FI60713C - SAOSOM TILLVAEXTREGULATORER FOER VAEXTER ANVAENDBARA SALTER OCH ESTRAR AV 2,3: 4,6-DI-0-ISOPROPYLIDEN-2-KETOGULONSYRA - Google Patents

Description

1 ΙβΙ i11) ADVERTISING, EXTERNAL, SU snn + χ IBJ (") UTLÄGGNINGSSKRIFT OU fl ό C / 4« Patent granted 10 03 1932 Patent meddelat v (51) Kv.lk.3 / lnt.a.3 C 07 H 9 / 0 * SUOMI — FINLAND (21) ^ μμ «ιμι · -ρμμμ ^ ι 78333 ^ (22) H» k * mlipilvt - AmBfcnlnpdtg 01.11.78 '' (23) AlkupUvi - Gittl | htud «| 02.08.73 (41 ) Become Public - Bllvlt offtmllg 01.11.7 8

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Patents and registries in the 'An * ek' n uttagd oct. uti. »knft * n pubitcnd 30.11.81 (32) (33) (31) Py / d« «y * Tuoik« u «—Bajlrd priovltet 03.08.72 26.02.73, 02.0U.73 USA (US) 277538, 335607, 3U7035 (71) F. Hoffmann-La Roche & Co. Aktiengesellschaft, Basel,

Switzerland-Switzerland (CH) (72) William Szkrybalo, Verona, NJ, USA (7U) Oy Kolster Äb (5U) 2,3: U, 6-di-O-isopropylidene-2-ketogulonic acid salts used as plant growth regulators and esters - Säsill tillväxtregulatorer för växter användbara salter ocr estrar av 2,3: U, 6-di-O-isopropyl-den-2-ketogulonsyrosyrra (62) Separated from application 2U39 / 73 (patent 56919) -Avdelad frän trap 73 (patent 56919)

The invention relates to salts and esters of 2,3: 1,6-di-O-isopropylidene-2-ketogulonic acid having the general formula: CH3O for use as plant growth regulators.

--R'-XH20 II

wherein N is 1, then R 'is ammonium; ammonium substituted with one or more C 1-2 alkyl or hydroxy C 1-4 alkyl groups; straight chained or branched C12-4alkenyl, C1-4alkenyl or C2-4alkynyl. or halo-C 1-6 alkyl; and when n is 2, then R 'is calcium; magnesium or C 1-4 alkylene, n is the number 1 or 2, and X is the number 0 or 1.

The term "C 1-6 alkylene" as used herein means a divalent substituent formed from straight or branched aliphatic hydrocarbons having from 1 to 7 carbon atoms and bonded through two different carbons. The term "lower C 1-4 alkyl" embraces both straight-chain and branched saturated aliphatic groups having 1 to 7 carbon atoms, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, etc. -alkenyl "and C 1-6 alkynyl groups which may be straight-chain or branched include butenyl, pentenyl, 1,1-dimethylpropenyl, propargyl, butynyl, pentynyl, hexadiynyl, heptadiynyl and possible isomers of these compounds. A particularly preferred alkynyl group is a propargyl group.

The term "halo-C 1-4 alkyl" embraces straight-chain or branched alkyl groups having 1 to 7 carbon atoms and in which one or more of the hydrogen atoms has been replaced by halogen, such as, for example, 2,2,2-trichloroethyl, 2,2-dichloro- ethyl, 2-chloroethyl, 4-chlorobutyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-bromo-1,2,2,2-tetrafluoroethyl, 2,2,3,3, N, N-heptafluorobutyl and so on.

A preferred group of compounds of the invention are those compounds of formula II wherein, when n is 1, R 'is substituted ammonium, straight or branched C 1-4 alkyl, C 1-4 alkenyl or C 2-4 alkynyl as defined above. , or halo-C 1-4 alkyl, and when n is 2, then R '"is calcium, magnesium or C 1-6 alkylene, and n and X are as defined above.

These compounds are salts and esters of 2,3: 1,6-di-O-isopropylidene-2-ketogulonic acid.

The starting material for the preparation of the compounds of formula II is 2,3: 1,6-di-O-isopropylidene-2-keto-L-gulonic acid monohydrate, which is a known commercial preparation used as an intermediate in the preparation of L-ascorbic acid. It is prepared by oxidizing diacetone-L-sorbofuranose in an alkaline or neutral medium. Diacetone L-sorbofuranose is obtained by the reaction of L-sorbose with acetone in the presence of a strong acid.

The novel compounds of the present invention are prepared by a) reacting 2,3: 1,6-di-O-isopropylidene-2-keto-L-gulonic acid of the formula:

3> T

C'0H V

CH3 CH3 to react in the presence of a base of general formula:

x-r5 VI

in which X is chlorine, bromine or p-toluenesulfonic acid ester and is straight-chain or branched C 3-12 alkyl, C 1-12 -alkenyl or N-alkynyl or halo-C 1 -C 12 -alkynyl alkyl; or b) if it is desired to prepare a compound of formula II wherein n is 2, reacting an acid of formula V in the presence of a base of the general formula:

ΧΓΗ6-Χ2 VII

with a compound of formula II wherein X 1 and X 2 represent chlorine, bromine or iodine and R 8 represents C 1-6 alkylene, or c) if desired to prepare a compound of formula II wherein n is number 2, an acid halide derived from an acid of formula V reacting to the general formula:

HO-Rg-OH IX

with a diol of formula wherein Rg is as defined in formula VII, or d) in the case where it is desired to obtain a salt of formula II wherein n is 1 and R 'is ammonium or ammonium substituted by one or more C 1-2 alkyl, or hydroxy-C 1-6 alkyl, the acid of formula V is contacted with the general formula: U 60713

fC

With a compound of formula H9 wherein R8 and R1 are hydrogen, C1-4alkyl or hydroxy-C1-4alkyl, or when n is 2 and R 'is calcium or magnesium, the acid of formula V is contacted with calcium hydroxide or with magnesium hydroxide.

