DE2414590A1 - GROWTH REGULATORS FOR PLANTS - Google Patents

Description

Dr. Ing. A, from dw Weift Dr. FiWiZ ijiiifif

PATENT ADVOCATE

2 6. UFO in 2414590

RAN 6102/6

F. HoiFmann-La Roche & Co. Aktiengesellschaft, Basel / Switzerland Growth regulators for plants

The invention "relates to agents for regulating plant growth, the one or more compounds of the general formula

-R.XH 0

409842/1113

in which, when η is the number 1, R is hydrogen; Sodium; Potassium; Hydrazinium; Morpholineum; Thiomorpholinium; 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; straight or branched aliphatic Hydrocarbyl; 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, lower alkenyl, lower alkynyl, lower alkoxy, halo-lower alkyl, pormyl, 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 optionally with one, two or three nitro, lower alkyl, halogen,

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Cyano, lower alkoxycarbonyl, lower alkylcarbonyl, methylenedioxy, amino or amino substituted by mono- or di-lower alkyl can be substituted; 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, the amino group being mono- or di-substituted with lower alkyl, hydroxy-lower alkyl, halo-lower alkyl, halophenyl, cyclopentyl or cyclohexyl; Hydrazino-lower alkyl; Furyl or furyl-lower alkyl »and, if η is the number 2, R calcium, magnesium or lower alkylene, R-,, R _? , R-, and R. hydrogen, straight-chain or branched aliphatic lower hydrocarbyl, halo-lower alkyl, aryl, optionally substituted by halogen, nitro, lower alkyl or lower alkoxy, or R-, and R _? together and R, and R. together each represent a saturated ring with 3 to 8 carbon atoms, η represents the number 1 or 2 and X represents the number O or 1; as well as enantiomers and racemic mixtures.

These agents are especially useful as post-emergence and pre-emergence run plant growth regulators and as herbicides. The invention also relates to methods of using them Middle.

409842/1113

The invention also relates to new compounds of the general formula

C-O

RIXH ₂ O

II

wherein, when η is the number 1, R ^{1 is} hydrogen; Sodium; Potassium; Hydrazinium; Morpholinium; Thiomorpholinium; 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; straight or branched chain aliphatic hydrocarbyl; 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, lower alkenyl, lower alkynyl, lower alkoxy, halo-lower

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alkyl, formyl, lower alkylcarbonyl, lower alkoxycarbonyl, cyano, halogen, nitro, hydroxy, lower alkoxyformamido, T -reido, methylenedioxy, amino or amino substituted by 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 can optionally be substituted with one, two or three nitro, lower alkyl, halogen, cyano, lower alkoxycarbonyl, lower alkylcarbonyl, methylenedioxy, amino or amino substituted by mono- or di-lower alkyl ; Morpholino-lower alkyl; TMomorpholino-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; Puryl or puryl lower alkyl; and when η is the number 2, R 'is calcium; Magnesium or lower alkylene, R ^, R ' ₂ , R' and R 'lower alkyl, lower alkenyl, lower alkynyl, halo-lower alkyl, aryl, optionally substituted by halogen, nitro, lower alkyl or lower alkoxy, or R ¹ , and R '~ together and R ^f _ and

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R ¹ . together each denotes a saturated ring with 3 to 8 carbon atoms, η represents the number 1 or 2 and X represents the number 0 or 1, enantiomers and racemic mixtures, but for the case that R ^{f is} hydrogen, ammonium, methyl, sodium or potassium and R ^, R ^! ₂ , R 'and R ¹ mean lower alkyl, the lower alkyl group comprises more than 1 carbon atom.

These compounds are also useful in the aforementioned means and methods.

Preferred plant growth regulators for the purposes of the present invention are because of them Kachauflauf plant growth regulating activity, especially compounds of the formula

VXH ₂ O

wherein when η is 1, R "is hydrogen, sodium, potassium, ammonium, substituted Ammonium, straight or branched aliphatic hydrocarbyl, or halo-low alkyl and when η is 2 R "calcium, 409849/1113

III

Magnesium or lower alkylene, R ", R", R "and R" hydrogen, straight-chain or branched aliphatic lower hydrocarbyl, halo-lower alkyl, aryl or R "., And R" _? together and R 'and R "together are each a saturated ring having 3 to 8 carbon atoms, η. and X have the meaning indicated in formula I, and -ßnantiomere and racemic mixtures.

24U590

Another preferred group of compounds are those of the general formula

■ R "'.XH ₂ O

wherein, when η is 1, R "'is hydrogen, sodium, potassium, ammonium, substituted ammonium, straight-chain or branched aliphatic hydrocarbyl or halo-lower alkyl and, when η is 2, R ¹ " is calcium, magnesium or lower alkylene, η and X have the meaning given above, as well as enantiomers and racemic ones

0 9 8 L ? / 1 1 1 Ά

Mixtures.

The compounds encompassed by the above formulas I, II, III and IV all have the D configuration because they are derived from the naturally occurring 2-ketohexose, D-fructose. D-fructose is the only known naturally occurring form of fructose; however, the corresponding enantiomer of D-fructose, namely the L-fructose can be produced synthetically. Attention is drawn to the fact that those corresponding to D-fructose Compounds with the L-configuration and racemic mixtures of these compounds are prepared in a completely analogous manner by using L-fructose as a starting material instead of D-fructose, or as a starting material Mixture of D- and L-fructose used if the appropriate racemic mixture is sought. The preparative methods are exactly the same regardless of whether a compound of the D-form, the L-form or the corresponding racemic mixture is used as the starting material. Accordingly, all structural formulas, as they are shown below and above, are not as to understand those that are supposed to describe a specific or an absolute configuration, but this one Structural formulas describe all possible configurations, i.e. they include in particular the enantiomers and the racemic mixtures. The examples and other descriptions apply unless expressly stated otherwise emphasizes the racemic compounds.

The compounds encompassed by the formulas I, II, III and IV have post-emergence and / or pre-emergence plant growth regulating activity and herbicides Activity. However, it outweighs the post-emergence growth-regulating effect, as most of the compounds have this effect and this activity is in control

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the growth of weeds that appear in the lawn.

The term "plant growth ^{regulator 11} as used herein means a compound or a composition which exerts an influence on the maturation and metabolism of plants. A plant growth regulator thus exerts numerous effects on plant growth". However, not all compounds active as plant growth regulators act on the plants in the same way. For example, they can affect growth by delaying or stimulating final growth, and / or by stimulating side growth, and they can inhibit new growth such as sprout formation in bush plants, sprouting of tubers and rhizomes, and sprout growth. Such regulators can affect flowering plants by preventing early flowering and by decreasing or increasing the number of flowers. Fruit-bearing trees and bushes can be influenced by increasing the number, size and quality of the fruits, by forming seedless fruits, by accelerating aging and ripening and by stimulating fruit and / or leaf waste. Both flowering and fruiting plants can be influenced by accelerating the plant sleep and maintaining the dormancy of the buds. A plant growth regulator can provide selective control of weeds after they emerge by reducing their strength and resilience so that they cannot spread and re-multiply.

Typical uses of γοη plant growth regulators include:

Prevention of entrapment of grain; Increase in the formation of harvestable tea leaves through favoring the lateral branches;

A 0 9 8 L ? / 1 11: J

-JO-

Prevents potatoes and onions from sprouting during storage;

Suppression of the growth of grass, trees, bushes and other vegetation on decorative lawns, in parks, on golf courses and along roads; Accelerated fruit ripening and thus relief mechanical harvesting through single or less frequent picking;

Defoliation of the cotton plant to enable mechanical harvesting;

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

Facilitating the mechanical harvesting of nuts by accelerating ripening, stimulating cracking the shells and acceleration of the waste; Protecting fruits from frost by stimulating a early sleep and / or prevention of premature cessation of rest;

Increasing the flow of latex from rubber plants; Increasing the frost resistance of winter cereals; Decrease in the 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;

Increasing the color and quality of fruits; Protection of grain from drought; Stimulating the side growth of potted plants such as heather, azaleas, chrysanthemums and geraniums; Retardation of the growth of potted plants such as

U 0 9 8 L 11 11 1 'S

-4A -

24H590

Poinsethia, petunias and chrysanthemums; Stimulating the side growth of young trees such as e.g. apple: - or pear trees;

The term "straight-chain or branched aliphatic hydrocarbyl" 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 grouping , but apart from that it can be saturated or unsaturated, ie they are alkyl, alkenyl or alkynyl groups. 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" denotes groups that have a carbon skeleton with up to 7 carbon atoms. The term "lower alkyl" includes both straight-chain and branched, saturated aliphatic groups which carry 1 to 7 carbon atoms, such as, for example, methyl, ethyl, n-propyl, isopropyl, η-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-dimethy1-propenyl, propargyl, butynyl, 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 alkylcarbonyloxy or lower alkoxycarbonyl-lower alkyl refers to straight or branched chain hydrocarbons, which have up to 7 carbon atoms,

such as methyl, 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 can 1, 2 or 3 hydrogen atoms through a substituent such as alkyl, alkynyl, alkoxy or halo-lower alkoxy. The term "halo-lower alkyl," halo lower alkenyl "or halo-lower alkynyl" includes straight-chain or branched alkyl, alkenyl or alkynyl groups with 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-1,1,2,2-tetrafluoroethyl, 2,2,3,3,4,4,4-heptafluorobutyl, 3,4,4-trifluoro-3-butenyl etc. The names ammonium, hydrazinium, Morpholinium, etc. defines, for example, the corresponding salts of the 2-keto-gluconic acid derivatives of 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 ^: · .- '. -or one or more of the carbon atoms are replaced by a halogen, preferably fluorine, chlorine or 3 bromine.

Exemplary representatives that fall under the formula I. and the effect as a plant growth regulator and / or develop a herbicidal effect are:

U 0 9 8 L ? / 1 1 1 '. <

-43-

2414530

A. New connections

2 ₁ 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;

2,3-0-13opropylidene-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-gluconic acid;

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

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

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

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

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

4 0 9 8 L? / 1 1 1 3

2AH590

2,3-0-iuopropylidene-4,5-0- (1,1,1,3,3,3-hexachloroisopropylidene) -2-keto-D-gluconic acid;

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

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

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

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

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

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

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

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

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

2.3-0-isopropylidene-4, 5-0- (1,1,1-tribromisopropyliden) -2-keto-D-gluconic acid;

2,3: 4,5-Di-O- (2-chloroethylidene) -2-keto-D-gluconic acid :,

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

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

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

2,3: 4,5-Di-O- (2,2-dichloroethylidene) -2-keto-D-gluconic acid;

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

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

2,3: 4,5-Di-O- (2-fluoroethylidene) -2-keto-D-gluconic acid;

2,3: 4,5-Di-O- (1,3-difluoroisopropylidene) -2-keto-D-gluconic acid ;

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

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

2,3: 4,5-Di-O- (2,2-difluoroethylidene) -2-keto-D-gluconic acid;

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

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

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

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

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

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

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

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

2,3: 4,5-Di-O- (1,1,3,3-tetrabromoisopropylidene) -2-keto-D-gluconic acid: ,

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

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

2-keto-D-gluconic acid monohydrate; 2,3: 4,5-di-0-cyclohexylidene-2-keto-D-gluconic acid; 2,3: 4,5-di-O- (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 -D.i-0-isopropylidene-2-keto-D-gluconic acid monohydrate;

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

Preferred compounds within the scope 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-O-isopropylidene-2-keto-D-gluconate; n-pentyl-2,3: 4,5-di-O-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-O-isopropylidene-2-keto-D-gluconate;

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Isoamyl 2,3: 4,! P-di-O-isopropylidene-1-keto-D-gluconate; 2-butyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-glucon-it; 2-bromoethyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate;

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

Bis-2,3: 4, S-di-O-isopropylidene ^ -keto-D-gluconate-ethylene glycol ester;

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

Ally1-2,3: 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-glucona t; Ammonium 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate;

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

2-propynyl-2,3: 4, i-di-O-isopropylidene-1-keto-D-gluconate;

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-gluconate; 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, in particular of grass and weeds as well as other undesirable plants that happen to be under the aware Mix planted plants. Although the compounds have a pre-emergence plant growth-regulating effect, however, they are particularly useful when used as casseroles as plant growth regulators or as fruit fall-inducing Funds are used. The post-emergence effectiveness of the active compounds in the context of the present invention is by controlling the growth of undesirable Plants occupied. For example, it hasn't been like that before

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possible, a post-emergence control of Digitaria sanguinalis to be carried out with a post-emergence herbicide; however, this succeeds with the active compounds according to the present invention Invention because they greatly slow down the growth and maturation of this grass and so the sowing and prevent this grass from spreading.

When checking lawns, especially house lawns and industrial lawns (for example golf courses), it has been shown that a maximum delay in growth, as manifested by a reduction in the height of the grass compared to an untreated control, of approximately AO-SOfo should be aimed for is, with a delay in grass growth of 50º is preferred. A delay of less than AOfo must already be classified as ineffective, as it does not allow the necessary aesthetic effect to appear visually and also does not reduce the necessary maintenance of the lawn. On the other hand, a delay in growth by more than 60 degrees is also undesirable, since the lawn takes on a barren appearance and is quickly infiltrated with weeds and other undesirable plants.

