DK143683B - PLANT FOR REGULATION OF PLANT GROWTH - Google Patents

Description

(19) DENMARK

(¾

| p (12) PUBLICATION MANUAL od 143683 B

DIRECTORATE OF THE PATENT AND TRADEMARKET SYSTEM

(21) Application No. ** 250/73 (51) JmCI * ft QJ j | A3 / Q0 (22) Submission date 2 Aug. 1973 (24) Race day 2 Aug. 1973 (41) Aim. accessible **. February 197 ** (44) Presented 28. s ep. 1981 (86) International application no.

(86) International Filing Day (85) Continuation Day (62) Application No. - (30) Priority 3- Aug. 1972, 277538, US Feb 26 1973, 335607, us

Apr 2 1973, 3 ** 7035, US

(71) Applicant F. HOFFMANN-LA ROCHE & CO. SHARE COMPANY, CH-4002 Ba = cell, CH.

(72) Inventor William Szkrybalo, US.

(74) Plougmann & Vingtoft Patent Bureau.

(54) Plant growth control agent.

The present invention relates to a plant growth control agent, which is characterized in that, in addition to the usual carriers as active ingredient, it contains one or more compounds of general formula I

CH3 .CH3) Λ 3 1 3 / \ 0 - R * XH 0 3 y) —g 2 1- / o 0 ^ in CH3 CH3 - _ n 2 143663 where n represents the number 1 or 2 and, when n is the number 1, R represents hydrogen; sodium; potassium; ammonium; ammonium substituted one or more times with alkyl of 1-7 carbon atoms, alkenyl of 2-7 carbon atoms or hydroxyalkyl of 1-7 carbon atoms; alkyl of 1 to 20 carbon atoms; alkenyl having 2-20 carbon atoms; alkynyl having 2 to 20 carbon atoms; or haloalkyl of 1-7 carbon atoms; and where n is the number 2, R represents calcium, magnesium or the alkyl of 1-7 carbon atoms and X represents the number 0 or 1 as enantiomeric or racemic mixtures.

These agents are particularly useful as post-harvest and pre-harvest plant growth regulators and as herbicides.

Some of the above compounds of formula I are novel and these novel compounds have the general formula II

CH, CH,

V

/lake

/ \ l / ^ C— 0 - R «.XHo0 II

Where n is the number 1 or 2 and when n is the number 1, R 'represents ammonium; ammonium substituted by one or more C 1-6 alkyl, C 2-7 alkenyl or hydroxy C 1-4 alkyl groups; C3_2Q alkyl; C2_2 () - alkenyl; C 2 -C 8 alkynyl or halo-C 1-6 alkyl; and where n is the number 2, R 'represents calcium, magnesium or C 1-7 alkylene; and X is as defined in formula I as enantiomeric or racemic mixtures.

These compounds are also useful for use in the above agents.

3 143683

The compounds of Formulas I and II listed above all have L-configuration as they are derived from the naturally occurring ketohexose, L-sorbose. L-Sorbose is the only known, naturally occurring form of sorbose; however, the corresponding enantiomer of L-sorbose, namely D-sorbose, can be synthetically prepared. In particular, it is pointed out that the compounds corresponding to L-sorbose with D-configuration and racemic mixtures of these compounds can be prepared in quite analogous way, instead of L-sorbose, as D-sorbose as starting material, or a mixture of D and L sorbose is used as the starting material to prepare the corresponding racemic mixture. The preparative methods are exactly the same, regardless of whether a starting material of the L-form, the D-form or the corresponding racemic mixture is used as starting material.

By analogy, all structural formulas listed above and below are also not to be understood as those which illustrate a particular or absolute configuration, but the structural formulas illustrate all possible configurations, ie. in particular they include the enantiomers and the racemic mixtures. Examples and other descriptions, when no other term is given, refer to the racemic compounds.

The compounds of formulas I and II have post-emergence and / or pre-emergence plant growth regulating and herbicidal activity. However, the post-solution growth regulating effect is dominant, as most compounds have this effect and this effect is suitable for controlling weed growth occurring in lawns.

The term "plant growth regulator" as used herein describes e.g. a compound which either delays or stimulates the growth of head or twigs or plant sprouts. Such a compound is capable of exerting influence (delay or stimulation) on flowering, onset of flowering, germination or branching, parthenocarpy, fruit and / or leaf drop and fruit and / or leaf maturation. Furthermore, this means understanding the effect and influence on the transport of matter in the plant, e.g. a stimulation of the juice flow and / or of the metabolism or e.g. an increase in the sugar content of the plant; a herbicidal influence is also understood.

4 U3683 For example. this regulatory effect in lawns delays the growth of grass, and it can further cause increased root germination. In shrub plants, this regulatory activity delays longitudinal growth while simultaneously stimulating lateral growth.

The term "C1-20 (or c3_2 () -) alkyl, C2_2 () - alkenyl and c2_2Q alkynyl" means straight or branched groups. The term "alkylene" denotes a divalent straight-chain or branched alkylene group having 1-7 carbon atoms. The term "C 1-7 alkyl" includes both straight and branched alkyl groups containing 1-7 carbon atoms, e.g. methyl, ethyl, n-propyl, isopropyl and n-butyl. The term "C 2 -alkenyl" describes both straight-chain and branched-chain alkenyl groups containing 2-7 carbon atoms, e.g. allyl, propenyl, butenyl, pentenyl, 1,1-dimethylpropenyl and possible isomers of these compounds.

The term "halo-C1-7 alkyl" encompasses straight-chain and branched-chain alkyl groups of not more than 7 carbon atoms, with one or more hydrogen atoms being replaced by halogens, e.g. 2,2,2-trichloroethyl, 2,2-dichloroethyl, 2-chloroethyl, 4-chlorobutyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-bromo-1,1,2,2-tetrafluoroethyl and 2,2, 3,3,4,4,4-heptafluorobutyl.

Preferred compounds of formula I for use in the compositions of the invention are: 2,3: 4,6-di-O-isopropylidene-2-keto-L-gulonic acid monohydrate allyl-2,3: 4,6-di-O- isopropylidene-2-keto-L-gulonate potassium-2,3: 4,6-di-0-isopropylidene-2-keto-L-gulonate ammonium-2,3: 4,6-di-0-isopropylidene-2 keto-L-gulonate calcium-2,3: 4,6-di-O-isopropylidene-2-keto-L-gulonate dimethylammonium-2,3: 4,6-di-O-isopropylidene-2-keto-L gulonate N-ethanolammonium-2,3: 4,6-di-O-isopropylidene-2-keto-L-gulonate methyl-2,3: 4,6-di-O-isopropylidene-2-keto-L-gulonate ethyl -2,3: 4,6-di-O-isopropylidene-2-keto-L-gulonate n-butyl-2,3: 4,6-di-O-isopropylidene-2-keto-L-gulonate 3-chloropropyl -2,3: 4,6-di-O-isopropylidene-2-keto-L-gulonate n-hexyl-2,3: 4,6-di-O-isopropylidene-2-keto-I-gulonate n-heptyl -2,3: 4,6-di-O-isopropylidene-2-keto-L-gulonate n-octyl-2,3: 4,6-di-O-isopropylidene-2-keto-L-gulonate n-nonyl -2,3: 4,6-di-O-isopropylidene-2-keto-L-gulonate n-undecyl-2,3: 4,6-di-O-isopropylidene-2-keto-L-gulonate 2.2.2 - trichloroethyl-2,3: 4,6-di-O-isopropylidene-2-ke two-L-gulonate n-dodecyl-2,3: 4,6-di-O-isopropylidene-2-keto-L-gulonate n-propyl-2,3: 4,6-di-O-isopropylidene 2-keto-L-gulonate-1-propyl-2,3: 4,6-di-O-isopropylidene-2-keto-L-gulonate n-decyl-2,3: 4,6-di-O-isopropylidene 2-keto-L-gulonate 2- bromethyl-2,3: 4,6-di-O-isopropylidene-2-keto-L-gulonate 2-butyl-2,3: 4,6-di-O-isopropylidene 2-keto-L-gulonate 1- amyl-2,3: 4,6-di-O-isopropylidene-2-keto-L-gulonate bis-2,3: 4,6-di-0-isopropylidene-2 keto-gulonate-ethylene glycol ester tert-butyl-2,3: 4,6-di-0-isopropylidene-2-keto-L-gulonate 2- pentynyl-2,3: 4,6-di-0-isopropylidene-2 keto-L-gulonate 1- hexyn-3-yl-2,3: 4,6-di-O-isopropylidene-2-keto-L-gulonate 3-methyl-1-butin-3-yl-2,3: 4,6-di-O-isopropylidene-2-keto-L-gulonate 5-hexenyl-2,3: 4,6-di-O-isopropylidene-2-keto-L-gulonate 3-pentyl-2,3: 4 6-di-O-isopropylidene-2-keto-L-gulonate dichloromethyl-2,3: 4,6-di-0-isopropylidene-2-keto-L-gulonate 2.2-dichloroethyl-2,3: 4,6 -di-O-isopropylidene-2-keto-L-gulonate-2-chloroethyl-2,3: 4,6-di-O-isopropylidene-2-keto-L-gulonate-4-chlorobutyl-2, 3: 4,6-di-O-isopropylidene-2-keto-L-gulonate 2.2.2-trifluoroethyl-2,3: 4,6-di-O-isopropylidene-2-keto-L-gulonate 2-fluoroethyl 2,3: 4,6-di-O-isopropylidene-2-keto-L-gulonate 2-bromo-1,2,2,2-tetrafluoroethyl-2,3: 4,6-di-O-isopropylidene-2 -keto-L-guononate 2,2,3,3,4,4,4-heptafluorobutyl-2,3: 4,6-di-O-isopropylidene-2-keto-L-guononate 2.2 , 3,3,4,4,5,5-octafluoropentyl-2,3: 4,6-di-0-isopropylidene-2-keto-L-gulonate.