The salts of DAG are prepared in the usual way. For this purpose, DAG is added to the aqueous base solution with vigorous stirring at room temperature. In this event, the pH of the solution is maintained above J. Upon completion of the reaction, excess water is removed under high vacuum. Anhydrous acetone (about 10 volumes) is then added until a syrup is formed and stirred overnight. The white crystalline precipitate formed is filtered off, washed with acetone and dried. In the case of non-volatile bases, equivalent amounts of acid are added. When volatile bases are used, for example ammonium hydroxide or dimethylamine, an excess of base is used and the unreacted excess is then evaporated in vacuo.

Since DAG is not stable under standard esterification conditions, such as according to Fischer, novel esters of DAG are prepared by reaction with, for example, the corresponding C 1-6 alkyl, C 1-6 alkenyl or C 1-6 alkynyl halides in basic under conditions at room temperature using inert organic solvents such as dimethylformamide (DMF). Esters are insoluble in water but soluble in methanol, acetone, ethanol, chloroform, pentane, benzene, ether, etc.

The reaction of an acid of formula V with an alcohol of formula IX can be carried out by reacting these reactants in the presence of a dicyclohexylcarbodiimide (equivalent amount) in an inert organic solvent. Preferred solvents are methylene chloride, dimethylformamide, ether, tetrahydrofuran or ethyl acetate (cf. also Tetrahedron 21, 3531 (1965)).

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

In another embodiment, ammonia (25 equimolar amount) is added to an aqueous solution of 2,3-, 6-di-O-isopropylidene-2-keto-L-gulonic acid. A clear solution is obtained, the pH of which is adjusted to 8 by dropwise addition of ammonia (25%).

5,60713

In Chemical Abstracts 1061 + 3e (193), is 2,3: 6, U-diisopropyl! -dene-2-oxo-L-gulonic acid and its potassium salt and methyl ester reference. However, no use has been reported for these compounds. UG Patent Publication No. 2,301,811 describes the preparation of 2-keto-L-gulonic acid from the 2,3,6,6-dialkylidene intermediate. It also states that corresponding esters can be prepared. However, these compounds are not reported to have a plant growth regulating effect.

The compounds of formula II all have the L-configuration because they are all due to the naturally occurring ketohexose, L-sorbose. L-sorbose is the only known naturally occurring form of sorbose; however, the enantiomer corresponding to L-sorbose, namely D-sorbose, can be prepared synthetically. In particular, it is pointed out that compounds having the D-configuration corresponding to L-sorbose and racemic mixtures of these compounds can be prepared in a completely analogous manner by using D-sorbose instead of L-sorbose as starting material or by using a mixture of D- and L-sorbose, respectively. the purpose is to prepare a racemic mixture. The production methods are exactly the same regardless of whether a compound in L-form or D-form or a similar racemic mixture is used as a starting material.

The compounds of the formula II have post-emergence and / or pre-emergence plant growth regulating activity and herbicidal activity. However, the growth-regulating effect after germination is more predominant because most compounds have this effect and because this activity is suitable for controlling the growth of weeds in the grass field.

As used herein, the phrase "plant growth regulator" describes a compound that either slows or promotes the growth of major or minor branches or the growth of plant shoots, respectively. Such a compound is capable of influencing (slowing or promoting) flowering, flowering, varietal or branching, parthenocarpia, fruit and / or leaf fall, and fruit and / or leaf inflammation. Furthermore, it may have an effect on the transport of substances inside the plants, for example by promoting the flow and / or metabolism of the plant fluid or, for example, an increase in the sugar content of the plant, and also a herbicidal effect.

In lawns, for example, this control effect causes a slowdown in lawn growth and can also contribute to increased root shoot formation. In shrub plants, this regulatory activity contributes to a slowing of length growth while promoting width growth.

The most preferred compound of the invention is N-ethanolammonium 2,3: N-di-O-isopropylidene-2-keto-L-gulonate.

The active compounds are particularly useful in plant growth control preparations, in particular in the control of the growth of grasses and weeds and also of other undesired plants which have been accidentally mixed with deliberately cultivated plants. Although the compounds have a plant growth regulating effect before germination, they are particularly useful when used after germination to regulate plant growth or as a fruit fall agent. The post-emergence efficacy of the active compounds in the context of the present invention is demonstrated by the control of the growth of undesired plants. Thus, it has not hitherto been possible to carry out post-emergence control of Digitalia sanguinalis growth, however, with the active compounds of the present invention which strongly slow the growth and inflammation of this herb and thus prevent the seeding and spread of this herb.

Lawn control, especially yard and industrial lawns (e.g. golf courses), has shown that a maximum growth retardation of about U0-60% mn must be sought, which can be shown as a decrease in grass height compared to untreated control, with a 50% grass growth retardation being most preferred. . A deceleration of less than Uo% must already be considered ineffective, because then the necessary aesthetic effect cannot yet be observed and the necessary care work on the lawn is not reduced. On the other hand, a growth retardation of more than f> 0% is not desirable because the lawn acquires a barren appearance and begins to grow rapidly weeds and other unwanted plants.

The active compounds show a herbicidal action against coloring weeds, for example Matricaria species, and other weeds, such as Papaver rhoeas, Stellaria media and Capsella Bursa pastoris.

In particular, the compounds can be used as growth regulators for the following plants: a) grasses such as Agropyran repens, Bromus inermis, Bromus erectus, Deschampsia flexuosa, Alopecurus pratensis, Arrhenatherum elatius, Dactylis glomerata, Festuca pratensis, Trisetum flavescens, Holcus lanatus, L

Poa annua, Poa neumoralis, Festuca ovina, Festuca rubra, Festuca nigrescens,

Cynosurus cristatus, Agrostis schraderiana, Agrostis stolonifera, Phleum pratense, Phleum nodosum, Cynodon dactylon, Stenotaphrum secundatum, Paspalum notatum,

Ermochloa olphiuroides and other grasses and weeds; sugar cane and cereals such as rice, cow, rye, barley, oats, sorghum, etc.

