CH618845A5 - Plant growth regulators - Google Patents

Description

The invention relates to tradable agents for regulating plant growth, comprising a carrier and one or more compounds of the general formula

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wherein when n is 1, R is hydrogen; Sodium;

Potassium; Hydrazine; Morpholinium; Thiomorpholinium; 25 piperazinium; Ammonium; Ammonium substituted with one or more lower alkyl, lower alkenyl, lower alkynyl, cycloalkyl with 3 to 6 carbon atoms, halo lower alkyl, hydroxy lower alkyl, aryl or benzyl, optionally substituted with halogen, nitro, lower alkyl or lower alkoxy; 30 alkyl, alkenyl or alkynyl; Hydroxy lower alkyl; lower alkoxy lower alkyl; lower alkenyloxy lower alkyl; lower alkynyloxy lower alkyl; lower alkyl sulfonyloxy lower alkyl; Arylsulfonyloxy lower alkyl; Aryl or benzyl, optionally substituted with one, two or three lower alkyl, 35 lower alkenyl, lower alkynyl, lower alkoxy, halo-lower alkyl, formyl, lower alkylcarbonyl, lower alkoxycarbonyl, cyano, halogen, nitro, hydroxy, lower alkoxyformamido, ureido , Methylenedioxy, amino or amino substituted with mono- or di-lower alkyl; Halo-lower alkyl; Halo-lower 40 alkenyl; Halo-lower alkynyl; lower alkoxycarbonyl-lower alkyl; Phosphono lower alkyl; Thiophosphono lower alkyl; lower alkylaminocarbonyl lower alkyl; lower alkylthio-lower alkyl; Arylthio-lower alkyl; Cycloalkyl, optionally substituted with halogen, nitro, lower alkyl or lower 45 alkoxy; Phenoxy-lower alkylcarbonyloxy-lower alkyl, where the phenoxy group optionally substituted with one, two or three nitro, lower alkyl, halogen, cyano, lower alkoxycarbonyl, lower alkylcarbonyl, methylenedioxy, amino or amino with mono- or di-lower alkyl can; Morpholino lower alkyl; Thiomorpholino lower alkyl; Piperazino lower alkyl; Phenylamino-lower alkyl or benzylamino-lower alkyl, the phenyl group optionally being substituted by halogen; Amino lower alkyl; Amino lower alkyl, the amino group being mono- or 55 di-substituted with lower alkyl, hydroxy-lower alkyl, halogen-lower alkyl, halophenyl, cyclopentyl or cyclohexyl; Hydrazino lower alkyl; Furyl or furyl-lower alkyl; and if n is the number 2, R is calcium, magnesium or lower alkylene, R ^ R2, Rs and R4 is lower hydrogen, 60 is lower alkyl, lower alkenyl or lower alkynyl, halo-lower alkyl, aryl, optionally substituted by halogen, nitro, lower alkyl or lower alkoxy, or Rj and R2 together and / or Ra and R4 together each represent the addition to a saturated ring having 3 to 8 carbon atoms, n represents the number 1 or 2 and X represents the number 0 or 1; as well as enantiomers and racemic mixtures.

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

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The invention further relates to methods of using these agents.

The compounds of the general formula

0-0 —-RiXHpO

R

wherein when n is 1, R 'is hydrogen; Sodium; Potassium; Hydrazine; Morpholinium; Thiomorpholinium; Piperazinium; Ammonium; Ammonium substituted with one or more lower alkyl, lower alkenyl, lower alkynyl, cycloalkyl having 3 to 6 carbon atoms, halo-lower alkyl, hydroxy-lower alkyl, aryl or benzyl, optionally substituted with halogen, nitro, lower alkyl or lower alkoxy; Alkyl, alkenyl or alkynyl; Hydroxy lower alkyl; lower alkoxy lower alkyl; lower alkenyloxy lower alkyl; lower alkynyloxy lower alkyl; lower alkyl-sulfonyloxy-never-the alkyl; Arylsulfonyloxy lower alkyl; Aryl or benzyl, optionally substituted with one or two lower alkyl, lower alkenyl, lower alkynyl, lower alkoxy, halo-lower alkyl, formyl, lower alkylcarbonyl, lower alkoxycarbonyl, cyano, halogen, nitro, hydroxy, lower alkoxy-formamido, ureido , Methylenedioxy, amino or amino substituted with mono- or di-lower alkyl; Halo-lower alkyl; Halo-lower alkenyl; Halo-lower alkynyl; lower alkoxy-carbonyl-lower alkyl; Phosphono lower alkyl; Thiophosphono lower alkyl; lower alkylaminocarbonyl lower alkyl; lower alkylthio-lower alkyl; Arylthio-lower alkyl; Cycloalkyl, optionally substituted with halogen, nitro, lower alkyl or lower alkoxy; Phenoxy-lower alkylcarbonyloxy-lower alkyl, where the phenoxy group may optionally be substituted with mono- or di-lower alkyl with one, two or three nitro, lower alkyl, halogen, cyano, lower alkoxycarbonyl, lower alkylcarbonyl, methylenedioxy, amino or amino ; Morpholino lower alkyl; Thiomorpholino lower alkyl; Piperazino lower alkyl; Phenyl-amino-lower alkyl or benzylamino-lower alkyl, where the phenyl group is optionally substituted by halogen, amino-lower alkyl; Amino-lower alkyl substituted with mono- or di-lower alkyl, hydroxy-lower alkyl, halo-lower alkyl, halophenyl, cyclopentyl or cyclohexyl; Hy-drazino-lower alkyl; Furyl or furyl-lower alkyl; and,

when n is 2, R 'is calcium; Magnesium or lower alkylene, R'1; R'2, R'3. and R'4 lower alkyl, lower alkenyl, lower alkynyl, halo-lower alkyl, aryl, optionally substituted with halogen, nitro, lower alkyl or lower alkoxy, or R'i and R'2 together and R'3 and R'4 together each represent a saturated ring with 3 to 8 carbon atoms, n represents the number 1 or 2 and X represents the number 0 or 1, enantiomers and racemic mixtures, but in the event that R 'is hydrogen, ammonium, methyl, sodium or potassium and R'1; R'2, R's and R'4 lower alkyl mean the lower alkyl group includes more than 1 carbon atom, are new.

These compounds are also useful in the means and methods mentioned above.

Preferred plant growth regulators for the purposes of the present invention are, because of their post-emergence plant growth-regulating activity, in particular compounds of the formula

R "

C_0 __RVXH_0

R "

wherein when n is 1, R "is hydrogen, sodium, potassium, ammonium, substituted ammonium, alkyl, alkenyl or alkynyl or halo-lower alkyl and, when n is 2, R" is calcium, magnesium or lower alkylene, R "1; R "2, R" 3 and R "4 are hydrogen, straight-chain or branched aliphatic lower hydrocarbyl, halo-lower alkyl, aryl or R" i and R "2 together and R", 3 and R "4 together each have a saturated ring 3 to 8 carbon atoms, n and X have the meaning given in formula I, and enantiomers and racemic mixtures.

Another preferred group of compounds are those of the general formula

CH.

CH.

.0 —0 - —R "1 .XH" 0

CH.

wherein, when n is 1, R '"is hydrogen, sodium, potassium, ammonium, substituted ammonium, alkyl, alkenyl, alkynyl or halo-lower alkyl and, when n is 2, R'" is calcium, magnesium or lower alkylene, n and X the previous5

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have the meaning given above, and enantiomers and racemic mixtures.

The compounds encompassed by the above formulas I, II, III and IV all have the D configuration since they are derived from the naturally occurring 2-ketohexose, D-fructose. D-fructose is the only known form of fructose that occurs naturally; however, the corresponding enantiomer of D-fructose, namely L-fructose, can be produced synthetically. It is particularly pointed out that the compounds corresponding to the D-fructose with the L configuration and racemic mixtures of these compounds can be prepared in a completely analogous manner by using the L-fructose instead of D-fructose as a starting material or as a starting material a mixture of D- and L-fructose is used if the corresponding racemic mixture is aimed for. The preparative methods are exactly the same, regardless of whether one uses a compound of the D-form, the L-form or the corresponding racemic mixture as the starting material. Accordingly, all structural formulas, as shown below and above, are not to be understood as those which are intended to describe a specific or an absolute configuration, but rather to describe all possible configurations, i.e. they include in particular the enantiomers and the racemic mixtures. Unless expressly stated otherwise, the examples and other descriptions relate to the racemic compounds.

The compounds encompassed by formulas I, II, III and IV have post-emergence and / or pre-emergence plant growth-regulating activity and herbicidal activity. However, the post-emergence growth regulating effect predominates, since most compounds have this effect and this activity is suitable for controlling the growth of weeds which occur in the lawn.

The term “plant growth regulator” as used here denotes a compound or a composition which has an influence on the maturation and metabolism of plants. A plant growth regulator thus has numerous effects on plant growth. However, not all compounds active as plant growth regulators act on the plants in the same way. E.g. they can affect growth by delaying or stimulating final growth, and /

or by stimulating side growth and they can inhibit new growth such as the formation of root shoots in bush plants, the sprouting of tubers and rhizomes and the growth of shoots. Such regulators can affect flowering plants by preventing early flowering and by reducing or increasing the number of flowers. Fruit-bearing trees and bushes can be influenced by increasing the number, size and quality of the fruit, by forming seedless fruit, by accelerating aging and ripening and by stimulating fruit and / or leaf waste. Both flowering and fruiting plants can be influenced by accelerating plant sleep and maintaining bud rest. A plant growth regulator can selectively control weeds after they emerge by reducing their potency and resistance so that they cannot spread and multiply.

Typical uses of plant growth regulators include:

Prevention of trapping grain;

Increasing the formation of harvestable tea leaves by favoring the side branches;

Prevention of sprouting potatoes and onions during storage;

Suppressing the growth of grass, trees, shrubs and other vegetation on decorative turf, in parks, on golf courses and along roads;

■ Accelerate fruit ripening and thus facilitate mechanical harvesting through one-off or less frequent picking;

Defoliate the cotton plant to allow mechanical harvesting;

Preventing new growth of defoliated cotton plants and thus reducing the staining of the fiber during mechanical harvesting; Increasing the quality of the harvest e.g. the sugar content of cane sugar, beet, grapefruit, grapes and other fruits;

Facilitating the mechanical harvesting of nuts by accelerating the ripening, stimulating the breaking of the shells and accelerating the waste;

Protect fruits from frost by stimulating early sleep and / or preventing early rest;

Increasing the latex flow of rubber plants;

Increase the frost resistance of winter cereals;

Reducing flowering or shooting of lettuce, sugar beet and tobacco;

Control of sprout formation in tobacco;

Stimulation of increased fruit set in soybeans, peanuts, cotton, tomatoes, melons and other fruits;

Increase the color and quality of fruits;

Protection of grain from drought;

Stimulation of the side growth of potted plants such as Heather, azaleas, chrysanthemums and geraniums;

Delaying the growth of potted plants such as Poinsethia, petunias and chrysanthemums;

Stimulation of the side growth of young trees such as Apple or pear trees.

The term “alkyl, alkenyl or alkynyl” as used here denotes a monovalent substituent which has 1 to 20 carbon atoms and consists exclusively of carbon atoms and hydrogen atoms and which contains no aromatic group, but apart from that can be saturated or unsaturated. The term “lower alkylene” denotes a divalent substituent which consists of straight-chain or branched aliphatic hydrocarbons having 1 to 7 carbon atoms and is bonded via 2 different carbon atoms. The term "lower" refers to groups that have a carbon skeleton with up to 7 carbon atoms. The term “lower alkyl” encompasses both straight-chain and branched, saturated aliphatic groups which have 1 to 7 carbon atoms, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, etc. The term “lower alkenyl” or “lower Alkynyl describes both straight-chain and branched unsaturated aliphatic groups which contain 2 to 7 carbon atoms, such as, for example, allyl, propenyl, butenyl, pentenyl, 1,1-dimethylpropenyl, propargyl, butinyl, pentynyl, hexadiynyl, heptadiynyl and possible isomers of these Links. A particularly preferred group is the propargyl group.

The term "lower alkyl" in combinations such as lower alkoxy, lower alkylcarbonyl, lower alkoxycarbonyl, halo lower alkyl, phenoxy lower alkyl carbonyloxy or lower alkoxycarbonyl lower alkyl refers to straight-chain or branched hydrocarbons which have up to 7 carbon atoms such as Me5

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thyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl etc. The term “aryl” describes aromatic hydrocarbons with 6 to 14 carbon atoms, such as phenyl, naphthyl or anthryl. In these aromatic hydrocarbons, 1, 2 or 3 hydrogen atoms can be substituted by a substituent such as e.g. Alkyl, alkynyl, alkoxy or halo-lower alkoxy can be replaced. The term "halo-lower alkyl," halo-lower alkenyl "or halo-lower alkynyl" encompasses straight-chain or branched alkyl, alkenyl or alkynyl groups having up to 7 carbon atoms, in which 1 or more hydrogen atoms are replaced by halogens, such as, for example, 2 , 2,2-trichloroethyl, 2,2-dichloroethyl, 2-chloroethyl, 4-chlorobutyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-bromo-l, l, 2,2-tetrafluoroethyl, 2nd , 2,3,3,4,4,4-heptafluorobutyl, 3,4,4-trifluoro-3-butenyl etc. The term ammonium, hydrazinium, morpholinium etc. defines for example the corresponding salts of the 2-keto-gluconic acid derivatives of the formula I or II. The term "cycloalkyl" describes an alicyclic hydrocarbon with 3 to 6 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

The term “substituted ammonium” refers to ammonium radicals in which one or two of the hydrogen atoms have been replaced by a lower alkyl, lower alkenyl or hydroxyalkyl substituent. The term “halo-lower alkyl” describes a lower alkyl group in which one or more of the hydrogen atoms are replaced by a halogen, preferably fluorine, chlorine or bromine.

