FR2523122A1 - BENZYL ETHER DERIVATIVES OF PENTITOLS, PROCESSES FOR PREPARING THEM AND PHYTOSANITARY PRODUCTS GROWTH REGULATORS CONTAINING SUCH COMPOUNDS - Google Patents

Abstract

THE INVENTION CONCERNS NEW DERIVATIVES OF BENZYL ETHERS OF PENTITOLS. THEY RESPOND TO THE FORMULA (CF DRAWING IN BOPI) IN WHICH ONE OF THE SYMBOLS REPRESENTS A RADICAL -CH (R) -R AND THE FOUR OTHERS REPRESENT EACH A RADICAL - (CO) -R. IN THESE FORMULAS R REPRESENTS HYDROGEN OR A CC ALKYL, R AN AROMATIC HYDROCARBON RADICAL POSSIBLY CARRIER OF ONE OR MORE SUBSTITUENTS TAKEN IN THE ENTIRE SET CONSTITUTED BY THE ALKYLS IN CC, THE ALCOXY IN CCBS, THE PHENOXY POSSIBLY POSSIBLE POSSIBLY SUBSTITUTED PHENYLES, HALOGENS, THE NITRO GROUP AND THE RADICAL TRIFLUOROMETHYL, R HYDROGEN OR A CC ALKYL POSSIBLY SUBSTITUTED AND N IS EQUAL TO 0 OR 1. THESE COMPOUNDS ARE GROWTH SUBSTANCES: THEY ALLOW THEY PARTICULAR ON VEGETATIVE AND GENERATIVE DEVELOPMENT OF LEGUMES, SUCH AS SOY.

Description

The invention relates to novel benzyl ethers of

  pentitols, processes for preparing these compounds as well as growth regulating phytosanitary products which contain such compounds. Regulating compounds on growth are already known and are already in use.

  introduced some into practice.

  Known products of this type, such as those based on triiodobenzoic acid or based on

  bis-o-isopropylidene-2,3,4,6-O-L-xylohexulofuran

  or its sodium salt, are not, however, indicated by satisfactory qualities of action or do not act

  only when applied at high doses.

  It is furthermore known to use benzyl-

  loxymethyl-2 tetrahydrofuran as herbicide (first

  published specification of patent application DE 2 724 677), the

  which, because of its phytotoxicity, causes damage

to plants.

  It was therefore necessary to develop, this was the technical problem that arose, a product that had a broad regulatory effect on plant growth.

  field of action while sparing the plants.

  This technical problem is solved

  according to the invention, thanks to a product characterized in that it contains at least one compound corresponding to the general formula I:

CH 2 Y

i 2 i CH O y ()

I 2

CH O y

I 3

CH O Y 5

C 2 5

  in which one of the substituents Y represents a radical:

CH R 2

R 1 R 1

2 2523122

  R represents hydrogen or a C 1 -C 4 alkyl radical and R 2 represents an aromatic hydrocarbon radical optionally bearing one or more substituents taken from the group consisting of C 6 alkyls and C 6 C 7 alkoxides; optionally substituted phenoxy, the

  optionally substituted phenyls, halo

  genes, the nitro group and the trifluoro- radical

methyl,

  and the other four Y subtituents, which can be identified as

  or different, each represents a radical (CO) n -R 3 o R 3 represents hydrogen or an optionally substituted C 1 -C 4 alkyl radical and

n is equal to O or l.

  The compounds according to the invention can

  exist in the form of optical isomers, possibly

  also in the form of geometric isomers

  to isomers and their mixtures are also part of

the subject of the invention.

  The compounds according to the invention

  come remarkably well for the regulation of plant growth in different crops and, by their field of activity as well as their ability to be tolerated,

  they surpass, surprisingly, the known compounds

  in the same sense as mentioned above.

  Since the compounds comply with the

  provoke, on plants, both

  qualitative and quantitative cations as changes

  of metabolism they must be classified among the regula-

  growth promoters, which are indicated by the possi-

following applications.

3 2523122

  Inhibition of vegetative growth of woody and fruity plants, for example on roadsides, railway installations, etc.

  to prevent the appearance of exuberant vegetation

  Inhibiting the growth of cereals in order to prevent lodging or breaking of stems,

  or cotton to increase the harvest.

  Action on the branching of vegetative and generative organs in the case of ornamental plants or cultivated plants with a view to increasing the number of flowers, or, in the case of tobacco and tomato, in

  to prevent the formation of lateral discharges.

  Improvement of the quality of products, for example increase of the sugar content in the case of sugar cane, sugar beet or fruits,

  and standardization of the maturity of the products

  ter, which leads to higher yields.

  Increased resistance to weather factors

  such as cold and drought.

  Action on latex flow in rubber plants

  Chouc. Development of parthenocarpic fruit, sterility

  of pollen and action on sex also

  possibilities of application.

  Control of germination of seeds or beans

  geonnement. Defoliation or action on fruit abscission

  in order to facilitate the harvest.

  The compounds according to the invention are used

  in particular to act on the development of

  vegetative and generative effects of certain legumes, such as

as soy.

  The doses to be applied generally vary,

  depending on the purpose in view, between 0.005 and 5 kg of

  active area per hectare but may also be

higher.

  The timing of the application depends on the objective

  target and climatic conditions.

