CS235314B2 - Plant growth regulating agent and method of its efficient substance production - Google Patents

Abstract

Novel benzyl ether derivatives of pentites of the general formula I <IMAGE> (in which 1 of the Y1-5 symbols represents -CHR1-R2, R1 representing H or C1-C4-alkyl and R2 representing aromatic hydrocarbon optionally substituted by one or more substituents selected from C1-C6- alkyl, C1-C6-alkoxy, -O-CH2-O-, optionally substituted phenoxy, optionally substituted phenyl, Hal, -NO2, -CN and -CF3, and each of the other 4 Y1-5 symbols represents -(CO)n-R3, R3 representing H or optionally substituted C1-C4-alkyl and n representing 0 or 1) have a plant growth-regulating action, being particularly suitable for influencing the vegetative and generative growth of leguminous plants, for example soya bean plants, and accordingly may be made up with suitable carriers into plant growth-regulating preparations and may be used for treating seeds, living plants and areas of land.

Description

The present invention relates to plant growth regulating compositions which contain the novel benzene ether derivatives of pentites and to a process for the preparation of the active ingredient contained therein.

Compounds with a plant growth regulating effect are already known and in part even already established in practice.

However, in practice known products of this kind, such as those based on trisphosphonic acid or on the basis of 2,3: 4,6-dioO-Osopropyldiene-aafa-L1 and its sodium salts, however, have a corresponding quality of action or act only at higher doses.

Furthermore, it is known to desert 2-benzylmethyl ethyl hydrofuran as a herbicidal composition (DE-OS 27 24 67'7), which, however, damages plants as a result of its phytotoxicity.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a composition which exhibits a regulating effect on plant growth with a broad spectrum of activity and at the same time sparing the plants.

According to the invention, this object is achieved by a composition characterized in that it contains, as active substance, at least one pentene benzo ether terate of the formula I (I),

CH-О-Y.

I ch - o - Y

AND

CH - O -

IJ

CH - O - Y.

I4

CH 2 -O -Y 5 wherein one of Y is a group of formula

CH - H2

I * 1 and the four longer substituents Y are the same or different and denote a group of the formula

- ICO) _n - R, where.

R1 represents hydrogen or an alkyl radical having 1 to 4 carbon atoms,

R2 denotes a phenyl radical which is optionally one or more substituted C1-C6 alkyl and / or C1-C6 alkoxy and / or phenoxy and / or phenyl and / or halogen and / or nitro and / or trifluoromethyl and / or cyano,

R 1 is hydrogen or C 1 -C 4 alkyl, and n is 0 or I.

The compounds according to the invention behave as optical and optionally also as geomeric isomers. Single isomers and mixtures thereof are also within the scope of the invention.

The compounds according to the invention are particularly suitable for regulating the growth of various crop plants and with their spectrum of action and tolerable! exceed the same effects of the aforementioned products known in practice.

Since the compounds of the present invention tend to have additive and acidic properties. changes in plants, as well as changes in plant metabolism, are classified in the class of plant growth regulators that have these moieties released:

For suppressing vegetative growth of woody plants and tylins, for example at roadside, rails etdj, to prevent lush growth to suppress grain growth to prevent lodging or cracking; to increase cotton yield ·

To affect the branching of vegetative and genitive organs in ornamental or cultural plants, to increase the use of flowers or in tobacco and tomatoes to suppress offshooting.

To improve:! fruit fermentation, such as an increase in the sugar content of sugar cane, sugar cane, sugar beet or fruit, and compensation for fruit ripening leading to higher yields.

To increase resistance to climatic influences such as cold and drought.

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To affect the amount of latex formed in rubber bands. Possible applications include the formation of parthenocarpic fruits, pollen sterility and influencing gender.

To control seed germination or seed buds. To deflect or affect the falling of the fruit to facilitate harvesting.

The compounds of the invention are particularly useful for influencing vegetative and generative growth in certain legueinoses, such as soybean.

M ^ oživ! Depending on the purpose, the active ingredient employed is from 0.005 to 5 g of active ingredient / h, but higher doses may also be used.

The time of use is governed by the purpose of humiliation and climatic conditions.

Among the compounds according to the invention, in particular those compounds in which, in the general formula (I), denotes hydrogen or alkyl of from 1 to 4 carbon atoms, in particular meyl, Rg is phenyl, yc (R) is phenyl, yc (R) is phenyl. γ, 4-chlorophenyl-, 2,6-di-phenyl, 2,4-di-phenyl, γ-di-phenyl, 2,4,6-trichlorophoyl, α-bromide, γ, 2,4-dibroifen, 2,6 -libroiphenyl, 2,4,6-triboifeoyl, 2-biphenyls, γ-fluorophenyl-4-fluorophenyl-2,4-difluorophenyl, 2-methylphenyl, γ-methylphenyl, 1,4-hexylphenyl, 1,4-fluorophenyl 3-Phenoxyphenyl, 2-oxo-phenyl, 4-oxo-phenyl, 4-oxo-phenyl, 4-oxo-phenyl, 1,2-phenoxy-phenyl, 3-phenoxy-4-oxo-phenyl or γ-nitrophenyl, H 1 represents hydrogen, C 1 -C 4 alkyl preferably meefl, ethyl or propyl and n is 0 or 1.