(b) trees and shrubs, such as fruit trees, such as apple, pear, peach, cherry and citrus trees, as well as cocoa, tea, coffee, banana, rubber, olive and walnut trees; (c) ornamental plants such as sea buckthorn, white beech, light cedar, juniper, rose, azalea, chrysanthemums, Poinsethia, alpine pansy, Pyracantha, forsythia, magnolias, petunias and bromeliads; 7 6071 3 d.) Arable crops such as cotton, soybeans, peanuts, tobacco, flax, sugar beet and pineapple; (e) vegetable species such as Solanaceae (eg tomatoes), legumes, pumpkin, melon, etc .; (f) berries such as strawberries, blueberries, raspberries and blackberries.

These compounds are also beneficial because they reduce the need to prune vines in vineyards.

In order to obtain a uniform distribution of the active compounds in growth regulators, the compound or compounds are mixed with conventional excipients, modifiers, diluents or humectants commonly used in herbicides and thus formed into soluble, emulsions, emulsifiable concentrates, dispersions, powders or granules.

Liquid compositions of the active ingredient or ingredients for direct injection may be prepared, for example, as aqueous solutions, where possible, or as solutions in solvent mixtures containing, for example, acetone, methanol, dimethylformamide in a ratio of 90: 8: 2 (v / v).

Emulsifiable concentrates containing 25 to 50% or more of the active ingredient, depending on its solubility, can be prepared using suitable solvents, for example, N-methylpyrrolidine, dimethylformamide, etc., emulsifiers, etc., are added in an amount sufficient to provide the desired properties of the composition.

Although solutions consisting of a solvent and a compound of the invention are suitable for greenhouse experiments, they are not particularly useful for field experiments. Wettable powders are also not particularly useful because DAG derivatives must be solubilized in order to develop the necessary activity. Therefore, the acid is most preferably prepared as a soluble powder together with a buffering agent, because buffering the acid to pH 5-9 is essential.

The acid can also be converted to an emulsion concentrate using N-methyl-2-pyrrolidone or nitropyrrolidone as follows:

Weight- $ of the total composition

Active substance 50

Atlox 2081B k N-methyl-2-pyrrolidone or nitro, pyrrolidone

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

The salts are water soluble and do not require any special formulation.

The DAG esters are formulated as emulsifiable concentrates with a xylene base, 8,60713 which can then be mixed with water. Emulsions containing up to 25 ~ 50% by weight of active ingredient can be prepared from these concentrates. The following are typical emulsifiable concentrates of DAG esters.

Weight- # of the entire mixture

Active substance 25 50

Xylene 71 k 6

Atlox 3 ^ 03 2

Atlox 3UoU 2

Emulphor EL 620 - 2

Drewmulse GMC-8 - 2

Atlox 3I + 03 is a mixture of polyoxyethylene ethers, polyoxyethylene glycerol and alkylarylsulfonate.

Atlox 3 ^ 0U is a mixture of polyoxyethylene alkylaryl ether and alkylarylsulfonate.

Emulphor EL 620 is a polyethylated vegetable oil.

Drewmulse GMC-8 is a low molecular weight saturated coconut fatty acid mono-glyceride.

A concentrated solution of sodium 2,3-k, 6-di-O-isopropylidene-2-keto-L-gulonate (95 wt.%) And sodium dioctyl sulfosuccinate (5 wt.%) Is prepared and spray dried. This gives a wettable powder which is completely water soluble.

In one embodiment, the finely divided sodium 2,3,3,6-di-O-isopropylidene-2-keto-L-gulonate is mixed with pumice grains. To this dry mixture is added 10 # by weight of the mixture of water. A portion of the sodium salt of 2,3: h, 6-di-O-isopropylidene-2-keto-L-gulonic acid is then soluble and serves as a means of removing the remaining insoluble sodium 2,3-U, 6-di-O-isopropylidene-2 -bonding of L-gulonate to pumice granules.

The reported usage levels are based on the results presented here and have not been reported to such an extent that all possible cases were included, as several factors affect the usage levels. For example, the amount of application varies not only with different plant species, but with a particular plant species, for example depending on factors such as plant size, plant age, compound used, season, soil quality and weather conditions at the time of application, such as air temperature, light intensity, rain and wind. In addition, if the compounds or preparations are used by irrigating the soil, higher concentrations are necessary because the plant in this use will be treated indirectly compared to direct treatment by applying the compound or preparation to leaves or stems, for example by spraying the plant.

9 60713

The amount of active ingredient in the plant growth regulating compositions thus varies depending on the plants to be controlled, the amount of application required, the mode of application, the active ingredient used and the degree of plant growth control desired. In general, the preparations contain less than 50% of active ingredient in ready-to-spray form.

“Basically, the amount of active ingredient to be used is chosen so as to achieve effective control of plant growth. As already exemplified above, the amount of active ingredient used in lawn control is such that the normal growth rate is slowed by 40-60%. Correspondingly, the choice of the minimum amount of use is determined by the minimum amount that can cause the desired growth retardation at the lower limit. Correspondingly, the maximum application rate is determined by the amount of active ingredient which gives the desired growth retardation at the upper limit, i.e. in the case of grasses used for ornamental lawns, the amount that still avoids the poor growth appearance of the ornamental lawn, but which, on the other hand, prevents too rapid lawn growth and does not cause unwanted chlorosis (i.e. grass yellowing). In tomato plants, the selection criteria for effective growth retardation are different because a dwarf plant that does not cause losses in fruit quality or quantity is highly desirable. Parameters of effective growth-regulating activity in such plants are slowed height and side growth as a maximum effect. The amount of active ingredient that meets these selection criteria or 3aa at the time of these effects is determined according to these aspects on tomato plants. In order to obtain the maximum growth-regulating effect after emergence, 0.5 ~ 20 kg or more per hectare is used. These amounts are based on the weight of the active substance. Similarly, the maximum post-emergence growth-regulating activity is generally obtained in amounts of 1-15 kg or more of active ingredient per hectare. The preferred dosage range for spray solutions is from 10 to 100,000 ppm, depending on which plant species is treated and which compound is selected for treatment. A very preferred dose range is generally 100-20,000 ppm.

