LU84682A1 - BENZYLAETHER DERIVATIVES OF PENTITES, METHOD FOR PRODUCING THESE COMPOUNDS AND THEIR CONTAINING AGENTS WITH GROWTH REGULATORY EFFECT FOR PLANTS - Google Patents

Description

SCHERING AG

* - ^ Industrial property protection 5 The invention relates to new benzyl ether derivatives of pentitene, processes for the preparation of these compounds and agents containing them with growth-regulating action for plants.

10 compounds with growth regulatory activity are already known and some have even been put into practice.

Products of this type which are known in practice, such as those based on 15 triiodobenzoic acid or on the basis of 2,3-4, 6-di-0-isopropylidene-aL-xylohexulofuranuronic acid and its sodium salt, however, are not distinguished by or have the appropriate action qualities only with an increased application rate.

t 20 The use of 2-benzyloxymethyltetra-hydrofuran as herbicidal agent has also become known (DE-OS 27 24 677), which, because of its phytotoxicity, damages plants.

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

3® The object is achieved according to the invention by a means; that is characterized by a content of at least one compound of the general formula

CH - 0 - Y

35 1 2 1 J CH - 0 - Y_ I 2 CH - 0 - Y „I 3 CH - 0 - Y.

I 4 CH2 - 0 - * 5, 1 s 4o ▼ î h0- Ctl.ris, lIn B "ruh" Hans-Jürgen Hamann Postal address: SCHERING AG · D-1C00 Berlin 85. Postfach es 0311 c 0r. Hemr Hannse * Karl Otto Mlîteisjensctieid 'Df. Horst Witzei r ,,, «». -A_ .. JT-7 5 »#. .__ .. ^ Ä rostscfteoc-account! Berim-West 1175-101, Sankleitzahf 10010Q10 - Chairman of the Supervisory Board : Dr. cduard v. ScnwartZKoppen Beniner Commerzoann A3, Berlin. Kon: o No. 108 7006 00. Bankleitzani 100 * 30 00 = seat of the company: Berlin and BergKamen Berliner Disconto-Bank AG. Berlin. Kcmo-Nr.241 / 50Û8. Sanxleitzani 10070000 9 Handelsrecisrer 'AG £ hariattenfturr «MBS ses n An komon uoc nn *« Berliner Hanflels-GeeeHsetiafr * Ffantrfurrftr Sank _ (Uriin. «\

_.8_ SCHERING AG

* "G * w * rbRch * r Legal protection 5 in which one of the substituents Y represents the group - CH - R2 R1 and the four other substituents Y are 10 or different and each represent the group - (CO) - R_ n 3 - , in which R ^ is hydrogen or a C ^ -C ^ alkyl radical, 15 one optionally one or more times by Cj-Cg-

Alkyl and / or C ^ -Cg-alkoxy 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 radical, R ^ hydrogen or a optionally substituted C 1 -C 4 alkyl radical and n represent 0 or 1.

2 5 The compounds according to the invention occur as optical, optionally also as geometric isomers. The (individual isomers and their mixtures also belong to the subject of the invention.

3 ° The compounds according to the invention are outstandingly suitable for regulating plant growth in various crop plants and, surprisingly, in their range of activity and in their tolerability surpass the products mentioned in the introduction having the same direction of action.

Since the compounds according to the invention cause both qualitative and quantitative changes in plants and also changes in the metabolism of the plants, I 40 -3- Ï SaVhann «“ Iclrl oliô ÄÄ "Ham * n" P ° S, anSCnr'ft: SCHE? , 1NG AG '0-0 »Berlin 65 - Poatfad, 650311 i, zttr * TTr:? AEauardvarÄÄiiMSK» «' u. AG Kamnn MRR iSrÜnlr 10070000

I SCHERINGAG

* GmAGditr SichtisdRiti 5 classify them in the class of plant growth regulators, which are characterized by the following possible applications.

Inhibition of vegetative growth in woody and herbaceous plants, for example on roadsides, track systems, etc., in order to prevent excessive growth. Growth inhibition in cereals to prevent storage or twisting. -1, in cotton to increase yield.

Influencing the branching of vegetative and generative organs in ornamental or cultivated plants to increase the number of flowers or in tobacco and tomato to inhibit side shoots.

20th

Improvement in fruit quality, for example an increase in the sugar content of sugar cane, sugar beet or fruit, and more uniform ripening of the crop, which leads to higher yields.

25th

Increased resistance to climatic influences such as cold and drought.

Influencing the latex flow in rubber plants.

30th

Education of parthenocarpic fruits, pollen sterility and gender interference are also possible applications.

Control of seed germination or sprouting of 35

Buds.

Defoliation or influencing of the fall of fruit to facilitate harvesting.

-10- a ho 3 Xor'tan <l: i? R'Herb «* * si" is · 0r- Christian Bruhn. Hans-Jürgen Hamann Postal address: SCHERING AG - D-1000 Seriin 65 - Postfat * SS 03 ni Dr Heinz HannseKarl Otto Mitlelstenscneid - Dr Horst Witzei "... ——« ne nnnaoiRBii B "- Postsciiecic account: 3erlin.West 1175-101. Bank code number 10010010 - Chairman of the Supervisory Board. 0r.Eduard v. Sdiwartzkoppan Beniner CommerzeanK AG, Berlin, Konio No. 108 7006 00 Bankleitzani 100 400 00 § Company headquarters: 3eriin and SergKamen Berliner Discomo-Banlc AG, Berlin, account no.241 / 5003 Bankleitzani 19070000 / Commercial register: AG Charlonenpurg 93 HP.B. 263 and AG Kamen HRB 0061 Berliner Hanaeis-Gesellsäiaft - rranxlurter 3anlt Benin

: i SCHERING AG

j. -10i- Commercial legal protection 5 The compounds according to the invention are particularly suitable for influencing the vegetative and generative growth in some legumes, such as soybeans.

Depending on the application, the application rates are generally from 0.005 to 5 kg of active ingredient / ha, but can also be used, if appropriate, in higher application rates.

The application time depends on the application objective and the climatic conditions.

Of the compounds according to the invention, the effects described are particularly characterized by those in which, in the general formula I given above, 20 is hydrogen or C 1 -C 4 -alkyl, preferably methyl, R 2

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-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 3,4-dioxymethylenephenyl, 2-phenoxyphenyl, 3-phenoxyphenyl, 2-nitrophenyl or 3-

Nitrophenyl, R_ hydrogen, C -C.-alkyl, preferably 30 .. J 1 ’

Methyl, ethyl, propyl or chloromethyl and n represents 0 or 1 · i, The compounds according to the invention can be used either alone, in a mixture with one another or with other active compounds. If necessary, defoliants, pesticides or pesticides can be added depending on the desired purpose.

-11- tS, - - - * s 40 «r 4 Board: Dr. Herbert Asmis - Dr. Christian BruhnHans-Jürgen Hamann Postal address: SCHERING AG - D-IOOO Berlin BS. Pn, "" π, "m" ^ Dr. Heinz Hannse - Karl Otto Mitteistenscheid - Or. Horst Witzei _ _ _ „. .. “· πιη es PO Box 550311 ^ orsitzanoer Dr · Eauard V 3dlWart: KCPPen Bankfeitzahl 1M« 000 § Registered office: Benin uno Bergkamei 'Berliner Disconto-BanK AG. 3erlm. Account number. 241/5008 Sankleitrahi tM700at o / Commercial Register: AG CharlottenBurg S3 HRB 233 u. AG Kamen HRB 0051 Berliner Handels-Gesellschaft - Frankfurter Samt - Berlin / Kûnto.Nr 14-3A9 in om nn * *

j SCHERING AG

* Gcwcrbnchar legal protection 5 If a broadening of the spectrum of effects is intended, other biocides can also be added. For example, active compounds from the group of triazines, aminotriazoles, anilides, diazines, uracils, aliphatic carboxylic acids and halocarboxylic acids, substituted benzoic acids and arylcarboxylic acids, hydrazides, amides, nitriles, esters of such carboxylic acids, carbamic acid and thiocarbamic acid esters, are suitable as herbicidally active mixture partners. Urea, 2,3 »6-trichlorobenzyloxypropanil, rhodan containing agents - = tel and other additives.

, 15th

Other additives are, for example, also non-phyto-toxic additives which can result in a synergistic increase in activity with herbicides, such as wetting agents, emulsifiers, solvents and oily additives.