Exemplary representatives which fall under the formula I and which act as a plant growth regulator and / or have a herbicidal action are:

A. New connections

2,3-0-isopropylidene-4,5-0-benzylidene-2-keto-D-gluconic acid;

2,3-0-isopropylidene-4,5-0- (p-methoxybenzylidene) -2-keto-D-gluconic acid;

2,3-0-isopropylidene-4,5-0- (3-pentylidene) -2-keto-D-gluconic acid;

2,3-0-isopropylidene-4,5-0-methylene-2-keto-D-gluconic acid;

2,3-0-isopropylidene-4,5-0-ethylidene-2-keto-D-gluconic acid;

2,3-0-isopropylidene-4,5-0- (2-butylidene) -2-keto-D-gluconic acid;

2,3-0-isopropylidene-4,5-0-cyclohexylidene-2-keto-D-glu-cons acid;

2,3: 4,5-di-0- (3-pentylidene) -2-keto-D-gluconic acid;

2,3: 4,5-di-0-ethylidene-2-keto-D-gluconic acid;

2,3: 4,5-di-0-benzylidene-2-keto-D-gluconic acid;

2,3: 4,5-di-0- (p-methoxy-benzylidene) -2-keto-D-gluconic acid;

2,3-0-isopropylidene-4,5-0- (2-chloroethylidene) -2-keto-D - gluconic acid;

2,3-0-isopropylidene-4,5-0- (1,3-dichloroisopropylidene) -2-keto-D-gluconic acid;

2,3-0-isopropylidene-4,5-0- (l, l, 3-trichloroisopropylidene) - 2-keto-D-gluconic acid;

2,3-0-isopropylidene-4,5-0- (l, l, l, 3-tetrachloroisopropyl-idene-2-keto-D-gluconic acid;

2,3-0-isopropylidene-4,5-0- (2,2-dichloroethylidene) -2-keto-D-gluconic acid;

2,3-0-isopropylidene-4,5-0- (1,1,3,3-tetrachloroisopropyl-idene) -2-keto-D-gluconic acid;

2,3-0-isopropylidene-4,5-0- (1,1,3,3-pentachloroisopropylidene) -2-keto-D-gluconic acid;

2,3-0-isopropylidene-4,5-0- (2,2,2-trichloroethylidene) -2-keto - D-gluconic acid;

2,3-0-isopropylidene-4,5-0- (l, l, l, 3,3,3-hexachloroisopropylidene) -2-keto-D-gluconic acid;

2,3-0-isopropylidene-4,5-0- (2-fluoroethylidene) -2-keto-D - gluconic acid;

5 2,3-0-isopropylidene-4,5-0- (1,3-difluoroisopropylidene) -2-keto-D-gluconic acid;

2,3-0-isopropylidene-4,5-0- (l, l, 3-trifluoroisopropylidene) - 2-keto-D-gluconic acid;

2,3-0-isopropylidene-4,5-0- (1,1,3,3-tetrafluoroisopropyl-10-idene) -2-keto-D-gluconic acid;

2,3-0-isopropylidene-4,5-0- (2,2-difluoroethylidene) -2-keto-D-gluconic acid;

2,3-0-isopropylidene-4,5-0- (1,1,3,3-tetrafluoroisopropyl-idene) -2-keto-D-gluconic acid; 15 2,3-Ö-isopropylidene-4,5-0- (l, l, l, 3,3-pentafluoroisopropyl-idene) -2-keto-D-gluconic acid;

2,3-0-isopropylidene-4,5-0- (2,2,2-trifluoroethylidene) -2 - keto-D-gluconic acid;

2,3-0-isopropylidene-4,5-0- (l, l, l, 3,3,3-hexafluoroisopropyl-20 idene) -2-keto-D-gluconic acid;

2,3-0-isopropylidene-4,5-0- (2-bromoethylidene) -2-keto-D - gluconic acid;

2,3-0-isopropylidene-4,5-0- (1,3-dibromoisopropylidene) -2-keto-D-gluconic acid; 25 2,3-0-isopropylidene-4,5-0- (l, l, 3-tribromoisopropylidene) - 2-keto-D-gluconic acid;

2,3-0-isopropylidene-4,5-0- (2,2-dibromoethylidene) -2-keto-D-gluconic acid;

2,3-0-isopropylidene-4,5-0- (l, 1,3,3-tetrabromoisopropyl-30 idene) -2-keto-D-g! Uconic acid;

2,3-0-isopropylidene-4,5-0- (2,2,2-tribromoethylidene) -2 - keto-D-gluconic acid;

2,3-0-isopropylidene-4,5-0- (l, l, l-tribromoisopropylidene) - 2-keto-D-gluconic acid; 35 2,3: 4,5-di-0- (2-chloroethylidene) -2-keto-D-gluonic acid;

2,3: 4,5-di-0- (1,3-dichloroisopropylidene) -2-keto-D-gluconic acid;

2,3: 4,5-di-0- (l, l, 3-trichloroisopropylidene) -2-keto-D-glu-cons acid;

40 2,3: 4,5-di-0- (l, l, l, 3-tetrachloroisopropylidene) -2-keto-D-gluconic acid;

2,3: 4,5-di-0- (2,2-dichloroethylidene) -2rketo-D-gluconic acid;

2,3: 4,5-di-0- (1,1,3,3-tetrachloroisopropylidene) -2-keto-D-45 gluconic acid;

2,3: 4,5-di-0- (2,2,2-trichloroethylidene) -2-keto-D-gluconic acid;

2,3: 4,5-di-0- (2-fluoroethylidene) -2-keto-D-gluconic acid;

2,3: 4,5-di-0- (1,3-difluoroisopropylidene) -2-keto-D-glu-50 cons acid;

2,3: 4,5-di-0- (l, l, 3-trifluoroisopropylidene) -2-keto-D-glu-cons acid;

2,3: 4,5-di-0- (l, l, l, 3-tetrafluoroisopropylidene) -2-keto-D-gluconic acid;

55 2,3: 4,5-di-0- (2,2-difluoroethylidene) -2-keto-D-gluconic acid;

2,3: 4,5-di-0- (l, l, 3,3-tetrafluoroisopropylidene) -2-keto-D-gluconic acid;

2,3: 4,5-di-0- (l, l, l, 3,3-pentafluoroisopropylidene) -2-keto-60 -D-gluconic acid;

2,3: 4,5-di-0- (2,2,2-trifluoroethylidene) -2-keto-D-gluconic acid;

2,3: 4,5-di-0- (l, l, l, 3,3,3-hexafluoroisopropylidene) -2-keto-D-gluconic acid; 65 2,3: 4,5-di-0- (2-bromoethylidene) -2-keto-D-gluconic acid;

2,3: 4,5-di-0- (1,3-dibromoisopropylidene) -2-keto-D-glu-cons acid;

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2,3: 4,5-di-0- (l, l, 3-tribromoisopropylidene) -2-keto-D-glu-cons acid;

2,3: 4,5-di-0- (2,2-dibromoethylidene) -2-keto-D-gluconic acid;

2,3: 4,5-di-0- (1,1,3,3-tetrabromoisopropylidene) -2-keto-D-gluconic acid;

2,3: 4,5-di-0- (2,2,2-tribromoethylidene) -2-keto-D-gluconic acid;

2,3: 4,5-di-0- (l, l, l-tribromoisopropylidene) -2-keto-D-glu-cons acid;

2,3: 4,5-di-0-cyclohexylidene-2-keto-D-gluconic acid; 2,3: 4,5-di-0- (2-butylidene) -2-keto-D-gluconic acid; 2,3: 4,5-di-0-methylene-2-keto-D-gluconic acid.

B. Other connection

2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconic acid monohydrate.

Furthermore, salts, for example alkali, alkaline earth, ammonium and substituted ammonium salts as well as esters, for example lower alkyl, lower alkenyl and lower alkynyl esters of the above-mentioned gluconic acids, are also effective as plant growth regulators and / or herbicides.

Preferred compounds in the context of the invention are: methyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate; Ethyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate; n-butyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate; n-propyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate; Isopropyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate; n-dodecyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate; n-pentyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate; Calcium 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate; n-decyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate; Benzyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate; Isoamyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate; 2-butyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate; 2-bromoethyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluco-

nat;

N -ethanolammonium-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate;

Bis-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate-ethylene-glycol ester;

2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconic acid monohydrate;

Alyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate; Sodium 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate; Potassium 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate; Ammonium 2,3: 4,5-di-0-isopropylidene-2-keto-D-glu-conate;

Dimethylammonium 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate;

2-propynyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-glu-conate.

Particularly preferred compounds are: sodium 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate; Ammonium 2,3: 4,5-di-0-isopropylidene-2-keto-D-glu-conate;

n-butyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate. The active compounds are particularly useful in agents for regulating plant growth, particularly grass and weeds, as well as other undesirable plants that happen to mix with the plants that are deliberately planted. While the compounds have pre-emergence plant growth regulating effects, they are particularly useful when used as post-emergence plant growth regulators or as crop-inducing agents. The post-emergence activity of the active compounds in the context of the present invention is demonstrated by controlling the growth of undesired plants. For example, it has so far not been possible to carry out a post-emergence control of Digitaria san-guinalis with a post-emergence herbicide; however, this is achieved with the active compounds according to the present invention, since they greatly slow down the growth and ripening of this grass and thus prevent the grass from being seeded and spreading.

In the control of turf, particularly domestic turf and industrial turf (for example golf courses), it has been shown that a maximum growth retardation, as manifested by a reduction in the height of the grass compared to an untreated control, of about 40-60% is to be aimed for, with a delay of grass growth of 50% being preferred. A delay of less than 40% must already be classified as ineffective, since it does not visually reveal the necessary aesthetic effect and does not reduce the necessary maintenance work for the lawn. On the other hand, a delay in growth of more than 60% is also undesirable since the lawn takes on a barren appearance and is quickly infused with weeds and other undesirable plants.

The active compounds show herbicidal activity especially against weed weeds, for example Matri-caria species and other weeds such as Papaver rhoeas, Stellaria media and Capsella bursa pastoris.

These compounds are particularly active in and against the following plants:

a) Grasses such as Agropyron repens, Bromus inermis, Bro-mus erectus, Deschampsia flexuosa, Alopecurus pratensis, Arrhenatherum elatius, Dactylis glomerata, Festuca pratensis, Trisetum flavescens, Holcus lanatus, Lolium perenne, Poa annvas, Poa prumaensum , Festuca rubra, Festuca nigrescens, Cynosurus cristatus, Agrostis schraderiana, Agrostis stolonifera, Phleum pratense, Phleum nodosum, Cynodon dactylon, Stenotaphrum secundatum, Paspaium notatum, Ermochloa olphiuroides and other weed or weed grasses; Sugar cane and cereals such as grain, rice, wheat, rye, barley, oats, etc .;

b) trees and shrubs such as fruit trees such as apple, pear, peach, cherry and citrus, as well as cocoa, tea, coffee, bananas, gum, olives and nut trees;

c) Ornamental plants such as privet, hornbeam, white cedar, juniper, rose, azalea, chrysanthemum, poinsethia, cyclamen, pyracantha, forsythia, magnolia, petunia and bromeliads.

d) field plants such as cotton, soybean, peanuts, tobacco, flax, sugar beet and pineapple;

e) vegetables such as Solanaceae (e.g. tomatoes), legumes, pumpkins, melons, etc .;

f) berries such as strawberries, blueberries, raspberries, blueberries, blackberries and currants.

These compounds are also useful because they reduce the cutting of the vines in the vineyards.

In order to achieve a uniform distribution of the active compounds in the growth-regulating agents according to the invention, the compound or the compounds are mixed with conventional auxiliaries, modifiers, diluents or conditioning agents which are customary for herbicides and thus form solutions, emulsions, emulsifiable concentrates, Formulations of dispersions, dusts, granules or wettable powders.

Liquid formulations of the active ingredient (s) for direct spraying can be prepared, for example, as aqueous solutions - wherever possible - or as solutions in solvent mixtures, for example acetone, methanol, dimethylformamide in a ratio of 90: 8: 2

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(Volume / volume) included. In the case of 2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconic acid, buffered (pH 6-10) formulations are produced, for example by adding potassium hydrogen sulfate or organic amines such as, for example, diethanolamine, triethanolamine etc. to aqueous solutions containing 1% Tween 20 or other non-phytotoxic wetting agents. Buffering of the solutions is necessary because it is known that 2,3: 4,5-di-O-iso-propylidene-2-keto-D-gluconic acid is unstable in aqueous solutions with a pH below 6.

Emulsifiable concentrates which contain 25-50% or more of active ingredient depending on its solubility can be prepared in suitable solvents, for example N-methylpyrrolidine, dimethylformamide, etc. Surfactants, for example wetting agents, dispersants, emulsifiers, etc., are added in a sufficient amount to achieve the desired characteristics of the formulation.

Wettable powders are made using an inert diluent such as kaolin. A typical spray solution formulated with a wettable powder contains, for example, the active ingredient, about 1% to about 5% of inert diluent, minor amounts of dispersant, wetting agent and anti-foaming agent, and the appropriate and necessary amount of water.

