CS269020B1 - 5-Hydroxy-2- (hydroxymethyl) -4Hpyran-4-one derivatives and their preparation - Google Patents

Abstract

The solution concerns 5-acyl-or 5,7--diacyl derivatives of 5-hydroxy-2-/hydroxymethyl/-4H-pyran-4-one of the general formula I, where R represents naphthyl or phenyl substituted by a methyl group, a nitro group, a chlorine atom, R. represents a hydrogen atom or a methyl group, n is 0 to 3, and R' represents a bromine or chlorine atom, a pyridine group, an azido group, 2-methyl-4-chlorophenoxyacetyloxy(-2,4-dichlorophenoxyacetoxy- or hydroxy group. The mentioned substances are used as fungicides and herbicides. The substances are prepared by acylation of the compound of the general formula II with a reactive acid derivative of the general formula III, where R, R^, R' and n have the above-mentioned meanings.

Description

1 CS 269020 B1

This invention relates to 5-hydroxy-2- (hydroxymethyl) -4H-pyran-4-one derivatives. Certain 5-hydroxy-2- (hydroxymethyl) -4H-pyran-4-one derivatives of Ichimoto et al. Biol. Chem., 39, 1311 (1975)] and Dobias et al. [eiologia 32, 417/1977] disclose antifungal, antibiotic and bacteriostatic properties. Producers of 5-hydroxy-2- (hydroxymethyl) -4H-pyran-4-one are, for example, Aspergillus strains Beelik, A., AdvancesCarbohyd. Chem., 11, 145 (1950)]. Reaction of carboxylic acid derivatives with 5-hydroxy-2- (hydroxymethyl) -4H-pyran-4-one to form mono. resp. diacyl derivatives are described by Beelik, A., Purves V.C .; Can. O. Chem. 33, 1361 (1955). Nucleophilic exchange of chlorus with nitrogen nucleophiles in 2-chloromethyl derivatives is described by Ettel Jettel, V., Hebek, O .; Coll. Czech. Chem. Commun. .15, 356 (1950)].

According to the present invention, the compounds of formula (I) are 5-hydroxy-2- (hydroxymethyl) -4H-pyran-4-one derivatives of general formula R-O-CH- (CH2) n-C-O (1). ch2-r

wherein R is naphthyl or phenyl substituted independently with methyl, nitro or chloro, R 1 is hydrogen or methyl, n is 0 to 3 and R is bromine or chlorine, pyridine and 2-methyl-4-chlorophenyl; noxyacetoxy) 2,4-dichlorophenoxyacetoxy oxy hydroxy or azido and a process for the preparation thereof, wherein 0.9 to 1.0 molar parts of the compound of the formula II

O HO η / 11 /.

CH-R

wherein R * is as defined above, reacts with 0.9 to 1.3 molar portions of the carboxylic acid reactive reactant of formula III R-O-t 1

H- (CH 2) n -COOH (111). wherein R 1, R 6 are as defined above, such as chloride or anhydride, at a temperature of -15 to 110 ° C for 0.5 to 12 hours. If the reactive derivative is an acid chloride, the reaction is preferably carried out in the presence of a base. In a particular case, the addition of a base is replaced by the fact that the reaction is carried out in a basic solvent.

The compounds of formula (I) exhibit herbicidal and fungicidal activity, and these compounds can therefore be used as plant protection agents. The compounds interfere with the division of plant cells, thereby causing undesirable growth of undesirable plants. The compounds can be characterized as auxin growth regulators similar to other phenoxyacetic acid derivatives. The compounds of the present invention can be applied analogously to other pesticidally active compounds in the form of solutions or as suitable suspensions.

Processes for preparing the compounds of the invention are generally accomplished by adding 0.9 to 1.3 molar parts of reactive derivative to 1 molar portion of the 5-hydroxy-2- (hydroxymethyl) -4H-pyran-4-one derivative of the formula II substituted acids of formula III. In general, an acid halide, especially a chloride or bromide, an acid anhydride or a mixed anhydride, or a reactive acid ester, may be used as the reactive derivative. When working with an acyl halide, it is preferred to use basic agents such as acapro. alkali metal carbonates or tertiary organic bases, in particular CS 269020 B1 is used pyridine. The acylation reaction can be carried out in a beige or aqueous-organic medium. Suitable anhydrous media are ketones such as cetone or ethyl acetate. The mixing of the reaction components mostly takes place at a temperature of -15 to 50 ° C, preferably 0 to 5 ° C.

