DE2239412C3 - 2-Halogenäthyl-methyl-diorganooxysilane and Mittet to regulate plant growth - Google Patents

Description

good water solubility, which makes them im The flow of sap from the plants is distributed everywhere and their effect not only in the desired location (fruit, but z. B. noticeable in the form of an unpleasant flow of resin over the whole plant, so not »Can only be used on fruit abscission alone can, and also has too long a permanent effect.

Certain haloalkyrmethylsilanes are also known as herbicidal active ingredients (cf. USA patents 33 90976, 33 90977 and J. K. Leasure et al J. Mod. Chem. 9,949 [1966]). 2-chloroethyl-methyldimethoxysilane was published by J. K. Leasure et al. (loc. citl produced, but has no herbalistic effect.

U.S. Patent 3,183,076 describes l-chlorothyl-methyl-dialkoxy-silane. the to promote germination, leaf detachment, etc. can be used.

The invention relates to new active ingredients 2-haloalhyl-methyl-diorganooxysilanes containing agents, which are in the different vegetable development stages have a stimulating or retarding effect on plant growth and the disadvantages of Do not have 2-t hloräthylphosphonsüure. Because of The very good stability of these active ingredients, these agents contain in addition to the usual carriers. Distribution means. Light and oxidation stabilizers do not have a stabilizing acid additive and are therefore applicable without restriction. The new means intervene in the physiological processes of plant development a and can be used for various purposes related to the increase in yield, the Em (relief and the Labor saving in cultural-technical measures. The various effects of these active ingredients essentially depend on the time of application, based on the stage of development of the seed or the plant, as well as the concentrations used.

By appropriate treatment with the invention Means can accelerate the ripening process in plants and thereby also a better one and achieve more even ripening of fruits or other parts of the harvest, which is the case with various types of fruit and other cultures are of great economic importance.

It has been found that the proposed (2-haloethyl) -methyl-diorgano-oxy-silanes in particular excellent for regulating fruit fall (fruit abscission). The invention Means and active ingredients are as effective for abscission of olives as for fruit abscission known commercial product 2-chloroethylphosphonic acid clearly superior, as extensive comparative tests have shown. The harvest of fruits Nuts and berries are traditionally made by hand. In the course of rationalization in the Agriculture, other methods of harvesting the fruit have been suggested. There are different types for this mechanical devices have been developed. Damage such mechanical devices but usually the plants and the crop. It was found that fruits either without or brought to waste with little mechanical assistance and thus harvested more economically can be, if the trees, shrubs, perennials before the ripeness of the fruit with the erfindungsaemäße Active ingredients are treated.

The promotion of fruit fall can also be exploited in such a way that through early application the active ingredients chemical thinning of the young fruits is achieved. This is desirable in the case of excessive, natural fruit set, as z. B. often occurs with apples, peaches or citrus fruits.

With the new means the vegetative plant growth and influences the ability to germinate, flower formation, fruit development and formation promoted by separation tissues. In addition, the supporting tissue was removed from the treated plants the stem strengthened. The formation of undesirable stingers in various types of plants, such as in the case of tobacco and azaleas, it is greatly reduced, and vegetative growth in vines is also inhibited. The new compounds also act to promote secretion, e.g. B. »ird the latex river at Hevea brasiliensis promoted, an effect that is of great economic importance. As tests have shown, the Rooting of seedlings and cuttings as well as tuber formation in potatoes promoted. Except the emergence of dormant rhizomes takes place at the same time, which is particularly important for various perennial weeds such as couch grass, johnson grass and C yperus. which can then be easily destroyed by herbicide or are to be contained. The germinability of seeds is promoted at low concentrations, prevented at higher. Both the one and the other effect are of economic importance.

With many ornamental and cultivated plants there is a control of flowering date and number of flowers possible. This effect plays a particularly important role with pineapples. If all plants bloom at the same time, harvesting takes place within a comparatively short time.

In the case of pumpkins and other plants, there is a shift in the flower sex differentiation in favor of female flowers. Influencing the flower sex differentiation can in practice potentially z. B. as an aid in hybridizations in seed breeding or to increase yield, z. B. at Cucurbits, find use.

By influencing the formation of flowers. the flowering genus and vegetative growth can the active ingredients used according to the invention the harvest yield of plants (e.g. fruits, seeds, leaves) increase significantly.

The shoot and root growth can be regulated by the active ingredients in a concentration-dependent manner will. In this way it is possible to inhibit the growth of the plants. Of economic interest is here z. B. the attenuation of grass growth on roadsides and roadsides or on lawns, because this can reduce the frequency of grass clippings.