  With regard to the actions described above

  certain of the compounds in accordance with the invention are particularly marked: they are in particular those in formula I of which R 1 represents hydrogen or a C 1 -C 4 alkyl radical, preferably a methyl, R 2 represents a phenyl radical, chloro-2 phenyl, chloro-3

  phenyl, 4-chlorophenyl, 2,6-dichlorophenyl, dichloro-

  2,4-phenyl, 3,4-dichlorophenyl, 2,4,6-trichlorophenyl, 4-bromo-phenyl, 2,4-dibromo phenyl, 2,6-dibromo phenyl, 2,4,6-tribromo phenyl, fluoro 2-phenyl, 3-fluoro-phenyl, 4-fluoro-phenyl, 2,4-difluorophenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 3,4-dimethylphenyl, 2-methoxyphenyl, methoxy- Phenyl, 4-methoxyphenyl, methylene-3,4-dioxyphenyl, 2-phenoxyphenyl, 3-phenoxyphenyl, nitro-2-phenyl or 3-nitro-phenyl, R 3 is hydrogen, C 1 -C 4 -alkyl , preferably a

  methyl, an ethyl or a propyl, or a chloro-

  methyl, and N is 0 or 1.

  The compounds in accordance with the invention may be used alone, mixed with one another or mixed with other active ingredients.

  according to the intended purpose, defoliants, phyto-

  sanitary or pest control products.

  If it is desired to extend the scope of activity, other biocides can also be added. For example, as herbicide partners,

  active groups belonging to the triazine, amino-

  triazoles, anilides, diazines, uracils, aliphatic carboxylic and halocarboxylic acids, substituted Esbenzoic and arenecarboxylic acids, hydrazides, amides, nitriles and esters of these carboxylic acids, carbamic and thiocarbamic esters,

  ureas, 2,3,6-trichlorobenziloxypropanol,

  containing thiocyanates, as well as other additives. By "other additives" is also meant, for example, non-phytotoxic additives which, when combined with herbicides, may increase their action by a synergistic effect, such as wetting agents, emulsifiers, solvents and oily additives. It is good to apply active ingredients

  of the invention, or mixtures thereof, in the form of

  positions, such as powders, spreading agents,

  granules, solutions, emulsions or suspensions

  pensions, containing liquid carriers or diluents

  and / or solid and possibly wetting agents, adhesives

  solvents, emulsifiers and / or dispersants.

  Suitable liquid carriers include

  for example water, aliphatic hydrocarbons or aromatics

  ticks, such as benzene, toluene and xylenes,

  as well as cyclohexanone, isophorone, dimethylsul-

  foxide, dimethylformamide and also fractions

of mineral oils.

  The solid supports will for example be mineral soils, such as Tonsil, silica gel, talc, kaolin, Attaclay, limestone and silica,

  or plant products, such as flours.

  As surfactants, for example, the

  Calcium lignin-sulfonate, poly-ethoxy-

  alkylphenols, naphthalenesulfonic acids and their salts, phenol-sulphonic acids and their salts, formaldehyde condensation products,

  sulphates of fatty alcohols as well as benzene sulphuric

substituted fonic and their salts.

  The proportion of the active ingredient (s)

  in the various formulations may vary

  In this way, products will be able to

  hold for example from about 10 to 80% by weight of active ingredients, from about 90 to 20% by weight of liquid carriers

  or solids and possibly up to 20% by weight of

  factive. The spreading of the products can be done in the usual way, for example with water as a support in the form of slurries which are sprayed with

  doses of about 100 to 1000 liters / hectare. It is also

  possible to apply the products by the so-called "low volume" process and the so-called "very low volume" process, as well as

  only in the form of microgranules.

  The following constituents are used for preparing formulations: A wettable powders (powders for slurries) a) 80% by weight of active ingredient% by weight of kaolin and% by weight of surfactants based on the sodium salt of N methyl-N-oleyl-taurine and calcium salt of lignin-sulfonic acid; b) 50% by weight of active ingredient% by weight of clay minerals% by weight of pitch derived from the treatment of cellulose and% by weight of surfactants based on a mixture of the calcium salt of lignin-sulfonic acid and polyglycol ethers of alkylphenols; c) 20% by weight of active ingredient% by weight of clay minerals 5% by weight of pitch derived from the treatment of cellulose and% by weight of surfactants based on a mixture of the calcium salt of lignin sulfonic acid and polyglycol ethers of alkylphenols; d) 5% by weight of active ingredient% by weight of Tonsil% by weight of pitch from the treatment of cellulose and% by weight of surfactants based on a product of

densification of fatty acids.

  B Emulsifiable concentrate% by weight of active ingredient% by weight of xylene% by weight of dimethylsulfoxide and 5% by weight of a mixture of a polyethoxylation product of nonylphenol and of dodecylbenzenesulphonate

of calcium.

  C Paste% by weight of active ingredient 5% by weight of a sodium aluminosilicate% by weight of a polyethoxylation product of cetyl alcohol which contains 8 moles of ethylene oxide 2% by weight of h 2 O pins% by weight of a polyethylene glycol and

23% by weight of water.