Particularly preferred compounds are: sodium 2,3: 4,6-di-O-isopropylidene-2-keto-L-gulonate / 2-propynyl-2,3: 4,6-di-O-isopropylidene-2-keto -L-gulonate and n-pentyl-2,3: 4,6-di-O-isopropylidene-2-keto-L-gulonate, and preferred agents of the invention contain these compounds or N-ethanolaminonium-2,3: 4, 6-di-0-isopropylidene-2-keto-L-gulonate.

The active compounds are particularly useful agents for regulating plant growth, especially of grass and weeds, as well as other undesirable plants, which happen to mix with deliberately planted plants. The compounds have a plant growth regulating effect for pre-harvest, but they are especially useful when used as post-plant growth regulators or as fruit drop inducers. The post-action effect of the active compounds in the compositions of the invention is demonstrated by controlling the washing of undesirable plants. Thus, it has e.g. it has not previously been possible to perform post-emergence control of Digitaria sanguinalis with a post-emergence herbicide; however, this is successful with the active compounds in the agents of the present invention, as they strongly pull out the washing and maturation of this grass, thus preventing the sowing and thus the propagation of this grass.

When regulating lawns, especially garden lawns and industrial lawns (eg golf courses), it has been found that a maximum delay of growth, which is manifested by a reduction in grass height compared to an untreated control, has been sought. . 40 - 60S, with a grass growth delay of 50% being preferred. A delay of less than 40% must be considered ineffective as it does not give a visual impression of the necessary aesthetic effect, nor does it reduce the necessary care work with the lawn. On the other hand, a reduction of growth of more than 60% is also not desired, as the lawn assumes a tacky appearance and is rapidly propagated with weeds and other unwanted plants.

The active compounds have high herbicidal activity especially against cornflower weeds, e.g. Matricaria Species and other weed species such as Papaver rhoeas, Stellaria media and Capsella bursa pastoris.

These compounds are particularly effective in and against the following plants: (a) Grasses such as Agropyron repens, Bromus inermis, Bromus erectus, Deschampsia flexuosa, Alopecurus pratensis, Arrhenatherum elatius, Dactylis glomerata, Festuca pratensis, Trisetum flavescens, Holcus lanat , Poa neumoralis, Festuca ovina, Festuca rubra, Festuca nigrescens, Cynosurus cristatus, Agrostis Schraderiana, Agrostis stolonifera, Phleum pratense, Phleum nodosum, Cynodon dactylon, Stenotaphrum secundatum, Paspalum notatum, Ermochloum notatum, Ermochloum sugar cane and cereals such as corn, rice, wheat, rye, barley and oats; (b) trees and shrubs, e.g. fruit trees such as apples, pears, peaches, cherries and citrus, as well as cocoa, tea, coffee, bananas, rubber, olives and nuts; η 143983 (c) ornamental plants such as leagues, ebony, white cedar, juniper, roses, azaleas, chrysanthemums, poinsethia, alfalfa, pyracantha, forsythias, magnolias, petunia and Bromeliaceae; (d) field plants such as cotton, soybeans, peanuts, tobacco, flax, sugar beet and pineapple; (e) vegetables such as Solanaceae (eg tomatoes), legumes, pumpkins and melons; (f) berries such as strawberries, cranberries, raspberries, blueberries, blackberries and blackberries.

Furthermore, these compounds are useful as they reduce the pruning of wine on the vineyards.

To obtain a regular distribution of the active compounds in the growth regulating agents, the compound or compounds are mixed with conventional, herbicides usual adjuvants, modifiers, diluents or conditioning agents and thus formulated into solutions, emulsions, emulsifiable concentrates, dispersions, powders, or granulates. wettable powders.

Liquid formulations of the active substance (s) for direct injection may e.g. are prepared in the form of aqueous solutions where possible or as solutions in solvent mixtures such as e.g. contains acetone, methanol and dimethylformamide in a ratio of 90: 8: 2 (v / v). In the case of 2,3: 4,6-di-0-isopropylidene-2-keto-L-gulonic acid, also known as DAG, buffered preparations (pH 5-8) are prepared, e.g. by adding potassium hydrogen sulfate or organic amines such as diethanolamine and triethanolamine to aqueous solutions containing 1% Tween 20 or other non-phytotoxic wetting agents. The buffering of the solutions is necessary as it is known that DAG is unstable in aqueous solutions having a pH below 5

Emulsifiable concentrates containing 25 - 50% or more of active substance depending on its solubility can be prepared in suitable solvents, e.g. N-methylpyrrolidone and dimethylformamide.

8 143683

Surfactants, e.g. wetting agents, dispersing agents, and emulsifying agents are added in sufficient quantity to achieve the desired properties of the composition.

Various modes of application may be better adapted to the numerous purposes to which the active compounds may be used when adding compounds which improve dispersion, adhesion, rain resistance and penetration, e.g. fatty acids, waxes / resins, wetting agents, emulsifiers, mineral or plant oils and binders. Similarly, the biological spectrum of the compounds or agents can be made much broader by the addition of substances having bactericidal, herbicidal and fungicidal properties, or they can be added to fertilizers, chelating agents and other plant growth regulators.

The amounts of use indicated are based on the results given here and are not described so broadly that all possible cases are covered, as numerous factors influence the quantities of use. Eg. the amount varies not only depending on the different plant species, but also within a particular species, e.g. depending on factors such as plant size and plant age, the particular compound used, the season, the soil type and climatic conditions at the time of use such as air temperature, light intensity, rain and wind. Furthermore, when the compounds or agents are used to moisten the soil, higher concentrations are necessary as the plants are thus treated indirectly in comparison with a direct treatment by applying the agent or compound to leaves and stems, e.g. by spraying on the plants.

The amount of the active substance in plant growth regulators therefore varies depending on the plants to be treated, the amount of application required, the method of application, the active substance used and the extent of control of the plant growth that is being sought.

In general, the agents in spray-ready form contain less than 50% of active substance.

In principle, the amount of active ingredient used is selected in such a way that effective control of plant growth is achieved. As for example. As stated above, the treatment of lawns is such an amount of active ingredient that a delay of the normal growth rate of 40-60% is obtained. Similarly, the choice of the minimum amount of use is determined from the minimum amount of active ingredient which is capable of inducing the lower limit of the desired growth delay. The choice of the maximum amount is similarly determined by the amount of active ingredient which produces the upper limit of the desired growth delay, ie. in the case of lawns used as ornamental lawns, the amount which does not give the lawn a starved appearance but, on the other hand, prevents excessive grass growth and does not cause unwanted chlorosis (ie the yellow of the grass). For tomato plants, the criteria for an effective growth delay are different, in particular, a dwarf-like plant is desired, which does not lead to loss of fruit quality or quantity. The parameters for an effective growth regulating effect in such plants are delayed length growth and improved or non-delayed lateral growth as minimum power and delayed length and lateral growth as maximum power.