Seed germination, buds and rhizomes and the formation of side shoots can be promoted or inhibited by the active substances mentioned, depending on the concentration used will. In this way, seed germination and the emergence of dormant rhizomes in weeds can be promoted which makes it easier to kill these weeds with herbicides. On the other hand, it can the undesirable development of stingy shoots in dumped tobacco plants prevents grazing.

The possibility of using the agents according to the invention for certain plants should also be emphasized trigger the leaf fall. The harvest of tree-like plants is made much easier if one

beforehand the cotton plants by means of these compounds defoliated. In the case of plants that are to be grafted, defoliation can reduce transpiration be reduced.

Tests also showed that fruit and blossom thinning occurs in fruit trees. Farther are z. B. for oranges, melons, apricots, peaches, Tomatoes, bananas, blueberries, figs, coffee, pepper and pineapple are the fruit ripening and Fruit coloring accelerates and improves. The ripening of tobacco leaves is also accelerated and improved. The fruit detachment is made much easier by the formation of separating tissue. This is of great economic importance for mechanical harvesting, ζ. B. of citrus fruits, of Olives, stetu fruit or pome fruit or soft fruit, nuts or subtropical fruits. Through suitable Application of the above substances can be used in different crops such as cotton, green beans, green peas, Ornamental shrubs and young plants defoliation can be achieved.

The extent and nature of the effect depend on various factors, in particular Application time in relation to the stage of development of the plant and the application concentration tion. However, these factors in turn differ depending on the type of plant and the desired effect. For example, areas of the bottle will be treated during the entire growing season; Ornamental plants, in which the intensity and number of flowers should be increased, before the formation of the flower system; Plants whose fruits are used respectively. are recycled at a corresponding distance before the Harvest. The application of the active ingredients takes place in the form of solid or liquid means both above ground Plant parts as well as in the ground or on the ground. Application to the above ground is preferred Parts of plants for which solutions or aqueous dispersions are best suited. For the treatment of the growth substrate (the soil) are solutions and dispersions as well as dusts, Granulates and grit suitable.

The essential promotion of the detachment of citrus fruits and bean leaves with the invention Means was determined by the following experiments:

The active ingredients are used as solutions on branches with good fruit hangings from various orange trees sprayed on in concentrations of 0.2 and 0.4%. After 14 days, the experiments were carried out according to that of W. C. Wilson and C. H. Hendershott developed method, (Proc. Am. Soc. Hort. Sc, 90, 123 to 129 [1967]) evaluated. The force required to remove a fruit is expressed in kilograms definitely.

The exact experimental methodology was as follows:

On orange trees of the variety listed below were individual branches that were at least 15 to 20 ripe Fruit, sprayed with an agent of the two active ingredient concentrations 0.4 and 0.2%. 7 days after the application, the picking force to be used was determined for 10 fruits treated in the same way determined with the help of a spring balance and the mean value formed from the 10 measured data.

The agents with the following active ingredients of the formula I resulted in the following in this experiment tabulate tear-off forces in kilograms *) and percentage reductions in the picking forces that veri filet

Equally with Fnichlen on untreated trees to be established.

W irksJolT concentrate AbrciUkr-ifl Picking force Oraiifcn- No. tration rcduction Mirte l ".il (klEl'l in O 18th 0.4 3.2 66 Navel 0.2 6.9 25th 19th 0.4 0 0.2 0 100 Hamlin Fruit fall 77 0.4 <0.5 > 95 0.2 <0.5 > 95 Hamlin 78 0.4 <0.5 > 95 Hamlin 0.2 <0.5 > 95 13th 0.4 <0.5 > 95 Hamlin 0.2 <0.5 > 95 24 0.4 <0.5 > 95 Hamlin 0.2 <0.5 > 95 28 0.4 3.8 55 Hamlin

*) Ahreisskrafl · - 0.5 kp means the fruits can be can be easily removed so that no more force can be exercised wvden

In bean leaf abscission tests, segments of bean leaves of the "Tempo" variety are converted into a Solution of 0.002% active ingredient immersed and 4 to 8 segments per active ingredient for 6 days left in the active ingredient solution under controlled conditions. On certain days after the start of treatment the number of abscesses that have occurred (constriction of the stem on the leaf-side Abscission zone).

