HU203831B - Compositions for controlling growth of plants containing maleinic acid derivatives as active components and process for producing the active components - Google Patents

Abstract

Maleic acid salt and monoester deriv plant growth regulators of formula (I) are prepd from maleic-anhydride acid and appropriate alcohol. In formula (I): A = (a) or (b) gps; R = hydrogen or alkyl gp; R1 = hydrogen-, halogen- or allyl gp; R2 and R3 = hydrogen or halogen.

Description

FIELD OF THE INVENTION The present invention relates to plant growth controlling compositions containing maleic acid monoesters as active ingredients and to a process for the preparation of new maleic acid monoesters.

Succinic acid 2,2-dimethylhydrazole is known to be used as an active ingredient in growth regulators (daminozide, Alar 85 WP; L.G. Nickell, Platn Growth Regulators Agricultural Uses, Springer Verlag, Berlin-Heidelberg-New York, 1982).

It is also known that the mono- and di-aryloxyethyl esters and the mono- and dihydrazides and diethyl esters of succinic acid have a smaller or greater effect on plant growth (Hungarian Patent No. 193,768; Bőig. Akad. Nauk 1987.40 (1): 85-88 and (2): 87-90.)

It has been found that the maleic acid monoesters of formula (I) and their agriculturally useful salts have plant growth regulating activity and are useful as active ingredients in plant growth regulating compositions.

In the general formula (I)

A is phenoxyethyl of formula (a) or naphthyloxyethyl of formula (b) and in formula (a)

R ^{1 is C} 1 -C 4 alkyl, r 2 is halogen.

Alkyl is preferably methyl and halogen is preferably chlorine.

Salts of the compounds of formula (I) are agriculturally suitable bases, i.e., at the dosage employed, the treated plants may be non-toxic salts, such as alkali metal and alkaline earth metal salts.

The present invention also relates to a process for the preparation of compounds of formula (I).

Compounds of formula (I) may be prepared by reacting maleic anhydride with an alcohol of formula A-OH, as defined above.

The maleic anhydride and the corresponding alcohol are suitably reacted in a melt. The use of a solvent medium is generally neglected. A substantially equivalent mixture of maleic anhydride and alcohol of the general formula OH is melted at a temperature of up to 60 ° C and the melt is stirred for 15-25 hours at about 55-60 ° C. The product is conveniently formed with a water immiscible solvent such as ether, chloroform, The solvent is removed under reduced pressure, the residue is dissolved in sodium bicarbonate solution and the resulting aqueous solution is washed with an organic solvent such as ether, chloroform, dichloromethane or benzene. concentrated mineral acid such as hydrochloric acid or sulfuric acid is then used, followed by extraction with an organic solvent such as ether, chloroform, dichloromethane or benzene. After removal of the solvent under reduced pressure, the product is purified, if necessary, by recrystallization

The process may also be carried out in a suitable solvent medium.

The preparation of maleic acid monoalkyl esters by reacting maleic anhydride with the corresponding alcohol in a melt is described by M. Dymicky and Ri. Buchanan; OrganicPreparation andProceduresInt., 17, 121-131 (1985).

The resulting compound can be converted to its salt with a suitable base.

The following examples illustrate the details of the process of the invention

Example 1

Malinesav- [2- (4-chloro-2-methylphenoxy) ethyl] -and

Zter

A mixture of 19.6 g (0.2 mol) of malic anhydride and 37.3 g (0.2 mol) of (4-chloro-2-methylphenoxy) -ethanol was stirred at 55-60 ° C for 20 hours and The product is dissolved in 300 ml of ether. The ethereal solution was washed with water (4.130 mL) and evaporated under reduced pressure. up to pH 2. The precipitated product is extracted with 3200 ml of ether and the ethereal solution is decolorized with charcoal and dried over sodium sulfate. After removal of the solvent under reduced pressure, the product is extracted with hexane / benzene (6: 4). recrystallize (500 mL) to give 40.0 g (702%) of product

Elemental analysis data and physicochemical parameters of the compound are given in Table 1.

