SK278063B6 - 5-methoxy-2-arylomethylcarboxymethyl-4h-pyran-4-ons and method of their preparation - Google Patents

Abstract

5-Methoxy-2-aryloxymethylcarboxymethyl-4H-pyran-4-ons of general formula I, where R1 is hydrogen, methyl, or chlorine, R2 is hydrogen, methyl or chlorine, R3 and R4 are the same or different and mean hydrogen or chlorine are prepared by reaction of halide of aryloxymethylcarboxylic acid of general formula II with 5-hydroxymethyl- -2-methoxy-4H-pyran-4-on in medium of organic solvent as acetone, methylethylketone, dimethylformamide and other, by using of agent bounding the halogenhydrogen and at temperature 0 degrees of Celsius to boiling temperature of used organic solvent.

Description

Technical field

The invention relates to 5-methoxy-2-aryloxymethylcarboxymethyl-4H-pyran-4-ones and a process for their preparation.

BACKGROUND OF THE INVENTION

2- (N- / 2-cyanoethylthiocarbamosulfenylmethyl-5-hydroxy-4H-pyran-4-ones) and their complex compounds with Zn and Ni as fungicides are known from the literature (U.S. Pat. No. 3,799,945, U.S. Pat. No. 3,852,444), further known are 2-hydroxymethyl-3- (N, N-dialkyldithiocarbamidomethyl) -5-hydroxymethyl-4H-pyran-4-ones (DE 2625 823), 2- (pyridyl-5-pyrrolidon-5-ylcarboxymethyl) ) -5-hydroxy-4H-pyron-4-one 15 (JP 60 233 071) as well as 2- (2-arylalkylamino-hydroxy) ethyl-4-alkoxy-4H-pyran-4-one (JP 59 122 485) .

Organophosphorus compounds of oxy-4H-pyran-4-ones are also known which are effective as insecticides, miticides and nematicides (JP 62 29593, US 4 608 367). Various aryloxyalkanecarboxylic acid esters, for example 2,4-dichlorophenoxycarboxylic acid esters (J. Ord. Chem. 12, 426/1947, Botan. Gaz. 107, 476/1946), 2,4,5-trichlorophenoxyacetic acid esters, affect plant growth 20. (Weeds 5,121 (1957)). These may include, for example, surfactants such as emulsifiers or dispersing agents, such as liquid solvents or solid carriers.

According to the invention, the active compound content can be varied within a wide range according to the intended use, from 0.0001 to 5% by weight. preferably from 0.001 to 0.5 wt.

DETAILED DESCRIPTION OF THE INVENTION

To 100 cm ^{3 of} acetone was added 7.8 g of 5-methoxy-2-hydroxymethyl-4H-pyran-4-one (0.05 mol) and 5.1 g of triethylamine (0.05 mol). Then, with vigorous stirring, 11 g of 2-methyl-4-chlorophenoxyacetic acid chloride (0.05 mol) was added at 20 ° C, which rose to 54 ° C 10 minutes after the addition. The reaction mixture was then stirred at the same temperature for 1 hour until the reaction was complete. After cooling to 10 ° C, the reaction mixture was poured into 500 cm ^{3 of} ice water with stirring. The precipitated solid was filtered off and purified by crystallization from cyclohexanone after drying. 14.1 g of white crystalline 5-methoxy-2- (2-methyl-4-chlorophenoxymethylcarboxymethyl) -4H-pyran-4-one with a melting point of 100.3 DEG C. were obtained.

Elemental analysis for C 20 H 11 ClO 6 (M 338.73)

SUMMARY OF THE INVENTION

The present invention provides 5-methoxy-2-aryloxymethylcarbonylmethyl-4H-pyran-4-ones of formula I

calculated: 10.46% Cl found: 10.52% C1 H NMR (COCl) 2.23 3.72 4.7

4.9 δ (ppm) CH 1 -Ar CH 1 -O

-CO-CH, -O C-CH, -O

6.25 - 7.65

H - aroma.

wherein R ¹ is hydrogen or methyl, R ¹ is hydrogen, methyl or chlorine, R ³ and R ⁴ are the same or different and are hydrogen or chlorine, and a process for their preparation. The process according to the invention consists in the formation of an aryloxymethyl carboxylic acid halide of the formula Π

wherein R ¹ , R ² , R ³ and R ⁴ are as defined above and X is chlorine or bromine is treated with 5-methoxy-2-hydroxymethyl-4H-pyran-4-one in an organic solvent environment such as acetone, methyl ethyl ketone , methyl isobutyl ketone, dimethylformamide, dimethylsulfoxide, ethyl acetate, dioxane or acetic acid nitrile and using a reagent such as sodium carbonate, potassium carbonate and tertiary amines, such as triethylamine or pyridine, binding the resulting hydrogen halide at 0 ° C up to boiling of the organic solvent used.