Different types of applications can be better adapted to the numerous purposes for which the active compounds can be used by adding compounds that improve dispersion, adhesion, resistance to rain and penetration, such as fatty acids, waxes, resins, Wetting agents, emulsifiers, mineral or vegetable oils, binders etc. In the same way, the biological spectrum of these compounds or agents can be greatly broadened by adding substances which have bactericidal, herbicidal, fungicidal properties or by adding fertilizers, chelating agents and other plant growth regulators.

Examples of herbicides and growth regulators which can be added to the compounds according to the invention are:

2,2-dichloropropionic acid,

N- (4-aminobenzenesulfonyl) methyl carbamate,

2-chloro-4-ethylamino-6-isopropylamino-l, 3,5-triazine,

4-chloro-2-oxobenzothiazolin-3-yl acetic acid,

5-bromo-6-methyl-3- (l-methyl-n-propyl) uracil,

3,5-dibromo-4-hydroxybenzonitrile, D, N-ethyl-2- (phenylcarbamoyloxy) propionamide, N- (4-bromo-3-chlorophenyl) -N'-methoxy-N'-methyl-urine-

material,

Methyl 2-chloro-9-hydroxyfluorene-9-carboxylate, N'-4- (4-chlorophenoxy) phenyl-N, N-dimethylurea, isopropyl-N- (3-chlorophenyl) carbamate, 2,3,5 , 6-tetrachloroterephthalic acid dimethyl ester (DCPA), 2,4-dichlorophenoxyacetic acid,

4-isopropylamino-6-methylamino-2-methylthio-l, 3,5-tri-azine,

n-butyl-9-hydroxyfluorene-9-carboxylate, naphthoxy-acetic acid,

3.6-dichloro-2-methoxybenzoic acid, (±) -2- (2,4-dichlorophenoxy) propionic acid,

9,10-dihydro-8a, 10a-diazoniaphenanthrene-2A,

N '- (3,4-dichlorophenyl-N, N-dimethylurea,

Gibberellic acid,

Indolylacetic acid,

Indolyl butyric acid,

4-hydroxy-3,5-di-iodobenzonitrile,

N '- (3,4-dichlorophenyl) -N-methoxy-N-methylurea,

4-chloro-2-methylphenoxyacetic acid,

4- (4-chloro-2-methylphenoxy) butyric acid,

(±) -2- (4-chloro-2-methylphenoxy) propionic acid,

N- (benzothiazol-2-yI) -N, N-dimethylurea,

N '- (3-chloro-4-methoxyphenylj-N, N-dimethylurea,

l, 2,3,6-tetrahydro-3,6-dioxopyridazine,

N '- (4-chlorophenyl) -N-methoxy-N-methylurea,

N '- (4-chlorophenyl) -N, N-dimethylurea,

Naphthylacetic acid,

N-1-naphthylphthalamic acid,

2,4-dichlorophenyl-4-nitrophenyl ether,

l, r-dimethyl-4,4'-bipyridylium-2A,

3- (m-tolylcarbamoyloxy) phenyl carbamate,

4-amino-3,5,6-trichloropicolinic acid, 4,6-bis-isopropylamino-2-methylthio-l, 3,5-triazine, N- (3,4-dichlorophenyl) propionamide, isopropyl-N-phenylcarbamate,

5-amino-4-chloro-2-phenylpyridazin-3 (2H) -one, N-dimethylamino succinic acid, 2-chloroethylphosphoric acid, tributyl-2,4-dichlorobenzylphosphonium chloride,

2.4.5-trichlorophenoxypropionic acid,

2.3.6-trichlorobenzoic acid, 2-chloro-4,6-bis-ethylamino-1,3,5-triazine, sodium chloroacetate,

2,4,5-trichlorophenoxyacetic acid,

5-chloro-6-methyl-3-t-butyluracil, 4-ethylamino-2-methylthio-6-t-butylamino-1,3,5-triazine - (terbutryn),

2,3,5-triiodobenzoic acid, 1,1,4-trimethyl-6-isopropyl-5-propionyl-indane. Exemplary fungicides which can be added to the compounds according to the invention are: 2,4-dichloro-6- (o-chloroaniline) -S-triazine, 2,4,5,6-tetrachloroisophthalic acid nitrile, p-dimethylaminophenyldiazo sodium sulfonate, 1 , 4-dichloro-2,5-dimethoxybenzene, manganese-ethylene-bis-dithiocarbamate, zinc-ethylene-bis-dithiocarbamate,

Coordination product of zinc and manganese-ethylene-bis-dithiocarbamate,

Methyl l- (butylcarbamoyl) -2-benzimidazole carbamate, 2- (4-thiazole) benzimidazole,

cis-N - [(trichloromethyl) thio] -4-cyclohexene-1,2-di-carboximide.

The application amounts given are based on the results presented here and are not described in such a broad manner that all possible cases are included, since numerous factors influence the use amounts. For example, the amount may vary not only between different plant species, but also within a certain species, for example depending on factors such as the plant size and the age of the plant, the particular compound used, the season, the type of soil and climatic conditions at the time of use, such as air temperature , Light intensity, rain and wind. Furthermore, if the compounds or the agents are used by soaking the soil, higher concentrations are necessary, since in this type of application the plant is treated indirectly compared to a direct treatment when the agent or the compound is applied to leaves and stems, for example by Spray on the plant.

The amount of active ingredient in plant growth regulating agents accordingly varies depending on the plants to be controlled, the required application amount, the type of application, the active ingredient used and the extent of control of the plant growth

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is sought. In general, the compositions contain less than 50% by weight of active ingredient in the ready-to-spray form.

Basically, the amount of active ingredient that is used is selected so that an effective control of plant growth is achieved. As already mentioned above, for example, the amount of active ingredient used to control the lawn causes a delay in the normal growth rate of 40-60%. Accordingly, the selection of the minimum amount used is determined by the minimum amount of active ingredient which is able to bring about the lowest limit of the desired growth retardation. The selection of the maximum use amount is determined accordingly by the amount of active ingredient which causes the upper limit of the desired growth retardation, i.e. in the case of grasses which are used for ornamental turf, the amount which avoids a barren appearance of the ornamental turf, but on the other hand prevents the turf from growing too quickly and does not cause undesired chlorosis (i.e. the grass turns yellow). For tomato plants, the criteria for effective growth retardation are different, since a dwarf plant that does not result in loss of fruit quality or quantity is particularly desirable. The parameters for an effective growth-regulating activity in such plants are delayed length growth and increased or non-delayed side growth as a minimum effect and delayed length and side growth as a maximum effect. The amount of active ingredient that meets these criteria or causes them is determined from such points of view, for example on the tomato plant. In order to achieve the greatest post-emergence growth-regulating effect, amounts of 0.5 kg to 20 kg or more are used per hectare. These amounts are based on the weight of the active compound. In the same way, the greatest post-emergence growth-regulating activity is generally obtained with amounts which are between 1 to 15 kg or more of active ingredient per hectare. A preferred dosage interval for spray solutions is between 10 to 100,000 ppm depending on the plant species to be treated and the compound selected for it. A particularly preferred dosage is generally between 100 and 20,000 ppm.

Another advantage of using the active substances according to the invention is the absence of any permanent effect on the plants or of a regulating effect which remains in the soil. These compounds decompose slowly and there is a consequent decrease in activity. This effect has advantages because a) a short-term effect that can be extended by subsequent further treatment is achieved;

b) the normal growth conditions of the plant resume as the activity decreases; and c) there are no harmful residues either on the plant or in the soil.

The length of the delay effect varies depending on the compound used and other factors such as the type of plant treated, climatic conditions, etc.

Although the compounds according to the invention have a plant growth-regulating and herbicidal activity, they are practically non-toxic to animals. For example, in rats the acute toxicity is above 5000 mg / kg for sodium 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate. The decomposition products, initially 2-keto-D-gluconic acid and finally carbohydrates, are also non-toxic.

It goes without saying that not all compounds encompassed by formulas I and II are active against all plants. However, each of the active connections shows in

Activity against a specific plant or plants, and this activity is a function of the compound. As will be described in more detail below, a particular advantage of the present invention is that the growth-regulating agents, when used for the treatment of different plants, develop pre-emergence and post-emergence growth-regulating activity and herbicidal activity, the spectrum of the plants in question being extremely broad. The growth-regulating activity of the active compounds is underpinned by the subsequent micro-experiments to determine the activity of the post-run effect.

The growth-retarding effect of 2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconic acid and salts and esters of this compound in various plants is demonstrated below by greenhouse experiments.

The compounds to be investigated can be formulated as kaolin as an inert diluent as a 25% wettable powder and suspended in water. However, these compounds can also be formulated as a 2% solution in acetone containing 1% wetting agent. This solution is diluted with an equal amount of water shortly before spraying.

In the method used, seeds of the plants to be examined are sown in 450 ml plastic pots with sterilized clay soil, which has known physical properties. The moment of sowing is selected so that all plant species reach a growth stage at the same time, which is suitable for the investigations. Before the compounds to be examined are used, the plants are cut to a certain height (simulated mowing). The plants are kept in the greenhouse before and after application of the compounds to be examined. Mercury lamps produce 16 hours of light a day. The test substances are applied by spraying, the amount to be sprayed being 1000 liters per hectare.

The growth-regulating effects are measured after 2 to 4 weeks. The post-emergence growth retarding effect is determined by measuring the height of the youngest fully developed leaf. The result can be expressed in percentages by comparing the values found for a treated and an untreated plant.

The test results are summarized in Tables I to IX below:

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TABLE I

Post-emergence growth-retarding effect on Poa pratensis.

TABLE II

Post-emergence growth-retarding effect on Poa Pratensis

Grass height, cm, 26 compound (formulated as a 25% net powder after treatment) dose dose

6 kg / ha 3 kg / ha

Compound (formulated as a 2% solution in acetone)

2-propynyl 2,3: 4,5-di-O-isopropyl-idene-2-keto-D-gluconate

9.7

17.5

Ethyl 2,3: 4,5-di-O-isopropylidene - 2-keto-D-gluconate

11.2

13.7

n-Pentyl 2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate

12.0

13.2

4-chlorobutyl 2,3: 4,5-di-O-isopropyl-iden-2-keto-D-gluconate

11.5

13.8

2-chloroethyl 2,3: 4,5-di-O-isopropyl-idene-2-keto-D-gluconate

12.8

14.0

n-Octyl 2,3: 4,5-di-O-isopropylidene-2-keto-D-gluuconate

13.2

13.3

n-Propyl 2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate

12.3

18.7

Sodium 2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate

8.2

11.5

n-Dodecyl 2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate

13.0

14.5

n-Butyl 2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate

13.5

15.7

3-chloropropyl 2,3: 4,5-di-O-isopropyl-iden-2-keto-D-gluconate

12.2

13.2

n-Decyl 2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate

13.7

14.3

Methyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate

15.0

12.7

n-Nonyl 2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate

16.2

15.2

n-Hexyl 2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate

17.3

13.0

Allyl 2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate

15.7

17.5

Potassium 2,3: 4,5-di-O-isopropylidene - 2-keto-D-gluconate

9.2

14.3

Control (untreated)

17.3

17.3

10th

Grass height compared to control%, 14 days after treatment dose dose 8 kg / ha 4 kg / ha

Potassium 2,3: 4,5-di-O-isopropyl

iden-2-keto-D-gluconate 29 43

I5 ammonium 2,3: 4,5-di-O-isopropyl-idene-2-keto-D-gluconate 27 37

Methyl 2,3: 4,5-di-O-isopropyl-

iden-2-keto-D-gluconate 75 88

20 ethyl 2,3: 4,5-di-O-isopropyl

iden-2-keto-D-gluconate 37 57

n-propyl 2,3: 4,5-di-O-isopropyl

iden-2-keto-D-gluconate 77 96

25 n-pentyl 2,3: 4,5-di-O-isopropyl-iden-2-keto-D-gluconate 63 88

2-propynyl 2,3: 4,5-di-O-isopropyl-iden-2-keto-D-gluconate 73 78

30 benzyl 2,3: 4,5-di-O-isopropyl

iden-2-keto-D-gluconate 89 86

3-chloropropyl 2,3: 4,5-di-O-isopropyl-iden-2-keto-D-gluconate 86 92

35 Allyl 2,3: 4,5-di-O-isopropyl-iden-2-keto-D-gluconate 94 95

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TABLE III

Post-emergence growth-retarding effect on Lolium Perenne

45

Compound (formulated as a 25% wettable powder)

Grass height, cm, 26 days after treatment dose dose 12 kg / ha 6 kg / ha so sodium 2,3: 4,5-di-O-isopropyl-iden-2-keto-D-gluconate n-octyl 2,3: 4,5-di-O-isopropyl-idene-2-keto-D-gluconate

55 4-Chlorobutyl 2,3: 4,5-di-O-isopropyl-iden-2-keto-D-gluconate

Ammonium 2,3: 4,5-di-O-isopropyl-idene-2-keto-D-gluconate

60 n-pentyl 2,3: 4,5-di-O-isopropyl-iden-2-keto-D-gluconate n-butyl 2,3: 4,5-di-O-isopropyl-iden-2-keto- D-gluconate

65

n-Hexyl 2,3: 4,5-di-O-isopropyl-idene-2-keto-D-gluconate

17.0 19.3 19.7 20.3 20.0 20.3 20.0

22.0 20.7 21.3 20.7 23.0 21.0 20.7

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TABLE III (continued)

TABLE IV (continued)

Compound (formulated as a 25% wettable powder)

Grass height, cm, 26 days after treatment

Dose Dose 12 kg / ha 6 kg / ha

Compound (formulated as a 25% 5 wettable powder)

Grass height, cm, 27 days after treatment

Dose dose 12 kg / ha 6 kg / ha n-decyl 2,3: 4,5-di-O-isopropyl-

iden-2-keto-D-gluconate 20.8 22.0

2-chloroethyl 2,3: 4,5-di-O-isopropyl-

iden-2-keto-D-gluconate 20.0 22.3

Allyl 2,3: 4,5-di-O-isopropyl

iden-2-keto-D-gluconate 21.3 21.7

Methyl 2,3: 4,5-di-O-isopropylidene

-2-keto-D-gluconate 20.7 22.0

Ethyl 2,3: 4,5-di-O-isopropylidene

-2-keto-D-gluconate 20.7 20.7

n-dodecyl 2,3: 4,5-di-O-isoprópyliden-

-2-keto-D-gluconate 22.0 22.0

Control (Untreated) 22.3 22.3

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n-Propyl 2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate

2-chloroethyl 2,3: 4,5-di-O-isopropyl-idene-2-keto-D-gluconate

Methyl 2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate

15 ..