Tests with agents that contained the following active ingredients gave excellent results:

2-chloroethyl- (methyl-diethoxy) -silane,

2-chloroethyl- (methyl-dioctyloxy) -silane,

2-bromoethyl- (methyl-dioctyloxy) -silane,

2-chloroethyl- (methyl-dibenzoxy) -silane,

2-bromoethyl- (methyl-dibenzoxy) -silane,

2-chloroethyl- (methyl-dipropinyl- (2 ') - oxy) -silane,

2-chloroethyl- (methyl-dibutenyl- (2 ') - oxy) -silane,

2-chloroethyl- (methyl-di-4'-methoxybenzoxy) -

silane,

2-chloroethyl- (methyl-diacetoxy) -silane,
2-chloroethyl- (methyl-di-4'-chlorobenzoxy) -silane,
2-chloroethyl (methyl-di-2'-chloroethoxy) silane,
2-ChloräthyHmethyl-di-hexynyl- (3 ') - oxy) -silane.

Agents according to the invention are produced in a manner known per se by intimate mixing and grinding the active ingredients with carrier substances, optionally with the addition of opposite to the active ingredients inert dispersing agents or solvents.

Active ingredient concentrates dispersible in water, d. H. Wettable powder, pastes and emulsion concentrates represent active ingredient concentrates that are diluted with water to any desired concentration can be. They consist of an active ingredient, a carrier and optionally a stabilizing agent Additives, surface-active substances and anti-fouling agents and, if necessary, solvents

lone. The active ingredient concentration in these agents is 0.5 to 80%.

The wettable powders and pastes are obtained by combining the active ingredients with the customary dispersants and the customary pulverulent carriers in suitable devices mixed and wedged until homogeneous.

These mixtures can also contain additives stabilizing the active substance and / or nonionic, anionic active substances and cation-active substances are added, for example, the adhesive strength of the active ingredients improve on plants and parts of plants (adhesives and adhesives) and / or better wettability (Wetting agent). Examples of possible adhesives are: olein-lime mixture, Cellulose derivatives (methyl cellulose, carboxymethyl cellulose), hydroxyethylene glycol ether of Mono- and dialkylphenols, ligninsulphonic acid, their alkali and alkaline earth salts, polyethylene glycol ethers (Carbowaxe), fatty alcohol polyglycol ethers, condensation products of ethylene oxide, propylene oxide, Polyvinyl pyrrolidones, polyvinyl alcohols. Condensation products of urea formaldehyde as well Latex products. The active ingredients are mixed, ground and sieved with the additives listed above and happens that in the wettable powders the solid fraction has a grain size of 0.02 to 0.04 and in the Pastes of 0.03 mm.

For the production of emulsion concentrates and pastes, dispersants as described in the preceding Sections were listed, common organic solvents and water used.

The solvents have to be practically odorless, not phytotoxic and have no effect on the active ingredients be inert.

The agents according to the invention can also be used in the form of solutions. For this becomes the active ingredient or several active ingredients of the general formula I in suitable organic Solvents, solvent mixtures or water. Aliphatic solvents can be used as organic solvents and aromatic hydrocarbons, their chlorinated derivatives, alkylnaphthalenes, mineral oils can be used alone or as a mixture with one another. The solutions are said to be the active ingredients in one Concentration range from 1 to 20% included.

The solid working-up forms such as dusts, scattering agents and granules contain solid carriers, as listed above, and optionally additives stabilizing the active ingredient. The grain size of the carrier materials is expediently up to about 0.1 mm for dusts, about 0.075 to 0.2 mm for grit and 0.2 mm or more for granulates. The active ingredient concentrations in the solid preparation forms are 0.5 to 80%.

All of the active ingredient concentrates listed can also contain light stabilizers and antioxidants.

Granulate ^to

The following substances are used to produce a 5% granulate:

5 parts of 2-chloroethyHmethyl-di-2'-chloroethoxy) - 6s

silane,

0.25 part of epichlorohydrin, 0.25 part of cetyl polyglycol ether, 3.50 parts of polyethylene glycol ("CJrbowax"), 91 parts of kaolin (grain size 0.2 to 0.8 mm).

The active substance is mixed with epichlorohydrin and dissolved with 6 parts of acetone, then is Polyethylene glycol and cetyl polyglycol ether added. The solution obtained in this way is sprayed onto kaolin and then the acetone evaporated in vacuo.