The active compounds show herbicidal activity particularly against corn blood weeds, for example Matricaria 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, Bromus erectus, Deschampsia flexuosa, Alopecurus pratensis, Arrhenatherum elatius, Dactylis glomerata, Festuca pratensis, Trisetuni flavescens, Holcus lanatus, Lolium perenne, Poa annua, Poa neumoralis, Poa pratensis, Festuca ovina, Festuca rubra, Festuca nigrescens, Cynosurus cristatus, Agrostis

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schraderiana, Agrostis stolonifera, Phleum pratense, Phleura nodosnm, Cynodon dactylon, Stenotaphrum secundatum, Paspalum notatum, Ermochloa olphiuroides, and other turf or weed grasses; Sugar cane and cereals such as grain, rice, wheat, rye, barley, oats, etc .;

b) Trees and bushes such as fruit trees, such as apple, pear, peach, cherries 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 bromeliad.

d) crops such as cotton, soybeans, peanuts, tobacco, flax, sugar beet and pineapple;

e) Vegetables such as Solanaceae, (for example tomatoes), legumes, pumpkins, melons, etc .;

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

These compounds are also useful as they reduce the pruning of the vines in the vineyards.

To ensure a uniform distribution of the active compounds in the growth regulating agents according to the invention to achieve, the compound or compounds are conventional, common for herbicides Auxiliaries, modifiers, diluents or conditioning agents mixed and in this way to solutions, emulsions, emulsifiable concentrates, dispersions, Formulated dusts, granules or wettable powders.

24U590

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 containing, for example, acetone, methanol, dimethylformamide in a ratio of 90: 8: 2 (volume / volume). In the case of 2,3: 4,5-di-0-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 diethanolamine. Triethanolamine etc. to aqueous solutions containing 1% Tween 20 or other non-phytotoxic wetting agents. Buffering the solutions is necessary because it is known that 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconic acid is unstable in aqueous solutions with a pH below 6.

Emulsifiable concentrates that are $ 25-505 or more of active ingredient, depending on its solubility, can be prepared in suitable solvents are, for example N-methylpyrrolidine, dimethylformamide etc. Surfactants such as wetting agents, dispersants, emulsifiers, etc. become added in sufficient quantity to achieve the desired characteristics of the formulation.

Wettable powders are made using an inert diluent such as kaolin. For example, a typical spray solution formulated with a wettable powder will contain the active ingredient, about 1% to about 5% inert diluent, minor amounts of dispersant, wetting agent and antifoam agent, and the appropriate and necessary amount of water ^

24U590

Different types of applications can better suit the numerous purposes for which the active ones Let connections be adapted when using connections that increase dispersion, adhesion, resistance against rain and improve penetration, adds like fatty acids, waxes, resins, wetting agents, emulsifiers, Mineral or vegetable oils, binders, etc. In the same way, the biological spectrum of these compounds or greatly broaden the agent by adding substances that 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 admixed with the compounds according to the invention, are:

2,2-dichloropropionic acid,

N- (4-aminobenzenesulfonyl) methyl carbamate,

2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine,

4-chloro-2-oxob enz οthiazοlin-3-y1-es setic acid, 5-bromo ~ 6-methyl-3- (1-methyl-n-propyl) uracil, 3,5-dibromo-4-hydroxybenzonitrile, D, N-ethyl-2- (phenylcarbamoyloxy) propionamide,

N- (4-bromo-3-chlorophenyl) -N'-methoxy-N'-methyI-urea,

Methyl - ^ - chloro-S-hydroxyfluorene-Q-carboxylate,

N -4- (4-chlorophenoxy) -phenyl-N, N-dimethy! Urea,

Isopropyl N- (3-chlorophenyl) carbamate,

2,3,5, δ-tetrachloroterephthalic acid dimethyl ester (DOPA),

2,4-dichlorophenoxy-acetic acid,

4-isopropylamino-6-methylamino-2-methylthio-1,3,5-triazine,

n-butyl-9-hydroxyfluorene-9-carboxylate,

Naphthoxy acetic acid,

3,6-dichloro-2-methoxybenzoic acid,

4098 * 7/1113

(-) - 2- (2,4-dichlorophenoxy) propionic acid, 9,10-dihydro-8a, 10a-diazoniaph.enanthren.-2A, N '- (3,4-dichlorophenyl-N, IT-dimethylurea f, G-ibberellic acid,

Indolylacetic acid,

Indoly! Butyric acid,

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

IT '- (3,4-dichlorophenyl) -N-methoxy-N-ethylurea f,

4-0h.lor-2-methylph.enoxy-acetic acid, 4- (4-chloro-2-methylphenoxy) butyric acid, (-) - 2- (4-chloro-2-methy! Phenoxy) propionic acid, Ii- (Benzo thiazol-2-yl) -IT, IT'-dimethyl urine to ff,

N '- (3-Ch! Or-4-methoxyphenyl) -NN-dimethylurea,

1,2,3,6-Tetrahydro-3,6-dioxopyridazine, U '- (4-chlorophenyl) -IT-methoxy-IT-methylurea, N ' - (4-chlorophenyl) -N, N-dimethy ! urea, naphthylacetic acid,

IT-l-naphthylphthalamic acid, 2,4-dichlorophenyl-4-nitroph.enyl-ath.er, 1,1 '-dimethyl-4,4 ^r -bipyridylium-2A, 3- (m-Tolylcarbamoyloxy) phenylcarbamate, 4-amino -3,5,6-trichloropicolinic acid,

4,6-bis-isopropylamino-2-πlethylthio-1,3 f 5-triazine,

N- (3,4-Dichlorph.enyl) -propionaiaid, Isopropyl-iT-phenylcarbamate, 5-Aniino-4-chloro-2-phenylpyridazin-3 (2H) -one, JT-Dimethylainino-succinic acid, 2-chloroethyl-phosphorous acid, Tributyl-2,4-dichlorobenzyl-phosphonium chloride, 2,4,5-trichlorophore-enoxypropionic 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-l, 3, 5-triazine (terbutryn),

2,3, 5-triiodobenzoic acid,

1,1,4-trimethyl-6-isopropyl-5-propionyl-indane.

Exemplary fungicides which the compounds according to the invention can be added are:

2,4-DiChIOr-S- (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-dithio carbamate,

Methyl 1 (butylcarbamoyl) -2-benzimidazole carbamate, 2- (4-TMazole) -benzimidazole,

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

The stated application amounts are based on the results presented here and are not of such a nature broadly described to include all possible cases as numerous factors affect the amounts used. For example, the amount can not only vary between different plant species, but also, within a particular species, for example depending on factors such as the plant size and the age of the plant, the particular compound used, the time of year, the type of soil and climatic conditions at the time of use, such as air temperature, light intensity, rain and wind. Furthermore, if the connections or the means are used by soaking the soil, higher concentrations are necessary, as with this type of application the plant is treated indirectly

U O 9 B Ll / 11 1 '6

versus direct treatment "upon application of the agent or compound on leaves and stems, for example by spraying on the plant.

The amount of active ingredient in plant growth regulators Means varies accordingly depending on the plants to be controlled, the required Application amount, the type of application, the active ingredient used and the degree of control of the plant growth, that is strived for. In general, the agents in the ready-to-spray form contain less than 507 ° of active ingredient.

Basically, the amount of active compound _f which reaches the application, chosen such that an effective plant growth control is achieved. For example, as already stated above, such an amount of active ingredient is used in the control of the lawn that the normal growth rate of 40-60'jS is delayed. Correspondingly, the selection of the minimum amount to be 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 that causes the upper limit of the desired growth retardation, ie in the case of grasses that are used for ornamental lawns, the amount that avoids a sparse appearance of the ornamental lawn, however on the other hand, prevents the lawn from growing too quickly and does not cause undesirable chlorosis (ie the grass turns yellow). For tomato plants, the criteria for an effective growth retardation are stored differently, since a dwarf-like plant that does not cause any loss of fruit quality or quantity is particularly desirable. The parameters for effective growth regulating activity in golden plants

U 0 9 8 4 2 Π 1 1 3

24H590

are delayed growth in length and increased or not delayed Side growth as a minimum effect and delayed length and side growth as a maximum effect. The amount of active substance that meets these criteria or these caused is determined from such points of view, for example on the tomato plant. To the greatest To achieve a growth-regulating effect, quantities of 0.5 kg to 20 kg or more per hectare are required used. These amounts are based on the weight of the active compound. In the same way becomes the largest Post-emergence growth regulating activity generally in amounts ranging between 1 to 15 kg or more active ingredient per hectare are obtained. A preferred dosage interval for spray solutions is between 10 to 100,000 ppm depending on the plant species being treated and the compound being is selected for this. A particularly preferred dosage is generally between 100 and 20,000 ppm.

Another advantage of using the inventive Active ingredients are the absence of any permanent effect on the plants or a regulating effect, which remains in the ground. These compounds slowly decompose and there is thus a consequent decrease of activity. This effect has advantages because

a) a short-term effect, which can be prolonged by subsequent further treatment, is achieved;

b) the normal growth conditions of the plant return to the extent that the activity decreases; and

c) no harmful residues remain either on the plant or in the soil.

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

2414530

Although the compounds of the invention a Having 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 effective against all plants are active. However, each of the active compounds shows activity against one in the context of the present invention specific plant or plants and this activity is a puncture of the connection. As in the following in more detail is a particular advantage of the present

Invention that the growth regulating agents when using for the treatment of different plants pre-emergence and post-emergence, growth-regulating effectiveness and herbicide Develop activity, the spectrum of the plants in question being extraordinarily broad. The growth regulating The activity of the active compounds is determined by the following microscopic experiments to determine the activity the Machauflauf effect underpinned.

The growth retarding effect of 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconic acid as well as salts and esters of this compound in various plants is described below demonstrated by greenhouse experiments.

The compounds to be investigated can be formulated as wettable powders using kaolin as the inert diluent and suspended in water. However, these compounds can also be used as a 2% solution in acetone,

4 0 9 8 I 2 f 1 1 1 3

which contains 1% wetting agent. This solution will be shortly before. sprayed with an equal amount of water.

In the method used, seeds of the plants to be examined are sown in 450 ml plastic pots with a sterilized clay base that has known physical properties. The moment of sowing is chosen 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). Before and after application of the compounds to be investigated, the plants are kept in the greenhouse. Mercury lamps produce 16 hours of light per day. The test substances are applied by spraying, the "sprayed amount" 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 formed sheet ". The result can be obtained by comparison of the values found for a treated and an untreated plant are expressed in percentages.

The test results are in the following Tables I to IX summarized;

24H590

Table I.

Post-emergence retarding effect on Poa pratensis.

Compound (formulated as a grass height, cm, 26
25 $ wettable powder) days after treatment

Dose 6kg / ha dose 3kg / ha

2-propynyl 2,3: 4,5-di-0-iso-

propylidene-2-keto-D-gluconate 9.7 17.5

Ethyl 2,3: 4,5-di-0-isopropyl-

iden-2-keto-D-gluconate 11.2 13.7

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

iden-2-keto-D-gluconate 10.3 16.5

n-? entyl 2,3: 4,5-di-0-isopropyl-

iden-2-keto-D-gluconate 12.0 13.2

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

iden-2-keto-D-gl'uconate 11.5 13.8

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

iden-2-keto-D-gluconate 12.8 14.0

n-octyl 2,3: 4,5-di-0-isopropylidene-

2-keto-D-gluconate 13 »2 13» 3

n-propyl 2,3: 4,5-di-0-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

24H590

n-dodecyl 2,3: 4,5-di-0-isopropylidene-

2-keto-D-gluconate 13.0 14.5

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

2-keto-D-gluconate 13.5 15.7

3-chloropropyl 2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate. 12.2 13.2

n-decyl 2,3: 4,5-di-0-isopropylides-

2-keto-D-gluconate 13.7 14.3

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

2-keto-D-gluoonate 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

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

iden-2-keto-D-gluoonate 14.8 14.8

Potassium 2,3: 4,5-di-0-isopropylidene-

2-keto-D-gluconate 9.2 14.3

Control (Untreated) 17.3 17.3

0 9 8 L? / 1 1 I 3

2AU590

Table II

Post-emergence growth retarding effect on Poa pratensis

Compound (formulated as a grass height compared to the 2 <fo solution in acetone) control %, 14 T-ige after

Treatment dose 8 kg / ha dose 4 kg / ha

Potassium 2,3: 4,5-di-0-isopropyl-

iden-2-keto-D-gluconate 29 43

Ammonium 2,3: 4,5-di-0-isopropyl-

iden-2-keto-D-gluconate 27 37

Methyl 2,3: 4,5-di-0-isopropyl-

iden-2-keto-D-gluconate 75 88

Ethyl 2,3: 4,5-di-0-isopropyl-

iden-2-keto-D-gluconate 37 57

n-propyl 2,3: 4,5-di-0-isopropyl-

iden-2-keto-D-gluconate 77 96

n-pentyl 2,3: 4,5-di-0-isopropyl-

iden-2-keto-D-gluconate 63 88

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

Benzyl 2,3: 4,5-di-0-isopropyl-

iden-2-keto-D-gluconate 89 86

24U590

3-chloropropyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-glucorate 86 92

Allyl 2,3: 4,5-di-0-isopropyl-

iden-2-keto-D-glaconate 94 95

Table III

Post-emergence growth retarding effect on Lolium Perenne

Compound (formulated as a grass height, cm, 25 $ wettable powder) days after treatment

Dose 12 kg / ha dose 6 kg / ha

Sodium 2,3: 4,5-di-0-isopropyl-

iden-2-keto-D-gluconate 17.0 22.0

n-Octyl 2,3: 4 »5-di-O-isopropyl-

iden-2-keto-D-gluconate 19.3 20.7

4-chlorobutyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate 19.7 21.3

Ammonium 2,3: 4,5-di-0-isopropyl-

iden-2-keto-D-gluconate 20.3 20.7

n-pentyl 2,3: 4,5-di-0-isopropyl-

iden-2-keto-D-gluconate 20.0 23.0

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

iden-2-keto-D-glucona ± 20.3 21.0

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

iden-2-keto-D-gluconate 20.0 20.7

n-decyl 2,3: 4,5-di-0-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

4 0 9 8 L1f 1113

2AU590

2-cyanoethyl 2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate 21.0 22.3

Allyl 2,3: 4,5-di-0-isopropyl-

iden-2-keto-D-gluconate 21.3 21.7

Methyl 2,3: 4,5-di-0-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-0-isopropylidene-

2-keto-D-gluconate 22.0 22.0

Control (Uh-treated) 22.3 22.3

4 O 9 8 L? / 1 1 1 : ·;

24U590

Table IV

Post-emergence growth-retarding effect on Digitaria sanguinalis.

