NL8300489A - BENZYL ETHER DERIVATIVES OF PENTITES, METHOD FOR PREPARING THESE COMPOUNDS AND AGENTS WITH PLANT GROWTH CONTROLLING ACTION, CONTAINING THESE COMPOUNDS - Google Patents

Description

j »* VO 4563

Title: Benzyl ether derivatives of pentites, method of preparing these compounds as well as plant growth control agents containing these compounds.

The invention relates to novel benzyl ether derivatives of pentites, methods of preparing these compounds, and plant growth control agents containing these compounds.

Compounds with a growth-regulating effect are already known and have even been partially applied in practice.

Products of this kind known in practice, such as those based on triiodobenzoic acid or based on 2,3: 4,6-di-0-isopropylidene-α-L-xylohexulofuranuronic acid: and the sodium salt thereof are not distinguished by suitable working qualities or working only when using large quantities.

Furthermore, the use of 2-benzyloxymethyltetrahydrofuran as a herbicide has become known (German Offenlegungsschrift 27 24 677), which is harmful to plants due to its phytotoxicity.

The object of the present invention is to provide an agent which has a growth-regulating effect with a wide spectrum of action while at the same time preserving the plants.

This object was achieved according to the invention by an agent, characterized by a content of at least one compound of the formula 1 of the formula sheet, in which one of the substituents Y represents the group of the formula 2 and the other four substituents Y are equal or are different and each represent the group of formula 3, wherein R 1 is hydrogen or an alkyl group with 1 to 4 carbon atoms, 25 E-2, optionally one or more times by alkyl with 1 to 6 carbon atoms and / or alkoxy with 1 up to 6 carbon atoms and / or optionally substituted phenoxy and / or optionally substituted phenyl and / or halogen and / or the nitro group and / or the trifluoromethyl group substituted aromatic hydrocarbon group, hydrogen or optionally substituted alkyl group having 1 to 4 carbon atoms and n 0 or 1 .

8300489 t i - 2 -

The compounds according to the invention exist as optical, optionally also as geometric isomers. The individual isomers and their mixtures are also within the scope of the invention.

The compounds according to the invention are eminently suitable for controlling the plant growth in different cultivated plants and surprisingly surpass in terms of their range of action as well as in terms of their compatibility the products of the same action direction known in the preamble.

Since the compounds of the invention produce qualitative and quantitative changes in plants as well as changes in plant metabolism, they must be classified in the plant growth regulator class, which are distinguished by the following uses.

Inhibition of vegetative growth in woody and herbaceous plants on, for example, the edges of roads, railway installations and others, in order to prevent growth. Growth inhibition in grain to prevent precipitation or bending, in cotton to increase the harvest.

Influencing the branching of vegetative and generative organs in ornamental or cultivated plants to increase flower formation or in tobacco and tomatoes to inhibit their shoots.

Improvement of the fruit quality, for example an increase in the. sugar content in sugar cane, sugar beets or fruit · and a more even ripening of the harvest, which leads to higher yields.

25 Increase resistance to climatic influences, such as cold and drought.

Influencing the flow of latex in rubber plants.

Formation of partenocarpous fruits, pollen sterility and sex influence are also possible applications.

30 Checking the germination of seeds or bud sprouting.

Defoliation or influencing of the fruit fall to facilitate harvesting.

The compounds according to the invention are particularly suitable for influencing vegetative and generative growth in some legumes, such as, for example, soy.

Depending on the application purpose, the amounts to be used are generally 0.005 to 5 kg of active substance per ha, but can optionally be used in larger amounts.

5 The application time depends on the application purpose and the climatic conditions-

The compounds according to the invention are distinguished in particular by the described actions, those compounds in which in the formula 1 hydrogen or alkyl of 1 to 4 carbon atoms, preferably methyl, R 1 -phenyl, 2-chlorophenyl, 3-chlorophenyl , 4-chlorophenyl, 2,6-dichlorophenyl, 2,4-dichlorophenyl, 3,4-dichlorophenyl, 2,4,6-trichlorophenyl, 4-bromophenyl, 2,4-dibromophenyl, 2,6-dibromophenyl, 2,4,6-tribromo-phenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,4-difluorophenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 3,4-dimethylphenyl, 15 2-methoxyphenyl , 3-methoxyphenyl, 4-methoxyphenyl, 3,4-dioxymethylenphenyl, 2-phenoxyphenyl, 3-phenoxyphenyl, 2-nitrophenyl or 3-nitrophenyl, R 1 hydrogen, alkyl of 1 to 4 carbon atoms, preferably methyl, ethyl, propyl or chloromethyl and n represent 0 or 1,

The compounds according to the invention can be used alone, mixed with one another or with other active substances. Optionally, jugs, defoliants, plant protection agents or agents for controlling harmful plants and animals may be used depending on the desired purpose.