A period of 0.5 to 12 hours is required to react. The isolation of the compounds is carried out by known procedures followed by purification, crystallization or chromatography.

The details of each preparation process are set out in the following examples of implementation, without being limited to these exclusive embodiments. Example 1 5- (2-Methyl-4-chlorophenoxyacetoxy) -2- (hydroxymethyl) -4H-pyran-4-one To 2.8 g of 5-hydroxy-2- (hydroxymethyl) -4H-pyran-4-one and 3.1 ml of triethylamine in 80 ml of acetone are added in portions of 3.7 g of 2-methyl-4-chlorophenoxyacetyl chloride in 10 ml of acetone at 15 ° C. The reaction mixture was stirred at the same temperature for 5 hours. The resulting triethylamine hydrochloride is then filtered off and the filtrate is concentrated in vacuo. Crystallization from ethanol yielded 5.5 g of 5- (2-methyl-4-chlorophenoxyacetoxy) -2- (hydroxymethyl) -4H-pyran-4-one with m.p. Mp 135-137 ° C. @ 1 H NMR (DMSO-d6, .delta. = 4.36 (2H, s, CH2), 1.5 (2H, s, CH2), 6.46 (1H, s, H3), 7.4-6.9 (3H, m). 2θ /0 (η /. Example 2 5- / 2-Methyl-4-chlorophenoxyacetoxy) -2- (pyridiniummethyl) -4H-pyran-4-one chloride To 3.6 g of 5-hydroxy-2-chloromethyl. 4.1 g of 2-methyl-4-chlorophenoxyacetyl chloride are added to the 4H-pyran-4-one in 20 ml of pyridine and the reaction mixture is stirred for 12 hours at room temperature and the excess pyridine is then distilled off under vacuum. yield 6.2 g of 5- (2-methyl-4-chlorophenoxyacetoxy) -2- (pyridiniummethyl) -4h-pyran-4-one chloride with mp 186-189 ° C NMR / DMSO-d 6 / cf = 2.17 (3H, s, CH2), 5.9 (2H, s, CH2), 4.71 (2H, s, CH2), 6.87 (1H, s, H3), 6.4-7.9 / 5H , m, ΗθΓ0 (η /. Example 3 5- / 2,4-Dichlorophenoxyacetoxy) -2- / hydroxymethyl / -4H-pyran-4-one

Analogously to the procedure of Example 1, using 2,4-dichloro-phenoxyacetic acid chloride and obtaining 4.1 g (82%) of 5- (2,4-dichlorophenoxyacetoxy) -2- (hydroxymethyl) -4H- pyran-4-one with tt Mp 125-127 ° C. 1 H NMR (DMSO-d 6) δ 4.36 (2H, s, CH 2), 1.5 (2H, s, CH 2), 6.46 (1H, s, H 3), 7.4-6.9 /3H,m.Haron)/. Example 4 5- (2-Methyl-4-chlorophenoxyacetoxy) -2- (bromomethyl) -4H-pyran-4-one To 3.5 g of 5-hydroxy-2- (bromomethyl) -4H-pyran-4-one in 50 ml of acetone and water, 0.1 N sodium hydroxide solution is added such that the resulting pH is 8 followed by 3.4 g of 2-methyl-4-chlorophenoxyacetyl chloride and the reaction mixture is stirred for 30 minutes. The acetone is distilled off and the precipitated product is filtered off. 4.9 g of 5- [2-methyl-4-chloro-phenoxyacetoxy] -2-bromomethyl-4H-pyran-4-one with m.p. 82-85 ° C. NMR (DMSO-d6): [delta] = 4.73 (2H, s, CH2), 5.11 (2H, s, CH2), 6.75 (1H, s, H3), 7.25-7.01 / 3H , m, Hgrorn /. Examples 5 to 21

The following derivatives were prepared analogously to Example 4 and are shown in Table 1. the structure of the fear was confirmed by elementary analysis and spectral data. Example 22 5- (2-Methyl-4-chlorophenoxyacetoxy) -2- (2-methyl-4-chlorophenoxyacetoxymethyl) -4H-pyran-4-one

Following the procedure of Example 2 using 2-methyl-4-chlorophenoxyacetic acid arydride, 7.1 g of 5- (2-methyl-4-chlorophenoxyacetoxy) -2- (2-methyl-4-chlorophenoxyacetoxymethyl) is obtained. -4H-pyran-4-one with tt 80-83 ° C. NMR (acetone-dg) = 4.9 (2H, s, CH 2), 4.74 (2H, s, CH 2), 5.01 (2H, s, CH 2), 6.5 / 1H, s.hLj / .7 , 1 - 5.8 / 6H, m, CS 269020 B1 3