The 5-methoxy-2-aryloxymethylcarboxymethyl-4H-pyran-4-ones of the invention can be used in agriculture as herbicides and plant growth regulators. For this purpose, they can be formulated in liquid form as a concentrate, solution, emulsion and suspension, or solid forms such as powder, granulate and paste. These are prepared by known methods, e.g. by mixing the active ingredient with Example 2

To 100 cm @ ³ of acetic acid nitrile were added, with stirring, 5.1 g of triethylamine (0.05 mol) and 7.8 g of 5-methoxy-2-hydroxymethyl-4H-pyran-4-one (0.05 mol). After cooling the reaction mixture to 5 ° C, 11.6 g of 2-methyl-4-chlorophenoxy-2-propionic acid chloride was added over 5 minutes. Then the reaction mixture was stirred at room temperature for 2 hours. The acetic acid nitrile was distilled off from the reaction mixture under reduced pressure, the residue was stirred with water, filtered off and, after drying, the product crystallized from toluene. 9.2 g of crystalline 5-methoxy-2 - [(1- (2-methyl-4-chlorophenoxyethyl) carboxymethyl) -4H-pyran-4-one, m.p. 102.3 ° C, were obtained.

Elemental analysis for C 17 H 17 ClO 6 (M 352.75) calculated: 10.05% Cl found: 10.41% C1

'HNMR (COC1 ₃ ) δ (ppm) 1.58 CH5-CH < 2.16 The CH-N 3.65 Chi-0 4.73 CH3-CH-CO 4.86 O-CO-CH? - C 6.3 - 7.3 H - aroma.

Example 3

To 80 tin of ^3- methyl ethyl ketone was added with stirring g of pyridine (0.05 mol) and 7.8 g of 5-methoxy-2-hydroxymethyl-4H-pyran-4-one (0.05 mol). The reaction mixture was heated to 40 ° C at which 8.5 g of phenoxyacetic acid chloride (0.05 mol) was added over 10 min. Next, the reaction mixture was stirred for 1 h

SK 278063-6 at 60 ° C, then cooled and poured into 500 cm ^{3 of} ice water with stirring. The precipitated solid was collected by filtration and recrystallized from toluene. 7 g of white crystalline 5-methoxy-2 (phenoxymethyl-carboxymethyl) -4H-pyran-4-one having a temperature of 42.5 ^e C were obtained.

Elemental analysis for C 15 H 15 O 6 (M 290.26) calculated: 62.1% C, 5.1% H found: 62.3% C, 4.9% H 1 H NMR (COCl)

3.62

4.59

4.9

6.5 - 7.3 δ (ppm)

Chi-0

CO - CH? - O Ar C-CH 1 -OH - aroma.

The soil surface leveled and irrigated. The test substances at the dosages listed in the table were applied by spraying directly onto the soil after sowing (pre-emergence treatment). The experiments were carried out under greenhouse conditions. Administered volume samples diluted with water, corresponded in all cases, the volume of 1000 1 ha ^'first Dimethylamine salt of 2-methyl-4-chlorophenoxyacetic acid (DMA-MCPA) was used as standard. The degree of damage to the test plants was assessed visually and expressed by a 0 to 5 rating scale, in which grade 0 stands for plants normally developed, grade 5 stands for dead plants. The results are shown in Table 1. The evaluation was performed 20 days after application.

Example 4

To 70 cm ^{3 of} dimethylformamide, 5.3 g of sodium carbonate (0.05 mol) and 7.8 g of 5-methoxy-2-hydroxymethyl-4H-pyran-4-one (0.05 mol) were added with stirring. At room temperature, 10.3 g of 4-chlorophenoxyacetic acid chloride (0.05 mol) was then added with stirring, raising the temperature to 46 ° C. Stirring was continued for 1 h at 55 ° C. After cooling, the reaction mixture was poured into 400 cm ^{3 of} ice-water with stirring. The precipitated solid was collected by filtration and purified by crystallization from toluene. Thus 7.1 g of white crystalline 5-methoxy-4H-pyran-4-one with a melting point of 109.7 ° C are obtained.

Table 1:

Effect of test compounds on plant growth and development after application to soil until emergence.

Elemental analysis for the calculated: 10.9% Cl found: 11.0% Cl 1 HNMR (COCl ₃ ) 3.65 4.61 4.92 6.5 - 7.3 ₁₅ HbCl 10 (M 324.71) δ ( ppm)

CHi-O CO-CH3-OAr C-CH3-OH-aroma.