If a broadening of the spectrum of action is envisaged, other biocides can also be added. For example, herbicide active mixture partners are active substances from the group of triazines, aminotriazoles, anilides, diazines, uraciles, aliphatic carboxylic acids and halocarboxylic acids, substituted benzoic acids and aryl carboxylic acids, hydrazides, amides, nitriles, esters of such carboxylic acid esters, carbamic acid esters and thiocarbamic acid esters, urea compounds, 2,3,6-trichlorobenzyloxypropanil, rattan containing agents and other additives suitable.

Among other additives should also be understood, for example, also non-phytotoxic additives which can provide a synergistic increase in activity with herbicides, such as wetting agents, - - ---- - '..........

8300489 4 t - 4 - emulsifiers, solvents and oily additives.

Preferably, the active substances according to the invention or the mixtures thereof are in the form of preparations such as powders, spreading agents, granulates, solutions, emulsions or suspensions, with the addition of liquid and / or solid carriers and connecting agents, respectively. optionally of wetting agents, adhesives, emulsifying agents and / or dispersing aids.

Suitable liquid carriers are, for example, water, aliphatic and aromatic hydrocarbons such as benzene, toluene, xylene, cyclohexanone, isophorone, dimethyl sulfoxide, dimethylformamide, and further mineral oil fractions.

Suitable solid carriers are mineral earths, for example "Tonsil", silica gel, talc, kaolin, "Attaclay", limestone, silicic acid and vegetable products, for example fine powders.

As surfactants, there may be mentioned, for example, calcium lignin sulfonate, polyoxyethylene alkyl phenol ethers, naphthaline sulfonic acids and salts thereof, phenol sulfonic acids and salts thereof, formaldehyde condensates, fatty alcohol sulfates and substituted benzene sulfonic acids and salts thereof.

The content of the active substance or active substances in the different preparations can vary within wide limits. The agents contain, for example, about 10 to 80% by weight of active substances, about 90 to 20% by weight of liquid or solid carriers and optionally up to 20% by weight of surfactants.

The spreading of the agents can be done in the usual manner, for instance with water as a carrier in amounts of spray liquid of about 100 to 1000 l per ha. An application of the agents in the so-called low-volume and ultra-low-volume method is also possible, as well as an application in the form of so-called micro-granulates.

For example, the following ingredients are used to prepare the compositions: A- Spray powders a) 80% by weight of active ingredient 15% by weight of kaolin 8300489 * 5-5% by weight of surfactants based on the sodium salt of N methyl N-oleyl taurine and the calcium salt of lignin sulfonic acids.

b) 50 wt% active substance 5 40 wt% clay minerals 5 wt% cell pitch 5 wt% surfactants based on a mixture of the calcium salt of lignin sulfonic acid with alkyl phenol polyglycol ether.

C) 20 wt% active ingredient 70 wt% clay minerals 5 wt% cell pitch 5 wt% surfactants based on a mixture of the calcium salt of lignin sulfonic acid with alkyl phenol polyglycol-15 ethers.

d) 5 wt% active substance 80 wt% Tonsil ..

10 wt% cell pitch 5 wt% surfactants based on a fatty acid condensation product B. Emulsion concentrate 20 wt% active substance 40 wt% xylene 35 wt% dimethyl sulfoxide 25 5 wt% mixture of nonylphenylpolyoxyethylene or calcium dodecyl benzene sulfate.

C. Paste 45 wt% active ingredient 5 wt% sodium aluminum silicate 30 15 wt% cetyl polyglycol ether with 8 moles ethylene oxide 2 wt% spindle oil 10 polyethylene glycol 23 parts water.

8300489 ~ ..............

- 6 -

The new compounds of the invention can be prepared, for example, by i) A) Compounds of formula 4 wherein one of the substituents Y 'represents the group of formula 2 and the four other substituents Y' represent hydrogen 5, a) with compounds of formula 5 or b) with compounds of formula 6 or c) with compounds of formula 7 optionally reacting in the presence of acid-binding agents and / or a catalyst or B) Compounds of formula 8 in which one of the substituents Y "is the group of formula 2 and the other four substituents Y ”each in pairs represent an optionally substituted methylene group of formula 9, optionally in the presence of organic solvents and acidic catalysts such as sulfuric acid, p-toluenesulfonic acid, hydrochloric acid, ammonium chloride, phosphoric acid, silicic acid and acid ion exchange resins at temperatures from 0 to 100 ° C, preferably from 40 to 80 ° C, hydrolyses, wherein and R ^ the above meanings and R4 and R4 may each be the same or different and each time hydrogen, an alkyl group with 1 to 10 carbon atoms, a substituted alkyl group with. 1 to 10 carbon atoms, any. substituted arylalkyl group, wherein alkyl has 1 to 3 carbon atoms, a cycloaliphatic hydrocarbon group of 3 to 8 carbon atoms, a single or multiple alkyl with 1 to 6 carbon atoms and / or halogen and / or alkoxy of 1 to 6 carbon atoms and / or : the nitro group and / or the trifluoromethyl group substituted aromatic hydrocarbon group or R ^ and R ^ represent a polymethylene group - (CEL) -, X a halogen atom, preferably a chloro-2 m atom, and Z a halogen atom or the group R ^ QSC ^ O represent and m represents the integer 4 or 5.