The active compounds according to the invention or mixtures thereof are expediently in the form of preparations, such as powders, scattering agents, granules, solutions, emulsions or suspensions, and the addition of liquid and / or solid carriers or diluents and, if appropriate, wetting agents, Adhesion, emulsifying and / or dispersing agent3 applied.

^ 0 Suitable liquid carriers are, for example, water, aliphatic and aromatic hydrocarbons, such as benzene,> toluene, xylene, cyclohexanone, isophorone, dimethyl sulfoxide,

Dimethylformamide, still mineral oil fractions.

33 Mineral soils are suitable as solid carriers. play Tonsil, silica gel, talktun, kaolin, attaclay, limestone, silica and vegetable products, for example flours.

-12- I 4o e · | 0?. 'ΗΪΓμ: η0 £ μ * SÄ MiKe? Shtens ^ erà ^ r / Î (^ i "wÎÎze | n Postal address: SCHERING AG - D-1000 Berfin« 5 PO Box 650311 1 1 ”An5'? T5ratS? N £ duard v- ^ wartzKoppan Berliner ^ mmeraöfnKAG ^ rllilKonVo ^ r. ^ MTMeOofaSweitzahl 10040000 5 Registered office: Benin and BergKamen Serlmer Disconto-Ban * AG, 3erlin. Account No. 241/5008. BanKleitzam 100 700 00 O / Commercial Register: AG Charlottenourg 93 HRB 233 and AG Kamen HRB 0061 Berliner Handeli-GesellsÄatt - Frankfurter Sanft - Berlin

. "SCHERING AG

Commercial «· Legal protection 5 Examples of surface-active substances include calcium ligninsulfonate, polyoxyethylene alkylphenol ethers, naphthalenesulfonic acids and their salts, phenolsulfonic acids and their salts, formaldehyde condensates, fatty alcohol sulfates and substituted benzenesulfonic acids and their salts.

10th

The proportion of the active ingredient (s) in the various preparations can vary within wide limits. For example, the agents contain about 10 to 80 percent by weight of active ingredients, about 90 to 20 percent by weight of liquid or 15 solid carriers and optionally up to 20 percent by weight of surface-active agents.

The agents can be applied in the customary manner, for example using water as a carrier in spray liquor amounts of 20 to about 100 to 1000 liters / ha. Use of the agents in the so-called low-volume and ultra-low-volume process is just as possible as their application in the form of so-called microgranules.

25 For example, the following ingredients are used to prepare the preparations: A. Spray powder a) 80 percent by weight of active ingredient 30 c 15 percent by weight of kaolin »5 percent by weight of surfactants based on> the sodium salt of N-methyl-N-oleyl-taurine clay - the calcium salt lignin sulfonic acid.

35 b) 50 weight percent active ingredient 4θ weight percent clay minerals 5 weight percent cell pitch 5 weight percent surfactants based on a mixture of the calcium salt of lignin-e sulfonic acid with alkylphenol polyglycol ether.

I 40 - * 3- i ÄÄÄ âÂÏ. » Hamann SCHERING AG · D-1000 Berlin 85 - Pottteeh «0311 i Chairman of the Autsicmsrat: Dr. Eduard v Stftwartzkoooen är ^ 1334000a = seat of the company: Benin and Bergkaraen Berliner Disconto-Bank AG. Berlin. Como no. 241/5008. Bankieitzafll 10070000 p / Commercial Register: AG Charlottenburg 33 HRB 253 u. AG Kamen HP.B 0061 Berliner Handels-Geseilscftatt - Frankfurter Bank -, Berlin,

SCHERINGAG

j * -3ϊ% ια— GmrctfeRdrar legal protection 5 c) 20 weight percent active ingredient “70 weight percent clay minerals 5 weight percent cell pitch 5 weight percent surfactants on the

Based on a mixture of the calcium salt of lignin sulfonic acid with alkylphenol polyglycol ether.

10 d) 5% by weight of fabric 80% by weight of Tonsil 10% by weight of cell pitch 5% by weight of surface-active substances based on a fatty acid conditioning product.

B. Emulsion concentrate 20 percent by weight of active ingredient 20 40 percent by weight of xylene 35 percent by weight of dimethyl sulfoxide 5 percent by weight of mixture of nonylphenyl polyoxyethylene or calcium dodecylbenzenesulfonate.

25- C. Paste 45 percent by weight of active ingredient 5 percent by weight of sodium aluminum silicate 15 percent by weight of cetyl polyglycol ether with 8 moles of ethylene oxide 30 2 percent by weight of spindle oil 10 percent by weight of polyethylene glycol 2.3 parts of water.

^ The new compounds of the invention can be

Prepare example by A) Compounds of the general formula "/ λ -14- a 40

V

4 d ": HD / nn» rl01κί, ΐSIS SCHf, NG AG “^ 000 *** * 'Port', 6S« 11 4 Chairman of the * Supervisory Board: Or. Sauard v. Schwartzfcoppen

£ Registered office of the company: Berlin and mountain names Berliner Disconto-BanK AG. Berlin. Account number. 241 / soog SanWeitzanl ioOTOOOO

a / Commercial register: AG Charlouenpuro 93 MBB283 u. AG Kamen HRBC0S1 Berliner Handele-Geseiiscnatt - Frannfuner Sank - .. Berlin.

1 ’'SCHERING AG

(. - 2 ^ F— 'Commercial' Legal protection 5 ch2 - 0 - Ti CH - 0 - Y'2 in - o - CH - 0 - Y4

CH2 - 0 - Y £ II

10 in which one of the substituents Y 'is the group - CH - R2 and the' four other substituents Y "are hydrogen, ^ a) with compounds of the general formula

R3 - CO - X III

or ----------- b) with compounds of the general formula

R, - Z IV

20 * or c) with compounds of the general formula

R '- CO - 0 - CO - Rj V

if appropriate in the presence of acid-binding agents and / or a catalyst, or 25 ----- B) compounds of the general formula CH · - 0 - Y »1 2 1 CH - 0 - Y» CH - 0 - Y »

™ <! H - 0 - YV

30 j 4

CH2 - 0 - Y »VI

in which one of the substituents Y ”, the group —CH-H2 r“ 35 1 and the other four substituents Y ”each in pairs an optionally substituted methylene group | 40> SNvR5. -15- ~ Board of Directors: Dr. Herbert AsmliDr. Christian BruhnHans-Jürgen Hamann Postal address: SCHERING AGD-1000 Berlin S5Pox PO Box 650311; Dr.Hein2 HannsaKarl Otto Mittalslenschaid Or. Horst Witzel Postscna <* - Account: Berlin-West 1175-101. Bank code 100 10010 - Chairman of the Residency Council: Dr. Edward v. Schwartzkoppan Beniner Commerzbank AG. Berlin. Account number. 103 7005 oo. Bank code 100 400 00 B Registered office: Berlin and Bergkamen Berliner Disconto-Bank AG. Berlin. Account no.241 / 5008. BanklaitzaM 10G 71 »00 3. Commercial register: A6 Charlottenburg 93 HR8 283 u. AG Kamen HRB 0081 Berliner Handels-Gesellschaft - Frankfurter Bank -. Berlin.

SCHERINGAG

* Commercial Radriuehtdz 5 mean, 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 acidic ion exchange resins at temperatures from 0 to 100 ° C, preferably from 40 to 80 ° C, 10 hydrolyzed, wherein R ^, Rg R ^ have the meaning given above and R ^ and R ^ can each be the same or different and each hydrogen, a C ^ -C ^ Q alkyl radical, a substituted C ^ -C ^ alkyl radical , an optionally substituted aryl-C ^ -C ^ -alkyl radical, a C ^ -Cg-cycloaliphatic hydrocarbon radical, one or more times by C ^ -Cg-alkyl and / or halogen and / or C ^ Cg-alkoxy and / or the nitro group and / or the trifluoromethyl group substituted aromatic hydrocarbon radical or R ^ and R ^ 20 together represent a polymethylene group - (CH ") -, X represents a halogen atom, preferably a chlorine atom, and Z represents a halogen atom or the radical R ^ OSO ^ O - represent n and m are the integers 4 and 5.