Wettable powder

For the production of (a) 40% and (b) 50%, (c) 25% and (d) a 10% wettable powder the following components are used:

(A) 40 parts of 2-chloroethyl- (methyl-dioctyloxy) -silane,

5 parts of lignin sulfonic acid sodium salt, 1 part of dibutyl naphthalenesulfonic acid

Sodium salt,
54 parts of silica;

(b) 50 parts of 2-chloroethyl (methyl-di-dodecyloxy) -

silane,

5 parts of alkylarylsulfonate ("Tinovetin B"), 10 parts of calcium lignosulfonate, 1 part champagne chalk — hydroxyethyl

cellulose mixture (1: 1), 20 parts of silica,
14 parts of kaolin;

(c) 25 parts of 2-chloroethyl- (methyl-di-4'-methoxy-

benzoxy) silane,

5 parts of oleyl methyl tauride Na salt, 2.5 parts of naphthalenesulfonic acid formaldehyde

Condensate,

0.5 parts of carboxymethyl cellulose, 5 parts of neutral potassium aluminum silicate, 62 parts of kaolin;

(d) 10 parts of 2-chloroethyl- (methyl-di-4'-chloro-benz-

oxy) silane

3 parts mixture of the sodium salts of saturated fatty alcohol sulfates,

5 parts of naphthalenesulfonic acid formaldehyde

Condensate,
82 parts of kaolin.

The active ingredients are intimately mixed with the additives in suitable mixers and mixed with the appropriate Grind mills and rollers. This gives wettable powders which, with water, form suspensions Dilute to any desired concentration. Such suspensions find z. B. Application for removing unwanted stinging shoots, for tillering lawns, for rooting seedlings and cuttings.

Emulsion concentrate

For the production of 25% emulsion concentrates

(A) 25 parts of 2-chloroethyl (methyl-di-benzoxy) -silane,

5 parts mixture of nonylphenol polyoxyethylene and calcium dodecylbenzenesulfonate 70 parts of xylene;

(b) 25 parts of 2-chloroethyl (methyl-di-ethoxy) -silane, 10 parts mixture of nonylphenol polyoxy

ethylene and calcium dodecylbenzenesulfonate, 65 parts of cyclohexanone

609626/233

mixed together. This concentrate can be mixed with water to form emulsions at suitable concentrations be diluted. Such emulsions are suitable for thinning flowers and fruits, for accelerated thinning Ripening of fruits and to promote fruit and leaf detachment.

Among the 2-haloethyl-methyl-diorganooxy-silanes, new and preferred active ingredients are those which of the formula I.

O - R ₁

X-CH ₁ -CH ₁ -Si-OR,

CH,

U)

15th

in which X is chlorine or bromine, R ₁ and R _{2 are} optionally substituted by chlorine, C _{1 -C 8} alkoxy, C ₄ -C ₈ alkoxyalkoxy, C ₃ -C ₆ alkenyloxy, phenoxy, phenyl. C ₃ -C ₀ cycloalkyl, Q-Cg-alkylthio, C _r C ₈ -alkoxycarbonyl. Tetrahydropyranyl, tetrahydrofuranyl, thieny I, dioxanyl or dioxoanyl substituted C [-C ₁₈ -alkyl radicals, Cj-C ^ -alkenyl radicals, Cj-C ^ -chloralkenyl radicals. Cj-Cg-alkynyl radicals, Cj-C ^ -cycloalkyl radicals, optionally one or more times by chlorine or bromine _{, C 1} -C ₄ alkyl, C ₁ -C ₄ alkoxy, C _{1 -C 4 alkylthio, C 1 -C 8} alkanoyl optionally mono- or polysubstituted by chlorine, C, -C ₁ -C ₈ -alkoxy substituted benzyl or a C or Cj-Cg-alkoxycarbonyl substituted phenyl radicals, ₈ alkyl or C ₂ -C ₁₈ alkanoyl. with the proviso that R ₁ and R ₂ do not both embody the meth'yl radical if X is chlorine.

The invention also relates to these new compounds of the formula I and to processes for their preparation.

The production of the new 2-HalogenäthyI-methyldiorganooxy-silane of the formula I is carried out according to the invention by adding a 2-haloethyl-methyl-dichlorosilane of the formula II in a manner known per se

40 cl

X-CH ₂ -CH ₂ -Si-Ci (II)

CH ₃

in which X is chlorine or bromine,

(A) with one equivalent each of two different alcohols or with 2 equivalents of the same alcohol R ₁ OH and / or R ₂ OH or

(b) with 2 equivalent of a QC ^ alkanecarboxylic acid or its anhydride and reacting gewünschten- PaIIs in the thus obtained silane of formula 111

X-CH ₂ -CH ₂ -Si- (O-CO-AIkVl) ₂

55

CH ₃

(III)

gradually exchanging one or both alkanoyl radicals for ^ ⁰ radicals of alcohols RjOH or R ₂ OH.