The amount of active substance that meets or elicits these criteria is determined by such criteria, e.g. on tomato plants. To achieve the greatest post-regrowth growth regulating effect, amounts of 0.5 - 20 kg or more are used per day. acres. These amounts are based on the weight of the active compound. In the same way, the greatest post-regrowth growth regulating effect is generally obtained with amounts of 1 to 15 kg or more active ingredient per day. acres. A preferred dosing range for spray solutions is between 10 and 100000 ppm depending on the species of plant to be treated and the compound selected for this. A particularly preferred dosage amount is generally between 100 and 20000 ppm.

A further advantage of using the active substances in the compositions of the invention is the lack of any sustained effect on the plants or a regulatory effect that remains in the soil. These compounds decompose slowly and thus result in a continuous decrease in activity. This effect has advantages as a) a short-term effect is obtained which can be extended by subsequent further treatment; b) the normal growth conditions of the plant occur proportionally with the activity decreasing; and (c) no harmful residues remain in the plant or in the soil.

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The effect of the delay effect varies depending on the compound used and other factors, e.g. the treated plant species and the climatic conditions.

Although the compounds of the present invention have a plant growth regulating and herbicidal effect, they are practically non-toxic to animals. Eg. no rats died when fed DAG or the sodium salt of DAG in an amount of 4 g / kg body weight. (LDC "value is approx.

16 g / kg (mouse)). The degradation products, initially 2-keto-L-gulonic acid and then carbohydrates, are also non-toxic.

Obviously, not all compounds included in Formula I are active against all plants. However, all the active compounds of formula I have activity against a specific plant or plants, and this activity is a function of the compound. As described below, a particular advantage of the present invention is that the growth regulating agents used in the treatment of various plants have pre-harvest and post-blossom growth regulating activity and herbicidal activity where the spectrum of the plants in question is extremely wide. The growth regulating effect of the active compounds in the agents is illustrated by the micro-experiments listed below for activity determination of post-action effect.

A. Study of 2,3: 4,6-di-0-isopropylidene-2-keto-L-gulonic acid and its salts and esters.

The growth retardant effect of preferred compounds in grass species is investigated below by greenhouse experiments, especially the post-harvest effect of Digitaria sanguinalis and Poa pratensis.

The compounds to be investigated are dissolved in a solvent mixture consisting of 90 parts by volume of acetone, 8 parts by volume of methanol and 2 parts by volume of dimethylformamide.

The grass (Digitaria sanguinalis) is 10 days old and slightly less than 2.5 cm high. Ogås Poa pratensis is cut to a height of approx. 2.5 cm before using that compound.

The compounds are sprayed on the grasses in solution in quantities of 0.5 -8 kg / hectare. The effect, ie the growth delay, is determined by measuring the grass height and grass weight, ie. of the mown grass after 11 - 26 days.

n 143683 In the experiments, 3 standard compounds are included as references. The maleic anhydride (6-hydroxy-3- (2H) -pyridazinone) is used in aqueous solution, i.e. as a water-soluble concentrate (300 g / liter). Further, n-butyl-9-hydroxyfluoro- (9) -carboxylate, hereinafter referred to as IT-3233, and methyl-2-chloro-9-hydroxyfluoro- (9) -carboxylate, hereinafter referred to as IT-3456, are used. , in the solvent mixture described above.

Additional reference compounds which may be used are CCC (2-chloro-ethyltrimethyl-ammonium chloride), Alar (N-dimethylamino succinic acid), 2,4 - D (2,4-dichlorophenoxy-acetic acid), MCPA (2-methyl 4-chlorophenoxy-acetic acid), CMPP (2-methyl-4-chlorophenoxy-propionic acid), Ioxynil (3,5-diiodo-4-hydroxy-benzonitrile) and Ethrel (2-chloroethyl-phosphoric acid).

The test results are summarized in Tables I and II below.

12 143683

Table I

Post-growth growth slowing effect of 2,3,4,6-di-O-isopropylidene-2-keto-L-gulonic acid (DAG) and derivatives thereof.

Grass height in cm days after treatment

Compound Dose / kg Digitaria Poa _hectar_sanguinalis pratens! s 11 days 18 days 26 days

Untreated control ~ 10 l ·? · '? 7.0 DAY 8 1.67 4.0 3.5 4 3.0 5.3 4.5 2 3.8 7.5 6.0.

1 5.2 9.0 8.0 0.5 7.2 11.3 7.0 DAG methyl 8 2.3 3.3 3.0 ester 4 3.5 6.7 5.0 2.5 10 10 6.0 1 7.0 11.8 7.5 0.5 10.2 12.3 7.0 DAG ethyl 8 2.2 6.3 6.0 ester 4 4.3 8, 3 7.5 2 8.2 10.8 7.5 1 9.5 11.8 6.5 0.5 11.5 12.3 6.5 DAY-n-bu- 8 3.0 4.7 5 , 0 type ester 4 3.7 6.7 6.5 2 5.3 9.3 7.5 1 7.5 11.5 7.5 0.5 9.2 13.3 7.0 DAY-allyl-8 2.5 3.0 3.5 ester 4 3.2 6.2 4.5 2 5.0 10.0 5.0 1 6.7 12.0 7.0 0.5 8.8 13.0 7 0

Maleic Acid 4 5.8 6.3 4.0 Hydrazide IT-3233 1 8.8 12.5 6.0 IT-3456 1 8.7 9.8 5.5

Table II

The weight of the green tips of Digitaria sanguinalis and Poa pratensis cut after post-treatment with growth-retarding compounds.

Weight, grams, days after treatment

Compounds Dose, kg / Digitaria Poa _ hectare_ sanguinalis_pratensis_ ____18 days_26 days

Untreated control - 18.9 4.6 DAY 8 4.4 2.7 4 9.0 5.2 2 14.0 5.7 1 12.4 8.5 0.5 20.8 4.4 DAG methyl - 8 6.1 2.7 ester 4 13.0 5.3 2 18.3 5.3 1 19.3 5.7 0.5 19.4 5.7 DAG Ethyl 8.10 o 3.5 ester 4 13.5 5.3 2 18.3 5.1 1 19.3 4.2 0.5 18.9 3.2 DAG-n-butyl 8 6.2 3.0 ester 4 10.2 4 , 2 2 17.9 4.3 1 19.6 4.1 0.5 21.1 4.8 DAG allyl 8 8.3 2.0 ester 4 14.9 4.0 2 18.8 3, 7 1 20.1 3.3 0.5 21.1 5.0

Maleic Acid 4 4.7 1.9 Hydrazide IT-3233 1 10.4 4.4 IT-3456 1 10.2 4.2 14 143683

Of the compounds studied, 2,3: 4,6-di-0-isopropylidene-2-keto-L-gulonic acid (DAG) has been found to be the most active in growth retardation of Digitaria sanguinalis, where methyl-, n- butyl and allyl ester have similar effect. DAG is more effective against Digitaria sanguinalis and Poa pratensis than maleic acid and the other two reference compounds in comparable dosage.

Since solutions in conventional solvents are not very suitable for use in the field, DAG and similar derivatives are tested in emulsifiable preparations (25% active substance, 41% xylene, 2% Atlox 3404 and 2% Atlox 3403). Several esters are tested in the solvent mixture indicated. Further, aqueous solutions of DAG containing 1% Tween 20 (polyoxysorbitan monostearate) are prepared - either unpuffed or buffered to pH 5-7. Aqueous salts of DAG salts, which also contain Tween 20, are included in the test.

Growth-delaying studies were performed on a plant spectrum consisting of e.g. Digitaria sanguinalis, soybeans and tomatoes, where the plants were treated when they were approx. 2 weeks old. During the treatment, the Digitaria sanguinalis plants were approx. 2 cm tall, the soybean plants approx. 5 - 6 cm tall with the first leaves, and the tomato plants were 3-4 cm tall with 3-4 real leaves. Either aqueous solutions, solvent mixtures or emulsifiable concentrates of the active substances were sprayed.

The results of these studies of DAG, as well as of salts and esters thereof, in various formulations are given in Table III, in which the delaying effect is numerically indicated. The rating scale is as follows: 0 - no visible growth delay 1, 2, 3 - slightly delayed effect, the plants show little or no reduction in growth on visible parts of plants 4, 5, 6 - no growth delay, the plants show reduced growth on visible parts of plants 7, 8, 9 - severe delay, plants show little or no growth 10 - no growth.