Compound (formulated as a grass height, cm, 27
25 $ wettable powder) days after treatment

Dose 12 kg / ha dose 6 kg / ha

Ammonium 2,3: 4,5-di-0-isopropyl-

iden-2-keto-D-gluconate 11.3 30.3

Potassium 2,3: 4,5-di-0-isopropyl-

iden-2-keto-D-gluconate 9.7 33.0

Sodium 2,3: 4,5-di-0-isopropyl-

iden-2-keto-D-gluconate 9.0 29.7

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

iden-2-keto-D-gluconate 17.3 35.0

n-pentyl 2,3: 4,5-di-0-isopropyl-

iden-2-keto-D-gluconate 22.0 25.7

4-chlorobutyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate 26.0 26.7

3-chloropropyl 2,3: 4,5-di-0-isopropylidene-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-0-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 x 27.7 29.7

2-cyanoethyl 2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate 30.0 32.0

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

n-propyl 2,3: 4,5-di-0-isopropylidene-

2-keto-D-gluconate 30.3 30.0

2-chloroethyl 2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate 28.7 30.7

Methyl 2,3: 4,5-di-0-isopropylidene-

2-keto-D-gluconate 33.3 33.0

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

2-keto-D-gluconate 34.7 31.3

Control (untreated) 35.3 35.3

Table V

Post-emergence growth retarding effect on Triticum aestivum "Probus"

Compound (formulated as a plant height, mm, 25% wettable powder) days after treatment

Dose 6 kg / ha dose 2 kg / ha

η-butyl 2,3: 4,5-di-0-isopropyl-

iden-2-keto-D-gluconate. 78 87

Potassium 2,3: 4,5-di-0-isopropylidene-

2-keto-D-gluconate 73 82

Ammonium 2,3: 4,5-di-0-isopropyl-

iden-2-keto-D-gluconate 75 75

Sodium 2,3: 4,5-di-0-isopropylidene-

2-keto-D-gluconate 75 80

4-chlorobutyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate 85 87

Ethyl 2,3: 4,5-di-0-isopropylidene-

2-keto-D-gluconate 92 90

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

2-keto-D-gluconate 93 100

2-cyanoethyl 2,3: 4,5-di ^ O-isopropylidene-2-keto-D-gluconate 95 88

U 0 9 8 U 7 1 11 1 -6

24U590

n-Nonyl 2,3: 4,5-di-O-isopropylden-

2-keto-D-gluconate% 93

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

2-keto-D-gluconate 93 93

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

2-keto-D-gluconate 97 85

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

2-keto-D-gluconate 98 90

3-chloropropyl 2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate 98 90

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

2-keto-D-gluconate 98 92

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

2-keto-D-gluconate 97 100

Zone control (untreated) 100 100

A09842 / 1113

Table VI

Post-emergence growth-retarding effect on Hordeum
distichon "nymph"

Compound (formulated as a plant height, cm, 25-6 wettable powder) days after treatment

Dose 6 kg / ha dose 2 kg / ha

η-butyl 2,3: 4,5-di-0-isopropyl-

iden-2-keto-D-gluconate 24.9 34.2

n-hexyl 2,3: 4,5-di-0-isopropyl-

iden-2-keto-D-gluconate 27.6 38.0

n-pentyl 2,3: 4,5-di-0-isopropyl-

iden-2-keto-D-gluconate 33.4 41.4

2-chloroethyl 2,3: 4,5-di-0-isopro-

pylidene-2-keto-D-gluconate 25.8 37.8

Allyl 2,3: 4,5-di-0-isopropylidene-

2-keto-D-gluconate 34.3 40.0

2-propynyl 2,3: 4,5-di-0-isopropyl-

iden-2-keto-D-gluconate 32.4 45.3

n-Nonyl 2,3: 4,5-di-0-isopropylidene-

2-keto-D-gluconate 27.7 38.0

n-propyl 2,3: 4,5-di-0-isopropylidene-

2-keto-D-gluconate 33.3 43.2

n-octyl 2,3: 4,5-di-0-isopropylidene-

2-keto-D-gluconate 35.4 44.2

4098i? / 1113

n-Dodecyl 2,3: 4 »5-di-O-isopropylidene-

2-keto-D-gluconate 38.2 44.1

Control (untreated) 44.2 44.2

0-9842 / 11 1 '■ *

Table VII

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

Compound (formulated as a $ 25 wettable powder)

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

n-Pentyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate 132

160

Methyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate 132

167

Cyanomethyl 2,3: 4 »5-di-0-isopropylidene-2-keto-D-gluconate 135

132

Ethyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate 135

147

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

135

163

2-cyanoethyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate 143

158

4-chlorobutyl 2,3: 4 »5-di-O-isopropylidene-2-keto-D-gluconate 145

A098A2 / 1113 157

2AU590

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

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

2-keto-D-gluconate 150 158

n-dodecyl 2,3: 4,5-di-0-isopropylidene-

2-keto-D-gluconate 148 153

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

2-keto-D-gluconate; 150 150

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

2-keto-D-gluconate 152 150

n-Octyl 2,3: 4,5 - ^. i-O-isopropylidene-

2-keto-D-gluconate 160 150

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

2-keto-D-gluconate. 158 162

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

2-keto-D-gluconate 162-130

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

2-keto-D-gluconate 168 120

Potassium 2,3: 4,5-di-0-isopropylidene-

2-keto-D-gluconate 165 153

Control (untreated) 181 181

Alar

(N-dimethylamino succinic acid

semihydraaid) 148 151

409847/1 1 1 3

24U590

Table VIII

Post-emergence growth retarding effects on Vitis

vinifera

Connection (formulated
as a 2% solution in
Acetone)

concentration

ppm plant height compared to control

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

isopropylidene-2-keto-D-

gluconate

4000 1000 40 51

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

4000 1000 69 80

Ethyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate 1000 68

83

n-propyl 2,3: 4,5-di-0-iso-4000

propylidene-2-keto-D-gluconate 1000

n-pentyl 2,3: 4,5-di-0-iso-4000

propylidene-2-keto-D-gluconate 1000

57 75

36 41

n-octyl 2,3: 4,5-di-0-iso-4000 propylidene-2-keto-D-gluconate 1000 39 65

Ammonium 2,3: 4,5-di-0-iso-4000 propylidene-2-keto-D-gluconate 1000 39 65

409842/1113

Table IX

Expressed Nachauflaufwachstumsverzögernde effect of 10 compounds of the formula I on various plants in fo the control.

link Echinochloa Setaria Alopecurus Avena
fatua Rumex Pagopyrum Sinapis - Daucus Datura Chrysan
themum. 2,3: 4,5-di-0-iso-
propylidene-2-keto-
_o D-gluconic acid 20th 40 80 - 60 40 - - - 30th 50 CO
oo potassium 2,3: 4,5-di-
* "* O-isopropylidene-2-
^ ⁰ keto-D-gluconate 10 40 - - 30th 60 - 50 30th 10 _ * Ammonium 2,3: 4,5-di-
- »O-isopropylidene-2-
~ keto-D-gluconate * - 20th - 50 50 40 30th 30th 10 2-propynyl 2,3: 4,5-
di-O-isopropylidene
2-keto-D-gluconate 20th 50 10 - - 40 60 10 - - n-pentyl 2,3: 4,5-di-
O-isopropylidene-2-kei
to-D-gluconate
I. 20th 60 20th 30th - 80 - . - 3-chloropropyl 2,3: 4, ^
di-O-isopropylidene-2-
ke t od gluc onate 60 30th 20th - 30th - - -

069ΗΫΖ

link Echinochloa Setaria Alopecia
curus Avena
fatua Rumex Pagopyrum Sinapis Daucus Datura Chrysan
themum n-octyl 2,3: 4,5-di-
O-isopropylidene-2-
keto-D-gluconate 10 60 30th " 50 .. 10 Allyl 2,3: 4,5-di-O-
isopropylidene-2-keto-
D-gluconate 30th 10 HB _r 20th 30th " 10 n-propyl 2,3: 4,5-di-O-
isopropylidene-2-keto-
D-gluconate _ 50 30th 40 _ Benzyl 2,3: 4-, 5-di-O-
isopropylidene-2-keto-
D-gluconate - 10 - - - 20th 40 - - - *

The post-emergence growth retarding effect of 2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconic acid is examined on different plants.

The plants to be examined are allowed to grow in plastic pots which contain mixed fertilizers. The seeds are sown in such a way that all plant species reach the appropriate stage of growth for the study at the same time. the Plants are grown in greenhouses and remain in them for the entire duration of the experiment. Means Mercury lamps produce 16 hours of light per day.

The compound under investigation is made as a wettable powder using kaolin as an inert diluent such as formulated as follows:

Vfo 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconic acid 2,5fo kaolin
$ 96 water

and small amounts of wetting agent and anti-foaming agent.

This suspension is sprayed onto the plants in amounts of 10 kg / hectare of active compound. 21 days after spraying the growth retardation is determined by measuring the height of the plant and comparing it to the height of an untreated plant certainly.

The test results are in the table below

X summarized.

409842/1113

Table X

Plant height, mm, 21 days after spraying

Plant species

Avena fatua Echinochloa crus-galli Fagopyrum vulgare Sorghum vulgar Sinapis alba Setaria faberii Datura stramonium Alopecurus pratensls Chrysanthemum segetum Rumex obtusifolius Stellaria media Daucus carota

control 2.3: 4.5 MO
isopropylidene
2-ket ο-D-glu-
cons acid 400 420 360 260 430 150 200 160 300 130 280 90 160 120 380 80 130 60 200 70 150 100 170 160

409842/1113

These data illustrate the growth retarding effects of 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconic acid in different plants. For example, in Alopecurus pratensis, a G-ras, which is very similar to a lawn grass is, a very good delay is achieved without chlorosis (yellowing of the grass). At Chrysanthemum segetum very good plant regulation is achieved without any harm to the plant.

In the following Tables XI and XII, the post-emergence and pre-emergence growth retarding effect of an aqueous Solution of ammonium-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconic acid combined in 12 useful and harmful plants.

The ammonium salt is diluted with deionized water which contains 1% Tween 20 (polysoxysorbitan monostearate) as a surface-active agent, the P n value being adjusted to 7.0. In both cases, atrazine [2-chloro-4- (ethylamino) -6- (isopropylamino) -5-triazine] is used as a comparison substance in the investigations into post-emergence and pre-emergence growth-retarding effects. The atrazine is applied in 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 examining the post-emergence retarding effect, it is preferable to cover the seeds with sand rather than soil, which gives better sensitivity. The height the earth layer is about 4.5 cm while that of the sand layer is about 5-6 mm.

4098 & 7/1 1 13

2AH590

When examining the pre-emergence retarding effect, a sandy loam soil is used and the moment des Sowing is chosen so that all plants have a suitable stage of growth at the same time, usually the appearance of the first fully formed leaf.

Both the post-emergence and pre-emergence examinations are carried out at a dose of 8 kg of active substance per hectare. The pre-emergence retarding effect is determined after 21 and 27 days and the post-emergence retarding effect after 18 and 27 days,

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

- no visible growth retardation, 2, 3 - slight delay, the plants show little or no reduction in growth on visible parts of the plant, 5 »6 - moderate growth retardation, plants show reduced growth on visible parts of the plant
, 8, 9 - severe lag, plants show little or no growth
- no growth.