In formula II of the starting materials, X denotes chlorine or bromine, R ₁ and R ₂ in the formulas of the alcohols have the meanings given under formula I, "alkyl" in formula III is an alkyl radical having 1 to ITC atoms

The process is preferably carried out in the presence of a solution which is inert to the reactants or diluents carried out. Aprotic solvents such as aliphatic are particularly suitable and aromatic hydrocarbons, e.g. B. hexane. Cyclohexane, benzene, toluene, xylene, halogenated Hydrocarbons such as chlorinated ethylene, carbon tetrachloride. Chloroform, chlorobenzene, as well Ethers and similar compounds, such as diethyl ether and tetrahydrofuran.

To achieve a complete conversion, the alcohols used as reactants can also be used. Carboxylic acids and carboxylic anhydrides, used in excess, serve as solvents or diluents.

Furthermore, it may be necessary to add the reaction mixture to add an acid-binding agent. Tertiary amines are particularly suitable for this purpose.

The reaction temperatures are in the range from 0 to 100 ° C., the reaction time can between a few minutes and several days. It depends largely on the responsiveness of the deployed Alcohols.

Of the two starting materials of the formula II , the chlorine compound is known.

The starting material of the formula II in which X is bromine has not yet been described in the literature.

This 2-bromo-ethyl-methyl-dichlorosilane is after known methods produced by reaction of ethyl-methyl-dichlorosilane with bromine accordingly that of K. W. M i c h a e 1 (J. ora. Chem., 34, 2832 [1969]) for the preparation of 2-bromoethyltrichlorosilane process described or by HBr addition to vinyl-methyl-dichlorosilane analogously one of A. I. B ο u r η e (J. Chem. Soc, Sect. C. 1970, 1740) specified reaction method. As a catalyst for these addition reactions, UV light, peroxides and radical initiators serve.

The following examples are provided for illustrative purposes of the method according to the invention. In the following table are those according to the Examples prepared as well as others prepared by the route described in the examples /, '- Halogenathyl-methyl-silane of formula I summarizes.

The temperatures are given in degrees Celsius, the pressure in torr.

e i s ρ i e 1 1

43 g of 2-chloroethyl-methyl-dichloro-silane are dissolved in 56 g of acetic anhydride and left to stand closed for 21 hours at room temperature. The reaction product is evaporated in vacuo. 36.5 g of 2-chloroethyl-methyl-diacetyloxy silane, boiling point 71 to 73 ° / 0.8 Torr, nff = 1.4369, are obtained

Calculated found .

C 37.5, H 5.8;
C 37.2, H 5.7.

Example 2

19.3 g of 2-chloroethyl (methyl-diacetyloxy) -silane are dissolved in 40 ml of absolute benzene. At 50 °, 10.8 g of benzylalkonol in 20 ml of absolute benzene are added over the course of 60 minutes. The mixture is stirred for 4½ hours at 50 to 55 °. The reaction mixture is evaporated in vacuo and one obtains

¹ Y

11, Og 2-chloroethyl - methyl-acetyloxy - benzyloxysilane, B.p. 105 to 110 / 0.03 torr, / r = 1.4963.

Calculated
found .

C 52.8, H 6.3;
C 52.8, H 6.4.

Example 3

35.5 g of 2-chloroethyl-methyl-dichloro-silane are in Dissolved 350 ml of absolute diethyl ether. At -5 to -10 °, 43.2 g of benzyl alcohol are obtained within Added 5 minutes and then within 30 minutes 31.6 g of absolute pyridine. solved in 100 ml of absolute ether. The mixture is stirred for a further 1 hour at 0 ° and then under reflux for 18 hours.

The reaction mixture is filtered, the filtrate washed quickly with ice-cold water, dried and evaporated in vacuo. 52.9 g of 2-chloroethyl-methyl-dibenzoxysilane, boiling point 138 to 14170.005 Torr, nf = 1.5339 are obtained.

Calculated ... C 63.5, H 6.6, Cl 11.0. Si 9.1; found .... C 63.5. H 6.55. Cl 11.1. Si 9.1.

Example 4

19.6 g of 3-hexyn-1-ol are dissolved in 200 ml of absolute diethyl ether. It is cooled to -10 to -5 ', 15.8 g of absolute pyridine are added and a solution of 17.7 g of 2-chloroethyl-methyl-dichloro-silane in 50 ml of absolute dietary ether is then added dropwise within one hour at the same temperature to. The mixture is then stirred at 0 'for 1 hour, at room temperature for 2 hours and under reflux for 18 hours. It is then filtered, and the filtrate is quickly washed with ice-cold water, dried and evaporated in vacuo. 22.5 g of 2-chloroethyl-methyI-dihexynyl- (3 ') -oxysilane are obtained. 190-195 ° '0.005 Torr. nf = 1.4695.