The compounds of the invention may be used either alone or in combination with one another or with other active ingredients. Alternatively, it can be used depending on the purpose! add dampening agents, plant protection agents, or pest control agents.

If it is intended to extend the spectrum of rum effect, it is also possible to add further! hLocidy. Suitable herbicidally active ingredients in the mixtures are, for example, active substances selected from the group consisting of tris (4), amino (s), amine, hazin, uracil, aliphatic carboxylic acids and halocarboaxylic acids, substituted benzoic acids and arylcarboxylic acids, hydrazides, amides, nitriles, esters. such esters of kerbolic acids, esters of kerbamic acid and thiocarbamic acid, urea, 2,3,6-trichlorobenzyloxypropahn, compositions containing them.

Rhodan and other additives.

The term refers to other additives for example also ifytotoxic ^ n ^ Ké additives that may generate -s herbicides a synergistic increase in action, including but not limited _smiCedla) eeuugátory, solvents and oily additives.

The active substances according to the invention or their mixtures are expediently used in the form of preparations such as powders, powders, granules, solutions, emulsions or suspensions, from the addition of liquid and / or solid carriers or diluents and, if necessary, auxiliaries such as Adhesives, tackifiers and / or dispersants.

Suitable liquid carriers are, for example, water, aliphatic and aromatic hydrocarbons such as benzene, toluene, xylene, cyclohexanone, isobutyl, dimethylsulfoxil, diethylmethylthio, and mineral oil fractions.

Suitable solid carriers are mineral soils, for example tonail, IIIcagal, mothers, kaolin, clay, chalk, silicic acid, and plant products, for example flours.

Surfactants which may be mentioned are, for example, calcium ligands, polyoxyalkylene-phenoxyethanes, olefinsilphonic acids or their salts, phenoxilphonic acids and their salts, formaldehyde condensation products, aliphatic alcohol sulphates and substituted benzenesulphonic acids and their salts.

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The proportion of active compound (s) in the various compositions can vary within wide limits. For example, the composition contains up to 80% by weight of the active ingredient, about 90 to 20% by weight of the liquid or solid carrier, as well as optionally up to 20% by weight of the surfactant.

The use of the composition can be carried out in a conventional manner, for example using water as carrier at a spray rate of about 100 to 1000 liters / ha. It is also possible for the composition to be used in the so-called uoloobjeum and ultromolobeomic processes, such as their application in the form of a fluid called οΙΙ οο γθποζΙ.

For example, the following ingredients are used to make the preparations:

And, Dust

(a) 80% by weight, active substance% by weight, kaolin by weight, surfactants based on N-meetl-N-oleyltaurine sodium salt and lindinsilfonic acid calcium salt.

b)% by weight, active substance% by weight, ionic minerals% by weight, foamed pitch% by weight, surfactants based on the calcium salt of ligoinsufonic acid

c) an alkylphenol polyglycol ether.

% W active ingredient% w jíootých wt% minerals, cellulose pitch wt%, surfactant based on the calcium salt of SMUs ligo ^ ⁿ 8ulOonové with alkylphenol (ether.

d) 5% by weight, active ingredient% by weight, up to% by weight, foamed pitch, surfactant not based on condensation prodrugs.

B. Poured concentrate% by weight, active ingredient% by weight, xylene-% by weight, diyayl sulfoxide ·% by weight, sodium norolfaoyl polyoxyethylene or calcium dodecylbenzene sulfooate.

C. Paste by weight, active ingredient by weight, sodium aluminosilicate by weight, cetyl glycol ether with 8 moles of ethylene oxide by weight, spindle oil by weight, polyethylene glycol by parts of water.

The active ingredient for the plant growth regulating agent according to the invention is prepared by the preparation of compounds of the formula VI

CH ₂ -O-Y, t

CH-0 1 (No

CH - O - Y, ‘t

CM - 0 - Y4

AND

CH ₂ -O -Y in which one of the substituents) denotes a group of formula c

- CH - R ₂

I * 1 with the other four sub-substituents ϊ denotes in pairs optionally substituted methylene groups of the formula

hydro ski for přítomnnoti optionally in a solvent and the acidic catalyst, at a temperature ranging from ⁰ to ¹⁰⁰ ° C and above them ^h o ^{d 0} to 4 · ⁶⁰ ° C, and ^{p y} Rita resulting sloučeni.n formula II

CHg-O-Y, l

CH - O - Y ₂ .