An additional advantage of using the active compounds according to the invention is that they do not have any lasting effect on plants or a regulating effect which would remain in the soil. These compounds degrade slowly, resulting in a decrease in activity.

This phenomenon has advantages because: a) a short-term effect is obtained, which can be extended by further treatment; (b) normal plant growth conditions reappear as activity decreases; (c) no harmful residues remain on the plant or in the soil.

10 6071 3

The duration of the retarding effect varies depending on the compound used and other factors such as the species of plant treated, weather conditions, etc.

Although the compounds of the invention have plant growth regulating properties and herbicidal activity, they are practically non-toxic to animals. Decomposition products, 2-keto-L-gulonic acid and carbohydrates are likewise non-toxic.

It will be appreciated that not all compounds of formula II are active in all plants. However, within the scope of the present invention, each of the active compounds exhibits activity and against a particular plant or plants, and this activity is one of the purposes of the compound. As will be described in more detail below, it is a particular advantage of the present invention that the growth regulators, when used to treat a variety of plants, have pre- and post-emergence growth-regulating potency and herbicidal activity, with a very wide spectrum of plants. The growth-regulating activity of the active compounds is supported by the following microassays to determine the activity of the post-emergence effect.

A. Experiments with salts and esters of 2,3 ', U, 6-di-O-isopropylidene-2-keto-L-gulonic acid

The growth inhibitory effect of the preferred compounds is demonstrated in the following herbs in greenhouse experiments, especially after emergence in experiments with Digitaria sanguinalis and Poa pratensis.

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

The grass (Digitaria sangyinalis) was 10 days old and slightly less than 2.5 cm tall. Poa pratensis was also cut to a height of about 2.5 cm before the compounds in question were used.

Compounds were sprayed at rates of 0.5 ~ 8 kg / ha on grasses. Effect i.e. growth retardation was determined by measuring grass height and grass weight, i. weight of cut grass after 11-26 days.

The experiments included 3 standard compounds as controls. Maleic acid hydrazide (6-hydroxy-3- (2H) -pyridazinone) was used as an aqueous solution, i.e. as a water-soluble concentrate (300 g / l). Further, n-butyl 9-hydroxyfluorene- (9) -carboxylate, hereinafter referred to as IT-3233, and methyl 2-chloro-9-hydroxyfluorene- (9) -carboxylate, hereinafter referred to as IT-3-ol, were used in the solvent mixture described above. * 56.

The test results are summarized in the following Tables I and TI.

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Table I

Growth retardation effect of 2,3,6,6-di-O-isopropylidene-2-keto-L-gulonic acid (DAG) derivatives after germination.

Plant height in cm after days of treatment

Compound Dose Digitaria Poa kg / ha sanguinalis pratensis 11 days 18 days 26 days Untreated control - 10 11.7 7.0 DAG-n-butyl ester 8 390 U, 7 5 »0 (Example 2) U 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

Maleic acid hydrazide H 5.8 6.3 U, 0 IT-3233 1 8.8 12.5 6.0 IT-3 ^ 56 1 8.7 9.8 5.5

Table II

Weight of green grass tips of Digitaria sanguinalis and Poa pratensis when cut after emergence after treatment with growth retardants.

Weight in g after days of treatment

Compound Dose Digitaria Poa kg / ha sanguinal Pratensi3 18 days 26 days Untreated control - 18.9 U, 6 DAG-n-butyl ester 8 6.2 3.0 (Example 2) U 10.2 h, 2 2 17.9 U , 3 1 19.6 U, 1 0.5 21.1 U, 8

Maleic acid hydrazide U U, 7 1.9 IT-3233 1 10, k U, l + IT-3U56 1 10.2 U, 2 12 6071 3

When solutions of common solvents are not very suitable under field conditions, DAG and similar derivatives were tested as emulsifiable compositions.

(25% active ingredient, 1 »1% xylene, 2% Atlox 3 ^ 0U, 2% Atlox 3 ^ 03U. Atlox 3 ^ 03 is a mixture of polyoxyethylene ethers, polyoxyethylene glycerol and alkylarylsulfonate. products are manufactured by Atlas Co. USA Several esters were tested in said solvent mixture, in addition to aqueous solutions containing DAG, 1% Tween 20 (polyoxysorhitan monostearate) both buffered and buffered to pH 5_T. likewise contained Tween 20.

Growth inhibition studies were performed on the following plants:

Digitaria sanguinalis, soybeans and tomatoes, at which time the plants were treated at approximately 2 weeks of age. When treated, Digitaria sanguinalis was approximately 2 cm high, soybean plants with first leaves about 5 ~ 6 cm high, and tomatoes with 3-U actual leaf were 3 ~ ^ cm high. Water-soluble, solvent mixtures or emulsifiable concentrates of the active ingredients were sprayed.

The results of these experiments with DAG, salts and esters in different compositions are shown in Table III, where the deceleration efficiency is shown in numbers. The rating scale is defined as follows: 0 - no visible retardation 1,2,3 - slight retardation, little or no retardation in the visible parts of the plant L, 5,6 - moderate retardation, reduced growth in the visible parts of the plants 7,8, 9 - strong deceleration, little or no growth in plants 10 - no growth.