Ethyl 2,3: 4,5-di-O-isopropylidene - 2-keto-D-gluconate

Control (untreated)

30.3

28.7

33.3

34.7 35.3

30.0

30.7

33.0

31.3 35.3

20th

TABLE V

Post-emergence growth retarding effect on Triti-cum aestivum «Probus»

25th

TABLE IV

Post-emergence growth-retarding effect on Digitaria sanguinalis.

Compound (formulated as a 25% wettable powder)

Plant height, mm, 29 days after treatment dose dose 6 kg / ha 2 kg / ha

30th

Compound (formulated as a 25% wettable powder)

Grass height, cm, 27 days after treatment dose dose 12 kg / ha 6 kg / ha

35

Ammonium 2,3: 4,5-di-O-isopropyl

iden-2-keto-D-gluconate 11.3 30.3

Potassium 2,3: 4,5-di-O-isopropyl

iden-2-keto-D-gluconate 9.7 33.0 sodium 2.3: 4,5-di-O-isopropyl-

iden-2-keto-D-gluconate 9.0 29.7 n-pentyl 2,3: 4,5-di-O-isopropyl-

-iden-2-keto-D-gluconate 22.0 25.7

4-chlorobutyl 2,3: 4,5-di-O-isopropyl-

iden-2-keto-D-gluconate 26.0 26.7

3-chloropropyl 2,3: 4,5-di-O-isopropyl-

iden-2-keto-D-gluconate 20.0 26.7

2-propynyl 2,3: 4,5-di-O-isopropylidene

-2-keto-D-gluconate 26.3 30.7

n-decyl 2,3: 4,5-di-O-isopropylidene

-2-keto-D-gluconate 26.7 29.7

Allyl 2,3: 4,5-di-O-isopropylidene

-2-keto-D-gluconate 27.3 32.0

n-butyl 2,3: 4,5-di-O-isopropylidene

-2-keto-D-gluconate 27.7 29.7

n-hexyl 2,3: 4,5-di-O-isopropylidene

-2-keto-D-gluconate 28.0 30.3

n-octyl 2,3: 4,5-di-O-isopropylidene

-2-keto-D-gluconate 29.0 31.0

40

45

50

55

n-Butyl 2,3: 4,5-di-O-isopropyl-idene-2-keto-D-gluconate

Potassium 2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate

Ammonium 2,3: 4,5-di-O-isopropyl-idene-2-keto-D-gluconate

Sodium 2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate

4-chlorobutyl 2,3: 4,5-di-O-isopropyl-iden-2-keto-D-gluconate

Ethyl 2,3: 4,5-di-O-isopropylidene ■ 2-keto-D-gluconate n-decyl 2,3: 4,5-di-O-isopropylidene - 2-keto-D-gluconate n- Nonyl 2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate

Allyl 2,3: 4,5-di-O-isopropylidene - 2-keto-D-gluconate n-hexyl 2,3: 4,5-di-O-isopropylidene - 2-keto-D-gluconate n- Pentyl 2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate

60:

65

3-chloropropyl 2,3: 4,5-di-O-isopropyl-idene-2-keto-D-gluconate

2-propynyl 2,3: 4,5-di-O-isopropylidene - 2-keto-D-gluconate n-dodecyl 2,3: 4,5-di-O-isopropylidene - 2-keto-D-gluconate

Control (untreated)

78 73 75 75 85

92

93 95 93

97

98

98

98

97 100

87

82

75

80

87

90

100

93

93

85

90

90

92

100 100

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TABLE VI

Post-emergence growth-retarding effect on Hor-deum distichon «Nymph»

TABLE VII (continued)

Compound (formulated as a 25% 5 wettable powder)

Compound (formulated as a 25% wettable powder)

Plant height, cm, 24 days after treatment dose dose 6 kg / ha 2 kg / ha

Plant height, mm, 25 days after treatment dose "dose 6 kg / ha 1.5 kg / ha n-butyl 2,3: 4,5-di-O-isopropyl-

iden-2-keto-D-gluconate 24.9 34.2 n-hexyl 2,3: 4,5-di-O-isopropyl-

iden-2-keto-D-gluconate 27.6 38.0 n-pentyl 2,3: 4,5-di-O-isopropyl-

iden-2-keto-D-gluconate 33.4 41.4

2-chloroethyl 2,3: 4,5-di-O-isopropyl-

iden-2-keto-D-gluconate 25.8 37.8

Allyl 2,3: 4,5-di-O-isopropylidene

-2-keto-D-gluconate 34.3 40.0

2-propynyl 2,3: 4,5-di-O-isopropyl-

iden-2-keto-D-gluconate 32.4 45.3

n-nonyl 2,3: 4,5-di-O-isopropylidene

-2-keto-D-gluconate 27.7 38.0

n-propyl 2,3: 4,5-di-O-isopropylidene

-2-keto-D-gluconate 33.3 43.2

n-octyl 2,3: 4,5-di-O-isopropylidene

-2-keto-D-ghiconate 35.4 44.2

n-dodecyl 2,3: 4,5-di-O-isopropylidene

-2-keto-D-gluconate 38.2 44.1

Control (untreated) 44.2 44.2

10th

Ammonium 2,3: 4,5-di-O-isopropylidene - 2-keto-D-gluconate n-dodecyl 2,3: 4,5-di-O-isopropylidene - 2-keto-D-gluconate

Sodium 2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate

15

n-Decyl 2,3: 4,5-di-O-isopropylidene '-2-keto-D-gluconate

20th

25th

n-octyl 2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate i

n-Hexyl 2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate

Allyl 2,3: 4,5-di-O-isopropylidene - 2-keto-D-gluconate n-butyl 2,3: 4,5-di-O-isopropylidene - 2-keto-D-gluconate

Potassium 2,3: 4,5-di-O-isopropylidene-30 -2-keto-D-gluconate

Control (untreated)

Alar

(N-dimethylaminosuccinic acid 35 semihydrazide)

150

148

150

152

160

158

162

168

165 181

148

158 153 150 150

150

162

130

120

153 181

151

TABLE VII

Post-emergence growth-retarding effect on Malus silvestris (apple).

TABLE VIII

Post-emergence growth-retarding effects on Vitis 40 vinifera

Compound (formulated as a 25% wettable powder)

Plant height, mm, 25 days after treatment dose dose 6 kg / ha 1.5 kg / ha

Compound (formulated as a 2% solution in acetone)

Concentration ppm

% Plant height compared to control

45 ■

n-pentyl 2,3: 4,5-di-O-isopropyl

iden-2-keto-D-gluconate 132 160

Methyl 2,3: 4,5-di-O-isopropyl-

iden-2-keto-D-gluconate 132 167

Ethyl 2,3: 4,5-di-O-isopropyl-

iden-2-keto-D-gluconate 135 147

2-chloroethyl 2,3: 4,5-di-O-isopropyl-iden-2-keto-D-gluconate 138 157

n-Nonyl 2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate 138 168

n-Propyl 2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate 135 163

4-chlorobutyl 2,3: 4,5-di-O-isopropyl-iden-2-keto-D-gluconate 145 157

3-chloropropyl 2,3: 4,5-di-O-isopropyl-idene-2-keto-D-gluconate 140 138

Potassium 2,3: 4,5-di-O - isopropylidene-2-keto-D - gluconate

50 methyl 2,3: 4,5-di-O-iso-propylidene-2-keto-D-glu-conate

Ethyl 2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate

55

n-Propyl 2,3: 4,5-di-O-iso-propylidene-2-keto-D-gluconate n-pentyl 2,3: 4,5-di-O-iso-propylidene-2-keto-D -glu-60 conat n-octyl 2,3: 4,5-di-O-iso-

propylidene-2-keto-D-glu

conat

65 ammonium 2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate

4000 1000

4000 1000

4000 1000

4000 1000

4000 1000

4000 1000

4000 1000

40 51

69 80

68 83

57 75

36 41

39 65

39 65

618 845 14

TABLE IX

Post-emergence growth retarding effect of 10 compounds of the formula I on various plants expressed as% for control.

Connection S »,., Sin.pl, D,« »» Da. ™

2,3: 4,5-di-O-isopropylidene

-2-keto-D-gluconic acid 20 40 80 - 60 40 - - 30 50

Potassium 2,3: 4,5-di-O-iso-

propylidene-2-keto-D-gluconate 10 40 - ■ - 30 60 - 50 30 10

Ammonium 2,3: 4,5-di-O - isopropylidene-2-keto-D-glu

conat - 20 - - 50 50 40 30 30 10

2-propynyl 2,3: 4,5-di-O - isopropylidene-2-keto-D-glu

conat 20 50 10 - - • 40 60 10 - -

n-pentyl 2,3: 4,5-di-O-iso-

propylidene-2-keto-D-gluconate - 60 20 30 - 80 - - - 20

3-chloropropyl 2,3: 4,5-di-O - isopropylidene-2-keto-D-glu-

conat 20 60 30 20 - 30 - - - -

n-octyl 2,3: 4,5-di-O-iso-

propylidene-2-keto-D-gluconate 10 60 30 - - 50 - - 10 - allyl 2,3: 4,5-di-O-isoprop-

pylidene-2-keto-D-gluconate -'30 10 - - 20 30 - - 10

n-propyl 2,3: 4,5-di-O-iso-

propylidene-2-keto-D-gluconate - 50 30 - - 40 - - - - benzyl 2,3: 4,5-di-O-isoprop-

pylidene-2-keto-D-gluconate - 10 - - - 20 40 - - -

The post-emergence growth-retarding effect of 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconic acid is investigated in various plants.

The plants to be examined are grown in plastic pots containing mixed fertilizers. The 45 seeds are sown in such a way that all plant species simultaneously reach the growth stage suitable for the study. The plants are grown in greenhouses and remain in them throughout the trial. Mercury lamps are used to produce 50 lights per day for 16 hours.

The compound to be investigated is formulated as a wettable powder using kaolin as an inert diluent as follows:

1% 2,3: 4,5-di-0-isopropylidene-2-keto-D-glucon-55

acid 2.5% kaolin

96% water and small amounts of wetting and anti-foaming agents.

This suspension is sprayed onto the plants in amounts of 10 kg / hectare of active compound. 21 days after spraying, the growth delay is determined by measuring the plant height and comparing it with the height of a 65 untreated plant.

The test results are summarized in Table X below.

TABLE X

Plant height, mm, 21 days after spraying

Plant species

control

2.3; 4,5-di-O-iso-propylidene-2-keto-D-gluconic acid

Avena fatua

400

420

Echinochloa crus-galli

360

260

Fagopyrum vulgare

430

150

Sorghum vulgare

200

160

Sinapis alba

300

130

Setaria faberii

280

90

Datura stramonium

160

120

Alopecurus pratensis

380

80

Chrysanthemum segetum

130

60

Rumex obtusifolius

200

70

Stellaria media

150

100

Daucus carota

170

160

15

618845

These data illustrate the growth retardant effect of 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconic acid in various plants. For example, Alopeeu-rus pratensis, a grass that is very similar to lawn grass, has a very good delay without chlorosis (yellowing of the grass). Chrysanthemum se-getum achieves very good plant regulation without any damage to the plant.

Tables XI and XII below show the post-emergence and pre-emergence growth-inhibiting effects of an aqueous solution of ammonium-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconic acid in 12 crops and harmful plants - summarized.

The ammonium salt is diluted with deionized water containing 1% Tween 20 (polysoxysorbitan monostearate) as a surface active agent, the pH being adjusted to 7.0. In both cases, atrazine [-2-chloro-4- (ethylamino) -6- (isopropylamino) -5-triazine] was used as a comparative substance in the studies on post-emergence and pre-emergence growth-retarding effects. The atrazine is applied at a dose of 2 kg / ha in solution in an acetone, methanol and DMF mixture (90: 80: 2 v / v).

The various useful and harmful plants are sown in 7.5 cm high plastic pots.

When testing for post-emergence retarding effects, the seeds are preferably covered with sand rather than earth, which provides better sensitivity. The height of the earth layer is approximately 4.5 cm, while that of the sand layer is approximately 5-6 mm.

When examining the pre-emergence retarding effect, a sand-like loam soil is used and the moment of sowing is selected so that all plants simultaneously reach a suitable growth stage, usually the appearance of the first fully developed leaf.

Both the post-emergence tests and the pre-emergence tests are carried out at a dose of 8 kg of active ingredient per hectare. The pre-emergence delaying effect is determined after 21 and 27 days and the post-emergence delaying effect 15 after 18 and 27 days.