Haror / 2.22 / 4H, s. ° C 5 2 -CH 4 -4-Cl-Phz · H 3 OH 158 to 162 6 2,4-diNO 2 -Ph H 1 OH 152 to 160 7 2,3,5-triCl-Ph H 1 Cl 148 to 154 8 2-Cl-4-NO 2 -Ph H 1 OH 165 to 167 9 2-Cl-4-NO 2 -Ph ch 3 OH 157 to 160 10 2-CH-4-Cl-Ph H O Cl 66 to 71 11 2,4-diCl-Ph H 0 2,4-diCl -Ph-O-CH 2 -CO 2 85 to 88 12 2-CH 3 -4-Cl-Ph CH 3 Cl 129 to 133 13 2-CH 3 -4- Cl-Ph ch3 0 Br 115 to 118 14 2-CH3-4-Cl-Ph ch3 OH 109 to 114 15 2-naphthyl HOH OH 154 to 157 16 2-naphthyl H O Cl 132 17 2-naphthyl H O Br 127 to 132 18 2-CH 3 -4-Cl-Ph H O N 3 95 to 98 19 2,4-diCl-Ph H O Cl 92 to 96 20 2,4-diCl-Ph H Br 90 to 95 21 2, 4-diCl-PhHN3 87-92

Ph = phenyl Example 23 5- (2-Methyl-4-chlorophenoxyacetoxy) -2- (2-methyl-4-chlorophenoxyacetoxymethyl) -4H-pyran-4-one

A mixture of 2 g of 2-methyl-4-chlorophenoxyacetic acid chloride and 6.7 g of 5-hydroxy-2-hydroxymethyl-4H-pyran-4-one was heated at reflux in 20 ml of toluene for 1.5 hours. Charcoal is added actively to the reaction mixture and is filtered to yield 3.5 g of 5- (2-methyl-4-chlorophenoxyacetoxy) -2- (2-methyl-4-chlorophenoxyacetoxymethyl) -4H-pyran-4- it with tt 80-83 ° C. Example 24

Effect of the active compound of the formula X on the growth of subapical segments of wheat wheat coleptide compared to indolylacetic acid (IAA). Substance Concentration mg.dm% Increment% Inhibition 10 44.02 27.68 IAA 50 47.83 21.42 100 30.42 50.01 10 45.65 25.00 15 50 65.54 22.00 100 27, 29 47.92 Stock solutions were prepared in ethanol and applied to a live 3% solution and

Claims (4)

CS 269020 B1 Charosis. The culture was run for 20 hours at 24 ° C. Herbicidal effect in pre-emergence application Substance from Example No. A. sativa 0. miliaceum L. sativum S. alba 1 1 1,5 5 5 3 1 2,5 5 5 4 0 1 5 5 2 1 1,5 5 5 Antifungal effect Phytophthora Fusarium Alternaria from example No. infestans nivale spp 4 5 3 5 7 4 3 5 13 5 5 4 17 5 1 4 Scale rating with limit values: 5 - very strong effect0 - weak effect SUBJECT MATTER 1. 5-Hydroxy-2- (hydroxymethyl) -4H-pyran-4-one derivatives of general formula (I) wherein R is naphthyl or phenyl substituted independently with methyl, nitro or chloro, R 1 is hydrogen or methyl, n is 0 to 3, and R * is bromine or chlorine, pyridine, 2-methyl-4-chlorophenoxyacetyloxy-> 2,4-dichlorophenoxyacetyloxy- or hydroxy or azido. 2. A process for preparing derivatives according to claim 1, wherein 0.9 to 1 molar parts of the compound of formula (II) wherein R * is as defined above, is reacted with 0.9 to 1.3 molar parts of the acid reactive reactant of formula (III) RO-CH-CH 2 CH 2 CO 3 / III / CS 269020 B1 5 wherein R 1, Ran are as defined above, as is the chloride or anhydride at -15 to 110 ° C for 0.5 to 12 hours. 3. Process according to claim 2, wherein when the reactive acid derivative of formula (III) is chloride, the reaction is carried out in the presence of a base. 4. Process according to claim 2, characterized in that the reaction is carried out in basic solvent.