Table III

Herbicidal activity after budding of DAG and derivatives

Deceleration effect in 13 days

Compound Form Dose Digitaria Soybean Tomato kg / ha sanguinal DAG water 89 9 9

Calcium salt k 8 89 28 7.3 6 1 U, 7 3 5 0.5 3.7 1 5 13 6071 3

Table III .continued

Deceleration effect in 13 days

Compound Form Dose Digitaria Soybean Tomato kg / ha sanguinal DAG-n-butyl ester SM 8 9 6 7 (Example 2) 1+ 8 6 6,7 2 7 3 5 15 1,3 5 0,5 1+ 0 0 DAG-n butyl ester EC 8 10 9 8 (Example 2) h 9 * 3 9 7 »3 2 7.7 8.3 8 1 5.7 78 0.5 3.7 5 3

Maleic acid hydride 87 10 5.7 Racid 1 + 7 10 3 2 5 9 1 Water 10 90 0.5 0 9 0 IT-3I + 56 SM 8 5.7 8 5 1 + 5 8 5 2 3 85 10 85 0, 5 0 8 5 DAG-ammonium salt water 89 9 9 1 + 9 7,7 8 28 6,7 6 11+ 3,3 5 0,5 1+ 2 5 DAG-n-dode-SM 8 8 5 8 ethyl ester (example 5) 1 + 7 3 7 2 1+ 3 6,3 12 2 2,3 0,5 2 2 2 DAG-n-dode- EC 8 8,7 8,3 6,3-ester n 6071 3

Table III .continued

Deceleration effect in 13 days

Compound Form Dose Digitaria Soybean Tomato kg / ha sanquinalis (Example 5) 1+ 8 6.3 6.3 2 3 .5 i », 3 13 5 ^ 0.5 0 5 3

Control EC 9 8.3 SM = active substance dissolved in solvent EC = emulsifiable concentrate for salts of water - DAG, water contains 1% Tween.

The inorganic salts and esters of DAG were almost as active as DAG itself. The experimental results show that the salts and esters of DAG are more active than maleic anhydride and the reference compound IT 3 ^ + 56 in inhibiting the growth of Digitaria sanquinalis after emergence and only slightly less active in inhibiting the growth of soybean after emergence.

The following Table IV contains experimental results for 12 different useful plants and weeds when the plants were sprayed when they were approximately 2 weeks old. Four representative esters of DAG (2,3: β-di-O-isopropylidene-2-keto-L-gluconic acid) were compared to the standard i.e. to maleic anhydride. The same grading scale as in Table III was used.

Tomato seedlings slow down the growth strongly. Instead, progress is observed in the development of lateral growth, so that an entirely dwarf, shrub-like plant emerges. It should be noted that neither the quality nor the quantity of the fruit changes.

Table IV

Growth retardation effect of 2,3: 1,6-di-O-isopropylidene-2-keto-L-gulonic acid (DAG) derivatives

Compound Composition Dose Daily. Echino- Maize Digitaria Sorghum kg / ha chloa sanqui- halepense crus- Nalis Galli DAG-n-bu- Solvent 8 13 6 6 8 8 style mixture k teri 2 1 + 0 7 6 (example 2) 1 205 2 0, 5 0 0 0 0 15 6071 3

Table IV .continued

Compound Composition Dose Daily. Echino- Maize Digitaria Sorghum kg / ha chloa sanqui- halepense crus- naii s Galli _

Maleic Water 8 13 b 0 7 7 Acid _ Köl 7 Hydrazide 2 3 0 3 b 1 2 0 2 2 0,5 0 0 0 0 DAG-n-pro- Solvent 8 1U 8 - 7 7 blade (example 3)

Table IV .continued

Compound Composition Poa pra- Oats Rice Soy- Sugar- Tomato Wheat Wild ”tensis bean beet oats DAG-n- Solvent 9 U695 5 5 ^ butyl mixture 3 5 8 3 b 33 ester 8 0 3 3 1 3 2 2 (example 2) 7 022 0 0 0 0 0 0000 0 00

Maleic Water 9 3503 7 23 Acid q 2 b 7 0 6 22 Hydrazide 7 03βθ 6 22 7 0020 0 20 2 0000 0 0 0 DAG-n- Solvent - ____ - - 7 propylene mixture ester (Example 3)

Table IV continues

Compound Composition Dose Daily. Echinochloa Sorghum Digitaria kg / ha crusgalli halepense sanguinalis DAG-di- Water 8 21 8 7 10 methyl- 8 1U 8 9 10 ammomum- salt k 13 7 5 9 2 13 5 3 8 1 13 b 2 7 '6 6071 3

Compound Composition Dose Daily. Echinochloa Sorghum Digitaria kg / ha crusgalli halepense sanguinali3 DAG-n- SM 8 11+ 10 9 10 pentyl- i * 13 7 7 q ester oi i * (example H) 2 13 5 5 8 1 13 2 5 7 DAG-iso- SM 8 il * 7 8 8 propyl ester (Example 6) DAG-n-Water 8 lU 9 9 9 ethanol 1 * 13 7 7 9 ammonium salt 2 13 5 6 8 1 13 ^ 5 7

Water and SM mean the same as in Table III.

In Tables III-IV, the dose of salts, esters and other analogs of DAG was not calculated as the equivalent amount of acid.

Although the main field of application of the growth regulators according to the invention is the use for growth control after germination, the active compounds of the formula II can also be used before germination. The pre-emergence activity of DAGs is demonstrated by the n-propyl ester of DAG. The ester is sprayed at a rate of 8 kg / ha. A strong growth retardation (i.e. little or no growth) is observed in Sorghum halepense, Amaranthus so. and Digitaria sanguinalis after 20 and 27 days.