The results of these tests are shown in Tables XI and XII, in which the delay effect is given numerically. The rating scale is defined as follows:

20 0 - no visible growth retardation

1, 2, 3 - slight delay, the plants show little or no reduction in growth in visible parts of the plant 4, 5, 6 - moderate growth delay, plants show 25 reduced growth in visible parts of the

plant

7, 8, 9 - severe delay, plants show little or no growth 10 - no growth.

TABLE XI

Pre-emergence growth-retarding effect of ammonium 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconic acid

Delaying effects After 21 days After 27 days

Plant NH + 4 salt gtndïd NH + * salt stnSrd

Cyperus esculentus

8th

4th

8th

5

Avena fatua

2nd

10th

1

10th

Datura stramonium

4th

5

2nd

9

Abutilon theophrasti

3rd

10th

3rd

10th

Sorghum halepense

5

0

4th

0

Amaranthus sp.

2nd

8th

2nd

9

Brassica kaber

3rd

10th

3rd

10th

Setaria glauca

6

9

6

9

Echinochloa crus-galli

6

10th

7

10th

Digitaria sanguinalis

6

10th

8th

10th

Cirsium arvense

4th

9

4th

10th

Ipomoea sp.

3rd

8th

2nd

10th

The ammonium salt of 2,3: 4,5-di-0-isopropylidene-2-65-keto-D-gluconic acid shows a good pre-emergence growth-retarding effect in certain plant species, e.g. Cyperus esculentus, Echinochloa crus-galli and Digitaria san-guinalis.

618 845 16

TABLE XII

Post-emergence growth-retarding effect of ammonium 2,3: -4,5-di-0-isopropylidene-2-keto-D-gluconic acid

Delaying effects After 18 days After 27 days

Plant nH + j salt atrazin gajz atrazin

■ anze 4 öalz standard 4 courts standard

Cyperus esculentus

5

10th

9

10th

Avena fatua

4th

10th

4th

10th

Datura stramonium

4th

10th

8th

10th

Abutilon theöphrasti

7

10th

5

10th

Sorghum halepense

5

5

7

4th

Amaranthus sp.

4th

8th

5

7

Brassica kaber

8th

10th

10th

10th

Setaria glauca

6

9

5

10th

Echinochloa crus-galli

6

10th

8th

10th

Digitaria sanguinalis

8th

9

9

10th

Cirsium arvense

5

10th

7

10th

Ipomoea sp.

9

10th

9

10th

At a dose of 8 kg / ha, the ammonium salt of 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconic acid shows a very good post-emergence growth-retarding effect in most of the plant species examined, especially in Cyperus esculentus , Echinochloa crusgalli and Digitaria sangui- 35 nalis.

It has also been found that a growth regulating agent containing one of the compounds of general formulas I, II, III and IV, when sprayed onto fruiting trees, significantly increases the force that must be used to separate the fruit from the stem reduced.

This is the result of a comparison with untreated trees. It has also been found that fruits harvested with the aid of the growth regulators according to the invention are relatively free from injuries and rotting 45.

The agents according to the invention can be applied to the fruit-bearing trees in liquid or solid formulations. The application can follow over the roots, the stems, the branches, the leaves or the fruits. For example, the fruit dropping agents according to the present invention can be sprayed or dusted onto the trees from the aircraft, or applied to the base of the trees so that these agents are absorbed by the roots. A preferred method of use and also the most effective is to apply the agents in the form of an aqueous spray solution. If desired, a formulation based on a suitable organic solvent, such as an oily spray solution, can be used. 60

In order to achieve the greatest effect when using the normal fruit dropping agents according to the present invention, the agent is preferably used one to two weeks before the fruit is harvested, depending on the temperature. In areas where rain must be expected, namely in the period between the application of the product and the harvest, it is advisable to add a conventional adhesive to the formulations. Typical examples of such adhesives include, for example, glue, casein, salts of alginic acid, cellulose gum and corresponding derivatives, polyvinylpyrrolidone, invert syrup, grain syrup, etc.

The fruiting agents according to the invention contain compounds of the formulas I, II, III and IV as the active ingredient. If desired, conventional, inert materials such as those used in agriculture can be used, in particular if the agents in question are used to treat trees and also in conjunction with active ingredients of known fruiting agents come into use, are mixed. Such auxiliaries also include, for example, surface-active compounds, carrier materials, adhesives, stabilizers, etc.

The concentration of active ingredient of the general formulas I, II, III and IV in the new fruit products according to the present invention vary; but in order to achieve an optimal effect it is necessary that a sufficient amount is used. For example, an aqueous spray solution contains from about 0.05% to about 1.5% (weight percent) of active ingredient. The concentration obviously varies depending on the fruit and the size of the tree or bush. The dosage is the one that actually makes harvesting easier. In the case of spray solutions, the aqueous solution containing the fruit drop agent is sprayed in such a way that the tree is covered with a complete spray coating. This requires the use of approximately 300 to approximately 9000 liters of a dilute solution [approximately 0.1-1% (weight percent) active ingredient] per hectare, depending on the number and size of the trees to be treated.

In order to prepare a preferred spray formulation which contains the fruit-falling agent according to the present invention, the active ingredient or a salt thereof is dispersed or dissolved in a carrier such as water. From 0.1% to about 0.5% (weight percent) based on the weight of the carrier material, surfactant can be added to the liquid spray solution. Typical surfactants are Triton®-B-1956, a water-dispersible resin

17th

618845

based surface-active agent that is manufactured by Rohm and Haas. Furthermore, X-77 (Chevron-Ortho), a non-ionic surface-active agent which contains alkylaryl-polyoxyethylene glycols, free fatty acids and isopropanol as the basic substance, can be used.

The fruit dropping agents according to the present invention cause the fruit to fall from a whole number of fruit trees. Typical fruits of this type are, for example, orange, grapefruit, olives, apples, cherries, tomatoes, etc. They also work in conjunction with other crops, such as cotton and soybeans (here leaf falls).

As already mentioned, the fruit dropping agents are sprayed onto the trees in the form of aqueous solutions.

In this regard, the invention also includes equivalent amounts of water-soluble salts of compounds of formulas I and II. Such salts include, for example, the sodium salt, the potassium salt, the ammonium salt, etc.

The fruiting agents according to the invention are adjusted to a pH of 6-10 by means of a buffer, for example by adding potassium hydrogen sulfate to the aqueous solution.

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

Wettable powders are made using an inert diluent such as kaolin. A typical spray solution formulated with a wettable powder contains, for example, the active ingredient, about 1% to about 5% of inert diluent, minor amounts of dispersant, wetting agent and anti-foaming agent, and the appropriate and necessary amount of water.

The effect of the new fruit dropping agents is illustrated below on Phaseolus vulgaris.

The compounds to be examined are formulated as a wettable powder and mixed with lanolin. The lanolin paste obtained contains 5000 or 1000 ppm of active substance.

In the method used, seeds of the plant to be examined are 1.5 cm deep in a small plastic pot, which is a mixture with known physical and chemical properties consisting of 50% sterilized clay soil and 50% Optimasoil (80% peat and 20% clay and fertilizer ) contains, sown. 14 days later, when the first leaves are fully formed, the seedlings are cut just above the surface of the soil. The stem is cut 2 cm above the seed lobe. The petioles of the first leaves are cut to a length of 0.5 cm and treated with the lanolin paste. The stems of the plants are placed in a small container filled with tap water in the greenhouse for five days. The examinations are repeated 8 times for each dose. The growth-regulating effect is measured 4 and 6 days after treatment.

The falling of the petioles is measured by counting the non-fallen petioles. The fall effect is expressed in percentages by comparison with the effect measured on an untreated plant.

The test results are summarized in Table XIII below.

TABLE XIV Fall effect on Phaseolus vulgaris

connection

% Petiole fall concentration (ppm) 5000 1000

Sodium 2,3: 4,5-di-O-isopropyl-io-iden-2-keto-D-gluconate

2-propynyl 2,3: 4,5-di-O-isopropyl-idene-2-keto-D-gluconate

Ammonium 2,3: 4,5-di-O-isopropyl-15 iden-2-keto-D-gluconate

Allyl 2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate n-pentyl 2,3: 4,5-di-O-isopropyl-20 idene-2-keto-D-gluconate n-Propyl 2,3: 4,5-di-O-isopropyl-idene-2-keto-D-gluconate

25th

n-Hexyl 2,3: 4,5-di-O-isopropyl-iden-2-keto-D-gluconate n-dodecyl 2,3: 4,5-di-O-isopropyl-iden-2-keto-D -gluconate

30 n-butyl 2,3: 4,5-di-O-isopropyl-iden-2-keto-D-gluconate n-octyl 2,3: 4,5-di-O-isopropyl-iden-2-keto- D-gluconate

35 3-Chloropropyl 2,3: 4,5-di-O-iso-propylidene-2-keto-D-gluconate

4-chlorobutyl 2,3: 4,5-di-O-isopropyl-iden-2-keto-D-gluconate

40 2-chloroethyl 2,3: 4,5-di-O-isopropyl-idene-2-keto-D-gluconate

55 70 50 45 45 20 20 25 20 15 15 5 0

40 15 50 40 45 15 15 20 15 20 15 5 5

Whether used as a fruit dropping agent or as a pre-emergence or 45 post-emergence herbicide, i.e. once used as plant growth regulators, the compounds of formulas I, II, III and IV can be prepared and formulated as described above and below. 50 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconic acid monohydrate is a well-known commercial preparation. It is produced by oxidation of 2,3: 4,5-di-O-isopropylidene-β-D - fructopyranose, which in turn is obtained by reacting D-fructose with acetone in the presence of a strong acid 55. The process for making diisopropylidene fructopyranose is illustrated by U.S. Patent No. 3,607,862.

The new compounds of formula I can be prepared by 60 a) an acid of the general formula

65

618845

18th

OH

R

1

wherein R 1, R 2, R 3 and R 4 have the meaning given in formula I,

with a compound of the general formula

X — R5 VI

wherein X is chlorine, bromine or a p-toluenesulfonic acid ester and R5 alkyl; Alkenyl; Alkynyl; Hydroxy lower alkyl; lower alkoxy lower alkyl; lower alkenyloxy lower alkyl; lower alkynyloxy lower alkyl; lower alkylsulfonyloxy lower alkyl; Arylsulfonyloxy lower alkyl; Benzyl, optionally substituted with one or two lower alkyl, lower alkenyl, lower alkynyl, lower alkoxy, halo-lower alkyl, formyl, lower alkylcarbonyl, lower alkoxycarbonyl, cyano, halogen, nitro, hydroxy, lower alkoxyformamido, ureido, methylenedioxy, amino or amino substituted with mono- or di-lower alkyl; Halo-lower alkyl; Halo-lower alkenyl; Halo-lower alkynyl; lower alkoxycarbonyl-lower alkyl; Phosphono lower alkyl; Thiophosphono lower alkyl; lower alkylaminocarbonyl lower alkyl; lower alkylthio-lower alkyl; Arylthio-lower alkyl; Cycloalkyl, optionally substituted with halogen, nitro, lower alkyl or lower alkoxy; Phenoxy-lower alkylcarbonyloxy-lower alkyl, where the phenoxy group may optionally be substituted with mono- or di-lower alkyl with one or two nitro, lower alkyl, halogen, cyano, lower alkoxycarbonyl, lower alkylcarbonyl, methylenedioxy, amino or amino; Morpholino lower alkyl; Thiomorpholino lower alkyl; Piperazino lower alkyl; Phenylamino-lower alkyl or benzylamino-lower alkyl, where the phenyl group is optionally substituted by halogen; Amino lower alkyl; Amino-lower alkyl substituted with mono- or di-lower alkyl, hydroxy-lower alkyl, halo-lower alkyl, halophenyl, cyclopentyl or cyclohexyl; Hydrazino lower alkyl; Means furyl or furyl-lower alkyl,

in the presence of a base, or b) if a compound of the formula II in which n is the number 2 is desired, an acid of the formula V with a compound of the general formula

Xx-R0-X2 VII

where Xt and X2 are chlorine, bromine or iodine and R0 is lower alkylene,

reacted in the presence of a base, or c) an acid chloride corresponding to formula V with an alcohol of the general formula

HO — R'5 VIII

wherein R'5 aryl, optionally substituted with one, two or three lower alkyl, lower alkenyl, lower alkynyl, lower alkoxy, halo-lower alkyl, formyl, lower alkylcarbonyl, lower alkoxycarbonyl, cyano, halogen, nitro, hydroxy, lower alkoxyformamido, Ureido, methylenedioxy, amino or amino substituted with mono- or di-lower alkyl means, or d) in the event that a compound of the formula II is sought, in which n is the number 2, an acid halide corresponding to the formula V with a diol of the general formula

HO — Re — OH IX

wherein RG has the meaning given in formula VII, or e) reacting an acid of formula V with an alcohol of formula VIII in the presence of p-toluenesulfonic acid chloride and pyridine, or f) reacting an acid of formula V with an alcohol of formula VIII in the presence of dicyclohexylcarbodiimide in an inert solvent, or g) in the event that a salt of the formula II is sought, in which n is 1 and R 'is hydrazinium; Morpho-linium; Thiomorpholinium; Piperazinium; Ammonium; Ammonium substituted with one or more lower alkyl, lower alkenyl, lower alkynyl, cycloalkyl having 3 to 6 carbon atoms, aryl or benzyl, optionally substituted with halogen, nitro, lower alkyl or lower alkoxy; Halo-lower alkyl or hydroxy-lower alkyl means an acid of the general formula V with a compound of the general formula

R7

Nd X

I Rs

R9

wherein R7, R8 and Rg are hydrogen, lower alkyl, lower alkenyl, lower alkynyl, cycloalkyl having 3 to 6 carbon atoms, halo-lower alkyl, hydroxy-lower alkyl, aryl or benzyl, optionally substituted with halogen, nitro, lower alkyl or lower alkoxy means

or with hydrazine, morpholine, thiomorpholine or piperazine or, if n is 2, in contact with calcium hydroxide or magnesium hydroxide.