  In order to prepare the novel compounds which are the subject of the invention, it is possible for example: A) to react compounds corresponding to the general formula: CH Yi

CH O Y '

o Y '

CH O Y '

CH 2 O Y

  wherein one of the substituents Y 'represents a radical

callus

-CH R 2

  R 1 and the other four substituents Y 'are each hydrogen, a) with compounds of the general formula

R 3 CO X (III)

  or b) with compounds of the general formula

R 3 Z (IV)

  or 9 with compounds of the general formula

R 3 CO O CO R 3 (V)

  optionally in the presence of acid acceptors and / or a catalyst, or B) hydrolyzing compounds of the general formula:

CH O

eyelash O -

CH O Y-i (VI) l H O Y ^

2 H O -5

  wherein one of the substituents Y "represents a radical

-CH-R 2

  IR 1 and the other four substituents Y "are associated in pairs, each pair representing an optionally substituted methylene radical of formula R 1/4, optionally in the presence of organic solvents, as well as acidic catalysts, such as sulfuric acid, p-toluenesulfonic acid, hydrochloric acid, ammonium chloride, phosphoric acid, silicic acid as well as ion exchange resins, at temperatures of 0 to 100 ° C., preferably 40 to 80 ° C. C, the various symbols present S in the preceding formulas have the following meanings R 1, R and R having the meanings previously

2 3

  The data, R 4 and R 5, which may be the same or different, each represents hydrogen, a C 1 -C 10 alkyl radical or a C 1 -C 10 alkyl radical.

  substituted aryl- (C 1 -C 3) alkyl radical.

  substituted, a cycloaliphatic hydrocarbon radical

  C 3 -C 8, an aromatic hydrocarbon radical optionally bearing one or more substituents taken from the group consisting of C 1 -C 6 alkyls, halogens, C 1 -C 6 alkoxy, nitro and the trifluoromethyl radical, or else R 4 and R 5 together form a polymethylene radical - (CH 2) m -, X represents a halogen atom, preferably

  chlorine, Z represents a halogen atom or a radical

  cal R 3 OSO 2 O and m denotes an integer equal to 4

or 5.

  As radicals R 4 and R 5 carried by the group

  substituted ethylene, for example hydrogen, as C 1 -C 10 alkyl radicals, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, 2,2-dimethylpropyl, n-pentyl radicals, n-heptyl, n-octyl and ndecyl, in

  as substituted C 1 -C 10 alkyls, the chloroalkyl radicals

  methyl, bromomethyl, fluoromethyl, dichloromethyl, tri-

  fluoromethyl, trichloromethyl, hydroxymethyl, methoxy-

  methyl, ethoxymethyl, phenoxymethyl, 4-chlorophenoxy-

  methyl, chloroethyl, bromethyl, 2-ethoxyethyl and phenoxy-

  2 ethyl, as cycloaliphatic hydrocarbon radicals

  C 3 -C 8 cyclopropyl, cyclopentyl and cyclopentyl radicals.

  hexyl, as aryl- (Cl-C 3) alkyl, the ben-

  2-phenylethyl and 2-phenylethyl as aromatic hydrocarbon radicals phenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 3,4-dichlorophenyl, 4-methoxy radicals

  phenyl, 4-nitro phenyl and 2,4-dichlorophenyl.

  The pentitol derivatives (VI) which are preferred as starting materials are in particular 1) those in which Y "represents a radical

-CH R 2

IF

  R 1 and each of the pairs (Y ", Y 'e) and (Y", Y ") represents an optionally substituted methylene radical R 4 2) those in which Y" 3 represents a radical

CH R

1 2

R 1

  and each of the pairs (Y "1 ', Y" 2) and (Y "4, Y" 5) represent

  an optionally substituted methylene radical, and 3) those in which Y "5 represents a radical

-CH R

R 1

  and each of the pairs (Y ", Y" s 2) and (Y 3, Y 4) represent

  an optionally substituted methylene radical.

  The reaction can be carried out between 0 and 1500 C but it is generally between the temperature

  ambient temperature and the reflux temperature of the reaction mixture

nel.

  The reaction time is from 1 to 72 hours.

  To synthesize the compounds according to the invention, the reaction partners are used in

  approximately equimolar amounts.

  Suitable solvents are solvents which are inert with respect to the bodies participating in the reaction. The choice of solvents or suspending media depends on the

  the nature of the alkyl or acyl halides or sulphides

  As well as the nature of the acid acceptors used, the solvents and suspension media may be, for example, ethers, such as diethyl ether, diisopropyl ether,

  tetrahydrofuran and dioxane, hydrocarbons

  such as petroleum ether, cyclohexane, hexane, heptane, benzene, toluene and xylenes of carbonitriles, such as acetonitrile, and

  carboxamides, such as dimethylformamide.

  Suitable acid acceptors include organic bases such as triethylamine, N, N-dimethylaniline and pyridine bases, or inorganic bases, such as oxides, hydroxides and carbonates of alkaline earth metals or alkali metals. are liquid, such as

  pyridine can be used as solvents at the same time.

  As catalysts for variant A, it is possible to use onium compounds such as ammonium compounds, phosphonium compounds or quaternary arsonium compounds.

  as well as sulfonium compounds.

  Also suitable are polyglycol ethers,

  more particularly cyclic, such as the compound 18-cou-

  -6, and tertiary amines such as tributyl-

  amine Compounds that are preferred are compounds

  quaternary ammonium compounds, such as benzyl chloride

  triethylammonium and tetrabutylammonium bromide.

  The compounds according to the invention which have been prepared by the processes mentioned above can be isolated from the reaction mixture by conventional methods: for example, the solvent can be distilled off, for example.

  put into play, under normal pressure or under reduced pressure.

  or perform precipitation by water or extract It is generally possible to obtain a high degree of purity if one carries out a purification by

  column chromatography or by fractional crystallization

tioned.