40984? / 1113

Table XI Pre-emergence growth retarding effect of ammonium 2,3: 4.5-di-0-

isopropylidene-2- keto-D-gluconic acid

To Retarding effect After 27 Days NH * salt 21 days NH * salt Atrazine
default plant 8th 'Atrazine
default 8th 5 Cyperus esculentus 2 4th 1 10 Avena fatua 4th 10 2 9 Datura stramonium 3 VJl 3 10 Abutilon theophrasti VJl 10 4th 0 Sorghum halepense 2 0 2 9 Amaranthus sp. 3 8th 3 10 Brassica kaber 6th 10 6th 9 Setaria glauca 6th 9 7th 10 Echinochloa crus-galli 6th 10 8th 10 Digitaria sanguinalis 4th 10 4th 10 Oirsium arvense 3 9 IV) 10 IpomOea sp. 8th

CTl CO O

24H590

The ammonium salt of 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconic acid shows good pre-emergence growth retarding properties
Effect on certain plant species such as Gyperus esculentus, Echinochloa crus-galli and Digitaria sanguinalis.

409842/1113

plant Tabel XII Ammonium 2,3: 4,5-di-0- Delay effect After 27 Days Post-emergence Cyperus esculentus growth retarding Effect of isopropylidene-2-keto-D-gluconic acid 18 days NE With salt Atrazine
default Avena fatua Atrazine
default 9 10 Datura stramonium To 10 4th 10 Abutilon theophrasti NH + salt 10 8th 10 Sorghum halepense 5 10 VJl 10 Amaranthus sp. 4th 10 7th 4th Bras s ic a kab er 4th 5 VJl 7th Setaria glauca 7th 8th 10 10 Echinochloa crus-galli VJl 10 5 10 Digitaria sanguinalis 4th 9 8th 10 Cirsium arvense 8th 10 9 10 Ipom oea sp. 6th 9 7th 10 6th 10 9 10 8th 10 VJl 9

Cn CO O

24U590

The ammonium salt of 2,3: 4t5-di-0-isoprop.ylidene-2-keto-D-gluconic acid shows at a dose of 8 kg / ha a very good post-emergence growth retarding effect in most of the investigated Plant species, especially Cyperus esculentus, Echinochloa crusgalli and Digitaria sanguinalis.

409842/1113

It has also been found that a growth regulating agent which is one of the compounds of the general Formulas I, II, III and IV contain the force that is used when spraying on fruit-bearing trees must be significantly reduced in order to separate the fruit from the stem. This is evident from a comparison with untreated trees. It was also found that fruits, with the help of the growth regulators according to the invention harvested are relatively free from injury and rot.

The compositions according to the invention can be applied to the fruit-bearing trees in liquid or solid formulation be applied. The application can be on the roots, the trunks, the branches, the leaves or the fruits follow. For example, the fruit precipitating agents according to the present invention can be taken from the aircraft be sprayed or dusted on the trees, or applied to the base of the trees to make them Funds are absorbed through the roots. A preferred method of application, and also the most effective, is application the means in the form of an aqueous spray solution. If necessary, a formulation based on an appropriate organic solvent, such as an oily spray solution, can be used.

In order to achieve the greatest effect when using the normal fruit fall agents according to the present invention, the agent is preferably used one to two weeks before the fruit harvest - depending on the temperature. In areas where rain is to be expected, namely in the period between the application of the agent and the Harvest, a customary adhesive is expediently mixed into the formulations. Common examples of this Adhesives include, for example, glue, gases, salts

409842/1113

24H590

Alginic Acid, Oellulose Gum and Corresponding Derivatives, Polyvinyl pyrrolidone, invert syrup, grain syrup, etc.

The fruit fall agents according to the invention contain compounds of the formulas I, II, III and IV as active ingredients. If desired, conventional, inert materials, how they are used in agriculture, especially when the means concerned are used to treat trees serve and also come in connection with active ingredients of known fruit fall agents for use, are added. 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 fall agents according to the present invention vary, but in order to achieve an optimal effect it is necessary that a sufficient amount is used. Thus, an aqueous spray solution contains from about 0.05 to about 1.5fo (percent by weight) of active ingredient. Understandably, the concentration 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 falling agent is sprayed in such a way that the tree is covered with a gapless spray coating. This requires the use of approximately 300 to approximately 9000 liters of a dilute solution (approximately 0.1? A, (percent by weight), active ingredient) per hectare, depending on the number and size of the trees to be treated.

To create a preferred spray formulation, containing the fruit fall agent according to the present invention, the active ingredient or a salt thereof is in a carrier such as

409842/11 13

24U59G

Water dispersed or dissolved. The liquid spray solution can be based on $ 0.1 to about 0.5% (weight percent) based on the weight of the substrate, surfactant can be added. Typical surfactants are Triton ^ -B-1956, a water-dispersible resin-based constructed surfactant manufactured by Rohm and Haas. Furthermore, X-77 (Chevron-Ortho), a non-ionic surfactant based on alkylaryl-polyoxyethylene glycols, free fatty acids and isopropanol can be used.

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

As mentioned earlier, the fruit precipitants are used sprayed on the trees in the form of aqueous solutions.

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

The fruit fall agents according to the invention '.-.' Ground set a pH of 6-10 by means of a buffer, for example by adding potassium hydrogen sulfate to the aqueous Solution.

409842/1113

24U590

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

Wettable powders are made using an inert diluent such as kaolin. For example, a typical spray solution formulated with a wettable powder will contain the active ingredient, about 1 / S to about 5fo of inert diluent, minor amounts of dispersant, wetting agent and antifoam agent, and the appropriate and necessary amount of water.

The effect of the new fruit fall agents is illustrated below using Phaseolus vulgaris.

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

In the method used, seeds of the plant to be examined are placed 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% 0ptimasoil (8G? S peat and 20 ^ clay and Contains fertilizers), 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. For each dose, the examinations are carried out 8 times

409 8 42/1113

2AHÖ30

repeated. The growth-regulating effect is measured 4 and 6 days after treatment.

The fall of the petioles is measured by the not fallen petioles are counted. The drop effect is expressed in percentages by comparison with the effect measured on an untreated plant.

The test results are summarized in Table XIII below.

24Uo9ö

Table XIV

Falling effect on Phaseolus vulgaris

link

Cyanomethyl 2,3: 4,5-di-0-isopropylide en-2-ket ο-D-gluconate

fo petiole fall

Concentration (ppm)

1000 100

50

Sodium 2,3: 4,5-di-Q-isopropylidene-2-keto-D-gluconate 55

40

2-propynyl 2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate 70

15th

Ammonium 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate 50

50

Allyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate 45

40

n-Pentyl 2,3: 4,5-di-Q-isopropylidene-2-keto-D-gluGonate 45

45

n-propyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate 20th

15th

n-Hexyl 2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate 20th

15th

n-Dodecyl 2,3: 4,5-di-Q-isopropylidene-2-keto-D-gluconate 25th

20th

409842/1113

24145

n-butyl 2,5: 4,5-dI-O-isopropylidene-

2-keto-D-gluconate 20 15

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

2-keto-D-gluconate 15 20

3-chloropropyl 2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate 15 15

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

2-chloroethyl 2,3: 4,5-di-O-isopropylidene-2-keto-D-glugonate O 5

40984 2/1113

Whether now. as a fruit fall remedy or as a pre-emergence or each casserole herbicide, i.e. as soon as it is used as a If plant growth regulators are used, the compounds of the formulas 1, II, III and 17 can be prepared and be formulated as in the foregoing and in It is described below,

2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconic acid monohydrate is a well-known commercial preparation. It is produced by the oxidation of 2,3: 4j5-di-0-isopropylidene-ß-D-fructopyranose which in turn through. Implementation of D-fructose with acetone is obtained in the presence of a strong acid. The process for the preparation of Diisopropyliden-fruotopyranose is by

U.S. Patent Ho 3,607,862 illustrates

The novel compounds of the present invention can be prepared by a) an acid of the general formula

wherein R ₁ , R 2, R, and R, which have the meaning given in formula I, with a compound of the general formula

409842/1113

_ 61-

XR ₅ VI

wherein X is chlorine, bromine or a p-toluene sulfonic acid ester and Rj- straight or branched chain aliphatic.es hydrocarbyl; 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 two or three lower Alkyl, lower alkenyl, lower alkynyl, lower alkoxy, halo-lower alkyl, pormyl, lower alkylcarbonyl, lower alkoxycarbonyl, cyano, halogen, Nitro, hydroxy, lower alkoxyformainido, ureido, Methylenedioxy, amino or amino substituted with mono- or di-lower alkyl; Halo-lower alkyl; Halo-lower alkenyl; Halo-down 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 alkoxyι phenoxy-lower alkylcarbonyloxynieder alkyl, where the phenoxy group is optionally lower with one two or three nitro Alkyl, halogen, cyano, lower alkoxycarbonyl, lower alky! Carbonyl, methylenedioxy, amino or amino substituted by mono- or di-lower alkyl may be substituted; 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-down

409842/1113

alkyl; Amino-lower alkyl substituted with mono- or di-lower alkyl, hydroxy-lower alkyl, halo-lower alkyl, halophenyl, cyclopentyl or cyclohexyl; Hydrazino-lower alkyl; Furyl or furyl-lower alkyl means, reacts in the presence of a base, or

b) for the Pall that a compound of the formula II is sought is, where η is the number 2, one is an acid of the formula V with a compound of the general formula

^X 1 - ^{R 6 - X} 2 ^VI1

wherein X ₁ and Xp are chlorine, bromine or iodine and Rg is lower alkylene, is reacted in the presence of a base, or

c) one of the formula V corresponding acid chloride with an alcohol of the general formula

HO-E 'VIII

wherein RV is aryl optionally substituted with one, two or three lower alkyl, lower alkenyl, lower alkynyl, lower alkoxy, halo-lower alkyl, formyl, lower alkylcarbonyl, lower Alkoxy carbonyl, cyano, halogen, ITi tro, hydroxy, lower alkoxyformamido, ureido, Methylendiozyj amino or amino substituted with mono- or di-lower alkyl

means,
implements, or

d) in the event that a compound of the formula II The aim is, where η is the number 2, one of the formula V corresponding Acid halide with a mole of general formula

409842/1113

.63 ..

HO-R ₆ -OH ■ IZ

where R ^. that given in formula VII

Has meaning,
implements, or

e \ an acid of the formula Y with an alcohol of the formula VIII in the presence of p-Ioluenesulfonsäurechlorid and pyridine, or

f) an acid of the formula V with an alcohol of Formula VIII reacts 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 η is the number 1 and R 'is hydrazineum; Morpholineum; Thiomorpholinium; Piperasinium; Ammonium; Ammonium substituted with one or more lower alkyl, lower alkenyl, lower alkynyl, cycloalkyl with 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 a 3 acid of the general formula V with a compound of the general formula

wherein R ₇ , R _Q and Rq are hydrogen, lower alkyl, lower alkenyl, lower alkynyl, cycloalkyl with 3 to 6 carbon atoms, halo-lower alkyl, hydroxy-lower alkyl, aryl or benzyl, optionally substituted by halogen, nitro, lower alkyl or lower alkoxy , means,

or with hydrazine, morpholine, thiomorpholine or piperazine or, when η is 2, with calcium hydroxide or magnesium hydroxide brings in contact.

409842/1113

24H590

The salts of 2.3: 4.5- £> i-O-isopropylden-2-keto-D-gluconic acid are produced in the usual way. For this purpose, this compound becomes one with vigorous stirring a suitable solution of a base is added at room temperature. In this process, the solution is at a pH above 7 held. After the reaction has ended, the excess water is removed in a high vacuum. Anhydrous acetone (un- ' about 10 parts by volume) is then added to the resulting syrup and stirred overnight. The white crystalline precipitate which forms is filtered, washed with acetone and dried. In the case of non-volatile bases will be equivalent amounts of acids 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 in vacuo.

Since the acid is not stable under the usual esterification conditions such as, for example, the esterification according to Fischer is, one provides the new esters by reacting with, for example, the corresponding lower alkyl, lower alkenyl or lower alkynyl halides under basic conditions at room temperature by using inert organic solvents such as dimethylformamide (DMF) 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 the formula V with an alcohol of the formula VIII is preferably carried out in pyridine as Solvent and carried out in the presence of equivalent amounts of 'p-toluenesulfonic acid chloride. The mixture will heated to a temperature range of approximately 5 ° to approximately 50 °, preferably room temperature (cf. also J. Am Ghem. 3oc. 77, 6214 (1955)).

Furthermore, an acid of the formula V can be mixed with an alcohol Λ09842 / 1113

of formula VIII are reacted by adding these reactants in the presence of an equimolar amount Dicyclohexylcarbodiimide in an inert organic solvent to react. 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 indeed suitable for greenhouse experiments, but are not particularly useful for field experiments. Wettable powders cannot generally be used either, since the compounds have to 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 buffering at a pH of 6-10 is essential for the acid. The acid can also be formulated as an emulsion concentrate using N-Methy 1-2-pyrrolidone or ITitropyrrolidone as shown below:

'/ o (percent by weight) of the total formulation

2,3: 4,5-Di-O-isopropylidene-2-keto-D-gluconic acid 50

Atlox 2081B 4

N-Methy1-2-pyrrolidone or Nitropyrrolidone 46

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

The salts are soluble in water and do not require any special ones

Formulation.