Further studies with DAG and its salts were performed on a wide variety of grasses, cereals, ornamentals, perennials, and vegetables.

The effect of ammonium salt and n-butyl ester on DAG as a growth retardant on Brazilian pepper (Schinus terebinthifolius Raddi) and sumac wood (Rhus spp) was studied. The leaves of the plants were sprayed until a gapless spray layer was obtained. Maintain CF-125 (a mixture of methyl 2-chloro-9-hydroxyfluorene-9-carboxylate, methyl 9-hydroxyfluorene-9-carboxylate and methyl 2,7-dichloro-9'-hydroxyfluorene-9-carboxylate was used as reference substances. ). 1 * 3 days after spraying, notes are made of slowing or stopping growth, leaf fall and leaf deformity. Table V shows the results in numbers. The rating scale was as follows: 0 - no effect 1 - height growth slowed 2 - height growth inhibited 3 - height growth inhibited and deformed leaves appear U - leaves completely dropped, new leaves are small and deformed.

it 6071 3

Table V

Growth regulating effect on Brazilian pepper and sumac tree after i + 3 days treatment

Compound Concentration spray- Brazilian Sumac in solution $ in pepper Untreated - 00 control DAG-ammonium-0.25 + 1% Tritol ^ B-1956 0 0 salt "0.5 + 1 2 1.0 +" 2 2 DAG-n -butyl 0.25 + 2% oil 0 0 ester (Example 2) 0.5 + 2% oil 0 2 1.0 + 2 # oil 1 2 1.0 0 2

maintain

CF-125 0.5 3 U

Tritol ^ -195 ^ is a water-dispersible surfactant based on synthetic resin, manufactured by Rohm & Haas. Maintain CF-125 is a mixture of methyl 2-chloro-9-hydroxyfluorene-9-carboxylate, methyl 9-hydroxyfluorene-9-carboxylate and methyl 2,7-dichloro-9-hydroxyfluorene-9-carboxylate.

The oil adjuvant used in the above compositions is a standard kerosene generally used in herbicidal compositions, especially when the herbicide is used to treat woody plants. This oil helps both the penetration of the active ingredient and its adhesion. The compositions in Table V used an emulsifiable non-phytotoxic spray oil, Sun Oil 11E.

It was further found that when sprayed a growth regulator containing a compound of general formula II on fruit-bearing trees, it substantially reduces the force required to separate the fruit from the stem.

This is obtained by comparison with untreated wood. It was further found that the fruits harvested with growth regulators had relatively little damage and spoilage.

Fruit drop preparations can be applied to fruit-bearing trees in liquid or solid compositions. Use can be on roots, stems, branches, leaves or fruits. Fruit drop preparations can be sprayed or dusted, for example, from an airplane on trees or taken to the ground at the root of the trees so that the roots absorb it from it. The preferred method of use, which is also the most effective, is the application of the preparations in the form of aqueous spray solutions. If desired, a composition based on a suitable organic solvent, such as an oily spray solution, may also be used.

In order to obtain the greatest effect in the use of normal fruit drop preparations, the preparation is preferably used 1-2 weeks before harvesting, depending on the temperature. In areas where the possibility of rain between the use of the preparation and harvest is to be taken into account, a conventional fixing agent is suitably mixed into the preparation. Examples of such common fixing agents are glue, casein, salts of alginic acid, cellulose gum and the like, polyvinylpyrrolidone, invert syrup, corn syrup and the like.

If desired, inert substances used in agriculture can be mixed in, especially if these substances act as wood treatment agents, and they can also be used in combination with known fruit drop agents. Such excipients also include, for example, surfactants, carriers, adhesives, stabilizers, and the like.

The concentrations of the active compounds of the general formula II in the new fruit drop agents vary, but it is necessary to use a sufficient amount to obtain the optimum effect. Thus, the aqueous spray solution contains from about 0.05 to about 1.5% (w / w) of active ingredient. The concentration naturally varies depending on the type of fruit and the size of the tree or shrub. The dosage is such that the harvest is really easier. In the case of spray solutions, an aqueous solution containing a fruit drop agent is sprayed so that the wood is covered with a gapless spray layer. This requires about 300 to about 9,000 liters of diluted solution (about 0.1 to 1% by weight of active ingredient) per hectare, depending on the number and size of the trees to be treated.

To prepare a preferred spray solution containing a fruit drop agent, the active ingredient or a salt thereof is dispersed or dissolved in a carrier such as water. A surfactant may be added to the liquid spray solution from 0.1 to about 0.5 weight percent of the carrier. Typical surfactants are (H)

Tritoir ^ B- ^ ö, a water-dispersible resin-based surfactant prepared by Rohm & Haas. Furthermore, X-77 (Chevron-Ortho), a nonionic surfactant containing alkylaryl polyoxyethylene glycols, free fatty acids and isopropanol can be used.

Fruit dropers affect the fall of fruit from many different fruit trees. Typical fruit trees of this kind are, for example, orange, grapefruit, olive, apple, cherry trees, etc. They also act in co-crops with other useful crops, such as cotton and soybeans (these cause leaf fall).

19 6071 3

As already mentioned, fruit drop agents are sprayed on the trees as aqueous solutions. Equivalent amounts of water-soluble salts of the compounds of the formula II can also be used in a corresponding manner. Such salts include ammonium salts and substituted ammonium salts.

In cases where the compounds used are insoluble in water, emulsifiable concentrates or wettable powder compositions are prepared from the active ingredient, which can be dispersed in water and thus form a spray-on.

Wettable powders are prepared using an inert diluent alone, for example kaolin. A typical spray solution prepared from a wettable powder contains, for example, the active ingredient, about 1 to about 5% of an inert diluent, minor amounts of dispersants, wetting agents and antifoams, and a corresponding and necessary amount of water.