Example 5
(Production of a raw material)

42.3 g of vinylmethyldichlorosilane are ^{cooled to -5 to 0 "J.} At this temperature, hydrobromic acid is passed in under UV irradiation for 30 to 45 minutes. After HBr uptake has ended, the solution is left to stand overnight under a nitrogen atmosphere at room temperature. 61 is obtained , 6g of the new compound 2-bromoethylmethyl-dichlorosilane, bp 94 to 96757 Torr.

Calculated ... C 16.2. K 3.2. Cl 31.9, Si 12.6:
found .... C 16.2, H 3.2, Cl 31.0, Si 13.0.

Example 6
(Production of a raw material)

40

45

Table I.

No. R ₁ --- R,

12th

Compounds of Formula I.
O-R ₁

X-CH ₂ -CH ₂ -Si-OR ₂ CH ₃

A mixture of 142.3 g of vinylmethyldichlorosilane and 1 g of anhydrous AlCl ₃ is cooled to -5 to 0 °. At this temperature, hydrochloric acid is passed in under UV irradiation for 90 minutes a bath temperature of at most 15 ° in a flask cooled with dry ice. 177.5 g of the known 1-C-methyl-methyl-dichloro-silane, bp 82 to 847 68 Torr, are obtained.

Calculated ... C 20.3, H 3.9, Cl 60.0, Si 15.8;

Found ... C 20.8, H 3.9, Cl 59.0, Si 16.4.