CH - O - Y ₃ (II)

AND

CH - O - Y

AND

CH 2 -O -Y in which one of the substituents I 'denotes a group

- CH - 'R ₂ ' l

The four other sub-substituents (1) are hydrogen, reacted as needed in one second stage (III).

a) with a compound of formula III

- CO - X or

b) 86 with a compound of formula IV

R3-Z or (IV)

c) a compound of formula V

K i = CO - O - CO - R 3 (V), optionally in the presence of an acid binding agent and / or a catalyst, wherein:

R, Rj and Rj are as defined above and

R 8 and R 8, which may be the same or different, denote hydrogen, a C 1 -C 3 alkyl radical, a C 1 -C 3 phenylalkyl radical, a C 3 -C 8 cycloaliphatic hydrocarbon radical or a phenyl radical, optionally once or optionally substituted by C1-C6 alkyl and / or halogen and / or C1-C6 alkoxy and / or nitro or / or trifluoromethyl, or

R e R j together represents a polymethyl group of the formula

X represents a halogen atom, preferably a chlorine atom,

Z represents a halogen atom or a radical of formula ROSOgO- and m is an integer of 4 or 5.

The radicals R and R8 of a substituted methylene group are hydrogen, alkyl of 1 to 10 carbon atoms, for example mmeyl, style, propyl, isopropyl, n-butyl, sec-butyl, 2,2-dimethyl-1-propyl, n-pentyl, n-heptyl, n-octyl, n.decyl, C 3 -C 8 -cycloaliphatic hydrocarbon radical, for example cyclopropyl, cyclopentyl, cyclohethyl, phenylalkyl with 1 to 6 carbon atoms; 3 carbon atoms in the alkyl moiety, for example benzyl, 2-phenylethyl, phenyl, optionally mono- or polysubstituted with C1-C6 alkyl, / or halogen and / or C1-C6 alkoxy and / or or an oltrio group and / or a triltoomethyl group such as phenyl, 2-chlorophenyl, 1,1-chlorophenyl, chlorophenyl, 3,4-dichlorophenyl, 4-methophenylphenyl, 4-methophenylphenyl, 4-methophenylphenyl, 4-methophenylphenyl, 2-chlorophenyl, 4-methophenylphenyl, 4-methophenylphenyl, , 4-dichlorophthol, and optionally

R 4 and R together denote a tolleethylto group of the formula - (CR 8) -, wherein 'is an integer of 4 or 5

Particularly suitable as starting materials are the pentite derivatives of formula (71) wherein

1. Y, denotes the remainder of the formula

- CH - r ₂

I and Y ₂ together with Y ₁ and Y ₂ together with Y ₈ denote an optionally substituted methylene group of the formula

C

2. Y ^ denotes the remainder of the formula a Ϊ, together with Y ₂ and Y ^ together

3. Yg denotes the remainder of the formula

- CH - R2 1

Λ

Yg represents an optionally substituted methylene group - a

- CH - R2 1

R.

and Y, together with Y 2 and Y 2 together with Y 2, represents an optionally substituted methylene group.

Reactions ^to rea towering obstructions ^h ^ s ^p ro ^B im at taplotě ^d of 0 to ¹⁵⁰ ° C, ^b of ^the VSA ECN ^of between room temperature and míítnooti reflux temperature of the respective reaction mixture. The reaction time is 1 to 72 hours.

In the synthesis of the compounds of the invention, the reactants are killed in approximately equimolar multiplication. Suitable reactants are solvents inert to the reactants. The choice of the solvent or suspending agent is determined by the use of the corresponding alkyl or acyltologenide and / or di-alkylstate and the acceptor acid used. As the disintegrating agent or suspending agent, for example, there may be mentioned ethers such as diethyl ether, diisooropolyether, hydrofuran and dioxane; acetonntril and carboxamides thou ^power in such dimetylforaamid.

Suitable acid acceptors are organic bases, such as, for example, triethylamine, Ν, Ν-dimethylene and pyridine bases or inorganic bases such as alkaline earth and alkali metal oxides, hydroxides and carbonates. Liquid bases such as pyridine can be used simultaneously as solvents. Anionic compounds such as quaternary ammonium, phosphonium and arsonium compounds as well as sulfonium compounds are suitable as catalysts.

The same are suitable. polyglycol ethers, especially cyclic ones such as 18-krown-6, and tertiary amines such as tributylaine. Particularly suitable compounds are quaternary ammonium compounds, such as, for example, benzyltriethylomonium chloride and tetrabutonium bromide.

The compounds produced according to the invention can be isolated from the reaction by conventional means, for example by distilling off the solvent used at normal or reduced pressure, precipitation with water or extraction. An increased degree of purity can generally be achieved by purification by means of column chromatography or fractional purification.

Compounds of the invention are cr ^ i ^ ⁱ ^ j.dla colorless liquid odorless, sparingly soluble in water and exceptionally soluble in aliphatic uhlovodlcích such as petroleum ether, hexane, pentane and cyclo-lohexan, readily soluble in halogenated uhlnvodlcích such as chloroform , mmeylene chloride and tetrachloamethane, aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as diethyl ether, tetrathlfurane, and dioxane; but also form colorless, crystalline particles which are odorless and sparingly soluble in aliphatic and aromatic hydrocarbons, limited to well soluble in halogenated hydrocarbons such as chloroform. and tetramethylmethylamines, ketones such as carboxylic acid amides such as diolefin, sulfoxides such as is the sulfonoxil, nitriles of carboxylic acids, such as δ, т, И, lower alcohols, such as οο ^ ιι ^, ethanol in water. In particular, water, acetic acid and acetic acid are suitable as solutions for the purification.