Table III

i5 143633

Post-herbicide effect of DAG and its derivatives.

Delaying effect after 13 days.

Combine- Fonn Dose kg / Digitaria Soybeans Tomatoes part se_hectar_sanguinalis DAY * SM 8 8 6.7 8 4 7 3 8 263 7.3 15 2 5 0.5 4.3 1 1.1 DAY water 8 9 9 10 4 9 8 9.7 2 8 7 9 1 6 6.7 8.7 0.5 5 6.7 8.3 DAY water 8 9 9 10 4 9 9 9 2 7.7 7.7 8.3 1 6.7 7 7 0.5 4 6 8 DAY Nautical 8 8.3 9 9 Triumph Salt 4 9 8 8 2 7 6.3 5.7 1 4 3.7 6.3 0.5 3 0 3 DAY Potassium 899 8 unalloyed 4 9 8 7.7 2 7.3 7.3 6.7 153 4.7 0.5 2 0 5 DAY AMMO water 899 9 nium salt 4 9 7.7 8 2 8 6.7 6 1 4 3.3 5 0.5 4 2 5

Table III continued 16 143683 DAY, Calcium Water 8 9 9 9 Cium Salt 488 9 2 8 7.3 6 1 4.7 3 5 0.5 3.7 1 5 DAY-ME 8 8 9 9 7.7 483 5 ter 2 4 1 3.3 13 0 0 0.5 0 0 0 DAG-n-SM 8 9 6 7 -butyl-4 8 6 6.7 ester 2 7 3 5 1 5 1.3 5 0.5 4 0 0 DAG-n-EC 8 10 9 8 -butyl-4 9.3 9 7.3 ester 2 7.7 8.3 8 1 5.7 7 8 0.5 3.7 5 3

Male water 8 7 10 5.7 acid hy- 4 7 10 3 drozide 259 1 10 9 0 0.5 0 9 0 IT-3456 SM 8 5.7 8 5 458 5 2 3 8 5 10 8 5 0.5 0 8 5 17 143883

Table III continued DAG-allyl SM 8 8.3 8 9 ester 4 7.3 8 8.3 2 5.3 7.3 5 1 4 1.3 1 0.5 2.7 0 0 DAY n-do SM 8 8 5 8 decylester 4 7 3 7 2 4 3 6.3 122 2.3 0.5 2 2 2 DAY n-do-EC 8 8.7 8.3 6.3 decylester 4 8 6.3 4, 3 235 4.3 13 5 4 0.5 0 5 3

Control EC - - 9 8.3 * SM = active substance dissolved in solvent EC - emulsifiable concentrate Yand - a) for salts of DAG the water contained 1 $ Tween b) for DAG the pH of the water is set to 5 and 1 # is added. Tween and 10 # isopropyl alcohol.

The activity of DAG in aqueous solutions is enhanced by buffering to a pH range of 5 - 8, an effect attributed to the increasing stability of DAG in this pH range. This enhancing effect was greater in soybeans and tomato plants than in Digitaria sangui-nalis. The inorganic salts and esters of DAG were almost exactly as active as DAG itself. The test results show that DAG, salts and esters are more active than maleic acid hydrazide and reference compound IT 3456 as a post-growth growth inhibitor for Digitaria sanguinalis, and only slightly less active as post-growth growth inhibitor for soybeans.

The following Table IY contains experimental results from 12 different crops and weeds where the plants were sprayed, 18 143683 when they were approx. 2 weeks old. 4 representative esters of DAG (2,3: 4 »6 - di-O-isopropylidene-2-keto-L-gulonic acid) are compared with the standard, i.e. maleic. The same assessment scale as in Table III is used.

In tomato plants, longitudinal growth is greatly delayed. Instead, stimulation of the development of lateral twigs is observed so that a total branched, bushy plant is formed. It is remarkable that neither the quantity nor the quality of the fruits changes.

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Q) H g 22 143683 In Tables III and IV, the dosage of the salts, esters and other analogues and DAG were not calculated on acid equivalent.

Although the main field of application of the growth regulators of the invention is as post-growth growth regulators, the active compounds of formula I can also be used as precursors. Eg. the precursor herbicidal effect of the DAG compounds is shown by the n-propyl ester of DAG. The ester is sprayed in an amount of 8 kg / ha. Strong growth delay (i.e., little or no growth at all) for Sorghum tail brush, Amaranthus sp. and Digitaria sanguinalis may appear after 20 and 27 days.

Further studies of DAG and its salts are carried out using a variety of grasses, cereals, ornamental plants, perennials and vegetables.

Growth delay studies have been performed on several grass species, using emulsifiable concentrates of DAG in nitropyrrolidone.

All species with the exception of Lolium are sprayed 4 days after cutting. Iiolium is cut and sprayed on the same day. The effect on the plants, ie. the growth delay is found when measuring the grass height after 19 or 21 days after spraying.

Maleic acid hydrazide (MH) and chlorfuranol (CF) are included as reference compounds. The results are summarized in Table V below.

23 143683

Table V

Post-harvest growth inhibitory effect.

A. Growth inhibition after 19 days, grass height, cm.

Connect- DAY DAY DAY MH Untreated control control dosage kg a.i. / ha 12 18 24 3

grass

Agropyron repens 7.2 6.3 5.3 10.7 14.7

Bromus inermis 10.2 8.2 7.3 12.3 14.3

Bromus erectus 8.5 7.7 7.7 9.5 12.0

Deschampsia flexuosa 3.2 3.4 3.4 3.3 3.6

Alopecurus pratensis 10.3 9.7 7.7 14.3 17.0

Arrhenatherum elatius 7.8 7.3 6.8 11.7 16.7

Dactylis glomerata 11.7 10.8 9.7 13.3 18.0

Festuca pratensis 9.5 8.5 7.7 12.0 14.3

Trisetum flavescens 9.0 8.5 9.7 11.7 38.0

Holcus lanatus 8.0 7.7 7.8 10.5 14.3 lolium perenne 14.3 12.7 13.3 13.3 18.7 * a.i. = active substance.

24 143683 B. Growth delay after 21 days, grass height, cm.

Connect- DAY DAY DAY C? Untreated control control dosage kg a.i./ha 48 16 1

grass

Poa annua 8.7 7.3 7.0 7.5 8.7

Poa nemoral 18.3 6.8 7.2 8.7 22.3 | Ρρσ +1 ιλο ovina 14.0 7.5 9.3 9.0 15.0 F0 s tue 3.

rubra 18.3 13.3 12.8 11.7 18.7

Festuca nigrescens 13.0 8.5 8.3 10.5 12.8

Cynosurus cristatus 10.7 6.8 7.0 9.5 12.0

Agrostis Schraderiana 6.7 4.7 5.0 5.3 7.7

Agrostis stolonifera 6.7 4.0 4.0 5.2 6.7

Phleum pratense 11.7 11.0 10.7 10.8 12.3

Phleum nodosum 7.3 6.5 7.0 7.0 8.2

Cynodon daetylon 10.8 7.3 7.3 7.0 10.7

Table VI shows the influence of DAG and its sodium salt on barley and wheat. The height is measured 41 days after the spraying.

25 U3083

Table YI

Plant height, cm 41 days after spraying

Build Wheat

Plant age at treatment, days 28 10 28 10

Compound Formulation Dosage, see kg ai / ha DAG Emulsifiable concentrate 6 51.5 41.5 62.8 42.5 "12 48.4 47.1 58.5 40.5 DAY sodium water 6 45.4 43.4 46.6 37.5 recycled water 12 32.9 33.9 33.6 25.0

Untreated Control - 48.6 47.6 61.3 43.3

The effect of DAG (in an emulsifiable concentrate) in nitropyrrolidone on two hedge species is summarized in Table VII. In the case of Carpinus betulus, the visual observation 2 months after the determination according to Table VII showed a stronger growth retarding effect than that given in Table VII. The amount of active substance in the solvent is given in percent in Table VII.

Table VII

Hedge height, cm, 34 days after spraying

Compound Thuja fastigiata Carpinus occidentalis betulus

Untreated Control 70 52 DAY, 0.5 $ 33 48 DAY, 1.0 $ 25 15 DAY, 2.0 $ 18 48 26 143683

The effect of DAG on apples and wine in comparison with two reference compounds, CCC and Alar (succinic 2,2-dimethylhydrazide), is listed in Table VIII.