Example 2

Maleic acid (beta-naphthoyl) ethyl ester g (025 gmol) maleic anhydride and 47 g (025 gmol) beta-naphthoxyethanol were stirred at 55-60 ° C for 10 hours. Water (200 ml) was added and the mixture was decanted at 90 ° C, then slowly dissolved in 400 ml of 5% sodium bicarbonate solution and extracted with ether (2.250 ml). acidified with ice water to give a brown precipitate, washed with ice water, recrystallized from 70 g methanol / 15 g water to give 46.0 g (64.5%) of product.

Elemental analysis data and physicochemical parameters of the compound are shown in Table 1.

HU 203831 Β

Table 1

number Compound melting point EJemanallzis% H the tai number. Signal 1H-NMR band (ppm) acid ester C-C Η H Λ rl R2 • c bowl. c song. poop song. First (the) Me the 72-73 54.84 54.84 437 4.60 12.85 12.45 6.38 s (2H) Second (B) - - 90-93 66.36 67.36 4.83 439

The formulations of the present invention comprise the active compounds of formula I together with at least one of a liquid and solid carrier or diluent and a surfactant. The formulations may also contain other additives customary in agricultural practice.

The compositions of the present invention will generally contain from 0.01 to 95% by weight, preferably 0.1 to 90% by weight, of active ingredient.

Solid carriers or diluents for use in the compositions of the present invention include natural or artificial mineral products such as silica, clay, talc, attapulgite, kaolin, calcium and aluminum silicate, calcium carbonate, dolomite, additional plant product such as sawdust, natural or artificial resin, etc. They are.

The liquid carrier or diluent is an aliphatic, aromatic, araliphatic or cyclic hydrocarbon such as benzene, toluene, xylene, cyclohexanol, cydohexanan; water; an alcohol such as isopropanol; glycol; petroleum fractions; chlorinated hydrocarbon; a ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone and the like. may

When the carrier is water, the composition of the invention also contains a surfactant in addition to the active ingredient.

Ionic or nonionic emulsifying, dispersing or wetting agents may be used as surfactant additives in the compositions of the present invention.

Preferred polycondensates of ethylene oxide and fatty acid derivatives, polycondensates of ethylene oxide and alkylphenyl and arflophenol, alkali metal and alkaline earth metal salts of lignin sulfonic acid, aldl-arylsulfonic acid, sulfobutyric acid esters and the like.

Reference is made to U.S. Patent No. 3,713,804, which discloses a variety of surfactant additives for use in agriculture.

The compositions of the invention may be in various solid or liquid forms.

Solid formulations include dusts, granules, microgranules and powders. These solid preparations are usually used directly without further dilution

Formulations suitable for use in liquid or liquid form include wettable powders, emulsifiable solutions and concentrates, suspendable powders, solutions, in particular water-dilutable concentrates, emulsions and dispersions.

Dusts generally contain from 0.1 to 5% by weight of active ingredient together with a carrier

Agranulates and mlcrogranules generally have an active ingredient content of 0.5 to 10% by weight. Granules are prepared in a known manner, for example by impregnation. These compositions may also contain other additives, for example, to control the release of the active ingredient.

Wettable powders typically contain from 20 to 95% by weight of a solid carrier and a surfactant such as a wetting or dispersing agent.

To obtain wettable powders, the active ingredient is thoroughly mixed with the additives and then ground to a dry powder. The resulting powder can be well named and suspended, diluted to any concentration with water and sprayed onto the plants.

Emulsifiable concentrates or solutions contain the active ingredient in an amount of from 1 to 50% (w / v) in a solvent such as an aromatic hydrocarbon, preferably in the presence of a surfactant, in particular in the presence of an emulsifier. The emulsifiable concentrates may be diluted with water to any concentration before use.