25th

The radicals and R_ of the substituted methylene group are to be understood as hydrogen, C 1 -C 4 -alkyl, for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, 2,2-dimethyl -l-propyl, n-pentyl, n-heptyl, n-octyl, n-decyl, substituted C.-C. -Alkyl for example 30 1 10

Chloromethyl, bromomethyl, fluoromethyl, dichloromethyl, tri- ^ *. fluoromethyl, trichloromethyl, hydroxymethyl, methoxymethyl, ethoxymethyl, phenoxymethyl, 4-chlorophenoxymethyl, chloroethyl, bromoethyl, 2-ethoxyethyl, 2-phenoxyethyl, C ^ -Cg-cycloaliphatic hydrocarbons for example cyclo-propyl, cyclopentyl, cyclohexyl, aryl-C ^ C ^ alkyl, for example benzyl, 2-phenylethyl, aromatic hydrocarbon radicals, for example phenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 3s ^ -0ichlorophenyl, 4-methoxyphenyl, 4-nitro-a 40 phenyl, 2 , 4-dichlorophenyl. -16- T - - Z Board: Or. Herbert Asmis · Or. Christian Bruhn · Hans-Jürgen Hamann Postal address: SCHERING AG - 0-1000 Berlin K - Postfaöt 650311 t 0r-He, nz Hannse - Karl Ono Mmelsienscfteid Dr. Horst Witzei. α »_____—« w ... g Λ Ä rû «scntcK * KontO! B * flm-West 1175-101, Binlclâitzehï 10010010 - Chairman of the Supervisory Board *: Or. Couard y. Scfiwartzkoppen Berlin CommerzoanK AG. 3erfin. Konro no. 108 7006 00. Sanic.'eftzaftl 100 400 00 s „Headquarters of the Geseilseftaft: 3erim and Sergkamen Berliner Disconto-Banic AG. Berlin. Account number. 241/5908. Bankfeitzmm 10G 700 00 - l4ap * rtel <rftai5Jf »rr AR Rharlnftanhtir« c? uOD non .. 1ί_ · ββί · Λ · <Beflinaf H * nne (C »Re« i * if * maft - Prankfurtar _ Oa.iin

j SCHERING AG

I —1-6- Commercial Redrissdiufs I 5 Preferred pentite derivatives VI as starting materials are I in which I l) Y * J the rest - CH - r2 I i 2 R1 I 10 I and YjJ and Y ^ together and Y '£ and Y ^ together I represent an optionally substituted methylene group I 15 5 I and I 2) Y '^ the rest - CH - Rg I »1 I 20 1 I and Y" and Y "together and Y £ and Y £ together each I is an optionally substituted methylene group and I 3) Y "is the radical 25 - <fH - R 2 I R 1 xmd Y" and Y £ together and Y "and Y '£ together each I. -. An optionally substituted methylene group.

I The reaction of the reactants takes place between 0 ° I and 150 ° C, but generally between room temperature I and the reflux temperature of the corresponding reaction device. The reaction time is 1 to 72 hours.

I 35 I The I reactants are used in approximately equimolar amounts for the synthesis of the compounds according to the invention. Suitable reaction media are inert to the reactants! Solvent. The choice of solution or Sus- I | ^ 0 -17-

I * Or ^ Hein ^ H ^ nn ^^^ r ^ Otto M ^ Ue? 5te * s ^ e ^ rU 0nr ^ oarâ ^ W ^ t2e | n SCHMINÔ Αβ - O-lfl »BwBn B; PortW, «OUI

I | Chairman of the Auis.atsrat: Dr. Edward v. Sdwartzkoopen 100 «B 00 K g jaitz of the company: Berlin and Serçkamen Berliner Disconto-Bank AG, Berlin, account no. 241/5006. Bank security 100 10000 I,? /Commercial register; AG Charlottenöurg 93 HR8 283 u. AG Kamen HRB 0061 Berliner Handels-Gesellschaft - Frankfurter Bank -, Berlin,

I / · kt. si defl Oa.ui.ita .. · I am% wnA

I ï

I SCHERINGAG

* · _17- G * w * Alich * rR * drts * chuö 5 pensionsmittel depends on the use of the corresponding alkyl or acyl halides as well as dialkyl sulfates and the acid acceptors used. Examples of solvents or suspending agents which may be mentioned are ethers, such as diethyl ether, diisopropyl ether, tetrahydrofuran and dioxane, aliphatic and aromatic hydrocarbons, such as petroleum ether, cyclohexane, hexane, heptane, benzene, toluene and xylene, carboxylic acid nitriles, such as acetonitrile and dimethylformearearea .

* 5 Suitable acid acceptors are organic bases, such as, for example, triethylamine, 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 also be used as solvents.

20th

Suitable catalysts for process variant A are onium compounds, such as quaternary ammonium, phosphonium and ArsOnium compounds as well as sulfonium compounds.

25th

Also suitable are polyglycol ethers, in particular cyclic ones, such as, for example, 18-crown-6, and tertiary amines, such as, for example, tributylamine. Preferred compounds are quaternary ammonium compounds, such as, for example, 20 benzyltriethylammonium chloride and tetrabutylammonium bromide.

The compounds according to the invention prepared by the abovementioned processes can be isolated from the reaction mixture by the customary processes, for example by distilling off the solvent used at normal or reduced pressure, by precipitation with water or by extraction. An increased degree of purity can generally be obtained by purification by column chromatography and by fractional crystallization. -18-

1 OrHemt: H ° / nnSVbf.Ä P ° Itans <* rm: SCHERING AG04000 Berlin 6S. Pos tfart * 5 03 TI

| Chairman of the Auf, dttarat,: Dr Eduard v. Flashing I ... ΑΓ5 ______ U «™. iÏÏÏÏ

1 SCHERINGAG

i 1 -iS— Gwratblidwr Legal protection 5 The compounds according to the invention are generally almost colorless and odorless liquids that are sparingly soluble in water, conditionally soluble in aliphatic hydrocarbons such as petroleum ether, hexane, pentane and cyclohexane, readily soluble in halogenated hydrocarbons such as Chloro-10 roform, methylene chloride and carbon tetrachloride, aromatic hydrocarbons such as benzene, toltiol and xylene, 3 ethers such as diethyl ether, tetrahydrofuran and dioxane,

Carboxylic acid nitriles such as acetonitrile, ketones such as acetone, alcohols such as methanol and ethanol, carboxylic acid amides such as dimethylformamide and sulfoxides such as dimethyl sulfoxide, but also colorless and odorless crystalline bodies that are poorly soluble in aliphatic and aromatic hydrocarbons, moderately to well soluble in halogenated hydrocarbons such as Chloroform and carbon tetrachloride, ketones such as acetone, carbamic acid amides such as dimethylformamide,

Sulfoxides such as dimethyl sulfoxide, carbonitriles such as acetonitrile, lower alcohols such as methanol, ethanol and water.

25 Particularly suitable solvents for recrystallization are water, methanol, acetonitrile and ethyl acetate.

The following examples illustrate the preparation of the benzyl ether derivatives of pentites according to the invention.

30 35 ä 40 - * T * 4 Board: Dr. Herbert Asmi «· Or. Christian Hruhn · Hans-Jürgen Hamann Postal address: SCHEHING AG - D-1000 Berlin ¢ 5. Postfach SS 0311 f Dr- H * "" 2 Hannsa - Karl Otto Mitteistenscne ^ Or. Horst Waal Postschedt-Komo: Beriin-West 1175-101. Bank sorting ^! 100, «10 - Chairman of the Supervisory Board-. Or. Eduard v. Schwartzkoppen Berlin Commerzaank AG. Berlin, account no. 108 7006 00. Sort code i «* 00 00

5 Company headquarters: Berlin and Bergkamen Berliner Oiscomo-Sank AG. Berlin. Account number. 241/5 (06. Sanctuaryafil 1 «7« M

5 Commercial register: AG Charlottenburo 93 HRR 283 u in Kamen HRR mn Berliner Handeis-Gesellschaft - Frankfurter Bank - Berlin

i 10 SCHERING AG

* 19 Geweiblfch «R« dits * d »utx 5 EXAMPLE 1 5-0- (2,6-dichlorobenzyl) -xylitol 277j0 g (0.708 mol) 5-0- (2,6-dichlorobenzyl) -1.2: 3 , 4-bis-O-isopropylidene-xylitol are introduced and, with stirring, 10 are mixed with 752.2 ml of 1,5-a sulfuric acid. Then 3rd

Stirred at 70 ° C for hours and then the reaction mixture was left to stand at room temperature overnight.