409842/11 13

24U590

The esters of formula I are formulated as emulsifiable concentrates based on xylene, which are then mixed with water can. 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
Overall mix the 25th 50 71 46 2 - 2 - - 2 2

Active ingredient xylene
Atlox 3403 Atlox 3404 Emulphor EL 620 Drewmulse GMG-8

Atlox 3403 is a mixture of polyoxyethylene ethers,

Polyoxyethylene glycerine and alkylarylsulfonate.

Atlox 3404 is a mixture of polyoxyethylene alkylaryl ethers

and an alkyl aryl sulfonate.

Emulphor EL 620 is a polyethylated vegetable oil.

Drewmulse GMG-8 is the monoglyceride of a low molecular weight,

saturated coconut fatty acid.

A concentrated solution consisting of sodium 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate (95% weight percent) and sodium dioctyl sulfosuccinate (5% weight percent) is prepared and spray-dried. A wettable 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. To this dry mixture, $ 10 of the weight of this mixture is added to water * Part of the sodium salt of the 2,3: 4,5-Di-0-iso-

Propylidene-2-keto-l-gluconic acid is now dissolved and serves as a means of removing the remaining undissolved sodium 2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate to bind to the pumice stone granules.

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

In a further embodiment, the mixture is stirred to an aqueous solution of 2,3: 4,5-Bi-0-isopropylidene-2-keto-D-gluconic acid Ammonia (25 $ equimolecular amount) added. A clear solution with a pH of 8 is obtained. by adding ammonia drop by drop (25 $ ig) adds.

Compounds in which the 4,5-O-isopropylidene group is replaced by another grouping are produced by the so-called "ketal exchange reaction". Pure 2.3: 4> 5-Di-0-isopropylidene-2-keto-D-gluconic acid is used for this purpose dissolved in the desired ketone, aldehyde, ketal or acetal and added an acid catalyst. Leave these connections can also be produced by using a similar ketal exchange reaction and for this purpose 2,3: 4,5-di-O-isopropylidene-ß-D-fructopyranose used as starting material and the product obtained is then oxidized.

Representatives of the ketones and aldehydes which can be used in the preparative process are those of the general formula ^ -, in which R _{1n is,} for example, methyl,

^R ₁₀ - ⁰ - ^R ii

Ethyl, lower alkyl-phenyl or p-methoxyphenyl and R, -Methyl, Can be ethyl, lower alkyl or hydrogen. Typical connections of this type are for example

409842/1113

- 6δ -

24-590

Diethyl ketone, methyl ethyl ketone, paraldehyde, benzaldehyde and p-methoxyaldehyde. Ketones in which the two radicals R ₁₀ and R _{11 are} very large do not prove to be particularly favorable, since these radicals sterically hinder the reaction. If an asymmetrical aldehyde or ketone is used, the more voluminous residue is found in the "exo" position (R ₁ in formula I) after the reaction has taken place and is responsible for a new center of asymmetry.

Any strong acid can be used as a catalyst. A preferred catalyst is perchloric acid. Further representatives of such acids are sulfuric acid, hydrochloric acid, p-toluenesulfonic acid and methanesulfonic acid and trifluoromethanesulfonic acid.

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

Compounds in which both isopropylidene groups are replaced by other groups are based on Sorbose produced by the in Chem. Ber. 63 »843 (1930) is followed. In this method, a suitable ketone or a suitable aldehyde is used Fructose in the presence of a strong acid as a catalyst, for example sulfuric acid, at room temperature or implemented below room temperature. Thereafter, the intermediate product thus obtained is in alkaline or neutral The reaction medium is oxidized.

In the production of Bi-0-alkylidene-fructopyranose is preferably used as the acid catalyst perchloric acid, hydrochloric acid, p-toluene sulfonic acid, etc., wherein

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24H590

sulfuric acid is particularly preferred.

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

In the subsequent preparation of the acid from

The oxidation of the fructopyranose intermediate is carried out in a neutral or alkaline medium, using oxidizing agents such as sodium permanganate, potassium dichromate, potassium permanganate / potassium hydroxide and sodium hypochlorite / ITi ^ ⁺ . The last two oxidizing agents mentioned are preferred. Oxidation can also be accomplished catalytically 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, using ketones and aldehydes of the general formula R ₁ a-0- ^r tv in which R _{12 can be} halo-lower alkyl and R ₁ , halo-lower alkyl or hydrogen, active compounds of the general formula I, in which

R. and R 'or R _n, alkyl representing R _0, R ^ and R. Halo-lower. 12 12 5 4

The following examples illustrate the invention. All temperatures are given in degrees Celsius.

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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 added with stirring mixed and heated to reflux temperature. The resulting water is condensed and stored in a Dean-Stark water separator removed. 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 2,3: 4,5-Di-0-isopropylidene-β-D-fructopyranose of melting point 94-95 °.

Example 2

Ammonium salt of 2.5: 4-5-di-0-isopropylidene-2-keto-D-gluconic acid

To a solution of 23.8 g of potassium hydroxide and 15.8 g Potassium permanganate in 250 ml of water are stirred with 26 g of 2,3: 4,5-di-0-isopropylidene-ß-D-fructopyranoae, which as in Example 1 was prepared, was added. The solution is heated to 50 ° -60 ° while stirring and for two hours kept at this temperature. Then 15.8 g of potassium permanganate are added and the mixture is stirred at 50 ° -60 ° continued overnight. The solution is filtered and the filtrate is concentrated to 125 g, cooled to 0 °, to pH 2.0 brought and extracted 3 times with methylene chloride. The methylene chloride is removed and concentrated ammonium hydroxide admitted. Evaporation of the excess ammonia under vacuum gives the ammonium salt. By recrystallization

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_ 71 -

24M59Q

13.5 g of ammonium 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconic acid are obtained from chloroform from a melting point of 190 ° -200 °.

Example 3

In analogy to Examples 1 and 2, various disubstituted glyconic acids and their salts can be prepared. Using diethyl ketone instead of acetone in Example 1, 2,3: 4,5-di-0- (3-pentylidene) -2-keto-D-gluconic acid is prepared. With methyl ethyl ketone instead of acetone, 2,3: 4,5-di-O- (2-butylidene) -2-keto-D-gluconic acid is produced. With cyclohexanone, 2,3: 4,5-di-0-cyclohexylidene-2-keto-D-gluconic acid is produced. With chloral as the reagent, 2,3: 4,5-di-O- (2,2,2-trichlpräthylidene) -2-keto-D-gluconic acid is produced. Similarly, other G-luconic acid derivatives in which R ₁ , Rp, R_ and R are hydrogen, straight-chain or branched hydrocarbyl, halo-lower alkyl or aryl or when R 1 and R together and R and R together are saturated rings with 3 "to 8 carbon atoms mean to be produced.

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

To a solution of 10 g of anhydrous potassium carbonate in 75 ml of dimethylformamide are added with stirring at room temperature 3-3.7 g of 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconic acid monohydrate and then given 25 g of ethyl bromide. Stirring is continued for 3 days at room temperature. That Mixture x is then filtered to remove inorganic salts and the dimethylformamide by distillation in Vacuum (approx. 60 ° and approx. 10 Torr) removed. 20 ml of acetone are added to dissolve the remaining ether. Undissolved inorganic salts are filtered off. The filter-

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cake is washed out with 10 ml of acetone. The filtrate will added to the solution containing the ester and the crude product isolated by vacuum distillation of the solvent. Vacuum distillation at 94 ° and 0.1 mm Hg is obtained 16.4 g of ethyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate.

According to this generally applicable provision, ■ 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 manufactured. Using a molar ratio of 1: 1, 2-bromoethyl 2.3: 4 becomes> 5-di-O-isopropylidene-2-keto-D-gluconate manufactured.

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

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

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 with Washed 10 ml of acetone. The filtrate is combined with the ester solution and then in vacuo to a syrup concentrated. The vacuum distillation at 92 ° and at 0.1 mm Hg gives 19.4 g of liquid methyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate.

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Example 6 n-Buty1 ^ 2.3: 4.5-di-0-isopropylidene-2-keto-D-gluconate

While stirring, 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 removed in this way. 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 of acetone. The filtrate is combined with the ester solution and concentrated in vacuo. Vacuum distillation at 96 ^° C. (0.1 mm) yields 19.7 g of n-butyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate.

In a similar way, other straight-chain and branched, aliphatic hydrocarbyl and halo-lower alkyl esters getting produced.

Example 7 Sodium 2.3-0-isopropylidene-4.5-0-ethylidene-2-keto-D-

gluconate

48 g of 2,3: 4,5-Qi-0-isopropylidene-2-keto-D-gluconic acid are dissolved in 250 g of paraldehyde. Five drops of 10 perchloric acid are added and the reaction is then allowed to proceed for 12 days at room temperature with constant monitoring, by means of thin-layer chromatography or gas-liquid chromatography. The solution is then added, with vigorous stirring, to 16.8 g of sodium bicarbonate which was slurried in 100 ml of water. Excess paraldehyde and excess water are des-

409842/1 1 13

tilled. The residue is recrystallized from alcohol / water and sodium 2,3-0-isopropylidene-4,5-0-ethylidene-2-keto-D-gluconate is obtained. Refer to the physical chemical data (nuclear magnetic resonance spectrum, mass spectrum, infrared spectrum) on the following structure;

.COONa

In the same way as described above, other 2,3-0-isopropylidene-4,5-0- (R ₁ -Rp) -2-keto-D-gluconic acids (structure I), wherein the R-, and R_- Substituents straight-chain or branched, aliphatic lower hydrocarbyl, halo-lower alkyl, aryl, or R, and R_ together represent a saturated ring with 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 Methylene chloride and, while stirring and cooling with ice, 3.2 ml of thionyl chloride are added dropwise. After 3 hours 5.9 ml of 2-chloroethanol are added to the reaction solution at room temperature and the mixture is then stirred for a further 3 hours. The reaction solution is then taken up in methylene chloride and successively with ice-cold 2N hydrochloric acid,

409842/1113

Washed N sodium hydroxide solution and water, the organic phase dried over sodium sulfate and evaporated. The residue is purified on a silica gel column and then distilled. 5 g of oily product are obtained, boiling point 129 ° C./0.02 Torr.

The following compounds can be prepared in analogy to the above examples:

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

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-

gluconate;

n-heptyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-glucoiiat,

Bp 135-136 ° (0.01 mm Hg);

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

Bp 124 ° (0.02 mm Hg);

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

Bp 95 ° (0.01 mm Hg);

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

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

(p-A ethoxycarbonyl) phenyl 2,3: 4,5-di-O-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;

α-naphthyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate; 3,4- (methylenedioxy) phenyl 2,3: 4,5-di-0-isopropylidene-

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2-keto-D-gluconate;

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

n-Dodecyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate, Bp 119 ° (0.01 mm Hg);

n-propyl 2,3: 4, S-di-O-isopropylidene - ^ - keto-D-gluconate,

Bp 101 ° (0.005 mm Hg);

n-Pentyl 2,3: 4,5-di-0-isopΓopyliden-2-keto-D-gluconate ^

Bp 106 ° (0.005 mm Hg);

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

Bp 126 ° (0.03 mm. Hg);

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

Bp 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, S-di-O-isopropylidene ^ -keto-D-glaconate;

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

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

Bp 106 ° (0.05 mm Hg);

Dimethyl ammonium 2,3: 4,5-di-0-isopropylidene-2-keto-

D-gluconate;

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

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

3-chloropropyl 2,3: 4,5-di-Q-isopropylidene-2-keto-D-gluconate, Bp 112 ° (0.02 mm Hg);

(Ethoxycarbonyl) methyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate, Bp 89-90 ° (0.02 mm Hg);

Cyclohexyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate; Bp 103 ° (0.025 mm Hg)

Cyanomethyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate, Bp 102-103 °; (0.005 mm Hg)

2,4,6-trichlorophenyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate;

(12-propargyloxy) dodecyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate;

24Ί4590

Iao-propyl 2,3: 4 »5-di-0-isopropylidene-2-keto-D-gluconate; 2-hydroxyethyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-

gluconate;

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

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

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

2- [2- (phenoxy) propionyloxy] ethyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate;

2-propynyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate, bp 103 ⁰ C (0.025 mm Hg);.