methyl
methyl
ethyl
ethyl
iso-propyl
Butyl

1-methylpropyl
Pentyl

Hexyl

Hexyl

Heptyl

2-ethylhexyl

1-methylheptyl

Octyl

Octyl

Nonyl
Decyl

Dodecyl

Dodecyl

Hexadecyl

Octadecyl

Octadecyl

2-chloroethyl

6-chlorohexyl

2-methoxyethyl

2-ethoxyethyl

2-butyloxyethyl

2-allyloxyethyl

2- (l-MethyläthenoyI-

oxyethyl

43 2- (2-ethoxyethoxy) ethyl

2-phenoxyethyl

2-ethylthioethyl

2-oaylthioethyl

1-phenylethyl

3-phenylpropyl

2-propenyl

2-butenyl

2-butenyl

Physical Dalcn Fp .; Kp./Torr: / I ₁ ,

Cl bp 77725

Br Kp. 90-91725

Cl bp 84-86716

Br Kp. 94-96720

Cl bp 88-90714

Cl bp 92-9570.3

Cl bp 7270.3

Cl bp 13570.5

Cl bp 135-1407

0.05
Br «-: = 1.4484

Cl bp 155-1607

0.05

Cl n <° = 1.4441

Cl n? = 1.4408

Cl bp 13470.001

Br bp 14670,001

Cl η ": = 1.4446

Cl η: '= 1.4446

Cl η ' = 1.4517

Br η "= 1.4592

Cl m.p. 26-3 Γ

Cl m.p. 26-30 °

Br m.p. 30 °

Cl bp 121-1257 0.001

Cl bp 150-1567

0.001
Cl bp 100-105 ° /

0.001

Cl bp 104-1097

0.001
Cl ny = 1.4411

Cl bp 125-1307 0.001

Cl η "' = 1.4578

Cl η% = 1.4442

Cl η? = 1.5311

Cl bp 160-1657

0.001

Cl n'S = 1.4822 α »? = 1.5179 Cl η? = 1.5211 α bp 50-5470.15

α bp 100-1077 0.55

Br bp 94-9670,005

13th

continuation R, ---- R; X Physical Daicn \ r. 20th ' 55 ' 03 \ J R, R, λ; - 0 R, ^ R, - ((IR,
R, lsi: ' R, R, = -co- X X Physical data Fp .: Kp. Torr: n " H, CO,.) - CH ₂ - methyl Rj is: M.p .; Kp / Torr: n " No. 3.7-dimethyl-6-oetenyl Cl η ■ = 1.4647 05 methyl Benzyl methyl Cl 3,7-dimethyl Cl / ι = 1.4797 ■ ^S 102 60 3-Tri II normet hy I phenyl "abellc Il ethyl
Ά 'ι 1 1 Cl η = 1.4676 52 2,6-octadienyl
9-octadecenyl Cl / ι = 1.4644 25th 06 Alnyl Benzyl methyl Br 53 2-propynyl Cl Bp. 64 70 0.1 I.
IO "■ Ο ^{l CH} 2- \ r iso-Props I
Pemy!
Heptyl Cl η: = 1.4710 55 2-propynyl Br Kp. 98 - 100 '' rr τ- 09 Undecyl Ethyl methyl Cl 56 0.005 I. 30th 65 ; _S ^L -CH _: - IO Undecyl Pentyl methyl Cl Br η = 1.5490 57 2-butynyl Cl η- ?: = 1.4762 OS 11th
IT Heptadecyl Octyl methyl Cl 3-hexynyl Cl Kp. 190-195 I. 35 \ _n J — LH, - 12th Fa at le III Cl / ί = 1.4670 58 0.005 \) 13th
14th
17th 2-butynyl methyl C! 59 3-chloro-2-butenyl Cl Bp 105-110 H ₁ C 19th \ 'r. 0.001 40 20th 2-butenyl methyl Cl 61 3- Phenyi-2-propeny 1 Cl η " = 1.5632 23 24 4-chloro-ethyl
benzyl CI Cl ιΓ 1.4510 3- phenyl-2-propeny 1 Br / r; = 1.5741 4-chloro-ethyl Br 62 Cyclododecyl Cl ni = 1.4939 25th benzyl 63 Butoxycarbonylmethyl Cl π; -: ¹ = 1.4478 3,7-di-ethyl α 64 Cyclohexyl Cl Bp. 120-125
0.001 45 26th methyl- 66 Cyclohexylmethyl Cl Bp. 118 - 1 23.
0.001 2 / 6-octenyl X Physical
Oil 68 Cyclohexylmethyl Br π ff = 1.4845 28 4-meth-ethyl Cl Cl Kp. 71 737Ο.8 69 S-cyclohexylpropyl Cl / iff = 1.4634 oxybenzyl Br Bp 80 8170.3 70 3,4-dimethylcyclohexyl Cl / y? = 1.4707 50 29 CI Kp. 81-827-2 71 3,5-dimethylcyclohexyl
(-) Borneyl
Cyclopropyl-methyl Cl
Cl
Cl / iff = 1.4647
M.p. 55-58
/ JV = 1.4596 Br Kp. 93-967
η πι 72 Benzyl Cl Bp. 138-141 "/
0.005 30th Cl
Cl
CI W, \ / I
Bp 7570.08
/ ι if = 1.4302
IV ' = 1.4340 73
75
76 Benzyl Br 150-154 ° / 0.01 131 CI M.p. 37 " 77 4-chlorobenzyl Cl / iS = 1.5434 132 Br M.p. 37-39 " 78 4-chlorobenzyl Br / ι? = 1.5554 Cl M.p. 64 " 79 4-methoxybenzyl Cl nf = 1.5375 133 80 2,4-dich] orbenzyl Cl nf = 1.5604 81 4-methylbenzyl Cl / i? = 1.5291 R-. Physical 82 Phenyl Cl nf = 1.5393 134 Data 83 4-chlorophenyl Cl / if = 1.5503 Bp 105-1107 84 3-chlorophenyl Cl / 7? = 1.5506 0.03 85 3,4-dicblophenyl Cl Mp 43-47 ° Kp. 140-1477 86 3,5-dichlorophenyl Cl M.p. 54-56 ° 0.01 87 4-bromophenyl Cl n <? = 1.5760 Bp 4270.5 88 4-methoxyphenyl Cl η S- '= 1.5436 Bp 8770.001 89 3-methoxyphenyl Br π? - 1.5528 Kp. 105-1107 90 3-methoxypheayl Cl ηΨ = 1.5425 0.005 91 4-butyloxyphenyl Cl η? = 1.5212 Kp. 76-807 92 3-tert-butylphenyl Cl nff = 1.5230 0.02 93 3-methylphenyl
3-methylphenyl Cl
Br η? = 1.5300
nff = 1.5461 Kp. 78-807 94 3,4-dimethylphenyl Cl ni? = 1.5346 0.02
η S ¹ = 1.4974 95
96 3-formylphenyl Cl M.p. 91-93 »? = 1.5155 97 4-methylthiophenyl Cl nl ° = 1.5942 98 4-ethoxycarbonyl Cl M.p. 94-96 η? = 1.4532 99 phenyl 100 3-ethoxycarbonyl σ n? = 1.5275 phenyl η? = 1.4762 101

Claims (4)