The following examples develop a process for the preparation of the benzyl ether derivatives of the pennils of the invention.

Example 1

5-O- (2,6-Lichloro-benzyl) pШ

277.0 g (0.708 tfol) 5-0- _(2-l 6 lichOrítizyt) -1,2: 3,4-IIS-0-i8oproρyliltn-nlitj stirring was reacted with 752.2 ml of 1.5 N hydrochloric acid sulfuric. Subsequently, the reaction mixture was stirred for 3 hours at 70 ° C and was not stirred overnight at RT. While stirring, ²⁵ ml of 32% sodium hydroxide solution are added dropwise at ²⁵ DEG C., and the action solution is extracted three times with 200 ml of triethyl acetate each time.

The extracts are transformed twice with 100 ml of water each time, dried over magnesium sulphate, filtered and concentrated in vacuo. Colorless knyls were obtained, which were then triturated with a cold 1: 1 mixture of H 2 O and His propyl ether and subsequently dried to constant temperature at 50 psi. Yield: 2012.0 g = 91.7% of theory 5-0- (2,6-c ^h l ^{i s} lor eno ^{ztl tyit} -n j. Drowning ^{-1 tans: 82-83} ° C

C ^ u · thin-film omotrngalite (DC):

Eluent: chloroform / motanol 4: 1, the value of B _f; 0.34

Analysis:

calculated: 46.32% C, 5.18% H, 22.79% Cl; Found: C, 46.48; H, 5.10; Cl, 22.37

Example 2

3-O- (2,6-dichlorobenzyl) -1,2: 4,5-tetra-O-methyl-adonite

_From 3.11 g (0.01 mol) of 3-0- (2,6-dichlorobenzyl) -adonitu, _Л 0 22 g (0.001 mol) h ^ nzyHi ^ i ^ i ^ l ^; ^! EmonluimCloridu and 25, 23 g (0.2 mol) of methanesulfate were mixed in 20 ml of methylene chloride. With vigorous stirring, while cooling at about 30 ° C, mo ^{g (} 0.25 mol potassium potassium dissolved in 15 ml of water) was added dropwise. After stirring for 3 hours at room temperature, the reaction mixture was refluxed for one more hour. . the reaction mixture is diluted with 150 ml water and extracted twice with 150 ml ethyl acetate. the extracts washed with water, dried over magnesium sulfate, the filtered was zahussí. the oil obtained was distilled-U is below taličkotym chilled ^d ICEM ^(t ep ^L O ^T and ^la Zn ² ° ^of 0 ° ^C / 26 Pa ^{to 7).} Yield: 2.90 g = 79.1% of theory 3-0- (2,6-dichlorobenzyl) -1,2: _4> 5-O-TSTR -methyladonite.

n _D ² ?: 1 ^, 519 8 '

DC: eluent = 1: 1 acetic acid / acetic acid, Rf value: 0.29

Analysis:

calculated: 52.32% C, 6.58% H, 19.00% Cl;

Found: C, 51.82; H, 6.48; Cl, 20.13

Example 3 ‘

1-O- (2,6-dichlorobenzyl) -2,3,4,5-tetra-O-acetyl-D-arbitil

5.0 g (0.016 mol) of 1-O- (2,6-dichlorobenzyl) -D-arabityl in a mixture of 20 ml of pyridine and 20 ml of scstanhydride were stirred for one hour at room temperature and then allowed to stand overnight. The reaction mixture was dissolved in 150 ml of toluene and the solution evaporated to dryness under a water pump vacuum. The residue was added to an additional 150 ml of toluene and evaporated again in vacuo. The oil obtained was removed in portions with 300 ml of acetic acid. The ethyl acetate extracts were washed with water, dried over magnesium sulfate and filtered, and the tulles were evaporated. The oily residue crystallized upon washing with a small amount of diisopropyl ether. Yield: 5.80 g = 75.7% of theory 1-O- (2,6-dichloro-benzoyl-2,3,4,5-ethyl-8-O-ethyl-D-atabits) Melting point: 89-90 ° C

DC: eluent · = acetic acid tolssoethylsstst 1: Analysis: 1, R _f value: 0.47 calculated: 50,11% C, 5.49% H, 14.79% Cl; found: 50,58% C, 5.49% H, 14.80% Cl.

