds of cucumbers, oats, wheat were laid out in Petri dishes and 4 ml of the test compound were poured with a concentration of 0.01 to 100 mg / L. Then the Petri dishes were placed in a thermostat for two days. Germination temperature 25 ^o C. At the expiration of the specified period, the effectiveness of the substance was compared with the control (distilled water). Efficiency indicators were the root length, shoot length, and plant weight. The test results are summarized in table. 1. The data table. 1 indicate the presence of biological activity of the claimed substance. In comparison with the prototype of the claimed substance is phytotoxic in relation to the taken biotests.

 Example 3. Corn seeds were sown in vegetation vessels with a diameter of 35 cm with simultaneous sowing of a mixture of weeds, consisting of monocotyledonous (millet chicken, blue bristle) and dicotyledonous plants (radish gherkin, molyevka, shiritsa). Simultaneously with sowing, preparations were introduced in a dose of 2-4-6 kg / ha. Repeat 6-fold. 4 weeks after seeding, the effectiveness of the substance was determined. The test results are given in table. 2. The data show that the claimed substance is superior in efficiency to the prototype.

 Thus, the biological tests showed that the claimed compound has herbicidal activity and in terms of effectiveness exceeds the taken prototype.

Claims (1)

4-Methyl-4- (1,1-dichloro-2-cyclopropylmethoxyethyl) -1,3-dioxane of the formula

possessing herbicidal activity.

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