Since oranges can be considered as typical fruits, the harvesting of which is facilitated by the use of chemical fruit drop agents, the effect of the new fruit drop agents on orange trees is demonstrated.

The sodium salt of 2,3,6,6-di-O-isopropylidene-2-keto-L-gulonic acid was tested as a fruit drop agent with citrus fruits, for example oranges. Prepare aqueous solutions containing 0.05%> 0.1 #, 0.25 #, 0.5% and $ 1.0 (w / w) of this sodium salt and 0.5% Triton B-1956 · These solutions are sprayed with Valencia -orange trees, seedless marsh grapefruit trees (Sumpfgrapefruite) and red grapefruit trees. One week after spraying, the only noticeable effect is a slight leaf fall on those trees treated with the higher dose. Two weeks after spraying, most oranges and grapefruits have fallen from trees treated with a dose of at least 1 #. About half of the fruit had fallen from the trees treated with the 0.5% dose and the fruit still in them was rather poorly attached.

In addition to the fruit-dropping effect, the fruit also had a clear color enhancement, for example a much deeper and darker color than that of the incomprehensible trees.

The sugar content and total solids content of the treated fruits were also increased compared to the untreated trees.

Similar results were obtained by spraying, for example, a preparation containing 2,3: U, 6-di-O-isopropylidene-2-keto-L-gulonic acid ammonium salt or diethanolammonium salt or n-butyl ester.

Whether the compounds of formula II are used as fruit dropers or as pre-emergence or post-emergence herbicides, they can be prepared and formulated as described above and as described in the summary.

so 60 71 3

Example 1

Ethyl 2,3: ^ »6-di-0-isopropylidene-2-keto-L-Bulonaatti

To a solution of 100 g of anhydrous potassium carbonate in 9 kS ml of dimethylformamide is added, with stirring at room temperature, 292.2 g of 2,3: 1,6-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 2k hours. The mixture is then filtered to remove inorganic salts and the dimethylformamide is removed by distillation in vacuo (about 60 ° and about 10 Torr). Add 200 mL of acetone to dissolve the remaining ether. Insoluble inorganic salts are filtered off. The filter cake is washed with 100 ml of acetone. The filtrate is added to the ester-containing solution. The solvent is evaporated in vacuo to about 500 ml and the crude product is isolated by cooling this solution to 5 °. The crude product is recrystallized from methanol / acetone to give 20 g of ethyl 2,3,6,6-di-O-isopropylidene-2-keto-L-gulonate, m.p. 99 to 100.5 ° C.

According to this generally applicable method, starting from 2,3: 1 +, 6-di-O-isopropylidene-2-keto-L-gulonic acid and 1,2-dibromoethane in a molar ratio of 2: 1 bis-ester: bis-2.3: ^, 6-di-0-isopropylidene-2-keto-L-gulonaatti-ethylene glycol.

Example 2 n-Butyl 2,3-N, 6-di-Q-isopropylidene-2-keto-L-gulonate

To a suspension of 100 g of anhydrous potassium carbonate in 9 to 6 ml of dimethylformamide is added with stirring 2,3: 1,6-di-O-isopropylidene-2-keto-L-1 gulonic acid monohydrate (292.2 g) and then 197 g n-butyl iodide. The mixture is stirred at room temperature for 1 * 8 hours, then the inorganic salts are filtered off. Dimethylformamide is removed by vacuum distillation. 200 ml of acetone are added to the residue, and the inorganic salts still present are removed by filtration. The filter cake is washed with 100 ml of acetone. The filtrate is combined with the ester solution and evaporated in vacuo. Recrystallization of the residue from methanol-acetone gives 172 g of colorless crystals of n-butyl 2,3: 1,6-di-O-isopropylidene-2-keto-L-gulonate having a melting point of 53.9-56-8 °.

Example 3 n-Propyl 2,3-N, 6-di-O-isopropylidene-2-keto-L-gulonate n-propyl 2,3: 1 *, 6-di-O-isopropylidene-2-keto L-gulonate is prepared analogously to the methods described in Examples 1-2 using 200 g of 1-bromopropane as the halide. Yield 150 g, melting point 80-81 ° C.

Example U

n-pentyl 2,3-H, 6-di-O-isopropylidene-2-keto-L-gulonate n-pentyl 2,3: 1,6-di-O-isopropylidene-2-keto-L-gulonate is prepared 2 '6071 3 analogously according to the working instructions of Examples 1-2 using 300 g of 1-bromopentane as halide in the reaction. Yield 503 g, boiling point 195 ° 0 / 0.5 'I'orr.

Example 5 n-Dodecyl-2,3-1,4-di-O-isopropylidene-2-keto-L-guonate n-Dodecyl-2,3,6-di-O-isopropylidene-2-keto L-gulonate was prepared analogously to the working instructions of Examples 1-2 by reacting 100 g of 1-bromododecane with the halide. Yield 75 g after two recrystallizations of ethanol. Melting point 10.5 ° C.

Example 6

Isopropyl 2,3-N, 6-di-O-isopropylidene-2-keto-L-gulonate Isopropyl 2,3: N, 6-di-O-isopropylidene-2-keto-L-gulonaut is prepared analogously according to the working instructions of Examples 1 and 2 by reacting 250 g of 2-bromopropane. Yield 116.8 g melting point 107.5-109 ° C.

Other straight-chain and branched aliphatic hydrocarbyl and halogen lower alkyl esters can be prepared in a similar manner. Example 7 2-Chloroethyl 2,3: 1,6-di-O-isopropylidene-2-keto-L-gulonate 6 g of 2,3: 1,6-di-O-isopropylidene-2-keto-L-gulonic acid (anhydrous) is dissolved in 1U of pyridine and 3.2 ml of methylene chloride, and 3.2 ml of thionyl chloride are added dropwise to the solution under stirring and ice-cooling. After 3 hours at room temperature, 5.9 ml of 2-chloroethanol are added to the reaction mixture and then stirred for a further 3 hours. The reaction solution is then extracted with methylene chloride and washed successively with ice-cold 2N hydrochloric acid, 2N sodium hydroxide and water, the organic phase is dried over sodium sulfate and evaporated to dryness. The residue is purified on a silica gel column and then distilled. 5 g of an oily product are obtained, b.p. 88 ° C / 0.01 Torr.