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

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

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

2,3: 4,5-di-O- (p-methoxybenzylidene) -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- (1,1,3-trichloroisopropylidene) -2-keto-D-gluconic acid;

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

2,3-0-isopropylidene-4,5-0- (1,1,1,3,3-pentachloroisopro-409842/1113

pyliden) -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- (1,1,1,3,3,3-hexachloroisopropylidene) -2-keto-D-gluconic acid;

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

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

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

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

2,3-0-isopropylidene-4,5-0- (1,1,1,3 »3-pentafluoroisopropylidene) -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- (1,1,1,3,3,3-nexafluoroisopropylidene) -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;

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

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

409842/1113

2,3-0-Isopropylidene-4, 5-0- (1,1,1-tribromoisopropylidene) -2-keto-D-gluconic acid;

2,3: 4,5-di-0-methylene-2-keto-D-gluconic acid; 2,3 ^ 4,5-di-0-ethylidene-2-keto-D-gluconic acid; 2,3: 4,5-di-O- (2-butylidene-2-keto-D-gluconic acid; 2,3: 4,5-di-0-cyclohexylidene-2-keto-D-gluconic acid;

2,3: 4,5-Di-O- (2-chloroethylidene) -2-keto-D-gluconic acid;

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

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

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

2,3: 4,5-Di-O- (2,2-dichloroethylidene) -2-keto-D-gluconic acid;

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

2,3: 4,5-di-O- (2,2,2-trichloroethylidene) -2-keto-D-glucoic acid;

2,3: 4,5-Di-O- (2-fluoroethylidene) -2-keto-D-gluconic acid;

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

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

2,3: 4,5-di-O- (I, 1,1,3-tetrafluoroisopropylidene) -2-keto-D-gluconic acid; 2,3: 4,5-Di-O- (2,2-difluoroethylidene) -2-keto-D-gluconic acid;

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

2,3: 4,5-di-O- (I, 1,1,3,3-pentafluoroisopropylidene) -2-keto-D-gluconic acid ;

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

2,3: 4,5-di-O- (1,1,1,3,3,3-hexafluoroisopropylidene) -2-keto-D-gluconic acid ; 2,3: 4,5-di-O- (2-bromoethylidene) -2-keto-D-gluconic acid;

409842/1113

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

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

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

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

2,3: 4,5-Di-O- (2,2,2-tribromathylidene) -2-keto-D-gluconic acid ;

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

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

Bis (2-hydroxyethyl) ammonium 2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate;

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

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

Pentyl 2,3 · 4,5-di-0-sec-butylidene-2-keto-D-gluconate, Bp 99-100 ° (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, Bp 85 ° (0.005 mm Hg);

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

Ethyl 4,5-O-ethylidene-2,3-0-isopropylidene-2-keto-D-gluconate, Bp 80-90 ° (0.01 mm Hg);

2-cyanoethyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate, Bp 93 ° (0.003 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-gluconate, Bp 134 ° (0.005 mm Hg);

24U590

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

4098-42 / 1113

Claims (203)