  The compounds according to the invention are generally

  usually almost colorless and almost odorless liquids, which are poorly soluble in water, soluble under certain conditions in aromatic hydrocarbons, such as petroleum ether, hexane, pentane and cyclohexane, and very soluble in halogenated hydrocarbons, such as chloroform, methylene chloride and tetrachloride

  carbon, aromatic hydrocarbons, such as benzene,

  zene, toluene and xylenes, ethers, such as diethyl ether, tetrahydrofuran and dioxane,

  carbonitriles, such as acetonitrile, ketones, such as

  acetone, alcohols, such as methanol and ethanol;

  carboxamides, such as dimethylformamide, and sulfoxides, such as dimethylsulfoxide, but they can also be in the form of crystalline solids

  colorless and odorless, which are poorly soluble in hydro-

  aliphatic or aromatic carbides and moderately to very

  soluble in halogenated hydrocarbons, such as chlorine

  roform and carbon tetrachloride, des-ketones, such

  than acetone, carboxamides, such as dimethylformat-

  sulfides, such as dimethylsulfoxide,

  carbonitriles, such as acetonitrile, lower alcohols

  such as methanol and ethanol, and water.

  As solvents for recrystallization it

  It is particularly advisable to use water, metha-

  N, acetonitrile and ethyl acetate.

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

EXAMPLE 1

(2,6-Dichlorobenzyl) -0-5 xylitol.

  We start by putting in the reaction vessel

  277.0 g (0.708 mol) of (2,6-dichlorobenzyl) -O-5-bis-propylidene-O-1,2: 3,4 xylitol and add

  stirring, 752.2 ml of 1.5 N sulfuric acid.

  following 70 C for 3 hours, then let stand

  reaction mixture overnight at room temperature.

  After this, while stirring, 95 ml of a 32% sodium hydroxide solution are added dropwise at 25 ° C. and the reaction mixture is extracted three times.

  each time with 200 ml of ethyl acetate.

  The extracts are then washed twice with 100 ml of water each time and dried over sodium sulfate.

  magnesium, filtered and concentrated under reduced pressure.

  Colorless crystals are obtained which are macerated with a cold mixture of equal parts of diethyl ether and di-isopropyl ether and

  then dried at room temperature under 270 mbar

only at constant weight.

  202.0 g of (2,6-dichlorobenzene) are thus collected.

  benzyl) -O-5 xylitolsoit 91.7% of the theoretical amount.

Melting point: 82.degree.

  Thin layer chromatography (TLC) with a mixture of chloroform / methanol as the eluent

* 4/1: Rf value = 0.34.

  Analysis: Calculated C 46.32% H 5.18% Cl 22.79%

  Found C 46.48% H 5.10% Cl 22.37%.

EXEMPLE'2

  (2,6-Dichlorobenzyl) -3-3 tetrakis-methyl-O-1,2,4,5 adonitol. 3.11 g (0.01 mol) of (2,6-dichlorobenzyl) O 3 -3 adonitol, 0.22 g (0.001 mol) of benzyltriethylammonium chloride and 23 g (0 g) were first placed in the vessel. 2 mol) of dimethyl sulphate in 20 ml of methylene chloride To the mixture thus obtained, 14.0 g (0.25 mol) of hydroxide are added dropwise while cooling to about 30 ° C. and stirring vigorously. of potassium in solution in 15 ml of water After shaking

  for 3 hours at room temperature

  in another 1 hour at reflux is then diluted with 150 ml of water and extracted three times with 150 ml of ethyl acetate each time the extracts are washed with water, dried over magnesium sulfate, filtered and The remaining oil is distilled using a bulb tube

  (bath temperature: 200 C / 0.3 mbar).

  2.90 g of (2,6-dichlorobenzyl) -3-3-tetrakis-methyl-O1,2: 4,5 adonitol are thus collected, ie

79.1% of the theoretical amount.

  n D = 1.5198 TLC with a mixture of toluene and ethyl acetate at a ratio of 1/1:

Rf = 0.29.

  Analysis: Calculated C 52.32% H 6.58% C 1 19.30%

  Found C 51.82% H 6.48% Cl 20.13%.

EXAMPLE 3

  (2,6-Dichlorobenzyl) -O-1 tetrakis-acetyl-O-

2,3,4,5 D-arabitol.

  We start by shaking for 1 hour at the temperature

  ambient temperature 5.0 g (0.016 mol) of (2,6-dichlorobenzyl) -

  0-1 D-arabitol in a mixture of 20 ml of pyridine and ml of acetic anhydride 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 vacuum of trom-

  To the residue 150 ml of additional

  toluene and concentrated again under reduced pressure.

  The remaining oil is taken up, per portion S, with 300 ml

  The ethyl acetate extracts are washed with ethyl acetate.

  with water; It is dried over magnesium sulfate, filtered and evaporated. The oily residue crystallizes after having been macerated with a small amount of oxide.

of di-isopropyl.

  5.80 g of (2,6-dichlorobenzyl) -O-1-tetrakis-acetyl-O-2,3,4,5-D-arabitol are collected, ie 75.7% of the

theoretical amount.

Mp = 8990C.

  TLC with, as an eluent, a mixture of equal parts of

  toluene and ethyl acetate: Rf value = 0.47.

  Analysis: Calculated: C 50.11% H 5.49% C 1 14.79%

  Found: C 50.58% H 5.49% Cl 14.80%.