In analogy to the above examples, in particular according to Examples 1, 2 and 7, the following compounds can be prepared: ammonium 2,3-N, 6-di-O-isopropylidene-2-keto-L-gulonate, m.p. 177.5-17 ° C, 5 ° C, calcium 2,3-N, 6-di-O-isopropylidene-2-keto-L-gulonate, m.p. 265-267 ° C, dimethylammonium 2,3-k, 6-di-O-isopropylidene-2-keto-L-gulonate. mp. 155-165 ° C, N-ethanolammonium 2,3: 1,6-di-O-isopropylidene-2-keto-L-gulonate, m.p. 208-209 ° C, n-butyl 2,3-N, 6-di-O-isopropylidene-2-keto-L-gulonate, m.p. -5-57 ° C, 3-chloropropyl-2,3: 1 +, 6-di-O-isopropylidene-2-keto-L-gulonate, b.p. 130 ° C / 0.005 Torr, pc n-hexyl-2,3: 1,6-di-O-isopropylidene-2-keto-L-gulonate, n-1: 1, 1 + 51, n-heptyl-2, 3: U, 6-di-O-isopropylidene-2-keto-L-gulonate, b.p. 102-103 ° C / 0.01 Torr, n-octyl-2,3: 1,6-di-O-isopropylidene-2-keto-L-gulonate, n-1: i, 538, 22 6071 3 n -Nonyl-2,3-i, 1,6-di-O-isopropylidene-2-keto-L-gulonate, trans: 1,1'-O, n-undecyl-2,3-β, 6-di-O- -isopropylidene-2-keto-L-gulonate thiol: 1, 1, 555, 2,2,2-trichloroethyl-2,3: 1, 6-di-O-isopropylidene-2-keto-L- gulonate,:; p. Mp 66 ° C, n-dodecyl-2,3: 6-di-O-isopropylidene-2-keto-L-gulonate, m.p. 10.5 ° C, n-propyl-2,3,6,6-di-O-isopropylidene-2-keto-1L-gulonnate, m.p. 107.5 ° C, n-Decyl-2,3-i, 1,6-di-O-isopropylidene-2-keto-L-gulonate, b.p. 193 ° C / 0.5 Torr, 2-bromoethyl 2,3-N-di-O-isopropylidene-2-keto-L-gulonate, b.p. 157 ° C / 0.1 Torr, 2-butyl 2,3-i, 6-di-O-isopropylidene-2-keto-L-gulonate> m.p. 95 DEG-96.5 DEG C., 1-amyl-2,3, 6-di-O-isopropylidene-2-keto-L-gulonate, b.p. 135 ° C / 0.1 Torr, *> is 2,3-i, 1,6-di-O-isopropylidene-2-keto-L-gulonate-ethylene glycol ether, m.p. 150-151 ° C, t-butyl 2,3-N, 6-di-O-isopropylidene-2-keto-L-gulonate, m.p. 120 ° C, 2-pentynyl-2,3-i, 6-di-O-isopropylidene-2-keto-L-gulonate, b.p. 130-132 ° C / 0.001 Torr, 1-hexyn-3-yl-2,3-yl, 6-di-O-isopropylidene-2-keto-L-gulonate, b.p. liters 1-1 UU ° C / - 0.001 Torr, 3-methyl-1-butyn-3-yl-2,3: 1,6-di-O-isopropylidene-2-keto-L-gulonate, m.p. 89-91 ° C, 5-hexenyl-2,3-i, 6-di-o-isopropylidene-2-keto-L-gulonate, b.p. 92 ° C / 0.005 Torr, 3-pentyl-2,3-β, 6-di-isopropylidene-2-keto-L-gulonate, m.p. 76.5-77.5 ° C, 2-chloroethyl 2,3, 6-di-O-isopropylidene-2-keto-L-gulonate, b.p. 88 ° C / 0.01 Torr, t-chlorobutyl 2,3-β, 6-di-O-isopropylidene-2-keto-L-gulonate, b.p. 129 ° C / 0.01 Torr, 2,2,2-trifluoroethyl 2,3-ol, 6-di-O-isopropylidene-2-keto-L-gulonate, m.p.

90-92 ° C, 2-fluoroethyl 2,3: * +, 6-di-O-isopropylidene-2-keto-L-gulonate, m.p. 70-72 ° C 2-propynyl-2,3-i, 6-di-o-isopropylidene-2-keto-L-gulonate, m.p. 91.5 ° 92.5 ° O, n-pentyl-2,3-i, 6-di-O-isopropylidene-2-keto-L-gulonate, b.p. 195 ° 0 / 0.1 Torr.

Claims (2)

23 1. Salts and esters of 2,3: 1,6-di-O-isopropylidene-2-keto-gulonic acid for use as plant growth regulators, having the general formula: CH3 s "'A / \ \ XC— 0 - R' * XH 0/0 .0 3 n wherein, when n is 1, R 'is ammonium, ammonium substituted by one or more C 1-4 alkyl or hydroxy-C 1-4 alkyl groups, straight-chain or branched C 3-12 alkyl, C 1-4 alkyl; N-alkenyl or C 2-12 alkynyl or halo-C 1-6 alkyl, and when n is 2, R 'is calcium, magnesium or C 1-6 alkylene, n is 1 or 2, and X is 0 or 1. 2. N-ethanolammonium 2,3: 1,6-di-O-isopropylidene-2-keto-L-gulonate.