The groups R 1 and R 1 of the substituted methylene group are to be understood to mean hydrogen, alkyl of 1 to 10 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, 2 , 2-dimethyl-1-propyl, n-pentyl, n-heptyl, n-octyl, n-decyl, substituted alkyl of 1 to 10 carbon atoms, for example chlorine-8300489 '...... ...... ...........

-7.- methyl, bromomethyl, fluoromethyl, dichloromethyl, trifluoromethyl, tri-chloromethyl, hydroxymethyl, methoxymethyl, ethaxymethyl, phenoxymethyl, 4-chlorophenoxymethyl, chloroethyl, bromoethyl, 2-ethoxyethyl, 2-phenoxyethyl, cycloaliphatic hydrocarbons with 3 up to 8 carbon atoms, for example cyclopropyl, cyclopentyl, cyclohexyl, arylalkyl wherein alkyl has 1 to 3 carbon atoms, for example benzyl, 2-phenylethyl, aromatic hydrocarbon groups, for example phenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 3,4- dichlorophenyl, 4-methoxyphenyl, 4-nitrophenyl, 2,4-dichlorophenyl.

Preferred pentite derivatives as starting materials. of formula 8 are those in which 1} Y "^ the group of formula 2 and and together. and and Y'1 ^ together each represent an optionally substituted methylene group of formula 9 and 2) Y" ^ the group of formula 2 and Y "^ and Y" ^ together and Y "^ and Y" ^ together each an optionally substituted methylene group and 3) Ynj. the group of formula 2 and Y "^ and Y" ^ together and Y "^ and Y" ^ together represent an optionally substituted methylene group.

The reaction partners are reacted, between 0 and 150 ° C, but generally between room temperature and the temperature at which the corresponding reaction mixture is refluxed.

The reaction time is 1 to 72 hours.

The reactants are used in approximately equimolar amounts to prepare the compound according to the invention. Suitable reaction media are inert solvents with respect to the reactants. The choice of the solvents or suspending agents depends on the use of the corresponding alkyl or acyl halides and dialkyl sulfates and the acid acceptors used. As solvents or suspending agents, for example, ethers such as diethyl ether, diisoproyl ether, tetrahydrofuran and dioxane, aliphatic and aromatic hydrocarbons, such as petroleum ether, cyclohexane, hexane, heptane, benzene, toluene, and xylene, carboxylic nitriles, such as acetonitriles and carboxylic acid amines such as acetonitriles and carboxylic acid amines, can be mentioned dimethylformaitfide.

8300489

<0 V.

- 8 -

Suitable acid acceptors are organic bases such as, for example, triethylamines, Ν, Ν-dimethylaniline, and pyridine bases or organic bases, such as oxides, hydroxides and carbonates of the alkaline earth and alkali metals. Liquid bases such as pyridine can be used simultaneously as a solvent. are applied.

Onium compounds are used as catalysts for process variant A. suitable, such as quaternary ammonium, phosphonium and arsonium compounds, as well as sulfonium compounds.

Also suitable are polyglycol ethers, in particular cyclic, such as, for example, 18-Krone-6, and tertiary amines, such as, for example, tributylamine. Preferred compounds are quaternary ammonium compounds, such as, for example, benzyltriethylammonium chloride and tetrabutyl ammonium bromide.

The compounds of the invention prepared according to the above process can be isolated from the reaction mixture according to the usual methods, for example by distilling off the used solvent at normal or reduced pressure, by precipitation with water or by extraction. An increased degree of purity can usually be achieved by column chromatographic purification as well as fractional crystallization.

The compounds of the invention are usually nearly colorless and odorless liquids, sparingly soluble in water, sparingly soluble in aliphatic hydrocarbons, such as petroleum ether hexane, pentane and cyclohexane, readily soluble in halogenated hydrocarbons, such as chloroform, methylene chloride and carbon tetrachloride, aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as diethyl ether, tetrahydrofuran and dioxane, carboxylic nitriles such as acetonitriles, ketones such as acetone, alcohols such as methanol and ethanol, carboxylic amides such as dimethyl sulfoxides such as dimethyl sulfoxides but also colorless and odorless crystalline materials, which are sparingly soluble in aliphatic and aromatic hydrocarbons, are moderately to readily soluble in halogenated hydrocarbons, such as chloroform and carbon tetrachloride, ketones such as acetone, carboxylic amides such as dimethylformamide, sulfoxides such as dimethyls ulphoxide, carboxylic nitriles such as acetonitriles, lower alcohols, 8300489% - 9 - such as methanol, ethanol and water.

Suitable solvents for recrystallization are in particular water, methanol, acetonitrile and vinegar esters.

The preparation of the benzyl ether derivatives of pentites according to the invention is further illustrated by the following examples.