  The other components are prepared in a similar way.

  according to the invention which are cited in the following table. EXAMPLE 4 (Dichloro-2,4-benzyl) -O-5-xylitol (2-chloro-benzyl) -O-xylitol 6 (2-methylbenzyl) -O-xylitol-7-dichloro-2 6 benzyl) -Ol L-arabitol 8 (2,6-Dichlorobenzyl) -O-1 D-arabitol 9 (Dichloro-2,6-benzyl) -O-3-adonitol (2,4,6-Tribromo-benzyl) -0-5 xylitol J.1 Benzyl-05 xylitol 12 (2,6-Dichlorobenzyl) -0-5 tetrakis-acetyl 1,2,3,4 xylitol 13 (2,4,6-Tribromo-benzyl) -O-tetrakis-acetyl-0 -1, 3,4-xylitol 14 (2,4,6-Tribromo-benzyl) -3-adonitol (4-chloro-benzyl) -0-xylitol 16 (4-Bromo-benzyl) -O-5-xylitol 17 3,4-Dichloro-benzyl) -0-xyl-18-ol (3-methyl-benzyl) -0-xylitol 19 (4-methylbenzyl) -0 -5-xylitol (3,4-Dimethylbenzyl) -0-5 xylitol 21 ( 3-chlorobenzyl) -0-5 xylitol 22 (4-cyano-benzyl) -0-5 xylitol 23 (2,6-Dichlorobenzyl) -0-3

1,2,4,5-tetrakis-acetyl

Nitol Zonstante physique

Mp 96-980 ° C

Mp: 52-540 ° C .;

Mp = 59610 ° C

F = 122-240 ° C

Mp = 124-260 ° C .;

M.p. 116-170 ° C .;

M.p. 132-33 o C

Mp 47-50 ° C

n D 1.4876

F = 106-070 ° C

M.p. 132-340 ° C .;

F 109-09.50 C

M.p. 110-12 ° C

F -122-2-3C

M.p. 54-56 to C

Mp 98-990 ° C

Mp = 72-740 ° C .;

F, = 90-920C

Mp = 119-210 ° C

= 144

n 144 D N o l, e z N'de

the example

  Naom constant of the sephysic compound

(Trifluoromethyl-3-benzyl) -

  0-5 xylitol (3-fluorobenzyl) -0-5 xylitol (4-fluorobenzyl) -0-5 xylitol (2,4,6-Tribromo-benzyl) -O-1 D-arabitol (2-Fluoro-benzyl) - 0-5 xylitol (2,6-Dichlorobenzyl) -0-5 tetrakis-methyl-0-1,213,4 xylitol

Mp 61-630 ° C

Mp = 72-74.50 ° C .;

Mp = 76,780 ° C

F = 156-57 ° C

  D 20 = 1.5243 n D 20 = 1.5186 (2,6-Dichlorobenzyl) -O-1 tetrakismethyl-0-2,4,4,5 L-arabitol (2,4-Dichloro-benzyl) -0 5-Tetrakis-methyl-1,2,3,4-xylitol (2,6-Dichlorobenzyl) -O-1-tetrakis-methyl-0-213.4.5 Darabitol (Tribromo-214.6-Benzyl) -0-5 tetrakis-methyl-0-1, 2,3,4 xylitol (Tribromo-214,6 benzyl) -O-1 tetrakis-methyl-0-213,415 D-arabitol

(2-chloro-6-fluoro-benzyl) -

0-5 xylitol

36 <2-chloro-6-fluoro-benzyl) -

0-1 D-arabitol

37 (2-chloro-6-fluoro-benzyl) -

0-3 adonitol

38 (2-chloro-6-fluoro-benzyl) -

  0-5 tetrakis-acetyl-0-1,2 13,4 xylitol

= 1.5177

D n D = 1.5205 n D 2.0 n D

= 1.5616

= 1.5668

  F = 70-7 C F = 138 139 c D = 1.5297 n D = 1.4809

39

(2-chloro-6-fluoro-benzyl) -

  0-5 tetrakis-methyl-O-1, 2,3,4 xylitol n D = 1,4972 n D

= 1.5201

  The starting bodies used to pre-

  the compounds according to the invention are known

  or can be prepared by known methods.

  The following examples illustrate the preparation of the starting bodies.

EXAMPLE 40

  (2,6-Dichlorobenzyl) -0-5 bis-isopropylidene-O-

1,2: 3,4 xylitol.

  We begin by placing in the reaction vessel

  116.13 g (0.5 mole) of bis-isopropylidene-O-1,2: 3,4 xylitol with 119.96 g (0.5 mole) of 2,6-dichlorobromide.

  benzyl and 4.5 g (0.019 mole) of benzyl tri

  After stirring very vigorously, a solution of 100 g of sodium hydroxide (2.5 mol) in the mixture obtained at room temperature is added dropwise to the mixture obtained at room temperature.

  ml of water: the temperature rises slowly

  50 ° C and goes back down, in about an hour, to room temperature. Then, to complete the reaction, it is stirred for a further hour at 50 ° C. and then diluted.

  with 500 ml of ice water and the reaction mixture is extracted

  Each time with 150 ml of ethyl acetate the organic phase is washed twice with each time

  300 ml of water, dried over magnesium sulphate, filtered

  and evaporated to dryness at 40 ° C under reduced pressure.

  The residue is subjected to fractional distillation. 150.0 g of the compound are collected, ie 76.7% of the theoretical amount.

  Boiling point below 0.13 mbar: 163 C;

n = 1.5080.

  n TLC with, as eluent, a 4/1 mixture of toluene

  and ethyl acetate: Rf value = 0.52.

  Analysis: Calculated C 55.25% H 6.18% Cl 18.12%

  Found C 55.66% H 6.46% C 18.03%.