. 95 ml of 32% sodium hydroxide solution are then added dropwise with stirring at 25 ° C. and the reaction solution is extracted three times with * 5 200 ml of ethyl acetate.

The extracts are then washed twice with 100 ml of water, dried over magnesium sulfate, filtered and concentrated in vacuo. Colorless crystals are obtained, which are digested with a cold 1: 1 mixture of diethyl and diisopropyl ether and then dried to constant weight at room temperature / 200 torr.

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

25 mp: 82-83 ° C

TLC: mobile phase: chloroform / methanol 4: 1

Rf value: 0.3¾

Analysis: Ber. C 46.32% H 5.18'5® CI 22.79%

Found C 46.48% H 5 »10% CI 22.37% 30 35 -20- 1 40 • j Board of Directors: Or. HerOert Asmis · Or. Christian Bruhn · Hans-Jürgen Hamann Postal address: SCHERING AG · D-1000 Berlin 55 · PO Box «ta 11 L Dr. Heinz HannasKarl Otto Mittelstenscheid Dr. Horst Witzei Postschedt-Komo: Berlin-West 1175-101. Bank code 10010010 -f Chairman of the Supervisory Board: Dr. Edward v. Schwartzkoppen Berlin Commerzsank AG. Berlin, account no. 108 700600. Banklenzanl 100400 00 E Registered office of the company: Berlin and Bergkamen Berliner Oisconto-Bank AG. Berlin. Como no. 241/5006. Bank code 10070000 3 r Handelsrealster: AG Charlottenbura 93 HRB 263 u. AG Kamen HflB nüfit Berliner Handels-Gesellschaft - Frankfurt Ban * Berlin.

> <i

I SCHERING AG

* Γ "20- G * werfsllch * fR * drt» * dtutz 5 EXAMPLE 2 3-0- (2,6-dichlorobenzyl) -1.2: 4,5-tetra-O-methyl-adonite 3.11 g ( 0.01 mol) of 3-0- (2,6-dichlorobenzyl) -adon.it, 0.22 g (0.001 mol) of benzyltriethylamraonium chloride and 25.23 g of 10 (0.2 mol) of dimethyl sulfate are placed in 20 ml of methylene chloride While stirring vigorously, 14.0 g (0.25 mol) of potassium hydroxide, dissolved in 15 ml of water, are added dropwise to the mixture at cooling at about 30 ° C. After stirring for three hours at the temperature of the mixture, the mixture is left under 15 for one hour The mixture is then refluxed, diluted with 150 ml of water and extracted twice with 150 ml of ethyl acetate each time.

The extracts washed with water, dried over magnesium sulfate and filtered are concentrated. The remaining oil is distilled at the Kugelrohr (bath temperature-20 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 nD20: 1.5198

25 D

TLC: mobile phase = toluene / ethyl acetate 1: 1

Rf value: 0.29

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

Found C 51.82% H 6.48% CI 20.13% I 40

Jj board: Dr. Herbert AamisDr. Christian BruhnHans-Jürgen Hamann Postal address: SCHERING AG0-1000 Berlin es - Postfach 65 (311 * Dr. Heinz Hanns. Karl Otto MitteistenscneidOr.Horst Witzei postal check account: Berlin-West 1175-101. Bank sorting 10010010 3 Chairman of the Supervisory Board: Or. Eduard v. Schwartzkoopen Berliner Commerzaanx AG, Berlin, Komo-Nr. 108 700600. Bank routing number 100 40000 Ξ Registered office: Berlin and Bergkamen Berliner Disconto-Bank AG. Berlin. Account No. 241/5006 Bank sorting name 1 »70000 .3 / Real estate: AG Charlottenbura 93 HRB 283 and AG Kamen HRB 0061 Berliner Kendels-Gesellschaft - Frankfurter Bank -, Benin.

SCHERINGAG

_21- Weight * 5 EXAMPLE 3 1-0- (2,6-dichlorobenzyl) -2,3,4,5-tetra-O-acetyl-D-arabitol-5 10 g (0.016 mol) 1-0 - (2,6-dichlorobenzyl) -D-arabite are first stirred in a mixture of 20 ml of pyridine and 20 ml of acetic anhydride for one hour at room temperature and then left to stand overnight. 150 ml of toluene are added to the reaction mixture and the solution is evaporated to dryness under a water jet vacuum. The residue is mixed with a further 150 ml of toluene and again concentrated under vacuum.

^ The remaining oil is taken up in portions with 300 ml of vinegar. The ethyl acetate extracts washed with water, dried over magnesium sulfate and filtered are evaporated. The oily residue crystallizes after digestion with a little diisopropyl ether.

20th

Yield: 5.80 g s 75.7% of theory l-0- (2,6-dichlorobenzyl) -2.3 * 4.5-tetra-0-acetyl-D-arabitol

Pp .: 89-90 ° C

2 ^ DC: eluent = toluene / ethyl acetate 1: 1

Rf value: 0.47

Analysis: Berv C 50.11% H 5 * 49% 01 14.79%

Found C 50.58% H 5.49% CI 14.80% 30

The further connections according to the invention can be produced in an analogous manner.

35: ko -22- 4 Board: Dr. Herbert AsmisDr. Christian BruhnHans-Jürgen Hamann Postal address: SCHERING AGD-1000 Berlin CS - Postfach CS0311 à DrHemZ HannM 'Kar' 0tt ° M ,,: el51ensctlei <1 'DrHorst Witzel Postscheck account: Barlin-West iitMOI . Bank code 10010010. - Chairman of the Supervisory Board: Dr. Edward v. Schwartzkoppen Beniner Commerzpank AG. Barlin, account no. 108 7006 00. Bank code 100 «0 00 5 Company headquarters: Berlin and Berghamen Berliner Disconto-Bank AG. Berlin. Kcnto no. 241/5008. Bank code 100 7m 00, commercial register: AG Charlottenburg 33 HRB 283 u. AG Kamen HRB 0061 Berliner Handels-Gesellschaft - frankfurter Bank -, Berlin,

I SCHERINGAG

-_22_-z, Gtimbltdnr Legal protection 5 Example physical

No. Name of the compounds Constant 4 5-0- (2, 4-dichlorobenzyl) xylitol mp .: 96-98 0 5 5-0- (2-chlorobenzyl) xylitol mp: 52-54 0

6 5-0- (2-methylbenzyl) xylitol mp: 59-61 C

10 7 1-0- (2,6-dichlorobenzyl) -L-arabite m.p .: 122-24 ° C

8 1-0- (2,6-dichlorobenzyl) -D-arabite mp: 124-26 C

9 3-0- (2,6-dichlorobenzyl) adonite mp: 116-17 C

10 5-0- (2,4,6-tribromobenzyl) xylitol mp: 132-33 0

11 5-0-benzyl-xylitol mp: 47-50 C

* 5 "12 5-0- (2,6-dichlorobenzyl) -1,2,3,4-tetra-20. 1,4876 0-acetyl-xylitol" 13 5-0- (2,4,6-tribromobenzyl ) -1,2,3 »4-tetra- 0