The longer compounds of the invention are obtained in an analogous manner:

Example δ. Name of the compound Physical constant 4 5-O- (2,4-dichlorobenzyl) -xylit mp: 96-98 ° C 5 5-O- (2-chlorobenzyl) -xylit mp: 52 to 54 ° C 6 5-O- (2-methylbenzyl) -xylit mp: 59-61 ° C 7 1-O- (2,6-dichlorobenzyl) -L-ara biot mp: 122-124 ° C 8 1-O- (2,6-dichlorobenzyl) -D-arabite mp: 124-126 ° C 9 3-O- (2,6-dichlorobenzyl) -adonite mp: 116-117 ° C 10 5-O- (2,4,6-tribromobenzyl) - Qr lit mp: 132-133 ° C 1 1 5-O-benzzl-2Xlit mp: 47-50 ° C 12 5-O- (2, .alpha.-dihydrobenzyl) -1,2,3,4-tetra ^{, and} O-acetyl- -xylit n _D ²⁰ : 1.487 6 13 5-O- (2,4,1) -1,2,3,4-tetra-O- -aceeyl-oxrlit mp: 106-107 ° C 14 3-O- (2,4,6-trifluoromethyl) adonitone mp: 132-134 ° C 15 Dec 5- ° - (4-chlorobenzyl) -xylite · tt: ^e 109 F 109.5 ° C 16 5-O- (4 - (-) - 71) - xHt mp: 110-112 ° C. 17 5-O- (3,4-dichloro-biphenyl) -xylite mp: 122-123 ° C 18 5-O-3-methyl; mp: 54-56 ° C 19 Dec 5-O- (4-methylbenzyl) -yl mp: 98-99 ° C 20 May 5-O-3,4-dimethylbenzyl) -yl mp: 72-74 ° C 21 5-O- (3-chlorobenzyl) -xylit mp: 90-92 ° C 22nd 5-O- (2-cyano-2-yl) -oxyl mp: 119-121 ° C 23 3-O- (2,6-dichlorothienzyl) -1,2,4,5-tetra-O-acetyl- -adonit n _p ²⁰ : 1.494 1 24 5-0- (3-tifluoromethylbenzyl) - χ1it TT 61 ^e 63 ° C 25 5-O- (3-fluorobenzyl) -xylit mp: 72 to 74.5 ° C 216 5-O- (4-fluorobenzyl) -xylit TT 76 ^e 78 ° C 27 Mar: 1-O- (2,4,6-thiazolomyl) -D-arabite mp: 156 ^e 157 ° C. 28 \ 5-O- (2-fluorobenzyl) -xylit nD ²⁰ : 1.524 3 29 5-O- (2,6-di-chlorobenzyl) -1,2,3,4-tetra-O-methyl- -xyUt n _p ²⁰ : 1.518 6 30 1-O- (2,6-dichlorobenzyl) -2,3,4,5-tetre-0-mmyl- -L-er ^ l ^ l.t. nC ²⁰ : 1.520 1 31 5-O- (2,4-dichlorobenzyl) -1,2,3,4-tetra-O-methyl- -xylit NP ²⁰ : 1, 517 7 32 1-O- (2,6-Dichlorobenzyl) -2,3,4,5-tetra-) methyl-D- -erabit np ² ° _: 1.520 5 33 5-O- (2,4,6-trbrlomienzyl) -1,2,3,4-tetra-O-methyl- -tylit. np ²⁰ . 1,561 6 34 1-O- (2,4,6-thiazolomyl) -2,3,4,5-tetrahydro-0-methyl- -D-erabit n _p ²⁰ : 1.566 8 35 5-O- (2-chloro-6-fluorobenzyl-1H) mp: 70 ^{B to} 71 ° C 36 1-O- (2-Chlob-6-fluorobezzyl) -D-arebit mp: 138 139 ° C 37 3-O- (2-chloro-6-fluorobenzyl) -adonite n _p ²⁰ _: 1.529 7 38 5-O- (2-Chlob-6-fluorobenzyl) -1,2,3,4-tetra-O- -Bcetyl-xyy.it NP ²⁰ : 1,480 9 39 5-O- (2-chloro-6-fluorobenzyl) -1,2,3,4-tetra-O- -meey1 - χ1it n _p ²⁰ : 1.497 2

Mp = melting point

1

The starting compounds for the preparation of the compounds according to the invention are known per se or are prepared by known methods.

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

Example 40

* 5- 0- _(2> 6-dichlorbeJiayl) -1,2: _3> 4-bis-O-isoproppliden 2xlit '

116.13 g (0.5 mol) of 1,2,2,4,4-bia-2-carboxylic acid, and mixed with 1 9.96 g. g (0.5 mol) 2,6-dichlorobenzyirroyidide and 4.5 g (0.019 mol) benzyltriemonium chhoride · Under particularly vigorous stirring, a solution of 100 g of sodium hydroxide (2.5 mol) in ^{e 12 of} 5 ml of water is added dropwise, while the limb slowly rises to about ⁵⁰ ° C and drops again to one minute over one hour. Subsequently to the completion of the reaction, the reaction mixture followed by stirring for one hour at 50 ° C, diluted 5 ° C ⁰ ml tattooed ^HY and ^{n e} in the ^soil and extracted tower ^d y 15 ° ml acetic acid ethyl ester. The organic phase was dveltariá-T ^ 300 ml of water, dried over magnesium sulfate, filtered and dried uu va ^to sum up at 4 ^0C. The opera is fractionally refined. VjHíž ^: ¹⁵⁰ 0 ^g = 76.7% t-rin. Boiling point = 163 ° C / 13 P ^a; Jp ²⁰ : 1.508 C. DC: eluent = toluene / ethyl acetate 4: 1. _Rf value: 0.52

Analysis:

calculated: 55.25% C, 6.18% H, 18.12% Cl;

Found:% C, 55.66;% H, 6.46;% Cl, 18.03.