Table VIII

Height, cm, weeks after treatment.

11 weeks 9 weeks

Compound Dosage Apples Wine $> a.i.

Untreated Control - 25.4 21.4 DAY 0.1 25.7 16.5 DAY 0.2 17.7 13.2 DAY 0.4 9.8 15.0 CCC 0.2 23.2 24.5

Alar 0.2 31.2 26.0

Table IX shows the effect of DAG on Geranium in comparison with CCC as a comparison compound.

Table IX

Height, cm, 4 weeks after spraying.

Eoncentration

a.i. ppm. DAY CCC

8000 16.0 13.6 4000 14.2 13.0 2000 15.7 14.3 1000 15.9 14.4 500 17.1 17.2 250 19.4 16.4

Untreated Control 20.0 27 143683 Growth delay in Chrysanthemum morifolium induced by DAG and Alar as comparative compound is given in Table X. The letters a.i. means active substance.

Table X

Average length, cm, of the side shoots 4 weeks

Compound Dosage ppm. after treatment DAY 3000 16.6 2000 17.8 1000 19.3 500 17.9 250 18.0

Alar 4000 (a.i.) 17.3

Untreated control - 20.9

Table XI shows the effect of DAG and Ethrel (2-chloroethane phosphonic acid) as a comparison compound on tomatoes irrespective of plant height and number of flowers.

Table XI

Height, cm, of the tomato plants 30 days after spraying

Age at spraying, days 32 60 ''

Compound Dosage ppm.

DAY 1000 25.7 52.3 4000 17.3 34.0

Ethrel 1000 (a.i.) 27.0 54.3. 4000 (a.i.) 15.0 27.3

Untreated Control - 34.3 56.7 28 143683

Table XI continues

Number of flowers 30 days after spraying

Age at spraying, days 32 60

Compound Dosage ppm.

DAY. 1000. 6.3 20.0 4000 2.3 8.7

Ethrel 1000 (a.i.) 3.7 15.0 4000 (a.i.) 3.0 0

Untreated Control - 6.8 5.0 DAG, the ammonium salt of DAG and the n-butyl ester of DAG are investigated as growth retardants for Brazilian pepper, (Schinus terebinthi-folius Raddi) and Sumach (Rhus spp.). The plant leaves are sprayed so long that an unbroken spray coating is formed. As a comparative compound, Maintain CF-125 (a mixture of methyl 2-chloro-9 9-carboxylate).

At 43 days after spraying, the moulting or non-emergence of longitudinal growth, leaf drop and leaf deformation is measured. In Table XII the results are numerically indicated. The rating scale has the following appearance: 0 - No effect 1 - delayed longitudinal growth 2 - interrupted longitudinal growth 3 - longitudinal growth interrupted and deformed leaves 4 - complete leaf drop, new leaves are small and deformed.

29 143683

Table XII

Yeast regulating effect on Brazilian pepper and Sumach, 43 days after treatment

Compound Concentration Brazilian Sumach in syringe solution in i

Untreated control - 0 0 DAY 0.25 + Il oil 0 0 DAY 0.5 + 2% oil 0 1 DAY 1.0 + 2% oil 1 2 DAY 1.0 0 2 DAY ammonium salt 0.25 + 1 # Triton ^ 0 1 B-1956 ® "0.5 + l / 0" 1 2 "1.0 + li" 2 2 DAG-n-butyl ester 0.25 + 2fo oil 0 0 0.25 + 2i oil 0 2 1.0 + 2 $ oil 1 2 1.0 0 2

Maintain CF-125 0.5 3 4

Triton® B-1956® is a water-dispersible, artificial resin-based surfactant manufactured by Rohm and Haas. Maintain CF-125 is a mixture of methyl 2-chloro-9-hydroxy-fluoro-9-carboxylate, methyl-9-hydroxyfluoro-9-carboxylate and methyl-2,7-dichloro-9-hydroxy-fluoro-9- carboxylate.

The oil excipient used in the above compositions is a standard petroleum distillate usually used in herbicide preparations, especially when the herbicide is to be used in the treatment of woody plants. This oil supports both the penetration and the adhesion of the active substance. Sun oil 11E, an emulsifiable, non-phytotoxic spray oil, is used in the compositions of Table XII.

The herbicidal effect of DAG, both alone and in combination with e.g.

2,4-D, in multi-species spray solution is listed in Table XIII below. The results in Table XIII refer to a spray solution of DAG, an emulsifiable concentrate in nitropyrrolidone. The figures should be understood as a percentage of the control values calculated on untreated plants.

31 143583

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The herbicidal effect of DAG, either alone or in combination with 2.4-D, has been studied on Daucus carota (wild carrots), where an emulsifiable concentrate is injected into nitropyrrolidone. Table XIV shows the percentage value of epinasty 4 and 18 days after spraying. (Epinastia is an undesirable growth in which parts of the plant bend outwards and often grow downwards). The results in Table XI7 show that DAG increases the effect of 2,4-D.

Table XI7

Percent Epinasty

Compound dosage • kg a.i./ha After 4 days After 18 days

Untreated Control 0 0 DAY - 8 0 0 2.4- D (Na) - 1 15 50

DAY + 2,4-D

8 + 1 80 95 8 + 0.5 80 80 4 + 1 90 90

Thus, preferred growth regulating compounds in the agents of the invention are 2,3: 4,6-di-0-isopropylidene-2-keto-L-gulonic acid (DAG), the corresponding sodium, potassium, ammonium, calcium and dimethylammonium salts, as well as the alkyl and alkynyl esters of this compound, especially the propargylic ester.

Furthermore, it has been found that a growth regulator containing one of the compounds of the general formula i, when sprayed on fruit-bearing trees, significantly reduces the force to be used to separate the fruit from the branch.

This can be seen by a comparison with untreated trees. Furthermore, it has been found that fruits harvested by the growth regulators of the invention are relatively free from damage and advice.

33 143683

The present compositions can be applied to fruit-bearing trees in liquid or solid preparations. The application can be via the roots, stem, branches, leaves or fruits. Eg. For example, the present fruit fall agent may be sprayed or sprayed over the trees by an airplane or it may be placed at the foot of the trees so that the agent is absorbed through the roots. A preferred method of use, which is also the most effective, consists in the use of the agent in the form of an aqueous spray solution. If desired, a composition based on a suitable organic solvent, e.g. an oily syringe solution.

To obtain the greatest effect using normal fruit drop agents of the present invention, the agent is preferably used 1-2 weeks prior to fruit ripening, depending on the temperature. In areas where rain may be expected in the period between the use of the agent and the maturation, a conventional adhesive is suitably added to the composition. Common examples of such adhesives are e.g. glue, casein, alginic acid salts, cellulose gum and similar derivatives, polyvinylpyrrolidone, invert syrup and corn syrup.

The disclosed fruit fallers contain as active ingredient compounds of formula I. If desired, conventional inert materials used in agriculture may also be incorporated, especially when the agents in question are used for the treatment of trees and also used in conjunction with known fruit fall agents.

Such auxiliaries are e.g. also surfactants, carriers, adhesives and stabilizers.

The concentration of the active formula of general formula I in the novel fruit drop agents varies; however, in order to obtain an optimal effect, a sufficient amount is required. Thus, an aqueous spray solution contains approx. 0.05 - approx. 1.5% by weight of active substance. The concentration varies, of course, depending on the fruit and the size of the tree or bush. The dosage is the one that then actually facilitates maturation.

In spray solutions, the aqueous solution containing the fruit drop agent is sprayed in such a way that the tree is covered with an unbroken spray membrane. This requires an application of approx. 500 - approx. 9000 liters of a dilute solution (about 0.1-1% by weight of active ingredient) ha, depending on the number and size of the trees to be treated.

To prepare a preferred spray composition containing the fruit drop agent, the active substance or salt thereof is dispersed or dissolved in a carrier, e.g. water. The liquid spray solution can be added 0.1 - approx. 0.5% by weight (based on the weight of the carrier) surfactant. Typical surfactants are Triton ®-B-1956, a resin-dispersible, resin-based surfactant manufactured by Rohm and Haas. In addition, X-77 (Chevron-Ortho), a non-ionic surfactant which contains as a basic substance, contains alkylaryl - polyoxyethylene glycols, free fatty acids and isopropanol.