The salts of 2,3: 4,5-di-0-isopropylidene-2-keto-D-glu-cons acid are prepared in the usual way. For this purpose, this compound is added to a suitable base solution at room temperature with vigorous stirring. In this process, the solution is kept at a pH above 7. After the reaction has ended, the excess water is removed under high vacuum. Anhydrous acetone (approximately 10 parts by volume) is then added to the resulting syrup and stirred overnight. The white crystalline precipitate that forms is filtered, washed with acetone and dried. In the case of non-volatile bases, equivalent amounts of acids are added. If volatile bases are used, for example ammonium hydroxide or dimethylamine, an excess of base is used, and the unreacted excess is then evaporated off in vacuo.

Since the acid is not stable under the usual esterification conditions, such as the esterification according to Fischer, the new esters are prepared by reaction with, for example, the corresponding lower alkyl, lower alkenyl or lower alkynyl halides under basic conditions at room temperature by inerting organic solvents such as dimethylformamide (DMF) are used. The esters are largely 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 VIII is preferably in pyridine as Lö5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

19th

618845

solvent and in the presence of equivalent amounts of p-toluenesulfonic acid chloride. The mixture is heated to a temperature interval of approximately 5 ° to approximately 50 °, preferably room temperature (see also J. Am. Chem. Soc. 77, 6214 (1955)).

Furthermore, an acid of formula V can be reacted with an alcohol of formula VIII by reacting these reactants in the presence of an equimolar amount of dicyclohexylcarbodiimide in an inert organic solvent. Preferred solvents are methylene chloride, dimethylformamide, ether, tetrahydrofuran or ethyl acetate [cf. also Tetrahedron 21, 3531 (1965)].

Solutions consisting of a solvent and a compound according to the invention are suitable for greenhouse tests, but are not particularly useful for field tests. Wetting powders are also not generally usable, since the compounds must be solubilized so that they can develop the necessary activity. The acid is therefore preferably produced as a soluble powder in combination with buffering agents, since a removal at a pH of 6-10 is essential for the acid. The acid can also be formulated as an emulsion concentrate using N-methyl-2-pyrrolidone or nitropyrrolidone as shown below:

% (Weight percent) of the total formulation

2,3: 4,5-di-O-isopropylidene

-2-keto-D-gluconic acid 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 alkylaryl sulfonates.

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

The esters of formula I are formulated as emulsifiable concentrates based on xylene, which can then be mixed with water. These concentrates can be used to produce emulsions which contain 25 to 50 percent by weight of active ingredient. Typical emulsifiable concentrates for these esters are given below.

Weight percent of the total mixture

Active ingredient

25th

50

Xylene

71

46

Atlox 3403

2nd

-

Atlox 3404

2nd

-

Emulphor EL 620

-

2nd

Drewmulse GMC-8

-

2nd

Atlox 3403 is a mixture of polyoxyethylene ethers, polyoxyethylene glycerin 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.

Drewmulse GMC-8 is the monoglyceride of a low-5 molecular, saturated coconut fatty acid.

A concentrated solution consisting of sodium 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate (95% by weight) and sodium dioctyl sulfosuccinate (5% by weight) is prepared and spray dried. A wettable io powder that is completely soluble in water is obtained.

In a further embodiment, finely powdered sodium 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate is mixed with pumice stone granules. 10% of the weight of this mixture of water was added to this dry mixture. A portion of the sodium salt of 2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconic acid is now dissolved and serves as a means to remove the undissolved sodium 2,3: 4,5-di- To bind 0-isopropylidene-2-keto-D-gluconate to the pumice stone granules.

In a further embodiment, an equimolar amount of diethanolamine is added to an aqueous solution of 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconic acid with stirring. A clear solution is obtained, the pH of which is adjusted to 8, by adding diethanolamine dropwise to 25.

In a further embodiment, ammonia (25% equimolecular amount) is added to an aqueous solution of 2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconic acid with stirring. A clear solution is obtained whose pH 30 is adjusted to 8 by adding ammonia (25%) dropwise.

Compounds in which the 4,5-O-isopropylidene group is replaced by another grouping are produced by the so-called “ketal exchange reaction”. For this purpose, 2,3: 4,5-di-0-isopropylidene-2-keto-D-glu-cons acid is dissolved in the desired ketone, aldehyde, ketal or acetal and an acid catalyst is added. These compounds can also be prepared by using a similar ketal exchange reaction and using 2,3: 4,5-di-O-iso-40 propylidene-β-D-fructopyranose as the starting material and then oxidizing the product obtained .

Representatives of the ketones and aldehydes which can be used in the preparative process are those of the general formula in which R10 can be, for example, methyl, ethyl, lower alkylphenyl or p-methoxyphenyl and Rn can be methyl, ethyl, lower alkyl or hydrogen. Typical compounds of this type are, for example, diethyl ketone, methyl ethyl ketone, paraldehyde, benzaldehyde and p-methoxyaldehyde. Ketones, in which the two residues R10 and Rn are very large, have not proven to be particularly favorable, since these residues hinder the reaction sterically. If an unsymmetrical aldehyde or ketone is used, the more voluminous residue is in the “exo” position (Ri in formula I) after the reaction has ended and is responsible for a new asymmetry center, so that any strong acid can be used as a catalyst. A preferred catalyst is perchloric acid. Other representatives of such acids are sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, methanesulfonic acid and trifluoromethanesulfonic acid.

65 A preferred temperature range for this reaction is between about -20 ° and about 50 °, with the range between 20 ° and 30 ° (room temperature) being particularly preferred.

618845

20th

Compounds in which both isopropylidene groups are replaced by other groups are prepared starting from sorbose by using the method described in Chem. Ber. 63.843 (1930). In this method, a suitable ketone or a suitable aldehyde is reacted with fructose in the presence of a strong acid as a catalyst, for example sulfuric acid, at room temperature or below room temperature. The intermediate product thus obtained is then oxidized in an alkaline or neutral reaction medium.

Perchloric acid, hydrochloric acid, p-toluenesulfonic acid, etc. is preferably used as the acid catalyst in the preparation of the di-O-alkylidene fructopyranose, with sulfuric acid being particularly preferred.

Since the reaction is exothermic, the process is carried out at room temperature or below room temperature, a particularly preferred temperature range being between approximately 0 ° and approximately -20 °.

In the subsequent production of the acid from the fructopyranose intermediate, the oxidation is carried out in a neutral or alkaline medium, using oxidizing agents such as sodium permanganate, potassium bichromate, potassium permanganate / potassium hydroxide and sodium hypochlorite / Ni2 +. The latter two oxidizing agents are preferred. Oxidation can also be catalytically accomplished using palladium or platinum and oxygen.

A suitable temperature range is between room temperature and 100 °, the range between approximately 50 ° and approximately 60 ° being particularly preferred.

In an analogous manner, one obtains of the general formula using ketones and aldehydes

R-12 C R-131

in which R12 can be halo-lower alkyl and R13 can be halo-lower alkyl or hydrogen, active compounds of the general formula I in which Ra and R2 or Rt, R2, Rä and R4 are halo-never-der alkyl.

The examples below illustrate the preparation of the active ingredients.

example 1

2,3: 4,5-di-O-isopropylidene-β-D-fructopyranose

A mixture of 200 g of D-fructose, 2 liters of acetone, 2 liters of pentane and 8 g of iron (III) chloride are mixed with stirring and heated to the reflux temperature. The resulting water is condensed and removed in a Dean-Stark water separator. After the theoretical amount of water has been removed, the mixture is cooled to 0 °, neutralized with 7 g of sodium hydroxide in 10 ml of water and filtered. The filtrate is treated with 10 g of Norit SG, filtered again and then concentrated to a syrup. Recrystallization from ether-pentane gives 164.4 g of 2,3: 4,5-di-O-isopropylidene-β-D-fructopyranose with a melting point of 94-95 °.

Example 2

Ammonium salt of 2,3: 4,5-di-0-isopropylidene-2-keto-D-gtuconic acid

26 g of 2,3: 4,5-di-O-isopropylidene-β-D-fructopyranose, which are described in Example 1, are added to a solution of 23.8 g of potassium hydroxide and 15.8 g of potassium permanganate in 250 ml of water with stirring was produced, added.

The solution is heated to 50 ° -60 ° with stirring and kept at this temperature for two hours. 15.8 g of potassium permanganate are then added and stirring is continued at 50 ° -60 ° overnight. The solution is filtered and the filtrate is concentrated to 125 g, cooled to 0 °, brought to pH 20 and extracted 3 times with methylene chloride. The methylene chloride is removed and concentrated ammonium hydroxide is added. Evaporation of the excess ammonia under vacuum gives the ammonium salt. Recrystallization from chloroform gives 13.5 g of ammonium 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconic acid with a melting point of 190 ° -200 °.

Example 3

Various disubstituted gluconic acids and their salts can be prepared analogously to Examples 1 and 2. Using diethyl ketone instead of acetone in Example 1, 2,3: 4,5-di-0- (3-pentylidene) -2-keto-D-glu-cons acid is produced. Using methyl ethyl ketone instead of acetone, 2.3: 4 , 5-Di-0- (2-butylidene) -2-keto-D-gluonic acid. With cyclohexanone, 2,3: 4,5-di-O-cyclohexyl-iden-2-keto-D-gluconic acid is produced. With chloral as the reagent, 2,3: 4,5-di-0- (2,2,2-trichloroethylidene) -2-keto-D - gluconic acid is produced. Similarly, other gluconic acid derivatives wherein R1 (R2, R3 and Rt are hydrogen, straight or branched hydrocarbyl, halo-lower alkyl or aryl, or when Ri and R2 together and R3 and R4 together represent saturated rings of 3 to 8 carbon atoms) can be prepared.

Example 4

Ethyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate

33.7 g of 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconic acid monohydrate and then 25 g of ethyl bromide are added to a solution of 19 g of anhydrous potassium carbonate in 75 ml of dimethylformamide with stirring at room temperature given. Stirring is continued for 3 days at room temperature. The mixture is then filtered to remove inorganic salts and the dimethylformamide is removed by distillation in vacuo (about 60 ° and about 10 torr). 20 ml of acetone are added to dissolve the remaining ether. Undissolved inorganic salts are filtered off. The filter cake is washed out with 10 ml acetone. The filtrate is added to the solution containing the ester and the crude product is isolated by vacuum distillation of the solvent. Vacuum distillation at 94 ° and 0.1 mm Hg gives 16.4 g of ethyl 2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate.

According to this generally applicable regulation, starting from 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconic acid and 1,2-dibromoethane in a molar ratio of 2: 1 the bis-ester: bis -2,3: 4,5-di-0-isopropylidene-2-keto-D - gluconate-ethylene glycol ester produced Using a molar ratio of 1: 1, 2-bromoethyl 2,3: 4,5 - di- O-isopropylidene-2-keto-D-gluconate.

Example 5

Methyl 2,3,4,5-di-0-isopropylidene-2-keto-D-gluconate

33.7 g of 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconic acid - monohydrate are added to a suspension of 10 g of anhydrous potassium carbonate in 75 ml of dimethylformamide with stirring, and then the solution with 25 g of methyl iodide are added. The mixture is stirred at room temperature for 3 days and then filtered to remove the inorganic salts. The dimethylformamide is distilled off in vacuo.

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618845

20 ml of acetone are added to the residue to bring the ester into solution. Undissolved inorganic salts are filtered off again. The filter cake is washed with 10 ml acetone. The filtrate is combined with the ester solution and then concentrated in vacuo to a syrup. Vacuum distillation at 92 ° and 0.1 mm Hg yields 19.4 g of liquid methyl 2,3: 4,5-di-0-isopropylidene-2-- keto-D-gluconate.

Example 6

n-butyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate

33.7 g of 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconic acid and then 25 g of n-butyl bromide are added to a suspension of 10 g of anhydrous potassium carbonate in 75 ml of dimethylformamide. The mixture is stirred for 3 days at room temperature, then filtered off and the inorganic salts are thus removed. The dimethylformamide is removed by vacuum distillation. 20 ml of acetone are added to the residue and any inorganic salts still present are filtered off. The filter cake is washed with 100 ml acetone. The filtrate is combined with the ester solution and concentrated in vacuo. Vacuum distillation at 96 ° C (0.1 mm) provides 19.7 g of n-butyl-2,3: 4,5-di-O-isopropyl-idene-2-keto-D-gluconate.

In a similar manner, further straight-chain and branched, aliphatic hydrocarbyl and halo-lower alkyl esters can be produced.

Example 7

S atrium-2,3-0-isopropylidene-4,5-0-ethylidene-2-keto-D - gluconate

48 g of 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconic acid are dissolved in 250 g of paraldehyde. Five drops of 70% perchloric acid are added and the reaction is then carried out for 12 days at room temperature under constant control by means of thin layer chromatography or gas-liquid chromatography. The solution is then added to 16.8 g of sodium bicarbonate slurried in 100 ml of water with vigorous stirring. Excess paraldehyde and excess water are distilled off in vacuo. The residue is recrystallized from alcohol / water and sodium 2,3-0-isopropylidene - 4,5-0-ethylidene-2-keto-D-gluconate is obtained. Physically chemical data (nuclear magnetic resonance spectrum, mass spectrum, infrared spectrum) refer to the following structure:

CH.