EXAMPLE I

5-0- (2,6-dichlorobenzyl) -xylite

227.0 g (0.708 mol) of 5-0- (2,6-dichlorobenzyl) -10 1,2,3,4-bis-0-isopropylidene xylite were started from, and the mixture was stirred with 752.2 ml of 1.5 N sulfuric acid. Then it was stirred at 70 ° C for 3 hours and then the reaction mixture was allowed to stand overnight at room temperature. 95 ml of 32% sodium hydroxide solution was then added dropwise with stirring at 25 ° C and the reaction solution was extracted three times with 200 ml of vinegar ester each time.

The extracts were then washed twice more with 100 ml of water each time, dried over magnesium sulfate, filtered and evaporated under reduced pressure. Colorless crystals were obtained, which was leached with a cold mixture of diethyl and diisopropyl ether and subsequently dried to constant weight at room temperature / 200 Torr.

Yield: 202.0 g = 91.7% of theory 5-0- (2,6-dichlorobenzyl) xylite

Freezing point: 82-83 ° C

DC r eluent: chloroform / methanol 4: 1 Rf value: 0.34

Analysis ; Ber. C 46.32% H 5.18% Cl 22.79%

Gev. C 46.48% H 5.10% Cl 22.37%

EXAMPLE II

3-0- (2,6-dichlorobenzyl) -1,2: 4,5-tetra-0-methyl-adonite 30.1 g (0.01 mol) 3-0- (2.6 were started from -dichlorobenzyl) adonite, 0.22 g (0.001 mol) benzyltriethylammonium chloride and 25.23 g (0.2 mol) dimethyl sulfate in 20 ml methylene chloride. With intensive stirring, 14.0 g (0.25 mol) of potassium hydroxide dissolved in 15 ml of water, were added dropwise to the starting mixture under cooling at about 30 ° C. After stirring at room temperature for 3 hours, it was refluxed for an additional hour. 150 ml of water were then diluted and extracted twice with 150 ml of vinegar each time. The extracts washed with water, dried over magnesium sulfate and filtered, were evaporated. The residual oil was distilled on a Kugelrohr (bath temperature 200 ° C / 0.2 Torr).

Yield: 2.90 g = 79.1% of theory 3-0- (2,6-dichlorobenzyl) - 1,2: 4,5-tetra-0-methyl-adonite 20 10 n H: 1.5198 DC: solvent = toluene / vinegar ester 1: 1

RF value: 0.29

Analysis: Ber. C 52.32% H 6.58% Cl 19.30%

Gev. C 51.82% H 6.48% CL 20.13%

EXAMPLE III

1-0- (2,6-dichlorobenzyl) -2,3,4,5-tetra-0-acetyl-D-arabite 5.0 g (0.016 mol) 1-0- (2,6-dichlorobenzyl) -D Arabite were added in a mixture of 20 ml. pyridine and 20 ml. acetanhydride was first stirred at room temperature for one hour and then left overnight. The reaction mixture was mixed with 150 ml of toluene and the solution was evaporated to dryness under a water jet vacuum. The residue was mixed with a further 150 ml of toluene and again evaporated under reduced pressure. The residual oil was taken up in portions with 300 ml of vinegar ester. The vinegar extracts washed with water, dried over magnesium sulfate and filtered, were evaporated. The oily residue crystallized after leaching with a little diisopropyl ether.

Yield: 5.80 g = 75.7% of theory 1-0- (2,6-dichlorobenzyl) - 2,3,4,5-tetra-O-acetyl-D-arabite

Freezing point: 89-90 ° C

DC: solvent = toluene / vinegar ester 1: 1

RF value: 0.47

Analysis: Ber. C 50.11% H 5.49% Cl 14.79% 35 Gev. C 50.58% H 5.49% Cl 14.80% 8 3 Ö 0 4 8 9 ............

- 11 -

The further compounds according to the invention could be prepared in an analogous manner.

Example Physical constant connections

No.

4 5-0- (2,4-dichlorobenzyl) -xylite Fp .: 96-98 ° C

5 5 5-0- (2-chlorobenzyl) -xylite Fp: 52-54 ° C

6 5-0- (2-methylbenzyl) -xylite Fp .: 59-61 ° C

7 l-0- (2,6-dichlorobenzyl) -L-arabite Fp .: 122-24 ° C

8 l-0- (2,6-dichlorobenzyl) -D-arabite Fp .: 124-26 ° C

9 3-Q- (2,6-dichlorobenzyl) adonite Fp .: 116-17 ° C

10 10 5-0- (2,4,6-tribromobenzyl) -xylite Fp .: 132-33 ° C

11 5-0-benzyl-xylite Fp .: 47-50 ° C

12 5-0- (2,6-dichlorobenzyl) -1,2,3,4-tetra-20anc.