0-acetyl-xylitol m.p.:106-07 C

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

15 5-0- (4-chlorobenzyl) xylitol m.p.:109-09.5 C

20 16 5-0- (4-bromobenzyl) xylitol mp: 110-12 C

17 5-0— (3,4-dichlorobenzyl) xylitol mp: 122-23 C

18 5-0- (3-methylbenzyl) xylitol mp: 54-56 C

19 5-0- (4-methylbenzyl) xylitol mp 98-99 C

20 5-0- (3 »4-dimethylbenzyl) xylitol mp .: 72-74 C

23 21 5-0- (3-chlorobenzyl) xylitol mp: 90-92 C

22 5-0- (4-cyanobenzyl) xylitol mp: 119-21 C

23 3-0- (2,6-dichlorobenzyl) -1,2,4,5-tetra-20; ^ ^ 0 — acetyl — adonite ^

24 5-0- (3-trifluoromethylbenzyl) xylitol mp: 61-63 C

30 25 5-0- (3-fluorobenzyl) xylitol mp: 72-74.5 C

26 5-0- (4-fluorobenzyl) xylitol m.p .: 76-78 C

27 1-0- (2,4,6-tribromobenzyl) -D-arabite m.p.:156-57 C

28 - 5-0— (2-fluorobenzyl) xylitol 11 ^ 243 29 5-0- (2,6-dichlorobenzyl) -1,2,3,4-tetra- “20. 1.5186 0-methyl-xylitol "30 1-0- (2,6-dichlorobenzyl) -2.3» 4.5-tetra-ru20: 1.5201 O-methyl-L-arabitol 31 5-0- ( 2,4-dichlorobenzyl) -1,2,3,4-tetra- η ^ 20: 1.5177 0-methyl-xylitol 32 1-0- (2,6-dichlorobenzyl) -2,3,4,5- tetra- - 20: 1,5205 O-methyl-D-arabit 1 40 - * 3- i Board: Dr. Herbert Asmis - Dr. Christian Bruhn · Hans-Jürgen Hamann Postal address: SCHERINGAG · D-1000 Berlin es 0311 | Dr. Heinz Hanns. · Kar. Otto Mittelstensche.d - Dr. Horst Witzel Postsch «* - Account: Berlin-West 1175-101. Bank code 100 10010 - the supervisory board presiding: Or. Eduard v. Schwartzkoppen Berliner Commerzaank AG. Berlin. Account No. 10B 7006 00. Number of bankia 100 400 00 E Registered office: Company: Berlin and Bergxamen Berliner Ciseonto-Bank AG. Berlin. Account No. 241/5008, Bankfeitzahl 10070000 S / Commercial Register; AG Charlottenburg 93 HRB 283 u AG Kamen HRB 0061 3erimer Handels-Gesellschaft - Frankfurter Bank -, Barlin,

SCHERING AG

_ Intellectual Property .

5 Example physical,

No. Name of the compounds Constant 33 5-0- (2,4,6-tribromobenzyl) - * 1 ^ 20: ^ - »56l6 1.2.3.4- tetra-0-methyl-xylitol 3¾ 1-0- (2.4 , 6-tribromobenzyl) - η ^ 20: 1.5668 10 2,3,4,5-tetra-0-methyl-D-arabite

35 5-0- (2-chloro-6-fluorobenzyl) - mp .: JO - fl ° C

xylitol

36 1-0- (2-chloro-6-fluorobenzyl) - mp: 138 -139 ° C

D-arabite 37 3-0- (2-chloro-6-fluorobenzyl) - n ^ 20: 1.5297.

.15 adonite 38 5-0- (2-chloro-6-fluorobenzyl) - n_20: 1.4809 1.2.3.4- tetra-0-acetyl-xylitol 39 5- ° - (2-chloro-6-fluorobenzyl) - n_20 ; 1.4972 1.2.3.4- tetra-O-methyl-xylitol 20 25 30 [. -24- 35 40 es co ·! Board: Dr. Herbert Asmls * Dr. Christian BruhnHans-Jürgen Hamann Postal address: SCHERING AG - D-10Û0 Berlin 65 - Postfach 650311 \ Dr * Heinz HannseKarl Otto Mittelstenscheid Horst Witzei Postsdiedc account: Berlin-West 1175-101, bank code 10010010 .j; Chairman of the Supervisory Board: Dr. Edward v. Sctiwartzkoppen Berl iner Commerzbank AG, Berlin, account no. 106 7006 00. Bank code 100 400 00

ί SCHERING AG

* 2 ^ ”Commercial legal protection 3 5 The starting products for the preparation of the compounds according to the invention are known per se or can be prepared by processes known per se.

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

EXAMPLE 4Θ-- 5-0- (2,6-dichlorobenzyl) -1.2: 3.4-bis-0-isopropylidene xylitol 116.13 g (0.5 mol) l, 2: 3,4-bis-0-isopropylidene -xylitol are introduced together with 119.96 g (0.5 mol) of 2,6-dichlorobenzylbroraid and 4.5 g (0.019 mol) of benzyltriethylammonium chloride.

A solution of 100 g of sodium hydroxide (2.5 mol) in 125 ml of water is added dropwise at room temperature 2Q with extremely vigorous stirring, the temperature slowly rising to about 50 ° C. and falling back to room temperature in the course of about an hour . Then, to complete the reaction, the mixture is stirred for a further hour at 50 ° C., then diluted 25- with 500 ml of ice water and the reaction mixture is extracted with 150 ml of ethyl acetate. The organic phase is washed twice with 300 ml of water each time, dried over magnesium sulfate, filtered and evaporated to dryness at 40 ° C. in vacuo. The residue is fractionally distilled.

30th

Yield: 150.0 g = 76.7% of theory 0.1 Torr - lé3 ° Ci V0: ^ 5 ° 8 ° DC: eluent = toluene / ethyl acetate 4: 1

Rf value 0.52 ^ Analysis: calc. C 55.25% H 6.18% CI 18.12%

Found C 55.66% H 6.46% CI 18.03% «-25 ^ - 5 4o 2 board. Dr. Herbert Ααιπία * Df.Christian BruhnHans-Jürgen Hamann Pastan * rtnrtfr * ^ ηεοικιγ αγ * n irwi n_n_ __ _ ^ T Dr. Heinz HannseKarl Otto Mittelstenscneid. Dr. Horst Witzei postal address. SCHESING AG - D-1000 Berlin 65. Postfach 65 0311 f Chairman of the Auisiditsrat: Or. Eduard v. Scnwartzkoppen 10010010 2, ^ _ _ .ΐϋΛϋμμΒπ Berliner CommenbenK AG, Berlin, account no. 108 7006 00 Number of banks in Hl = / S - <3ese.il5rt »«: Serun and BergKamen Serliner Oisconto-BanH AG. Berlin. Account no. 241/5008! BMWeite ^ iooTOoai ”

! . . "SCHERING AG

, L-> ~ GmNMfaiidwr RaditssdHiiz 5 EXAMPLE 4 ^ - 5-0- (2,4,6-tribromobenzyl) -1,2: 3,4-bis-0-isopropylidene-xylitol

A solution of 23 »2 g (0.1 mol) of 1.2: 3» 4-bis-O-isopropylidene-xylitol in 100 ml of toluene is slowly stirred with stirring to a Sus-10 pension of 2.88 g (0, 12 mol) of sodium hydride are added dropwise in 50 ml of toluene. When the addition is complete, the mixture is heated under reflux for two hours. Then a solution of - 40.78 S (0.1 mol) of 2,4,6-tribromobenzyl bromide in 50 ml of toluene is added dropwise and the mixture is heated for a further eight hours to reflux.

After cooling, the mixture is carefully washed three times with 150 ml of water; the organic phase is then dried over magnesium sulfate, filtered and concentrated in vacuo at 40 ° C. The remaining oil is still in a vacuum 20 (180 ° C bath temperature / 0.1 Torr) of traces

Source material exempted.

Yield: 37.6 g = 67.25% of theory 'η ^ 20: 1.5516 25 TLC: mobile phase = toluene / ethyl acetate 1: 1

Rf value = 0.52 t

Analysis: Ber. C 38.26% H 4.14%

Found C 37.99% H 4.04% 30 35 l ko. -26- 4Ï Board: Or. Herbert Asmis - Or. Christian Bruhn · Hans-Jürgen Hamann Postal address: SCHERING AG - D-10G0 Berlin S5 · Postfach K0311 i ®r · Μβ, ηϊ Hannse · Karl Otto Mittelstenscneid - Or. Horst Witte ! Postal check account: Berlin-West 1175-101. Bank sorting code 1X10010 -Ϊ Chairman of the Supervisory Board: 0r. Edward v. Expedition to Berlin CommerzSank AG. Berlin, Cont0 no. 108 7008 00. Bank sort code 100 ZOO 00

B / Registered office of the company: Berlin and Berskamen Berliner Disconto-Bank AG. 3 series. Account no.211 / 5008. Bank sort code 100 700 0Q

* .... «... f. . . _ ... —N «... HMrttMMP Han« lA (A./ÎM «llcr <n9ft - ηπ nvft irt * r BdMr Cuti ·

I SCHERINGAG

Commercial legal protection 5 The following starting products can be manufactured in an analogous manner.