CH.

.COONa

CH.

3rd

In the same way as described above, other 2,3-0-isopropylidene-4,5-0- (R1-R2) -2-keto-D-gluconic acid

ren (structure I), in which the Rx and R2 substituents straight-chain or branched, aliphatic lower hydrocarbyl, halo-lower alkyl, aryl, or Rj and R2 together represent a saturated ring having 3-8 carbon atoms.

Example 8

2-chloroethyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate

6 g of 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconic acid (anhydrous) are dissolved in 14 ml of pyridine and 3.2 ml of methylene chloride and, with stirring and ice cooling, dropwise with 3.2 ml of thionyl chloride transferred. After 3 hours at room temperature, 5.9 ml of 2-chloroethanol are added to the reaction solution and the mixture is then stirred for a further 3 hours. The reaction solution is then taken up in methylene chloride and washed successively with ice-cold 2 N hydrochloric acid, 2 N sodium hydroxide solution and water, 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, bp. 129 ° C / 0.02 torr.

The following compounds can be prepared analogously to the examples above:

p-nitrophenyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-glu-conate;

n-hexyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate, bp 163-164 ° (0.02 mm Hg);

p-chlorophenyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-glu-conate;

n-heptyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate, b.p. 135-136 ° (0.01 mm Hg);

n-octyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate, b.p. 124 ° (0.02 mm Hg);

n-nonyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate, b.p. 95 ° (0.01 mm Hg);

n-Undecyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate, 2,2,2-trichloroethyl 2,3: 4,5-di-0-isopropylidene-2-keto- D - gluconate;

Furfuryl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate; 2,3: 4,5-di-O-isopropylidene sorbyl 2,3: 4,5-di-0-iso-propylidene-2-keto-D-gluconate;

p-cyanophenyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-glu-conate;

(p-ethoxycarbonyl) phenyl 2,3: 4,5-di-0-isopropylidene-2 - keto-D-gluconate;

p- (tert-butyl) phenyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate;

p-acetylphenyl 2,3: 4,5-di-0-isopropylidene-2-keto-D - gluconate;

a-naphthyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluco-

nat;

3,4- (methylenedioxy) phenyl 2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate;

n-dodecyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate, b.p. 119 ° (0.01 mm Hg);

n-propyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate, bp 101 ° (0.005 mm Hg);

n-pentyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate, bp 106 ° (0.005 mm Hg);

Benzyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate, b.p. 126 ° (0.03 mm Hg);

n-decyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate, b.p. 109 ° (0.005 mm Hg);

Isoamyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate; 2-butyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate; 2-bromoethyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-glu-conate;

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618 845 22

Bis-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate; 2,3-0-isopropylidene-4,5-0- (2,2-difluoroethylidene) -2-keto-

ethylene glycol ester; -D-gluconic acid;

Allyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate, 2,3-0-isopropylidene-4,5-0- (l, l, 3,3-tetrafluoroisopropyl-

Bp 106 ° (0.05 mm Hg); iden) -2-keto-D-gluconic acid;

Dimethylammonium 2,3: 4,5-di-0-isopropylidene-2-keto- 5 2,3-0-isopropylidene-4,5-0- (l, l, l, 3,3-pentafluoroisopropyl-

-D-gluconate; iden) -2-keto-D-gluconic acid;

Hydrazinium 2,3: 4,5-di-0-isopropylidene-2-keto-D-glu-2,3-0-isopropylidene-4,5-0- (2,2,2-tri-luoroethylidene) -2 -

conat; -keto-D-gluconic acid;

N-ethanolammonium 2,3: 4,5-di-0-isopropylidene-2-keto-2,3-0-isopropylidene-4,5-0- (l, l, l, 3,3,3-hexafluoroisopropyl)

-D-gluconate; 10 iden) -2-keto-D-gluconic acid;

3-chloropropyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluco-2,3-0-isopropylidene-4,5-0- (2-bromoethylidene) -2-keto-D -nat, bp 112 ° (0.02 mm Hg); -gluconic acid;

(Ethoxycarbonyl) methyl 2,3: 4,5-di-0-isopropylidene-2,3,3-isopropylidene-4,5-0- (1,3-dibromoisopropylidene) -2-

-keto-D-gluconate, bp 89-90 ° (0.02 mm Hg); -keto-D-gluconic acid;

Cyclohexyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate, 15 2,3-0-isopropylidene-4,5-0- (l, l, 3-tribromoisopropylidene) -

Bp 103 ° (0.025 mm Hg); -2-keto-D-gluconic acid;

2,4,6-trichlorophenyl 2,3: 4,5-di-0-isopropylidene-2-keto-2,3-0-isopropylidene-4,5-0- (2,2-dibromoethylene) -2-keto -

-D-gluconate; -D-gluconic acid;

Isopropyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate; 2,3-0-isopropylidene-4,5-0- (l, l, 3,3-tetrabromoisopropyl-

2-hydroxyethyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-glu- 20 iden) -2-keto-D-gluconic acid;

conat; 2,3-0-isopropylidene-4,5-0- (2,2,2-tribromoethylidene) -2-

4-chloro-2-butynyl 2,3: 4,5-di-0-isopropylidene-2-keto-D- -keto-D-gluconic acid;

-gluconate; 2,3-0-isopropylidene-4,5-0- (1,1,1-tribromoisopropylidene) -

3-chloro-2-propenyl 2,3: 4,5-di-0-isopropylidene-2-keto--2-keto-D-gluconic acid;

-D-gluconate; 25 2,3: 4,5-di-0-methylene-2-keto-D-gluconic acid;

3-chloro-2-butenyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-2,3: 4,5-di-0-ethylidene-2-keto-D-gluconic acid;

-gluconate; 2,3: 4,5-di-0- (2-butylidene-2-keto-D-gluconic acid;

2- [2- (phenoxy) propionyloxy] ethyl 2,3: 4,5-di-O-isoprop-2,3: 4,5-di-0-cyclohexylidene-2-keto-D-gluconic acid;

pylidene-2-keto-D-gluconate; 2,3: 4,5-di-0- (2-chloroethylidene) -2-keto-D-gluconic acid;

2-propynyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate, 30 2,3: 4,5-di-0- (1,3-dichloroisopropylidene) -2-keto- D-gIu-

Bp 103 ° C (0.025 mm Hg); cons acid;

2,3-0-isopropylidene-4,5-0-cyclohexylidene-2-keto-D-gluu-2,3: 4,5-di-0- (l, l, 3-trichloroisopropylidene) -2-keto- D-

cons acid; -gluconic acid;

2,3-0-isopropylidene-4,5-0-benzylidene-2-keto-D-glucon- 2,3: 4,5-di-0- (l, l, l, 3-tetrachloroisopropylidene) -2- keto-D-

acid; 35 -gluconic acid;

2,3-0-isopropylidene-4,5-0- (p-methoxybenzylidene) -2-keto- 2,3: 4,5-di-0- (2,2-dichloroethylidene) -2-keto-D- glucon

-D-gluconic acid; acid;

2,3: 4,5-di-0- (3-pentylidene) -2-keto-D-gluconic acid; 2,3: 4,5-di-0- (l, l, 3,3-tetrachloroisopropylidene) -2-keto-D-

2,3: 4,5-di-0-benzylidene-2-keto-D-gluconic acid; -gluconic acid;

2,3: 4,5-di-0- (p-methoxybenzylidene) -2-keto-D-glucon- 40 2,3: 4,5-di-0- (2,2,2-trichloroethylene) -2 -keto-D-glucon-

acid; acid;

2,3-0-isopropylidene-4,5-0- (2-chloroethylidene) -2-keto-D- 2,3: 4,5-di-0- (2-fluoroethylidene) -2-keto-D- gluconic acid;

-gluconic acid; 2,3: 4,5-di-0- (1,3-difluoroisopropylidene) -2-keto-D-glu-

2,3-0-isopropylidene-4,5-0- (1,3-dichloroisopropylidene) -2- cons acid;

-keto-D-gluconic acid; 45 2,3: 4,5-di-0- (l, l, 3-trifluoroisopropylidene) -2-keto-D-glu-

2,3-0-isopropylidene-4,5-0- (l, 1,3-trichloroisopropylidene) - cons acid;

-2-keto-D-gluconic acid; 2,3: 4,5-di-0- (l, l, l, 3-tetrafluoroisopropylidene) -2-keto-D-

2,3-0-isopropylidene-4,5-0- (1,1,3,3-tetrachloroisopropyl-gluconic acid;

iden) -2-keto-D-gluconic acid; 2,3: 4,5-di-0- (2,2-difluoroethylidene) -2-keto-D-glucon-

2,3-0-isopropylidene-4,5-0- (2,2-dichloroethylidene) -2-keto-50 acid;

-D-gluconic acid; 2,3: 4,5-di-0- (l, l, 3,3-tetrafluoroisopropylidene) -2-keto-D-

2,3-0-isopropylidene-4,5-0- (1,1,3,3-tetrachloroisopropyl-gluconic acid;

iden) -2-keto-D-gluconic acid; 2,3: 4,5-di-0- (l, l, l, 3,3-pentafluoroisopropylidene) -2-keto-

2,3-0-isopropylidene-4,5-0- (1,1,1,3,3-pentachloroisopropyl- -D-gluconic acid;

iden) -2-keto-D-gluconic acid; 55 2,3: 4,5-di-0- (2,2,2-trifluoroethylidene) -2-keto-D-glucon-

2,3-0-isopropylidene-4,5-0- (2,2,2-trichloroethylidene) -2- acid;

-keto-D-gluconic acid; 2,3: 4,5-di-0- (l, l, l, 3,3,3-hexafluoroisopropylidene) -2-keto-

2,3-0-isopropylidene-4,5-0- (1,1,3,3,3-hexachloroiso- -D-gluconic acid;

propylidene) -2-keto-D-gluconic acid; 2,3: 4,5-di-0- (2-bromoethylidene) -2-keto-D-gluconic acid;

2,3-0-isopropylidene-4,5-0- (2-fluoroethylidene) -2-keto-D- 2,3: 4,5-di-0- (1,3-dibromoisopropylidene) -2-keto- D-glu-

-gluconic acid; cons acid;

2,3-0-isopropylidene-4,5-0- (1,3-difluoroisopropylidene) -2- 2,3: 4,5-di-0- (1,3,1-tribromoisopropylidene) -2-keto- D-glu-

-keto-D-gluconic acid; cons acid;

2,3-0-isopropylidene-4,5-0- (l, l, 3-trifluoroisopropylidene) -2- 2,3: 4,5-di-0- (2,2-dibromoethylidene) -2-keto- D-glucon

-keto-D-gluconic acid; 65 acid;

2,3-0-isopropylidene-4,5-0- (l, l, l, 3-tetrafluoroisopropyl-2,3: 4,5-di-0- (l, l, 3,3-tetrabromoisopropylidene) -2 -keto-D-

iden) -2-keto-D-gluconic acid; -gluconic acid;

23

618845

2,3: 4,5-di-0- (2,2,2-tribromoethylidene) -2-keto-D-gluconic acid;

2,3: 4,5-di-0- (l, l, l-tribromoisopropylidene) -2-keto-D-glu-cons acid;

Bis (2-hydroxyethyl) ammonium 2,3: 4,5-di-O-isopropyl-idene-2-keto-D-ghiconate;

Morpholinium 2,3: 4,5-di-0-isopropylidene-2-keto-D-glu-conate;

Pentyl 2,3: 4,5-di-0-sec-butylidene-2-keto-D-gluconate,

Bp 99-100 ° C (0.02 mm Hg);

Ethyl 2,3: 4,5-di-0-sec-butylidene-2-keto-D-gluconate,

Bp 94-95 ° (0.025 mm Hg);

Ethyl 4,5-0-sec-butylidene-2,3-0-isopropylidene-2-keto-D-gluconate, b.p. 85 ° (0.005 mm Hg);

4-chlorobutyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-glu-conate, bp 120 ° (0.005 mm Hg);

5 ethyl 4,5-0-ethylidene-2,3-0-isopropylidene-2-keto-D-gluconate, b.p. 80-90 ° (0.01 mm Hg);

Isopentyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate,

Bp 90 ° (0.01 mm Hg);

p-fluorobenzyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-glu-lo conate, b.p. 134 ° (0.005 mm Hg);

2,2,2-trifluoroethyl 2,3: 4,5-di-0-isopropylidene-2-keto-D - gluconate, b.p. 75 ° (0.025 mm Hg).