The present fruit fall agents cause fruit fall on a large number of fruit trees. Typical fruits of this type are e.g. oranges, grapefruit, olives, apples and cherries. They also interact with other useful plants, e.g. cotton and soybeans where leaf drop occurs.

As stated above, the fruit drop agents are sprayed onto the trees in the form of. aqueous solutions.

For this purpose, the invention also relates to agents containing similar amounts of water-soluble salts of compounds of formula I. Such salts are e.g. the sodium salt, the potassium salt and the ammonium salt.

The present fruit droplets containing 2,3: 4,6-di-0-isopropylidene-2-keto-I-gulonic acid (known as DAG) are adjusted to a pH of 5-8 by means of a buffer, e.g. by adding potassium hydrogen sulfate to the aqueous solution. This buffering is necessary for the known instability of DAG in aqueous solutions having a pH below 5.

In cases where the compounds to be used are water-insoluble, emulsifiable concentrates or wettable powders are made of the active substance which can be dispersed in water and thus form spray solutions.

DAG can be prepared as an emulsion concentrate using N-methyl-2-pyrrolidone or nitropyrrolidone as the solvent.

Wettable powders are prepared by using an inert diluent, e.g. kaolin. A typical spray solution formulated with a wettable powder contains e.g. the active substance, ca. 1 - approx. $ 5 inert diluent, minor amounts of dispersants, wetting agents and anti-foaming agents, and the corresponding and required amount of water.

Since oranges can be considered typical fruits that are more easily harvested by treatment with chemical fruit pellets, the effect of the new fruit pellets on orange trees is illustrated.

The sodium salt of 2,3: 4,6-di-O-isopropylidene-2-keto-L-gulonic acid is investigated as a citrus fruit decanter, e.g. oranges. Aqueous solutions are prepared containing 0.05, 0.1, 0.25, 0.5 and 1.0% by weight of this sodium salt and 0.5 $ triton B-1956. The solutions are sprayed on Valencia oranges, seedless marshmallow fruits and red grapefruit trees. One week after spraying, the only noticeable effect is a slight drop in the leaves treated with a higher dose. Two weeks after the spraying, most orange and grapefruit fruits have fallen from the trees treated with a dose of at least $ 1. Trees treated with a $ 0.5 dose have yielded approx. half of the fruits and the remaining fruits hang very loosely.

In addition to the fruit drop effect, the fruits also show a clear enhancement of the color, e.g. they have a significantly deeper and darker color than the untreated fruits.

The sugar content and total solids content of the processed fruits are slightly increased compared to untreated fruits.

Similar results are obtained by spraying e.g. the ammonium salt or diethylammonium salt or n-butyl ester of 2,3: 4,6-di-O-isopropylidene-2-keto-L-gulonic acid 36

The compounds of formulas I and II can be prepared and formulated as described above and below, depending on whether they are to be used as a fruit drop agent or as pre-run or post-run herbicide, ie. as soon as they should be used as plant growth regulators.

2,3: 4,6-di-O-isopropylidene-2-keto-I-gulonic acid monohydrate is a known commercial preparation and is an intermediate in the preparation of L-ascorbic acid. It is produced by the oxidation of diacetone-I sorbofuranose in an alkaline or neutral environment. Diaeetone-1-sorbofuranose is obtained by reacting I-sorbose with acetone in the presence of a strong acid.

The novel compounds in the compositions of the invention can be prepared by:

a) in the presence of a base, the acid of formula V is reacted

CH3. CH3 0 / o

\ ---— OH Y

\ o ch3

with a compound of the general formula VI

X-R5 VI

wherein X represents chloro, bromo or a p-toluenesulfonic acid ester and R5 represents C1-6 alkyl; C2_2Q alkenyl; C2_2 () - alkynyl; or halo-C 1-4 alkyl, or 37

b) for the preparation of a compound of formula II wherein n is 2, in the presence of a base, an acid of formula V reacts with a compound of general formula VII

X ^ R ^ X2 VII

12 X where X and X represent chlorine, bromine or iodine and R represents alkylene, or

c) for the preparation of a compound of formula II wherein n is 2, one of the acid of formula V derived from the acid halide id reactes with a diol of general formula IX

H0-R6-0H IX

wherein R 1 has the meanings set forth in Formula VII, or

d) for the preparation of a salt of formula II wherein n is 1 and R 'is ammonium; ammonium substituted once or more with C 1-7 alkyl, C 2-7 alkenyl or hydroxy-C 1-7 alkyl brings an acid of general formula V into contact with a compound of general formula X

.R7

W X

R8 Ry & 7 8 g wherein R, R and R · 7 represent hydrogen, C1-7 alkyl, C2-7 alkenyl or hydroxy-C1-6 alkyl, or, when n is 2, with calcium hydroxide or magnesium hydroxide.

The salts of DAG are prepared in the usual manner. To this, DAG is added with vigorous stirring to an aqueous solution of a base at room temperature.

38 143683

In this process, the solution is maintained at a pH above 7.

Upon completion of the reaction, the excess amount of water is removed in high vacuum. Anhydrous acetone (about 10 parts by volume) is then added to the resulting syrup, which is stirred overnight. The white crystalline precipitate which is formed is filtered, washed with acetone and dried. In the case of non-volatile bases, equivalent amounts of acids are added. If volatile bases are to be used, e.g. ammonia or dimethylamine, an excess of the base is used and the unreacted excess is then evaporated in vacuo.

Since DAG under usual esterification conditions, e.g. by esterification after Fischer is not stable, the novel esters are produced by DAG by reaction with e.g. the corresponding alkyl, alkenyl or alkynyl halides under basic room temperature conditions using inert organic solvents such as dimethylformamide. The esters are insoluble in water but soluble in methanol, acetone, ethanol, chloroform, pentane, benzene and ether.

Solutions consisting of a solvent and a compound of the invention are suitable for greenhouse experiments, but are not particularly suitable for field trials. Also, wettable powders are not generally useful as the DAG derivatives must be solubilized to exhibit the required activity. Therefore, the acid is preferably prepared in the form of a soluble powder in combination with buffering agents, since a buffering to a pH of 5-9 is essential for the acid. The acid may also be formulated as an emulsion concentrate using N-methyl-2-pyrrolidone or nitropyrrolidone as set forth below: Weight percent of the total preparation DAG 50

Atlox 2081B 4 N-Methyl-2-pyrrolidone or nitropyrrolidone 46

Atlox 2081B is a mixture of polyoxyethylene sorbitan esters of fatty acids and acidic resins as well as alkylarylsulfonates.

The salts are water soluble and need no special formulation.

The DAG esters are formulated as the xylene-based emulsifiable concentrate, which can then be mixed with water. From these concentrates emulsions can be prepared which contain 25 - 50% by weight of active ingredient. Typical emulsifiable concentrates for DAG esters are listed below.

% By weight of the total mixture

Active substance 50

Xylene 71 46

Atlox 3403 2

Atlox 3404 2 -

Emulphor EL 620 - 2

Drewmulse GMC-8 - 2

Atlox 3403 is a mixture of polyoxyethylene ethers, polyoxyethylene glycerol and alkylarylsulfonate.

Atlox 3404 is a mixture of polyoxyethylene alkyl aryl ether and an alkyl aryl sulfonate.

Emulphor EL 620 is a polyethylated vegetable oil.

Drive / Mulch GMC-8 is the monoglyceride of a low molecular weight saturated coconut fatty acid.

A concentrated solution of sodium 2,3: 4,6-di-0-isopropylidene-2-keto-L-gulonate (95% by weight) and sodium dioctylsulfosuccinate (5% by weight) is prepared and spray dried. A wettable powder is obtained which is completely soluble in water.

In another embodiment, finely powdered sodium 2,3: 4,6-di-O-isopropylidene-2-keto-L-gulonate is mixed with pumice granules. To this dry mixture is added an amount of water equal to 10% by weight of the mixture. Part of the sodium salt of 2,3: 4,6-di-O-isopropylidene-2-keto-L-gu-lonic acid is now dissolved and serves as a means to bind the remaining amount of unresolved sodium-2,3'4, 6-di-O-isopropylidene-2-keto-L-gulo-nat to the pumice granules.