Patent claims: 1. 2-haloethyl-methyl-diorganooxysilanes of Formula 1 0-R ₁
X - CH, -CH, -Si -O- R, (I) wherein X is chlorine or bromine, R ₁ and R, optionally by chlorine, C ₁ -C ₈ -AlkOXy. C ₄ -C ₈ -alkoxyalkoxy, Cj-Cfc-alkenyloxy, phenoxy, phenyl, C ₃ -Cp-cycloalkyl, Q-Cj-alkylthio, q-Ce-alkoxycarbonyl. Tetrahydropyranyl, tetrahydrofuranyl, thienyl, dioxanyl or dioxolanyl-substituted C ₁ -C ₁₈ -alkyl radicals, Oj-Cm-alkenyl radicals. CC ₁₈ -ChIOralkenyl radicals. Cj-Q alkynyl radicals. Cj-Qj-Cydoalkylreste, optionally mono- or polysubstituted by chlorine or bromine, C, -C ₄ alkyl, C ₁ -C ₄ -alkoxy, Qd-alkylthio. Q-Cg-alkanoyl or C ₁ -C ₈ -alkoxycarbonyl substituted phenyl radicals, optionally one or more times by chlorine. C ₁ -C ₈ -AIk) I or C, -C ₈ -alkoxy substituted benzyl or a C, -C ₁₈ alkanoyl, with the proviso that R ₁ and R ₂ do not both represent the methyl radical when X is chloro . 2. Process for the preparation of 2-haloethyl-methyl-diorganooxysilanes of formula 1 according to claim 1, characterized in that 2-haloethyl-methyl-dichloro-silane is used in a manner known per se of the formula II Cl X-CH ₂ -CH ₂ -Si-CI (II) CH ₃ in which X is chlorine or bromine, a) with one equivalent each of two different alcohols or with 2 equivalents of an identical alcohol R ₁ OH and / or R ₂ OH or b) with 2 equivalents of a Cj-Cn alkanecarboxylic acid or their anhydride reacts and, if desired, in the silane thus obtained Formula III X - CH ₂ - CH ₂ -Si- (O- CO- alkyl), CH ₃ (III) gradually exchanging one or both alkanoyl radicals for radicals of alcohols R ₁ OH or R ₂ OH. 3. Agent for regulating plant growth, characterized in that it is used as an active ingredient 2-haloethyl-methyl-diorganooxy-silane contains. 4. Means according to claim 3 for olive abscission. The invention relates to new 2-haloethyl-melhylsilanes and means for regulating plant growth to improve yield and facilitate harvesting agricultural, forestry and horticultural products and processes for the production of the new silanes. It has been found that the agents according to the invention and their active ingredients are surprisingly favorable Effect on the growth and differentiation of above and below ground parts of plants and -weave exercise. They are the well-known plant growth regulator 2 - chloroethane - phosphonic acid. which one of the active ingredients is closer in its mode of action is superior in some respects and is therefore a valuable addition to technology. The new agents for regulating plant growth are characterized in that they are as Active ingredient a 2-haloethyl-methyl-diorganooxysilane contain. This agent is preferably used to promote olive abscess. These 2-haloethyl-methyl-diorganooxy-silanes influence the growth of above and below ground parts of plants in different ways and have in the usual application concentrations have a low toxicity to warm blooded animals. The active ingredients call into this Concentrations also do not result in any morphological changes or damage that the entering into of the plant. The compounds are not mutagenic. Their effect is of the one herbicidal active ingredient and a fertilizer different. Rather, the effect corresponds to that can be observed when ethylene is applied to different parts of the plant. It is known that also the plant itself in different stages of development ethylene to different degrees produced, especially before and during the maturation process of the fruits and at the end of the growing season when the fruit and leaves are detached. Since the influence of ripening, fruit detachment and leaf detachment by chemical substances Tür the fruit, citrus fruit, pineapple and cotton cultivation has the greatest economic importance one can positively influence the development of the plant with ethylene-releasing agents from the outside In the meantime, different classes of substances have become known, with which individual such effects can be achieved. Such known compounds are either relatively unstable under weather conditions because they are very are sensitive to hydrolysis or phytotoxic. In the South African patent 68 1036 are ii-Halogenäthylphosphonsäurc derivatives as the plant growth regulating agents described. These compounds degrade in and on the Plant releasing ethylene and therefore resemble ethylene in terms of effect and breadth of effect. Because of However, these phosphonic acids and their derivatives are capable of their very low stability as compared to the ones made of them Not meeting requirements. Since they only work in an acidic environment, more precisely in a pH range below 5, are stable, the active ingredient concentrates must be stabilized by adding acids. This However, the addition of acid limits the scope of these active ingredients with regard to phytotoxic ones Effects a. In addition, the storage of such sensitive active ingredient concentrates is difficult connected. Further disadvantages of 2-C'hloräthanphosnhonsäure are yours as well as being corrosive