_. _, n_. * 1 / / o

O-acetyl-xylxet. D

13 5-0- (2,4,6-tribromobenzyl) -1,2,3,4-tetra-

O-acetyl-xylite Fp .: 106-07 ° C

14 3-0- (2,4,6-tribromobenzyl) -adonite Fp .: 132-34 ° C

5-0- (4-chlorobenzyl) -xylite Fp .: 109-09.5 ° C

16 5-0- (4-bromobenzyl) -xylite Fp .: 110-12 ° C

17 5-0- (3,4-dichlorobenzyl) xylite Fp .: 122-23 ° C

20 18 5-0- (3-methylbenzyl) -xylite Fp .: 54-56 ° C

19 5-0- (4-methylbenzyl) -xylite Fp.t 98-99 ° C

5-0- (3,4-dimethylbenzyl) -xylite Fp .: 72-74 ° C

21 5-0- (3-chlorobenzyl) -xylite Fp .: 90-92 ° C

22 5-0- (4-cyanobenzyl) -xylite Fp .: 119-21 ° C

25 23 3-0- (2,6-dichlorobenzyl) -1,4,4,5-tetra-20 ^ ^ 4941 O-acetyl adonite D ''

Q

24 5-0- (3-trifluoromethylbenzyl) -xylite Fp .: 61-63 C

5-0- (3-fluorobenzyl) -xylite Fp .: 72-74.5 ° C

26 5-0- (4-fluorobenzyl) -xylite Fp.r 76-78 ° C

27-1-0- (2,4,6-tribromobenzyl) -D = arabite Fp .: 156-57 ° C

28 5-0- (2-fluorobenzyl) -xylite: 1.5243

29 5-0- (2,6-dichlorobenzyl) -1,2,3,4-tetra-20. C1QC

n_: 1, olob

Q-methyl-xylite D

30 l-0- (2,6-dichlorobenzyl) -2,3,4,5-tetra-20-qi-35-methyl-L-arabite D '' 83 0 0 4 8 9 ...... ..... ................

- 12 -

Example Physical constant connections

No.

31 5-0- (2,4-dichlorobenzyl) -1,2,3,4-tetra-20-O-methyl-xylite nD '' 32 1-0- (2,6-dichlorobenzyl) -2,3, 4,5-tetra-20-O-methyl-dlarabite nD * '33 5-0- (2,4,6-tribromobenzyl) -1,2,3,4-tetra-20-nt x. n_ ί 1.5616

O-methyl-xylite D

34 l-0- (2,4,6-tribromobenzyl) -2,3,4,5-tetra-20 ^, O-methyl-D-arabite nD ''

10 35 5-0- (2-chloro-6-fluorobenzyl) -xylite Pp .: 70-7l ° C

36 l-0- (2-chloro-6-fluorobenzyl) -D-arabite Pp .: 138-139 ° C

20 37 3-0- (2-chloro-6-fluorobenzyl) -adonite: 1,5297 38 5-0- (2-chloro-6-fluorobenzyl) -1,2,3,4-tetra-20. , 0__

O-acetyl-xylxet D

15 39 5-0- (2-chloro-6-fluorobenzyl) -1,2,3,4-tetra-20-O-methyl-xylite nD * '

PP * freezing point.

The starting materials for preparing the compounds according to the invention are known per se or can be known per se known process.

The following examples serve to illustrate the preparation of the starting compounds.

EXAMPLE XL

5-0- (2,6-dichlorobenzyl) -1,2: 3,4-bis-O-isopropylidene xylite 25.13 g (0.5 mol) of 1,2: 3,4-bis- O-isopropylidene xylite together with 119.96 g (0.5 mole) of 2,6-dichlorobenzyl bromide and 4.5 g (0.019 mole) of benzyl triethyl ammonium chloride. A solution of 100 g of sodium hydroxide (2.5 mol) in 125 ml of water was added dropwise at room temperature while stirring very intensively, the temperature slowly rising to about 50 [deg.] C. and again in the course of about one hour. room temperature dropped. The mixture was then stirred for an additional hour at 50 ° C to complete the reaction, then it was diluted with 500 ml of ice water and the reaction mixture was extracted with 150 ml of vinegar ester each time. The organic phase was washed twice, 300 ml of water, each time, dried over magnesium sulphate, filtered and under reduced .......... 83 Ö Ö 4 8 9 * ____ ___ __ _ - 13 - third pressure at Evaporated at 40 ° C. The residue was fractionally distilled.

Yield: 150.0 g = 76.7% of theory. Boiling point 0.1 Torr = 163 ° C? nQ ^: 1.5080 5 DC: solvent = toluene / vinegar ester 4: 1 Ri value: 0.52

Analysis: Ber. C 55.25% H 6.18% Cl 18.12%

Gev. C 55.66% H 6.46% Cl 18.03%

EXAMPLE XII

5-0- (2,4,6-tribromobenzyl) -1,2; 3,4-bis-Q-isopropylidene xylite

A solution of 23.2 g (0.1 mol) of 1,2,4,4-bis-O-isopropylidene xylite in 100 ml of toluene was slowly stirred in a suspension of 2.88 g (0.12 mol) sodium hydride in 50 ml of toluene. After complete addition, the mixture was refluxed for 2 hours. A solution of 40.78 g (0.1 mol) of 2,4,6-tribromobenzyl bromide in 50 ml of toluene was then added dropwise and the mixture was refluxed for an additional 8 hours.