Example 41.

5-O- (2,4-trifluorobenzene) -1,2: 3,4-lis-O-isopropylptinidene

A solution of 23.2 g (0.1 mol) of 1,2: 3,4-lis-O-slopylpolyidimide in 100 ml of toluene is slowly added dropwise to a suspension of 2.88 g (0.12 mol) with stirring. sodium hydride in 50 mL toluene. After completion of the dropwise addition, the mixture was heated at reflux for 2 hours. Subsequently, a solution of 40.78 g (0.1 mol) of 2,4,6-tribromobenzyl bromide in 50 ml of toluene was added dropwise and the mixture was heated under reflux for an additional 8 hours.

After cooling, the mixture is gently washed three times with 150 ml of water each time; The organic phase was dried over magnesium sulfate, and concentrated in přefiteruje VA ^to uu at 4 ^0C. Found oil in ^the va uu (180 ° C bath temperature / n Pa) zteví stop default hard. Yield ^{37.6 g} = ^6, 7.25% of theory., ^P20 °: 551 ^ 6

DC: eluent = toluene ethyl acetate 1: 1, Rf value 0.52

Andýza:

calculated: 38.66% C, 44% H, found: 337.91% C, 4.44% H.

In a similar manner, the following compound can be prepared:

Example # Name of the compound Physical constant 42 3-O- (2,4-di-chlorobenzyl) -1,2: 4,5-bis-O- -8-propylpiperidone n. ²⁰ - 1,509 2 43 1-O- (2,4-dichlorobenzyl) -2,3: 4,5-Hs-O- -isopropylidan-L-8rabit n. ^20-1, 507 0 44 1-O- (2,4-di-chloro or bw-s-3-y)] -2,3: 4,5-bis-O- β-propylidene-D-arabite nD ²⁰ _ 1.507 1 45 1-0- (2,6-dichlorobenzyl) -2,3: 4,5-bis-O- —Isopropylidene-L-arabite nD ²⁰ = 1.507 5 46 1-0- (2,6 ^ 1οΜθχ ^ ηζζ1) -2,3: 4,5-bis-O- -isopropylidane-D-8rabit nD ²⁰ «1.509 3 47 3-O- (2H-dichlorobenzyl) -1,2: 4,5-bis-O- -isopropylidene-adenil Пц ²⁰ = 1,511 8 48 3-O- (2,4-6-β-γ-β-α) -1,2: 4,5-bis-O- - (is opropylidene) -adonite mp: 75 ° C 49 1-0- (2,4,6-trirooubanzzl) -2,3: 4,5-bis-O- - (Ssoyroyzlidao) -D-Arabite nD ²⁰ ”i, 544 7 50 5-O- (2-chloro-6-fluoro-benzyl) -1,2: 3,4-bis-O- - (isoprooplidee) xlit nD ^{20 to} 1, 491 6 51 1-O- (2-chloro-6-pheno-benzyl) -2,3: 4,5-bis-O- - (S8oyroyzlieao) -D-Arabite n ^ ²⁰ = 1.490 1 52 3-O- (2-chloro-6-phenoxy) -1,2: 4,5-bis-O- - (Isopгopylidene) -adonite nD ²⁰ = 1 491 8

The following examples illustrate the possibilities of using the compounds of the invention.

Example 53

Increased chlorophyll content and soybean seed deposition.

Soya. after splashing, sprayed with water-based emulsion of test compounds. The dose was 0.8 kg of active substance / ha. 4 weeks after spraying, the discs from the 2nd cannon leaf were punched out. From them tulle extracted chlorophyll and chlorophyll content determined.

The table shows the increase in chlorophyll content relative to the control.

Addition. the plants were monitored for the deployment of pods and flowers and calculated on% of the control). - Also these. data are shown in the table. The results obtained by using the compound according to the invention, compared to the contrast agents, achieved better tolerability or higher chlorophyll content and / or increased flower and legume deployment, respectively.

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Increase of chlorophyll content in%

Compounds of the invention

Deployment of pods and flowers in% of control

5-O- (2,6-dichlorobenzyl) -xylit 63.9 202 1-O- (2,6-dichlorobenzyl) -L-ara biot 43.0 129 1-O- (2,6-dichlorobenzyl) -D-arabite 37.2 ЮЗ 3-O- (2,6-dichlorobenzyl) -adonite 39.3 129 Comparative means according to DE-OS 27 24 677 2-Benzyloxymethyl-tetrahydrofurene 27.4 146 2,6-dichlorobenzyloxymethyl-tetrahydrofuran ⁺ 60.9 90

⁺ Phytotoxicity was manifested by etching

Example 54

Growth control effects of soybean and shrub beans after immersion.