Claims 1. Process for the preparation of compounds of the general formula R ¹ R ¹ C-O RIXH ₂ O wherein, when η is the number 1, R ^{1 is} hydrogen; Sodium; Potassium; Hydrazinium; Corpholinium; Thiomorpholinium; Piperaziniu = ^; Ammonium; Ammonium substituted with one or more lower alkyl, lower alkenyl, lower alkynyl, cycloalkyl with 5 to β carbon atoms, halu-lower alkyl, hydroxy-lower alkyl, aryl or benzyl, optionally substituted with halogen, nitro, lower alkyl or lower alkoxy; straight or branched chain aliphatic hydrocarbyl; 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, lower alkenyl, lower alkynyl, lower alkoxy, halo-lower 409842/1113 2AH590 alkyl, formyl, lower alkylcarbonyl, lower Alkoxycarbonyl, cyano, halogen, nitro, hydroxy, lower alkoxyformanido, ureido, methylenedioxy, Amino or amino substituted with nono- or di-lower Alkyl; Halo-lower alkyl; Halo-lower alkenyl; Halo-lower a3.kynyl; lower alkoxycarbonyl-lower alkyl; Phosphono-lower alkyl; Thiophosphono-lower alkyl; lower alkylamino-carbonyl-lower alkyl; lower alkylthio-lower alkyl; Arylthio-lower alkyl; Cycloalkyl, optionally substituted by halogen, nitro, lower alkyl or lower alkoxy; Phenoxy-lower alkylcarbonyloxy-lower alkyl, where the phenoxy group optionally nit one, two or three nitro, lower alkyl, halogen, cyano, lower alkoxycarbonyl, lower alkylcarbonyl, Methylenedioxy, amino or aniiio substituted be substituted by mono- or di-lower alkyl can; 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 by mono- or di-lower alkyl, hydroxy-lower alkyl, halo-lower alkyl, halophenyl, cyclopentyl or cyclohexyl; Hydrazino-lower alkyl; Puryl or furyl lower alkyl; and when η is the number 2, R ^{1 is} calcium; Magnesium or lower alkylene, R ¹ , R ¹ ₂ , R 'and R' lower alkyl, lower alkenyl, lower alkynyl, halo-lower alkyl, aryl, optionally substituted by halogen, nitro, lower alkyl or lower alkoxy, or R ¹ , and R '"together and R ¹ ^ and 409842/1113 24H590 R 'together each denote a saturated ring with 3 Ms 8 carbon atoms, η the number 1 or 2 and X the number 0 or 1, enantiomers and racemic mixtures, but for the case that R ^{1 is} hydrogen, ammonium, methyl, sodium or Potassium and R ^, R ' ₂ , R «and R · mean lower alkyl, the lower alkyl group comprises more than 1 carbon atom, characterized in that one a) an acid of the general formula where R- ,, R _? , R- and R. hydrogen, straight-chain or branched aliphatic lower hydrocarbyl, halo-lower alkyl, aryl, optionally substituted by halogen, nitro, lower alkyl or lower alkoxy, or R-, and Rp together and R-, and R, together each represent a saturated ring having 3 to 8 carbon atoms, with a compound of the general formula X-R, - VI 409847/1113 wherein X is chlorine, bromine, iodine or a p-toluenesulfonic acid ester and R ₁ . straight or branched chain aliphatic hydrocarbyl; Hydroxy-lower alkyl; lower alkoxy-lower alkyl; lower alkenyloxy-lower alley 1; lower alkynyloxy-lower alkyl; lower alkyl-sulfonyloxy-lower alkyl; Arylsulfonyloxy-lower alkyl; Benzyl, 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 by 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, wherein the phenoxy group optionally carries nit one, two or three nitro, lower alkyl, halogen, cyano, lower alkoxycarbonyl, lower alkylcarbonyl, methylenedioxy, amino or amino substituted by mono- or di-lower alkyl may be substituted ; Morpholino-lower alkyl; Thio morpholino-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 sub- 4098 42/11 13 -εό - substituted with mono- or di-lower alkyl, hydroxy-lower alkyl, halo-lower alkyl, halophenyl, cyclopentyl or cyclohexyl; Hydrazino-lower alkyl; Furyl or furyl lower alkyl means reacts in the presence of a base, or b) in the event that a compound of the formula II is sought is, wherein η is the number 2, one is an acid of the formula Y with a compound of the general formula wherein X-, and X _{2 are} chlorine, bromine or iodine and Rg is lower alkylene, is reacted in the presence of a base, or c) an acid chloride corresponding to the formula V with an alcohol of the general formula HO-R 'VIII wherein R 'is 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 by mono- or di-lower alkyl means, reacts, or d) in the event that a compound of the formula II
The aim is where η is the number 2, one of the formula V
corresponding acid chloride with a diol of the general formula HO-R, -OH IX 40984 _ 87 _ 2AH590 where Rg has the meaning given in formula VII,
implements, or e) an acid of the formula V is reacted with an alcohol of the formula VIII in the presence of p-tosyl chloride and pyridine, or f) 'an acid of the formula V with an alcohol of the 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 η is the number 1 and R ^{1 is} hydrazinium; Morpholinium; Thiomorpholinium; Piperazinium; Ammonium, ammonium substituted with one or more lower alkyl, lower alkenyl, lower alkynyl, cycloalkyl with 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 formula V with a compound of the general formula ^R 9 wherein R ", R _Q and R" are hydrogen, lower alkyl, lower alkenyl, lower alkynyl, cycloalkyl with 3 to 6 carbon atoms, halo-lower alkyl, hydroxy-lower alkyl, aryl or benzyl, optionally substituted by halogen, nitro, lower alkyl or lower alkoxy, or with hydrazine, morpholine, thiomorpholine or piperazine, or, when η is 2, with calcium hydroxide or magnesium hydroxide brings in contact. 0 9 8 λ? / 1 1 1 3 -83 - 24U590 2. The method according to any one of claims la or Ib, characterized in that potassium carbonate is used as the base and dimethylformamide as the solvent. 3. The method according to any one of claims lc or Id, characterized in that an acid binder and an inert solvent are used. 4. The method according to any one of claims lc or Id, characterized in that pyridine is used as the acid binder and methylene chloride as the inert solvent got. 5. Agent for regulating plant growth, characterized in that it is in addition to the usual carrier material a sufficient amount of one or more compounds of the general formula -R.XH 0 wherein, when η is the number 1, R is hydrogen; Sodium; Potassium; Etydrazinium; Morpholinium; Thiomorpholinium; Piperazineum3 ammonium; Ammonium substituted with one or more lower alkyl, lower alkenyl, lower alkynyl, Cycloalkyl, with 3 to 6 carbon atoms, 4 0 9 8 U ') / 1 11 - 83 ■ - 24H590 Halo-lower alkyl, hydroxy-lower alkyl, aryl or benzyl, optionally substituted with halogen, nitro, lower alkyl or lower alkoxy; straight chain or branched aliphatic3 Hydrocarby1; 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 substi tuated 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 alkoxyformaraido, ureido, methylenedioxy, amino or Amino substituted with nono- 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 optionally with one, two or three nitro, lower alkyl, halogen, Cyano, lower alkoxycarbonyl, lower alkylcarbonyl, Methylenedioxy, amino or amino substituted with mono- or di-lower alkyl, may be substituted; 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, the amino group being mono- or di-substituted with lower alkyl, hydroxy-lower alkyl, halo-lower alkyl, halopheny1, cyclopentyl or cyclohexyl; Hydrazino-lower alkyl; Furyl or furyl-lower alkyl; if η is the number 2, R calcium, magnesium or lower alkylene, R ,, R _? , R and R. Hydrogen, straight-chain or branched aliphatic lower hydrocarbyl, halo-lower alkyl, aryl, optionally substituted by halogen, nitro, lower alkyl or lower alkoxy, or R ₁ and R 1 together and R 1 and R together each have a saturated ring with 3 to 8 carbon atoms denote, η denotes the number 1 or 2 and X denotes the number 0 or; as well as enantiomeric and racemic mixtures
and / or contains salts thereof as an active ingredient. β. Means according to claim 5, characterized in that that there is one or more compounds of the general formula as active ingredient 409847/1113 24U590 VXH ₂ O _ η wherein, when η is the number 1, R "is hydrogen, sodium, potassium, ammonium, substituted Ammonium, straight or branched aliphatic hydrocarbyl, or halo-low alkyl and, when η is the number 2, R "calcium, magnesium or lower alkylene, R", R ", R "and R" are hydrogen, straight-chain or branched aliphatic lower Hydrocarbyl, halo-lower alkyl, aryl or R "and R" together and R "and R ". Together each form a saturated ring with 3 to 8 carbon atoms mean, η and X have the meaning given in formula I, and / or salts thereof. 7 .. Agent according to claim 6, characterized in that R ¹ ^, R " ₂ , R" and R "mean methyl. 8th . Agent according to claim 5, characterized in that it is one or more compounds of the general formula -9ft / " 24U590 O —R " contains. where R " ^{1 is} hydrogen; sodium; potassium; ammonium; substituted ammonium; calcium; magnesium, lower alkyl or lower alkylene, 403842/1113 24U590 9, means according to claim 5, characterized in that that it is the active ingredient 2,3: 4,5 -di-O-isopropylidene ^ -keto-D-gluconic acid monohydrate contains. 10. Composition according to claim 5, characterized in that it contains methyl 2,3: 4 _f 5-di-0-isopropylidene - 2-keto-D-gluconate as active ingredient, 11. Composition according to claim 5, characterized in that it contains ethyl 2,3: 4 , 5-di-0-isopropylidene-2-keto-D-gluconate as active ingredient. 12. Composition according to claim 5, characterized in that the active ingredient is n-butyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate contains. 13. Composition according to claim 5, characterized in that it is the active ingredient n-dodecyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate contains. 14. Composition according to claim 5 » characterized in that it contains allyl 2,3: 4,5-di-0-isopropylidene-2-keto-D.-gluconate as active ingredient. 15. Composition according to claim 5, characterized in that it is the active ingredient urodium - ^^^^ - di-O-isopropylidene-2-keto-D-gluconate contains. 16. Composition according to claim 5, characterized in that it is Ealium-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate as active ingredient contains. 17. Composition according to claim 5, characterized in that it is ammonium 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate as the active ingredient contains. 24H590 18th Composition according to claim 5 t characterized in that it as an active ingredient calcium 2,3: contains 4> 5-di-O-isopropylidene-2-keto-D-gluconate. 19. Composition according to claim 5, characterized in that the active ingredient is n-propyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate contains. 20. Composition according to claim 5, characterized in that it is benzyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate as the active ingredient contains. 21. Agent according to claim 5, characterized in that it is n-Penty1-2,3? 4,5-di-0-isopropylidene-2-keto-D-gluconate as active ingredient contains. 22. Composition according to claim 5, characterized in that it is dimethylammonium-2,3: 4,5-di-0-isopropylidene-2-keto-D-glucanate as the active ingredient contains. 23. Composition according to claim 5, characterized in that it is the active ingredient n-decyl-2,3: 4,5-di-O-isopropylidene-2-keto-P-gluconate contains. 24. Agent according to claim 5 »characterized in that it is isoamyl-2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate as active ingredient contains. 25. Composition according to claim 5, characterized in that it is 2-butyl-2,3: 4 »5-di-0-isopropylidene-2-keto-D-gluconate as the active ingredient contains. 26. Composition according to claim 5 »characterized in that it has 2-bromoethyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate as the active ingredient contains. 409842/1113 24H590 27 .. Means according to claim 5, characterized in that that the active ingredient is N-Aethanolaromonium - 2,3: 4,5-di-0-isopropylidene-2-keto-P-gluconate contains. 28 · Agent according to claim 5, characterized in that it contains bis-2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate-ethylene glycol ester as active ingredient contains. 2g. Agent according to claim 5, characterized in that it has 2-propynyl-2,3: 4,5 di-O-isopropylidene-2-keto-D-gluconate as active ingredient contains. 30. Means according to claim 5, characterized in that that the active ingredient is 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconic acid contains. 31. Means according to claim 5 »characterized in that that the active ingredient is hydrazinium 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate contains. 32. Agent according to claim 5, characterized in that it is 3-chloropropyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate as the active ingredient contains. 33 · Agent according to claim 5, characterized in that it is (ethoxycarbonyl) methyl 2,3: 4, 5-di-0-isopropylidene-2-keto-D-gluconate as active ingredient contains. 34. Means according to claim 5, characterized in that that the active ingredient is cyclohexyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-giuconate contains. 35. Means according to claim 5> characterized in that that the active ingredient is cyanomethyl-2,3: 4,5-di-O-isopropylidene- Contains 2-keto-D-gluconate. 409842/1113 2AU590 36. Agent according to claim 5, characterized in that the active ingredient is p-nitropheny1-2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate contains. 37. Agent according to claim 5, characterized in that the active ingredient is p-chlorophenyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate contains. 38. Agent according to claim 5, characterized in that the active ingredient is n-heptyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate contains. 39. Agent according to claim 5, characterized in that it contains n-octyl-2,3: 4 _f 5-di-0-isopropylidene-2-keto-D-gluconate as active ingredient. 40. Agent according to claim 5, characterized in that it contains n-nonyl-2,3: 4 _f 5-di-0-isopropylidene-2-keto-D-gluconate as active ingredient. 41 # Agent according to claim 5, characterized in that "the active ingredient is n-undecyl-2,3: 4,5-di-0-isopropylidene-2-keto'-I> -glu.conate contains. 42. Agent according to claim 5, characterized in that it has 2,2,2-trichloroethyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-glu.conate as active ingredient contains. 43. Composition according to claim 5, characterized in that it is used as the active ingredient Fur fury 1-2,3: 4, 5-di-O-isopropylidene- ■ Contains 2-keto-D-gluconate. 44. Agent according to claim 5, characterized in that the active ingredient is p-gyanophenyl-2,3: 4,5-di-0-isopropylidene- 409842/1113 24H590 Contains 2-keto-D-gluconate. 45. Medium according to claim 5, characterized in that it is the active ingredient (p-ethoxycarbonyl) phenyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate contains. 46. Agent according to claim 5, characterized in that the active ingredient is p- (tert-butyl) pheny1-2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate contains! 47. Agent according to claim 5, characterized in that the active ingredient is p-acetylphenyl-2,3: 4 »5-di-0-isopropylidene-2-keto-D-gluconate contains. 48. Agent according to claim 5, characterized in that it contains a-naphthyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate as active ingredient. 49. Composition according to claim 5, characterized in that it contains 3> 4- (methylenedioxy) pheny1-2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate as the active ingredient contains. 50. Agent according to claim 5, characterized in that it is 2- (2-methyl-3-phenyl) propyl-2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate as the active ingredient contains. 51. Agent according to claim 5, characterized in that it is 2,4,6-trichlorophenyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate as the active ingredient contains. 52. Means according to claim 5, characterized in that that it as an active ingredient (^ -PropargyloxyJ Contains O-isopropylidene-2-keto-D-gluconate. 24U590 53. Agent according to claim 5, characterized in that it is isopropyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-glu.conate as active ingredient contains. 54. Agent according to claim 5, characterized in that it is 2-hydroxyethyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate as the active ingredient contains. 55. Means according to claim 5, characterized in that that the active ingredient is 4-chloro-2-butynyl-2,3: 4,5-di-O-isopropylidene-2-keto-D-glu.conate contains. 56. Agent according to claim 5, characterized in that it is 3-chloro-2-propenyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate as the active ingredient contains. 57. Agent according to claim 5, characterized in that it has 3-chloro-2-butenyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate as the active ingredient contains. 58. Composition according to claim 5, characterized in that it contains 2- [2- (phenoxy) propionyloxy] ethy1-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate as the active ingredient contains. 59. Agent according to claim 5, characterized in that it has 2,3-0-isopropylidene-4,5-0- (2,2,2-trifluoroethylidene) -2-keto-D-gluconic acid as the active ingredient contains. 60. Agent according to claim 5, characterized in that it is 2,3-0-isopropylidene-4,5-0- (l, l, l, 3,3,3-hexafluoroisopropylidene) -2-keto-D- gluconic acid contains. 61. Agent according to claim 5, characterized in that it contains 2,3-0-isopropylidene-4,5-0- (2-broni- ethylidene) -2-keto-D-gluconic acid. 409842/1113 - 9 ⁽ J - 24U590 62 · Agent according to claim 5, characterized in that it has 2,3-0-isopropylidene-4,5-0- (1,3-dibromoisopropylidene) as active ingredient Contains -2-keto-D-gluconic acid. 63. Agent according to claim 5, characterized in that it has 2,3-0-isopropylidene-4,5-0- (l, l, 3-tribromoisopropylidene) -2-keto-D-gluconic acid as the active ingredient contains. 