EXAMPLE 41

  (2,4,6-Tribromo benzyl) -O-5-bis-isopropylidene

O-1,2: 3,4 xylitol.

  To a suspension of 2.88 g (0.12 hole) of sodium hydride in 50 ml of toluene, a solution of 23.2 g (0.1 mole) of bis is slowly added dropwise while stirring. isopropylidene-0-1,2: 3,4 xylitol in 100 ml of

  After the addition has been completed, the mixture is heated to reflux.

  flow for 2 hours A solution of 40.78 g (0.1 mol) of 2,4,6-tribromobenzyl bromide in 50 ml of toluene is then added dropwise and the mixture is heated.

at reflux for another 8 hours.

  After cooling, the mixture is carefully washed three times with 150 ml of water each time and then the organic phase is dried over magnesium sulfate, filtered and concentrated at 40 ° C. under reduced pressure.

  the remaining oil is removed under reduced pressure (temperature

  bath temperature of 180 C under 0.13 mbar) traces of the body

departure still present.

  37.6 g of the compound, ie 67.25% of

the theoretical quantity.

  D = 1.5516 TLC, eluant, an equal parts mixture of toluene and ethyl acetate: Rf value = 0.52 Analysis: calculated C 38.26% H 4.14%

Found C 37.99% H 4.04%.

  Bodies can be prepared in a similar manner

following start.

(See table next page) N O of

example

  Constant Name of Physical Compound (2,4-Dichlorobenzyl) -3-Bisopropylidene O 1,2,4,5 Adonitol (2,4-Dichlorobenzyl) -O-1-Bisopropylidene-0-2,3: 4,5 ( 2,4-Dichlorobenzyl) -O-1-bis-isopropylidene-02,3 '-4,5 arabitol (2,6-Dichlorobenzyl) -O-1-bis-isopropylidene-O 2, 3: 4, L-arabitol (2,6-Dichlorobenzyl) -O-1-bis-isopropylidene-0-213: 4.5 D-arabitol (2,6-dichloro-benzyl) -O-3-bis-isopropylidene-O-1, 2: 4.5 adonitol (Tribromo-2,4,6 benzyl) -O-3-bis-isopropylidene-O-1,2,2,5,5 adonitol (Tribromo-214,6 benzyl) -O-bis-isopropylidene 0 2,3: 4,5 Darabitol (2-chloro-6-fluoro-benzyl) -0-5 bis-isopropylidene-O-1,2,4,4-xylitol (2-chloro-6-fluoro-benzyl) -0-1 bis-isopropylidene-0-2,3: 4,5 Darabitol

(2-chloro-6-fluoro-benzyl) -0-3-

  bis-isopropylidene-0-1,2: 4,5 adoni tol n D

= 1.5092

  n = 1.5070D n D = 1.5071 n D = 1.5075

D O 159

F = 5093

  n = 1.5447 n D n D = 1.54416 D n = 1.4918 D The following examples illustrate the

  possibilities of applying the compounds according to the invention

  tion; the tests were carried out with the formulations described

2523122

EXAMPLE 53

  Increase in chlorophyll content

  and pod formation on soybeans.

  On soybean plants, an aqueous emulsion of one of the compounds to be tested is applied by post-emergence spraying. The dose applied is 0.8 kg of active ingredient per hectare. Four weeks after spraying,

  washers in the second primary sheet.

  Chlorophyll is extracted from these ron-

  and photometrically dose the chlorophyll a

  The results recorded in the table

  the increase in the chlorophyll content

report to the witness.

  The number of pods and flowers formed is also determined on the plants and the results are expressed in% relative to the control.

  contains the calculated values.

  It is found, by examining the table, that the compounds according to the invention are distinguished, compared to the comparison substances, by a better

  tolerance or higher chlorophyll contents.

  and / or by greater production of flowers and pods. Composed according to the production increase of the invention the content of chlo pods and rophyll in% flowers in relation to the witness

(2,6-Dichlorobenzyl) -

0-5 xylitol 63.9 202

(2,6-Dichlorobenzyl) -

0-1 L-arabitol 43.0 129

(2,6-Dichlorobenzyl) -

0-1 D-arabitol 37.2

(2,6-Dichlorobenzyl) -

  0-3 'adonitol 39.3 129 Comparative substance according to DE 2 -2 24 _J 7 J 7 _

Benzyloxymethyl-2 tetrahydrofuran

ranne 27.4 146

(2,6-Dichlorobenzyloxymethyl)

  tetrahydrofuran * 60.9 90 Phytotoxicity damage occurs

in the form of burns.

EXAMPLE 54

  Regulatory growth effects on soybean and kidney bean after disinfection

seeds.

  Dwarf bean seeds and soya beans are disinfected by pulverulent compositions of the active ingredients, at doses of 10, 50 and 100 g of material.

active for 100 kg of seed.

  The seeds are sown in culture tanks.

  The plants are grown in greenhouse conditions After three weeks of culture the symptoms are evaluated according to the following scale of 0 to 10: = no difference compared to the untreated control 5 = plants grouped in bunches , dark green, branched 1 = very strong grouping in boots, dark green

intense, strong branching.

  The results observed show that

  according to the invention are, with regard to the desired type of action, more effective than the compounds

comparison.