Suspendable powders are a very fine suspension of the powdered particles of the active ingredient in water in oil and are a liquid product in which the solid pellets do not settle. The active ingredient content is usually from 5 to 80% by weight

These concentrated suspensions are prepared by finely grinding the active ingredient and then dispersing the excipients in a liquid carrier46. These suspensions may be diluted to an arbitrary concentration in water immediately before use.

The composition of some representative compositions of the present invention is described in the following examples.

Example I

Wettable powder W

Active ingredient 1. 50% by weight of sodium lignin sulfonate 6% by weight of kaolin 44% by weight (B)

Active ingredient 2 50% by weight * Sodium lignin sulfonate 5% by weight *

HU 203 831 Β

isopropyl naphthalene sulfonate 1% by weight talc 44tömeg% <C> 1. active ingredient 90% by weight sodium dioctyl sulpho succinate 0,2tömeg% artificial silicate 9.8% by weight (D) 4. active ingredient 80tömeg% sodium alkyl naphthalene sulfonate 4tömeg% methylcellulose 2tömeg% diatomaceous 14% by weight Π. example Emulsifiable concentrate (THE) 1 active ingredient 250g ethylene oxide and alldl- -phenol condensate 30g Bargain-aryl-Kaldu sulfonate 50g 150-190 ° C petroleum fractions 670g (B) 3. active ingredient 400g ethylene oxide and alkyl- -phenol condensate 60g Sodium alkylaryl sulfonate braid 40g cyclohexanone 150 g xylene 400g (Q 4. active ingredient 400g ethylene oxide and tristyryl -phenol phosphate condensate 50g sodium alkyl benzene sulfonate 40g cyclohexanone 400g Example 227 Granulate l.hatóanyag 50g propylene glycol 25g vegetable oil 50g clay (0.2-0.6 mm) 950g

The effect of the plant growth regulating compositions of the present invention was tested in a laboratory and in a greenhouse

The active ingredient to be tested is treated with 50% wettable powder with 40% kaolin and 10% fatty alcohol sulfonate. The wettable powder was diluted to the ldvint concentration with water as required

In the laboratory, the cucumber seed was thoroughly wetted with a suspension of various active ingredients. Root and stalk lengths were measured on the tenth day and inhibitory or stimulatory effects were determined in control with distilled water (Table 2).

Growth regulator and phytotoxic effects on bean plants were also tested in a greenhouse. The potted plants were treated with two concentrations of 5 ml / plant spray juice in two true leaf states. After three treatments, the effect on span length was expressed as a percentage of the untreated control and the phytotoxic effect was also determined (Table 3).

It can be seen from the data in Tables 2 and 3 that the new drug has an anti-sprouting effect. It does not significantly reduce root growth compared to controls, but significantly reduces stem growth (Table 2) and significantly reduces span length (Table 3). The length-of-gap retardation effect is similar to the known succinic acid 2,2-dimethylhydrazide, sometimes better and has no phytotoxic effect (Table 3).

In the greenhouse, we examined the effect on sugar beet growth and leaf surface development, as well as the phytotoxic effect. The plants grown in the pots were treated with two concentrations of 3 ml / plant spray liquid in two true leaf states. Twenty days after treatment, the effect on plant height and leaf area was expressed as a percentage of untreated control. The adverse effects were determined (Table 4). The data in Table 4 show that the new active ingredient also has a growth inhibitory action on sugar beet. Compared to the untreated control and the known succinic acid 2,2-dimethylhydrazide, the retardation effect on plant height and leaf area development is better and has no phytotoxic effect (Table 4).

The plant growth retardant effect of the new active ingredient can be used in many horticultural and arable crops depending on the purpose. For example, in apples, it may be possible to positively influence the growth properties of young apple trees by reducing shoot growth and increasing flower bud formation.

This increases crop yields and accelerates crop rotation. For sunflowers, decreasing plant height and increasing stem diameter can provide opportunities to increase plant stamina and at the same time facilitate harvesting. And increasing the diameter of the plate can increase yields. Potential to increase productivity may be considered in sugar beet and maize cultures.