Beans and soybean were not contaminated with the powdered active ingredient in doses of 10, 50. e 100 g of active ingredient per 100 kg of seed. After 3 weeks the cultures were tested for appearance on a scale of 0 to 10 according to the following scheme:

= as untreated control = stunted growth, dark green, branched = very saline suppressed growth, dark green and strongly branched.

As the values obtained show, the desired effect is much stronger for the compounds of the invention than for the comparator.

Table

A compound of the invention

Quantity of effective bonitation substance in g / 100 kg of soy bean seed

5-O- (2,6-dichlorobenzyl) -xylit

1-O- (2,6-dichlorobenzyl) -L-arabite

1-O- (2,6-dichlorobenzyl) -D-arabite

Compound of the Invention Amount of active substance Bonitece in g / 100 kg * soybean bean seed

Continuation table

3-O- (2,6-dichlorobenzyl) -adonite 10 9 8 50 5 5 100 ALIGN! 3 5 5 '· O- (2,4-tribromo-benzyl) -Jlite 10 10 10 50 9 9 100 ALIGN! 9 9 2-benzyloxymethyl-tetrahydrofuran 10 10 9 50 10 9 / according to DE-OS 27 24 677) 100 ALIGN! 10 8 2,3: 4,6-di-O-18-fluorooylideo-alpha-L- 1 0 10 8 -xylohexulofurene - sodium salt 50 10 8 100 ALIGN! 10 7

Example 55

Increase in soybean yield

After emergence, the soybean was sprayed with an emulsion of the test compounds at a rate of 0.8 kg / ha. Four weeks after spraying, the number of seedlings and pods were seeded. The results are shown in the table. Data were recalculated to% of control. In addition, the percentage of growth suppression was determined.

The obtained results document that the compounds promote the deployment of the seedlings and the pods while suppressing growth. Comparative formulations showed this effect only to a lesser extent or phototoxic.

Table

Compounds of the invention % Growth inhibition Seeding of pods and perennials in% of control determination 5-O- (2-chlorobenzyl) -xylit 28 142 5-O- (2,6-dichloro-benzo-1-yl) -N-tetra-C-acetyl 1- -xylit 59 219 5-O- (2,4'-tribromobenzyl) 11,2,3,44-tetra-O-acetyl- -xyHt 44 173 1-o- (2,6-Dichlorobenzyl) -2,3,4,5-tetra-O-ac ethyl-D- -arabit 59 215 3-O- (2,4,6-tribromobenzyl) tadonite 49 188 5-O- (4-chlorobenzyl) -x / Ht 44 165 5-0- _(Γ 4t.b ombeozl1) -xylit 49 185 5-O- (3, 4-dichlorobenzyl) -xylit 0 1 15

Table continuation

Compounds of the invention % Override Suppression Non-matched puppets and flowers in% of her dansing 5-O- (3-methylbenzyl) -alphite 28 108 5-O- (4-methylbenzyl) xylit 33 204 5-O- (3,4-Dimethyl-benzyl) -xylit 33 204 5-O- (3-isobenzyl) -J-lithium 38 135 5-O- (6-cyanobenzyl) oxyHt 28 I 50 3-O- (2,6-di-benzobenzyl-1,4-S-tetra-O-ethyl-adonite) 204 5-O- (3-thiomethoxy-4-enz-4) -xylit 23 80 5-O- (3-fluorobenzyl) -xylite 33 204 10-O- (2,4,6-toiboombenzyl) -D-eoabit 33 188 5-O- (2-fluoro-benzyl) -xylit 28 92 Smoothing agent 2-Benyyloxymethyl-tetrahydrosiuoane (according to DE-OS 27 24 677) 135 toiododenzoic acid 69 73

SUBJECT T OF THE INVENTION

Claims (4)