After cooling, the mixture was carefully washed three times with 150 ml of water each time? the organic phase was subsequently dried over magnesium sulfate, filtered and evaporated under reduced pressure at 40 ° C. The residual oil was freed from traces of starting material still present under reduced pressure (180 ° C bath temperature / 0.1 Torr).

Yield z 37.6 g = 67.25% of theory 20 25 n ^ h: 1.5516 DC: solvent = toluene / vinegar ester 1: 1

Rf value = 0.52

Analysis: Ber. C 38.26% H 4.14%

Gev. C 37.99% H 4.04%. 30 The following starting materials could be prepared in an analogous manner.

.............. 83 0 0 48 9 - 14 -

Example Physical constant connections

No.

42 3-0- (2,4-dichlorobenzyl) -1,2: 4,5-bis-O-isopropylidene adonite nQ20 = 1.5092 43 1-0- (2,4-dichlorobenzyl) -2,3: 4,5-bis-5 O-isopropylidene-L-arabite nQ20 = 1.5070 44 1-0- (2,4-dichlorobenzyl) -2,3: 4,5-bis-Q-isopropylidene-D-arabite nQ20 = 1.5071 45 1-0- (2,6-dichlorobenzyl) -2,3: 4,5-bis-O-isopropylidene-L-arabite η ^ 20 = 1,5075 10 46 1-0- (2 , 6-dichlorobenzyl) -2,3: 4,5-bis-O-isopropylidene-D-arabite η ^ 20 = 1,5093 47 3-0- (2,6-dichlorobenzyl) -1,2: 4.5 -bis- O-isopropylidene adonite n ^ 20 = 1.5118 48 3-0- (2,4,6-tribromobenzyl) -1,2: 4,5-bis

15- (isopropylidene adonite Fp .: = 75 ° C

.. 49 l-0- (2,4,6-tribromobenzyl) -2,3: 4,5-bis-0- (isopropylidene) -D-arabite nQ20 = 1.5447 50 5-0- (2-chloro -6-fluorobenzyl) -1,2: 3,4-bis-0- (isopropylidene) -xylite η ^ 20 = 1.4916 20 51 l-0- (2-chloro-6-fluorobenzyl) -2,3: 4.5- bis-0- (isopropylidene) -D-arabite n ^ 20 = 1.4901 52 3-0- (2-chloro-6-fluorobenzyl) -1,2: 4.5-bis-0— (isopropylidene) -adonite η ^ 20 = 1.4918

The following examples illustrate the uses of the compounds of the invention in which the experiments with the described compositions were performed.

EXAMPLE LUX

Chlorophil content ever hoging and pod formation in soy.

Soybeans were sprayed with an aqueous emulsion of the compounds to be tested in a post-emergence process. The amount applied was 0.8 kg of active substance per ha. Discs were cut from the second fin blade four weeks after spraying.

The chlorophile was extracted from this and the chlorophilic α content determined photometrically.

35 'The table shows the increase in the chlorophilic a content compared to the control.

830 0 48 9.-15-

In addition, the pods and flowers were determined in the plants and calculated as a percentage of the control. The table contains these values.

The findings show that the compounds according to the invention are distinguished from the comparators by a better tolerance or a higher chlorophile content, respectively, a larger formation of flowers and pods.

TABLE

Compounds Chlorophilic increase of pods and flowers according to the invention the content in% in% of the control 5-0- (2,6-dichlorobenzyl) -xylite 63,9 202 1-0- (2,6-dichlorobenzyl) - L-arabite 43.0 129 1- 0- (2,6-dichlorobenzyl) -D-arabite 37.2 103 3-0- (2,6-dichlorobenzyl) adonite 39.3 129 15 Comparatives according to DE-OS 27 24 677___________ 2-benzylolymethyl-tetrahydrofuran 27.4 146 2,6-dichlorobenzyloxymethyl-tetra-20 hydrofuran * 60.9 90

* Phytotoxicity in the form of etching damage EXAMPLE LIV

Growth-regulating effects on soy and stock beans after disinfection. Stock beans and soybeans were disinfected with powdered preparations of the 25 active substances in amounts of 10, 50 and 100 g of active substance per 100 kg of seed used.

The seeds were placed in culture dishes. The plants were grown under greenhouse conditions. After 3 weeks of culture, symptoms were rated with numbers between 0 and 10. In addition, the following scheme served as untreated control 5 = swollen, dark green, branched 1 = very heavily swollen, intensive dark green, strongly branched.

As the findings show, the substances of the invention are more active in the desired action than the comparators.