Claims (67)

618845 •1 n wherein, when n is 1, R is hydrogen; Sodium; Potassium; Hydrazine; Morpholinium; Thiomorpholinium; Piperazinium; Ammonium; Ammonium substituted with one or more lower alkyl, lower alkenyl, lower alkynyl, cycloalkyl having 3 to 6 carbon atoms, halo-lower alkyl, hydroxy-lower alkyl, aryl or benzyl, optionally substituted with halogen, nitro, lower alkyl or lower alkoxy; Alkyl, alkenyl or alkynyl; Hydroxy lower alkyl; lower alkoxy lower alkyl; lower alkenyloxy lower alkyl; lower alkynyloxy lower alkyl; lower alkyl sulfonyloxy lower alkyl; Arylsulfonyloxy lower alkyl; Aryl or benzyl, optionally substituted with one or two lower alkyl, lower alkenyl, lower alkynyl, lower alkoxy, halo-lower alkyl, formyl, lower alkylcarbonyl, lower alkoxy-carbonyl, cyano, halogen, nitro, hydroxy, lower alkoxy-formamido , Ureido, methylenedioxy, amino or amino substituted with mono- or di-lower alkyl; Halo-lower alkyl; Halo-lower alkenyl; Halo-lower alkynyl; lower alkoxy-carbonyl-lower alkyl; Phosphono lower alkyl; Thiophospho-no-lower alkyl; lower alkylaminocarbonyl lower alkyl; lower alkylthio-lower alkyl; Arylthio-lower alkyl; Cycloalkyl, optionally substituted with halogen, nitro, lower alkyl or lower alkoxy; Phenoxy-lower alkylcarbonyloxy-lower alkyl, where the phenoxy group may optionally be substituted with mono- or di-lower alkyl with one, two or three nitro, lower alkyl, halogen, cyano, lower alkoxycarbonyl, lower alkylcarbonyl, methylenedioxy, amino or amino ; Morpholino lower alkyl; Thio-morpholino-lower alkyl; Piperazino lower alkyl; Phenyl-amino-lower alkyl or benzylamino-lower alkyl, where the phenyl group is optionally substituted by halogen; Amino lower alkyl; Amino lower alkyl, the amino group being mono- or di-substituted with lower alkyl, hydroxy-lower alkyl, halogen-lower alkyl, halophenyl, cyclopentyl or cyclohexyl; Hydrazino lower alkyl; Furyl or furyl-lower alkyl; when n is 2, R is calcium, magnesium or lower alkylene, Rj, R2, R3 and R4 are hydrogen, lower alkyl, lower alkenyl or lower alkynyl, halo-lower alkyl, aryl, optionally substituted by halogen, nitro, lower alkyl or lower alkoxy, or Rj and R2 together and / or R3 and R4 together each represent the addition to a saturated ring having 3 to 8 carbon atoms, n represents the number 1 or 2 and X represents the number 0 or 1; as well as enantiomers and racemic mixtures and / or salts thereof as active ingredient. 2. Composition according to claim 1, characterized in that it is one or more compounds of the general formula as active ingredient C_0 R " wherein if n is 1, R "is hydrogen, sodium, potassium, ammonium, substituted ammonium, alkyl, alkenyl, alkynyl or halo-lower alkyl and, if n is 2, R" is calcium, magnesium or lower alkylene, R "ls R" 2, R "3 and R" 4 are hydrogen, lower alkyl, lower alkenyl or lower alkynyl, halo-lower alkyl, aryl or R "i and R" 2 together and R "3 and R" 4 together each is a saturated ring having 3 to 8 carbon atoms, n and X have the meaning given in formula I, and / or salts thereof. 2nd PATENT CLAIMS 1. Commercial agent for regulating plant growth, characterized in that it is a carrier and one or more compounds of the general formula R. 3rd 618845 3rd CH. wherein when n is 1, R '"is hydrogen; sodium; potassium; ammonium; substituted ammonium; lower alkyl; and when n is 2, R' 'is calcium; Magnesium, or lower alkylene, contains. 3. Composition according to claim 1, characterized in that Rj, R2, Rî3 and R4 are methyl. 4th 4. Composition according to claim 1, characterized in that it is one or more compounds of the general formula as active ingredient .CH. CH. 5 5 5. Composition according to claim 1, characterized in that it contains 2,3: 4,5 di-O-isopropylidene-2-keto-D-gluconic acid monohydrate as active ingredient. 6. Composition according to claim 1, characterized in that it contains as active ingredient methyl 2,3: 4,5-di-O-isopropylidene - 2-keto-D-gluconate. 7. Composition according to claim 1, characterized in that it contains as active ingredient ethyl-2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate. 8. Composition according to claim 1, characterized in that it contains n-butyl-2,3: 4,5-di-O-isopropylidene - 2-keto-D-gluconate as active ingredient. 9. Composition according to claim 1, characterized in that it contains n-dodecyl-2,3: 4,5-di-O-isopropyl-den-2-keto-D-gluconate as active ingredient. 10th 10. Composition according to claim 1, characterized in that it contains allyl-2,3: 4,5-di-O-isopropylidene - 2-keto-D-gluconate as active ingredient. 10th IS 11. Composition according to claim 1, characterized in that it contains sodium 2,3: 4,5-di-O-isopropyl-den-2-keto-D-gluconate as active ingredient. 12. Composition according to claim 1, characterized in that it contains potassium 2,3: 4,5-di-O-isoproylidene-2-keto-D-gluconate as the active ingredient. 13. Composition according to claim 1, characterized in that it contains as active ingredient ammonium-2,3: 4,5-di-O-isopropyl-idene-2-keto-D-gluconate. 14. Composition according to claim 1, characterized in that it contains calcium 2,3: 4,5-di-O-isopropyl-idene-2-keto-D-gluconate as active ingredient. 15 15. Composition according to claim 1, characterized in that it contains n-propyl-2,3: 4,5-di-O-isopropyl-idene-2-keto-D-gluconate as the active ingredient. 16. Composition according to claim 1, characterized in that it contains benzyl-2,3: 4,5-di-O-isopropylidene - 2-keto-D-gluconate as the active ingredient. 17. Composition according to claim 1, characterized in that it contains n-pentyl-2,3: 4,5-di-O-isopropyl-idene-2-keto-D-gluconate as active ingredient. 18. Composition according to claim 1, characterized in that it contains as the active ingredient dimethylammonium-2,3: 4,5-di - O-isopropylidene-2-keto-D-gluconate. 19. Composition according to claim 1, characterized in that it contains n-decyl-2,3: 4,5-di-O-isopropylidene - 2-keto-D-gluconate as active ingredient. 20th 20. Composition according to claim 1, characterized in that it contains isoamyl-2,3: 4,5-di-O-isopropylidene - 2-keto-D-gluconate as the active ingredient. 20th 21. Composition according to claim 1, characterized in that it contains 2-butyl-2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate as active ingredient. 22. Composition according to claim 1, characterized in that it contains 2-bromoethyl-2,3: 4,5-di-O-isopro-pylidene-2-keto-D-gluconate as active ingredient. 23. Composition according to claim 1, characterized in that it contains N-ethanolammonium-2,3: 4,5-di - O-isopropylidene-2-keto-D-gluconate as active ingredient. 24. Composition according to claim 1, characterized in that it contains bis-2,3: 4,5-di-0-isopropylidene-2 - keto-D-gluconate-ethylene glycol ester as active ingredient. 25th 25. Composition according to claim 1, characterized in that it contains 2-propynyl-2,3: 4,5-di-O-isopropyl-idene-2-keto-D-gluconate as active ingredient. 25th 26. Composition according to claim 1, characterized in that it contains 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconic acid as active ingredient. 27. Composition according to claim 1, characterized in that it contains hydrazinium-2,3: 4,5-di-O-isopro-pylidene-2-keto-D-gluconate as the active ingredient. 28. Composition according to claim 1, characterized in that it contains 3-chloropropyl-2,3: 4,5-di-O-iso-propylidene-2-keto-D-gluconate as active ingredient. 29. Composition according to claim 1, characterized in that it contains as active ingredient (ethoxycarbonyl) methyl 2,3: 4,5 - di-O-isopropylidene-2-keto-D-gluconate. 30th 30. Composition according to claim 1, characterized in that it contains as the active ingredient cyclohexyl-2,3: 4,5-di-O-isopropyl-idene-2-keto-D-gluconate. 30th 31. Composition according to claim 1, characterized in that it contains p-NitrophenyI-2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate as active ingredient. 32. Composition according to claim 1, characterized in that it contains p-chlorophenyl-2,3: 4,5-di-O-iso-propylidene-2-keto-D-gluconate as active ingredient. 33. Agent according to claim 1, characterized in that it contains n-heptyl-2,3: 4,5-di-O-isopropyl-idene-2-keto-D-gluconate as the active ingredient. 34. Composition according to claim 1, characterized in that it contains n-octyl-2,3: 4,5-di-O-isopropylidene - 2-keto-D-gluconate as active ingredient. 35 35. Agent according to claim 1, characterized in that it contains n-NonyI-2,3: 4,5-di-O-isopropyl-iden-2-keto-D-gluconate as active ingredient. 35 36. center] according to claim 1, characterized in that it contains n-undecyl-2,3: 4,5-di-O-isopropyl-idene-2-keto-D-gluconate as the active ingredient. 37. Agent according to claim 1, characterized in that it contains 2,2,2-trichloroethyl-2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate as the active ingredient. 38. Composition according to claim 1, characterized in that it contains furfuryl-2,3: 4,5-di-O-isopropyl-idene-2-keto-D-gluconate as the active ingredient. 39. Agent according to claim 1, characterized in that it contains p-cyanophenyl-2,3: 4,5-di-O-iso-propylidene-2-keto-D-gluconate as active ingredient. 40 40. Composition according to claim 1, characterized in that it contains (p-ethoxycarbonyl) phenyl-2,3: 4,5 - di-O-isopropylidene-2-keto-D-gluconate as active ingredient. 40 41. Composition according to claim 1, characterized in that it is p- (tert-butyl) phenyl-2,3; 4,5: contains di - O-isopropylidene-2-keto-D-gluconate. 42. Agent according to claim 1, characterized in that it contains p-acetylphenyl-2,3: 4,5-di-O-iso-propylidene-2-keto-D-gluconate as active ingredient. 43. Agent according to claim 1, characterized in that it contains as active ingredient a-naphthyl-2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate. 44. Agent according to claim 1, characterized in that it contains 3,4- (methylenedioxy) phenyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate as active ingredient. 45 45. Agent according to claim 1, characterized in that it contains 2,4,6-trichlorophenyl-2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate as active ingredient. 45 46. Composition according to claim 1, characterized in that it contains isopropyl-2,3: 4,5-di-O-isopropyl-idene-2-keto-D-gluconate as the active ingredient. 47. Agent according to claim 1, characterized in that it contains 2-hydroxyethyl-2,3: 4,5-di-O-iso-propylidene-2-keto-D-gluconate as active ingredient. 48. Agent according to claim 1, characterized in that it contains 4-chloro-2-butinyl-2,3: 4,5-di-O-iso-propylidene-2-keto-D-gluconate as active ingredient. 49. Agent according to claim 1, characterized in that it contains 3-chloro-2-propenyl-2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate as active ingredient. 50 YY 50. Agent according to claim 1, characterized in that it contains 3-chloro-2-butenyl-2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate as active ingredient. 50 51. Agent according to claim 1, characterized in that it contains 2- [2- (phenoxy) propionyloxy] ethyl - 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate as the active ingredient. 52. Agent according to claim 1, characterized in that it contains 2,3-0-isopropylidene-4,5-0- (2,2,2 - trifluoroethylidene) -2-keto-D-gluconic acid as active ingredient. 53. Agent according to claim 1, characterized in that it contains 2,3-0-isopropylidene-4,5-0- (l, l, l, -3,3,3-hexafluoroisopropylidene) -2-keto-D as active ingredient - contains gluconic acid. 54. Composition according to claim 1, characterized in that it contains 2,3-0-isopropylidene-4,5-0- (2-bromoethylidene) -2-keto-D-gluconic acid as active ingredient. 55. Agent according to claim 1, characterized in that it contains 2,3-0-isopropylidene-4,5-0- (1,3-di-bromoisopropylidene) -2-keto-D-gluconic acid as active ingredient. 55 56. Composition according to claim 1, characterized in that it contains 2,3-0-isopropylidene-4,5-0- (l, l, 3 - tribromoisopropylidene) -2-keto-D-gluconic acid as active ingredient. 57. Agent according to claim 1, characterized in that it contains 2,3-0-isopropylidene-4,5-0- (2,2 - dibromoethylidene) -2-keto-D-gluconic acid as active ingredient. 58. Composition according to claim 1, characterized in that it contains 2,3-0-isopropylidene-4,5-0- (l, l, 3,3 - tetrabromoisopropylidene) -2-keto-D-gluconic acid as active ingredient. 59. Composition according to claim 1, characterized in that it contains 2,3-0-isopropylidene-4,5-0- (2,2,2 - tribromoethylidene) -2-keto-D-gluconic acid as active ingredient. 60. Agent according to claim 1, characterized in that it contains 2,3-0-isopropylidene-4,5-0- (l, l, l - tribromoisopropylidene) -2-keto-D-gluconic acid as active ingredient. 60 60 61. Agent according to one of claims 1-60, characterized in that it contains 0.01% to 95% by weight of the active ingredient. 62. Agent according to one of the claims 1-60 in concentrate form, characterized in that it contains 40% by weight to 95% by weight of the active ingredient. 63. Agent according to one of the claims 1-60 in spray-ready form, characterized in that it contains 0.01% by weight to 25% by weight of active ingredient. 64. Agent according to one of claims 1 to 6, characterized in that it also contains 1/16 to 1/4 parts by weight of 2,4-dichlorophenoxyacetic acid, based on one part by weight of the active ingredient of the formula I. 65. Process for the preparation of an agent for reacting plant growth according to claim 1, characterized in that at least one compound of the formula I is mixed with inert, solid or liquid auxiliaries. 65 618845 65 66. The method according to claim 65 for the preparation of an agent according to claim 1, characterized in that at least one compound of the formula I is mixed with pumice stone granules. 67. Use of the agent according to claim 1 as a regulator for the growth of plants.