SUBJECT T OF THE INVENTION 1. A composition for controlling the growth of roottin, which is a mildly active substance, comprises at least one benzyl ether derivative of the pentite of general formula I. CH - ⁰ - η CH-O-Y 2 AND CH-O-Y3 (I) I ^J CH-O-Y. t CH ₂ -0 Y 5 in which one of the tubstituents Ϊ denotes a group of samples - CH - r ₂ and the four longer tubstituents are the same or different and denote the group highly - (CQ) _n - R ₃ wherein ZW ^ <^: £ hydrogen or an alkyl radical T i EŽ 4 carbon atoms Rg denotes a phenyl radical which is optionally mono- or polysubstituted by C1-C6 alkyl and / or C1-C6 alkoxy and / or phenoxy and / or phenyl and / or halogen and / or nitro and / or trifluoromethyl groups and / or cyano, R is hydrogen or (C 1 -C 4) -alkyl and n is 0 or 1; 2. A composition according to claim 1, wherein the active ingredient comprises at least one pentyl benzyl ether derivative of the general formula (I) in which: R is hydrogen or alkyl of 1 to 4 carbon atoms, preferably methyl, R is 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-tribromophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,4-difluorophenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 3,4- dimethylphenyl, 2-methylphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-phenoxyphenyl, 3-phenoxyphenyl, 2-nitrophenyl or 3-nitrophenyl, R is hydrogen, alkyl of 1 to 4 carbon atoms, especially methyl, ethyl or propyl, and n is 0 or 1. 3. A composition according to claim 1, wherein the active ingredient comprises at least one compound selected from the group consisting of: 5-O- (2,6-dichlorobenzyl) xylite, 3-0- (2,6-di chlorbenzy1) -1, ^2, 4,5-0-metyladonit, 1-O- (2,6-dichlorobenzyl) -2,3,4,5-tetra-O- and cetyl-D-arabite, 5-O- (2,4-di-chlorobenzyl) xylite, 5-O- ( ^2- chlorobenzyl) xylite, 5-O- (2-methylbenzyl) xylite, 1-O- (2,6-dlchlorobenzyl) -L-arabite, 1-O- (2,6-dichlorobenzyl) -D-arabite, 3-O- (2,6-dichlorobenzyl) adonite, 5-O- (2,4,6-tribromobenzyl) xylite, 5-O-benzylxylite, 5-O- (2,6-dichlorobenzyl) -1,2,3,4-tetra-O-acetylxylite, 5-O- (2,4-tribromobenzyl) -1,2,3,4-tetra-O-acetylxylite, 3-O- (2,4,6-tribromobenzyl) adonite, 5-O- (4-chlorobenzyl) xylite, 5-O- (4-bromobenzyl) xyll, 5-O- (3,4-dichlorobenzyl) xylite, 5-O- (3-methylbenzyl) xylite, 5-O- (4-methylbenzyl) xylite, 5-O- (3,4-dimethylbenzyl) xyll, 5-O- (3-chlorobenzyl) xylite, 5-O- (4-cyanobenzyl) xylite, 3-O- (2,6-dichlorobenzyl) -1,2,4,5-tetra-O-acetylladonite, 5-O- (3-trifluoromethylbenzyl) xylite, 5-O- (3-fluorobenzyl) xylite, 5-O- (4-fluorobenzyl) xylite, 1-O- (2,4,6-tribromobenzyl) -D-arabit, 5-O- (2-fluorobenzyl) -xylite, 5-O- (2,6-dichlorobenzyl) -1,2,3,4-tetra-O-methylxylite, 1-O- (2,6-dichloro-benzyl) -2,3,4,5-tetra-O-methyl-L-arabite, 5-O- (2,4-dichlorobenzyl) -1,2,3,4-tetre-O-methyl-xylitol, 2353Н 1-O- (2,6-dichlorobenzyl) -2,3,4,5-tetra-O-methyl-D-arabite, 5-O- (2,4,6-tribromobenzyl) -1,2,3,4-tetra-O-methylxylite, 1-O- (2,4,6-tribromobenzyl) -2,3,4,5-tetra-O-methyl-D-arabite, 5-O- (2-chloro-6-fluorobenzyl) xylite, 1-O- (2-chloro-6-fluorobenzyl) -D-arabite, 3-O- (2-chloro-6-fluorobenzyl) adonite, 5-O- (2-chloro-6-fluorobenzyl) -1,2,3,4-tetra-O-acetylxylite; and 5-O- (2-chloro-6-fluorobenzyl) -1,2,3,4-tetra-O-methylxylit. 1 to 3, characterized in that the compounds are 4. A process for the preparation of an active compound according to the general formula VI CH _O - 0 - Ϊ. I ²¹ ch - o - Y_ I CH-O-Y. CH-O-Y AND CH ₂ - o - Y ₅ (VI) wherein one of the substituents ϊ '' denotes a group of the formula ε others The four X substituents in pairs of optionally substituted methylene groups of the formula hydrolyze, optionally in the presence of an organic solvent and acid catalysts, from 0 to 100 ° C, preferably from 40 to 80 ° C, and the compounds of formula II thus formed CH ₀ - 0 - Y. I ² CH - O - y ₂ AND CH - O - Y ₃ 1 ^J CH-0-Y. I ⁴ CH ₂ -O-Y ₅ wherein one of the substituents Y 'represents a group - CH - r ₂ R. (II), and the four other substituents Y 'destroy hydrogen, react in one second stage e) with a compound of formula III R3 - CO - X (III), or (b) with a compound of formula IV * 3 - z or (IV), c) with a compound of the formula v * 3 - CO - O - CO - R 3 (V), optionally in the presence of an acid binding agent and / or a catalyst, wherein: R 1, R ₂ , R ₃ , R 3 have the above meanings a R 4 and R 8, which may be the same or different, denote hydrogen, the alkyl radical β 1 to R 3 C --C,-C 3-C z-C z-Cty alkyl, a C,-C cyk-cycloaliphatic hydrocarbon radical, or a feoyl radical, or one or more times substituted with C až-C alky alkyl and / oebo halogen and / or 1 alkoxysktpinot EŽ 6 carbon atoms and / oebo nitroskupioou and / or trifluoromethyl ^ © methyl group oebo «4.8 K ₅ X is taken together to form a ethylene group of the formula - (CH 2) - represents a halogen atom, preferably a chlorine atom, a halogen atom or a radical of the formula R 10 O 10 O - and is an integer of 4 or 5.