8300489, * v, - 16 - TABLE

Compounds according to Quantity Evaluation of the invention active substance in stem soybean / 100 seed beans beans 5 5-0- (2,6-dichlorobenzyl) -xylite 10 8 8 50 3 5 100 3 4 l-0- (2,6 -dichlorobenzyl) -L-arabite 10 10 7 10 50 5 4 100 3 3 1- 0- (2,6-dichlorobenzyl) -D-arabite 10 88 50 6 5 100 3 4 15 3-0- (2,6- dichlorobenzyl) -adonite ..... 10 9 8 50 5 5 100 3 5- 5-0- (2,4,6-tribromobenzyl) -xylite 10 10 10 50 9 9 20 100 99

Comparatives 2-benzyloxymethyl-tetrahydrofuran 10 10 9 - - 'according to DE-OS 27 24 677) 50 10 9 100 10 8 25 2,3: 4,6-Di-O-isopropylidene αL- 10 10 8 xylohexulofuranuronic acid - sodium salt 50 10 8 100 10 7

LV

Harvest enhancement in soy

Soybeans were sprayed in an after-emergence process with aqueous emulsions of the test substances in an amount of 0.8 kg of active substance per hectare. Flowering and pod formation were determined four weeks after watering. The values for this are set out in the table. The results were expressed as a percentage of the control. In addition, the percentage growth inhibitions were determined.

The findings show that the substances promote pod and flower formation when the plants are swaged simultaneously. The comparators show this effect only weakly or were found to be phytotoxic to a certain extent.

........... 83 0 0 48 9 "......." ..... ..... .....

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TABLE

Compounds According to Growth Inhibition Pod and Flowering Invention Formation in% of Control 5 5-0- (2-chlorobenzyl) -xylite 28 142 5-0 ”(2r6-dichlorobenzyl) -1,2,3,4-tetra- Q-acetyl-xylite 59 219 5-0- (2,4,6-tribromobenzyl) - 1.2.3.4-tetra-0-acetyl-xylite 44 173 10 1-0- (2,6-dichlorobenzyl) - 2.3.4.5 - tetra-Q-acetyl-D-arabite 59 215 3-0- (2,4,6-tribromobenzyl) -adonite 49 188 5-0- (4-chlorobenzyl) -xylite 44 165 5-0- (4-bromobenzyl ) -xylite 49 185 15 5-0- (3,4-dichlorobenzyl] -xylite 0 115 5-0- (3-methylbenzyl) -xylite 28 108 5-0- (4-methylbenzyl) -xylite 33 204 5 -0- (3,4-dimethylbenzyl) -xylite .. 33 204 5-0- (3-chlorobenzyl) -xylite 38 135 20 5-0- (4-cyanobenzyl) -xylite 28 150 3-0- ( 2,6-dicilorobenzyl) - 1.2.4.5-tetra-Q-acetyl-adonite 59 204 5-0- (3-trifluoromethylbenzyl) -xylite 23 80 25 5-0- (3-fluorobenzyl) -xylite 33 204 1-0 - (2,4,6-tribromobenzyl) -D-arabite 33 188 5-0- (2-fluorobenzyl} -xylite 28 92

Comparatives 30 2-benzyloxymethyl-tetrahydrofuran 28 135 according to DE-OS '27 24 677)

Triiodobenzoic acid 69 73 * 8300489

Claims (7)