BOARD

  Ingredient according to the inven Dose of my Active grade rating in g for Soya beans 100 kg of dwarf seed (2,6-Dichlorobenzyl) -0-5 10 8 8 xylitol 50 3 5

3 4

  (2,6-Dichlorobenzyl) -O-1 10 10 7 L-arabitol 50 5 4

3 3

  (2,6-Dichlorobenzyl) -O- 11 10 8 8 D-arabitol 50 6 5

3 4

  (2,6-Dichlorobenzyl) -O-3 10 9 8 adonitol 50 5

3 5

  (2,4,6-Tribromo benzyl) -0-5 10 10 10 xylitol 50 9 9

9 9

T A B L E A U (continued)

Dose of my Rating

  Active Comparative Compound fume in g per 100 kg of seed Dwarf Soybean Benzyloxymethyl-2 Tetrath 10 10 9 Drofuran (DE-A 2 724 677) 50 10 9

10 8

  Sodium salt of 10 8 bis-isopropylidene-O-2,3-ol: 4,6 50 10 8 -Lexylohexulofuranuronic acid 100 7

EXAMPLE 55

  Increased productivity in the

case of soybeans.

  On soybean plants, powder is applied

  verifying, post-emergence, an aqueous emulsion of the compound

  to be studied at a dose of 0.8 kg of active

  Four weeks after spraying the number of flowers and pods appeared. The values obtained, expressed in% relative to the control, are given in the following table.

growth in%.

  The results found show that the compounds

  stimulate the production of pods and flowers and, in

  same time, the bundling of plants

  comparisons only exert this effect in a weak

  they are, in a way, phytotoxic

xic.

T A L EA U

  Compound according to the invention Inhibition Production of pods and growth flowers in% pai

in% compared to

  moin (2-chlorobenzyl) -0-5 xylitol 28 142

(2,6-Dichlorobenzyl) -0-5

  trakis-acetyl-0-1,2,3,4 xylitol 59,219 (Tribromo-2 14,6 benzyl) -0-5 tetrakis-acetyl-0-1,2,3,4 xylitol 44 173

(2,6-Dichlorobenzyl) -0-1 tetra-

  kis-acetyl-0-2,3,4,5 D-arabitol 59,215

(Tribromo-2,4,6 benzyl) -0-3 adeno

  Nitol 49 188 (4-chlorobenzyl) -0-5 xylitol 44 165 (4-Bromo-benzyl) -0-5 xylitol 49 185 (3,4-Dichlorobenzyl) -0-5 xylitol O 115 (3-Methylbenzyl) 0-5 xylitol 2,108 <4-methylbenzyl) -0-5 xylitol 33 204 (3,4-Dimethylbenzyl) -0-5 xylitol 33 204 <3-chlorobenzyl) -0-5 xylitol 38 135 <Cyano-3 4 benzyl) -0-5 xylitol 28 150

(2,6-Dichlorobenzyl) -0-3 tetra-

  kis-acetyl-0-1,2,4,5 adonitol 59 204 (3-Trifluoromethylbenzyl) -0-5 xylitol 23 80 (3-Fluoro-benzyl) -0-5 xylitol 33 204 (2,4,6-Tribromo) benzyl) -O-1 D-arabitol 33 188: Fluoro-2-benzyl) -0-5 xylitol 28 92 Comparative Compound

Benzyloxy 2-methyltetrahydro-

  furan (DE-A 2,724,677) 28,135 triiodobenzoic acid 69 73

RE V E N D I C A T IONS

  Derivatives of benzyl pentitol ethers having the general formula I

CH 2 O Y

CH O Y

CH _ _ y 3 (I)

CH Y

CH O Y

2 3

CH 2 0 y 5

  wherein one of the substituents Y represents a radical

cal:

CH R 2

  R 1 o R represents hydrogen or an alkyl radical R 1 in C -C and 1 4

  R 2 represents an aromatic hydrocarbon radical

  possibly carrying one or more

  substituents taken as a whole

  by the C 1 -C 6 alkyls, the alkoxy

  at C 1 -C 6, optionally substituted phenoxy

  killed, optionally substituted phenyls, halogens, nitro group and trifluoromethyl radical,

  and the other other substituents Y, which may be identical

  or different, each represents a radical (CO) n R n 3 o R 3 represents hydrogen or an optionally substituted C 4 alkyl radical and i 4

n is equal to O or l.

  2. Derivatives of benzyl pentitol ethers according to claim 1, wherein: R represents hydrogen or a C 1 -C 4 alkyl radical, preferably a C 1 -C 4 methyl, preferably a methyl, R 2 represents a phenyl radical, 2-chloro-phenyl, 3-chlorophenyl, 4-chlorophenyl, 2,6-dichlorophenyl, 2,4-dichlorophenyl,

  3,4-dichlorophenyl, 2,4,6-trichlorophenyl

Nyl, 4-bromo-phenyl, 2,4-dibromophenyl, 2,6-dibromo-phenyl, 2,4,6-tribromo-phenyl, 2-fluoro-phenyl,

  3-fluoro-phenyl, 4-fluoro-phenyl, difluoro-

  2,4 phenyl, 2-methylphenyl, 3-methylphenol

  Nyl, 4-methylphenyl, 3,4-dimethylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 3,4-methylenedoxyphenyl, 2-phenoxyphenyl, 3-phenoxyphenyl, 2-nitrophenyl or 3-nitro phenyl, R 3 represents hydrogen, a C 1 -C 4 alkyl radical, preferably a methyl, ethyl or propyl radical or a chloromethyl radical, and

n is OO or l.