Example Nine of the connections Physical

No. "Constant 10 42" 3-0- (2,4-dichlorobenzyl) -1.2: 4.5-bis- 0- isopropylidene adonite nD “= 1.5092 1- 0- (2,4-dichlorobenzyl) -2.3: 4.5-bis- n_20 = 1 5070 O-isopropylidene-L-arabite '44 1-0- (2,4-dichlorobenzyl) -2.3: 4.5-bis- _pn O-isopropylidene -D-arabite ^ = 1.5071 15 45 1-0- (2,6-dichlorobenzyl) -2.35-bis- n_20 O-isopropylidene-L-arabite u = 1.5075

¢ 5 l-0- (2,6-dichlorobenzyl) -2,3î4,5-bis- PQ

O-isopropylidene-D-arabitol u = 1.5093 47e 3-0- (2,6-dichlorobenzyl) -1.2: 4.5-bis- n "20 O-isopropylidene adonite w = 1.5H8

20 48 3-0- (2,4,6-tribromobenzyl) -1.2: 4.5-bis- Q

O- (isopropylidene) adonite m.p .: = 75 0 • 4 ^ 1-0- (2,4,6-tribromobenzyl) -2,3: 5-bis- O- (isopropylidene) -D-arabite u = 1 , 5447 5Ö 5-0-r2-chloro-6-fluorobenzyl) -1.2: 3.4- n ^ 20 = 1.4916- bis-0- (isopropylidene) xylitol 51 l-0- (2-chlorine -6-fluorobenzyl) -2,3î n ^ 20 = 1.4901 4.5- bis-0- (isopropylidene) -D-arabite 52 3-0- (2-chloro-6-fluorobenzyl) -1.2: η ^ 20 = 1.49Ϊδ 4.5- bis-0- (isopropylidene) adonite 30 The following examples explain the possible uses of the compounds according to the invention, the experiments being carried out with the preparations described.

35 40 -2? - »

CB

CO

·: Board of Directors: Dr. Herbert Asmis - Dr. Christian BruhnHans-Jürgen Hamann Postal address: SCHERING ASD-100Q Berlin 65 - P.O.Box 65 0311 i Dr. Heinz Hannse - Karl Otto Mittelstenscheid - Dr. Horst Witzei postal check account: Berlin-West 1175-101. Bank code 10010010 * Chairman of the Supervisory Board: Dr. Edward v. Schwartzkoppen Berlin Commerzbank AG. Berlin. Account number. 106700600. Bank number 100400 00

SCHERINGAG

-27-- Gewmfefidi «Legal Protection = 5 EXAMPLE 53

Chlorophyll content increase and. Pod approach to soy

Post-emergence soybeans were sprayed with an aqueous emulsion of the compounds to be tested. The application rate was 0.8 kg of active ingredient / ha. h weeks after the spraying, disks were punched out of the second leaflet.

The chlorophyl was extracted from this and the chlorophyll 15 a content was determined photometrically.

The table shows the increase in the chlorophyll a content compared to the control.

In addition, the number of pods and flowers in the plants was determined and calculated in% of the control. The table contains these values -

The results show that the compounds according to the invention> are distinguished from the comparative agents by better tolerability or higher chlorophyll contents or a higher flower and pod formation.

table

Compounds according to the invention chlorophyll pods and content increase flower batch 20 in% in% of the control 5-0- (2,6-dichlorobenzyl) xylitol 63.9 202 1-0- (2,6-dichlorobenzyl) -L- arabite ^ 3.0 129 1- 0- (2,6-dichlorobenzyl) -D-arabite 37.2 103 ^ 3-0- (2,6-dichlorobenzyl) adonite 39.3 129

Comparative agent according to DE-OS_27_24_677 2- benzyloxymethyl-tetrahydrofuran 27, ¾ 1 ^ 6 2,6-dichlorobenzyloxymethyl-tetra-60.9 90 hydrofuran * a ^ 0 * phytotoxicity in the form of etching damage -28- 4 DI: Ä Hamann postal address: SCHERING AG - D-10CD Berlin 55 · Postfach 650311 Ï Chairman of the Aufsientsrat · Dr „c-? Postschedt-Komo: Berlin-West 1175-101. Number of banks 10010010 2 Chairman of the Advisory Board. Dr. -duard v. Sctlwartzkoppen Sertiner CommerzüanK AG. Berlin. Account no.1D8700600. Bank sort code 100400 00

= Company headquarters: Berlin and Bergkamen 8erlmer Disconto-Bank AG. Berlin. Account number. 241/5008. Bank sorting code 1X7DOOO

o / Commercial register: AG Charlottenburg 93 MRB 283 u. AG Kamen HR3 0061 3erliner Hanoefs-Geseltscnait - Frankfurter Bank -, Berlin.

I SCHERING AG

--28- Gmmbfiditr Legal protection 5 'EXAMPLE 5¾

Growth regulatory effects on soybeans and bush beans after dressing

Bush beans and soybeans were dressed with powdery preparations of the active ingredients at rates of 10, 50 and 100 g of active ingredient per 100 kg of seed.

The seeds were placed in culture dishes. The plants a k were grown under greenhouse conditions. After 3 weeks of culture, the symptoms were rated with numbers between 0 and 15 10. The following scheme was used for this: 10 = like untreated control 5 = compressed, dark green, branched 1 = very strongly compressed, intensely dark green, strongly branched 20 As the results show, the substances according to the invention are more active in the desired mode of action than the comparison agents.

Table 25 Compounds According to the Invention Amount of Active Ingredient Bonitumote g / 100 kg Saat-Busch-Soybean Bean Bean 5-0- (2,6-dichlorobenzyl) -xylitol 10 -8 8 50 -3 5 100 3 4 on 1-0- (2nd , 6-dichlorobenzyl) -L-arabite 10 10 7 J 50 5 4 100 3 3 1-0- (2,6-dichlorobenzyl) -D-arabite 10 8 8 50 6 5 loo 3 4 3-0- (2, 6-dichlorobenzyl) adonite 10 98 35 50 5 5 100 3 5 5-0- (2,4,6-tribromobenzyl) xylitol 10 10 10 50 9 9 100 9 9 § 40 Z Board of Directors: Or. Herbert Asmis - pr . Christian Bruhn - Hans-Jürgen Hamann Postal address: SCHHRING AG D-1000 Berlin 65 · Poitfadi «0311 i Or. Heinz Hannse Kar Otto Mitteisienscheid · Dr Horst Witzei -. _ _ i-w.u «™ ww n a _____. Postal check account: Berlin-West 1175-101. Bank code 100 10010 - Chairman of the Supervisory Board, Or. Eduard v. Schwartzkoppen Berlin Commerzbank AG. Berlin. Account number. 108700600. Bank code 100 40000 E Registered office of the company: Berlin and BergKamen Berliner Oisconto-Bank AG. sertir .. Kcnto no.241 / 5008. Bank code 10070000 / Commercial register: AG Charlottenburg 93 HRB 283 u. AG Kamen URB 006t 3er Haneeis Gesetisehaft - Frankfurter Bank -. Berlin.

î „SCHERINGAG

|| * G * w * Hbüch «r legal protection 5, r. . . . .., V Active ingredient quantity, credit note

Comparative means g / 100 kg Saat-Busch-Soybean- ______________gut_bohne bean 2-Benzyloxymethyl-tetrahydrofuran 10 10 9 (according to DE-OS 27 2½ 677) 50 10 9 10 100 10 8 / 2.3 ï4,6-di-0-isopropy3idene -cc-L- 10 10 8 xylohexulofuranuronic acid - sodium salt 50 10 8 100 10 7 «15 20 y 25 30 35 -30 · -

à tiO

▼ u Board: Or. Herbert Asmis * Or. Christian Bruhn - Hans-Jürgen Hamann Postal address: SCHERING AG - 0-10Û0 Berlin 65 «Postfach 85 0311 i or- Heinz Hannse · Karl Otto Mmeistenscneid Dr. Horst Witzei postal check account: Berlin-West 1175-101. Refueling instructions 100 10010

- Chairman of the supervisory board: Dr. Edward v. Berlin-based CommerzBank AG. Berlin. Account number. 108 7006 00. Refueling instructions 100 400 OC

I Registered office of the company: Berhn and Bergkamen Berliner Disconto-Bank AG. Berlin. Como no. 241/5008. Bank sorting liability 100 700 00 C. . J. ». . . »Μ - i a. <I .... Peelinar UenHnfc ^ tjitedeAheft PeenvfiirlAP Rsnlr Rariin

l 'SCHERINGAG

i -30- ^. Legal protection I 5 EXAMPLE 55 '1. Yield increase in soybeans ------- - ------- 1 soybeans were sprayed in a post-emergence process with aqueous emulsion I of the substances to be tested at a rate of 0.8kg 1 10 active ingredient / ha. Four weeks after spraying, the flowers and pods were determined. The values for this are recorded in the table. The results were in%. ’Of control. In addition, the percentage 1 inhibitions of growth were determined.