40 143683

In another embodiment, an equimolar amount of diethanolamine is added to an aqueous solution of 2,3: 4,6-di-0-isopropylidene-2-keto-1-gulonic acid with stirring. A clear solution is obtained whose pH is adjusted to 8 by dropwise addition of diethanolamine.

In another embodiment, while stirring, 25% equimolar amount of ammonia is added to an aqueous solution of 2,3: 4,6-di-O-isopropylidene-2-keto-1-gulonic acid. A clear solution is obtained whose ρΉ value is set to 8 by the dropwise addition of 25 $ 1 s of ammonia.

2,3: 4,6-Di-O-isopropylidene-2-keto-L-gulonic acid is prepared below. application of the regulations according to Reichstein and Griissner, Helv.

Chim. Acta, 17, 311 (1934).

The preparation of compounds of formula I for use in the compositions of the invention is further illustrated by the following examples:

Example 1.

Ethyl-2,3: 4,6-di-0-isopropylidene-2-keto-Ii-gulonate.

To a solution of 100 g of anhydrous potassium carbonate in 946 ml of dimethylformamide is added with stirring at room temperature 292.2 g of 2.3: 4.6 - di-O-isopropylidene-2-keto-L-gulonic acid monohydrate (DAG monohydrate) and then 205 g of ethyl iodide. Stirring is continued at room temperature for 24 hours. The mixture is then filtered to remove inorganic salts and the dimethylformamide is removed by distillation in vacuo (about 60 ° C and about 10 mm Hg). 200 ml of acetone are added to dissolve the remaining ether. Dissolved inorganic salts are filtered off. Wash the filter cake with 100 ml of acetone. The filtrate is added to the solution containing the ester and the crude product is isolated by vacuum distillation of the solvent to an amount of Λ1. 500 ml and subsequent cooling of this solution to 5 ° C. The crude product is recrystallized from methanol or methanol / acetone to give 284 g of ethyl 2,3: 4,6-di-O-isopropylidene-2-keto-11-gulonate, m.p. 99 τ 100.5 ° C.

By this commonly used specification, the bis ester: bis-2,3: 4,6-di-0-isopropylidene-2-keto-L-gulonate-ethylene glycol ester is prepared from 2,3: 4,6-di-0-isopropylidene 2-keto-Ir-gulonic acid and 1,2-dibromo-ethane in a 2: 1 molar ratio.

Example 2.

Methyl-2,3: 4,6-di-0-isopropylidene-2-keto-Ii-gulonate.

To a suspension of 100 g of anhydrous potassium carbonate in 946 ml of dimethylformamide is added, with stirring, 292.2 g of 2,3: 4,6-di-O-isopropylidene-2-keto-1-gulonic acid monohydrate (DAG monohydrate). ) and then 205 g of methyl iodide are added to the solution. The mixture is stirred for 4 hours at room temperature and then filtered to remove inorganic salts. The dimethylformamide is distilled off in vacuo.

200 ml of acetone are added to the residue to dissolve the ester. Undissolved inorganic salts are filtered off again, the Pilter cake is washed with 100 ml of acetone. The filtrate is poured into the ester solution, which is then concentrated in vacuo to a yellow syrup which crystallizes on standing in the form of large prisms. Vacuum distillation at 127 - 129 ° C and 0.35 - 0.37 mm Hg gives 268 g of a colorless liquid which solidifies on standing. Methyl 2,3: 4,6-di-O-isopropylidene-2-keto-I-gulonate melts at 46.5 - 47.5 ° C.

Example 3 · n-Butyl-2,3: 4,6'-di-O-isopropylidene-2-keto-11-gulonate.

With stirring, a suspension of 100 g of anhydrous potassium carbonate in 946 ml of dimethylformamide is added to 292.2 g of 2.3: 4,6-di-O-isopropylidene-2-keto-I-gulonic acid monohydrate and then 197 g n-butyl iodide. The mixture is stirred for 48 hours at room temperature and then filtered to remove inorganic salts. The dimethylformamide is removed by vacuum distillation. To the residue is added 200 ml of acetone and the inorganic salts present are filtered off. Wash the filter cake with 100 ml of acetone. The filtrate is poured into the ester solution and evaporated in vacuo. To recrystallize the residue of methanol-acetone, 172 g of colorless crystals of n-butyl-2,3: 4,6-di-O-isopropylidene-2-keto-1-gulonate are obtained, mp 53.9 - 56.8 ° C .

Example 4

n-propyl-2,5: 4,6-di-0-isopropylidene-2-keto-Ii-gulonate.

n-Propyl-2,3: 4,6-di-O-isopropylidene-2-keto-11-gulonate is prepared by analogy to the requirements of Examples 1-3 using 200 g of 1-bromopropane as halide. Yield 150.6 g, m.p. 80 -81 ° C.

Example 5

n-pentyl-2,3: 4,6-di-0-isopropylidene-2-keto-L-gulonate.

n-Pentyl-2,3: 4,6-di-O-isopropylidene-2-keto-1-gulonate is prepared by analogy to the requirements of Examples 1-3 using 300 g of 1-bromopentane as a halide. Yield 503 g; boiling point 195 ° C / 0.5 mm Hg.

Example 6

N-dodecyl-2,3: 4,6-di-0-isopropylidene-2-keto-L-gulonate.

n-Dodecyl-2,3: 4,6-di-O-isopropylidene-2-keto-II-gulonate is prepared by analogy to the working specification set forth in Examples 1-3 using 100 g of 1-bromododecane as a halide. After two recrystallizations of ethanol, 75 g are obtained which melts at 10.5 ° C.

43

Example 7

Allyl-2,3: 4,6-di-0-isopropylidene-2-keto-I-gulonate.

Allyl-2,3: 4,6-di-O-isopropylidene-2-keto-I-gulonate is prepared by analogy to the working specification set forth in Examples 1-3 using 133 g of allyl bromide. Yield 282 g; mp 95 - 95.5 ° C.

Example 8.

Isopropyl-2,3: 4,6-di-0-isopropylidene-2-keto-L-gulonate.

Isopropyl-2,3: 4,6-di-O-isopropylidene-2-keto-L-gulonate is prepared analogously to the working specification set forth in Examples 1-3 using 250 g of 2-bromopropane. Yield 116.8 g; mp 107.5 - 109 ° C.

Similarly, further straight chain and branched aliphatic hydrocarbon and halogen lower alkyl esters can be prepared.

Example 9

2-Chloroethyl-2,3: 4,6-di-0-isopropylidene-2-keto-L-gulonate.

Dissolve 6 g of anhydrous 2,3: 4,6-di-O-isopropylidene-2-keto-1-gulonic acid in 14 ml of pyridine and 3.2 ml of methylene chloride, and with stirring and ice-cooling, 3.2 ml of thionyl chloride are added dropwise. After 3 hours at room temperature, 5.9 ml of 2-chloroethanol are added to the reaction solution, which is further stirred for 3 hours. The reaction solution is then taken up in methylene chloride and washed with ice-cold 2N hydrochloric acid, 2N sodium hydroxide solution and water in the order given, after which the organic phase is dried over sodium sulfate and evaporated. The residue is purified on a silica gel column and then distilled.

5 g of oily product are obtained; boiling point 88 ° C / 0.01 mm Hg.