The economic importance of the compositions of the invention is significant because they can help to increase the quantity and quality of agricultural production.

Other known plant growth regulating agents, as well as pesticides such as herbicides, fungicides, bactericides, insecticides and antidotes can be administered to the agents of the invention.

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Table 2

Active ingredient Concentration CUCUMBER Root mm Shit (Ppm) mm Control »increases Of K maleic 0.01 12.6 1063 + 53 - [2- (4-chloro-2- 0.1 12.4 883 -12.0 methyl-phenoxy) - 1.0 12.4 84.0 -163 ethyl] ester 10.0 12.5 813 -19.0 100.0 12.4 12.0 -88.1 Malinsav- (p- 0.01 12.3 1043 + 3.9 naphthoxy-bromoethyl) - 0.1 12.6 92.0 -83 -ester 1.0 12.4 83.0 -173 10.0 12.5 69.0 -31.4 100.0 12.6 13.0 -87.9 Control (untreated) 12.5 1003 -

Table 3

Active ingredient Concentration PUPPET Htotojdcftáa ( «) fzkózszám (Db) gap length (Wt%) (you) Effect on the untreated % of control Maleic acid [2- 0.01 3 173 -14.7 0.0 - (4-chloro-2- 0.05 3 17.0 -173 0.0 methyl-phenoxy) - 0.1 3 16.9 -17.6 0.0 -etfl] ester 0.15 2 13.4 -34.6 0.0 0.2 2 12.7 -38.7 0.0 Maleic acid (B- 0.01 3 173 -14.7 0.0 naphthoxy-bromoethyl) - 0.05 4 163 -20.9 0.0 -ester 0.1 4 15.3 -25.4 0.0 0.15 3 12.9 -37.1 0.0 03 3 12.8 -37.6 0.0 Tartaric acid- 0.01 3 18.0 -123 0.0 -23-dimetfl- 0.05 3 17.7 -13.7 0.0 -hydrazide (known) 0.1 2 15.7 -233 0.0 0.15 2 15.3 -25.4 0.0 0.2 2 12.9 -37.1 0.0 Control (untreated) - 5 203 - 0.0

Table 4

Sugar beet agent Concentration Height area of all leaves Rtotoxidtis ( "*) cm cm2 w Deviation from untreated control (*) Maleic acid [2- (4- 0.05 -22 -35 0.0 -kl6r-2-methyl- 0,025 -18 -25 0.0 phenoxy) ethyl] - .0125 -16 -11 0.0 Maleic (b- 0.05 -28 -36 0.0 naphthoxy-bromoethyl) - 0,025 -23 -27 0.0 -ester .0125 -14 -12 0.0 succinic 0.05 -21 -25 0.0 -23-dimethyl- 0,025 -14 -16 0.0 -hydrazide (known) .0125 -14 -8 0.0

Claims (4)

PATENT CLAIMS A plant growth regulator composition comprising as an active ingredient from 0.01 to 95% by weight of the maleic acid monoester of formula I, or an agriculturally acceptable salt thereof, A is phenoxyethyl of formula (a) or naphthyloxyethyl of formula (b) and in formula (a) R ^{1 is C} 1-4 alkyl, R ^{2 is} halogen, together with at least one of a solid or liquid carrier or diluent and a surfactant. Composition according to claim 1, characterized in that it contains an active ingredient of the formula (I), in which the active ingredient of the formula (a), in which R * alkyl in the formula (a) is a methyl group and R ^{2 is a} halogen atom chlorine atom. . 3. A composition according to claim 1 wherein the active ingredient is maleic acid [2- (4-dichloro-2-methylphenoxy) ethyl] ester or maleic (p-naphthloxyl) ethyl ester. A process for preparing the maleic acid monoesters of formula (I) as defined in claim 1 and reacting the maleic anhydride with an alcohol of formula A-OH, as described above, and optionally converting the resulting compound into its salt. converted.