64 · Agent according to claim 5, characterized in that the active ingredient is 2,3-0-isopropylidene-4,5-0- (2,2-dibromoethylidene) -2-keto-D-gluconic acid contains. 65. Agent according to claim 5, characterized in that it is 2,3-O-isopropylidene-4,5-O- (l, l, 3,3-tetrabromoisopropylidene) -2-keto-D-gluconic acid as the active ingredient contains. 66. Means according to claim 5> characterized in that that the active ingredient is 2,3-0-isopropylidene-4, 5-0- (2,2,2-tribromoethylidene) -2-keto-D-gluconic acid contains. '67. Means according to claim 5, characterized in that that the active ingredient is 2,3-0-isopropylidene-4,5-0- (l, l, l-tribromoisopropylidene) -2-keto-D-gluconic acid contains. 68. Composition according to any one of claims 5-67, characterized in that it is $ 0.01 to £ 95 / £ of at least one Compound, as defined in claims 5-67, contains. 69. Composition according to claim 68 in concentrate form, characterized in that it is $ 40 to $ 95 at least a compound as defined in claims 5-67. 409842/11 13 70. The composition of claim 68 in ready-to-spray form, characterized in that it is at least $ 0.01 to $ 25 a compound as defined in claims 5-67. 71. Agent for regulating plant growth, characterized in that it, in addition to the usual carrier material a sufficient amount of a mixture consisting of about 4 parts to about 16 parts of at least a compound as defined in claims 5-67 and one part contains 2,4-dichlorophenoxy-acetic acid. 409842/11 13 72. Process for regulating plant growth _f, characterized in that the plants to be regulated are treated with a sufficient amount of at least one compound as defined in claims 5-71. 73. Process for the production of an agent for regulating plant growth, characterized in that that you have a sufficient amount of at least one compound as defined in claims 5-71, with inert, solid or liquid auxiliaries like them are common in such agents, mixed. 74. Process according to Claim 73, characterized in that that at least one compound as defined in claims 9-71 is mixed with pumice stone granules. 75. Process according to Claim 73, characterized in that that one 2,3: 4,6 ~ di-0-isopropylidene-2-keto-L-gulonic acid with mixed with granulated pumice stone. 76. Use of one or more compounds as defined in claims 5-67 as Plant growth regulator. 409842/1113 24H590 77 · Compounds of the general formula C-O RiXH ₂ O wherein, when η is the number 1, R ^{1 is} hydrogen; Sodium; Potassium; Hydrazinium; Morpiiolinium; Thiomorpholine around; Piperazinium; Aamonium; 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, uritro, lower alkyl or lower alkoxy; straight or branched chain aliphatic hydrocarbyl; Hydroxy-lower alkyl; lower A3.koxy-lower alkyl; lower alkenyloxy-lower alkyl; lower alkynyloxy-lower alkyl; lower alkyl-sulfonyloxy-lower al ^ l; Arylsulfonyloxy-lower alVyl; Aryl or benzyl, optionally substituted by one two or three lower alkyl, lower alkenyl, lower alkynyl, lower alkoxy, halo-lower 409842/1113 alkyl, formyl, lower alkylcarbonyl, lower alkoxycarbonyl, cyano, halogen, nitro, hydroxy, lower alkoxyformainido, ureido, methylenedioxy, amino or amino substituted by nono- 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 can optionally be substituted with one, two or three nitro, lower alkyl, halogen, cyano, lower alkoxycarbonyl, lower alkylcarbonyl, methylenedioxy, amino or amino substituted by mono- or di ~ lower alkyl ; Morpholino-lower alkyl; Thioraorpholino-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; Furyl or furyl-lower alkyl; and when η is the number 2, R ^{1 is} calcium; Magnesium or lower alkylene, R ', R'p, R ¹ , and R' lower alkyl, lower alkenyl, lower alkynyl, halo-lower alkyl, aryl, optionally substituted by halogen, nitro, lower alkyl or lower alkoxy, or R ¹ , and R ' _? together and R'_ and 409842/11 1 * 3 24H590 R 'together each denote a saturated ring with 3 to 8 carbon atoms, η the number 1 or 2 and X the number 0 or 1, enantiomers and racenic mixtures, but for the case that R' is hydrogen, methyl, ammonium, sodium or Potassium and ϋ ^! _χ , R ' ₂ , R' and R · mean lower alkyl, the lower alkyl group comprises more than 1 carbon atom. 78. Compounds of the general formula 0- " R _a .XH ₂ 0 11.1 wherein when η is 1, Ra is hydrazinium; Morpholinium; Thiomorpholinium; Piperazinium; 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; ^ straight-chain or branched aliphatic hydroxycarbyl with more than one carbon atom; Hydroxy-lower alkyl; lower alkoxy-lower alkyl; lower alkenyloxy- lower 409847/1113 24H590 alkyl; lower alkynyloxy lower alkyl; lower alkylsulfonyloxy-lower alkyl; Arylsulfonyloxy lower alkyl; Aryl or benzyl, 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, Mtro, hydroxy, lower alkoxyforaaido, LTreido, methylenedioxy, amino or amino substituted with mono- or di-lower alkyl; Halo-lower alkyl; Halo low 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; Phenoxy-lower alkylcarbonyloxy-lower alkyl, the phenoxy group optionally with one, two or three nitro, lower alkyl, halogen, cyano, lower alkoxycarbonyl, lower alkylcarbonyl, methylenedioxy, amino or amino substituted with mono or di-lower alkyl may be substituted; Morpholino lower alkyl; Thiomorpholino-lower alkyl; Piperazino lower alkyl; Phenylamino-lower alkyl or benzylamino-lower alkyl, where the Phenyl group is optionally substituted with 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; Furyl or furyl low alkyl and, when η is the number 2, 409842/1113 R calcium, magnesium or lower alkylene, , R, .. and R. ^ lower alkyl, lower 24H590 Alkenyl, lower alkynyl, halo-lower alkyl, aryl optionally substituted with Halogen, nitro, lower alkyl or lower alkoxy or R ,, and Rp-, together and R ,, and R.-. together each represent a saturated ring with 5 to 8 carbon atoms, η represents the number 1 or 2 and X represents the number 0 or, -enantiomers and racemic Mixtures. 79 · Compounds of the general formula -R _b .XH ₂ 0 wherein, when η is 1, R,, substituted ammonium, straight-chain or branched aliphatic hydrocarbyl with more than one carbon atom or
Halo-lower alkyl and, if η is 2, R, calcium, magnesium or lower alkylene, R ", R" R "and R" ^ straight-chain or branched aliphatic lower hydrocarbyl, halo-lower alkyl, aryl or R ", and R "together and R" and R "together
each denotes a saturated ring with 3 to 8 carbon atoms, η and X have the meaning given in formula II, enantiomers and racemic mixtures. 409842/1113 _ 107 - 24H59Ö 80. Compounds according to claim 79, wherein R ¹ ^, R " ₂ , R" and R "are methyl. 81. Compounds of the general formula _c .XH ₂ 0 R, ₂ and wherein, when η is 1, R is straight-chain or branched, aliphatic hydrocarbyl having more than one carbon atom or halo-lower alkyl and, when η is 2, R lower alkylene, R ₁₂ , Rpp » ^R · *? ¹ ^ ^R 42 S ^erad- chain or branched aliphatic lower hydrocarbyl, halo-lower alkyl, aryl or R ₁₂ and R ₂₂ together and R_ ₂ and R ₂ together each represent a saturated ring with 3 to 8 carbon atoms, η the number 1 or 2 and X represent the number 0 or 1, enantiomers and racemic mixtures. 82. Compounds according to claim 81, wherein R _n , _{IO are} methyl.
4 ^ - 83 · Compounds of the general formula 4098A7 / 1113 - 10Ö - R _d .XH ₂ O 24H590 IV wherein, when η is 1, R, substituted ammonium, straight-chain or branched, aliphatic hydrocarbyl with more than one carbon atom or halo-lower alkyl and, when η is 2, R, calcium, magnesium or lower alkylene are η and X have the meaning given in formula II, enantiomers and racemic Mixtures. 84 · Compounds of the general formula C-O-R 24H590 wherein R is lower alkyl with 2 to 12 carbon atoms or lower alkylene with ² to carbon atoms. 85 · ethyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate. 86 · n-Butyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate. 87. n-Dodecyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate. 88. n-Propyl-2,3: 4, -di-O-isopropylidene-2-keto-D-gluconate. 89 · n-Pentyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate. 90. Benzyl 2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate. 91. n-decyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate, 92. Isoamyl-2,3: 4, S-di-O-isopropylidene ^ -keto-D-gluconate, 93. 2-butyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate, 94. 2-Bromoethyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate. 95 «bis-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate ethylene glycol ester. 96 Ally 1-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate. 409-842 / 1 1 1 3 24H590 97. Dimethylammonium 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate. 98. Hydrazinium-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate 99. N-ethanolammonium-2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate. 100. 3-chloropropyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate. 101. (ethoxycarbonyl) methyl-2,3: 4,5-di-0-isopropylidene-2-keto-P-gluconate. 102. Cyclohexyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate. 103. Cyanomethyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate. 104. p-Nitrophenyl-2,3: 4,5-di-0-isopropylidene-2-keto ~ B-gluconate. 105. n-Hexyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-D-gluconate. 106. p-Chlorophenyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate. 107. n-Heptyl-2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate. 108. n-octyl-2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate. * - Ill - 2AU590 109. n-Nonyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate. 110. n-Undecyl-2,3: 4, iJ-di-O-isopropylidene - ^ - keto-D-gluconate. Ill.2,2,2-Trichloroethyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate. 112. Furfuryl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate. 113 · 2,3: 4,6-di-O-isopropylidene-sorbyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-glu.conate. 114. p-Cyanophenyl-2,3: 4,5-di-0-isopropylidene-2-keto _r D-gluconate. 115. (p-ethoxycarbonyl) pheny 1-2,3: /], 5-di-O-isopropylidene-2-keto-D-gluconate. 116. p- (tert -butyl) phenyl-2,3: 4,5-di-O -isopropylidene-2-keto-D-gluconate. 117. p-Acetylphenyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate. 118. α-Naphthyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate. 119. 3,4- (methylenedioxy) phenyl-2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate. 120 2- (2-methyl-3-phenyl) propyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate '. 409842/1113 24U590 121. 2,4,5-trichlorophenyl-2,3: 4,5-di-O-isopropylidene-2-ke to-D-gluconate. 122. (12-propargyloxy) dodecyl-2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate. 123. Iso-propyl-2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate. 124 · 2-Hydroxyethy1-2,3: 4,5-di-O-isopropylidene-2-keto-D-gluconate. 125. 4-chloro-2-butynyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate. 126. 3-chloro-2-propenyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate. 127. 3-chloro-2-tutenyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate. 128. 2- [2- (phenoxy) propionyloxy]; ithyl-2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate. 129. 2-propynyl-2,3: 4,5-di- O -isopropylidene-2-keto-D-gluconate . 409842/11 1 3 130. Compounds of the general formula _0H. XH ₂ O where R-, · *, R _? , »IU-, and R. lower alkyl, with more than one carbon atom, lower alkenyl, lower alkynyl, halo-lower alkyl, aryl or R, ₇ and R _? _. together and R__ and R. ^ together each represent a saturated ring with 3 to 8 carbon atoms and X a number from Ü to 1, enantiomers, racemic mixtures and salts of these compounds. 131. 2,3-0-Isopropylidene-4,5-0-cyclohexylidene-2-keto-D-gluconic acid. 132. 2,3-0-Isopropylidene-4,5-0-benzylidene-2-keto- ^D -gluconic acid. 133 · 2,3-0-Isopropylidene-4,5-0- (p-methoxybenzylidene) -2-keto-D-gluconic acid. 134. 2,3: 4,5 -M-O- (3-pentylidene) -2-ke to-D-gluconic acid. 409842/1113 135 · 2,3: 4,5-üi-0-benzylidene-2-keto-D-gluconic acid. 136. 2,3: 4,5-di-O- (ρ-methoxybenzylidene) -2-keto-D-gluconic acid. 137. 2,3-0-Isopropylidene-4,5-0- (2-chloroethylidene) -2-keto-D-gluconic acid 138. 2,3-0-Isopropylidene-4,5-0- (1,3-dichloroisopropylidene) ■ 2-keto-D-gluconic acid. 139. 2,3-0-Isopropylidene-4,5-0- (1,1,3-trichloroisopropylidene) -2-keto-D-gluconic acid. 140 · 2,3-0-isopropylidene-4,5-0- (1,1,1,3-tetrachloroisoprο pylid en) -2-ke to-D-gluconic acid. 141. 2,3-0-Isopropylidene-4,5-0- (2,2-dichloroethylidene) -2-keto-D-gluconic acid. 142. 2,3-0-Isopropylidene-4,5-0- (1,1,3,3-tetrachloroisopropylidene) -2-keto-D-gluconic acid. 143. 2,3-0-Isopropylidene-4,5-0- (1,1,1,3,3-pentachloroisopropylidene) -2-keto-D-gluconic acid. 144. 2,3-0-Isopropylidene-4,5-0- (2,2,2-trichloroethylidene) -2-keto-D-gluconic acid. 145. 2,3-0-Isopropylidene-4,5-0- (1,1,1,3,3,3-hexachloroisopropylidene) -2-keto-D-gluconic acid. 146. 2,3-0-Isopropylidene-4,5-0- (2-fluoroethylidene) -2-keto-D-gluconic acid. 409842/1113 _ 115 - 147. 2,3-0-l-gopropylidene-4,5-0- (1,3-difluoroisopropylidene) -2-keto-D-gluconic acid. 148 · 2,3-0-Isopropylidene-4,5-0- (1,1,3-trifluoroisopropylidene) -2-keto-.D-gluconic acid. 149. 2,3-0-Isopropylidene-4,5-0- (1,1,1,3-tetrafluoroisopropylidene) -2-keto-D-gluconic acid. 150 · 2,3-0-1sopropylidene-4,5-O- (2,2-difluoroethylidene) -2-keto-E-gluconic acid. 151. 2,3-0-Isopropylidene-4,5-0- (1,1,3,3-tetrafluoroisopropylidene) -2-keto-D-gluconic acid. 152. 2,3-0-Isopropylidene-4,5-0- (1,1,1,3,3-pentafluoroisopropylidene) -2-keto-D-gluconic acid. 153 2,3-0-Isopropylidene-4,5-0- (2,2,2-trifluoroethylidene) ■ 2-keto-D-gluconic acid. 154. 2,3-0-Isopropylidene-4,5-0- (1,1,1,3,3,3-hexafluoroisopropylidene) -2-keto-D-gluconic acid. 155. 2,3-0-Isopropylidene-4,5-0- (2-l-dromethylidene) -2-keto-D-gluconic acid. 156. 2,3-0-Isopropylidene-4,5-0- (1,3-dibromoisopropylidene) -2-keto-D-gluconic acid. 157. 2,3-0-Isopropylidene-4,5-0- (1,1,3-tribromoisopropylidene) -2-keto-D-gluconic acid. 4 0 9 8 L ? / 1 1 1 3 - HG - 24U590 158 x 2, o-0-13opropylidene-4,5-0- (2,2-dibromo; ithylidene) -2-ke to-D-gluconic acid. 159. 2,3-0-Inopropylidene-4,5-0- (1,1,3,3-tetrabromoisopropylidene) -2-keto-D-gluconic acid. 160. 2,3-0-Inopropylidene-4,5-0- (2,2,2-tribroniethylidene) -2-keto-D-gluconic acid. 161 2,3-0-Isopropylidene-4,5-0- (1,1,1-tribromoisopropylidene) -2-keto-D-gluconic acid. 162. 2-Sodium 2,3-0-isopropylidene-4,5-0-ether ylidene-2-keto-D-gluconate. 163 · 2-chloroethyl-2,3; 4,5-di-0-isopropylidene-2-keto-D-gluconate. 164 x 2,3: 4,5-di-0-methylene-2-keto-D-gluconic acid. 165 · 2,3: 4,5-Di-O-ethylidene-2-keto-D-gluconic acid. 166. 2,3: 4,5-di-O- (2-butylidene) -2-keto-D-gluconic acid. 167. 2,3: 4,5-Di-0-cyclohexylidene-2-keto-D-gluconic acid. 168. 2,3: 4,5-Di-O- (2-chloroethylidene) -2-keto-D-gluconic acid. 169. 2,3: 4,5-Di-O- (1,3-dichloroisopropylidene) -2-keto-D-gluconic acid . 170. 2,3: 4,5-Di-O- (1,1,3-trichloroisopropylidene) -2-keto-D-gluconic acid . 2414690 171. 2,3: 4,5-di-O- (1,1,1,3-tetrachloroisopropylidene) -2-keto-D-gluconic acid. 172. 2,3: 4,5-Di-O- (2,2-dichloroethylidene) -2-keto-D-gluconic acid . 173. 2,3: 4,5-di-O- (1,1,3,3-tetrachloroisopropylidene) -2-keto-D-gluconic acid. 174 · 2,3: 4,5-di-O- (2,2,2-trichloroethylidene) -2-keto-D-gluconic acid . 175 · 2,3: 4,5-di-O- (2-fluoroethylidene) -2-keto-D-gluconic acid . 176. 2,3: 4,5-Di-O- (1,3-difluoroisopropylidene) -2-keto-D-gluconic acid . 177 x 2,3: 4,5-di-O- (1,1,3-trifluoroisopropylidene) -2-keto-D-gluconic acid. 178. 2,3: 4,5-di-0- (l, l, l, 3-tetrafluoroisopropylidene) -2-keto-D-gluconic acid. 179. 2,3: 4,5-Di-O- (2,2-difluoroethylidene) -2-keto-D-gluconic acid. 180. 2,3: 4,5-di-O- (1,1,3,3-tetrafluoroisopropylidene) -2-keto-D-gluconic acid. 181. 2,3: 4,5-di-O- (1,1,1,3,3-pentafluoroisopropylidene) -2-keto-D-gluconic acid. 182. 2,3: 4,5-Di-O- (2,2,2-trifluoroethylidene) -2-keto-D-gluconic acid . 4098Α9 / 11Ί3 24H590 183. 2,3: 4,5-Di-O- (1,1,1,3,3,3-hexafluoroisopropylidene) - _t 2-keto-D-gluconic acid. 184. 2,3: 4,5-Di-O- (2-bromoethylidene) -2-keto-D-gluconic acid. 185 -. 2,3: 4,5-di-0- (1,3-dibromoisopropylidene) -2-keto-D-gluconic acid. 186. 2,3: 4,5-di-O- (1,1,3-tritiromisopropylidene) -2-keto-D-gluconic acid . 187. 2,3: 4,5-Di-O- (2,2-dibromoethylidene) -2-keto-D-gluconic acid . 188. 2,3: 4,5-di-0- (1,1,3,3-tetrabromoisopropylidene) -2-keto-D-gluconic acid. 189. 2,3: 4,5-Di-O- (2,2,2-tribromoethylidene) -2-keto-D-gluconic acid ♦ 190. 2,3 ^ 4,5-di-O- (1,1,1-tribromoisopropylidene) -2-keto-D-gluconic acid. 191. Dodecyldimethylammonium 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate. 192. Bis (2-hydroxyethyl) ammonium 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate. 193 · Furfurylammonium 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate. 194. Morpholinium 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate. - α 19 - 195. Pentyl 2,3: 4,5-di-0-sec-butylidene-2-keto-D-gluconate. 196. Ethyl 2,3r4,5-di-0-sec-butylidene-2-keto-D-gluconate. 197. Ethyl 4,5-0-sec-butylidene-2,3-0-isopropylidene-2-keto-D-gluconate. 198. 4-chlorobutyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate. 199. Ethyl 4,5-0-ethylidene-2,3-0-isopropylidene-2-keto-D-gluconate. 200. 2-cyanoethyl 2,3: 4,5-di-0-isopropylidene-2-keto ^ D-gluconate. 201. Isopentyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluponate. 202. p-Fluorobenzyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate. 203. 2,2,2-trifluoroethyl 2,3: 4,5-di-0-isopropylidene-2-keto-D-gluconate. 40984? / 1113