  3. Benzyl pentitol ether derivative according to claim 1 taken from the group consisting of (2,6-dichlorobenzyl) -O-xylitol,

  (2,6-dichlorobenzyl) -3-3 tetrakis-methyl-

  0-1,2,4,5 adonitol, 2,6-dichlorobenzyl-O-1-tetrakis-acetyl-O-2,3,4,5-D-arabitol, 2,4-dichlorobenzyl- 0-5 xylitol, (2-chlorobenzyl) C 5 xylitol, (2-methyl-benzyl) -O-5-xylitol, 2,6-dichlorobenzene (2,6-dichloro-D -arab (2,6-dichloro-adonylol) benzyl) -O-1-benzyl) -O-1-bernzyl) -0-3 (tribromo-214,6-benzyl) -0 -5-xylitol

2 5 23 1 2 2

  6-Benzyl-O-xylitol, (2,6-dichlorobenzyl) -0-5 tetrakis-acetyl-01,2,3,4 xylitol / (2,4,6-tribromo-benzyl) -o -5 tetrakis-acetyl-O-1,2,3 14 xylitoyl (tribromo-2,4,6 benzyl) -O-3 adonitol, (4-chlorobenzyl) -5-xylitol, 4-bromo-benzyl ) -0-5 xylitol, (3,4-dichlorobenzyl) -05 xylitol) (3-methyl-benzyl) -0-xylitol, (4-methylbenzyl) -0 -5-xylitol, (dimethyl) 3,4 benzyl) -0-5 xylitol, (3-chlorobenzyl) -0-5 xylitol, (4-cyano-benzyl) -0-5 xylitol, (2,6-dichlorobenzyl) -0-3

tetrakis-ac 6 tyl-O 1,2,4,5 adeno

Nitol

3-trifluoromethylbenzyl)

  0-5 xylitol, (3-fluorobenzyl) -5-xylitol, (4-fluorobenzyl) -5-xylitoj, (2,4,6-tribromo benzyl) -C) -i D-arabitol (2-Fluoro-benzyl) -O-xylitol, (2,6-dichlorobenzyl) -5-tetrakis-methyl-O-1,2,3,4-xylitol (2,6-dichlorobenzyl) 1-tetrakis-methyl-0-2,3,4,5 L-arabitol, (2,4-dichlorobenzyl) -0-5 tetrakis-methyl Q-O l, 2,3,4 xylitol, (2,6-Dichlorobenzyl) -O-1-tetrakis-methyl-O-2,3,4,5-D-arabitol, (2,4,6-tribromo-benzyl) -0-5 tetrakis-methyl-O 11 2,3,4-xylitol, (2,4,6-tribromo-benzyl) -0,1-tetrakis-methyl-O-2,13,4,5D-arabitol,

(2-chloro-6-fluoro-benzyl) -

0-5 xylitol,

(2-chloro-6-fluoro-benzyl) -

0-1 D-arabitoli

(2-chloro-6-fluoro-benzyl) -

0-3 adonitol,

(2-chloro-6-fluoro-benzyl) -

  0-5 tetrakis-acetyl-011,2,3,4 xylitol and

2-chloro-6-fluoro-benzyl

0 -5 tetrakis-methyl Ol 1,2,3,4

xylj tol -

  4 Process for the preparation of ether derivatives

  benzyl pentitols according to any of the claims

  cations i to 3, characterized in that, in the presence of acid acceptors and / or a catalyst, compounds of the general formula II are reacted.

CH-O-T O

CH Y 4

CH O Y

2

  in which one of the symbols Y 'represents a radical

CH R 2

R 1

  and the four other symbols Y 'each represent the hydro-

  gene, with compounds corresponding to one of the general formulas III to V:

R CO X (III)

R 3 Z (IV)

R 3 CO O CO R 3 (V)

  formulas in which R 1, R 2 and R 3 have the significances

  X is a halogen atom, preferably chlorine, and Z is a

  halogen atom or radical R 305020-.

  5. Process for the preparation of ether derivatives

  benzyl pentitol salts. Any of the

  1 to 3, characterized in that, in the presence of organic solvents and acid catalysts, the compounds of general formula VI are hydrolysed at temperatures of from 0 to 100 [deg.] C., preferably from 40 to 80 [deg.] C.

CH O '

CH O Y 2

I

CH O Y (VI)

CH O Y 4

CH Y "

  in which one of the symbols Y "represents a radical

-CH-R 2

R 1

  R 1 and the other four symbols Y "are grouped in pairs, each pair thus formed representing an optionally substituted methylene radical:

/ R 5

  formulas in which R 1 and R 2 have the meanings given in claim 1, R 4 and RS, which may be identical or different, each represent hydrogen, an optionally substituted C 1 -C 10 alkyl radical, an aryl radical, C 1 -C 3) alkyl optionally substituted, a cycloaliphatic hydrocarbon radical C 3 -C 8, an aromatic hydrocarbon radical optionally bearing one or more substituents taken from the group consisting of C 1 -C 6 alkyls, halogen, C 1 -C 6 alkoxy, nitro and trifluoromethyl, or R 4 and R 5 together form a polymethylene radical - (CH 2) m -, and

  m is an integer of 4 or 5.

  6. Product having a regulating action on the growth of plants, product characterized in that it contains at least one compound according to any one

Claims 1 to 3.

  7. Product having a regulatory action on the growth of plants, according to claim 6, characterized in that it also contains supports

and / or adjuvants.

  8. Product according to one of the claims

  6 and 7 to use to act on the vegetative development

  and generative legumes, especially soy.

  9. Product having a regulatory action on plant growth, according to claim 6, which product contains an active ingredient prepared according to

one of claims 4 and 5.