By analogy to the above examples, especially Examples 1-3 and 9, the following compounds may be prepared:

Allyl-2,3: 4,6-di-O-isopropylidene-2-keto-11-gulonate, m.p. 94.5 - 95 ° C, potassium-2,3: 4,6-di-0-isopropylidene-2-keto -L-gulonate, m.p.> 300 ° C, ammonium-2,3: 4,6-di-O-isopropylidene-2-keto-11-gulonate, m.p. 177.5 - 178.5 ° C, calcium-2.3: 4,6-di-O-isopropylidene-2-keto-1-gulonate, m.p. 265-267 ° C, dimethylammonium-2,3: 4,6-di-0-isopropylidene-2-keto-E-gulonate, m.p. 155 - 165 ° C, N-ethanolammonium-2,3: 4,6-di-O-isopropylidene-2-keto-E-gulonate, m.p. 208-209 ° C, methyl-2.3: 4.6 -di-O-isopropylidene-2-keto-1-gulonate, m.p. 46.5 - 47.5 ° C, ethyl 2,3: 4,6-di-0-isopropylidene-2-keto-L-gulonate, m.p. 99 -105 ° C, n-butyl-2,3: 4,6-di-O-isopropylidene-2-keto-1-gulonate, m.p. 54-57 ° G, 3-chloropropyl-2,3: 4,6-dl- O-isopropylidene-2-keto-E-gulonate, boiling point 130 ° C / 0.005 mm Hg, 2.5 N-hexyl-2,3: 4,6-di-O-isopropylidene-2-keto-I-gulonate , = 1.4544, n-heptyl-2,3: 4,6-di-O-isopropylidene-2-keto-11-gulonate, bp 102 -103 ° C / 0.01 mm Hg, n-octyl 2,3: 4,6-di-0-isopropylidene-2 -keto-II-gulonate, nn = 1.4538, VP5 n-nonyl-2,3: 4,6-di-O-isopropylidene-2-keto-II-gulonate, nn = 1.4548, n-undecyl 2,3: 4,6-di-O-isopropylidene-2-keto-E-gulonate, = 1.4555, 2,2,2-trichloroethyl-2,3: 4,6-di-O-isopropylidene-2 -keto-1-gulonate, m.p. 65-66 ° C, n-dodecyl-2,3: 4,6-di-0-isopropylidene-2-keto-L-gulonate, m.p. 10.5 ° C, n-propyl -2,3: 4,6-di-O-isopropylidene-2-keto-L-gulonate, m.p. 80 -81 ° C, 1- propyl-2,3: 4,6-di-0-isopropylidene-2 keto-I-gulonate, m.p. 107.5 - 109 ° C, n-decyl-2,3: 4,6-di-0-isopropylidene-2-keto-1-gulonate, boiling point 193 ° C / 0.5 mm Hg, 2-Bromoethyl-2,3: 4,6-di-O-isopropylidene-2-keto-I-gulonate, b.p. 157 ° C / 0.1 mm Hg, 2-butyl-2,3: 4'-6-di-O-isopropylidene-2-keto-1; -gulonate, m.p. 95.5 - 96.5 ° C 1,1-amyl-2,5: 4,6-di-O-isopropylidene-2-keto-Ir * gulonate, b.p. 135 ° C / 0.1 mm Hg, bis-2,3: 4,6-di-O-isopropylidene-2-keto-1-gulonate ethylene glycol ester, m.p. 150-115 ° C, tert-butyl-2 3: 4,6-di-O-isopropylidene-2-keto-L-gulonate, m.p. 120 ° C, 2-pentynyl-2,3: 4,6-di-O-isopropylidene-2-keto-L -gulonate, boiling point 130 - 132 ° C / 0.001 mm Hg, 1- hexyn-3-yl-2,3: 4,6-di-O-isopropylidene-2-keto-L-gulonate, boiling point 141 - 144 ° C / 0.001 mm Hg, 3-methyl-1-butyn-3-yl-2,3: 4,6-di-O-isopropylidene-2-keto-L-gulonate, m.p. 89-191 ° C, 5-hexenyl 2,3: 4,6-di-0-isopropylidene-2-keto-L-gulonate, boiling point 92 ° C / 0.005 mm Hg, 3-pentyl-2,3: 4,6-di-0-isopropylidene-2 -keto-L-gulonate, m.p. 76.5 - 77.5 ° C, 2-chloroethyl-2,3: 4,6-di-0-isopropylidene-2-keto-L-gulonate, boiling point 88 ° C / 0 , 01 mm Hg, 4-chlorobutyl-2,3: 4,6-di-O-isopropylidene-2-keto-L-gulonate, boiling point 129 ° C / 0.01 mm Hg, 2,2,2-trifluoroethyl 2,3: 4,6-dx-O-isopropylidene-2-keto-L-gulonate, m.p. 90 - 92 ° C, 2-fluoroethyl-2,3: 4,6-di-0-isopropylidene-2-keto -L-gulonate, m.p. 70-72 ° C, sodium 2,3: 4,6-di-O-isopropy liden 2-keto-L-gulonate, m.p.> 300 ° C, 2-propynyl-2,3: 4,6-di-0-isopropylidene-2-keto-L-gulonate, m.p. 91.5 - 92.5 ° C, n-pentyl-2,3: 4,6-di-O-isopropylidene-2-keto-L-gulonate, b.p. 195 ° C / 0.1 mm Hg.

46 143683 The experimental reports below describe the deceleration of apple tree growth and the decay of bean plants, respectively.

Experimental Report I.

The purpose of the experiment is to detect acceleration or retardation of shoot growth on apple trees (Malus sylvestris).

The soluble test compounds are dissolved in an amount of 2% in acetone containing 1% wetting agent / emulsifier; this solution is diluted immediately before use with an equal amount of water. 1.5 kg of active ingredient is dissolved, emulsified or suspended in 1000 liters of water and this amount is used for 1 ha.

Seeds are put in wet sand for 10 days in refrigerator at 2 - 5 ° C. Then they were sown in a tray containing only "Optimasoil" (80% peat, 20% clay and fertilizer) with known physical and chemical properties. 21 days later, the sprouts are transferred to pots with a diameter of 7 cm and containing "Optimasoil". The plants are allowed to grow in the greenhouse for 50 - 60 days, depending on the season before the treatment. The plants are sprayed with dispersions of the test compounds in acetone and water or with aqueous suspensions of wettable powder formulations. If necessary, the natural daylight is supplemented with mercury vapor lamps so that the day becomes 16 hours long. For each dose, the experiment is repeated four times.

Two types of plant growth regulating effect are distinguished, namely shoot length reduction and defoliation. The degree of each effect is expressed as a percentage of the corresponding value obtained with untreated plants. Any solvent effect on control plants is offset by Abbott's formula.

results:

Plant height in cm 25 days after treatment 2-Chloroethyl-2,3: 4,6-di-O-isopropylidene-2-keto-1-gulonic acid 112 1.5 kg / ha

Untreated 181 47 143683

Experimental Report II.

The purpose of the experiment is to demonstrate the removal of bean plants. Plants of the species Phaseolus vulgaris are used.

A lanolin paste containing 1000 ppm test compound is used.

In seeds, 1.5 cans were sown deep in a small plastic pot 5 cm in diameter containing a mixture of 50% sterilized sand-blended clay soil and 50% "Optimasoil" (containing 80% peat and 20% clay and fertilizer) with known physical and chemical properties. 13 - 16 days later, when the primary leaves are fully developed, the sprouts are cut just above the soil surface. The stalk is cut to a length of 2 cm, measured from the seedlings. The leaf stalk with the primary leaves is cut to a length of 0.5 cm and treated with the lanolin paste. The stems of the cut plants are kept in a small container of tap water for 5 days in a greenhouse. For each dose, the experiment is repeated eight times.

The growth regulating effect is assessed 6 days after treatment.

The leaf drop on the silks is determined by counting the retained leaf stalks. The effect of solvent on the control plants is compensated for by Abbott's formula.

Results:% of leaf foliage 6 days after treatment 2-Propynyl-2,3: 4,6-di-0-isopropylidene-2-keto-L-gulonic acid 100 1000 ppm

Untreated 0

Claims (2)

Experimental Report I shows that undesirable height growth in apple trees can be severely restricted by a haloalkyl derivative, and Experimental Report II shows that the desired leaf drop in beans is obtained a few days after the treatment using an alkyl nyl derivative, while on the Untreated control plants do not occur at all. Claims. A plant growth control agent, characterized in that, in addition to the usual carriers as active ingredient, it contains one or more compounds of the general formula I CH3 Cfl3 / o A x * "oL. 1 / \ \ / - 0 - R.XH Where n represents the number 1 or 2 and, when n is the number 1, R represents hydrogen; sodium; potassium; ammonium; ammonium substituted one or more times by alkyl of 1-7 carbon atoms, alkenyl with 2-7 carbon atoms or hydroxyalkyl with 1-7 carbon atoms; alkyl with 1- 20 carbon atoms; alkenyl with 2-20 carbon atoms; alkynyl with 2- 20 carbon atoms; or haloalkyl with 1-7 carbon atoms; and where n is the number 2 R represents calcium, magnesium or alkyl of 1-7 carbon atoms and X represents the number 0 or 1 as enantiomeric or racemic mixtures. Agent according to claim 1, characterized in that it contains as an active substance sodium 2,3,3,6,6-di-0-isopropylidene-2-keto-L-gulonate.