The results show that the substances promote the pods and flowers with simultaneous upsetting of the plants. The comparative agents only showed this effect to a weak degree 1 or proved to be somewhat phytotoxic.

I 20 Table I Compounds according to the invention Growth, pod and bloom assumption in% in% of the control 9 5-0- (2-chlorobenzyl) xylitol 28 142 25 5-0- (2,6-dichlorobenzyl) - l, 2,3i ^ - I tetra-O-acetyl-xylitol 59 219 9 5-0- (2,4,6-tribromobenzyl) -1,2,3 »4-tetra-O-acetyl-xylitol 44 173.

1 . 1- 0- (2,6-dichlorobenzyl) -2.3 »4.5- I tetra-O-acetyl-D-arabitol 59 215 30 3-0- (2,4,6-tribromobenzyl) adonite 49-188 I 5-0- (4-chlorobenzyl) xylitol 44 165 '5-0- (4-bromobenzyl) xylitol 49 185 9 5-0- (3f4-dichlorobenzyl) xylitol 0 115 5-0- (3-methylbenzyl ) -xylitol 28 1θ8 1 35 5-0- (4-methylbenzyl) -xylitol 33 2C) Zt 5-0- (3,4-dimethylbenzyl) -xylitol 33 2 ° 4 1 5-0- (3-chlorobenzyl) - xylitol 38 135 I 5-0- (4-cyanobenzyl) xylitol 28 150 I 3-0- (2,6-dichlorobenzyl) -l, 2,4,5- I <? , - tetra-O-acetyl-adonite 59 204 I a 40 -7 -3 ΐ- Ι 1 board: Or. Herbert Asmia Dr. Christian BruhnHans-Jürgen Hamann Postal address: SCHERING AGD-1000 Berlin 65 - Postfach 65 0311. Qr. Heinz HannsaKarl Otto MittetstenscheidOr.Horst Wittel Fostscfteck account: Berlin-West 1175-101. Bank code 10010010 B 3 Chairman of the Supervisory Board: Dr. Edward v. Scfiwarizkoppan Berliner Commerzbank AG. Berlin. Account number. 108700600. Bank code 100 40000 IS 1 seat of the company: Berlin and Bergkamen 8erlmer Oisconto-Bank AG. Berlin. Account number. 241/5008. Bank code 10070000 5, commercial register: AG Chariottenbura 93 HRB 283 u. AG Kamen HRB 0061 Berliner Handels-Gesellschaft - Frankfurter Bank -, Berlin.

I SCHERING AG

”31— GcwmfeBcfaer Raditssdnifz 5 Compounds according to the invention Wuchshem-Hüls en and flowering in% batch in% of

Control___ 5-0- (3-trifluoromethylbenzyl) xylitol 23 80 5-0- (3-fluorobenzyl) xylitol 33 20¾ 10 1--0- (214.6-tribromobenzyl) -D-arabitol 33 l88 5-0- ( 2-fluorobenzyl) xylitol 28 92

Comparative agent 2-benzyloxymethyl-tetrahydrofuran '28 135 15 (according to DE-OS 27 24 677)

Trijodbenzoic acid 69 £ 73 Board: Or. Herbert Asntis · Dr. Christian BrunnHans-Jürgen Hamann Postal address: SCHERING AG - D-iOOO Berlin 65 - Postfach BG311 A Df- Ha, nz HannseKart 0tto MitielstenscfteidDr. Horst Witzei Postscneöc account: Beriin-Weat 1175-101. Bank code 10010010 -2 Chairman of the Supervisory Board: Dr. Edward v. Schwartzkoppen Berlin Commerzbank AG. Berlin, account no. I0a 7006 00. BanXleitzinl 100 <001 E Registered office of the company: Berlin and Bergkamen Berliner Discomo-Bank AG. Berlin. Komo-Nr. 211/5006 Bankie.tzafu 100 700 00 2 HandiiKrMi <ir «r · AG Charlottenhtira 93 HBR 5M> Art Kamen HRSfiOfil ο6Γί» 0βΓ HandefS-GfrSellSCftafi - ΓΠΠΚιΙΙΠβΓ ÖÄilK Befilfl,

Claims (13)