Example 5

To 80 cm ^{3 of} dimethylsulfoxide was added 3.4 g of triethylamine (0.033 mol) and 5.2 g of 5-methoxy-2-hydroxymethyl-4H-pyran-4-one (0.033 mol) with stirring. Then, 9 g of 2,4,5-trichlorophenoxyacetic acid chloride (0.033 mol) was added at 0 ° C with stirring. Stirring was continued for 2 h at 70 ° C, after cooling the reaction mixture was poured into 400 cm ^{3 of} ice water. The precipitated solid was collected by filtration and purified by crystallization from toluene. 8.2 g of white crystalline 5-methoxy-2- (2,4,5-trichlorophenoxymethylcarboxymethyl) -4H- were obtained.

The compound is according to the invention dddd dBd lAt kfl.b · ¹ MUSTARD POHANKA cress OVOS PROSO First 5.0 5 2 5 1 2 2.5 5 2 5 0.5 l 1.25 5 1 5 0 0 0.0 1 0.5 0.5 0 0 12:51 0.5 Q 0 0 0 o.u 0 0 0 0 0 Second 5.0 5 5 5 5.5 5 2.5 5 < 5 2 5 1.25 5 5.5 5 0.5 > 5 0.65 5 5 5 0 0.5 0.51 5 1 4.5 0 0 12:16 2 0 0 0 0 5th 5.0 5 5 5 * 2 2.5 5 5 5 3 l 1.25 5 5 5 1 0 0.65 * .5 5.5 4.5 0 0 12:51 0.5 1 5.5 0 0 0.16 0 0 0 0 DMA.MCPA 5.0 5 5 1 1 itendard 2.5 5 2.5 0 0 1.25 5 1.5 0 0 0.65 5 0 0 0 0.51 5.5 0 0 0 0.16 0 0 0

pyran-4-one, m.p. 155.4 ° C. Elemental analysis calculated for: 30.1% Cl Found: 30.4% Cl 1 HNMR (COCh)

3.67

4.73

4.97

6.8 - 7.4

C _ls HnCjO ₆ (M 353.59) δ (ppm) H-CH

CO-CH 1 -O C-CH 3 -O-H-aroma.

Example 6

In test vessels filled with untreated arable land, the following are sampled as test objects: A - European Mustard (Sinapis awensis, Brassicaceae) B - Common Buckwheat (Fagopyrum vulgare, Polyganaceae) C - Common Cress (Lepidium sativum, Brassicaceae) D - Oat ( Avena Sativa, Poaceae) E - Millet (Panicum milliaceum, Poaceae)

Example 7

Seeds of buckwheat (Fagopyrum vulgare) were planted in 30 x 15 cm experimental pots filled with loamy soil and grown under greenhouse conditions to the cotyledon stage. After vyjednotení the same number of subjects at the stage of differentiation of the primary leaves were applied concentration of 1-1000 mg · l ¹ compound treatment hand sprayer at a working pressure of 0.2 bar. Both treated and untreated plants were kept under greenhouse conditions at 25 to 27 ° C for 15 days. The length increment of the stem from the treatment site to the vegetation peak of the stem was evaluated and expressed in bonitation grades (0-3) of efficacy compared to control (Table 2).

Table 2

n · tteainOlny r ·· t stems KonoentrOeis Prlanam? prlcistok stems / * / ^: M * / sliMonlno by vyntloru · checks First t. X * i X «X x % j « •. - i m 100 1 IM i 1 * 0.1 »1,5 ¹ 120.3. M. í - - ; soo {1000 'IM.2 00.0 M.6 21.2 • - 1) 2.0 71.í 10.2 M

hydrogen halide, at 0'C up to the boiling point of the organic solvent used.

End of document

Industrial usability

5-Methoxy-2-aryloxymethylcarboxymethyl-4H-pyran-4-ones can be used in agriculture as herbicides and plant growth regulators. They are used as a concentrate, solution, emulsion and suspension or in solid form as a powder, granulate and paste.

Claims (2)

PATENT CLAIMS A compound of the formula I wherein R ¹ is hydrogen or methyl, R ² is hydrogen, methyl, or chlorine, R ⁵ and R ⁴ are the same or different and are hydrogen; or 5-Methoxy-2-aryloxymethylcarboxyinetyl-4H-pyran-4ones chloro. A process for the preparation of 5-methoxy-2-aryloxymethylcarboxymethyl-4H-pyran-4-one according to claim 1, characterized in that to an aryloxymethylcarboxylic acid halide of the formula I wherein R ¹ is hydrogen or methyl, R ² is hydrogen, methyl or chlorine, R ³ and R ⁴ are the same or different and are hydrogen or chlorine, X is chlorine or bromine is treated with 5-methoxy-2-hydroxymethyl-4H-pyran-4one of the formula in an organic solvent from acetone , methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylsulfoxide, ethyl acetate, dioxane or acetic acid nitrile and using a reagent selected from the group consisting of sodium carbonate, potassium carbonate, or tertiary amines such as triethylamine or pyridine,