1. Benzyl ether derivatives of pentites of formula 1 of the formula sheet in which one of the substituents Y represents the group of formula 2 and the other four substituents Y are the same or different and each represents the group of formula 3, in which Hydrogen or an alkyl group of 1-4 carbon atoms, optionally singly or multiply by alkyl of 1-6 carbon atoms and / or alkoxy with. 1-6 carbon atoms and / or optionally substituted phenoxy and / or optionally substituted phenyl and / or halogen and / or the nitro group and / or the trifluoromethyl group substituted aromatic hydrocarbon group, Rg hydrogen or an optionally substituted alkyl group of 1-4 carbon atoms , and: n suggest 0 or 1. 2. Benzyl ether derivatives of pentites according to claim 1, wherein 15 R 1 hydrogen or alkyl, with 1-4 carbon atoms, preferably methyl, R 1 phenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2,6-dichlorophenyl, 2 4-dichlorophenyl, 3,4-dichlorophenyl, 2,4,6-trichlorophenyl, 4-bromophenyl, 2,4-dibromophenyl, 2,6-dibromomphenyl, 2,4,6-tribromophenyl, 2- fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,4-difluorophenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 3,4-dimethylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 3 , 4-dioxymethylene-phenyl, 2-phenoxy-phenyl ,. 3-phenoxyphenyl, 2-nitrophenyl or 3-nitrophenyl, R 2 hydrogen, alkyl of 1-4 carbon atoms, preferably methyl, ethyl, propyl or chloromethyl and 25 n 0 or 1. 3.5-0- (2,6-dichlorobenzyl) xylite 4.3-0- (2,6-dichlorobenzyl) -1,2,4,5-tetra-0-methyl-adonite 5.1-0- ( 2,6-dichlorobenzyl) -2,3,4,5-tetra-0-acetyl-D-arabite 6.5-0- (2,4-dichlorobenzyl) -xylite 30 7.5-0- (2-chlorobenzyl) ) -xylite 8.5-0- (2-methylbenzyl) -xylite 9.1-0- (2,6-dichlorobenzyl) -L-arabite IQ. 1-0- (2,6-dichlorobenzyl) -D-arabite ...... 83 0 0 48 9 ...........'------------ ---------------------------------------------— - 19 - 11 3-0- (2,6-dichlorobenzyl) -adonite 12.5-0- (2,4,6-tribromobenzyl) -xylite 13.5-0-benzylxylite 14.5-0- (2.6 -dichlorobenzyl) -1,2,3,4-tetra-O-acetyl-xylite 5 15. 5-0- (2,4,6-tribromobenzyl) -1,2,3,4-tetra-O-acetyl- xylite 16. 3-0- (2,4,6-tribromobenzyl) -adonite 17.5-0- (4-chlorobenzyl) -xylite 18. 5-0- (4-bromobenzyl) -xylite 19.5-0- (3,4-dichlorobenzyl) -xylite 10 20. 5-0- (3-methylbenzyl) -xylite 21.5-0- (4-methylbenzyl) -xylite 22.5-0- (3,4-dimethylbenzyl) - xylite 23.5-0- (3-chlorobenzyl) -xylite 24.5-0- (4-cyanobenzyl) -xylite 15 25. 3-0- (2,6-dichlorobenzyl) -1,2,4,5- tetra-O-acetyl-adonite 26.5-0- (3-trifluoromethylbenzyl) -xylite 27.5-0- (3-fluorobenzyl) -xylite 28.5-0- (4-fluorobenzyl) -xylite 29.1 0- (2,4,6-tribromobenzyl) -D-arabite 20 30.5-0- (2-fluorobenzyl) -xylite 31.5-0- (2,6-dichlorobenzyl) -1,2,3,4 -tetra-O-methyl-xylite 32.1-0- (2,6-dichlo orbenzyl) -2,3,4,5-tetra-0-methyl-L-arabite 33.5-0- (2,4-dichlorobenzyl) -1,2,3,4-tetra-0-methyl-xylite 34 1-0- (2,6-dichlorobenzyl) -2,3,4,5-tetra-0-methyl-D-arabite 25 35.5-0- (2,4,6-tribromobenzyl) -1,2 3,4-tetra-0-methyl-xylite 36. 1-0- (2,4,6-tribromobenzyl) -2,3,4,5-tetra-O-methyl-D-arabite 3 7. 5- 0- (2-chloro-6-fluorobenzyl) -xylite 38.1-0- (2-chloro-6-fluorobenzyl) -D-arabite 3 9. 3-0- (2-chloro-6-fluorobenzyl) -adonite 40 40.5-0- (2-chloro-6-fluorobenzyl) -1,2,3,4-tetra-0-acety1-xylite 41.5-0- (2-chloro-6-fluorobenzyl) -1, 2,3,4-tetra-O-methyl-xylite. 42. A process for the preparation of benzyl ether derivatives of pen-tits according to claims 1-41, characterized in that A) are compounds of formula 4, wherein one of the substituents Y 'is the group of formula 2 and the four other substituents Y 'represent hydrogen, 83 0 0 48 9 r <r - 20 - a) with compounds of formula 5 or b) with compounds of formula 6 or c) with compounds of formula 7: * * optionally in. presence of acid binding agents and / or a catalyst to react or B) compounds of formula 8 wherein one of the substituents Y "represents the group of formula 2 and the other substituents Y" each represent an optionally substituted methylene group of formula 9 in pairs. optionally in the presence of organic solvents as well as acidic catalysts at temperatures of 0 to 100 ° C, preferably 40 to 80 ° C, hydrolyses in which R 1, and R 1 have the above meaning and and R g may each be the same or different and each time hydrogen an alkyl group with 1 to 10 carbon atoms, a substituted alkyl group with 1 to 10 carbon atoms, an optionally substituted arylalkyl group in which alkyl has 1 to 3 carbon atoms, a cycloaliphatic. hydrocarbon group with 3-8 carbon atoms, a single or multiple alkyl substituted by 1 - 6 carbon atoms and / or halogen and / or alkoxy with 1 '- 6 carbon atoms and / or the nitro group and / or the trifluoromethyl group aromatic hydrocarbon group or and Rg together represent a polymethylene group - (CH_) -, X represents a halogen atom, preferably 2. a chlorine atom, and Z represents a halogen atom or the group R ^ OSC ^ O and m represents the integer 4 or 5- ^ 43. Plant growth regulating agent, characterized by a content of at least one compound according to claims 1 to 41. 44. Plant growth regulating agent according to claim 43, mixed with carriers and / or excipients. 45. Agent according to claims 43 and 44 for influencing vegetative and generative growth in legumes, in particular soy. Plant growth regulating agent according to claim 45, prepared by methods according to claim 42. 8300489 fH2 - 0 - γι 2 3 CH - o - Y ^ Cv p I 2 rH H2 - (CO) - R-CH. 0 - Y3 i 3 CH - O - CH - O - Y_ k? H2 - 0 - Ti 5 6 CH - O - T'9 is - o - Ï 'a - co -: c s3 - zi -> CH - O - Y4 CH ^ - ° - TL R, - CO - o - CO - P 3 3 8 CH2 - ° - Y ”- 9 CH- O - Y". "CH - O - Y" S - t 3 / CH - O - YV CH, - O - Y ”5 Schering Aktiengesellschaft 8300489