5 PATENT CLAIMS 1. Benzyl ether derivatives of pentites of the general formula ΪΗ2 - 0 * Y1 10 CH - 0 - Y2 CH - 0 - Y3 CH - 0 - Y .. 1 4 ch2-o-y5 I, in which one of the substituents Y represents the group 15. f1 - H2 and the four other substituents Y are the same or different and are each the group 20 - (CO) - R n 3, in which R ^ is hydrogen or a C ^ -C ^ alkyl radical, R ^ is optionally one or more times by C ^ -C ^ -25 alkyl and / or C 1 -C 6 -alkoxy and / or optionally substituted phenoxy and / or optionally substituted phenyl and / or halogen and / or the aromatic hydrocarbon radical substituted by the nitro group and / or the trifluoromethyl group, 30 R ^ hydrogen or an optionally substituted ^. C ^ -C ^ alkyl and n represent 0 or 1. 2. benzyl ether derivatives of pentites according to claim 1, 35. rin R ^ hydrogen or Cj-C ^ -alkyl, preferably methyl, R phenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, L · »I 2,6-dichlorophenyl , 2,4-dichlorophenyl, 3,4-dichlorophenyl, 2,4,6-trichlorophenyl, 4-bromophenyl, 2,4-di-1 40 -2- z Board of Directors: Dr. Herbert Asm «· Dr. Christian BruhnHans-Jürgen Hamann Postal address: SCHERING AG0-1003 Berlin S5Postbox K 0311; Or. Heini HannseKarl Otto MittelstenscneidDr. Horst Witzei PostscneÄ account: Berlin-West 117S-101. Bankieit2ahl 10010010 - Chairman of the Residency Council: Dr. Edward v. Schwartzkoopen Berliner Commerzsank AG. Berlin, account no. 108 7006 00. Bankieiizahl 100 400 00 S Company headquarters: Berlin and Bergkamen Berliner Disconto-Bank AG. Berlin. Como no. 211/5008. Bank code 100 700 00 I SCHERING AG Commercial ·? Redrtsschatz 5 bromphenyl, 2,6-dibromophenyl, 2,4,6-tribromophenyl, «2-fluorophenyl, 3-fluo: * T? Henyl» 4-fluorophenyl, 2, 4-difluorophenyl, 2-methylphenyl, 3- Methylphenyl, 4-methylphenyl, 3,4-dimethylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 3,4-dioxymethylbnphenyl, 2-fhenoxyphenyl, 10 3-phenoxyphenyl, 2-nitrophenyl or 3-nitrophenyl,: hydrogen, C ^ -C ^ alkyl, preferably methyl, ethyl, propyl or chloromethyl and n represent 0 or 1. 3. 5-0— (2,6-dichlorobenzyl) —xylxt k. 3-0- (2,6-dichlorobenzyl) -1,2,4,5-tetra-O-methyladonite 5, 1-0- (2,6-dichlorobenzyl) -2,3,4,5-tetra -O-acetyl-D-arabitol 6.5-0- (2,4-dichlorobenzyl) -xylxt 20 7.5-0- (2-chlorobenzyl) -xylitol 8.5--0- (2-methylbenzyl) xylitol 9. 1-0- (2,6-dichlorobenzyl) -L-arabite 10 * 1-0- (2,6-dichlorobenzyl) -D-arab it 11. 3-0- (2,6-dichlorobenzyl) - adonit 25 12. 5-0- (2,4,6-tribromobenzyl) xylitol 13► 5-0-benzyl-xylitol 14. 5-0- (2,6-dichlorobenzyl) -1,2,3,4- tetra-0-acetyl-xylitol 15. 5-0- (2,4,6-tribromobenzyl) -1,2,3,4-tetra-O-acetyl-xylitol 16. 3-0- (2,4,6-tribromobenzyl) adonite 30 17. 5-0— (4-chlorobenzyl) xylitol 18. 5-0- (4-brorabenzyl) xylitol - '19. 5-0- (3,4-dichlorobenzyl) xylitol 20. 5-Q- (3-methylbenzyl) xylitol 21. 5-0- (4- Methylbenzyl) xylitol 35 22. 5-0- (3 »4-dimethylbenzyl) xylitol 23. 5-0- (3-chlorobenzyl) xylitol 24. 5-0- (4-cyanobenzyl) xylitol 25. 3- 0- (2,6-dichlorobenzyl) -1,2,4,5-tetra-0-acetyl-adonite I 40 -3- Z Board of Directors: Dr. Herbert As mis · Christian Bruhn Hans-Jürgen Hamann Postal address: SCHERING AG · D-1000 Berlin ö Postfad, «0311 Cr. Heinz Hannse * Karl Otto MitteJstenscheid * Or Horst Witzei a - ^ _ 5 j = 'Postscnedt account: Berlm-Wesm75-1Q1. Bank routing number, 0010010 - Chairman of the Foreign Council. 0r. touard v. SdiwartzKoppen Berlin Commerzoamc AG. Berlin, account no. ioe 7006 00. BanKleitzafil 100 <00 0C £ Registered office: Berlin and Bergkamen Berliner Disconto-Bank AG. Berlin. Account number. 2 <1/5008. Bank routing 100700 00 3 Commercial register: AG CharlottenOuro 93 HRB on u AR K.ai.a une mai Beniner hanaels-Geseilsaiatt - Frankfurter- Sank -. Benin. <, SCHERINGAG i ”- Intellectual Property Law '5 26 · 5-0- (3-Trifluorometbylbenzyl) -xylit 27. 5-0- (3-Fluorobenzyl) -xylit 2Ö. 5-0- (4-fluorobenzyl) xylitol 29 · 1-0- (2,4,6-tribrorabenzyl) -D-arabitol 30 · 5-0- (2-fluorobenzyl) xylitol 10 31. 5-0- (2,6-dichlorobenzyl) -1,2,3 * 4-tetra-0-methyl-xylitol 32. 1-0- (2,6-dichlorobenzyl) -2,3,4,5-tetra-0-methyl -L-arabite 33.5-0- (2,4-dichlorobenzyl) -l, 2,3 »4-tetra-0-methyl-xylitol 34. 1-0- (2,6-dichlorobenzyl) -2.3 * 4,5-tetra-O-methyl-D-arabite 35. 5-0- (2,4,6-tribromobenzyl) -l, 2,3,4-tetra-O-methyl-xylitol ^ 36. l- 0- (2,4,6-tribromobenzyl) -2,3,4,5-tetra-O-metbyl-D- arabite 37. 5-0- (2-chloro-6-fluorobenzyl) xylitol 38. 1- 0- (2-chloro-6-fluorobenzyl) -D-arabite 39. 3-0- (2-chloro-6-fluorobenzyl) adonite 20 40. 5-0- (2-chloro-6-fluorobenzyl) -1 , 2,3,4-tetra-O-acetyl-xylitol 4l. 5-0- (2-chloro-6-fluorobenzyl) -1,2,3 * 4-tetra-0-methyl-xylitol 25% 3 ° «35 -4- 4o *? ** 'CB CO ü Board: Dr. Herbert AsmisDr. Christian BruhnHans-Jflrgen Hamann Postal address: SCHERING AGD-100Q Berlin öPostfach 65 0311 Z Dr. Heinz HannseKarl Otto Mittelstenscheid - Dr. Horst Witzei postal check account: Berlin-West 1175-101, bank code 10010010 Λ. Chairman of the supervisory board: Dr. Edward v. SchwartzkoDDen Berliner Commerzbank AG, Berlin. Account number. 106700800, Bankieitzahi 1004000t -4- SCHERING AG; | * G «commercial legal protection 10 42.A process for the preparation of benzyl ether derivatives of pentites according to claims 1 to ^ 3?, Characterized in that ^ A) compounds of the general formula <TH2-0 'Yi 15 9H - - 0 * Y2 CH - 0 - Y ^ CH - 0 - Y /, I 4 CH- - 0 - Y · II 2. j in which one of the substituents Y * is the group 20 - f - R2 K nnri the four other substituents Y 'are hydrogen, a) with compounds of the general formula 25. CO-X III or b) with compounds of the general formula r3-Z IV or 30 c) with compounds of the general formula r3-co-o-co-r3 V, if appropriate in the presence of acid-binding agents and / or a catalyst or 35 -5- 40 Λ iw · * Ξ Board: Dr. Herbert Aamis - Dr. Christian BruhnHans-Jürgen Hamann Postal address: SCHERING AG0-1000 Berlin 65 * PO Box 650311% DrHeinz HannseKarl Otto MlttelstenscheldDr. Horst Witzei postal check account: Berlin-West 1175-101, bank code 10010010 a, Chairman of the Supervisory Board: Dr. Edward v. Sdiwart2koppen Berliner Commerzbank AG, Berlin, account no. 108 7006 00, bank code 100 400 0, ', SCHERINGAG Gmcfblidm legal protection 5 B) Compounds of the general formula CH - 0 - Y "1 2 1 CH - 0 - CH - 0 - Y» ίκ - 0 - YV I 4 10 CH2 - 0 - Y £ VI in which one of the substituents Y "means the group -ch-r2 ri and the other four substituents Y" in pairs each represent an optionally substituted methylene group 2.0 5, optionally in the presence of organic solvents and acidic catalysts at temperatures of 0 to 100 ° C, preferably from 40 to 80 ° C, hydrolyzed, wherein R., R_ and R have the meaning given above and 1. j 25 R ^ and R ^ may each be the same or different and each hydrogen, a C ^ C ^ alkyl radical, a substituted C ^ -C ^ Q alkyl radical, an optionally substituted arylrC1-C ^ alkyl radical, a C ^ -Cg -cycloaliphatic hydrocarbon radical, an aromatic hydrocarbon radical or R ^ and substituted one or more times by C ^ -30 Cg-alkyl and / or halogen and / or C ^ -Cg-alkoxy and / or the nitro group and / or the trifluoromethyl group R ^ *. together represent a polymethylene group - (CH ^) ^ -, X represents a halogen atom, preferably a chlorine atom, and Z represents a halogen atom or the radical R ^ OSOgO- and m denotes the integer 4 and 5. -6- n s 4o τ Ü X; r *, 8nd: uDr · Herbert * SJ ™ S; Pf; “Hri3, ian Brubn Hans-Jürgen Hamann Postal address: SCHERING AG 0-1000 Berlin S5. P-stfaöi «0311 A Or. Heinz Hannse Karl Otto Mittelstenscneid · Or. Horst Witzei“. . "......" rjnasienn. ιΐη, "ΐΜ.Λ ·. <Μ ΐι.ι · ιΜ ·. · ι · .η. -j -. . Postal check account: Berlin-West 1175-101. Bank code 10010010 = Chairman of the Supervisory Board - Dr. = duard v. Schnwartzkoppen Berliner Commerzaank AG. Berlin. Kcnto no. 10S '006 00. Bankleitzani '00 400 00 c Company headquarters: Berlin and Bergkamen Berliner Oisconto-Sank AG. Berlin. Account number. 241/5008. Banxleiizeni ton 70000 B O Minii * l «ranicf * P * Afi Charlntfanfttirn Ql UQB 731> · aa udb nnn Rarliner _ H» nvfnMe · o i. I, .6. SCHERING AG Gtwerbfidwr RodrfMdurt * 43. Agents with growth regulatory activity for plants, characterized by a content of at least one compound according to claims 1 to 42 bis 44 «; Agents with growth regulatory effect for plants 10 according to claim 4 = 3 in a mixture with carriers and / or auxiliaries. - w 4 ^. Agent according to claims 43 and 44 for influencing the vegetative and generative growth in legumes, 1? especially soy. 46. Agents with growth-regulating action for plants according to claim 45, produced by processes according to claim 42 * 20 25 30 * * - -7- 35 l 40 «r À Board: Dr. Herber; Asrms · Or. Christian Brunn - Hans-Jürgen Hamann Postal address: SCHERING AG - 0-1000 Berlin 65 · Postfach 650311 i Dr-Ηβιπζ Hannse · Kar! on ° Mitteistenscneid Dr. Horst Witzei postal check account: Berlin-West 1175-101. Bank code number IC010010 - Chairman of the Supervisory Board: Or. Eduard v, Senwartzicoppen Berliner Commerzaanit AG. Berlin. Account no. 108 7006 00. SanKieitzshl 100 «WO 00 1 Company headquarters: Berlin and 3ergkamen Berliner Disconto-aantc AG. Berlin. Account number. 241/5008. Bank number IM 700 00